United States
 Environmental Protection
 .gency
Office of Solid Waste
and Emergency Response
Washington, DC 20460
November 1986
SW846
Third Edition
 Solid Waste
 Test Methods
 for Evaluating Solid Waste
Volume IB: Laboratory Manual
Physical/Chemical Methods

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                                       ABSTRACT


 4    This manual provides test procedures which  may be used to evaluate those
^properties of a solid waste which  determine  whether the waste 1s a hazardous
 waste within the definition of  Section  3001 of the Resource Conservation and
 Recovery Act (PL 94-580).   These  methods  are approved for obtaining data to
 satisfy the requirement of  40  CFR  Part  261,  Identification and Listing of
 Hazardous  Waste.      This   manual   encompasses   methods   for  collecting
 representative samples of solid  wastes,  and  for determining the reactivity,
 corroslvlty, 1gnitab1l1ty, and composition  of  the  waste and the mobility of
 toxic species present In the waste.
                                     ABSTRACT - 1
                                                          Revision
                                                          Date  September 1986

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VOLUME  ONE,

     SECTION B
                        Revision      0
                        Date  September 1986

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For sale by the Superintendent of Documents, U.S. Government Printing Office Washington, D.C. 20402

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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

     1.1 Introduction
     1.2 Quality Control
     1.3 Detection Limit and Quantification Limit
     1.4 Data Reporting
     1.5 Quality Control Documentation
     1.6 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
                                 CONTENTS -  1
                                                         Revision
                                                         Date  September 1986

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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 3020: ' Acid Digestion of Aqueous Samples and Extracts
                            for Total Metals for Analysis by Furnace
                            Atomic Absorption Spectroscopy
          Method 3040:  Dissolution Procedure for Oils, Greases, or
                            Waxes
          Method 3050:  Acid Digestion of Sediments, Sludges, and Soils
     3.3 Methods for Determination of Metals
          Method 6010:
Inductively Coupled
    Spectroscopy
Plasma Atomic Emission
Method 7000:
Method 7020:
Method 7040:
Method 7041:
Method 7060:
Method 7061:
Method 7080:
Method 7090:
Method 7091:
Method 7130:
Method 7131:
Method 7140:
Method 7190:
Method 7191:
Method 7195:
Method 7196:
Method 7197:
Method 7198:

Method 7200:
Method 7201:
Method 7210:
Method 7380:
Method 7420:
Method 7421:
Method 7450:
Method 7460:
Atomic Absorption Methods
Aluminum (AA, Direct Aspiration)
Antimony (AA, Direct Aspiration)
Antimony (AA, Furnace Technique)
Arsenic (AA, Furnace 'Technique)
Arsenic (AA, Gaseous Hydride)
Barium (AA, Direct Aspiration)
Beryllium (AA, Direct Aspiration)
Beryllium (AA, Furnace Technique)
Cadmium (AA, Direct Aspiration)
Cadmium (AA, Furnace Technique)
Calcium (AA, Direct Aspiration)
Chromium (AA, Direct Aspiration)
Chromium (AA, Furnace Technique)
Chromium, Hexavalent (Coprecipitation)
Chromium, Hexavalent (Colorimetric)
Chromium, Hexavalent (Chelation/Extraction)
Chromium, Hexavalent (Differential Pulse
Polarography)
Cobalt (AA, Direct Aspiration)
Cobalt (AA, Furnace Technique)
Copper (AA, Direct Aspiration)
Iron (AA, Direct Aspiration)
Lead (AA, Direct Aspiration)
Lead (AA, Furnace Technique)
Magnesium (AA, Direct Aspiration)
Manganese (AA, Direct Aspiration)
                                 CONTENTS - 2
                                                          Revision       0
                                                          Date   September  1986

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          Method 7470:

          Method 7471:
          Method
          Method
          Method
          Method
          Method
          Method
          Method
          Method
          Method
          Method
          Method
          Method
          Method
          Method
          Method
7480:
7481:
7520:
7550:
7610:
7740:
7741:
7760:
7770:
7840:
7841:
7870:
7910:
7911:
7950:
Mercury 1n Liquid Waste (Manual Cold-Vapor
    Technique)
Mercury 1n Solid or Semi sol id Waste (Manual
    Cold-Vapor Technique)
Molybdenum (AA, Direct Aspiration)
Molybdenum (AA, Furnace Technique)
Nickel (AA, Direct Aspiration)
Osmium (AA, Direct Aspiration)
Potassium (AA, Direct Aspiration)
Selenium (AA, Furnace Technique)
Selenium (AA, Gaseous Hydride)
Silver (AA, Direct Aspiration)
Sodium (AA, Direct Aspiration)
Thallium (AA, Direct Aspiration)
Thallium (AA, Furnace Technique)
Tin (AA, Direct Aspiration)
Vanadium (AA, Direct Aspiration)
Vanadium (AA, Furnace Technique)
Zinc  (AA, Direct Aspiration)
APPENDIX — COMPANY REFERENCES
                                CONTENTS - 3
                                                          Revision       0
                                                          Date   September  1986

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                          VOLUME  ONE.

                               SECTION B
ABSTRACT

TABLE OF CONTENTS

METHOD INDEX AND CONVERSION TABLE

PREFACE
CHAPTER ONE. REPRINTED — QUALITY CONTROL

     1.1 Introduction
     1.2 Quality Control
     1.3 Detection Limit and Quantification Limit
     1.4 Data Reporting
     1.5 Quality Control Documentation
     1.6 References
CHAPTER FOUR — ORGANIC ANALYTES

     4.1 Sampling Considerations
     4.2 Sample Preparation Methods

       4.2.1 Extractions and Preparations

          Method 3500:  Organic Extraction And Sample Preparation
          Method 3510:  Separatory Funnel Liquid-Liquid Extraction
          Method 3520:  Continuous Liquid-Liquid Extraction
          Method 3540:  Soxhlet Extraction
          Method 3550:  Sonication Extraction
          Method 3580:  Waste Dilution
          Method 5030:  Purge-and-Trap
          Method 5040:  Protocol for Analysis of Sorbent Cartridges from
                            Volatile Organic Sampling Train

       4.2.2 Cleanup

          Method 3600:  Cleanup
          Method 3610:  Alumina Column Cleanup
          Method 3611:  Alumina Column Cleanup And Separation of
                            Petroleum Wastes
          Method 3620:  Florisil Column  Cleanup
          Method 3630:  Silica Gel Cleanup
          Method 3640:  Gel-Permeation Cleanup
          Method 3650:  Acid-Base Partition Cleanup
          Method 3660:  Sulfur Cleanup
                                CONTENTS - 4

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    4.3  Determination of Organic Analytes

      4.3.1  Gas Chromatographic Methods

         Method 8000:  Gas Chromatography
         Method 8010:  Halogenated Volatile Organics
         Method 8015:  Nonhalogenated Volatile Organics
         Method 8020:  Aromatic Volatile Organics
         Method 8030:  Acrolein, Acrylonitrile, Acetonitrile
         Method 8040:  Phenols
         Method 8060:  Phthalate Esters
         Method 8080:  Organochlorine Pesticides and  PCBs
         Method 8090:  Nitroaromatics and Cyclic Ketones
         Method 8100:  Polynuclear Aromatic Hydrocarbons
         Method 8120:  Chlorinated Hydrocarbons
         Method 8140:  Organophosphorus Pesticides
         Method 8150:  Chlorinated Herbicides

      4.3.2  Gas Chromatographic/Mass Spectroscopic Methods

         Method 8240:  Gas Chromatography/Mass Spectrometry  for
                           Volatile  Organics
         Method 8250:  Gas Chromatography/Mass Spectrometry  for
                           Semi volatile Organics:  Packed Column
                           Technique
         Method 8270:  Gas Chromatography/Mass Spectrometry  for
                           Semi volatile Organics:  Capillary  Column
                           Technique
         Method 8280:  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  PCDD's/PCDF's

      4.3.3   High  Performance Liquid Chromatographic  Methods

         Method 8310:   Polynuclear Aromatic Hydrocarbons

     4.4 Miscellaneous Screening  Methods

         Method  3810:   Headspace
         Method  3820:   Hexadecane Extraction and  Screening of Purgeable
                            Organics
APPENDIX — COMPANY REFERENCES
                                CONTENTS - 5
                                                         Revision
                                                         Date  September 1986

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                          VOLUME  ONE,

                               SECTION C
ABSTRACT

TABLE OF CONTENTS

METHOD INDEX AND CONVERSION TABLE

PREFACE
CHAPTER ONE. REPRINTED — QUALITY CONTROL

     1.1 Introduction
     1.2 Quality Control
     1.3 Detection Limit and Quantification Limit
     1.4 Data Reporting
     1.5 Quality Control Documentation
     1.6 References
CHAPTER FIVE — MISCELLANEOUS TEST METHODS
          Method 9010:

          Method 9012:

          Method 9020:
          Method 9022:

          Method 9030:
          Method 9035:
          Method 9036:

          Method 9038:
          Method 9060:
          Method 9065:

          Method 9066:

          Method 9067:

          Method 9070:

          Method 9071:
Total and Amenable Cyanide (Colorimetric,
    Manual)
Total and Amenable Cyanide (Colorimetric,
    Automated UV)
Total Organic Hal ides (TOX)
Total Organic Hal ides (TOX) by Neutron
    Activation Analysis
Sulfides
Sulfate (Colorimetric, Automated, Chloranilate)
Sulfate (Colorimetric, Automated, Methyl thymol
    Blue, AA II)
Sulfate (Turbidimetric)
Total Organic Carbon
Phenolics  (Spectrophotometric, Manual 4-AAP With
    Distillation)
Phenolics  (Colorimetric, Automated 4-AAP with
    Distillation)
Phenolics  (Spectrophotometric, MBTH with
    Distillation)
Total Recoverable Oil & Grease (Gravimetric,
    Separatory  Funnel Extraction)
Oil & Grease Extraction Method for Sludge
    Samples
                                 CONTENTS - 6
                                                          Revision       0
                                                          Date   September  1986

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          Method 9131:

          Method 9132:
          Method 9200:
          Method 9250:

          Method 9251:

          Method 9252:
          Method 9320:
Total Coliform:  Multiple Tube Fermentation
    Technique
Total Coliform:  Membrane Filter Technique
Nitrate
Chloride (Colorimetric, Automated Ferricyanide
    AAI)
Chloride (Colorimetric, Automated Ferricyanide
    AAI I)
Chloride (Titrimetric, Mercuric Nitrate)
Radium-228
CHAPTER SIX — PROPERTIES
          Method 1320:
          Method 1330:
          Method 9040:
          Method 9041:
          Method 9045:
          Method 9050:
          Method 9080:

          Method 9081:

          Method 9090:

          Method 9095:
          Method 9100:
          Method 9310:
          Method 9315:
Multiple Extraction Procedure
Extraction Procedure for Oily Wastes
pH Electrometric Measurement
pH Paper Method
Soil pH
Specific Conductance
Cation-Exchange Capacity of Soils  (Ammonium
    Acetate)
Cation-Exchange Capacity of Soils  (Sodium
    Acetate)
Compatibility Test for Wastes and  Membrane
    Liners
Paint  Filter Liquids Test
Saturated Hydraulic Conductivity,  Saturated
    Leachate Conductivity, and  Intrinsic
    Permeability
Gross  Alpha & Gross Beta
Alpha-Emitting Radium Isotopes
                       PART  II   CHARACTERISTICS
CHAPTER SEVEN —   INTRODUCTION AND REGULATORY DEFINITIONS.

     7.1  Ignitability
     7.2  Corrositivity
     7.3  Reactivity

          Section  7.3.3.2:  Test Method to Determine Hydrogen Cyanide
                            Released  from Wastes
          Section  7.3.4.1:  Test Method to Determine Hydrogen Sulfide
                            Released  from Wastes

     7.4  Extraction  Procedure Toxicity
                                 CONTENTS - 7
                                                          Revision       0
                                                          Date   September  1986

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CHAPTER EIGHT —  METHODS FOR DETERMINING CHARACTERISTICS
     8.1 Ignilability
          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
     8.4  Toxicity
          Method 1310:  Extraction Procedure  (EP) Toxicity Test Method
                            and Structural Integrity Test
APPENDIX — COMPANY REFERENCES
                                 CONTENTS - 8
                                                          Revision      0	
                                                          Date  September 1986

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                          VOLUME  TWO
ABSTRACT

TABLE OF CONTENTS

METHOD INDEX AND CONVERSION TABLE

PREFACE
CHAPTER ONE. REPRINTED — QUALITY CONTROL

     1.1 Introduction
     1.2 Quality Control
     1.3 Detection Limit and Quantification Limit
     1.4 Data Reporting
     1.5 Quality Control Documentation
     1.6 References
                            PART IIISAMPLING
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
                                 CONTENTS - 9
                                                          Revision
                                                         Date  September  1986

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                            PART IV   MONITORING
CHAPTER ELEVEN — GROUND WATER MONITORING

     11.1 Background and Objectives
     11.2 Relationship to the Regulations and to Other Documents
     11.3 Revisions and Additions
     11.4 Acceptable Designs and Practices
     11.5 Unacceptable Designs and Practices
CHAPTER TWELVE — LAND TREATMENT MONITORING

     12.1 Background
     12.2 Treatment Zone
     12.3 Regulatory Definition
     12.4 Monitoring and Sampling Strategy
     12.5 Analysis
     12.6 References and Bibliography
CHAPTER THIRTEEN — INCINERATION

     13.1 Introduction
     13.2 Regulatory Definition
     13.3 Waste Characterization Strategy  .
     13.4 Stack-Gas Effluent Characterization Strategy
     13.5 Additional Effluent Characterization Strategy
     13.6 Selection'of Specific Sampling and Analysis Methods
     13.7 References
APPENDIX — COMPANY REFERENCES
                                CONTENTS -  10
                                                         Revision
                                                         Date  September  1986

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

    1110
    1310
    1320
    1330
    3005

    3010
    3020
    3040
    3050
    3500

    3510
    3520
    3540
    3550
    3580

    3600
    3610
    3611
    3620
    3630

    3640
    3650
    3660
    3810
    3820

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

   Eight (8.2
   Eight (8.4
   Six
   Six
   Three
   Three
   Three
   Three
   Three
   Four (4.2.1)

   Four (4.2.1)
   Four (4.2.1)
   Four (4.2.1)
   Four (4.2.1)
   Four (4.2.1)

   Four (4.2.2)
   Four (4.2.2
   Four (4.2.2
   Four (4.2.2
   Four (4.2.2
    Four  (4.2.2)
    Four  (4.2.2)
    Four  (4.2.2)
    Four  (4.4)
    Four  (4.4)
            Method Number.
Current Revision
    Four (4
    Four (4
    Three
    Three
    Three
(4.2.1)
(4.2.1)
Second Edition
0010
0020
0030
1010
1020
1110
1310
1320
1330
3005
3010
3020
3040
3050
None (new method)
3510
3520
3540
3550
None (new method)
None (new method)
None (new method)
3570
None (new method)
None (new method)
None (new method)
None (new method)
None (new method)
5020
None (new method)
5030
3720
6010
7000
7020
Number
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
                               METHOD  INDEX - 1
                                                          Revision      0
                                                          Date  September 1986

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

    7090
    7091
    7130
    7131
    7140

    7190
    7191
    7195
    7196
    7197

    7198
    7200
    7201
    7210
    7380

    7420
    7421
    7450
    7460
    7470

    7471
    7480
    7481
    7520
    7550

    7610
    7740
    7741
    7760
    7770
   Three
   Three
   Three
   Three
   Three

   Three
   Three
   Three
   Three
   Three

   Three
   Three
   Three
   Three
   Three

   Three
   Three
   Three
   Three
   Three

   Three
   Three
   Three
   Three
   Three

   Three
   Three
   Three
   Three
   Three

   Three
   Three
   Three
   Three
   Three
  7040
  7041
  7060
  7061
  7080

  7090
  7091
  7130
  7131
  7140

  7190
  7191
  7195
  7196
  7197

  7198
  7200
  7201
  7210
  7380

  7420
  7421
  7450
  7460
  7470

  7471
  7480
  7481
  7520
  7550

  7610
  7740
  7741
  7760
  7770
     0
     0
     0
     0
     0

     0
     0
     0
     0
     0

     0
     0
     0
     0
     0

     0
     0
     0
     0
     0

     0
     0
     0
     0
     0

     0
     0
     0
     0
     0

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

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

    7950
    8000
    8010
    8015
    8020

    8030
    8040
    8060
    8080
    8090

    8100
    8120
    8140
    8150
    8240

    8250
    8270
    8280
    8310
    9010

    9020
    9022
    9030
    9035
    9036

    9038
    9040
    9041
    9045
    9050
Chapter Number,
Third Edition
   Three
   Three
   Three
   Three
   Three

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

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

   Four  (4.3.1)
            Method Number,
                                     Current  Revision
Four
Four
(4.
(4.
    Four
    Four
(4,
(4,
    Four (4.3
              1)
              1)
    Four  (4.3.1)
    Four  (4.3.2)
         .2)
         ,2)
         .2)
    Four (4.3.3)
    Five

    Five
    Five
    Five
    Five
    Five

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

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

    9071               Five
    9080               Six
    9081               Six
    9090     .          Six
    9095               Six

    9100  .            ' Six
    9131               Five
    9132              . Five
    9200               Five
    9250               Five

    9251               Five
    9252               Five
    9310               Six
    9315               Six
    9320               Five

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

                       9071
                       9080
                       9081
                       9090
                       9095

                       9100
                       9131
                       9132
                       9200
                       9250

                       9251
                       9252
                       9310
                       9315
                       9320

                       HCN Test Method
                       H2S Test Method
                         0
                         0
                         0
                         0
                         0

                         0
                         0
                         0
                         0
                         0

                         0
                         0
                         0
                         0
                         0

                         0
                         0
                         0
                         0
                         0

                         0
                         0
                              METHOD   INDEX - 4
                                                         Revision      0
                                                         Date  September 1986

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                            PREFACE AND OVERVIEW
PURPOSE OF THE MANUAL
     Test Methods for Evaluating Solid Waste (SW-846)  is intended to provide  a
unified, up-to-date source of information  on sampling and analysis  related to
compliance with RCRA regulations.   It  brings together into one reference all
sampling and testing methodology approved by the Office of Solid Waste for use
in implementing the RCRA regulatory  program.  The manual  provides methodology
for collecting and testing representative samples of waste and other materials
to be monitored.  Aspects  of  sampling  and testing covered in SW-846 include
quality control, sampling  plan  development  and  implementation, analysis of
inorganic and  organic  constituents,  the  estimation  of  intrinsic physical
properties, and the appraisal of waste characteristics.

     The procedures described in this manual are meant to be comprehensive and
detailed, coupled  with  the  realization  that  the  problems  encountered in
sampling and analytical situations  require  a  certain amount of flexibility.
The solutions to these problems will  depend, in part, on the skill, training,
and experience of the analyst.    For  some  situations, it is possible to use
this manual  in  rote  fashion.    In  other  situations,  it  will   require  a
combination of technical abilities, using  the  manual as guidance rather than
in a step-by-step, word-by-word fashion.    Although this puts an extra burden
on the  user,  it  is  unavoidable  because  of  the  variety  of sampling and
analytical conditions found with hazardous wastes.
ORGANIZATION AND FORMAT
     This manual is divided into two  volumes.  Volume I focuses on laboratory
activities and is divided  for  convenience  into  three  sections.  Volume IA
deals  with  quality  control,  selection  of  appropriate  test  methods, and
analytical methods for metallic species.    Volume  IB consists of methods for
organic  analytes.    Volume  1C  includes  a  variety  of  test  methods  for
miscellaneous  analytes  and  properties  for  use  in  evaluating  the  waste
characteristics.  Volume II deals with sample acquisition and includes quality
control, sampling plan design and  implementation, and field sampling methods.
Included for the convenience  of  sampling  personnel  are discusssions of the
ground water, land treatment, and incineration monitoring regulations.

     Volume I begins with an overview  of the quality control precedures to be
Imposed upon the sampling and  analytical methods. The quality control chapter
(Chapter One) and the  methods  chapters  are  interdependent.  The analytical
procedures cannot be  used  without  a  thorough  understanding of the quality
control requirements and the means to  Implement them.  This understanding can
be  achieved only be reviewing Chapter One and the analytical methods together.
It  is expected that  individual  laboratories,  using  SW-846 as the reference
                                  PREFACE -  1
                                                          Revision      0
                                                          Date  September 1986

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

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

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

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

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

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

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

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


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                           CHAPTER ONE,  REPRINTED

                               QUALITY CONTROL

1.1  INTRODUCTION

     Appropriate use of data  generated  under  the  great range of analytical
conditions encountered  in  RCRA  analyses  requires  reliance  on the quality
control  practices  incorporated  into  the   methods  and  procedures.    The
Environmental Protection Agency generally  requires using approved methods for
sampling and analysis operations  fulfilling  regulatory requirements, but the
mere  approval  of  these   methods   does  not  guarantee  adequate  results.
Inaccuracies can  result  from  many  causes,  including  unanticipated matrix
effects, equipment malfunctions, and  operator  error.  Therefore, the quality
control component of each method is indispensable.

     The data acquired from  quality  control  procedures are used to estimate
and evaluate the information content  of  analytical data and to determine the
necessity or the effect of  corrective  action  procedures.  The means used to
estimate information content include precision, accuracy, detection limit, and
other quantifiable and qualitative indicators.

     1.1.1   Purpose of this Chapter

     This chapter defines the  quality  control procedures and components that
are mandatory  1n  the  performance  of  analyses,  and  indicates the quality
control information which must be generated with the analytical data.  Certain
activities in an integrated program to generate quality data can be classified
as management (QA) and other as  functional  (QC).  The presentation given here
is an overview of such a program.

     The following sections discuss some minimum standards for QA/QC  programs.
The chapter  is not a  guide  to  constructing quality assurance project plans,
quality control programs, or a  quality assurance organization. Generators who
are choosing contractors  to  perform  sampling  or   analytical work,  however,
should make  their choice only   after evaluating the  contractor's  QA/QC program
against the  procedures presented   in  these   sections.   Likewise,  laboratories
that sample  and/or analyze  solid wastes should similarily  evaluate their  QA/QC
programs.

     Most of the  laboratories who  will  use  this manual  also  carry out testing
other  than that called for  in  SW-846.     Indeed, many  user  laboratories have
multiple mandates,  including analyses  of  drinking  water, wastewater, air and
industrial hygiene  samples, and process   samples.   These laboratories will,  in
most cases,  already  operate  under an  organizational  structure  that includes
QA/QC.  Regardless of the extent   and  history of  their  programs,  the users  of
this manual  should   consider  the   development,   status,   and  effectiveness  of
their  QA/QC  program  in carrying out the testing described  here.
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     1.1.2  Program Design

     The initial step for any  sampling  or analytical  work should  be  strictly
to define the program goals.  Once the goals have been  defined,  a program must
be designed to meet them.   QA  and  QC  measures  will  be used  to  monitor the
program and to ensure that all  data generated are suitable for  their  intended
use.  The responsibility  of  ensuring  that  the  QA/QC measures are  properly
employed must be  assigned  to  a  knowledgeable  person  who  is not  directly
involved in the sampling or analysis.

     One approach that has  been  found  to  provide  a useful  structure for a
QA/QC program is the preparation  of  both  general program plans and  project-
specific QA/QC plans.

     The program plan  for  a  laboratory  sets  up basic laboratory policies,
including QA/QC, and may  include  standard  operating  procedures for  specific
tests.  The program plan serves  as an operational charter for the  laboratory,
defining its purposes, its organization*  and  its operating principles.   Thus,
it is an orderly  assemblage  of  management policies,  objectives,  principles,
and general procedures  describing  how  an  agency  or  laboratory Intends to
produce data of known and accepted  quality.    The elements of a program plan
and its preparation  are  described  in  QAMS-004/80  (see References, Section
1.6).

     Project-specific QA/QC plans differ  from  program plans in that  specific
details of a particular sampling/analysis program are addressed.  For  example,
a program plan might state that  all analyzers will be calibrated according to
a specific protocol given  in  written  standard  operating procedures for the
laboratory (SOP), while a project plan  would state that a particular  protocol
will be used to calibrate  the  analyzer  for  a specific set of analyses that
have been defined in the plan.  The  project plan draws on the program plan or
its  basic  structure  and  applies   this  management  approach  to  specific
determinations.  A given  agency  or  laboratory  would  have only  one quality
assurance program plan, but would  have  a  quality assurance project  plan for
each of its projects.  The elements  of a project plan and its preparation are
described in QAMS/005/80   (see  References,  Section  1.6)  and  are  listed in
Figure 1-1.

     Some organizations  may  find   it  inconvenient  or  even   unnecessary to
prepare a new project plan  for each  new set of analyses, especially analytical
laboratories which receive  numerous  batches  of  samples from various  customers
within and  outside   their  organizations.    For  these  organizations,  it is
especially important  that adequate QA management  structures exist and that any
procedures  used  exist  as   standard  operating  procedures   (SOP),   written
documents which detail an operation,  analysis   or action whose  mechanisms are
thoroughly prescribed  and  which  is  commonly   accepted  as  the  method for
performing certain routine  or repetitive   tasks.  Having copies of SW-846 and
all  its  referenced   documents in  one's   laboratory   is  not a  substitute for
having  in-house versions   of the   methods  written   to  conform  to specific
instrumentation, data needs,  and data quality requirements.
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                     FIGURE 1-1
       ESSENTIAL ELEMENTS OF A QA PROJECT PLAN

 1.   Title Page
 2.   Table of Contents
 3.   Project Description
 4.   Project Organization and Responsibility
 5.   QA Objectives
 6.   Sampling Procedures
 7.   Sample Custody
 8.   Calibration Procedures and  Frequency
 9.   Analytical Procedures
10.   Data Reduction, Validation, and Reporting
11.   Internal Quality Control Checks
12.   Performance and System Audits
13.   Preventive Maintenance
14.   Specific Routine Procedures Used to Assess Data
     Precision, Accuracy, and Completeness
15.   Corrective Action
16.   Quality Assurance Reports to Management
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     1.1.3  Organization and Responsibility

     As part of any measurement  program,   activities for the data generators,
data reviewers/approvers, and data  users/requestors  must be clearly defined.
While the specific titles of  these  individuals  will vary among agencies and
laboratories,  the  most   basic   structure  .will    include   at  least  one
representative of each of these three  types.  The data generator is typically
the individual who carries  out  the  analyses  at  the  direction of the data
user/requestor or a designate  within  or  outside  the  laboratory.  The data
reviewer/approver is responsible for  ensuring  that  the data produced by the
data generator meet agreed-upon specifications.

     Responsibility for  data  review  is  sometimes  assigned  to  a "Quality
Assurance Officer" or "QA Manager."    This  individual has broad authority to
approve or disapprove project plans, specific analyses and final reports.  The
QA Officer is independent from  the  data  generation activities.  In general,
the QA Officer is responsible  for  reviewing  and  advising on all aspects of
QA/QC, including:

     Assisting the data  requestor in specifying the QA/QC procedure to be used
     during  the program;

     Making  on-site evaluations  and  submitting  audit  samples  to assist in
     reviewing QA/QC procedures; and,

     f problems are detected, making recommendations to the data requestor and
     upper   corporate/institutional  management  to  ensure  that  appropriate
     corrective actions  are taken.

     In programs where  large and  complex  amounts  of data are generated from
both field and  laboratory  activities,  it  is  helpful to designate sampling
monitors, analysis monitors, and  quality  control/data  monitors to assist in
carrying out the program or project.

     The sampling monitor is responsible for field activities.  These include:

     Determining  (with  the  analysis  monitor)  appropriate sampling equipment
     and sample containers to minimize contamination;

     .Ensuring that  samples  are   collected,  preserved,  and  transported as
     specified in the workplan; and

     Checking that all  sample  documentation   (labels, field notebooks,  chain-
     of-custody records,  packing   lists)  is  correct  and  transmitting that
     information, along with the samples,  to the analytical  laboratory.

     The  analysis monitor is   responsible  for  laboratory activities.    These
 include:

     Training and  qualifying  personnel    in  specified  laboratory  QC  and
     analytical procedures, prior  to receiving  samples;
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     Receiving samples from  the  field  and   verifying   that  incoming  samples
     correspond to the packing list or chain-of-custody  sheet;  and

     Verifying that laboratory QC and analytical  procedures  are being followed
     as specified in the  workplan,  reviewing  sample  and  QC data during  the
     course of analyses, and,  if  questionable  data exist,  determining which
     repeat samples or analyses are needed.

     The quality control and data monitor is  responsible for QC activities  and
data management.  These include:

     Maintaining records  of  all  incoming  samples,  tracking  those  samples
     through   subsequent   processing    and   analysis,   and,   ultimately,
     appropriately  disposing  of  those  samples  at  the  conclusion   of  the
     program;

     Preparing quality control samples  for  analysis  prior to and during  the
     program;

     Preparing QC and sample data  for  review by the analysis coordinator and
     the program manager; and

     Preparing QC and sample data  for  transmission and entry into a computer
     data base, if appropriate.

     1.1.4   Performance and  Systems Audits

     The QA  Officer may carry out  performance and/or systems audits to ensure
that data of known and defensible  quality are produced during a program,.

     Systems audits are qualitative evaluations of all components of field and
laboratory   quality   control  measurement  systems.    They  determine  if the
measurement  systems are being used appropriately.   The audits may be carried
out before all  systems  are operational,  during  the  program, or after the
completion of the program.   Such   audits typically involve a comparison of the
activities given  in the QA/QC plan with those actually scheduled or performed.
A special type of systems  audit   is  the  data  management audit.  This audit
addresses only data collection  and management activities.

     The performance  audit   is  a  quantitative  evaluation of the measurement
systems of a  program.     It requires  testing  the  measurement systems with
samples of known  composition or  behavior  to evaluate precision and accuracy.
The performance audit is   carried  out  by  or  under  the  auspices of the QA
Officer  without  the   knowledge   of  the  analysts.    Since  this  is seldom
achievable,  many  variations are  used  that  increase  the  awareness of the
analyst as to the nature of  the audit material.
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     1.1.5  Corrective Action
     Corrective action procedures  should  be  addressed  1n the program plan,
project, or SOP.  These should Include the following elements:
     The  EPA  predetermined  limits   for  data  acceptability  beyond  which
     corrective action is required;
     Procedures for corrective action; and,
     For each measurement system, identification of the individual  responsible
     for initiating the corrective  action  and the individual  responsible for
     approving the corrective action, .if necessary.
     The need for corrective action may be identified by system or performance
audits or by standard QC  procedures.    The essential steps 1n the corrective
action system are:
     Identification and definition of the problem;
     Assignment of responsibility for investigating the problem;
     Investigation and determination of the cause of the problem;
     Determination of a corrective action to eliminate the problem;
     Assigning  and accepting responsibility for implementing the corrective
     action;
     Implementing the corrective action and evaluating Its effectiveness;  and
     Verifying  that the corrective action has eliminated the problem.
     The QA Officer should  ensure   that  these  steps  are taken and that the
problem which led to the corrective  action has been resolved.
     1.1.6  QA/QC Reporting to Management
     QA Project Program  or  Plans   should  provide  a  mechanism for periodic
reporting to management  (or  to  the  data  user)  on  the performance of the
measurement system and  the  data  quality.    Minimally, these reports should
include:
     Periodic   assessment  of  measurement   quality  indicators,  I.e.,  data
     accuracy,  precision and completeness;
     Results of performance audits;
     Results of system audits; and
     Significant QA problems and recommended solutions.
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     The  individual  responsible   within   the  organization  structure  for
preparing the periodic reports should  be  identified in the organizational  or
management plan.  The  final  report  for  each  project should also include a
separate QA section which summarizes data quality information contained in the
periodic reports.

       Other guidance on  quality  assurance  management  and organizations is
available from the Agency and  professional  organizations such as ASTM,  AOAC,
APHA and FDA.

     1.1.7  Quality Control Program for the Analysis of RCRA Samples

     An analytical quality control  program  develops information which can be
used to:

     Evaluate the  accuracy  and  precision  of  analytical  data  in order to
     establish the quality of the data;

     Provide an  indication of the need for corrective actions, when comparison
     with existing regulatory or  program  criteria  or data trends shows that
     activities  must be changed or monitored to a different degree; and

     To determine the effect of corrective actions.

     1.1.8  Definitions
ACCURACY:
ANALYTICAL  BATCH:
 BLANK:
Accuracy means the nearness of a  result or the mean (7)  of
a set of results to  the  true value.   Accuracy is assessed
by means of reference samples and percent recoveries.

The  basic  unit  for  analytical  quality  control  is the
analytical batch.    The  analytical  batch  is  defined as
samples which are  analyzed  together  with the same method
sequence  and  the  same  lots  of  reagents  and  with the
manipulations common to  each  sample  within the same time
period or in continuous  sequential  time periods.  Samples
in each batch should be of similar composition.

A blank is  an  artificial  sample  designed to monitor the
introduction of artifacts  into  the  process.  For aqueous
samples, reagent water is used  as a blank matrix; however,
a universal blank matrix does  not exist for solid samples,
and therefore, no  matrix  is  used.    The  blank is taken
through the appropriate steps of the process.
A reagent blank  is  an  aliquot  of  analyte-free water or
solvent analyzed with the  analytical   batch.  Field blanks
are aliquots of analyte-free  water  or solvents brought to
the field in sealed containers  and transported back to the
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CALIBRATION
CHECK:
CHECK SAMPLE:
laboratory with the  sample  containers.    Trip blanks and
equipment blanks are  two  specific  types of field blanks.
Trip blanks are not opened 1n  the field*  They are a check
on sample contamination  originating from sample transport,
shipping and from  site  conditions.   Equipment blanks are
opened  in  the   field   and   the   contents  are  poured
appropriately over or through the sample collection device,
collected  in  a  sample  container,  and  returned  to the
laboratory as a sample.    Equipment  blanks are a check on
sampling device cleanliness.

Verification of the ratio of instrument response to analyte
amount, a  calibration  check,  is  done  by  analyzing for
analyte standards in  an  appropriate solvent.  Calibration
check solutions are  made  from  a  stock solution which is
different from the stock used to prepare standards.

A blank which has been  spiked  with the analyte(s) from an
independent source in order to monitor the execution of the
analytical method 1s called a  check  sample.  The level of
the spike shall  be  at  the  regulatory  action level when
applicable.  Otherwise, the spike  shall  be at 5 times the
estimate of  the  quantification  limit.    The matrix used
shall  be  phase   matched   with   the  samples  and  well
characterized:   for  an  example,  reagent  grade water is
appropriate for an aqueous sample.
ENVIRONMENTAL
SAMPLE:
An environmental sample or field sample 1s a representative
sample of any material  (aqueous, nonaqueous, or multimedia)
collected   from  any  source  for  which  determination  of
composition or contamination is requested or required.  For
the purposes of this manual, environmental samples shall be
classified  as follows:

Surface Water and Ground Water;

.Drinking Water --   delivered   (treated  or untreated) water
designated  as potable water;

Water/Wastewater — raw source  waters for public drinking
water  supplies,    ground   waters,   municipal   influents/
effluents,  and industrial  Influents/effluents;

Sludge  — municipal sludges and Industrial sludges;

Waste --  aqueous   and  nonaqueous   liquid wastes, chemical
solids, contaminated soils, and industrial liquid and solid
wastes.
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MATRIX/SPIKE-
DUPLICATE
ANALYSIS:
MQL:



PRECISION:




PQL:





RCRA:

REAGENT GRADE:
REPLICATE SAMPLE:
STANDARD CURVE:
SURROGATE:
In matrix/spike duplicate analysis,  predetermined quantl-
        stock solutions of certain analytes are added to a
ties 01
added  to  a  sample  matrix  prior  to  sample extraction/
digestion and analysis.  Samples are split Into duplicates,
spiked and analyzed.  Percent recoveries are calculated for
each  of  the  analytes  detected.    The  relative percent
difference between the  samples  1s  calculated and used to
assess analytical  precision.    The  concentration  of the
spike should be  at  the  regulatory  standard level or the
estimated or actual method  quantification limit.  When the
concentration of the analyte 1n  the sample 1s greater than
0.1%, no spike of the analyte is necessary.

The  method  quantification  limit  (MQL)  is  the  minimum
concentration of  a  substance  that  can  be  measured and
reported.
Precision means the measurement  of  agreement  of a set of
                          themselves  without assumption of
                             the true result.  Precision is
replicate results  among
any prior information as to
assessed by means of duplicate/replicate sample analysis.
The practical quantitation limit  (PQL) is the lowest level
that can be  reliably  achieved  within specified limits of
precision and accuracy  during routine laboratory operating
conditions.

The Resource Conservation and Recovery Act.

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

A replicate  sample  is  a  sample  prepared  by dividing a
sample into  two  or  more  separate  aliquots.   Duplicate
samples are considered to be two replicates.
A standard curve is  a
known analyte standard
the analyte.
                        curve which plots concentrations of
                        versus  the  instrument response to
Surrogates  are  organic  compounds  which  are  similar to
analytes of Interest  1n  chemical composition, extraction,
and chromatography, but  which  are  not  normally found in
environmental samples.  These compounds are spiked into all
blanks, standards,  samples  and  spiked  samples  prior to
analysis.     Percent  recoveries  are  calculated  for each
surrogate.
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WATER:             Reagent,  analyte-free,   or  laboratory  pure  water  means
                   distilled or deionized water or Type II reagent water which
                   is  free  of  contaminants  that  may  interfere  with  the
                   analytical test in question.


1.2  QUALITY CONTROL

     The procedures indicated  below  are  to  be  performed for all analyses.
Specific  instructions  relevant  to  particular  analyses  are  given  in the
pertinent analytical procedures.

     1.2.1  Field Quality Control

     The sampling component of the Quality Assurance Project Plan  (QAPP) shall
include:                                               .    •

     Reference to or  incorporation  of  accepted  .sampling  techniques in the
     sampling plan;                    ,

     Procedures for documenting and  justifying  any field actions contrary to
     the QAPP;

     Documentation of all  pre-field  activities  such as equipment check-out,
     calibrations, and container storage and preparation;

     Documentation of field measurement  quality control data  (quality control
     procedures for such  measurements  shall  be  equivalent  to corresponding
     laboratory QC procedures);                        -

     Documentation of field activities;

     Documentation of  post-field  activities  including  sample   shipment and
     receipt, field team de-briefing and equipment check-in;

     Generation of quality control  samples including duplicate samples, field
     blanks, equipment blanks, and trip blanks; and

     The use of these samples in  the context of data evaluation,  with details
     of the  methods  employed   (including  statistical  methods)  and  of the
     criteria upon which the information generated will be judged.

      1.2.2  Analytical Quality Control

     A quality control operation  or  component  is  only  useful  if  it can be
measured or  documented.     The  following  components  of  analytical quality
control are related to  the  analytical  batch.   The  procedures described are
intended  to  be   applied  to  chemical  analytical  procedures;   although the
principles  are   applicable  to  radio-chemical  or  biological  analysis, the
procedures may not be directly applicable to  such techniques.
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     All quality control data and  records  required  by this section shall  be
retained by the laboratory and shall   be  made available to the data requestor
as appropriate.  The frequencies of  these procedures shall be as stated below
or at least once with each analytical batch.

          1.2.2.1  Spikes, Blanks and Duplicates

General Requirements

     These procedures shall be  performed  at  least once with each analytical
batch with a minimum of once per twenty samples.

                 1.2.2.1.1  Duplicate Spike

     A  split/spiked field sample shall be analyzed with every analytical batch
or once in  twenty  samples,  whichever  is  the  greater frequency.  Analytes
stipulated by the analytical  method,  by  applicable regulations, or by other
specific requirements must be spiked into the sample.  Selection of the sample
to be spiked and/or split depends  on the information required and the variety
of conditions within a  typical  matrix.    In some situations, requirements of
the site being sampled  may dictate  that  the sampling team select a sample to
be spiked and split based on a pre-visit evaluation or the on-site inspection.
This does not preclude  the laboratory's  spiking a sample of its own selection
as well.   In  other  situations  the  laboratory  may  select the appropriate
sample.  The  laboratory's  selection  should  be  guided  by the objective of
spiking, which is to determine  the  extent  of matrix bias or interference on
analyte recovery and sample-to-sample  precision.   For soil/sediment samples,
spiking is performed  at  approximately  3  ppm  and,  therefore, compounds in
excess  of this concentration  in  the  sample  may cause interferences for the
determination of the spiked analytes.

                 1.2.2.1.2  Blanks

     Each batch shall be accompanied  by  a  reagent blank.  The reagent blank
shall be carried through the entire analytical procedure.

                 1.2.2.1.3  Field Samples/Surrogate Compounds

     Every  blank,  standard,  and   environmental  sample   (including  matrix
spike/matrix duplicate  samples) shall be spiked with surrogate compounds prior
to purging or extraction.   Surrogates  shall be spiked into samples according
to the  appropriate analytical methods.   Surrogate spike recoveries shall fall
within  the control limits set by the laboratory  (in accordance with procedures
specified in  the  method  or  within  +20%)  for  samples  falling within the
quantification limits without  dilution.    Dilution  of   samples to bring the
analyte concentration into  the  linear  range  of  calibration may dilute the
surrogates below the  quantification  limit;  evaluation of analytical quality
then will rely  on  the quality  control  embodied  in  the check, spiked and
duplicate spiked samples.
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                 1.2.2.1.4  Check Sample

     Each analytical  batch  shall  contain  a  check  sample.     The analytes
employed shall be a representative  subset  of  the analytes to be determined.
The  concentrations   of   these   analytes   shall   approach   the  estimated
quantification limit in the matrix of  the check sample.  In particular,  check
samples for metallic analytes shall be  matched  to field samples in phase and
in generaT~matrix composition.

          1.2.2.2  Clean-Ups

     Quality control  procedures  described  here  are  intended for adsorbent
chromatography and back extractions applied  to organic extracts.  All batches
of adsorbents (Florisil, alumina, silica gel,  etc.) prepared for use shall be
checked for analyte recovery by running  the elution pattern with standards as
a column check.  The elution  pattern  shall be optimized for maximum recovery
of analytes and maximum rejection of contaminants.

                 1.2.2.2.1  Column Check Sample

     The elution pattern shall be reconfirmed  with a column check of standard
compounds after  activating  or  deactivating  a   batch  of  adsorbent.  These
compounds shall be  representative  of  each  elution   fraction.   Recovery as
specified in  the methods is considered  an  acceptable  column check.  A result
lower  than specified indicates  that  the  procedure  is not acceptable or has
been misapplied.

                 1.2.2.2.2  Column Check Sample Blank

     The check blank shall be run  after activating or  deactivating  a batch of
adsorbent.

          1.2.2.3   Determinations

                 1.2.2.3.1   Instrument Adjustment:  Tuning, Alignment, etc.

     Requirements   and   procedures   are    instrument- and  method-specific.
Analytical instrumentation  shall  be  tuned  and  aligned  in  accordance with
requirements  which  are  specific   to  the  instrumentation procedures employed.
Individual determinative procedures shall  be  consulted.  Criteria for initial
conditions and for  continuing confirmation   conditions  for  methods within  this
manual  are found in the appropriate procedures.

                 1.2.2.3.2  Calibration

     Analytical  instrumentation   shall  be   calibrated  in  accordance  with
requirements  which are   specific    to  the  instrumentation   and   procedures
employed.    Introductory   Methods  7000  and  8000 and appropriate  analytical
procedures   shall   be   consulted   for  criteria   for   initial   and   continuing
calibration.
                                   ONE - 12
                                                          Revision       0	
                                                          Date   September  1986

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                 1.2.2.3.3  Additional QC Requirements for Inorganic Analysis

     Standard curves used 1n the  determination of inorganic analytes shall  be
prepared as follows:

     Standard curves derived from  data  consisting  of  one reagent blank and
four concentrations shall be prepared for each analyte.  The response for each
prepared standard shall be based upon  the average of three replicate readings
of each standard.   The  standard  curve  shall  be  used with each subsequent
analysis provided that the standard  curve  is  verified by using at least one
reagent blank and one standard at  a level normally encountered or expected 1n
such samples.  The response for each  standard shall be based upon the average
of  three  replicate  readings  of  the  standard.    If  the  results  of the
verification are not within +10% of  the  original curve, a new standard shall
be prepared and analyzed.  If  the  results of the second verification are not
within +10% of the  original  standard  curve,  a reference standard should be
employee! to determine if  the  discrepancy  is  with  the standard or with the
instrument.  New standards should also  be  prepared on a quarterly basis at a
minimum.  All  data  used  in  drawing  or  describing  the  curve shall be so
indicated on the curve or  its  description.    A  record shall be made of the
verification.

     Standard deviations and relative  standard deviations shall be calculated
for the percent recovery  of  analytes  from   the spiked sample duplicates and
from the check samples.  These values shall be established for the twenty most
recent determinations  in each category.

                 1.2.2.3.4  Additional Quality Control Requirements for
                            Organic Analysis

     The following  requirements shall be  applied  to the  analysis of samples by
gas  chromatography,   liquid   chromatography   and   gas  chromatography/mass
spectrometry.

     The calibration   of each  instrument  shall   be  verified at  frequencies
specified  in the methods.  A new  standard  curve  must  be prepared as  specified
in the methods.

     The tune of   each   GC/MS  system used  for  the  determination of organic
analytes shall be  checked  with   4-bromofluorobenzene  (BFB)  for determinations
of volatiles and with  decafluorotriphenylphosphine  (DFTPP)  for determinations
of semi-volatiles.  The  required  ion abundance  criteria shall be met before
determination of any analytes.    If  the  system  does  not meet the required
specification for  one  or more  of  the   required  ions,  the  instrument must be
retuned and  rechecked   before  proceeding  with  sample analysis.   The tune
performance  check   criteria  must  be achieved   daily  or   for  each  12 hour
operating  period,  whichever is more frequent.

     Background  subtraction should  be   straightforward  and  designed only to
eliminate  column bleed or instrument  background  ions.   Background  subtraction
                                   ONE -  13
                                                          Revision      0
                                                         Date  September  1986

-------
actions resulting in  spectral  distortions  for  the  sole purpose of meeting
special requirements are contrary to  the  objectives of Quality Assurance and
are unacceptable.

     For determinations by HPLC  or  GC,  the  instrument calibration shall  be
verified as specified in the methods.

                 1.2.2.3.5  Identification

     Identification of all  analytes  must  be  accomplished with an authentic
standard  of  the  analyte.    When  authentic  standards  are  not available,
identification is tentative.

     For gas chromatographic determinations of specific analytes, the relative
retention time of the  unknown  must  be  compared  with  that of an authentic
standard.  For  compound  confirmation,  a  sample  and  standard shall be re-
analyzed  on  a  column   of   different   selectivity   to  obtain  a  second
characteristic  relative  retention  time.    Peaks  must  elute  within daily
retention time windows to be declared a tentative or confirmed identification.

     For gas  chromatographic/mass  spectrometric  determinations  of specific
analytes,  the  spectrum  of  the  analyte  should  conform  to  a  literature
representation of the spectrum  or  to  a  spectrum  of the authentic standard
obtained after satisfactory tuning  of  the  mass  spectrometer and within the
same twelve-hour working  shift  as  the  analytical spectrum.  The appropriate
analytical methods should be  consulted  for specific criteria for matching the
mass spectra, relative response factors, and relative retention times to those
of authentic standards.
                  1.2.2.3.6  Quantification

     The procedures   for  quantification  of  analytes  are  discussed  in the
 appropriate  general  procedures   (7000,  8000)  and  the  specific analytical
 methods.

     In some situations in  the  course  of determining metal analytes, matrix-
..matched calibration  standards  may  be  required.    These   standards shall be
 composed of  the   pure  reagent,   approximation  of  the  matrix,  and reagent
 addition of major interferents in  the samples.   This will be stipulated in the
 procedures.

     Estimation of the  concentration   of  an  organic  compound  not contained
 within the calibration  standard may  be  accomplished by comparing  mass spectral
 response of the compound  with that of   an internal standard.   The procedure is
 specified in the  methods.
                                   ONE - 14
                                                          Revision      0	
                                                          Date  September  1986

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1.3  DETECTION LIMIT AND QUANTIFICATION LIMIT

     The  detection  limit  and  quantification  limit  of  analytes   shall  be
evaluated by determining the noise  level   of  response for each sample in the
batch.  If analyte is present,  the  noise level  adjacent in retention time to
the analyte peak may  be  used.    For wave-length dispersive instrumentation,
multiple determinations of digestates with  no  detectable analyte may be used
to establish the noise level.  The method  of standard additions should then be
used to determine  the  calibration  curve  using  one  digestate or  extracted
sample in which the analyte was  not  detected.   The slope of the calibration
curve, m, should be calculated using the following relations:

     m     = slope of calibration line

     SB    = standard deviation of the average noise level

     MDL   = KSB/m

     For K = 3; MDL = method detection limit.

     For K = 5; MQL = method quantisation  limit.


1.4  DATA REPORTING

     The requirement of reporting analytical results on a wet-weight  or a dry-
weight basis is  dictated  by  factors  such  as:    sample matrix; program or
regulatory requirement; and objectives of the analysis.

     Analytical results shall be reported with the percent moisture or percent
solid content of the sample.


1.5  QUALITY CONTROL DOCUMENTATION

     The following sections   list  the  QC  documentation  which comprises the
complete analytical package.  This  package  should  be obtained from the data
generator upon request.  These forms,  or adaptations of these forms, shall be
used by  the data generator/reporter for inorganics  (I), or for organics  (0) or
both  (I/O) types of determinations.

      1.5.1  Analytical  Results (I/O:  Form I)

          Analyte  concentration.

          Sample weight.

          Percent  water (for  non-aqueous  samples when  specified).

          Final volume  of  extract  or  diluted sample.

          Holding  times (I:  Form X).


                                   ONE - 15
                                                          Revision      0 '
                                                         Date  September 1986

-------
1.5.2  Calibration (I:  Form II;  0:   Form V,  VI,  VII,  IX)
     Calibration curve   or  coefficients  of  the  linear  equation which
     describes the calibration curve.
     Correlation coefficient of the linear calibration.
     Concentration/response  data  (or  relative  response  data)   of the
     calibration check  standards,  along  with  dates  on which they were
     analytically determined.
1.5.3  Column Check (0: Form X)
     Results of column  chromatography check, with the chromatogram.
1.5.4  Extraction/Digestion (I/O: Form I)
     Date of the extraction for each sample.
1.5.5  Surrogates (0: Form II)
     Amount of surrogate spiked, and percent recovery of each surrogate.
1.5.6  Matrix/Duplicate Spikes (I:  Form V, VI; 0: Form III)
     Amount spiked, percent recovery,  and relative percent difference for
     each compound in the spiked samples for the analytical batch.
1.5.7  Check Sample (I: Form VII; 0: Form VIII)
     Amount spiked, and percent recovery of each compound spiked.
1.5.8  Blank  (I: Form III; 0: Form IV)
     Identity and amount of each constituent. .
1.5.9  Chromatograms (for organic analysis)
     All chromatograms for reported results, properly labeled with:
     -  Sample identification
     -  Method identification
     -  Identification of retention time of analyte on the chromatograms.
                             ONE - 16
                                                    Revision
                                                    Date  September 1986

-------
     1.5.10  Quantitative Chromatogram  Report  (0: Forms VIII,  IX, X)
          Retention  time of  analyte.
          Amount  Injected.
          Area  of appropriate  calculation  of detection  response.
          Amount  of  analyte  found.
          Date  and time of  injection.
     1.5.11  Mass Spectrum
          Spectra of standards  generated   from  authentic  standards (one for
          each  report for each compound detected).
          Spectra of analytes  from actual  analyses.
          Spectrometer identifier.
     1.5.12  Metal Interference Check Sample  Results (I:  Form IV)
     1.5.13  Detection Limit (I: Form VII; 0:  Form I)
          Analyte detection limits with methods of estimation.
     1.5.14  Results of Standard Additions (I: Form VIII)
     1.5.15  Results of Serial Dilutions (I:  Form IX)
     1.5.16  Instrument Detection Limits (I:  Form XI)
     1.5.17  ICP Interelement  Correction Factors and ICP Linear Ranges
     (when applicable) (I;  Form XII.  Form XIII).

1.6  REFERENCES
1.   Guidelines and   Specifications  for  Preparing  Quality Assurance Program
Plans,  September 20, 1980,  Office of Monitoring Systems and Quality Assurance,
ORD, U.S. EPA,  QAMS-004/80, Washington, DC 20460.
2.   Interim Guidelines  and  Specifications   for  Preparing Quality Assurance
Project Plans,  December 29,  1980,  Office  of  Monitoring Systems and Quality
Assurance, ORD, U.S. EPA, QAMS-005/80, Washington,  DC 20460.
                                  ONE - 17
                                                         Revision
                                                         Date  September 1986

-------
 Lab  K
                                                               Date
                                     COVER PACE
INORGANIC ANALYSES DATA PACKAGE

                        Case No.
                                                  Q.C.  Report  No.
                                   Sample  Num
EPA No.
Comments:
Lab ID No.
                     EPA No.
Lab ID No.
                                 ONE -  18
                                                         Revision      0
                                                         Date   September 1986

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LAB  NAME
LAb  SAMPLE  ID.  NO.
                                       Form I
Sarsple
No.
                                                           Date
INORGANIC ANALYSIS DATA SHLET
                       CASE  NO.
                       Lab  Receipt  Date
                       QC REPORT  NO.
                          Elements  Identified  and  Measured
Matrix: Water
Soil
Sludge uther
ug/L or ra^/kg dry weight (Circle One)
1. Aluminum 13. Magnesiuc
2. Antimony
3. Arsenic
A. bariurc
5. Beryllium
6. Cadmium
7. Calciuir,
8. Chromium
9. Cobalt
10. Copper
11. Iron
12. Lead
14.
13.
16.
17.
Ib.
19.
2u.
21.
22.
23.
Manganese
Mercury
Nickel
Potassium
Seleniur?
Silver
Sodiuc
Thallium
Vanadiura
Zinc
Precent Solids (:=)
Cyanide
Comnrnts:
                                              Lab Manager
                                 ONE -  19
                                                       Revision      0
                                                       Date  September  1986

-------
LAB NAMt
                                       Form II

                              Q.  C.  Report  No.
 INITIAL AND CONTINUING CALIBRATION VERIFICATION

	               CASK NO.    	
DATE
Compound Initial Calib
Metals:
1. Aluminum
2. Antimony
3. Arsenic
4. Barium
5. Beryllium
b. Cadmium
7. Calcium
b. Chromium
y. Cobalt
10. Copper
1 1 . Iron
12. Lead
13. Magnesium
14. Manganese
15. Mercury
True Value















Ib. Nickel
17. Potassium
16. Selenium
19. Silver
20. Sodium
21. Thallium
22. Vanadium
23. Zinc
Other:

Cyanide
Found























UNITS: ug/L
.* Continuing Calibration2
ZR



























True Value






















Found



















ZR



















i
i
i
Found




















/.k






















i i

i

i











Method4,1


















1







1  Initial Calibration Source
                          (,'otit inuioK  Calibration Source
  Indicate  Analytical Method Used:   F - 1CH; A - Flame AA; F -  Furnace AA
                                  ONE -  20
                                                          Revision      0
                                                          Date  September 1986

-------
LAB NAME
DATE
                                      Form  III
                              CJ. C. Report  No.
                                     BLANKS
CASE NO.
UMTb
Compound
Metals:
1. Aluminum
2. Antimony
3. Arsenic
4. Barium
5. beryllium
6. Cadcium
7. Calcium
8. Chromium
9. Cobalt
10. Copper
11. Iron
12. Lead
13. Magnesium
14. Manganese
15. Mercury
Ib. Nickel
17. Potassium
IB. Selenium
ly. Silver
2(J. Sodium
2.1. Thallium
22. Vanadium
23. Zinc
Other:

Cyanide
Initial
Calibration
Blank Value


























Continuing Calibration
1


























Blank Value
2 3




















































U


























Preparation Blar-'r-
Matrix: Matrix:
1 2


























 Reporting Units:aqueous,  u&/L;solid
                                ONE - 21
                                                                     0
 Revision
 Date   September 1986

-------
                                      Form IV
                             Q. C. Report No.
LAB NAME
1CP INTERFERENCE  CHECK SAMPLE
                        CASL NO.
DATE
                        Check Sample l.D.
                        Check Sample Source
                        Units:     ug/L

Compound
Metals:
1 . Aluminum
2. Antimony
3. Arsenic
fc. Barium
5. beryllium
6. Cadmium
7. Calcium
8. Chromium
9. Cobalt
10. Copper
11. Iron
12. Lead
13. Magnesium
14. Manganese
15. Mercury
16. Nickel
17. Potassium
IB. Selenium
ly. Silver
20. Sodium
21. Thallium
22. Vanadium
2J. Zinc
Other:

Control
Mean

























Limits1
Std. Dev.





















































True^




















































Initial
Observed


























7.R

























Final
Observed


























%R

























   Moan value based on n  =
   True value of EHA ICP Interference Check Sample or contractor standard.
                                ONE  -  22
                                                        Revision      0
                                                        Date   September 1986

-------
                                        Form V
                               Q. C.  Report No.
                                SPIKE SAMPLE RECOVERY
 LAB NAME
 DATE
CASE NO.
    Sample No.
Lab Sample ID No.
Units
                                Matrix

Compound
Metals:
1. Aluminum
2. Antimony
3. Arsenic
4. Barium
5. Beryllium
6. Cadmiuc
7. Calcium
8. Chromium
9. Cobalt
10. Copper
11. Iron
12. Lead
13. Magnesium
14. Manganese
15. Mercury
16. Nickel
17. Potassium
IB. Selenium
19. Silver
20. Sodium
21. Thallium
22. Vanadium
23. Zinc
Other:

Cyanide
Control Limit
IR


























Spiked Sample
Result (SSR)


























Sample
Result (SR)


























Spiked
Added (SA)



























ZR1


























1 *R = USSR - SK)/SAj x  100
"N"- out of control
NR1- Not required
Comments:
                                ONE -  23
                                                        Revision       0
                                                        Date   September 1986

-------
LAB NAME
DATE
                                     Form VI
                             Q« C. Report No.
                                    DUPLICATES
CASE NO.
    Sample No.
Lab Sample ID No.
Units
                               Matrix
Compound
Metals:
1. Aluminum
2. Antimony
3. Arsenic
4. Barium
5. Beryllium
6. Cadmium
7. Calcium
8. Chromiuc
9. Cobalt
10. Copper
11. Iron
12. Lead
13. Magnesium
14. Manganese
15. Mercury
16. Nickel
17. Potassium
la. Selenium
ly. Silver
20. Sodium
21. Thallium
22. Vanadium
23. Zinc
Other:

Cyanide
Control Limit1


























Sample(S)





















t




Duplicate^)













*












RPD2


























* Out of Control
1 To be added at a later date.              2 RPD = (|s - D|/((S +  D)/2)]  x 100
NC - Non calculable KPU due to  value(s) less than CRDL
                               ONE - 24
                                                      Revision      0
                                                      Date  September 1986

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                                       Form VII

                              Q.C. Report No.
 LAB  NAME
INSTRUMENT DETECTION LIMITS AND

   LABORATORY CONTROL SAMPLE

          CASE NO.
DATL
                                                              LCS NO.
Compound
Metals:
1. Aluminum
2. Antimony
3. Arsenic
4. Barium
5. Beryllium
fe. Cadmium
7 . Ca 1 c i UQ
8. Chromium
2. Cobalt
10. Copper
11. Iron
12. Lead
13. Magnesium
14. Manganese
15. Mercury
16. Nickel
17. Potassium
18. Selenium
19. Silver
20. Sodium
21. Thallium
22. Vanadium
23. Zinc
Other:

Cyanide
Required Detection
Limits (CRDL)-uK/!



























Instrument Detection
Limits (IDL)-ug/!'
ICP/AA Furnace
IDf 	 ID* 	

























NR

























I:K
Lab Control Sample
ug/L mfi/kp
(circle one)
True Found ZR


































1








































Mi - Not required
                                ONE - 25
                                                       Revision      0
                                                       Date  September 1986

-------
                                      Form VIII

                              Q.C.  Report No.
                              STANDARD ADDITION RESULTS
LAB NAME
UATt

tPA
Sample V






















CASE NO.


tlement






















Matrix






















0 ADD
ABS.






















1 ADD
CON .






















ABS-






















UMTS .' ug/L
2 ADD
CON.






















ABS.Z






















3 ADD
CON.






















AfcS.^






















FINAL
CON.3




















r*




















(
i
^ CON is the concentration added, ABS. is the instrument  readout  in  absorbance  or
  concentration.

•* Concentration as_ determined by ."•iSA
*"r" is the correlation coefficient.
+ - correlation coefficient is outsidu ot control window  of
                               ONE - 26
                                                       Revision       0
                                                       Date   September  1986

-------
 LAB NAME
 DATE
                                      Form IX
                              Q« C. Report No.
                                 ICP SERIAL DILUTIONS
CASE NO.
    Sample No.
Lab Sample ID Mo,
Units'.   ug/L
                                Matrix
Compound
Metals:
1 . Aluninun
2. Antimony
3. Arsenic
4. barium
5. Bervlliuc
6. Cadmium
7. Calcium
t>. Chromium
V. Cobalt
10. Copper
11. Iron
12. Lead
13. Magnesium
14. Manganese
15. Nickel
16. Potassiur.
17. Seleniur
lb. Silver
1^. Sodium
20. Thallium
/I . Vanadium
2.2. Zinc
OLhc-r :

Initial Sample
Concentration( I)
























Serial Dilution1
Result(S)
























A Difference2













, i
^









'  Diluted sample concentration corrected for  1:4 dilution (see Exhibit D)
2  Percent Difference     U ~ sl   x luu
                           1
Nk - Not Required, initial sample concentration less than 10 times IUL
NA - Not Applicable, analyte not determined  by  1CP
                                ONE - 27
                                                       Revision      0
                                                       Date  September 1986

-------
                                      Form  X
                             QC Report  No.
                                   HOLDING TIKES
 LAb  NAME


 DATE
CASE Nu.
EPA
Sample No.



























Matrix



























Date
Received



























Mercury
Prep Date



























Mercury
Holding Time1
(Days)



























CN Prep
Date



























CN
Holding Time1
(Davs)























t



'holding time is defined as number of days between the date received and the
sample preparation date.
                             ONE - 28
                                                    Revision      0
                                                    Date  September 1986

-------
 LAK  NAME
    Form XI
INSTRUMENT DETECTION LIMITS


                        DATE
ICP/Flame AA (Circle One)
Element
1 • Aluminum
2. Antimony
3. Arsenic
A. Barium
b. Beryllium
0. Cadciun
7. Calcium
6. Chromium
9. Cobalt
1U. Copper
11. Iron
12. Lead
Wavelength
(nm)












Model Number Furnace AA Number

IDL
(ug/L)












Element
13. Magnesium
14. Manganese

Wavelength
(no)


15. Mercury
16. Nickel
17. Potassium
IB. Selenium
19. Silver
20. Sodium
21. Thalliun
22. Vanadium
23. Zinc





IDL
(UE/L)












Footnotes: • Indicate the instrument for which the IDL applies with a "f" (for ICP
             an "A" (for Flame AA), or an "F" (for Furnace AA) behind the IDL valu

           • Indicate elements commonly run with background correction (AA) with
             a "b" behind the analytical wavelength.

           • If more than one ICP/Flame or Furnace AA is used, submit separate
             Forms XI-X111 for each instrument.
CUMMLNTb:
                                           Lab Manager
                               ONE - 29
                                                      Revision      0
                                                      Date  September 1986

-------
                                   Forn XII

                          ICP  Interelement Correction Factors
  LABORATORY

  DATE
ICP Model Number

Analyte
1. Antimonv
2. Arsenic
3. Bariuc
4. Bervllius
5. Cadcius
6. ChroEiur.
7. Cobalt
8. Copper
9. Lead
10. Manganese
11. Mercurv
12. Nickel
13. Potassiur:
14. Seleniuc
15. Silver
16. Sodium
17. Thallium
IB. Vanadium
r>. Zinc
Analyte
Wavelength
(no)


















Intereleraent. Correction Factors
for
Al


















i
Ca



















Fe

















Mg




















i




•








































































COMMENTS:
                                         Lab Manager
                                  ONE -  30
                                                        Revision      0
                                                        Date  September 1986

-------
                               Form XII

                          1CP Interelement Correction Factors
  LABORATOKY_

  DATE
ICP Model Nunber

Analyte
1. Antimony
2. Arsenic
3. bariutr.
4. BerylliuE
5. Cadmiuir.
6. Chromium
7. Cobalt
6. Copper
9. Lead
10. Manganese
11. Mercury
12. Nickel
13. Potassium
14. Selenium
15. Silver
16. Sodium
17. Thallium
18. Vanadium
iy. Zinc
Analyte
Wavelength
(nn)



















Interelement Correction Factors
for







































1



















1

























































1
















:























COMMENTS:
                                          Lab Manager
                                   ONE - 31
                                                          Revision      0
                                                          Date  September  1986

-------
 LAB  NAME


     DATE
                                Form XIII

                                   ICP  Linear  Ranges
                          TCP Model Number
Analyte
1. Aluminum
2. Antimony
3. Arsenic
4 . Bariur
5. Beryllium
6. Cadmium
7. Calcium
b. Chroniuni
9. Cobalt
10. Copper
1 1 . Iron
12. Lead |
Integration
Time
(Seconds )





.






Concen-
tration
(ug/L)











1
Ana 1 y t e
13. Magnesium
14. Manganese
15. Mercury
16. Nickel
17. Potassium
18. Selenium
19. Silver
20. Sodiur.
21. Thalliun:
22. Vanadiuir
23. Zinc

Integrat ion
Time
(Seconds )












Concen-
tration
(ug/L)












Footnotes:
Indicate elements not analyzed by ICP with the notation "NA".
COMMENTS:
                                           Lab Manager
                             ONE - 32
                                                    Revision      0
                                                    Date  September 1986

-------
                                           Organics Analysis Data Sheet
                                                          (Pagel)
                                                                                                        Sample Number
Laboratory Name:
                                                          Case No:
Lab Sample ID No	
Sample Matrix	
                                                          QC Report No:
Data Release Authorized By
                                                          Date Sample Received:
                                                  Volatile Compounds
                                   Date Extracted/Prepared:
                                   Date Analyzed:	__
                                   Conc/Di! Factor:  	
                                                               -PH.
                                   Percent Moisture: (Not Decanted).
CAS ug/lorug/Kg
Number (Circle One)
74-87-3
74-83-9
75-01-4
75-00-3
75-09-2
67-64-1
75-15-0
75-35-4
75-34-3
156-60-5
67-66-3
107-06-2
78-93-3
71-55-6
56-23-5
108-05-4
75-27-4
Chloromethane
Bromoniethane
Vinyl Cnio'ide
Chloroethane
Metnylene Chloride
Acetone
Carbon Oisulfide
1. 1-Dichloroethene
1. 1-Dichloroethane
Trans- 1. 2-Dichloroethene
Chloroform
1. 2-Dichloroethane
2-Butanone
1.1. 1-Trichloroethane
Carbon Tetrachloride
Vinyl Acetate
Bromodichloromethane

















CAS ug/lorug/Kg
Number , (Circle One)
78-87-5
10061-02-6
79-01-6
124-48-1
79-00-5
71-43-2
10061-01-5
110-75-8
75-25-2
108-10-1
591-78-6
127-18-4
79-34-5
108-88-3
108-90-7
100-41-4
100-42-5

1, 2-Dichloropropane
Trans- 1. 3-Oichloropropene
Trichloroethene
Dibromochloromethane
1.1. 2-Trichloroethane
Benzene
cis-1. 3-Dichloropropene
2-Chloroethylvinylether
Bromoform
4-Methyl-2-Pentanone
2-Hexanone
Tetrachloroethene
1.1.2. 2-Tetrachloroeihane
Toluene
Chlorobenzene
Ethylbenzene
Styrene
Total Xylenes


















                                                     Data Reporting Qualifiers
                                For reporting remits to EPA. the following results qualifiers are used.
                                Additional flags or footnotes e«plainmg results are encouraged However, the
                                definition of each flag must be anplicit
Value
If the resuli is a value greater than or equal to the detection limit.
report me value

Indicates compound was analyzed for but not detected Report the
minimum detection limit for the (ample with the U (e.g.. 100) based
on necessary concentration 'dilution action (This is not necessarily
the  instrument detection limn |  The footnote  should read  U-
Compound was analyied lor but not detected  The number is the
minimum attainable detection limit lor the sample

Indicates an estimated value   Tms flag is used either when
estimating a concentration for tentatively identified compounds
where a  1 1 response is assumed or when me mass spectral data
indicated the pretence of a compound that meets the identification
criteria but me result is less than the rpecified detection limit but
greater tnan tero  le g . 10JI  If limit o' detection is 10 ug 'I and a
concentration of 3 pg *l is calculated, report as 3J.
                                                                 Other
This flag applies to pesticide parameters where me identification nas
been  confirmed  by CC/MS   Single component pesncides^tO
ng 'ul in the final attract should be confirmed by GC MS

This flag is used when the analyte is found m me blank as wen as a
sample   It indicates possible• probable blank contamination and
warns the data user to lake appropriate action

Other specific flags and footnotes may be required to properly define
the results If used, they must be lully described and sucn description
attached to me data summary report
                                                             Form I
                                                   ONE  -  33
                                                                                      Revision   	0_
                                                                                      Date   September
                                                                                                      1986

-------
 Laboratory Name:
 Case No:	:	
                                                                           Sample Number
Date Extracted/Prepared: _

Date Analyzed. 	
 Organics Analysis Data Sheet
            (Page 2)

     Semivolatile Compounds

                       GPC Cleanup DYes DNo

	         Separatory Funnel Extraction QYes

	         Continuous Liquid - Liquid Extraction DYes
Cone/Oil Factor:
Percent Moisture (Decanted).
 CAS
 Number
   ug/lorug/Kg
     (Circle One)
CAS ug/lorug/Kg
Number . (Circle One
83-32-9
51-28-5
100-02-7
132-64-9
121-14-2
606-20-2
84-66-2
7005-72-3
86-73-7
100-01-6
534-52-1
86-30-6
101-55-3
118-74-1
87-86-5
85-01-8
120-12-7
84-74-2
206-44-0
129-00-0
85-68-7
91-94-1
56-55-3
117-81-7
218-01-9
117-84-0
205-99-2
207-08-9
50-32-8
193-39-5
53-70-3
191-24-2
Acenaphthene .
2. 4-Dinitrophenol
4-Nitrophenol
Oibenzofuran
2, 4-Dinitrotoluene
2, 6-Dinitrotoluene
Oiethylphthalate
4-Chlorophenyl-phenylether
Fluorene
4-Nitroaniline
4,.6-Dinitro-2-Methylphenol
N-Nitrosodiphenylamine (1)
4-Bromophenyl-phenylether
Hexachlorobenzene
Pentachlorophenol
Phenanthrene
Anthracene
Di-n-Butylphthalate
Fluoranthene
Pyrene
Butylbenzylphthalate •
3, 3'-Dichlorobenzidine
Benzo(a)Anthracene
bis(2-Ethylhexyl)Phthalate
Chrysene
Di-n-Octyl Phthalate
Benzo(b)Fluoranthene
Benzo(k)Fluoranthene
Benzo(a)Pyrene
Indenod . 2, 3-cd)Pyrene
Dibenz(a, h)Anthracene
Benzo(g. h, i)Perylene
































                                                 (1)-Cannot be separated Irom diphenylamine
                                             Form I
                                       ONE  - 34
                                                                  Revision       0
                                                                  Date  September 1986

-------
 Laboratory Name
 Case No  	
                                             Sample Number
Date Extracted/Prepared:
Date Analyzed:	
Conc/Dil Factor: 	
 Organics Analysis Data Sheet
            (Page 3)

         Pesticide/PCBs
                     GPC Cleanup DYes DNo
	        Separatory Funnel Extraction DYes
	        Continuous Liquid - Liquid Extraction DYes
Percent Moisture (decanted).
CAS ug/lorug/Kg
Number (Circle One)
319-84-6
319-85-7
319-86-8
58-89-9
76-44-8
309-00-2
1024-57-3
959-98-8
60-57-1
72-55-9
72-20-8
33213-65-9
72-54-8
1031-07-8
50-29-3
72-43-5
53494-70-5
57-74-9
8001-35-2
12674-11-2
11104-28-2
11141-16-5
53469-21-9
12672-29-6
11097-69-1
11096-82-5
Alpha-BHC
Beta-BHC
Delta-BHC
Gamma-BHC (Lindane)
Heptachlor
Aldrin
Heptachlor Epoxide
Endosulfan I
Dieldrm
4,4'-DDE
Endrin
Endosulfan II
4. 4--DDD
Endosulfan Sulfate
4,4'-DDT
Methoxychlor
Endrin Ketone
Chlordane
Toxaphene
Aroclor-1016
Aroclor-1221
Aroclor-1232
Aroclor-1242
Aroclor-1248
Aroclor-1254
Aroclor-1260


























                                   Vj  = Volume of extract injected (ul)
                                   V$  = Volume of water extracted (ml)
                                   Ws = Weight of sample extracted (g)
                                   V,  = Volume of total extract (ul)
                            orW.
                                              Form 1

                                       ONE - 35
                                                                  Revision        0
                                                                  Date  September 1986

-------
Laboratory Name:.

Case No:	
                            Organics Analysis Data Sheet
Sample Number
CAS
Number
V
•2.
a
A
6
fi
7
R
9
10
11
13
13
14
IS
IS
17
1fl
19
3f>
21
22
33
3d
3K
3fi
27
3B
3<>
30
Compound Name






























Fraction






























RT or Scan
Number






























Estimated
Concentration
(ug/lorug/kg)






























                                     Form 1, Pan B
                                   ONE - 36
                                                           Revision      0
                                                           Date  September 1986

-------
            Case No..
                         WATER SURROGATE PERCENT RECOVERY SUMMARY

                         	    Laboratory Name	

•AMPlt
NO.



























tOLUCNC-M
IH-110)

























•ft
(••-IIS)

























l.t OICHLOHO-
ETHANC-04
(M-1141



























NIIHO-
•CIIZCN009
(It- 114)


























t-'LUOKO-
eiPHtXri
(43- lie)


























UOPHENltL-
OI4
(13-141)




















































EMI-VOLATIL


























r

mCNOL-05
(10-14)

























t-riuOM>-
mCNOL
(11-100)

























2.4.6 TRIKROHO-
PHENOL
(10-113)

























-PESTICIOE--
oiaurtL-
CHIOHCHOATC
U4-1B4)

























     I
    00
O 70
(U O
ft <
(0 -••
  (/>

C/) O
n> 3
o
rt-
O>
vO
CD
C7>
            VALUES ARE OUTSIDE OF REQUIRED QC LIMITS
                                                       Volatiles:

                                                       Semi-Volatiles:

                                                       Pesticides:
. out of.

 out of.

 out of.
.; outside of QC limits

.; outside of OC limits

.; outside of QC limits
Comments:
                                                                FORM II

-------
SOIL SURROGATE PERCENT RECOVERY SUMMARY
Date September 1986
o
m
1
GJ
00
n>
<
J2.
o

0

MMM.B
NO.



























TOLUCNC-0*
ui-iir)

























»

























U OICm.000-
CTHXIC-D4

























NITKO -
(CNZCNC-OS

























j-riuono-
(90-tK)

























(ie-iif)

























Volat
VALUES ARE OUTSIDE OF REQUIRED OC LIMITS e .
oeitw-
Pestk



























EMI-VOLATIL




























7.7T






















,


IPS: ., nut of •
Vnlatilps* . out 0
idea: out o
f 	 .
f .

f-rioono-

























l.4.« TUtgHOHO-

























•-PE3TICIOE--
OttUtTL-

























outside of OC limits
outside of OC limits
outside of QC limits



                FORM II

-------
                               WATER MATRIX  SPIKE/MATRIX SPIKE DUPLICATE RECOVERY
            Case No.
Laboratory Name.
    OJ
    IO
FRACTION

VOA

SAMPLE NO.



B/N

SAMPLE NO.



API n

SAMPLE NO



PEST

bAMPLE NO.



COMPOUND

1 ,1 -Dichloroethene
Trichloroethene
Chlorobenzene
Toluene
Benzene
1 ,2.4.TrichlorobefUene
Acenaphth,:ne
2.4 Dinitrotoluene
Oi-n-Butylphthalate
Pyrene
N-Nitroso-Di-n-Propylamine
1 ,4-Dichlorobenzene
Pentachlorophenol
Phenol
2-Chlorophenol
4-Chloro-3-Methylphenol
4-Nitrophenol
Lindane
Heptachlor
Aldrin
Oieldrin
Endrin
4 4'-DOT

CONC. SPIKE
ADDED (uq/L)
























SAMPLE
RESULT
























CONC.
MS
























%
REC
























CONC.
MSD
























%
REC
























ppn

























t Q
RPD
14
14
13
13
11
28
31
38
40
31
38
28
50
42
40
42
50
15
20
22
18
21
27

: LIMITS
RECOVERY
61-145
71-120
75-130
76-1^5 __.
76-1?7
39-98
46-118
24-96
11-117
26-127
41-116
36 97
9 103
12 89
27-123
23 97
10 80
56 123
40 131
40 120
52-126
56-121
38-1 27

O
tu
            ADVISORY LIMITS
oo o
n> 3
o
r1-
O)

CT
fD
-i
00
CTv
RPD:
Conwr
VOAs 	
R/N
Ann
PFST
4»nt«f

	 out of 	
out nf
nut nf
nut nf


outside
outside
outside
outside

OC limits
QC limits
OC limits
QC limits

RECOVERY: VOAs 	 out of 	 :
B/N 	 , Out "'
ACID _ "»' "' , - - ;
PPST out nf - ;


outside
outside
outside
outside

OC
OC
OC
OC

limits
limits
limits
limits




                                                            FORM III

-------
                                   SOIL MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY
              Case No.
Laboratory Name.
     I

     o
O
fu
n> -^
co o
(D =J
CT
ft)
CO
cn
FRACTION
VGA
SAMPLE NO.
B/N
SAMPLE NO.
ACID '
SAMPLE NO.
PEST
SAMPLE NO.
COMPOUND
1 ,1 -Dicholorethene
Trichlorocthene
Chlorobenzene
Toluene .
Benzene
CONC. SPIKE
ADDED (iig/Kq)





1,2,4-Trichlorobenzene }
AcenapKthene
2,4 Dinitrotoluene
Dj-n-Butylphthalate
Pyrene
N-Nitrosodi-n-Propylamine
1 ,4-Dichlorobenzene
Pentachlorophenol
Phenol
2-Chlorophenol
4-Chloro-3-Methylphenol
4-Nitrophenol
Lindane
Heptachlor
Aldrin
Oieldrin
Endrin
4.4'DDT

















SA'MPLE
RESULT























CONC.
MS























%
REC























CONC.
MSD























%
REC























RPD























O.C LIMITS
RPD
22
24
21
21
21
23
19
47
47
36
38
27
47
35
50
33
50
50
31
43
38
45
50
RECOVERY
59172
62-137
60133
59-139
66142
38-107
31-137
28-89
29-135
35-142
41-126
28 104
17-109
2690
25-102
26-103
11-114
46-127
35130
34132
31-134
42-139
23134
              ADVISORY LIMITS
RPD: VOAs
R/N
Arm
PFST
Conwnents:




nut of nntsidp OC limits
nut nf . Qiit*iHp OO limit*
«M1 of OH'*'dP Or limit*
_ out of outsiHp OC linriit*





RFrOVFRY- VOA* out of out*idp Of! limits
R/N ...out of. . . OMt*irlp Or limit*
Arm out nf nnKiHp DP limit*
PfST nut of niit*iHp OC limits





                                                                 FORM III

-------
                                            METHOD  BLANK SUMMARY
          Case No.
Laboratory .Name.
O 73
a> n
ft>
a
a-
o
m
1
i— «





FLEIO




















OATC OF
ANALYSIS




















TRACTION




















MATRIX




















CONC.
LEVEL




















INST.IO




















CAS NUMBER




















COMPOUND (MSL.TIC OR UNKNOWN)




















CONC.




















UNITS




















CROL




















          Comments:
to
00
                                                           FORM IV

-------
               GC/MS  TUNING AND MASS CALIBRATION

                       Bromofluorobenzene (BFB)
  Case No..
  Instrument ID
                Laboratory Name.

                Date 	
         Time.
                        Data Release Authorized By:
  .m/e
ION ABUNDANCE CRITERIA
 ^RELATIVE ABUNDANCE
50
75
95
96
173
174
175
176
177
15.0 - 40.0% of the base p«ak
30.0 • 60.0% of the base peak
Base peak, 100% relative abundance
5.0 • 9.0% of the base peak
Less than 1.0% of the base peak
Greater than 50.0% of the base peak
5.0 • 9.0% of mass 174
Greater than 95.0%, but less than 101.0% of mass 174
5.0 - 9.0% of mass 176






( )'
( r
c )2
THIS PERFORMANCE TUNE APPLIES TO THE FOLLOWING
SAMPLES, BLANKS AND STANDARDS.
                                                Value in .parenthesis ii % mass 174.
                                                Value in parenthesis is % mass 175.
    SAMPLE ID
                   LAB ID
DATE OF ANALYSIS
TIME OF ANALYSIS
                                   FORM V


                            ONE - 42
                                                    Revision      0
                                                    Date  September  1986

-------
Case No..
Instrument ID
        GC/MS TUNING AND MASS CALIBRATION
         Decafluorotriphenylphosphine (DFTPP)
       	  Laboratory Name	

       	  Date 	Time	
                    Data Release Authorized By:
m/e
ION ABUNDANCE CRITERIA
                                        ^RELATIVE ABUNDANCE
51
68
69
70
127
197
198
199
275
365
441
442
443
30.0 -60.0% of mass 198
less than 2.0% of man 69
mass 69 relative abundance
less than 2.0% of mass 69
40.0 • 60.0% of mass 198
less than 1.0% of mass 198
base peak, 100% relative abundance
5.0 • 9.0% of mass 198
10.0 • 30.0% of mass 198
greater than 1.00% of mass 198
present, but less than mass 443
greater than 40.0% of mass 198
17.0 - 23.0% of mass 442

( )1

( )'








C )2
THIS PERFORMANCE TUNE APPLIES TO THE FOLLOWING ' Value in parenthesis is % mass 69.
SAMPLES, BLANKS AND STANDARDS. 2Value in parenthesis is % mass 442
SAMPLE ID




















LAB ID



.






-









DATE OF ANALYSIS




















TIME OF ANALYSIS




















                               FORM V

                         ONE - 43
                                              Revision      Q
                                              Date  September 1986

-------
                                    Initial Calibration Data
                                  Volatile HSL Compounds
 Case No:
 Laboratory Name
Instrument I D:  .
Calibration Date-
                Minimum RFfor SPCCis 0.300
                      (0.25 for Bromoform)
Maximum % RSD for CCC is 30%
Laboratory ID
Compound
Chloromethane
Bromomethane
Vinyl Chloride
Chloroethane
Methylene Chloride
Acetone
Carbon Disulfide
1, 1-Bichloroethene
1, 1-Dichloroethane
Trans-1. 2-Dichioroethene
Chloroform
1. 2-Dichloroeihane
2-Butanone
1.1. 1-Trichloroethane
Carbon Tetrachloride
Vinyl Acetate
Bromodichloromethane
1. 2-Dichloropropane
Trans-1. 3-Dichloropropene
Trichloroethene
Dibromochloromethane
1.1. 2-Trichloroethane
Benzene
cis-1. 3-Dichloropropene
2-Chloroethylvinylether
Bromoform
4-Methyl-2-Pentanone
2-Hexanone
Tetrachloroethene
1.1.2. 2-Tetrachloroethane
Toluene
Chlorobenzene
Ethylbenzene
Styrene
Total Xylenes

RF20

























,










RF50




































RF100




































RF150
























.











RF200




































RF



































%RSD



































CCC*
SPCC"
* *

•




*
» •

*






*







» *



» *
*
* *
•


RF -Response Factor (subscript is the amount of ug/L)
757 -Average Response Factor
%RSD -Percent Relative Standard Deviation
CCC -Calibration Check Compounds (•)
SPCC -System Performance Check Compounds (.
                                             Form VI
                                      ONE - 44
                                                                Revision       p
                                                                Date   September  1986

-------
                                   Initial Calibration Data
                                  Volatile HSL Compounds
 Case No:
 Laboratory Name.
                         Instrument I D:  .
                         Calibration Date:
                Minimum RF for SPCC is 0.300     Maximum % RSD for CCC is 30%
                      (0 25 for Bromoform)
 Laboratory IO
 Compound
RF20
RF
                                    50
RF
           100
RF150
RF
                     200
RT
%RSD
 CCC-
SPCC«
RF -Response Factor (subscript is the amount of ug/L)
fiT -Average Response Factor
%RSD -Percent Relative Standard Deviation
                         CCC -Calibration Check Compounds (•)
                         SPCC -System Performance Check Compounds (••)
                                            Form VI
                                        ONE - 45
                                                                  Revision       p
                                                                  Date   September 1986

-------
Case No:
Laboratory Name.
     Initial Calibration Data
 Semivolatile HSL Compounds
            (Pagel)
                  Instrument ID: _
	    Calibration Date:
               Minimum RF for SPCC is 0.050    Maximum % RSD for CCC is 30%
Laboratory ID
Compound
Phenol
bis(-2-Chloroethyl)Ether
2-Chlorophenol
1. 3-Dichlorobenzene
1. 4-Dichlorobenzene
Benzyl Alcohol
1. 2-Dichlorobenzene
2-Methylphenol
bis(2-Chloroisopropyl)Ether
4-Methylphenol
N-Nitroso-Di-n-Propylamme
Hexachloroethane
Nitrobenzene
Isophorone
2-Nitrophenol
2. 4-Dimethylphenol
Benzoic Acid
bis(-2-Chloroethoxy)Metriane
2. 4-Oichlorophenol
1 . 2, 4-Trichlorobenzene
Naphthalene
4-Chloroanilme
Hexachlorobutadiene
4-Chloro-3-Methylphenol
2-Methylnaphthalene
Hexachlorocyclopentadiene
2, 4. 6-Trichlorophenol
2, 4. 5-Trichloropheno!
2-Chloronaphthalene
2-Nitroaniline
Dimethy! Phthalate
Acenaphthylene
3-Nitroanilme
Acenaphthene
2, 4-Dmitrophenol
4-Nitrophenol
Dibenzofuran

RF20
















T










T

T


t

t
T


"50






































"BO

















> •




















RF120















x






















"160






































RF





































%RSD





































CCC«
SPCC««
*



»





* •



»



*



*
•

* *
»






»
» *
• *

Response Factor (subscript is the amount of nanograms)
RF -Average Response Factor
%RSD -Percent Relative Standard Deviation
CCC -Calibration Check Compounds j.)
                   SPCC -System Performance Check Compounds (••)
                   t -Not detectable at 20 ng
                                             Form VI
                                      ONE - 46
                                                                 Revision       0
                                                                 Date   September 1986

-------
  Case No:
  Laboratory Name
     Initial Calibration Data
 Semivolatile HSL Compounds
            (Page 2)
                   Instrument ID: _
	     Calibration Date:
                 Minimum RF for SPCC is 0.050     Maximum % RSD for CCC is 30%
Laboratory ID
Compound
2, 4-Dinitrotoluene
2, 6-Dmitrotoluene
Diethylphthalate
4-Chlorophenyl-Dhenylether
Fluorene
4-Nitroaniline
4. 6-Dinitro-2-Methylpheno!
N-Nitrosodiphenylamine (1)
4-Bromophenyl-phenylether
Hexachlorobenzene
Pentachloropheno!
Pnenanthrene
Anthracene
Di-N-Butylphthalate
Fluoranthene
Pyrene
Butylbenzylphthalate
3. 3'-Dichlorobenzidme
Benzo(a)Anthracene
bis(2-Ethylhexyl)Phthalaie
Chrysene
Di-n-Octyl Phthalate
Benzo(b)Fluoranthene
Benzo(k)Fluoranthene
Benzo(a)Pyrene
IndenoO. 2. 3-cd)Pyrene
Dib€nz(a, h)Anthracene
Benzo(g. h. i)Perylene

RF20





t
t



t


















«F50





























RF80





























RF120





























RF160





























IP




























VcRSD




























CCC-
SPCC"







»


*



*






*


*



Response Factor (subscript is the amount of nanograms)
R? -Average Response Factor
%RSD -Percent Relative Standard Deviation
CCC -Calibration Check Compounds (•)
                  SPCC -System Performance Check Compounds (••)
                  t - Not detectable at 20 ng
                  (1) -Cannot be separated from diphenylamine
                                              Form VI
                                       ONE - 47
                                                                  Revision       p
                                                                  Date   September  1986

-------
Case No:
Laboratory Name.
     Initial Calibration Data
 Semivolatile HSL Compounds
            (Page!)
                  Instrument ID: _
	,        Calibration Date:
               Minimum RF for SPCC is 0.050     Maximum % RSD for CCC is 30%
 Laboratory ID
 Compound
                        RF
                          20
              RF80
RF120
RF
                                  160
           RF
%RSD
 CCC«
SPCC'
Response Factor (subscript is the amount of nanograms)
R? -Average Response Factor
%RSD -Percent Relative Standard Deviation
CCC -Calibration Check Compounds (•)
                    SPCC -System Performance Check Compounds (••)
                    t -Not detectable at 20 ng
                                             Form VI
                                        ONE - 48
                                                                   Revision       0
                                                                   Date   September 1986

-------
                                Continuing Calibration Check
                                   Volatile HSL Compounds
 Case No:
 Laboratory Name.
 Contract No:	
Calibration Date:
Time: 	
 Instrument ID:
Laboratory ID:
Initial Calibration Date:
                Minimum RF for SPCC is 0.300
                      (0.25 for Bromoform)
Maximum %D for CCC is 25%
Compound
Chloromethane
Bromomethane
Vinyl Chloride
Chloroethane
Meihylene Chloride
Acetone
Carbon Disulfide
1. 1-Dichloroethene
1. 1-Oichloroethane
Trans-1. 2-Dichloroethene
Chloroform
1, 2-Dichloroe:hane
2-Butanone
1,1. 1-Trichloroethane
Carbon Tetrachloride
Vinyl Acetate
Bromodichloromethane
1, 2-Dichloropropane
Trans-1. 3-Dichloropropene
Trichloroethene
Dibromochloromethane
1.1. 2-Tnchloroethane
Benzene
cis-1, 3-Dichloropropene
2-Chloroethylvinylether
Bromoform
4-Methyl-2-Pentanone
2-Hexanone
Tetrachloroethene
1. 1.2, 2-Tetrachloroethane
Toluene
Chlorobenzene
Ethylbenrene
Styrene
Total Xylenes
RF



































RF50






























•




%D



































CCC


»




*


*






•












*

*


SPCC
» *







* •












'



* *



• *

* *



RFgg -Response Factor from daily standard die at 50 ug-'l
RF -Average Response Factor from initial calibration Form VI
%D -Percent Difference
CCC -Calibration Check Compounds (•)
SPCC -System Performance Check Compounds (••)
                                             Form VII
                                         ONE  - 49
                                                                    Revision       o
                                                                    Date   September  1986

-------
                                 Continuing Calibration Check
                                   Volatile HSL Compounds
 Case No:
 Laboratory Name.
 Contract No:	
                   Calibration Date

                   Time 	
 Instrument ID.
                   Laboratory ID:
                   Initial Calibration Date:
                 Minimum RF for SPCC is 0.300
                      (0.25 for Bromoform)
                   Maximum %D for CCC is 25%
 Compound
RF
             RF
                                              50
%D
CCC
SPCC
"F50 -Response Factor from daily standard file at 50 ug I
RF -Average Response Factor from initial calibration Form VI
                   °oD -Percent Difference
                   CCC -Calibration Cneck Compounds (•)
                   SPCC System Performance Check Compounds (••)
                                             Form VII
                                       ONE - 50
                                                                 Revision       o
                                                                 Date  September 1986

-------
                                Continuing Calibration Check
                                Semivolatile HSL Compounds
                                           (Pagel)
Case No:
Laboratory Name.
Instrument ID:
Calibration Date:
Time:	
                                                  Laboratory JD:
Initial Calibration Date:
                Minimum RF for SPCC is 0.050     Maximum %D for CCC is 25%
Compound
Phenol
bis{-2-Chloroethyl)Ether
2-Chlorophenol
1, 3-Dichlorobenzene
1 . 4-Dichlorobenzene
Benzyl Alcohol
1. 2-Oichlorobenzene
2-Melliylphenol
bis(2-chloroisopropyl)Ether
4-Methylphenol
N-Nitroso-Di-n-Propylamine
Hexachloroeihane
Nitrobenzene
Isophorone
2-Nitrophenol
2, 4-Dimeihylphenol
Benzoic Acid "f
biS(-2-Chloroethoxy)Meihane
2, 4-Dichlorophenol
1. 2. 4-Trichlorobenzene
Naphthalene
4-Chloroanilme
Hexachlorobutadiene
4-Chloro-3-Methylphenol
2-Methylnaphthalene
Hexachlorocyclopentadiene
2. 4. 6-Tnchlorophenol
2. 4. 5-Tnchloiophenol |
2-Chloronaphihalene
2-Nitroanilme f
Dimethyl Phthalate
Acenaphthylene
3-Nitroanilme f
Acenaphthene
2, 4-Dmitrophenol
4-Nitrophenol
Oibenzofuran
FT*





































R^BO





































%D





































CCC
*



*









*



*



*
*


*






«



SPCC










* *














• »








» *
* *

RFjQ -Response Factor from daily standard die at concentration
     indicated (50 total n»nognms)
RT -Average Response Factor from initial calibration Form VI
 + >Due to low response, analyze
   •t 80 total nanograms
 S>D -Percent Difference
 CCC -Calibration Check Compounds (•)
 SPCC -System Performance Check Compounds (••)
                                             Form VII


                                          ONE  - 51
                                                                     Revision        o
                                                                     Date  September 1986

-------
                                  Continuing Calibration Check
                                  Semivolatile HSL Compounds
                                              (Page 2)
Case No:
Laboratory Name
Instrument ID:
                                                     Calibration Date:
                                                     Time:  	
                                                     Laboratory ID.
                                                    . Initial Calibration Date:
                 Minimum RF for SPCC is 0.050     Maximum %D for CCC is 25%
Compound
2, 4-Dinitrotoluene
2. 6-Dinitrotoluene
Diethylphthalate
4-Chlorophenyl-phenylether
Fluorene
4-Nitroaniline t
4, 6-Dmitro-2-Methylphenol J
N-Nitrosodiphenylamine (1 )
4-Bromophenyl-phenyle!her
Hexachlorobenzene
Pemachlorophenol f
Phenanthrene
Anthracene
Di-N-Butylphthalate
Fluoranthene
Pyrene
Butylbenzylphthalate
3, 3'-Dichlorobenzidme
Benzofa (Anthracene
bis(2-Ethylhexvl)Phthalate
Chrysene
Di-n-Octyl Phthalaie
Benzo(b)Fluoranthene
Benzo(k)Fluoranthene
Benzo(a)Pyrene
IndenoO. 2. 3-cd)Pyrene
Oibenz(a, hJAnthracene
Benzo(g. h, i)Perylene
RF




























RF50




























%D




























CCC

-





»


*



*






»


*



SPCC




























RF^Q Response F.u-lur (ruin Oiiily Sl.inil.iul lilu .il njocenii.il
     indicated (50 total nanograms)
RT -AvufiiyL- Ri;s|)oi)ie F.iclor (ruin iinli.il t.ilibi.iliuii Form VI
"oD Peiceni Dil(uruiii;i/
  t-Due to low response, analyze
    at 80 total nanograms
                                                      CCC -Ciilibr.Miuii Check Cumyuumlb (•)
                                                      SPCC Sybloin Perlurni;ince Check Cuinuuumlb (. -I
                                                      11) -Crinnul l)c sepiirjtuJ (ruin Uiphenyl.unine
                                                Form VII
                                           ONE - 52
                                                                       Revision        Q
                                                                       Date   September  1986

-------
                                Continuing Calibration Check
                                Semivolatile HSL Compounds
                                           (Page1)
Case No:
Laboratory Name.
Instrument ID:
                   Calibration Date:
                   Time: 	
                                                  Laboratory ID.
                   Initial Calibration Date:
                Minimum RF for SPCC is 0.050     Maximum %D for CCC is 25%
Compound
RF
RF50
                            %D
CCC
SPCC
 RFgg -Response Factor from daily suml.iril file .11 concentration
     indicated (50 total nanograms)
 RT -Average Response F.itlor lron> niitml c.ilitji.inon Form VI
 •^•Oue to low response, analyze
   •t 80 total nanograms
                    %D -Percent Difference
                    CCC -Calibration Check Compuund:, (•)
                    SPCC System Performance Check Compounds I • • I
                                             Form VII
                                        ONE - 53
                                                                   Revision        o
                                                                   Date  September 1986

-------
                 Pesticide Evaluation Standards Summary
                                  (Page 1)
  Case No:
  Date o' Analysis;
Laboratory Name:.
       GC Column:.
       Instrument ID..
                       Evaluation Check for Linearity
Laboratory
ID
Pesticide
Aldnn
Endrin
4.4'. DDT(''
Dibutyl
Cnlorendate

Calibration
Factor
Eval. Mix A





Calibration
Factor
Eval. Mix B





Calibration
Factor
Eval. Mix C





%RSD
( <10%)




              Evaluation Check for 4,4'- DDT/Endrin Breakdown
                  (percent breakdown expressed as total degradation)

Eva! Mix B
72 Hour
Eval Mix B
Eval MixB
Eval Mix B
Eval Mix B
Eval Mix B
Eval Mix B
Eval MixB
Eval Mix B
Eval Mix B
Eval MixB
Eval Mix B
Laboratory
I.D.












Time of
Analysis












Endrin










r

4.4'- DDT












Combined '












(1) See Exhibit E, Section 7.5.4
(2) See Exhibit E. Section 7.3.1.2.2.1
                                  Form VIII
                                RCRA
                                4/86
                          ONE  - 54
                                                     Revision       Q
                                                     Date   September  1986

-------
       Pesticide Evaluation Standards Summary
                      (Page 2)
Evaluation of Retention Time Shift for Dibutyl Chlorendate
        Report all standards, blanks and samples
Sample No




















































Lab
I.D.




















































Time of
Analysis




















































Percent
Oiff.




















































SMO
Sample No.




















































Lab
I.D.




















































Time of
Analysis




















































Percent
Diff.




















































RCRA
Form VIM (Continued) 4/86
              ONE - 55
                                       Revision       Q
                                       Date  September 1986

-------
                           PESTICIDE/PCB  STANDARDS SUMMARY
         Case No..
Laboratory Name.

QC Column 	
                                                              GC Instrument ID
    o
    •z.
    m

    I

    CJ1
    en
O 70
01 n>

(0 -*

  _j.

 > O
  3
o
r*
n
vo
oo

COMPOUND
alpha -BHC
beta-BHC
delta-BHC
gamma -BHC
Heptachlor
Aldrin
Heptachlor Epoxide
Endosulfan I
Dieldrin
4,4'-DDE
Endrin
Endosulfan I
4,4'-DDD
Endrin Aldehyde
Endosulfan Sulfate
4. 4'- DDT
Methoxychlor
Endrin Ketone
Tech. Chlordane
alpha-Chlordane
gamma-Chlordane
Toxaphene
Aroclor - 1 0 1 6
Aroclor - 1 22 1
Aroclor - 1 232
Aroclor - 1 24 .
Aroclor - 1 248
Aroclor - 1 254
Aroclor - 1260
DATE OF AN
TIME OF AN/
LABORATORY
RT





























A| YRIfi
!>l Y«IS
t in
RETENTION
TIME
WINDOW





























CALIBRATION
FACTOR





























CONF.
OR
QUANT.



























\

DATE OF ANJ
TIME OF AN/I
LABORATOR'
RT





























M YRIR
1 YRIR
nn
CALIBRATION
FACTOR





























CONF.
OR
QUANT.






























PERCENT
DIFF. **





























                                                              ** CONF. = CONFIRMATION (*2O% DIFFERENCE)

                                                                 O'JANT.— OUANTITATIOM
                                                  FORM IX

-------
             Case No.
 P«stlcide/PCB Identification
	            Laboratory Name.
    en
    •vj
O 73
cu n
n — >•
(/> O
CO =3
O
ft)
n>
oo
SAMPLE
ID































PRIMARY
COLUMN































PESTICIDE/
PCB































RT OF
TENTATIVE
ID































RT WINDOW
OF APPROPRIATE
STANDARD
















-














CONFIRMATION
COLUMN































RT ON
CONFIRMATORY
COLUMN































RT WINDOW OF
APPROPRIATE
STANDARD































GC/MS
CONFIRMED

-------
                                CHAPTER FOUR

                              ORGANIC ANALYTES
4.1  SAMPLING CONSIDERATIONS

     4.1.1  Introduction

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


     4.1.2  Sample Handling and Preservation

     This section deals   separately  with  volatile and semivolatile organics.
Refer  to   Chapter  Two   (Table  2-16)   and  Table  4-1  of  this  Section for
recommended sample containers, sample  preservation, and sample  holding times.

     Volatile Organics

     Standard 40-mL  glass  screw-cap   VOA  vials  with  Teflon-faced silicone
septum may  be used for both liquid   and solid matrices.  The vials and  septum
should be soap and  water washed   and  rinsed with distilled deionized  water.
After thoroughly cleaning the vials  and septum,  they  should be placed in  a
muffle furnace and dried  at 105*C for   approximately  one hour.   (Note:   Do not
heat the  septum for extended periods of time, i.e.,  more than  one hr, because
the silicone  begins to slowly degrade  at 105*C).

     When collecting the  samples, liquids and  solids  should  be  introduced into
the vials gently to reduce agitation which might drive off volatile compounds.
Liquid samples should be  poured  into  the  vial  without introducing any air
bubbles within the vial as it  is   being filled.   Should bubbling occur as  a
result of   violent  pouring,  the   sample  must  be   poured  out   and the vial
refilled.   Each VOA vial  should be   filled  until  there is a meniscus over the
lip of the  vial.  The  screw-top  lid   with the  septum  (Teflon  side toward the
sample) should then be tightened onto  the vial.  After tightening  the lid, the
vial should be inverted and tapped  to  check for  air bubbles.  If there are any
air bubbles present the   sample  must   be  retaken.    Two VOA  vials  should be
filled per  sample location.

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

                                  FOUR - 1
                                                         Revision      0
                                                          Date   September 1986

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

     Semi volatile Organics  (This includes Pesticides and Herbicides.)

     Containers used to collect samples  for the determination of semi volatile
organic compounds should be  soap  and  water  washed followed by methanol (or
isopropanol) rinsing (see Section 4.1.4 for specific instructions on glassware
cleaning).  The sample containers should be of glass or Teflon and have screw-
top covers  with Teflon  liners.   In   situations where Teflon  is not available,
solvent-rinsed aluminum foil may be  used  as  a liner.  Highly acidic or basic
samples may react with  the  aluminum  foil, causing eventual contamination of
the sample.  Plastic containers or   lids  may  NOT  be used  for the storage of
samples due to  the  possibility  of  sample  contamination  from  the phthalate
esters  and  other  hydrocarbons  within the plastic.   Sample  containers should be
filled  with care  so  as  to   prevent   any portion of  the collected  sample coming
in contact  with the  sampler's gloves,  thus  causing contamination.   Samples
should  not  be  collected or  stored   in  the   presence of exhaust fumes.   If the
sample  comes  in contact with   the   sampler   (e.g.,   if  an  automatic  sampler is
used),  run  reagent water  through  the sampler and  use  as a  field blank.

      4.1.3   Safety

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

      4.1.4  Cleaning of Glassware

     In  the  analysis  of  samples containing   components  in the parts per billion
range,  the  preparation  of scrupulously  clean glassware is mandatory.   Failure
to do so can lead to a  myriad  of problems in the interpretation of the final
chromatograms  due  to  the  presence   of  extraneous   peaks  resulting  from
contamination.   Particular care must  be  taken  with  glassware such as Soxhlet
extractors,   Kuderna-Danish     evaporative    concentrators,   sampling-train
                                   FOUR - 2
                                                          Revision      0	
                                                          Date  September 1986

-------
components, or any other glassware coming 1n contact with an extract that will
be evaporated to a lesser volume.   The process of concentrating the compounds
of Interest 1n  this  operation  may  similarly  concentrate the contamination
substance, which may seriously distort the results.

    The basic cleaning steps are:

    1.  Removal of surface residuals Immediately after use;

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

    3.  Hot-water rinse to flush away flotated particulates;

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

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

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

    7.  Methanol rinse to flush off any  final traces of organic materials and
        remove the water; and

    8.  Flushing the Item immediately before use with some of the same solvent
        that will be used in the analysis.

    Each  of these eight fundamental  steps  will   be discussed  in the order  in
which  they appear above.

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

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

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


                                   FOUR - 3
                                                          Revision      0
                                                          Date   September 1986

-------
    3.   No  comments  required.

    4.   The most  common  and  highly  effective  oxidizing agent for removal of
        traces^ of organic  compounds  is  the traditional chromic acid solution
        made  up of ^$04  and   potassium  or  sodium  dichromate.  For maximum
        efficiency,   the  soak   solution  should  be  hot   (40-50°C).   Safety
        precautions  must be  rigidly observed in the handling of this solution.
        Prescribed safety  gear  should  include  safety goggles, rubber gloves,
        and apron.  The  bench area where this operation  is  conducted should be
        covered   with   fluorocarbon   sheeting   because   spattering   will
        disintegrate any unprotected surfaces.

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

    5,  6,  and 7.   No comments required.

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

    The drying and storage of  the  cleaned glassware  is  of  critical  importance
to prevent  the  beneficial   effects  of   the   scrupulous   cleaning from  being
nullified.   Pegboard drying  is  not   recommended  because  contaminants  can  be
introduced -to the  interior  of  the   cleaned   vessels.   Neoprene-coated  metal
racks are suitable for such  items   as  beakers,  flasks,  chromatographic  tubes,
and any glassware then  can be   inverted   and  suspended  to  dry. , Small  articles
such as stirring   rods,   glass   stoppers,   and  bottle  caps  can  be wrapped  in
aluminum foil and oven-dried a short  time  if oven space is  available.   Under
no  circumstances  should  such  small :  items  be  left  in  the  open without
protective covering.  The  dust  cloud   raised  by(   the  daily sweeping  of the
laboratory floor  can most effectively recontaminatie the clean glassware.

    As an  alternative to air drying,  the  glassware can be heated to a minimum
of 300*C to vaporize any organics.
                                  FOUR - 4
                                                         Revision      0
                                                         Date  September 1986

-------
   TABLE 4-1.  RECOMMENDED  SAMPLE CONTAINERS,  PRESERVATION TECHNIQUES, AND HOLDING  TIMES
Parameter
Container
       Preservative
Holding Time
Volatile Organics

  Concentrated Haste Samples   8-oz. wideraouth
                              glass with Teflon
                              liner

  Liquid Samples
    No Residual Chlorine
       Present
    Residual Chlorine
       Present
    Acrolein and
     Acrylonitrile
2 40-mL vials with
Teflon lined septum
caps
2 40-mL vials with
Teflon lined septum
caps
2 40-mL vials with
Teflon lined septum
caps
  Soil/Sediments and Sludges  4-oz (120-mL) widemouth
                             glass with Teflon liner
                                      None
4 drops cone.  HC1, Cool, 4°C
Collect sample  in a 4 oz. soil
VOA container which has been
pre-preserved with 4 drops of
10% sodium thiosulfate.  Gently
mix sample and  transfer to a
40-mL VOA vial  that has been
pre-preserved with 4 drops
cone. HC1, Cool to 4°C
Adjust to pH4-5, Cool, 4°C
                                   Cool, 4°C
                                   14  days
   14  days
   14 days
   14 days
                                  14 days
                                           FOUR - 5
                                                                       Revision       0	
                                                                       Date   September  1986

-------
   TABLE 4-1.   Continued
Parameter
Container
       Preservative
Balding Time
Semivolatile Organics

  Concentrated Waste Samples   8-oz. widemouth
                              glass with Teflon
                              liner

  liquid Samples
                                      None
    No Residual Chlorine
      Present
1-gal. or 2 1/2-gal.
amber glass with Teflon
liner
       Cool, 4°C
    Residual  Chlorine
      Present
1-gal. or 2 1/2-gal.
amber glass with Teflon
liner
Add 3 raL 10% sodiun
thiosulfate per
gallon, Cool, 4°C
  Soil/Sediments and Sludges   8-oz. widemouth glass
                              with Teflon liner
                                  Cool, 4°C
                                   14 days
Samples must be
extracted with-
in 7 days and
extracts ana-
lyzed within
40 days
Samples must be
extracted with-
in 7 days and
extracts ana-
lyzed within
40 days

   14 days
                                            FOUR - 6
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                                                                        Date   September  1986

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4.2  SAMPLE PREPARATION METHODS

     4.2.1  EXTRACTIONS AND PREPARATIONS
                                  FOUR - 7
                                                         Revision
                                                         Date  September 1986

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                                 METHOD 3500

                  ORGANIC EXTRACTION AND SAMPLE PREPARATION
1.0  SCOPE AND APPLICATION

     1.1  The  3500  Methods  are  procedures  for  quantitatively  extracting
nonvolatile and semi volatile organic  compounds  from various sample matrices.
Cleanup and/or analysis of  the  resultant  extracts  are described in Chapter
Four, Sections 4.2.2 and 4.3, respectively.

     1.2  Method 3580 describes a solvent  dilution technique that may be used
on non-aqueous nonvolatile and  semi volatile  organic samples prior to cleanup
and/or analysis.

     1.3  The 5000 Methods  are  procedures  for  preparing samples containing
volatile organic compounds for quantitative analysis.

     1.4  Refer to the specific method of interest for further details.


2.0  SUMMARY OF METHOD

     2.1  3500 Methods;  A  sample  of  a  known  volume  or weight is solvent
extracted.  The resultant extract is dried and then concentrated in a Kuderna-
Danish apparatus.  Other concentration  devices  or  techniques may be used in
place of the Kuderna-Danish  concentrator  if the quality control requirements
of the determinative methods are met (Method 8000, Section 8.0).

     2.2  5000 Methods;  Refer to the specific method of interest.


3.0  INTERFERENCES

     3.1  Samples requiring analysis  for  volatile  organic compounds, can be
contaminated by  diffusion  of  volatile  organics  (particularly chlorofluoro-
carbons and methylene  chloride)  through  the  sample container septum during
shipment and storage.  A field  blank  prepared from reagent water and carried
through sampling and subsequent storage and  handling  can serve as a check on
such contamination.

     3.2  Solvents, reagent, glassware,  and  other sample processing hardware
may yield  artifacts   and/or   interferences  to  sample  analysis.   All these
materials must  be  demonstrated  to  be   free  from  interferences  under the
conditions of the analysis  by  analyzing  method blanks.  Specific  selection of
reagents and purification of solvents by distillation in all-glass systems may
be required.  Refer to Chapter  One  for  specific  guidance  on  quality control
procedures.

     3.3   Interferences coextracted from   the  samples  will vary  considerably
from source  to  source.  If  analysis of an  extracted  sample is prevented due to
interferences,  further cleanup of the sample   extract may be necessary.  Refer
to Method  3600  for  guidance on cleanup procedures.

                                  3500 -  1
                                                         Revision      0	
                                                         Date   September 1986

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     3.4  Phthalate esters contaminate many  types  of products commonly found
in  the  laboratory.    Plastics,  in  particular,  must  be  avoided  because
phthalates are commonly used  as  plasticizers  and  are easily extracted from
plastic materials.  Serious phthalate contamination  may result at any time if
consistent quality control is not practiced.

     3.5  Glassware contamination  resulting  in  analyte  degradation;   Soap
residue on glassware may cause degradation of certain analytes.  Specifically,
aldrin, heptachlor, and most organophosphorous pesticides will degrade in this
situation.  This problem is  especially  pronounced with glassware that may be
difficult to rinse  (e.g.,  500-mL  K-D  flask).    These items should be hand-
rinsed very carefully to avoid this problem.


4.0  APPARATUS AND  MATERIALS

     4.1  Refer to  the specific method  of  interest  for a description of the
apparatus and materials needed.


5.0  REAGENTS

     5.1  Refer to  the specific method  of  interest  for a description of the
solvents  needed.

     5.2  Stock standards;   Stock  solutions may be prepared from pure  standard
materials or purchased as  certified  solutions..

          5.2.1   Purgeable  stock  standards:     Prepare  stock  standards  in
     methanol using assayed  liquids  or gases,  as appropriate.  Because of the
     toxicity  of   some   of  the   organohalides,  primary  dilutions   of these
     materials should be  prepared  in  a hood.

               5.2.1.1   Place  about   9.8  ml   of  methanol  in  a   10-mL tared
          ground-glass-stoppered volumetric flask.    Allow the flask  to stand,
          unstoppered, for about 10   min  or  until all  alcohol-wetted  surfaces
          have dried.  Weigh the flask to the  nearest 0.1 mg.

               5.2.1.2   Using  a  100-uL  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.

               5.2.1.3   Reweigh,   dilute  to   volume,   stopper,  then  mix  by
          inverting the  flask  several  times.   Calculate the  concentration 1n
          micrograms per microliter  (ug/uL) 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.
                                   3500 - 2
                                                          Revision
                                                          Date   September  1986

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               5.2.1.4  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.

               5.2.1.5  All standards  must  be  replaced  after  1  month, or
          sooner if comparison with check standards indicates a problem.

          5.2.2  Semi volatile stock standards:    Base/neutral   and acid  stock
     standards are prepared in  methanol.   Organochlorine pesticide standards
     are prepared in acetone.

               5.2.2.1  Stock standard solutions  should  be stored in Teflon-
          sealed  containers  at  4'C.     The  solutions  should  be  checked
          frequently for stability.   These  solutions  must be replaced  after
          six months,  or  sooner  if  comparison  with  quality control  check
          samples indicate a problem.

     5.3  Surrogate standards:  A surrogate standard (i.e., a chemically  inert
compound not expected to occur in  an environmental sample) should be added to
each sample, blank,  and  matrix  spike  sample  just  prior  to extraction or
processing.  The recovery of  the  surrogate  standard  is used to monitor for
unusual matrix  effects,  gross  sample  processing  errors,  etc.   Surrogate
recovery is  evaluated  for  acceptance  by  determining  whether the measured
concentration falls within the acceptance  limits.  Recommended surrogates for
different analyte groups  follow;  however,  these  compounds,   or others that
better correspond to the analyte group,   may  be used for other analyte groups
as well.  Normally three or more standards are added for each analyte group.

          5.3.1  Base/neutral  and  acid  surrogate  spiking  solutions:    The
     following are recommended surrogate standards.

               Base/neutral                       Acid

               2-Fluorobiphenyl                   2-Fluorophenol
               Nitrobenzene-ds                    2,4,6-Tribromophenol
               Terphenyl-di4                      Phenol-ds

               5.3.1.1  Prepare  a  surrogate  standard  spiking  solution  in
          methanol that contains the base/neutral compounds at a concentration
          of 100 ug/mL, and  the  acid  compounds  at  200 ug/mL for water and
          sediment/soil samples  (low- and  medium-level).   For waste samples,
          the concentration should  be  500  ug/mL  for base/neutrals and  1000
          ug/mL for acids.

          5.3.2  Organochlorine  pesticide  surrogate  spiking  solution:    The
     following  are   recommended   surrogate   standards  for  Organochlorine
     pesticides.

               Organochlorine pesticides

               Dibutylchlorendate  (DBC)
               2,4,5,6-Tetrachloro-meta-xylene  (TCMX)


                                  3500 -  3
                                                         Revision      0
                                                         Date  September 1986

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          5.3.2.1  Prepare a  surrogate  standard  spiking  solution at a
     concentration of 1  ug/mL  in  acetone  for  water and sediment/soil
     samples.  For waste samples,  the concentration should be 5 ug/mL.

     5.3.3  Purgeable surrogate  spiking  solution:    The  following are
recommended surrogate standards for volatile organics.

          Purgeable organics

          p-Bromof1uorobenzene
          l,2-Dichloroethane-d4
          Toluene-ds

          5.3.3.1  Prepare a surrogate spiking  solution (as described in
     Paragraph 5.2.1 or through secondary.dilution of the stock standard)
     .in methanol containing the .surrogate standards at a concentration of
     25 ug/mL.

5.4  Matrix spike standards:    Select  five  or  more analytes from each
     analyte group for use  in  a  spiking  solution.   The following are
     recommended matrix spike standard mixtures for a few analyte groups.
     These compounds, or  .others  that  better  correspond to the analyte
     group, may be used for.other analyte groups as well.
                                     >.••.•          '   '
     5.4.1  Base/neutral  and acid  matrix  spiking  solution:   Prepare a
spiking  solution  in  methanol  that  contains  each  of  the  following
base/neutral compounds at 100 ug/mL  and  the acid compounds at 200 ug/mL
for  water  and  sediment/soil  samples.    The  concentration  of  these
compounds should be  five  times.higher  for waste samples.

          Base/neutrals                      Acids

          1,2,4-Trichlorobenzene     .        Pentachlorophenol
          Acenaphthene      t                 Phenol
          2,4-Dinitrotoluene                 2-Chlorophenol
          .Pyrene                             4-Chloro-3-methylphenol
          N-Nitroso-di-n-propylamine .     .   4-Nitrophenol
          1,4-Dichlorobenzene                                   .

     5.4.2   Organochlorlne  pesticide matrix  spiking  solution:  Prepare a
spiking  solution   in  acetone   or  methanol  that  contains  the following
pesticides  in  the  concentrations   specified  for water  and  sediment/soil.
The  concentration  should  be five  times higher for  waste  samples.

          . Pesticide  '                        Concentration  (ug/mL)

          Lindane                                       0.2  ..
          Heptachlor                                   0.2
          Aldrin                                        0.2'
          Dieldrin                                      0.5
          Endrin                                        0.5
          4,4'-DDT                                      0.5
                              3500 -  4
                                                     Revision
                                                     Date   September  1986

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          5.4.3  Purgeable  matrix  spiking  solution:      Prepare   a   spiking
     solution  1n  methanol   that  contains   the  following  compounds  at   a
     concentration of 25 ug/mL.

               Purgeable organlcs

               1,1-Dichloroethene
               Trlchloroethene
               Chlorobenzene
               Toluene
               Benzene
6.0  SAMPLE COLLECTION, PRESERVATION,  AND HANDLING

     6.1  See  the  Introductory  material   to  the  Organic  Analyte Chapter,
Section 4.1.
7.0  PROCEDURE

     7.1  Semi volatile  organic  sample  extraction;    Water,   soil/sediment,
sludge,  and  waste  samples  requiring  analysis  for  base/neutral   and add
extractables and/or organochlorlne pesticides  must undergo solvent extraction
prior to analysis.  This  manual  contains  four  methods that may be used for
this purpose:  Method 3510; Method  3520;  Method  3540; and Method 3550.  The
method that should be used  on  a  particular sample, 1s highly dependent upon
the physical characteristics of  that  sample.    Therefore, review these four
methods prior to choosing one  1n particular.  Appropriate surrogate standards
and, 1f necessary, matrix spiking solutions  are  added to the sample prior to
extraction for all four methods.

          7.1.1  Method 3510:  Applicable  to the extraction and concentration
     of  water-Insoluble  and  slightly  water-soluble  organlcs  from aqueous
     samples.  A  measured  volume  of  sample  1s  solvent  extracted using a
     separatory funnel.  The extract 1s dried, concentrated and, 1f necessary,
     exchanged Into a solvent compatible  with  further analysis.  Method 3520
     should be used 1f  an  emulsion  forms between the solvent-sample phases,
     which can not be broken up by mechanical techniques.

          7.1.2  Method 3520:  Applicable  to the extraction and concentration
     of  water-insoluble  and  slightly  water-soluble  organics  from aqueous
     samples.  A  measured  volume  of  sample  is  extracted  with an organic
     solvent  in a continuous liquid-liquid  extractor. The solvent must have a
     density  greater  than  that  of  the  sample.    The  extract  is dried,
     concentrated and, if necessary, exchanged  into a solvent compatible with
     further  analysis.   The  limitations  of  Method 3510 concerning solvent-
     sample phase separation do not interfere with this procedure.
                                  3500 - 5
                                                         Revision
                                                         Date  September 1986

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          7.1.3   Method 3540:   This  is   a  procedure  for  extracting  nonvolatile
     and semi volatile organic  compounds- from   solids  such  as  soils,  sludges,
     and wastes.    A  solid  sample   is  mixed   with anhydrous  sodium  sulfate,
     placed into  an extraction thimble or  between  two  plugs  of  glass wool,  and
     extracted using an  appropriate solvent   in  a  Sbxhlet   extractor.   The
     extract is   dried,  concentrated and,   if necessary,  exchanged  into  a
     solvent compatible with further analysis.

          7.1.4   Method 3550:   This  method  is  applicable to the extraction of
     nonvolatile  and semi volatile organic  compounds  from solids such as  soils,
     sludges,  and wastes using  the   technique   of sonication.   Two procedures
     are detailed depending upon the expected concentration  of  organics  in  the
     sample; a low concentration and a   high concentration method.  In both,  a
     known weight of sample is mixed with  anhydrous  sodium sulfate  and solvent
     extracted using sonication.  The extract   is dried, concentrated and, if
     necessary,  exchanged into a solvent compatible  with further analysis.

          7.1.5   Method 3580:   This  method  describes  the technique of solvent
     dilution of  non-aqueous waste samples.     It  is  designed  for  wastes that
     may contain  organic chemicals at a  level greater than 20,000 mg/kg  and
     that are soluble in the dilution solvent.
          ;

     7.2  Volatile organic sample preparation;     There   are three  methods  for
volatile sample  preparation:  Method  5030;  Method 5040; and direct injection.
Method 5030 is the most  widely  applicable  procedure  for analysis  of  volatile
organics, while the direct injection  technique may  have limited applicability
to aqueous matrices.

          7.2.1  Method 5030:  This  method  .describes the technique of  purge-
     and-trap  for  the  introduction   of   purgeable  organics  into  a   gas^
     chromatograph.  This procedure is  applicable  for use with  aqueous samples
     directly  and  to  solids,  wastes,  soils/sediments,  and water-miscible
     liquids following  appropriate  preparation.     An   inert   gas is bubbled
     through  the  sample,  which  will   efficiently  transfer  the  purgeable
     organics from the aqueous phase to  the  vapor phase.  The vapor phase is
     swept through a sorbent  trap  where  the   purgeables are  trapped.   After
     purging is completed, the trap  is   heated and  backflushed with  the inert
     gas to desorb the purgeables onto a gas chromatographic column.   Prior to
     application  of   the  purge-and-trap  procedure,   all  samples (including
     blanks, spikes, and duplicates) should be spiked with surrogate  standards
     and,  if required, with matrix spiking compounds.

           7.2.2  Method  5040:  This method  is applicable to the investigation
     of  sorbent cartridges from volatile organic sampling train  (VOST).

     7.3   Sample analysis;  Following preparation   of  a  sample by one of the
methods  described  above,   the  sample   is  ready  for  further   analysis.   For
samples  requiring  volatile organic analysis,   application  of one of the three
methods  described  above  is  followed  directly by gas chromatographic analysis
(Methods 8010,  8015,  8020,  or  8030).    Samples  prepared for semi volatile
analysis may,  if   necessary,  undergo  cleanup   (See  Method  3600)   prior to
application of a specific  determinative method.


                                  3500 - 6
                                                         Revision      0
                                                         Date  September 1986

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8.0  QUALITY CONTROL

     8.1  Refer to  Chapter  One  for  specific  guidance  on  quality control
procedures.

     8.2  Before  processing  any  samples,  the  analyst  should  demonstrate
through the analysis of a reagent  water blank that all glassware and reagents
are interference free.  Each  time  a  set  of samples are processed, a method
blank(s)  should  be  processed  as  a  safeguard  against  chronic laboratory
contamination.  The blank samples should  be carried through all stages of the
sample-preparation and measurement.

     8.3  Surrogate standards should be added to all samples when specified in
the appropriate determinative method 1n Chapter Four, Section 4.3.

     8.4  A reagent blank, a  matrix  spike,  and  a duplicate or matrix spike
duplicate must be performed for each  analytical  batch  (up to a maximum of 20
samples) analyzed.

     8.5  For GC or GC/MS analysis,  the analytical system performance must be
verified by  analyzing  quality  control   (QC)  check  samples.   Method 8000,
Section  8.0  discusses  in  detail  the  process  of  verification;  however,
preparation of the QC check  sample  concentrate  is dependent upon the method
being  evaluated.

          8.5.1  Volatile  organic  QC  check   samples:     QC  check  sample
     concentrates containing each analyte of  Interest are spiked into reagent
     water  (defined as the  QC  check  sample)  and analyzed by purge-and-trap
      (Method 5030).  The concentration of  each analyte  1n the QC check sample
     1s 20  ug/L.  The evaluation  of system performance  is discussed  in detail
     in Method 8000, beginning with Paragraph 8.6.

          8.5.2  Semivolatile organic  QC  check  samples:    To  evaluate the
     performance of  the  analytical  method,  the  QC   check   samples must be
     handled 1n exactly the same manner  as actual samples.  Therefore, 1.0 mL
     of the QC  check  sample  concentrate  is  spiked   into  each of four 1-L
     aliquots of reagent water   (now  called  the QC check sample),  extracted,
     and then analyzed by GC.   The variety of semi volatile analytes  which may
     be analyzed by GC 1s such  that  the  concentration  of the  QC check sample
     concentrate  1s  different   for   the  different   analytical   techniques
     presented  in the manual.   Method  8000 discusses in detail  the  procedure
     of verifying the  detection  system   once  the  QC  check  sample has been
     prepared.  The concentrations of the  QC check  sample concentrate for the
      various methods  are as follows:

                8.5.2.1  Method  8040  -    Phenols;       The  QC  check  sample
           concentrate  should  contain  each  analyte  at a concentration of
           100  ug/mL  in 2-propanol.

                8.5.2.2  Method  8060  - Phthalate  esters;  The  QC check sample
           concentrate should  contain  thefollowinganalytes  at  the following
           concentrations  in acetone:  butyl benzyl  phthalate,  10  ug/mL; bis(2-
           ethylhexyl)phthalate,  50  ug/mL;  d1-n-octylphthalate,   50  ug/mL; and
           any  other phthalate at  25  ug/mL.

                                   3500 -  7
                                                          Revision     0
                                                          Date  September 1986

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               8.5.2.3   Method 8080  - Organochlorine pesticides and  PCBs;  The
          QC  check   sampleconcentrate   shouldcontain  each  single-component
          analyte at the following   concentrations  in  acetone:  4,4'-DDD, 10
          ug/mL; 4,4'-DDT,   10   ug/mL;   endosulfan  II,   10  ug/mL;  endosulfan
          sulfate,  10 ug/mL;  and  any   other single-component pesticide  at 2
          ug/mL.  If the method  is only  to  be used  to analyze  PCBs,  chlordane,
          or  toxaphene,  the  QC  check   sample  concentrate  should contain the
          most representative multicomponent  parameter   at  a  concentration of
          50  ug/mL  in acetone.

               8.5.2.4  Method 8090  - Nitroaromatics  and Cyclic  Ketones:  The
          QC  check   sample   concentrate   should   contain   each analyte at the
          following concentrations  in acetone:  each  dinitrotoluene  at
          20  ug/mL; and isophorone  and  nitrobenzene at  100 ug/mL.

               8.5.2.5  Method 8100  -  Polynuclear  aromatic  hydrocarbons:  The
          QC  check   sample   concentrate   should   contain   each analyte at the
          following concentrations  in   acetonitrile:    naphthalene,  100 ug/mL;
          acenaphthylene, 100 ug/mL; acenaphthene,  100  ug/mL;  fluorene,
          100  ug/mL;  phenanthrene,   100    ug/mL;   anthracene,  100  ug/mL;
          benzo(k)fluoranthene  5 ug/mL;  and any  other PAH at 10 ug/mL.

               8.5.2.6  Method  8120  -  Chlorinated  hydrocarbons;   The QC check
          sample concentrate  should  contain  each  analyte  at  the following
          concentrations in acetone:  hexachloro-substituted hydrocarbons,
          10  ug/mL; and any other chlorinated hydrocarbon, 100 ug/mL.


9.0  METHOD PERFORMANCE

     9.1  The recovery  of   surrogate   standards  is   used  to monitor unusual
          matrix effects, sample processing  problems,   etc.   The recovery  of
          matrix  spiking  compounds  indicates   the   presence or  absence  of
          unusual  matrix effects.

     9.2  The performance of  this   method   will  be   dictated  by the overall
          performance  of  the   sample   preparation  in  combination  with the
          analytical determinative  method.


10.0  REFERENCES

     10.1  None required.
                                  3500 - 8
                                                         Revision
                                                         Date  September 1986

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                                                                                                               METHOD 3500


                                                                                              ORGANIC EXTRACTION AND SAMPLE PREPARATION
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-------
                                 METHOD 3510

                 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 1n Section 4.3 of Chapter Four.

     1.2  This method Is  applicable  to  the  Isolation  and concentration of
water-Insoluble and  slightly  water-soluble  organlcs  1n  preparation  for a
variety of chromatographlc procedures.


2.0  SUMMARY OF METHOD

     2.1  A measured volume of sample, usually 1 liter,  at a specified pH (see
Table 1), 1s serially  extracted  with  methylene  chloride using a separatory
funnel.  The extract 1s dried, concentrated, and, as necessary,  exchanged into
a solvent compatible with the cleanup or determinative step to be used.


3.0  INTERFERENCES

     3.1  Refer to Method 3500.


4.0  APPARATUS AND MATERIALS

     4.1  Separatory funnel;  2-l1ter, with Teflon stopcock.

     4.2  Drying column;  20-mm  I.D.  Pyrex chromatographlc 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 elutlon solvent prior to packing the column with adsorbent.

     4.3  Kuderna-Danlsh  (K-D) apparatus;

          4.3.1  Concentrator tube:   10-mL, graduated (Kontes K-570050-1025 or
     equivalent).  Ground-glass  stopper  1s  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.
                                   3510 -  1
                                                         Revision
                                                         Date  September 1986

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   TABLE 1.   SPECIFIC EXTRACTION CONDITIONS  FOR VARIOUS  DETERMINATIVE METHODS

Determinative
method
8040
8060
8080
8090
8100
8120
8140,
8250*
8270b
8310

Initial
extraction
pH
< 2
as received
5-9
5-9
as received
as received
6-8
Ml
>11
as received

Secondary
extraction
pH
none
none
none
none
none
none
none
<2
<2
none
Exchange
solvent
required
for
analysis
2-propanol
hexane
hexane
hexane
none
hexane
hexane
none
none
acetonitrile
Exchange
solvent
required
for
cleanup
hexane
hexane
hexane
hexane
cyclohexane
hexane
hexane
^
Volune
of extract
required
for
cleanup (mL)
1.0
2.0
10.0
2.0
2.0
2.0
10.0
•»
Final
extract
volune
for
analysis (mL)
1.0, 10 .Oa
10.0
10.0
1.0
1.0
1.0
10.0
10)
1.0
1.0
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.

 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.
                                          3510 - 2
                                                                     Revision       0	
                                                                     Date   September  1986

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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).

     4.4  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 cap.

     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 water;   Reagent  water  is  defined  as  water  in which an
interferent is not observed at the  method detection limit of the compounds of
interest.

     5.2  Sodium hydroxide solution,   10  N:     (ACS)  Dissolve  40  g NaOH in
reagent water and dilute  to 100 ml.

     5.3  Sodium sulfate:  (ACS)  Granular,  anhydrous  (purified by heating at
400*C  for 4 hr  in a shallow tray).

     5.4  Sulfuric acid  solution  (1:1):   Slowly   add  50 ml of  ^04  (sp.  gr.
1.84)  to 50 ml  of  reagent water.

     5.5  Extraction/exchange  solvent;  Methylene  chloride,  hexane,
2-propanol, cyclohexane,  acetonitrile  (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.
                                  3510 - 3
                                                         Revision
                                                         Date  September 1986

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7.0  PROCEDURE

     7.1  Using a 1-liter graduated  cylinder,   measure  1  liter of sample  and
transfer it to the separatory funnel.    Add 1.0 ml of the  surrogate standards
to all  samples,  spikes,   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/uL of each base/neutral analyte  and  200 ng/uL 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.

     7.2  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 min 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.

     7.5  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 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.

     7.6  Repeat the extraction two more  times  using fresh portions of solvent
(steps 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  Paragraphs 7.3
through  7.5.   Collect and  combine   the  extracts and  label the combined extract
appropriately.

     7.8  If  performing GC/MS  analysis   (Method   8250   or  8270),  the  acid and
base/neutral  extracts may  be   combined  prior   to  concentration.  However, in
some  situations,  separate   concentration  and    analysis  of   the  acid  and
                                  3510 - 4
                                                         Revision      0
                                                         Date  September 1986

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base/neutral extracts may be preferable  (e.g.,  if for regulatory purposes the
presence  or  absence  of  specific  acid  or  base/neutral   compounds  at low
concentrations  must  be   determined,   separate   extract   analyses  may  be
warranted).

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

     7.10  Dry the extract by  passing  it  through a drying column containing
about 10 cm of anhydrous sodium sulfate.    Collect the dried extract in a K-D
concentrator.    Rinse  the  Erlenmeyer  flask,   which  contained  the solvent
extract, with 20-30 ml  of  methylene  chloride  and  add  it to the column to
complete the quantitative transfer.

     7.11  Add one or two clean boiling chips to the flask and attach a three-
ball Snyder column.    Prewet  the  Synder  column  by  adding  about  1 mL of
methylene chloride to the top of the column.  Place the K-D apparatus on a hot
water bath  (80-90*C) so that  the  concentrator  tube is partially immersed in
the 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 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 from  the  water bath and allow it to drain and
cool for at least 10 min.

     7.12   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 re-attach the  Snyder  column.   Concentrate the extract, as
described  in Paragraph 7.11,  raising  the  temperature  of the water bath, if
necessary,  to maintain proper distillation.

     7.13   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 Paragraph 7.14 or adjusted to 10.0 ml with the solvent last used.

     7.14   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 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  0.5  ml,  remove  the K-D
apparatus  from the  water bath and  allow  it to  drain  and cool for at  least  10
min.   Remove  the Synder 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.
                                   3510 - 5
                                                          Revision       0
                                                          Date   September  1986

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     7.15  The extract obtained (from either  Paragraph  7.13 or 7.14)  may now
be analyzed for analyte content  using  a  variety  of organic techniques.  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, 1t should be transferred to a Teflon-sealed screw-cap vial
and labeled appropriately.


8.0  QUALITY CONTROL

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

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


9.0  METHOD PERFORMANCE

     9.1  Refer to the determinative methods for performance data.


10.0  REFERENCES

1.  U.S. EPA 40 CFR Part  136,  "Guidelines  Establishing Test  Procedures for the
Analysis of Pollutants Under the Clean Water Act; Final Rule and Interim  Final
Rule and Proposed Rule,"  October 26, 1984.
                                   3510 - 6
                                                          Revision
                                                          Date   September 1986

-------
                                         METHOD 3510

                         SEPARATORY FUNNEL LIQUID-LIQUID EXTRACTION
7.1 I   Aad
    'surrogate
  standards to
  •11  samples.
  •Pikes,  and
     blanks
 7.Z
   Check end
   adjust pH
7.3-7.6
Extract 3 tines
                Yes
 7.7
       Collect
    •no combine
   extract* ana
       label
    O
                                                                               7.6
                                                                                   I Combine
                                                                                baae/neutral
                                                                                   extracts
                                                                                   prior to
                                                                               concentratIon
 I* CC/MS analy-

-------
                                 METHOD 3520

                     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
water-Insoluble and slightly soluble organics
chromatographlc procedures.
Isolation  and concentration of
1n preparation for a variety of
     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
1n 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,  1f  necessary, to a specific pH
(see Table 1), and extracted with  organic  solvent for 18-24 hr.  The extract
1s dried, concentrated, and, as necessary, exchanged Into a solvent compatible
with the determinative step being employed.


3.0  INTERFERENCES

     3.1  Refer to Method  3500.


4.0  APPARATUS AND MATERIALS

     4.1  Continuous liquid-liquid extractor;    Equipped  with Teflon or glass
connecting  joints  and  stopcocks  requiring  no  lubrication (Hershberg-Wolf
Extractor  --  Ace  Glass  Company,  Vlneland,   New  Jersey,  P/N  6841-10, or
equivalent).

     4.2  Drying  column;   20-mm  I.D.   Pyrex chromatographlc 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 elutlon solvent prior to  packing the column with adsorbent.
                                   3520 -  1
                                                         Revision      0
                                                         Date  September 1986

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   TABLE 1.   SPECIFIC EXTRACTION CONDITIONS  FOR VARIOUS  DETERMINATIVE METHODS



Determinative
method
8040
8060
8080
8090
8100
8120
8140,
8250*
8270b
8310
.
' . (
Initial
extraction
pH .
<2
as received
5-9
5-9
as received
as received
6-8
Ml
Ml
as received


Secondary
extraction
pH
none.
none
none
none
none
none
none
< 2
< 2
none
Exchange
solvent
required
for
analysis
2-propanol
hexane
hexane
hexane
none
hexane
hexane
none
none
acetonitrile
Exchange
solvent
required
for
cleanup
hexane .
hexane
hexane
hexane
cyclohexane
hexane
hexane
_
• -
, —
Volume
of extract
required
for
cleanup (mL)
1.0
2.0
10.0
2.0
2.0
2.0
10.0
—
—
—
Final
extract
volune
for
analysis (mL)
1.0, 10.08
10.0
10.0
1.0
1.0
1.0
10.0
1.0
1.0
1.0
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 OC/ECD.    .•     • •  .                                                -  • •

 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.
                                          3520 - 2
                                                                                     0
Revision
                                                                     Date  September 1986

-------
     4.3   Kuderna-Danish  (K-D)  apparatus;
          4.3.1   Concentrator tube:   10-mL, graduated  (Kontes  K-570050-1025 or
     equivalent).   Ground-glass  stopper  is   used   to  prevent  evaporation of
     extracts.
          4.3.2   Evaporation   flask:       500-mL    (Kontes    K-570001-500  or
     equivalent).   Attach to concentrator tube with  springs.
          4.3.3   Snyder column:    Three-ball   macro  (Kontes  K-503000-0121 or
     equivalent).
          4.3.4   Snyder  column:    Two-ball   micro   (Kontes   K-569001-0219 or
     equivalent).
     4.4  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 cap.
     4.7  pH indicator paper:  pH range including the desired extraction pH.
     4.8  Heating mantle;  Rheostat controlled.
     4.9  Syringe;  5-mL.
     4.10  Graduated cylinder:  1-liter.

5.0  REAGENTS
     5.1  Reagent water;   Reagent  water  is  defined  as  water  in which an
interferent is not observed at the  method detection limit of the compounds of
interest.
     5.2  Sodium hydroxide solution.  10  N:    (ACS)  Dissolve  40  g NaOH in
reagent water and dilute to 100 ml.
     5.3  Sodium sulfate:   (ACS)  Granular,  anhydrous (purified by heating at
400'C for 4 hr in a shallow tray).
     5.4  Sulfuric acid solution  (1:1):   Slowly  add  50 mL of ^04 (sp. gr.
1.84) to 50 ml of reagent water.
     5.5  Extraction/exchange   solvent;     Methylene   chloride,  hexane,  2-
propanol, cyclohexane, acetonitrile  (pesticide quality or equivalent).
                                  3520 - 3
                                                         Revision
                                                         Date  September 1986

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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  Using a graduated cylinder, measure  out 1 liter (nominal)  of sample
and transfer it to the continuous extractor.   Check the pH of the sample with
wide-range pH paper and adjust the  pH,  if  necessary, to the pH indicated in
Table 1.  Pi pet 1.0 mL  of  the  surrogate standard spiking solution  into each
sample into the extractor and mix well.    (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 of the surrogates and
matrix spiking  compounds  added  to  the  sample  should  result  in  a final
concentration of 100 ng/uL of each  base/neutral analyte and 200 ng/uL 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.

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

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

     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 as described in Section 7.7 through 7.11.

     7.5  Carefully, while stirring, adjust the pH  of the aqueous phase to <2
with sulfuric acid  (1:1).  Attach  a  clean distilling flask containing 500 mL
of methylene chloride to  the  continuous  extractor.     Extract for 18-24 hr,
allow to cool, and detach the distilling flask.

     7.6  If performing GC/MS analysis   (Method  8250  or 8270), the  acid and
base/neutral extracts may be  combined  prior   to  concentration.  However, in
some  situations,   separate  concentration  and   analysis  of  the  acid  and
base/neutral extracts may be preferable   (e.g.,  if for regulatory purposes the
presence  or   absence  of  specific  acid  or   base/neutral  compounds at low
concentrations  must  be   determined,   separate   extract  analyses  may  be
warranted).

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

     7.8  Dry  the extract by  passing   it   through  a  drying column containing
about 10 cm of anhydrous  sodium  sulfate.    Collect the dried extract  in  a K-D
                                   3520 -  4
                                                          Revision      0
                                                          Date  September  1986

-------
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.

     7.9  Add one or two clean boiling chips  to the flask and attach a three-
ball Snyder column.    Prewet  the  Snyder  column  by  adding  about  1 ml of
methylene chloride to the top of the column.  Place the K-D apparatus on a hot
water bath  (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 10-20 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 from  the  water bath and allow it to drain and
cool for at least 10 min.   Remove  the  Snyder column and rinse the flask and
its lower joints into the concentrator tube with 1-2 ml of extraction solvent.

     7.10   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 re-attach the  Snyder  column.   Concentrate the extract, as
described in Paragraph 7.9,  raising  the  temperature  of  the water bath, if
necessary,  to maintain proper distillation.

     7.11   Remove the Snyder column and  rinse  the flask and its lower joints
into the concentrator  tube  with  1-2  mL  of  methylene chloride or exchange
solvent.  If  sulfur  crystals  are  a  problem,  proceed  to  Method 3660 for
cleanup.  The  extract  may  be  further  concentrated  by using the technique
outlined in Paragraph 7.12 or adjusted to 10.0 ml with the solvent last used.

     7.12   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 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  0.5 ml, remove the  K-D apparatus  from  the water bath and allow  it to
drain and cool for  at least 10 min.  Remove the Synder 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  1.0-2.0 ml, as
indicated in Table  1, with  solvent.

      7.13   The extracts  obtained  may now be analyzed for  analyte content  using
a variety of  organic  techniques   (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  Teflon-sealed  screw-cap vial
and  labeled appropriately.
                                   3520 - 5
                                                          Revision      0
                                                               September  1986

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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.


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.-
                                   3520 - 6
                                                          Revision
                                                          Date   September 1986

-------
                                        METHOD 3320

                            CONTINUOUS LIQUID-LIQUID EXTRACTION
 7.1
	1   Add
    appropriate
  surrogate ana
 matrix  •piking
    solutions
 7.2
        Add
     methylene
    chloride  to
    distilling
      flask
                                                                             7. 13
                          Analyze using
                             organic
                           technique*
        Dry
      extract:
  collect  dried
 extract in K-0
  concentrator
 7.3 I
	1   Add
  reagent  water
  to extractor;
   extract for
    16-24  hrs
-LLJ
   Concentrate
  using  Snyder
 column  and K-O
   apparatus
7.S
aquec
e>
18-Z'
Clt
Adjust
PH Of
us phase:
tract for
I Mrs with
an flask
                                                      Is solvent
                                                      exchange
                                                      required?
                          7.6 I Combine
                              I acid end
                            base/neutral
                               extracts
                               prior to
                           concentration
7.12
tret
if r
ad]
Further
concen-
.e extract
lecassary;
ust final
volume


                                     3520 - 7
                                                                Revision       0
                                                                Date   September 1986

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                                 METHOD 3540

                             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  I.D., with 500-mL round-bottom flask.

     4.2   Drying column;   20-mm   I.D.   Pyrex chromatographic column with Pyrex
 glass wool  at bottom  and  a Teflon stopcock.
     NOTE:   Fritted glass  discs   are   difficult to decontaminate after highly
     contaminated extracts have been  passed  through.   Columns without frits
     may  be purchased.  Use  a small   pad  of  Pyrex glass wool to retain the
     adsorbent.  Prewash  the  glass wool pad  with 50 mL of acetone followed by
     50 mL of elution solvent prior  to  packing the column with adsorbent.

     4.3   Kuderna-Danish  (K-D) apparatus;

           4.3.1  Concentrator tube:  10-mL, graduated (Kontes K-570050-1025 or
     equivalent).   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.
                                   3540 - 1
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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).

     4.4  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  cap.

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

     4.8  Heating mantle:  Rheostat controlled.

     4.9  Syringe:  5-mL.

     4.10  Apparatus for determining percent moisture;

          4.10.1  Oven:  Drying.

          4.10.2  Desiccator.

          4.10.3  Crucibles:  Porcelain.

     4.11  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.  Fisher
Mortar Model 155 Grinder,  Fisher Scientific Co., Catalogue Number 8-323, or an
equivalent brand  and   model,  is   recommended  for   sample  processing.  This
grinder should handle   most  solid   samples,  except  gummy,  fibrous, or oily
materials.


5.0  REAGENTS

     5.1  Reagent water:   Reagent   water  is  defined  as  water  in which an
ihterferent  is not  observed  at the   method detection  limit of the compounds of
interest.

     5.2  Sodium sulfate:   (ACS) Granular  anhydrous  (purified  by washing with
methylene chloride  followed  by heating at 400*C for 4 hr  in a shallow tray).

     5.3  Extraction  solvents;

          5.3.1  Soil/sediment and  aqueous  sludge  samples shall be extracted
     using either of  the following  solvent systems.
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               5.3.1.1  Toluene/Methanol:    10:1   (v/v),   pesticide  quality or
          equivalent.

               5.3.1.2  Acetone/Hexane:     1:1   (v/v),   pesticide  quality  or
          equivalent.

          5.3.2  Other samples shall  be  extracted using  the  following:

               5.3.2.1  Methylene chloride:   pesticide  quality or  equivalent.

     5.4  Exchange solvents;    Hexane,   2-propanol,  cyclohexane,  acetonitrile
(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.

          7.1.2  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.

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

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

               q of sample  -  q of dry sample x 100 _ % moisture
                        g of  sample          x 10U " * moisture
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                                                         Date  September 1986

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     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/uL of each  base/neutral
analyte and 200 ng/uL  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.

     7.4  Place 300 ml of the  extraction  solvent (Section 5.3) 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 hrn

     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
100-125 ml of extraction  solvent to complete the quantitative transfer.

     7.8  Add one or two  clean boiling chips  to the flask and attach a three-
ball Snyder column.    Prewet  the  Snyder  column  by  adding  about   1 ml of
methylene chloride to the top of the  column.  Place the K-D apparatus on a hot
water bath  (15-20*C  above  the  boiling  point  of  the  solvent)  so that the
concentrator tube  is partially immersed  in  the  hot water and the entire lower
rounded  surface of the flask  is  bathed  with   hot vapor.  Adjust the vertical
position of the apparatus and the  water temperature, as  required,  to complete
the  concentration  in 10-20  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  from the
water bath  and  allow it  to  drain and  cool for at  least 10 min.

     7.9   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 Paragraph 7.6,   raising   the  temperature  of  the water bath, if
necessary,  to maintain proper distillation.

     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  technique
outlined in  Paragraph  7.9 or  adjusted to 10.0 ml with the solvent  last  used.


                                  3540 - 4
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   TABLE 1.   SPECIFIC  EXTRACTION  CONDITIONS  FOR VARIOUS  DETERMINATIVE METHODS



Determinative
method
80403
8060
8080
8090
8100
8120
8140
8250Y
8270a,C
8310



Extraction
PH
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
hexane
none
hexane
hexane
none
none
acetonitrile
Exchange
solvent
required
for
cleanup
hexane
hexane
hexane
hexane
cyclohexane
hexane
hexane
_
-
"
Volume
of extract
required
for
cleanup (mL)
1.0
2.0
10.0
2.0
2.0
2.0
10.0

-
"
Final
extract
volune
for
analysis (mL)
1.0, 10 .Ob
10.0
10.0
1.0
1.0
1.0
10.0
1.0
1.0
1.0
 To obtain separate acid and base/neutral extracts, Method 3650 should be performed following
concentration of the extract to 10.0 mL.

 Phenols may be analyzed, by Method 8040, using a 1.0 mL 2-propanol extract by OC/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.

The specificity of OC/MS may make cleanup of the extracts unnecessary.  Refer to Method 3600 for
guidance on the cleanup procedures available if required.
                                           3540  - 5
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     7.11  If further concentration 1s Indicated  1n  Table 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 1n 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  1n 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
0.5 mL, remove the K-D apparatus from the water bath and allow it to drain and
cool for at least 10 min.   Remove  the  Snyder column and rinse the flask and
its lower joints into the concentrator  tube  with  0.2 ml of solvent.  Adjust
the final volume to 1.0-2.0 ml, as Indicated in Table 1, with solvent.

     7.12  The extracts obtained may now be analyzed for analyte content using
a variety of  organic  techniques  (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 Teflon-sealed screw-cap vial
and labeled appropriately.


8.0  QUALITY CONTROL

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

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


9.0  METHOD PERFORMANCE

     9.1  Refer to the determinative methods for performance data.


10.0  REFERENCES

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

                                     SOXHLET EXTRACTION
 7. 1
       Use
   appropriate
cample Dandling
   technique
 7 .Z
    Determine
     percent
    moisture
                           7.7
                         Dry  and  collect
                         extract  In  K-D
                           concentrator
 7.3
     I   Add
    appropriate
  surrogate and
 matrix  spiking
    standards
                           4.6
                            Concentrate
                           using  Snyder
                         column and K-O
                            apparatus
                                                                             4.8  I

                                                                              Reconccntrate
                                                                              using  Snyder
                                                                             column  and K-O
                                                                               apparatus
 7.4
    I   Place
    Imethylene
     cnloride:
    acetone In
flask;  extract
 for 16-24 hrs
Analyze using
   organic
 techniques
                                     3540 -  7
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                                 METHOD 3550

                            SONICATION EXTRACTION
1.0  SCOPE AND APPLICATION

     1.1  Method 3550 Is  a  procedure  for  extracting  nonvolatile and semi-
volatlle organic compounds from  sol Ids  such  as  soils, sludges,  and wastes.
The sonlcatlon process ensures Intimate contact  of the sample matrix with the
extraction solvent.

     1.2  The method 1s  divided  Into  two  sections,  based  on the expected
concentration of  organlcs  1n  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 high concentration method (Individual organic components of
>20 mg/kg) 1s much simpler and therefore faster.

     1.3  It 1s highly recommended  that  the  extracts  be cleaned up prior to
analysis.  See Cleanup, Section 4.2.2 of Chapter Four, for applicable methods.


2.0  SUMMARY OF METHOD

     2.1  Low concentration method;   A  30-g  sample  1s mixed with anhydrous
sodium sulfate to form a free-flowing powder.  This 1s solvent extracted three
times using sonlcatlon.  The  extract  1s  separated from the sample by vacuum
filtration or  centrlfugatlon.    The  extract  1s  ready  for  cleanup and/or
analysis following concentration.

     2.2  High concentration method;   A  2-g  sample  1s mixed with anhydrous
sodium sulfate to form a free-flowing  powder.  This 1s solvent extracted once
using sonlcatlon.  A  portion  of   the  extract  1s removed for cleanup and/or
analysis.


3.0  INTERFERENCES

     3.1  Refer to Method 3500.


4.0  APPARATUS AND MATERIALS

     4.1  Apparatus  for grinding;   If the  sample will not pass through a 1-mm
standard sieve or cannot  beextruded  through  a  1-mm opening, 1t should be
processed  Into a homogeneous  sample  that  meets   these requirements.  Fisher
Mortar Model  155 Grinder, Fisher Scientific Co., Catalogue Number 8-323, or an
equivalent brand  and  model,   1s   recommended  for  sample  processing.  This
grinder  should handle  most   solid  samples,  except  gummy,  fibrous, or oily
materials.
                                   3550 -  1
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     4.2  Sonication:  A  horn-type  sonicator  equipped  with  a titanium tip
should be used.  The following sonicator,  or an equivalent brand and model,  1s
recommended:                             .
          Ultrasonic cell disrupter:  Heat  Systems - Ultrasonics, Inc., Model
          W-385 (475 watt) sonicator  or  equivalent  (Power wattage must be a
          minimum of 375  with  pulsing  capability  and  No.  200 1/2" Tapped
          Disrupter Horn) plus No. 207 3/4" Tapped Disrupter Horn, and No. 419
          1/8" Standard Tapered microtip probe.
     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 moisture;
          4.4.1  Oven:  Drying.
          4.4.2  Desiccator.
          4.4.3  .Crucibles:   Porcelain.
     4.5  Pasteur glass pipets;  Disposable,  1-mL.
     4.6  Beakers;  400-mL.
     4.7  Vacuum 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).                   '
          4.8.2  Evaporator   flask:      500-mL    (Kontes    K-570001-0500  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).                          "
     4.9  Boiling chips;   Solvent  extracted,  approximately  10/40 mesh  (silicon
 carbide or  equivalent).    ..-;••
     4.10   Water  bath:     Heated,  with  concentric   ring   cover,   capable of
 temperature control  (+5*C).   The  bath should  be used  in a hood.
                                   3550 - 2
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                                                          Date   September 1986

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     4.11  Balance;  Top-loading,  capable of accurately weighing  0.01  g.

     4.12  Vials and caps;  2-mL for GC auto-sampler.

     4.13  Glass scintillation vials;    At  least  20-mL,   with  screw-cap and
Teflon or aluminum foil liner.

     4.14  Spatula;  Stainless steel or Teflon.

     4.15  Drying column:  20-mm I.D.  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.

     4.16  Syringe;  5-mL.


5.0  REAGENTS

     5.1  Sodium sulfate;  Anhydrous and  reagent grade, heated at 400*C for
4 hr, cooled in a  desiccator, and   stored   in a glass  bottle.  Baker anhydrous
powder,  catalog #73898,  or equivalent.

     5.2 Extraction   solvents;      Methylene   chloride:acetone   (1:1,   v:v),
methylene chloride, hexane  (pesticide  quality or equivalent).

     5.3 Exchange solvents;    Hexane,   2-propano!,  cyclohexane, acetonitrile
 (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/sot!  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.
                                   3550 - 3
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                                                          Date   September 1986

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          7.1.3  Dry waste samples amenable  to  grinding:   Grind  or otherwise
     subdivide the waste so that it either  passes  through  a 1-mm  sieve or  can
     be extruded through a 1-mm  hole.     Introduce sufficient  sample into  the
     grinding apparatus to yield at least 10 g after grinding.

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

          7.2.1  Immediately after weighing  the  sample  for extraction,  weigh
     5-10 g of  the  sample  into  a  tared  crucible.   Determine the percent
     moisture by drying overnight at  105'C.    Allow  to cool  in  a desiccator
     before weighing:
               q of sampT- qdry sample x 100 = % mo1sture
     7.3  Determination of pH (if required):    Transfer  50  g of sample to a
100-mL beaker.  Add 50 ml of  water  and  stir  for 1 hr.  Determine the pH of
sample with glass electrode and pH meter while stirring.  Discard this portion
of sample.

     7.4  Extraction method for samples expected to contain low concentrations
of organics and pesticides «20 mg/kg):

          7.4.1  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  weight  to  the nearest 0.1 g.  Non-
     porous 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.  The sample  should  be free-flowing at this point.  Add
     1 mL of  surrogate  standards  to  all  samples,  spikes, 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/uL of each
     base/neutral analyte and 200 ng/uL 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 of the extract is lost due to loading of the
     GPC column.  Immediately add 100 ml of 1:1 methylene chloride:acetone.

          7.4.2  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.

          7.4.3  Sonicate for 3 min, with  output  control  knob set at 10 and
     with mode switch on Pulse and percent-duty cycle knob set at 50%.  Do NOT
     use microtip probe.
                                  3550 - 4
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                                                         Date  September 1986

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     7.4.4  Decant and  filter  extracts  through  Whatman  No.  41  filter
paper  using  vacuum  filtration  or  centrifuge  and  decant  extraction
solvent.

     7.4.5  Repeat the extraction two  or  more times with two additional
100-mL portions of solvent.  Decant off the extraction solvent after each
sonication.  On the  final  sonication,  pour  the entire sample into the
Buchner funnel and rinse with extraction solvent.

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

     7.4.7  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  100-125  ml  of  extraction  solvent to complete the
quantitative transfer.

     7.4.8  Add one or 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 1 ml,
remove the K-D apparatus  and allow it  to drain and cool for at least
10 min.

     7.4.9  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 Paragraph  7.4.8,   raising the temperature of  the
water bath, if necessary,  to maintain  proper distillation.

     7.4.10   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 Paragraph  7.4.11  or  adjusted   to  10.0 ml with  the
solvent last  used.

     7.4.11   Add a  clean  boiling chip   and  attach  a  two-ball micro-Snyder
column  to  the concentrator tube.     Prewet  the column by adding approxi-
mately  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 min.  At the proper   rate   of  distillation,  the balls  of  the column
will actively chatter,  but the  chambers  will not  flood.   When the  liquid
                              3550 - 5
                                                     Revision       0	
                                                     Date   September  1986

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   TABLE 1.   SPECIFIC EXTRACTION CONDITIONS FOR  VARIOUS DETERMINATIVE  METHODS



Determinative
method
80403
8060
8380
8090
8100
8120
8140
8250V
8270a,C
8310



Extraction
pH
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
hexane
none
hexane
hexane
none
none
acetonitrile
Exchange
solvent
required
for
cleanup
hexane
hexane
hexane
hexane
cyclohexane
hexane
hexane
_
-
~
Volune
of extract
required
for
cleanup (mL)
1.0
2.0
10.0
2.0
2.0
2.0
10.0

-
~
Final
extract
volune
for
analysis (mL)
1.0, 10. Ob
10.0
10.0
1.0
1.0
1.0
10.0
1.0
1.0
1.0
 To obtain separate acid and base/neutral extracts,  Method 3650 should be performed following
concentration of the extract to 10.0 mL.

 Phenols may  be analyzed, by Method 8940, using a 1.0 mL 2-propanol extract by GC/FID.  Method 8340
also contains an optional 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.   Refer to Method 3600 for
guidance on the cleanup procedures available if required.
                                           3550 -  6
                                                                       Revision       0	
                                                                       Date   September  1986

-------
     reaches an apparent volume of  approximately  0.5 ml,  remove  the  apparatus
     from the water bath and  allow  to  drain   and  cool  for  at  least  10 min.
     Remove the  micro-Snyder  column  and  rinse  its   lower   joint  into  the
     concentrator tube  with  approximately  0.2  ml  of  appropriate solvent.
     Adjust the final  volume to  the  volume  required   for cleanup or  for  the
     determinative method (see Table 1).

          7.4.12  Transfer the concentrated extract  to  a clean screw-cap vial.
     Seal the vial with a  Teflon-lined  lid  and  mark the level on  the vial.
     Label with the sample number and  fraction  and  store in the dark at  4*C
     until ready for analysis or cleanup.

     7.5  Extraction method  for  samples  expected   to  contain   high  concen-
trations 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 200 ng/uL of
     each base/neutral analyte  and  400  ng/uL  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  min at output control  setting 5
     and with mode switch on pulse  and  percent duty cycle of 50%.  Extraction
     solvents are:

           1.  Nonpolar compounds,  i.e., organochlorine pesticides and
               PCBs:  hexane.

           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
                                   3550 -  7
                                                         Revision      0
                                                         Date  September  1986

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     5.0 ml in  a  concentrator  tube  if  further  concentration is required.
     Follow Paragraphs  7.4.6  through  7.4.12  for  details on concentration.
     Normally, the 5.0 ml extract is concentrated to.1.0 ml.

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


8.0  QUALITY CONTROL

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

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


9.0  METHOD PERFORMANCE

     9.1  Refer to the determinative methods for performance data.


10.0  REFERENCES

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

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.
                                   3550 - 8
                                                          Revision
                                                          Date   September  1986

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                                        METHOD 3550

                                   SONICATION EXTRACTION
7. J I
    I Prepare
 samples using
  appropriate
method for the
 •taste matrix
7 .Z
7.5.2
 Add anhydrous
 sodium sulfate
   to sample
     Determine
   the percent
of moisture in
   the sample
                         7.5.3
  Is organic
concentration
 expected to
  be 
-------
                                    METHOD 3550

                               SONICATION EXTRACTION
                                    (Continued)
o
                                                 Oo sulfur
                                              crystals form?
                                                                       Use *•thod 3660
                                                                         far cleanup
                                                    Further
                                                 concentrate
                                                and/or adjust
                                                   volume
                                3550 - 10
                                                           Revision       0
                                                           Date  September  1986

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                                 METHOD 3580

                               WASTE DILUTION
1.0  SCOPE AND APPLICATION

     1.1  This method describes  a  solvent  dilution  of  a non-aqueous  waste
sample prior to cleanup and/or analysis.     It is designed for wastes  that  may
contain organic chemicals at a  level   greater  than 20,000 mg/kg and  that  are
soluble in the dilution solvent.

     1.2  It is recommended that an  aliquot  of the diluted sample be cleaned
up.  See the Cleanup section of this chapter for methods (Section 4.2.2).


2.0  SUMMARY OF METHOD

     2.1  One gram of sample is weighed into  a capped tube, and the sample is
diluted to 10.0 mL with an appropriate solvent.


3.0  INTERFERENCES

     3.1  Refer to Method 3500.
4.0  APPARATUS AND MATERIALS

     4.1  Glass scintillation vials:  At least 20-mL, with Teflon or aluminum-
foil-lined screw-cap.

     4.2  Spatula:  Stainless steel or Teflon.

     4.3  Balance:  Capable of weighing 100 g to the nearest 0.01 g.

     4.4  Vials and caps;  2-mL for GC autosampler.

     4.5  Disposable pi pets;  Pasteur.

     4.6  Test tube rack.

     4.7  Pyrex glass wool.

     4.8  Volumetric flasks;  10-mL (optional).


5.0  REAGENTS

     5.1  Sodium sulfate;  (ACS)  Granular,  anhydrous (purified by heating at
400*C for 4 hr in a shallow tray).
                                  3580 - 1
                                                         Revision
                                                         Date  September 1986

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     5.2  Solvents;   Methylene  chloride  and  hexane  (pesticide  quality  or
equivalent).


6.0  SAMPLE COLLECTION, PRESERVATION,  AND HANDLING

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


7.0  PROCEDURE

     7.1  Samples consisting of  multlphases  must  be  prepared  by the phase
separation method (Chapter Two) before extraction.

     7.2  The sample dilution may  be  performed  in a 10-mL volumetric flask.
If disposable glassware  1s  preferred,  the  20-mL  scintillation vial may be
calibrated for use.   Simply  pipet  10.0  mL  of  extraction solvent into the
scintillation vial and mark the bottom of the meniscus.  Discard this solvent.

     7.3  Transfer approximately 1  g  of  each  phase  (record  weight to the
nearest 0.1 g) of  the  sample  to  separate  20-mL  vials or 10-mL volumetric
flasks.  Wipe the  mouth  of  the  vial  with  a  tissue  to remove any sample
material.  Cap the vial before  proceeding  with  the next sample to avoid any
cross-contamination.

     7.4  Add 2.0 mL surrogate  spiking  solution  to  all samples and blanks.
For the sample in each analytical  batch  selected  for spiking, add 2.0 mL of
the matrix spiking standard.  For base/neutral-acid analysis, the amount added
of the surrogates  and  matrix  spiking  compounds  should  result  1n a final
concentration of 200 ng/uL of each  base/neutral analyte and 400 ng/uL 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.    See  Method  3500  for details on the surrogate
standard and matrix spiking solutions.

     7.5   Immediately  dilute to  10  mL  with  the  appropriate  solvent.   For
compounds  to be analyzed by  GC/ECD, e.g., organochlorine pesticides and PCBs,
the dilution solvent should be hexane.   For base/neutral and acid semivolatile
priority pollutants, use methylene chloride.   If dilution is to be cleaned up
by gel permeation  chromatography  (Method 3640),  use methylene chloride as  the
dilution solvent  for all compounds.

     7.6   Add 2.0  g of anhydrous sodium  sulfate to  the sample.

     7.7   Cap and  shake the sample for 2 min.

     7.8   Loosely  pack disposable  Pasteur pipets  with  2-3 cm glass wool plugs.
Filter the extract through  the glass wool and collect  5 mL of the extract 1n a
tube or vial.
                                   3580-2
                                                          Revision       0
                                                          Date  September  1986

-------
     7.9  The extract 1s  ready  for  cleanup  or  analysis,   depending on the
extent of Interfering co-extractives.


8.0  QUALITY CONTROL

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

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


9.0  METHOD PERFORMANCE

     9.1  Refer to the determinative methods for performance data.


10.0  REFERENCES

      10.1  None applicable.
                                  3580 - 3
                                                         Revision
                                                         Date  September 1986

-------
                                          METHOD 3580

                                        WASTE DILUTION
   Does sample
contain more than
   one phase?
                                                                                 o
 Use phase
separat Ion
  method
(chapter 2)
                                                                               7.5
Dilute with
appropriate
  •olvent
  7.31

    Transfer 1 g
   of aach phase
    to separate
 vials or flasks
  7.4
                                               7.6
                                               Add anhydrous
                                                  ammonium
                                                  sulfate
          Add
       surrogate
        spiking
     solution to
     all samples
     and blanks
  7 .A
                                                                              7.7
                                               Cap and shake
         Add
  matrix spiking
    standard to
 sample selected
    for spiking
                                                                              7.6
                                               Filter through
                                                 glass wool
     Q
                                                  Cleanup
                                                    or
                                                  analyze
                                      3580 -  4
                                                                Revision       0
                                                                Date  September  1986

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                                 METHOD 5030

                               PURGE-AND-TRAP
1.0  SCOPE AND APPLICATION

     1.1  This method  describes  sample  preparation  and  extraction  for the
analysis  of  volatile  organics  by  a  purge-and-trap  procedure.     The gas
chromatographic determinative steps are found in Methods 8010,  8015,  8020, and
8030.  Although applicable  to  Method  8240,  the purge-and-trap procedure is
already incorporated into Method 8240.

     1.2  Method 5030 can be  used  for  most  volatile organic compounds that
have boiling points below 200*C (vapor pressure is approximately equal  to
mm Hg @ 25*C) and are insoluble or slightly soluble in water.  Volatile water-
soluble compounds  can  be  included  in  this  analytical technique; however,
quantisation limits  (by  GC  or  GC/MS)  are  approximately  ten times higher
because of poor purging efficiency.   The  method is also limited to compounds
that elute as sharp  peaks  from  a  GC  column packed with graphitized carbon
lightly coated with a  carbowax.   Such compounds include low-molecular-weight
halogenated hydrocarbons, aromatics,  ketones,  nitriles, acetates,  acrylates,
ethers, and sulfides.

     1.3  Water  samples  can  be   analyzed  directly  for  volatile  organic
compounds  by  purge-and-trap  extraction  and  gas  chromatography.    Higher
concentrations  of  these  analytes  in  water  can  be  determined  by direct
injection of the sample into the chromatographic system.

     1.4  This  method  also  describes   the  preparation  of  water-misdble
liquids, solids, wastes, and soil/sediments for analysis by the purge-and-trap
procedure.


2.0  SUMMARY OF METHOD

     2.1  The purge-and-trap process;   An  inert  gas  is bubbled through the
solution at ambient temperature,  and  the volatile components are efficiently
transferred from the aqueous phase  to  the  vapor  phase.  The vapor is  swept
through a sorbent column where  the  volatile  components are adsorbed.  After
purging is completed, the sorbent column  is heated and backflushed with  inert
gas  to desorb the components onto a gas chromatographic column.

     2.2  If  the 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
water  in a specially designed purging chamber.    It  is  then analyzed by purge-
and-trap GC  following the normal water  method.
                                   5030 -  1
                                                          Revision
                                                         Date  September  1986

-------
3.0  INTERFERENCES

     3.1  Impurities In the purge .gas  and from organic compounds out-gassing
from the plumbing ahead of the .trap account for the majority of contamination
problems.  The analytical system must be demonstrated to be free from contami-
nation under the  conditions  of  the  analysis  by running laboratory reagent
blanks.  The use of non-TFE  plastic coating, non-TFE thread sealants, or flow
controllers with rubber components in the purging,device-should be avoided.

     3.2  Samples  can  be  contaminated  by  diffusion  of  volatile organics
(particularly methylene chloride and fluorocarbons) through the septum seal  of
the sample vial during shipment and  storage.   A field reagent blank prepared
from reagent water and. carried  through sampling and handling protocols serves
as a check on such contamination.

     3.3  Contamination by carryover  can  occur  whenever high-level and low-
level samples are analyzed  sequentially.   Whenever an unusually'concentrated
sample is analyzed, it should be  followed  by an analysis of reagent water to
check for cross-contamination.. The  trap  and  other  parts of the system are
subject to contamination;  therefore,  frequent  bake-out  and  purging of the
entire system may be required.

     3.4  The   laboratory  where  volatile  analysis  is  performed   should be
completely free of solvents.


4.0  APPARATUS  AND MATERIALS

     4.1  Microsyringes;   10-uL, 25-uL,  100-uL,  250-uL, 500-uL,  and  1,000 uL:
These syringes  shouldbe  equipped  with  a  20-gauge   (0.006-in  I^D.) 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  Balance;  Analytical, capable  of accurately weighing 0.0001 g, and a
top-loading balance capable of weighing  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  Uner.

     4.6  Volumetric flasks;    10-mL  and.  100-mL,   class  A with  ground-glass
stoppers.

     4.7  Vials;  2-mL,  for GC autosampler.

     4.8  Spatula;  Stainless  steel.
                                   5030 - 2
                                                          Revision       0
                                                          Date   September  1986

-------
     4.9  Disposable pi pets;  Pasteur.

     4.10  Purge-end-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.

          4.10.1  The recommended purging chamber  1s  designed to accept 5-mL
     samples with a water column at  least  3  cm deep.  The gaseous headspace
     between the water column and the  trap  must  have a total volume of less
     than 15 mL.  The purge gas  must  pass through the water column as finely
     divided bubbles with a diameter  of  less  than  3-mm at the origin.  The
     purge gas must be introduced no more than 5 mm from the base of the water
     column.  The sample purger,  illustrated  in Figure 1, meets these design
     criteria.    Alternate  sample  purge   devices  may  be  used,  provided
     equivalent performance is demonstrated.

          4.10.2  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 s111 cone-coated packing be inserted at
     the inlet to extend the life of the trap (see Figures 2 and 3).  If it is
     not necessary to  analyze  for  dichlorodifluoromethane  or other fluoro-
     carbons of similar volatility,  the  charcoal   can  be eliminated and the
     polymer increased to fill 2/3  of  the  trap.   If only compounds boiling
     above 35*C are to be analyzed,  both  the  silica gel and charcoal can be
     eliminated and the polymer  increased  to  fill  the entire trap.  Before
     initial use,  the  trap  should  be  conditioned  overnight  at  180°C by
     backflushing with an inert gas flow of at least 20 mL/min.  Vent the trap
     effluent to the hood, not to the  analytical column.  J'rior to daily use,
     the trap should be  conditioned  for  10  min at  180°C with backflushing.
     The  trap  may  be   vented   to   the  analytical  column  during  daily
     conditioning; however,  the  column  must  be  run through the  temperature
     program prior to  analysis of samples.

          4.10.3  The  desorber  should be  capable  of  rapidly  heating the trap
     to  180°C for desorption.   The  polymer  section of the trap should  not be
     heated higher than  180*C,   and  the  remaining  sections should not  exceed
     220*C  during bake-out  mode.  The desorber design  illustrated  in  Figures 2
     and 3  meet  these  criteria.

          4.10.4  The  purge-and-trap device  may   be   assembled  as a  separate
     unit or may be  coupled to  a gas  chromatograph,  as shown  in  Figures 4 and
     5.

          4.10.5  Trap Packing  Materials

                4.10.5.1   2,6-Diphenylene    oxide   polymer:       60/80   mesh,
          chromatographic  grade (Tenax GC or equivalent).

                4.10.5.2   Methyl  silicone  packing:    OV-1  (3%)  on  Chromosorb-W,
          60/80  mesh or  equivalent.


                                   5030 -  3
                                                          Revision       0
                                                          Date   September 1986

-------
        OPTIONAL
        FOAM TRAP
Exit 14 Inch 0. 0.


14 mm 0. D.


Inlet 14 Inch 0. D.
Inch 0. D. Exit
   10 mm Glass Frit
   Medium Porosity
                                Simple Inlet
                                2-Way Syringe Valve
                                17 cm, 20 Gauge Syringe Needle
                                6 mm 0. D. Rubber Septum
                                  "•10mm 0. D.
                                      Inlet
                                      * Inch 0. 0.
                         V16 Inch 0. D.
                         Stainless Stee.'
                                                        13x Molecular
                                                        Sieve Purge
                                                        Gas Filter
                                                        Purge Gas
                                                        Flow Control
                        Figure 1. Purging chamber.
                      5030 -  4
                                                  Revision       0
                                                  Date   September  1986

-------
    Packing Procedure
Construction
_ Compression
Glass Wool 5 mm
I
Activated |
Charcoal 7.7 cm


i

Grade 15





Silica Gel 7.7 cm


•
Tenax 7.7cr
•
3% OV-1 1 cm ;
Glass Wool 5 mm



n


=
^*
1
y?
^
#
\
N^
^
^
^;
S
,>'•
'•'*•
^

7n/Foot
Resistance
Wire Wrapped •<
Solid
(Double Layer)

T
^
-~C
~*^^
^v
I
c
15cm ^




7S7/Foot •
Resistance
Wire Wrapped
Solid
(Single Layer)
c
C
>
<

' V
C
c
Bern *~
d
"" )^— Fining Nut
^ ^ and Ferrules
^
^M
**
•^
^
^•1

i^
^V
— **
^^
JWM
|M«
^^
D
s
J
/
*»
^
• '

" >
^
^%
5
J 	
>
>
* /
>J
i+s


Thermocouple/
Controller
Sensor


*£"
y2
'/~
I
Tub
• o.ic

Electronic
Temperature
Control and
Pyrometer

ing 25 cm
)5 In. I.D.
0.125 In. O.D.
Stainless Steel
          Trap Inlet
Figure 2. Trap packings and construction for Method 8010.
                5030  -  5
                                          Revision       p
                                          Date  September  1986

-------
            Packing Procedure
                       Construction
Glass Wool   5 mm
   Tenax    23 cm
3% OV-1   1 cm ^ ;

Glass Wool   5 mm
1
f
* wrr
K
i
*
'£/.
                   Trap Inlet
Compression Fitting Nut
and Ferrules

   14 Ft. ?n/Foot Resistance
   Wire Wrapped Solid
                                                               Thermocouple/Controller Sensor
                                                                     Electronic
                                                                     Temperature
                                                                     Control and,
                                                                     Pyrometer
                                                              Tubing 25 cm
                                                              OV105 In. I.D.
                                                              •0:125 In. O.D.
                                                              Stainless Steel
          Figure 3. Trap packing and construction for Methods 8020 and 8030.
                                5030  -  6
                                                             Revision        p	
                                                             Date  September 1986

-------
      en
      o
      CO
      o
 O 70
 a> n
 r* <
 n ->.
CO O
0> 3
                                        Carrier Gas Flow Control

                                      Pressure Regulator
                                                                             Liquid Infection Ports
                                 Purge Gas
                                 Flow Control
                                13X Molecular
                                Sieve Filter
                     ^
                           Column Oven
D                                                                                                                         Confirmatory Column
                                                                                                                       elector
                                                                                                                         Analytical Column
Valve-3
Optional 4-Port Column
Selection Valve
         Trap Inlet (Tenax End)

               Resistance Wire
                                                                                                                                   Heater Control
                  Note: All Lines Between Trap and GC
                        Should be Heated to 80°C.
                                                                           Valve-2
VO
00
                                         Figure 4.  Purgc-and trap system, purge-sorb mode, for Methods 8010, 8020, and 8030.

-------
      en
      o
      CO
      o
      oo
O 73
O> O>
n> -••
CO O
O> 3
a>
                                           Carrier Gas Flow Control

                                          Pressure Regulator
                                                                                Liquid Injection Ports
                                    Purge Gas
                                    Flow Control
                                   13X Molecular
                                   Sieve Filter
                           Column Oven
                                                                                                                             Confirmatory Column
                                                                                                                       To Detector
                                                                                                                             Analytical Column
Valve-3
Optional 4-Port Column
Selection Valve
         Trap Inlet (Tenax End)

               Resistance Wire
                                                                                                                                       Heater Control
                   Note:  All Lines Between Trap and GC
                         Should be Heated to 80°C.
                                                                              Valve- 2
                                                 Figure 5. Purge-and trap system, desorb mode, for Methods 8010,8020, and 8030.

-------
               4.10.5.3  Silica  gel:     35/60  mesh,   Davison,   grade   15   or
          equivalent.

               4.10.5.4  Coconut charcoal:   Prepare from Barnebey Cheney,
          CA-580-26 lot #M-2649, by crushing through 26 mesh  screen.

     4.11  Heater or heated oil bath;     Should  be capable of maintaining  the
purging chamber to within 1*C over a temperature range from ambient to  100°C.


5.0  REAGENTS

     5.1  Reagent water;   Reagent  water  is  defined  as water  in which an
interferent is not observed at the  method detection limit of the compounds of
interest.

          5.1.1  Reagent water may be generated  by passing trap water through
     a carbon filter bed containing  about  500  g of activated carbon (Calgon
     Corp., Filtrasorb-300 or equivalent).

          5.1.2  A water purification system  (Millipore Super-Q or equivalent)
     may be used to generate reagent water.

          5.1.3  Reagent water  may also  be   prepared  by boiling water for 15
     min.  Subsequently,  while  maintaining  the  water  temperature at 90*C,
     bubble a contaminant-free  inert gas  through  the  water for 1 hr.  While
     still hot, transfer the water to a narrow-mouth screw-cap bottle and seal
     with a Teflon-lined septum and cap.

     5.2  Methanol;  Pesticide  quality or   equivalent.   Store away from other
solvents.
 6.0   SAMPLE  COLLECTION,  PRESERVATION, AND HANDLING

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


 7.0   PROCEDURE

      7.1   Initial  calibration;   Prior to using this introduction technique for
 any  GC  method, the system must   be  calibrated.  General calibration procedures
 are  discussed 1n  Method   8000,   Section  7.4, while the specific determinative
 methods and  Method 3500  give  details on preparation of standards.

           7.1.1   Assemble a purge-and-trap device that meets the specification
      in Section 4.10.  Condition the trap overnight at 180*C in the purge mode
      with  an inert gas flow of   at  least  20 mL/min.  Prior to use, condition
      the trap daily  for  10 min  while  backflushing at 180*C with the column at
      220*C.
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         7.1.2  Connect the purge-and-trap device to a gas. chromatograph.

         7.1.3  Prepare  the  .final   solutions   containing   the  required
    .concentrations of calibration  standards,  including surrogate standards,
    directly in the purging  device.    Add  5.0  ml  of reagent water to the
    purging device. . The 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
    f,,.diameter of the 14-gauge needle  that  forms the sample inlet will permit
    insertion of the 20-gauge needle.    Next,  using a 10-uL or 25-uL micro-
    syringe equipped with a long needle (Paragraph 4.1), take a volume of the
    secondary dilution solution containing  appropriate concentrations of the
    calibration standards.  Add the  aliquot of calibration solution directly
    .to the,reagent  water  in  the  purging  device  by  inserting the needle
    1 through the sample inlet.   When  discharging  the contents of the micro-
    : syringe, be;sure that the end  of  the syringe needle is well beneath the
    surface of the reagent  water.    Similarly,  add  10  uL of the internal
    standard solution.  Close the 2-way syringe valve at the sample inlet.

         7.1.4  Carry out  the  purge-and-trap  analysis  procedure using the
    specific conditions given in Table 1.    ......

         7.1.5  Calculate response  factors   or  calibration  factors for each
    analyte of interest using the procedure  described in Method 8000,  Section
	 7;4.  -   •         •  •              '       •  •  •   •

         7.1.6  The  average  RF  must  be   calculated  for  each   compound.   A
    system performance check  should be  made before  this calibration  curve  is
    used.   If the  purge-and-trap   procedure is  used  with Method 8010, the
    following five  compounds   are   checked   for  a   minimum  average  response
    factor:    chloromethane;   1,1-dichloroethane;   bromoform;  1,1,2,2-tetra-
    chloroethane;  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:

               7.1.6.1   Chloromethane;     This  compound  is   the   most likely
          compound to be  lost if the purge flow  is too fast.

               7.1.6.2   Bromoform;   This  compound  is  one of the  compounds most
          likely  to be  purged very  poorly if the purge flow  is too slow.   Cold
          spots  and/or  active sites  in  the transfer  lines may  adversely affect
          response.

               7.1.6.3   Tetrachloroethane  and   1,1-dichloroethane;      These
          compounds are degraded by  contaminated  transfer  lines in purge-and-
          trap  systems  and/or active sites in trapping materials.

     7.2   On-going calibration;   Refer   to  Method  8000, Sections 7.4.2.3  and
7.4.3.4 for details on  continuing  calibration.
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TABLE 1.  PURGE-AND-TRAP OPERATING PARAMETERS
                                           Analysis Method
                             8010
                8015
                 8020
                8030
Purge gas
Purge gas flow rate
 (mL/min)
Purge time (m1n)
Purge temperature (*C)
Desorb temperature (*C)
Backflush Inert gas flow
  (ml/mln)
Desorb time (min)
Nitrogen or  Nitrogen or
  Helium

    40
11.0 + 0.1
  Ambient
   180

  20-60
    4
  Helium

    20
15.0 + 0.1
  85 + 2
   180

  20-60
   1.5
Nitrogen or  Nitrogen or
  Helium       Helium
    40
12.0 + 0.1
  Ambient
   180

  20-60
    4
    20
15.0 + 0.1
  85 + 2
   180

  20-60
   1.5
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7.3  Sample preparation:

     7.3.1  Water samples:

          7.3.1.1  Screening  of  the   sample  prior  to  purge-and-trap
     analysis  will  provide  guidance  on  whether  sample  dilution  is
     necessary  and  will  prevent  contamination  of  the purge-and-trap
     system.  Two screening techniques that  can be utilized are:  the use
     of an automated headspace sampler (modified Method 3810),  interfaced
     to a- gas  chromatograph  (GC),  equipped  with  a  photo  ionization
     detector (PID), in series with an electrolytic conductivity detector
     (ECD); and extraction of  the  sample  with hexadecane (Method 3820)
     and analysis of the extract on a GC with a FID and/or an ECD.

          7.3.1.2  All samples and standard  solutions must be  allowed to
     warm to ambient temperature before analysis.

          7.3.1.3  Assemble the  purge-and-trap  device.    The operating
     conditions for the  GC  are  given  in  Section  7.0 of the specific
     determinative method to be employed.

          7.3.1.4  Daily GC  calibration  criteria  must  be  met (Method
     8000, Section 7.4) before analyzing samples.

          7.3.1.5  Adjust the purge gas flow rate (nitrogen or helium) to
     that shown in Table 1,  on  the purge-and-trap device.  Optimize the
     flow  rate  to  provide  the  best  response  for  chloromethane and
     bromoform, if these  compounds  are  analytes.   Excessive flow rate
     reduces chloromethane  response,  whereas  insufficient flow reduces
     bromoform response.

          7.3.1.6  Remove the plunger from  a  5-mL  syringe and attach a
     closed syringe valve.  Open the sample or standard bottle, which has
     been allowed  to come to  ambient temperature, and carefully pour the
     sample  into  the   syringe  barrel  to  just  short  of overflowing.
     Replace the syringe  plunger  and  compress  the  sample.   Open the
     syringe valve and vent any  residual  air while adjusting the sample
     volume to 5.0 ml.   This  process  of taking an aliquot destroys the
     validity of the   liquid  sample  for  future analysis; therefore, if
     there  is only one VOA vial, the analyst should fill a  second syringe
     at this time  to protect  against  possible  loss of sample integrity.
     This second sample   is  maintained  only  until  such  time when the
     analyst has   determined  that   the  first   sample  has been analyzed
     properly.   Filling  one 20-mL syringe would  allow the  use of only one
     syringe.  If  a second analysis  is  needed from a syringe, it must be
     analyzed within 24  hr.    Care  must  be  taken  to prevent air  from
     leaking into  the  syringe.

           7.3.1.7   The following  procedure   is   appropriate for diluting
     purgeable samples.   All  steps  must be performed without delays  until
     the  diluted sample  is  in a gas-tight syringe.
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          7.3.1.7.1   Dilutions  may  be  made  1n  volumetric  flasks  (10-
     mL to 100-mL).   Select the volumetric  flask  that will  allow for
     the  necessary   dilution.       Intermediate   dilutions may be
     necessary for extremely large  dilutions.

          7.3.1.7.2   Calculate   the approximate   volume   of reagent
     water to be  added  to  the volumetric  flask selected and add
     slightly less than this quantity  of reagent  water  to the  flask.

          7.3.1.7.3   Inject the proper  aliquot  of samples from the
     syringe prepared in Paragraph  7.3.1.5  into the flask.  Aliquots
     of less than 1-mL are  not  recommended.    Dilute  the sample to
     the mark with reagent water.   Cap the flask, invert, and shake
     three  times.    Repeat  the  above procedure  for   additional
     dilutions.

          7.3.1.7.4   Fill a 5-mL syringe with the diluted sample as
     in Paragraph 7.3.1.5.

     7.3.1.8  Add 10.0 uL  of  surrogate  spiking solution (found in
each determinative method, Section  5.0) and, if applicable, 10 uL of
internal standard spiking  solution  through  the  valve  bore  of the
syringe; then close  the valve.   The surrogate and internal standards
may be mixed and added as a single  spiking  solution.  Matrix spiking
solutions, 1f indicated, should be   added  (10  uL) to the sample at
this time.

     7.3.1.9  Attach  the  syringe-syringe   valve  assembly  to  the
syringe valve on the purging  device.     Open the syringe valves and
inject the sample into the purging  chamber.

     7.3.1.10  Close both valves and  purge  the sample for the time
and at the temperature specified in Table 1.

     7.3.1.11  At the conclusion of the  purge time, attach the trap
to the chromatograph,  adjust  the  device  to  the desorb mode, and
begin  the  gas  chromatographic  temperature  program  and  GC data
acquisition.  Concurrently, introduce  the  trapped materials to the
gas chromatographic column  by   rapidly  heating  the  trap to  180*C
while backflushing the trap with inert  gas between 20 and 60 mL/min
for the time  specified in Table  1.

     7.3.1.12  While  the  trap  is  being  desorbed  into  the  gas
chromatograph, empty the purging chamber.    Wash the chamber with a
minimum of two 5-mL flushes  of  reagent water (or methanol followed
by reagent water)  to  avoid   carryover  of pollutant compounds  into
subsequent analyses.

     7.3.1.13 After desorbing the  sample,   recondition  the trap by
returning the purge-and-trap device to the purge  mode.  Wait 15 sec;
then close the syringe valve on  the purging device to begin gas  flow
                         5030 -  13
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                                               Date  September 1986

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    through the trap.    The  trap  temperature  should be maintained at
    180*C for Methods 8010  and  8020,  and  210*C  for Methods 8015 and
    8030.  Trap temperatures up  to  220'C may be employed; however, the
    higher temperature will shorten the useful  life of the trap.  After
    approximately  7 min, turn off  the  trap heater and open the syringe
    valve to stop  the gas flow through the trap.  When cool, the trap is
    ready for the  next sample.

         7.3.1.14   If the initial analysis of  a sample or a dilution of
    the  sample  has a concentration  of analytes that exceeds the initial
    calibration  range,  the  sample  must  be  reanalyzed  at  a higher
    dilution.   When a  sample  is  analyzed  that has saturated response
    from a compound, this analysis  must  be followed by  a blank reagent
    water analysis.  If  the blank analysis 1s not free of Interferences,
    the  system  must be decontaminated.    Sample analysis may not resume
    until a  blank  can be analyzed that is free of interferences.

         7.3.1.15   All dilutions should keep  the   response of the  major
    constituents  (previously  saturated peaks)  in   the upper half of the
    linear  range of the  curve.   Proceed to Method  8000 and the specific
    determinative  method for  details  on calculating analyte response.

    7.3.2  Water-misdble  liquids:

         7.3.2.1   Water-miscible liquids are  analyzed  as water samples
    after  first diluting them at least 50-fold with reagent water.

         7.3.2.2   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  reagent water.  Transfer immediately to a
    5-mL gas-tight syringe.

         7.3.2.3   Alternatively, prepare  dilutions  directly  in a 5-mL
     syringe  filled with  reagent  water by  adding at least 20 uL, but not
    more than  100-uL of  liquid  sample.  The  sample  is  ready for  addition
    of  surrogate   and,   if  applicable,  internal   and   matrix  spiking
     standards.

     7.3.3   Sediment/soil and waste   samples:     It  is  highly recommended
that all  samples of this  type be screened prior  to  the  purge-and-trap GC
analysis.  These  samples  may  contain  percent  quantities of purgeable
organics that will   contaminate   the   purge-and-trap  system, and  require
extensive cleanup  and   instrument  downtime.     See  Paragraph 7.3.1.1 for
recommended screening  techniques.    Use  the   screening  data to determine
whether to  use the   low-level  method   (0.005-1   mg/kg)  or the  high-level
method (>1  mg/kg).

          7.3.3.1   Low-level   method:     This   is  designed  for   samples
     containing individualpurgeable   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-level  method  is  based  on
                             5030 - 14
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purging a  heated  sediment/soil  sample  mixed  with  reagent water
containing the surrogate  and,  1f  applicable,  Internal  and matrix
spiking standards.  Analyze  all  reagent blanks and standards under
the same conditions as the samples.

          7.3.3.1.1  Use a 5-g sample  If the expected concentration
     1s <0.1  mg/kg  or  a  1-g  sample  for expected concentrations
     between 0.1 and 1 mg/kg.

          7.3.3.1.2  The GC system should  be  set  up as in Section
     7.0 of the specific determinative  method.  This should be done
     prior to  the  preparation  of  the  sample  to  avoid  loss of
     volatiles  from  standards  and   samples.     A  heated  purge
     calibration  curve  must   be   prepared   and   used  for  the
     quantisation of all samples analyzed with the low-level method.
     Follow the initial  and  dally calibration instructions, except
     for the addition of a  40*C  purge temperature for Methods 8010
     and 8020.

          7.3.3.1.3  Remove the plunger  from  a  5-mL Luerlock type
     syringe  equipped  with   a   syringe   valve  and  fill  until
     overflowing  with  reagent  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 and
     Internal standard solution  to  the  syringe through the valve.
     (Surrogate spiking solution and  internal standard solution may
     be mixed together.)    Matrix  spiking  solutions, if Indicated,
     should be added  (10 uL)  to the sample at  this time.

          7.3.3.1.4  The sample  (for  volatile organics) consists of
     the  entire contents of   the   sample  container.  Do not  discard
     any  supernatant   liquids.     Mix   the   contents  of  the sample
     container with  a narrow  metal   spatula.    Weigh  the amount
     determined 1n  Paragraph  7.3.3.1.1   into  a  tared purge  device.
     Note and record the actual weight  to the  nearest 0.1 g.

          7.3.3.1.5   In certain  cases,   sample   results are  desired
     based  on a dry-weight   basis.    When   such  data is desired,  a
     portion  of  sample for   moisture determination  should be  weighed
     out  at  the   same time as   the   portion  used  for analytical
     determination.     Immediately after weighing   the  sample  for
     extraction,  weigh 5-10  g of   the   sample  into  a  tared  crucible.
     Determine  the  percent   moisture  by  drying  overnight  at 105*C.
     Allow  to cool  1n  a desiccator before weighing:
            q of sa1-drY samP1e x 100 =  % moisture
                         5030 - 15
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          7.3.3.1.6  Add  the  spiked  reagent   water  to   the  purge
     device,   which  contains  the  weighed  amount  of sample,  and
     connect  the device to the purge-and-trap system.
          NOTE:   Prior to the  attachment of the purge device,  steps
          7.3.3.1.4 and  7.3.3.1.6  must  be  performed rapidly  and
          without interruption to  avoid  loss  of volatile organics.
          These  steps must  be  performed  in  a  laboratory free of
          solvent fumes.

          7.3.3.1.7  Heat the sample to 40'C + 1°C (Methods 8010  and
     8020) or to 85°C +  2*C  (Methods  8015 and 8030) and purge  the
     sample for the time shown in Table 1.

          7.3.3.1.8  Proceed  with  the , analysis  as  outlined   in
     Paragraphs  7.3.1.11-7.3.1.15.   Use  5  ml  of the same reagent
     water as in the reagent blank.   If saturated peaks occurred or
     would occur  if  a  1-g  sample  were  analyzed, the  high-level
     method must be followed.

     7.3.3.2  High-level 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.  An  aliquot of
the extract is added to  reagent  water containing surrogate and, if
applicable, internal and matrix  spiking  standards.  This is purged
at the temperatures  indicated  in  Table  1.    All samples with an
expected concentration of  >1.0  mg/kg  should  be  analyzed by this
method.

          7.3.3.2.1  The sample (for  volatile organics) consists of
     the entire contents of  the  sample  container.  Do not discard
     any supernatant  liquids.    Mix  the  contents  of  the sample
     container with a narrow  metal  spatula.  For sediment/soil  and
     waste that are insoluble  in methanol, weigh 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 moisture of the sample  using the procedure in Paragraph
     7.3.3.1.5.  For waste that   is  soluble  in methanol, 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.   Pi pet  10.0 ml of methanol into the
     vial and  mark  the  bottom   of the  meniscus.    Discard  this
     solvent.)

           7.3.3.2.2  Quickly add  9.0 ml  of methanol;  then  add  1.0 ml
     of the  surrogate  spiking  solution   to   the vial.  Cap and shake
     for  2 min.
           NOTE:  Steps   7.3.3.2.1   and   7.3.3.2.2  must be performed
           rapidly  and  without  interruption to avoid  loss  of volatile
           organics.  These  steps   must   be performed in a  laboratory
           free  from  solvent  fumes.
                         5030 -  16
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     7.3.3.2.3  Pipet approximately 1 ml of the extract to a GC
vial for storage, using a  disposable pipet.  The remainder may
be  disposed  of.    Transfer  approximately  1  ml  of reagent
methanol 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.

     7.3.3.2.4  The GC system should  be  set  up as in Section
7.0 of the specific determinative  method.  This should be done
prior to the addition of the methanol extract to reagent water.

     7.3.3.2.5  Table 2 can be used  to determine the volume of
methanol extract to  add  to  the  5  ml  of  reagent water for
analysis.   If  a  screening  procedure  was  followed, use the
estimated concentration  to  determine  the appropriate volume.
Otherwise, estimate the concentration  range of the sample from
the low-level analysis to determine the appropriate volume.  If
the sample was submitted as a high-level sample, start with 100
uL.    All  dilutions  must  keep  the  response  of  the major
constituents  (previously saturated peaks)   in the upper half of
the linear range of the curve.

     7.3.3.2.6  Remove the plunger from  a  5.0-mL Luerlock type
syringe  equipped  with   a   syringe   valve  and  fill  until
overflowing  with  reagent  water.    Replace  the  plunger and
compress the water to vent  trapped  air.   Adjust the volume to
4.9 ml.  Pull the plunger  back  to  5.0 ml to allow volume for
the addition of the sample extract and of standards.  Add
10  uL of internal standard  solution.    Also add the volume of
methanol extract determined in Paragraph 7.3.3.2.5 and a volume
of  methanol solvent  to  total  100  uL  (excluding methanol in
standards).

     7.3.3.2.7  Attach the syringe-syringe  valve assembly to the
syringe valve on the purging device.   Open the syringe valve and
inject  the water/methanol sample into the purging chamber.

     7.3.3.2.8   Proceed with  the  analysis as  outlined  in the
specific determinative method.  Analyze all reagent blanks on the
same instrument  as that used  for   the samples.  The standards and
blanks  should also contain  100  uL  of  methanol to simulate the
sample  conditions.

     7.3.3.2.9   For    a   matrix     spike   in   the    high-level
sediment/soil   samples,   add  8.0  ml   of   methanol,   1.0  ml  of
surrogate  spike  solution  and   1.0  ml  of  matrix spike solution.
Add a  100-uL  aliquot  of this  extract to 5 mL of water  for  purging
 (as per Paragraph  7.3.3.2.6).
                    5030 - 17
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                                           Date  September 1986

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TABLE 2.  QUANTITY OF METHANOL EXTRACT REQUIRED FOR ANALYSIS OF HIGH-LEVEL
          SOILS/SEDIMENTS
                Approximate
            Concentration Range
      Volume of
   Methanol  Extract3
              500-10,000 ug/kg
            1,000-20,000 ug/kg
            5,000-100,000 ug/kg
           25,000-500,000 ug/kg
         100 uL
          50 uL
          10 uL
100 uL of 1/50 dilution b
     Calculate appropriate  dilution  factor  for  concentrations exceeding this
table.    .

     aThe volume of methanol added to 5  mL of water being purged should be kept
constant.  Therefore, add to  the  5-mL  syringe  whatever volume of methanol is
necessary to maintain a volume of 100 uL added to the syringe.

     ^Dilute an aliquot  of  the  methanol  extract  and  then  take  100 uL for
analysis.                          •
                                  5030 - 18
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                                                         Date  September 1986

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     7.4  Sample analysis;

          7.4.1     The samples  prepared  by  this  method  may  be analyzed by
     Methods 8010, 8015, 8020,  8030,   and  8240.     Refer  to these methods for
     appropriate analysis conditions.


8.0  QUALITY CONTROL

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

     8.2  Before  processing  any  samples,  the  analyst  should  demonstrate
through the analysis of a  reagent  water  method blank that all glassware and
reagents are interference free.  Each  time  a set of samples is extracted, or
there is a change in reagents, a  method  blank should be processed as a safe-
guard against chronic laboratory contamination.    The blank samples should be
carried through all stages of the sample preparation and measurement.

     8.3  Standard  quality   assurance  practices  should  be  used  with this
method.  Field  replicates should be collected to validate the precision of the
sampling technique.  Laboratory replicates   should be analyzed to validate the
precision of the  analysis.    Fortified  samples  should be carried through all
stages of sample  preparation  and  measurement;  they  should  be analyzed to
validate the sensitivity  and  accuracy  of  the  analysis.    If the fortified
samples do not  indicate  sufficient  sensitivity  to  detect  <1  ug/g of the
analytes in the  sample,  then  the  sensitivity  of  the instrument should be
increased, or the sample  should be subjected to additional cleanup.


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.
                                   5030 - 19
                                                          Revision
                                                          Date   September 1986

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                             METHOD 5030

                        PUHGE-ANO-TRAP METHOD
C    •—    )
  7. 1
     o
       Calibrate
       GC system
     and prepare
       standards
 7.1.2
                                                    7.1.4
     Carry out
  purge-end-trap
     analysis
       Assemble
  purge-and-trap
    device  and
  condition trap
 7.1.3
                                                 7.1.5
      Calculate
     response  or
calibration  factor*
  for each analyte
     (Method  8000,
    Section  7.4)
  Connect  to  gas
  chromatograph
 7.1.3
                                                    7. 1.6
     Calculate
  average  RF  for
   each compound
  Prepare  final
    solutions
     O
    0
                     5030  - 20
                                               Revision       0	
                                               Date  September  1986

-------
                                          METHOD SO30

                                     PURG6-ANO-TRAP METHOD
                                           (Continued)
 7.3.31
Prepare  ••mples
   •nd 
-------
                                 METHOD 5040

                 PROTOCOL FOR ANALYSIS OF SORBENT CARTRIDGES
                    FROM VOLATILE ORGANIC SAMPLING TRAIN
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 sorberit
cartridges using a volatile organic  sampling  train, . VOST  (1).  Much of the
description for purge-and-trap GC/MS analysis  is  described in Method. 8240 of
this chapter.  Because the  majority  of  gas  streams sampled using VOST Will;
contain a high concentration of water,  the  analytical method is based on the
quantitative  thermal  desorption  of  volatile   POHCs  from  the  Tenax  and
Tenax/charcoal traps and analysis by  purge-and-trap  GC/MS.  For the purposes
of definition, volatile POHCs are  those  POHCs  with boiling points less than
100'C.                                                                    ~.  -;

     1.3  This method  is  applicable  to  the  analysis  of  Tenax and Tenax/
charcoal  cartridges  used  to  collect  volatile  POHCs  from  wet  stack'gas
effluents from hazardous waste incinerators.

     1.4  The sensitivity of the  analytical  method for a particular volatile
POHC depends on the  level  of  interferences  and  the presence of detectable
levels of volatile POHCs in blanks.  The desired target detection limit of the
analytical method is  0.1  ng/L   (20  ng  on  a  single  pair  of traps),for a
particular volatile  POHC  desorbed  from  either  a  single  pair of Tenax and
Tenax/charcoal cartridges or by thermal desorption of up to six pairs of traps
onto a single pair of  Tenax  and  Tenax/charcoal traps.  The resulting single
pair of traps is then thermally desorbed and analyzed by purge-and-trap GO/MS*

      1.5  This  method  is  recommended  for  use  only  by  experienced,1 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
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.


                                  5040 - 1
                                                         Revision      0
                                                         Date  September 1986

-------
     en
     0
     j^
     o

      i

     ro
 O 73
 O> ft)
 rt <
  -••
   CO
   .4.
 GO O
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r+
(b I
Flow
GC/
CH:
o-j;
A
N2 A ••:
, . ., , ,*,., ,.._.., k!/ M "
® p -.^
it. ji prit Ssj
*"TL"<- \ 1
^P Thermal t
/^"\ D^nrplion , 	 ;_ 	 )
Chamber
i
Heated
Line
( Flow During J
Desorption
to
MS Flow During
1 Adsorption 1
j-1 "A*-!-*-!"-! • i
i i><|>ci>q>q H
r» T • T • T» i •
Analytical Trap
with Heating Coil
_ (0.3cm diameter
by 25cm long)
1" H20
Purge (T) 3
* Column ^-^
c / » \ _
\y T
© s
0c
                                                                                      He or
                                                                                      3-0
   Vent



3%OV-I (1cm)


Tenax  (7.7cm)


Silica Gel (7.7cm)


Charcoal  (7.7cm)
                                        Figure 1. Schematic diagram of trap desorp lion/analysis system.
00
cr>

-------
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 car-
     tridges, use Supelco  "clamshell"  heater;  for  Inside/Outside VOST car-
     tridges, user fabricated unit is required) should be capable of thermally
     desorbing the sorbent resin tubes.   It should also be capable of heating
     the tubes to 180  +  10*C  with  flow  of organic-free nitrogen or helium
     through the tubes.

     4.2  Purge-and-trap unit;

          4.2.1  The purge-and-trap unit consists  of three separate pieces of
     equipment:  the sample  purger,  trap,  and  the  desorber.  It should be
     capable of  meeting  all  requirements  of  Method  5030  for analysis of
     purgeable organic compounds from water.

     4.3  GC/MS  system;  As described in Method 8240.


5.0  REAGENTS

     5.1  Reagent water;    Reagent  water   is  defined  as  water  in which an
interferent  is not observed at the method detection limit of the parameters of
interest.

          5.1.1   Reagent water may be generated by passing tap water through  a
     carbon  filter bed  containing  about   450  g  of activated carbon  (Calgon
     Corporation, Filtrasorb-300, or equivalent).

          5.1.2   A water purification  system  (Millipore Super-Q or equivalent)
     may  be  used to  generate  reagent water.

          5.1.3   Reagent water   may   also   be  prepared  by  boiling distilled
     water  for  15   min.     Subsequently,   while  maintaining  the temperature
     at 90*C,  bubble a  contaminant-free inert  gas through the water for 1 hr.
     Allow  the water to cool   to  room   temperature while  continuing to bubble
     the  inert gas   through  the water.    This  water  should be transferred
     directly to the purge-and-trap apparatus  for use.

          5.1.4   Other  methods  that can be  shown to produce organic-free water
     can  be  used.
                                   5040 - 3
                                                          Revision       0
                                                          Date  September  1986

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    5.2  Analytical trap reagents:

         5.2.1  2,6-Diphenylene oxide polymer:  Tenax (60/80 mesh),  chromato-
    graphic grade or equivalent.

         5.2.2  Methyl silicone packing:    3%  OV-1  on  Chromosorb W (60/80
    mesh) or equivalent.

         5.2.3  Silica gel:   Davison  Chemical  (35/00  mesh),  Grade 15, or
    equivalent.

         5.2.4  Charcoal:  Petroleum-based (SKC Lot 104 or equivalent).

    5.3  Stock standard solution:

         5.3.1  Stock standard  solutions will  be prepared from pure standard
    materials or  purchased  as   certified  solutions.    The stock standards
    should be  prepared  in  methanol  using  assayed  liquids  or  gases, as
    appropriate.   Because  of   the  toxicity  of  some  of the organohalides,
    primary dilutions of these  materials  should  be  prepared  in a hood.  A
    NIOSH/MESA-approved toxic gas respirator  should  be used when the analyst
    handles high  concentrations of such materials.

         5.3.2  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.

    5.4  Secondary dilution  standards;

         5.4.1  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.

    5.5  4-Bromofluorobenzene  (BFB)  standard;

          5.5.1   Prepare a  25 ng/uL  solution  of BFB  in  methanol.

    5.6   Deuterated benzene;

          5.6.1   Prepare a  25 ng/uL  solution  of benzene-ds 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.
                                  5040 - 4
                                                         Revision
                                                         Date  September 1986

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7.0  PROCEDURE

     7.1  Assembly of PTD device;

          7.1.1  Assemble a purge-and-trap desorptlon  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 1t be
     similar in analytical behavior to  the  compounds of Interest and that 1t
     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  djo-ethylbenzene and d4-l,2-d1chloroethane.  One
     adds 50 ng of BFB to all  sorbent  cartridges (in addition to one or more
     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  methanollc  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-uL syringe
     with clean methanol and drawing air  into the syringe to the 1.0-uL mark.
     This is followed  by  drawing  a  methanol1c  solution of the calibration
     standards (containing 25 ug/uL  of  the  internal standard) to the 2.0-uL
     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  1n 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
                                  5040 - 5
                                                         Revision      0
                                                         Date  September 1986

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    of  the characteristic  ions of  each  analyte against the concentration of
    the  internal   standard  and  calculate  response  factor  (RF)  for each
    compound,  using Equation 1.
          RF  =  AsCis/A1sCs
(1)
     where:
          As    =   Area  of  the  characteristic  ion  for the analyte to
                     be measured.

          Ais  =   Area  of  the  characteristic  ion  for the internal
                     standard.

          Cjs  =   Amount (ng)  of the internal  standard.

          Cs    =   Amount (ng)  of the volatile POHC in  calibration
                     standard.

     If the RF value over  the  working  range   1s  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/Ajs versus RF.

          7.2.6  The working calibration curve or  RF  must be verified on each
     working day   by  tfie   measurement  of one  or more   of  the calibration
     standards.  If the response varies  by  more than +25% for any  analyte,  a
     new calibration standard  must be prepared and analyzed,  for that analyte.

     7.3  The schematic of the PTD-GC/MS  system   is   shown  in Figure 1. The
sample cartridge  is placed  in  the  thermal  desorption  apparatus  (for Inside/
Inside VOST cartridges,  use  Supelco  "clamshell" heater; for Inside/Outside
VOST cartridges,  user fabricated unit is  required) and  desorbed 1n  the purge-
and-trap system by heating to  180'C for  10  min   at  a flow rate of  40 mL/mln.
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  adsor-
bent trap into  the  GC/MS  system  according  to  the procedures  described  1n
Method 8240.

     7.4  Qualitative identification;

          7.4.1  The  procedure  for  qualitative  identification of volatile
     POHCs using this protocol is described in Method  8240.

     7.5  Calculations;

          7.5.1  When   an   analyte   has   been   qualitatively  Identified,
     quantification 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 1on, a secondary
     characteristic ion should be used.
                                  5040 - 6
                                                         Revision      0
                                                         Date  September 1986

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     7.5.1.1  Using the Internal  standard calibration procedure,  the
amount of analyte 1n  the  sample  cartridge Is calculated using  the
response factor (RF) determined In Paragraph 7.2.5 and Equation 2.

     Amount of POHC  =  ASC^S/A^SRF                              (2)

where:

     As   =  Area of the characteristic 1on for the analyte to be
             measured.

     AJS  =  Area for the characteristic ion of the internal
             standard.

     C^s  =  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.  These values should then be blank
corrected.  Guidelines for blank correction of sample cartridges are
outlined below.

          7.5.1.3.1   After all blanks  (field and  trip) are analyzed,
     a  paired t-test should be used to determine  whether trip blanks
     are  significantly  different  from   field   blanks.     If  no
     difference  1s  found, then   the  mean  and standard deviation of
     the combined  field and trip blanks  for each  POHC of  Interest is
     calculated.

          7.5.1.3.2  If, when  using the  paired t-test, the  field and
     trip blanks are  determined  to  be   different,  then  the field
     blank  (or the  mean of  multiple field blanks) associated with a
     particular  run should  be   used  as   the  blank value for that
     particular  run.

      7.5.1.4  Next,    for    each    sample/POHC     combination,   a
determination must  be made  as  to  whether   a particular  sample 1s
significantly different  from the associated  blank.   If  the mean of
the  trip and  field  blanks is   used,  then  a sample is different from
the  blank  if:

  measured            mean
 (sample value) -  (blank  value) > (3 x blank standard deviation)

 (If  an  individual  field  blank  is   used as  the  blank  value,  the above
criteria do not  apply.)   If the  sample Is  determined to be  different
from the blank according  to   the   above criteria, then the emission
value  of a   particular  POHC   1s  blank-corrected by subtracting the
mean blank  value from the measured  sample  value.
                         5040 - 7
                                                Revision       0
                                                Date  September  1986

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               7.5.1.5   If, according  to  the  above  procedures,  the sample
         cannot be distinguished  from the blank  (I.e., for a given POHC there
         1s  a  high sample value and high blank value or there 1s a low sample
         value and low  blank  value), the  measured sample value 1s not blank-
         corrected.  In this case,  the  measured  sample  value 1s used to
         calculate a maximum   emission  value  (and  therefore  a minimum ORE
         value) for that particular run.

               7.5.1.6   The observation  of   high concentrations  of POHCs of
         Interest   1n   blank   cartridges    Indicates   possible   residual
         contamination  of the sorbent cartridges prior to shipment to and use
         at  the site.    Data that  fall  1n  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  1n   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.

               7.5.1.7   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.
8.0  QUALITY CONTROL

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

     8.2  Each laboratory that  uses  this  method  is  required  to operate a
          formal quality control program.    The  minimum requirements of this
          program consist of an Initial demonstration of laboratory capability
          and the analysis of blank Tenax and Tenax/charcoal cartridges spiked
          with the  analytes  of  Interest.    The  laboratory  1s required to
          maintain performance records to define  the quality of data that are
          generated.    Ongoing  performance  checks  must  be  compared  with
          established performance criteria to  determine if results are within
          the expected precision and accuracy limits of the method.

          8.2.1  Before performing any analyses,  the analyst must demonstrate
     the ability  to  generate  acceptable  precision  and  accuracy with this
     method.  This ability is established as described in Paragraph 7.2.

          8.2.2  The  laboratory  must  spike  all  Tenax  and  Tenax/charcoal
     cartridges with the internal standard(s) to monitor continuing laboratory
     performance.  This procedure 1s described 1n Paragraph 7.2.

     8.3  To  establish  the  ability  to  generate  acceptable  accuracy  and
precision, the analyst must  spike  blank  Tenax and Tenax/charcoal cartridges
with the analytes of interest at two concentrations in the working range.

                                  5040 - 8
                                                         Revision      0
                                                         Date  September 1986

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          8.3.1  The average response  factor  (R)   and the standard deviation
     (S)  for each must be calculated.

          8.3.2  The average recovery and  standard deviation must fall  within
     the  expected range for determination of volatile POHCs using this method.
     The  expected range for recovery  of  volatile   POHCs using this method 1s
     50-150%.

     8.4   The analyst  must  calculate  method, performance  criteria  for the
1nternal  standard(s).

          8.4.1  Calculate  upper  and   lower   control   limits  for  method
     performances  using  the   average   area   response   (A)  and  standard
     devlatlon(s) for internal standard:

           Upper Control Limit (UCL)  =  A + 3S.
           Lower Control Limit (LCL)  =  A - 3S.

     The  UCL and LCL can be  used  to construct control charts that are useful
     in observing trends in performance.   The control limits must be replaced
     by  method  performance  criteria  as  they  become  available  from  the
     U.S. EPA.

     8.5  The laboratory is required to spike all sample cartridges (Tenax and
Tenax/charcoal) with internal standard.

     8.6  Each day, the  analyst  must  demonstrate  through analysis of blank
Tenax and Tenax/charcoal cartridges and  reagent water that interferences from
the analytical system are under control.

     8.7  The daily  GC/MS  performance  tests  required .for  this method are
described in Method 8240.
9.0  METHOD  PERFORMANCE

     9.1  Refer to the determinative methods for performance data.


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.
                                   5040 - 9
                                                         Revision
                                                         Date  September  1986

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                            METHOD S040

            PROTOCOL FOR ANALYSIS OF SORBENT CARTRIDGES

               FROM VOLATILE ORGANIC SAMPLING TRAIN
1
7.1.1


Aaeemble
purge and trap
deaorptlon
device
                                  Expel
                              contents of
                                syringe
                              through GC
                           Injection port
7.1.2
       Connect
       thermal
     desorptlon
      device;
     calibrate
      ayatem
7.8.1
                          7.2.4
                                                     7.3
                               I  Piece
                               J  sample
                               cartridge
                            In desorptlon
                              apparatus:
                            desorb In P-T
      Analyze
  trap by P-T-D
GC/HS procedure
  (Method 8240)
Select Internal
   atandard
                          7.2.5
                                                     7.3
 Oeaorb Into
 GC/HS system
 (Method 6240)
       Analyze
        each
    calibration
   atanderd for
both cartridges
    (aee 7.3]
7.2.31
     » Prepare
    calibration
atandarde using
flaah avaporat.
    technique
7.2.5
                                                    7.4.1
 Qualitatively
   Identify
volatile POHCs
(Method 8240)
      Tabulate
  area reaponae
  and calculate
raaponae factor
7.2.41
Direct gmm flow
 through trapa
   o
Verify reaponae
factor each day
                          7.5.1
  Use primary
characteristic
   Ion for
quantification
                                                    7.5.1.1
    Calculate
    amount of
   analyte In
     aample
                      5040 -  10
                                                Revision       0
                                                Date  September 1986

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                                         METHOD 5040

                         PROTOCOL FOR ANALYSIS OF SORBENT CARTRIDGES

                            FROM VOLATILE ORGANIC SAMPLING TRAIN
                                          (Continued)
                                                                              7.5.i.elOuallfy
                                                                                      data
                                                    Is concentr.
                                  Sum
                          •mount of POHCs
                             of interest
                            over Z traps
                               with regard
                              to  validity:
                              report blank
                           data separately
   Oo Internal
stand, recoveries
  fall outside
     control
      limit
                                                                              accuracy of the
                                                                               data  for all
                                                                               •nalytes from
                                                                              that cartridge
                           Blank correct
                           using paired
                              t-test
                                                    7.5.1.3  Find
                                                             mean
                              trip
                          different from
                           field blanks?
    and standard
    deviation of
  combined field
 and trip blanks
Use field blank
as blank value
                                                         Determine
                                                       if sample  is
                                                        different
                                                       from blank
                             Is cample
                          different from
                              blank?
   Blank correct
  •mission value
       of a
 particular POHC
  Use measured
sample value to
calculate a
•mlaslon value
                                    5040 - 11
                                                               Revision       o
                                                               Date   September  1986

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4.2  SAMPLE PREPARATION METHODS


     4.2.2  CLEANUP
                                   FOUR - 8
                                                          Revision
                                                          Date  September 1986

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                                 METHOD 3600

                                   CLEANUP
1.0  SCOPE AND APPLICATION

     1.1  General;

          1.1.1  Injection of extracts 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:    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):    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   Hazardous   Substance Lists.   GPC is
     usually not applicable  for  eliminating extraneous peaks  on a  chromatogram
     which  interfere with  the analytes  of  interest.

           1.2.4 Sulfur  cleanup:   Useful   in  eliminating   sulfur  from sample
     extracts,  which may cause   chromatographic   interference with  analytes of
     interest.
                                   3600 - 1
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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 1n 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 compo-
sition 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.

                                   3600  - 2
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TABLE 1.  RECOMMENDED CLEANUP TECHNIQUES FOR INDICATED GROUPS OF COMPOUNDS
Analyte Group
Determinative3
   Method
   Cleanup
Method Option
Phenols                                 8040
Phthalate esters                        8060
Nitrosamines                            8070
Organochlorlne pesticides & PCBs        8080
Nitroaromatlcs and cyclic ketones       8090
Polynuclear aromatic hydrocarbons       8100
Chlorinated hydrocarbons                8120
Organophosphorous pesticides            8140
Chlorinated herbicides                  8150
Priority pollutant semivolatiles     8250, 8270
Petroleum waste                      8250, 8270
                 3630b, 3640, 3650, 8040C
                        3610, ,3620, 3640
                        3610, 3620, 3640
                        3620, .3640, 3660
                              3620, 3640
                        3611, 3630, 3640
                              3620, 3640
                              3620, 3640
                                    8150d
                        3640, 3650, 3660
                              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 Method 8150  Incorporates an  acid-base  cleanup  step as an Integral part of
the method.
                                   3600 -  3
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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 Inter-
ferences prevent analysis.  However,  the  experience of the analyst may prove
invaluable in determining which cleanup  methods  are needed.   As indicated 1n
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 deter-
mination depends on the selectivity  of  both the extraction procedure and the
determinative method and the required detection limit.

     7.5  Following cleanup, the sample 1s  concentrated to whatever volume 1s
required 1n the determinative method.    Analysis  follows as specified 1n 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 1s
applied to actual  samples.

     8.2  For sample extracts   that  are  cleaned  up,  the associated quality
control samples  (e.g.,  spikes,  blanks,  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.
                                   3600 - 4
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   METHOD 36OO

     CLEANUP
(    —    )
  7. 1
    Oo solvent
    extraction
  7.Z
        Analyze
     analyte  by
   determinative
    method from
      Sec. 4.3
                           7.3     Use
                                » cleanup
                                 method
                            specified for
                            the determin-
                             ative method
 Are analytes
undeterminable
due to Inter-
  ferences?
                            Concentrate
                             •ample to
                          required volume
  3600  - 5
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                             Date  September 1986

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                                 METHOD 3610

                           ALUMINA COLUMN CLEANUP
1.0  SCOPE AND APPLICATION

     1.1  Scope;  Alumina 1s  a  highly  porous  and granular form of aluminum
oxide.  It is available in  three  pH  ranges (basic, neutral,  and acidic)  for
use  in  column  chromatography.    It  1s  used  to  separate  analytes  from
interfering compounds of a different chemical polarity.

     1.2  General Applications  (Gordon and Ford):

          1.2.1  Basic (B) pH   (9-10):    USES:    Basic and neutral compounds
     stable to alkali,  alcohols,  hydrocarbons,  steroids, alkaloids, natural
     pigments.  DISADVANTAGES:    Can  cause polymerization, condensation, and
     dehydration reactions; cannot use acetone or ethyl acetate as eluants.

          1.2.2  Neutral  (N):   USES:    Aldehydes,  ketones, quinones, esters,
     lactones, glycoside.  DISADVANTAGES:    Considerably less active than the
     basic form.

          1.2.3  Addle  (A) pH  (4-5):    USES:    Acidic pigments  (natural and
     synthetic), strong  acids  (that  otherwise   chemlsorb to neutral and basic
     alumina).

          1.2.4  Activity grades:  Acidic,   basic,   or  neutral alumina can be
     prepared  in various  activity grades  (I  to  V),  according to  the Brockmann
     scale, by addition  of H20   to  Grade  1 (prepared by heating  at 400-450*C
     until no  more  H20 is lost).  The  Brockmann  scale  (Gordon and  Ford,
     p. 374)  is  reproduced below:

          Water  added  (wt. %):       0      3        6        10       15
          Activity  grade:            I      II      III       IV        V
          RF  (p-aminoazobenzene):   0.0    0.13     0.25     0.45     0.55

      1.3  Specific  applications;  This method  includes guidance for cleanup of
 sample  extracts  containing  phthalate  esters   and   nitrosamines.   For alumina
 column  cleanup of petroleum wastes, see Method  3611.


 2.0  SUMMARY  OF  METHOD

     2.1  The  column  1s  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.
                                   3610 - 1
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                                                          Date   September 1986

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3.0  INTERFERENCES

     3.1  A reagent blank should  be  performed  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  Chromatography column;  300-mm x  10-mm  I.D., with Pyrex glass wool
at bottom and a Teflon stopcock.
     NOTE:  Fritted glass  discs  are  difficult to decontaminate after highly
     contaminated extracts have been  passed  through.   Columns without frits
     may be purchased.  Use  a  small  pad  of  Pyrex glass wool  to retain the
     adsorbent.  Prewash the glass wool pad  with 50 ml of acetone followed by
     50 mL of elution solvent prior to packing the column with adsorbent.

     4.2  Beakers;  500-mL.

     4.3  Reagent bottle;  500-mL.

     4.4  Muffle furnace.

     4.5  Kuderna-Danish  (K-D)  apparatus;

          4.5.1  Concentrator tube:   10-mL, graduated  (Kontes K-570050-1025 or
     equivalent).  Ground-glass  stopper  is   used  to  prevent  evaporation of
     extracts.

          4.5.2  Evaporation    flask:       500-mL    (Kontes   K-570001-500  or
     equivalent).  Attach  to concentrator tube with springs.

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

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

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

     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  Vials;   Glass,  2-mL capacity, with  Teflon-lined screw  cap.

     4.9  Erlenmeyer  flasks;  50- and 250-mL.
                                   3610 - 2
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                                                          Date   September  1986

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5.0  REAGENTS

     5.1  Sodium sulfate;  (ACS)  Granular,   anhydrous (purified by heating at
400*C for 4 hr in a shallow tray).

     5.2  Eluting solvents;

          5.2.1  D1ethyl ether:  Pesticide quality or equivalent.

               5.2.1.1  Must be free of  peroxides,  as  indicated by EM Quant
          test strips (test strips  are  available  from EM Laboratories Inc.,
          500 Executive Blvd., Elmsford, New York 10523).

               5.2.1.2  Procedures recommended  for  removal  of peroxides are
          provided with the test strips.    After cleanup, 20 ml ethyl alcohol
          preservative must be added to each liter of ether.

          5.2.2  Methanol, pentane,  hexane,  methylene  chloride:   Pesticide
     quality or equivalent.

     5.3  Alumi na;

          5.3.1  For cleanup of phthalate extracts:  Alumina-Neutral, activity
     Super I, W200 series  (ICN Life  Sciences  Group, No. 404583).  To prepare
     for use, place  100  g  of  alumina  into  a  500-mL  beaker and heat for
     approximately 16 hr  at  400*C.    After  heating,  transfer  to a 500-mL
     reagent bottle.  Tightly seal and  cool  to room temperature.  When cool,
     add 3 mL of reagent water.  Mix thoroughly by shaking or rolling for
     10 min and let it   stand  for  at  least  2  hr.    Keep the bottle sealed
     tightly.

          5.3.2  For cleanup of nitrosamlne extracts:  Alumina-Basic, activity
     Super  I,  W200  series   (ICN   Life   Sciences  Group,  No.  404571,  or
     equivalent).  To prepare for use,  place  100  g of alumina into a 500-mL
     reagent  bottle  and  add  2  mL   of  reagent  water.    Mix  the alumina
     preparation thoroughly by  shaking  or rolling  for 10 min and  let it stand
     for at least  2 hr.    The  preparation  should be homogeneous before  use.
     Keep the bottle sealed tightly to  ensure proper  activity.

     5.4  Reagent  water;   Reagent  water  is  defined   as  water  in which an
 interferent is  not observed at  the  method detection  limit  of the  compounds of
 interest.
 6.0   SAMPLE COLLECTION,  PRESERVATION,  AND  HANDLING

      6.1  See the introductory  material   to   this   chapter,  Organic  Analytes,
 Section 4.1.
                                   3610 - 3
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                                                          Date   September  1986

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7.0  PROCEDURE

     7.1  Phthalate esters;

          7.1.1  Reduce the sample extract  volume  to  2 ml prior to cleanup.
     The extract solvent must be hexane.

        .  7.1.2  Place 10 g of alumina Into a chromatographlc column to settle
     alumina and.add 1 cm of anhydrous sodium sulfate to the top.

          7.1.3  Pre-elute the column with 40 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, quantitatively transfer
     the 2-mL sample extract  onto  the  column  using  an  additional 2 ml of
     hexane to complete the transfer.    Just  prior to exposure of the sodium
     sulfate layer to the air, add 35 ml_ of hexane and continue the elutlon of
     the column.  Discard this hexane eluate.

          7.1.4  Next, elute the column  with  140  ml  of  20% ethyl ether 1n
     hexane (v/v) into a 500-mL  K-D  flask equipped with a 10-mL concentrator
     tube.   Concentrate  the  collected  fraction.    No  solvent exchange 1s
     necessary.  Adjust  the  volume  of  the  cleaned  up extract to whatever
     volume 1s required (10.0 ml for Method 8060) and analyze.  Compounds that
     elute in this fraction are as follows:

                    Bis(2-ethylhexyl) phthalate
                    Butyl benzyl phthalate
                    D1-n-butyl phthalate
                    Diethyl phthalate
                    Dimethyl phthalate
                    Di-n-octyl phthalate.

     7.2  Nitrosamines;

          7.2.1  Reduce the sample extract to 2 ml prior to cleanup.

          7.2.2  Diphenylamine, if  present  in  the  original sample extract,
     must be separated from  the  nitrosamines if N-nitrosodiphenylamine 1s to
     be determined by this method.

          7.2.3  Place 12 g  of  the  alumina  preparation  into  a  10-mm I.D.
     chromatographic column.  Tap the column to settle the alumina and add
     1-2 cm of anhydrous sodium sulfate to the top.

          7.2.4  Pre-elute  the  column  with  10  ml  of  ethyl ether/pentane
     (3:7)(v/v).  Discard the eluate  (about  2  ml) and just prior to exposure
     of the sodium sulfate layer to  the air, quantitatively transfer the 2-mL
     sample extract onto the column  using   an  additional  2 ml of  pentane to
     complete  the transfer.
                                  3610 - 4
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                                                         Date  September 1986

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          7.2.5  Just prior to exposure  of  the  sodium  sulfate  layer to  the
     air,  add 70 ml of ethyl  ether/pentane (3:7) (v/v).   Discard the first
     10 ml of eluate.  Collect  the  remainder  of  the eluate in  a 500-mL  K-D
     flask equipped with a 10-mL concentrator tube.   This  fraction contains
     N-n1troso-di-n-propylami ne.

          7.2.6  Next, elute the  column  with  60  ml   of ethyl ether/pentane
     (1:1)(v/v), collecting the eluate in  a  second 500-mL K-D flask equipped
     with  a 10-mL concentrator tube.   Add  15 mL of  methanol  to the K-D flask.
     This  fraction will contain N-nitrosodimethylamine, most of the N-nitroso-
     di -n-propylamirie, and any diphenylamine that is present.

          7.2.7  Concentrate both fractions,  but  use   pentane to prewet  the
     Snyder column.  When the apparatus  is cool, remove the Snyder column  and
     rinse the flask and its lower joint into the concentrator tube with
     1-2 mL of pentane.  Adjust  the   final  volume  to  whatever is required in
     the appropriate  determinative  method  (Section  4.3  of  this chapter).
     Analyze the fractions.


8.0  QUALITY CONTROL

     8.1  Refer to Chapter  One  for  specific  quality control procedures  and
Method 3600 for cleanup procedures.

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

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

     9.1  Refer to the determinative methods for performance data.


10.0  REFERENCES

1.  Gordon, A.J.  and  R.A.   Ford,  The  Chemist's  Companion;   A Handbook of
Practical Data, Techniques, and  References(NewYork:John Wiley & Sons,
Inc.), pp. 372, 374, and  375,  1972.

2.  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.
                                  3610 - 5
                                                         Revision      0
                                                         Date  September 1986

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                            METHOD 361O

                      ALUMINA COLUMN CLEANUP
7.1.1
 Reduce cample
 extract volume
    to Z mL
7.1.2
                                                    7.Z.I
        Place
       alumina
Into chromato-
graphic column:
 aod anhydrous
sodium sulfate
7.1.3
   Pre-elute
  column with
    hexane
7.1.3
       Transfer
 •ample extract
     to column:
   •lute column
    with hexane
7.1.4
        Elute
       column
    with ethyl
ether in hexane
    Into flask
    Reduce cample
   extract volume
       to 2 mL
                                                 7.2.3
    Place alumina
    preparation in
   chromatographic
    column:  ado
  anhydrous sodium
      •ulfate
                                                 7.3.4
Pre-elute column with
 ethyl ether/pentane:
  transfer to column
   •nd edd pentane
                                                    7.2.3
        Elute with
       ethyl ether
        In pentane
        Into flask
                                                 7.a.6
  Elute column with
 ethyl ether/pentane:
  collect eluate In
    second flask:
    •dd methanol
7.1.4J

  Concentrated
    collected
    fraction;
 adjust volume
                                                 7.2.7
   Concentrate both
   fractions;  prewet
  Snyder column with
    pentane:  adjust
        volume
                       3610 - 6
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                                                  Date   September  1986

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                                 METHOD 3611

          ALUMINA COLUMN CLEANUP AND SEPARATION OF PETROLEUM WASTES
1.0  SCOPE AND APPLICATION

     1.1  Method 3611 was formerly Method  3570  in the Second Edition of this
manual.

     1.2  Scope;  Alumina is  a  highly  porous  and granular form of aluminum
oxide.  It is available in  three  pH  ranges (basic, neutral, and acidic) for
use  in  column  chromatography.    It  is  used  to  separate  analytes  from
interfering compounds of a different chemical polarity.

     1.2  General Applications  (Gordon and Ford):

          1.2.1  Basic  (B) pH   (9-10):    USES:    Basic and neutral compounds
     stable to alkali,  alcohols,  hydrocarbons,  steroids, alkaloids, natural
     pigments.  DISADVANTAGES:    Can  cause polymerization, condensation, and
     dehydration reactions; cannot use acetone or ethyl acetate as eluants.

          1.2.2  Neutral  (N):   USES:    Aldehydes,  ketones, quinones, esters,
     lactones, glycoside.  DISADVANTAGES:    Considerably less active than the
     basic form.

          1.2.3  Acidic (A) pH  (4-5):    USES:    Acidic pigments  (natural and
      synthetic), strong acids  (that  otherwise   chemisorb to neutral and  basic
     alumina).

          1.2.4  Activity grades:  Acidic,   basic,   or  neutral alumina can be
     prepared  in various  activity grades  (I  to  V),  according to  the Brockmann
      scale, by  addition of H20   to  Grade  1 (prepared  by heating  at 400-450'C
      until no more  H20  is lost).    The  Brockmann  scale  (Gordon  and Ford, p.
      374) is reproduced below:

          Water added (wt. %):       0       3        6        10        15
          Activity  grade:             I       II      III       IV        V
          RF  (p-aminoazobenzene):   0.0    0.13     0.25    0.45      0.55

      1.3  Specific  applications:  This method  includes  guidance for separation
 of petroleum wastes into aliphatic, aromatic,  and  polar fractions.


 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.
                                   3611  - 1
                                                          Revision
                                                          Date   September 1986

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3.0  INTERFERENCES

     3.1  A reagent blank should  be  performed  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.

     3.3  Caution must be taken to  prevent overloading of the chromatographic
column.  As the column loading for any of these types of wastes approaches
300 mg  of  extractable  organics,  separation  recoveries  will   suffer.   If
overloading is suspected,  an  aliquot  of  the  base-neutral extract prior to
cleanup may  be  weighed  and  then  evaporated  to  dryness.    A gravimetric
determination on the aliquot will  indicate the weight of extractable organics
in the sample.


4.0  APPARATUS AND MATERIALS

     4.1  Chroniatography column;  300-mm x  10-mm  I.D., with Pyrex glass wool
at bottom and a Teflon stopcock.
     NOTE:  Fritted glass  discs  are  difficult to decontaminate after highly
     contaminated extracts have been  passed  through.   Columns without frits
     may be purchased.  Use  a  small  pad  of  Pyrex glass wool to retain the
     adsorbent.  Prewash the glass wool pad  with 50 ml of acetone followed by
     50 ml of elution solvent prior to packing the column with adsorbent.

     4.2 .Beakers;  500-mL.

     4.3  Reagent bottle;  500-mL.

     4.4  Muffle furnace.

     4.5  Kuderna-Danish  (K-D)  apparatus;

          4.5.1  Concentrator tube:  10-mL, graduated  (Kontes K-570050-1025 or
     equivalent).  Ground-glass   stopper  is  used  to  prevent evaporation of
     extracts. .

          4.5.2  Evaporation    flask:       500-mL    (Kontes   K-570001-500  or
     equivalent).  Attach to concentrator tube with springs.

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

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

     4.6  Boiling  chips:  Solvent extracted,  approximately  10/40  mesh  (silicon
 carbide or  equivalent).
                                   3611 -  2
                                                          Revision      0
                                                          Date  September  1986

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     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  Erlenmeyer flasks;  50- and 250-mL.
5.0  REAGENTS

     5.1  Sodium sulfate;  (ACS)  Granular,   anhydrous (purified by heating at
400°C for 4 hr in a shallow tray).

     5.2  Eluting solvents;   Methanol,   hexane,  methylene chloride (pesticide
quality or equivalent).
                                                                         i
     5.3  Alumina;  Neutral  80-325  MCB  chromatographic grade or equivalent.
Dry alumina overnight at 130*C prior to use.

     5.4  Reagent water;   Reagent  water  is  defined  as  water  in which an
interferent is not observed at the  method detection limit of the compounds of
interest.
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 suggested that  Method  3650,  Acid-Base Partition Cleanup, be
performed  on the sample extract prior to alumina cleanup.

     7.2   Fill the glass chromatographic  column  to  about 20 cm with hexane.
Weigh out  10.0 g of alumina and add the alumina to the column.  Gently tap the
column to  distribute  the  alumina  evenly   (minimize chromatographic voids).
Alternatively, a slurry of alumina in hexane may be used to pack the column.

     7.3   Allow the alumina to settle and  then  add 1.0 g of anhydrous sodium
sulfate on top of the  alumina.

     7.4   Elute the column with 50 mL of hexane.  Let the solvent flow through
the column until the head of the  liquid in the column is just above the sodium
sulfate layer.  Close  the stopcock to stop solvent flow.

     7.5   Transfer 1.0 mL  of  sample  extract  onto  the  column.   Rinse out
extract vial with 1 mL hexane and add  it to the column immediately.  To avoid
overloading the column, it is suggested  that  no  more than 300 mg of extrac-
table organics be placed on the column (see Paragraph 3.3).
                                  3611 - 3
                                                         Revision
                                                         Date  September 1986

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     7.6  Just prior to exposure of the  sodium  sulfate to the air,  elute the
column with a total of 15 ml of hexane.   If the extract is in 1 ml of hexane,
and if 1 ml of hexane was  used  as  a  rinse,  then 13 ml of additional  hexane
should be used.  Collect the effluent in a 50-mL flask and label this fraction
"base/neutral aliphatics."  Adjust the flow rate to 2 mL/min.

     7.7  Elute the column with 100  ml  of methylene -chloride and collect the
effluent in a 250-mL flask.  Label this fraction "base/neutral aromatics."

     7.8  Elute the column with 100 ml of methanol  and collect the effluent in
a 250-mL flask.  Label this fraction "base/neutral  polars."

     7.9  Concentrate the extracts by  the  standard K-D technique to whatever
volume is required  (1-10 mL)  in the appropriate determinative method (Section
4.3 of this chapter).    Analyze  whichever  fractions contain the analytes of
interest.
8.0  QUALITY CONTROL

     8.1  Refer to Chapter  One  for  specific  quality control procedures and
Method 3600 for cleanup procedures.

     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   The  precision   and   accuracy   of   the   method   will   depend  upon  the
 overall performance  of the  sample  preparation  and analysis.

      9.2   A  rag  oil  sample  was analyzed   by  a  number  of  laboratories according
 to the  procedure outlined in  this   method.   The  results of  these  analyses  for
 selected  components  in the  rag  oil   are presented in Table 1.  Reconstructed
 ion  chromatograms from the  GC/MS analyses are  included as Figures  1 and  2.


 10.0  REFERENCES
             r
 1.   Gordon,  A.J.  and R.A.  Ford,   The   Chemist's Companion;   A Handbook of
 Practical  Data,  Techniques, and References(NewYork:John Wiley & Sons,
 Inc.),  pp. 372,  374,  and 375,  1972.

 2.   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.
                                   3611 - 4
                                                          Revision      0
                                                          Date  September 1986

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Table 1.  RESULTS OF ANALYSIS FOR SELECTED COMPONENTS IN RAG OIL
Compound
Naphthalene
Fluorene
Phenanthrene
2-Methyl naphthalene
Dibenzothiophene
Methyl phenanthrene
Methyl di benzothl ophene
Mean
Cone. (ug/g)a
216
140
614
673
1084
2908
2200
Standard
Deviation
42
66
296
120
286
2014
1017
%RSDb
19
47
18
18
26
69
46
                                                                         • n
                                Average Surrogate Recoveries
Nitrobenzene-ds                      58.6            11
Terphenyl-dj4                        83.0             2.6
Phenol-de                            80.5          27.6
Naphthalene-dg                       64.5           5.0
a Based on five determinations from three laboratories.

b Percent Relative Standard Deviation.
                                   3611  - 5
                                                          Revision
                                                          Date   September 1986

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                                  »IC                                         MTAi 0NNMI II .
                                  •1/27/04 Ut*tM                             CM.li 27CM.I II
                                  SMVLEi RAG OIL HM.9M. lilt OIL O.IOMH SMflE COCO MM. FRAC IOUG 55
                                  RANGE I C   I.2WO  LABEL i N 0. 4.«  QUMIi A  A. 1.0  BASEi U ?«,  3
 SCMIS  2ft TO 2790
OUT OF  200 10 2W*
                     HM.O
    OJ
    CT>
                        itC
O 73
Oi fD
r+ <
a> ->•
  00

C/) O
(T> 3
O
r+

i
CT
C»
                                        uuJ,
                7452^.
                                                                                                       T
                               Figure  1.   Reconstructed Ion chromatogram from GC/MS  analysis of the aromatic
                                           fraction from Rag 011

-------
                                    •1C                                          MTAi CRMM. II
                                    •I/IT/M IfcXlM                             CM.li 27011 •!
                                    SMflCt tflC OIL FV-I.3H. « IS •.IOMH SMflC CRCO M.IPH. FPrtC IflUC SS
                                    RMCCt C  I.27M UttCLt N •. <.S OIWHi A 9. 1.9 BftSCt  U 70.  3
OUT OF  2M TO
                      HM.e
     CO
o ^j
01 n>
<-t <
n> -••
   CO

co o
n> 3
o
rf
0)1
c»
               777379.
                                Figure 2.  Reconstructed 1on chromatogram from GC/MS  analysis of the  aliphatic
                                            fraction  from Rag 011

-------
                            METHOD 3611

     ALUMINA COLUMN CLEANUP AND SEPARATION OF PETROLEUM WASTES
 7. 1
                                                        o
    Cleanup
  using Method
     3650
 7.2
                                                  7.6
 Elute column with
  hexane:  collect
  eluent In flask;
label 'base-neutral
    allphatlcs*
       Fill
chromatographlc
  column with
  hexane:  add
    alumina
 7.3
                                                  7.7
 Elute column with
methylene chloride;
   collect eluent
  In flask:  label
  'base-neutral
    aromatlcs"
  Add anhydrous
 sodium sulfate
    on top of
    alumina
 7 .4
                                                 7.B
 Elute column with
 methanol:  collect
  eluent In flask;
label 'base—neutral
     polars"
  Elute column
  with hexane
                                                     7.9
    Concentrate
     extracts
 7.5
        Put
       sample
   extract onto
  column:  rinse
   extract vial
   with hexane
    0
                               3611 - 8
                                                          Revision        0
                                                          Date  September 1986

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                                 METHOD 3620

                           FLORISIL COLUMN CLEANUP
1.0  SCOPE AND APPLICATION

     1.1  Florisil,  a  registered  tradename  of   the  Floridin  Co.,   is  &
magnesium silicate with acidic  properties.    It  is  used for general  column
chromatography  as  a  cleanup  procedure  prior  to  sample  analysis  by gas
chromatography.

     1.2  General applications;    Cleanup  of  pesticide  residues  and other
chlorinated  hydrocarbons;   the   separation   of   nitrogen  compounds  from
hydrocarbons; the  separation  of  aromatic  compounds from aliphatic-aromatic
mixtures;  and  similar  applications  for  use  with  fats,  oils,  and waxes
(Floridin).  Additionally, Florisil  is  considered  good for separations with
steroids,  esters,  ketones,  glycerides,  alkaloids,  and  some carbohydrates
(Gordon and Ford).

     1.3  Specific applications;  This method includes guidance for cleanup of
sample extracts containing  the  following  analyte  groups: phthalate esters;
nitrosamines;   organochlorine    pesticides;    nitroaromatics;   haloethers;
chlorinated hydrocarbons; and organophosphorous pesticides.


2.0  SUMMARY OF METHOD

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

     3.1  A reagent blank should  be  performed  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  Beaker;  500-mL.

     4.2  Chromatographic column;  300-mm long  x  10-mm I.D. or 400-mm long x
20-mm I.D., to be specified in  Paragraph  7.0; 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

                                  3620 - 1
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                                                         Date  September 1986

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     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).  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.

          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).

     4.4  Muffle furnace.

     4.5  Reagent bottle;  500-mL.

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

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

     4.8  Erlenmeyer flasks;  50- and 250-mL.


5.0  REAGENTS

     5.1  Florisil:  Pesticide  residue   (PR)  grade   (60/100 mesh); purchase-
activated at  1250*F  (677'C),  stored  in  glass  containers with ground-glass
stoppers or foil-lined  screw  caps.

          5.1.1  Deact1vat1on of  Flor1s1l:   for  cleanup of phthalate esters.
     To prepare  for use, place 100  g of Florisil  into  a 500-mL beaker and  heat
     for approximately  16 hr  at   40°C.     After   heating, transfer to a 500-mL
     reagent  bottle.  Tightly seal  and   cool  to room temperature.  When  cool
     add 3 mL of reagent water:   Mix thoroughly by shaking or rolling for
     10 min and  let stand for at  least 2  hr.   Keep the bottle sealed tightly.

          5.1.2  Activation   of   Florisil:     for  cleanup  of  nitrosamines,
     organochlorine   pesticides    and    PCBs,    nitroaromatics,   haloethers,
     chlorinated hydrocarbons, and  organophosphorous   pesticides.  Just before
     use, activate each batch at   least   16  hr   at 130°C in a glass container
     loosely  covered with aluminum  foil.   Alternatively,  store the Florisil in
     an oven  at  130*C.    Cool   the  .Florisil   before   use  in a desiccator.
                                  3620 - 2
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                                                         Date  September 1986

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     (Florlsil  from  different  batches  or  sources   may  vary  in  adsorptive
     capacity.   To standardize the amount  of  Florisil  which  is  used,  the use
     of 1 auric  acid value is  suggested.    The referenced procedure  determines
     the adsorption  from  hexane  solution  of  lauric   acid   (mg)   per  g of
     Florisil.    The  amount  of  Florisil   to  be  used  for   each   column is
     calculated by  dividing  110  by  this  ratio  and   multiplying  by  20 g
     (Mills).)

     5.2  Sodium sulfate (ACS):   Granular,  anhydrous (purified  by  heating at
400*C for 4 hr in a shallow tray).

     5.3  Eluting solvents;

          5.3.1  Dlethyl ether:  Pesticide quality or equivalent.

               5.3.1.1  Must be free  of  peroxides  as  indicated by EM Quant
          test strips   (available  from  EM  Laboratories  Inc.,  500 Executive
          Boulevard, Elmsford, NY 10523).

               5.3.1.2  Procedures recommended  for  removal  of peroxides are
          provided with the test strips.    After cleanup, 20 ml ethyl alcohol
          preservative  must be added to each liter of ether.

          5.3.2  Acetone;  hexane; methylene chloride; pentane; petroleum ether
      (boiling  range 30-60'C):  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   Phthalate  esters;

           7.1.1   Reduce  the  sample  extract   volume  to  2 mL prior to cleanup.
      The  extract  solvent must  be  hexane.

           7.1.2   Place 10 g  of  Florisil   into   a  10-mm I.D.  chromatographic
      column.  Tap the column to settle  the Florisil  and add 1  cm of anhydrous
      sodium sulfate  to the top.

           7.1.3   Preelute the  column  with 40 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, quantitatively transfer
      the  2-mL sample extract  onto  the  column   using  an  additional  2  mL of
      hexane to complete  the  transfer.    Just  prior  to exposure of the sodium
      sulfate layer to the air,  add  40 mL of hexane and continue the elution of
      the  column.   Discard this hexane eluate.
                                   3620 - 3
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                                                          Date   September  1986

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         7.1.4  Next, elute the column  with  100  ml  of  20% ethyl ether in
    hexane  (v/v)  into a 500-mL  K-D  flask equipped with a 10-mL concentrator
    tube.   Concentrate  the  collected  fraction.    No  solvent exchange is
    necessary.  Adjust  the  volume  of  the  cleaned-up  extract to whatever
    volume  is  required   (10  ml  for   Method  8060)  and  analyze  by  gas
    chromatography.  Compounds that elute in this fraction are:

                Bi s(2-ethylhexyl)phthalate
                Butyl benzyl phthalate
                Di-n-butyl phthalate
                Diethyl phthalate
                Dimethyl phthalate
                Di-n-octyl phthalate

    7.2  Nitrosamines;

         7.2.1  Reduce the sample extract volume to 2 ml prior to cleanup.

         7.2.2  Place  22  g  of   activated    Fjlorisil  into  a  20-mm  I.D.
    chromatographic  column.  Tap the   column  to  settle the Florisil and add
    about  5 mm  of anhydrous  sodium sulfate to the top.

         7.2.3  Preelute the column with 40 ml  of ethyl ether/pentane  (15:85)
     (v/v).  Discard  the  eluate  and,  just  prior  to  exposure of  the  sodium
    sulfate layer to the air, quantitatively transfer the  2-mL sample extract
    onto the  column  using  an   additional  2  ml  of  pentane to  complete the
    transfer.

         7.2.4   Elute the  column with  90  ml   of ethyl ether/pentane  (15:85)
     (v/v)   and  discard   the eluate.      This  fraction   will   contain  the
    diphenylamine,  if it  is  present  in the extract.

          7.2.5   Next,  elute  the  column  with   100  ml  of  acetone/ethyl ether
     (5:95)  (v/v)  into a  500-mL   K-D   flask equipped with  a 10-mL  concentrator
     tube.   This fraction  will  contain  all   of  the  nitrosamines  listed  in the
     scope  of  the  method.

          7.2.6   Add 15 mL of methanol  to  the  collected fraction,  concentrate
     using  pentane to prewet  the K-D   column   and   set  the  water  bath at 70  to
     75*C.   When the apparatus  is  cool, remove  the Snyder  column  and rinse the
     flask  and its lower joint  into  the   concentrator   tube with  1  to  2 mL  of
     pentane.   Analyze by  gas chromatography.

     7.3  Organochlorine    pesticides,    haloethers,    and    organophosphorous
pesticides   (seeTables1   and2forfractionationpatternsof compounds
tested):

          7.3.1   Reduce the sample  extract  volume   to   10  mL prior to cleanup.
     The extract solvent  must be hexane.
                                  3620 - 4
                                                         Revision
                                                         Date  September 1986

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     7.3.2  Add a weight of  Flor1s1l   (nominally 20 g),  predetermined by
calibration, to a 20-mm I.D. chromatographic column.  Settle the Florisil
by tapping the column.  Add  anhydrous  sodium  sulfate to the top of the
Florisil to form a layer 1 to 2 cm  deep.  Add 60 ml of hexane to wet and
rinse the sodium sulfate and  Florisil.    Just  prior to exposure of the
sodium sulfate to air,  stop  the  elution  of  the hexane by closing the
stopcock on the chromatographic column.  Discard the eluate.

     7.3.3  Adjust the sample extract  volume  to  10  ml with hexane and
transfer it from the K-D concentrator tube to the Florisil column.  Rinse
the tube twice with 1-2 ml hexane, adding each rinse to the column.

     7.3.4  Place a 500-mL K-D  flask  and  clean concentrator tube under
the chromatographic column.  Drain  the  column  into the flask until the
sodium sulfate layer is nearly exposed.  Elute the column with 200 ml of
6% ethyl ether in hexane (v/v)  (Fraction  1)  using a drip rate of about
5 mL/min.  All of the haloethers  are  in  this fraction.  Remove the K-D
flask and set aside  for  later  concentration.   Elute the column again,
using 200 mL of 15%  ethyl  ether  in  hexane  (v/v) (Fraction 2), into a
second K-D flask.  Perform  a  third  elution  using  200 ml of 50% ethyl
ether in hexane (v/v) (Fraction 3),  and  a  final elution with 200 mL of
100% ethyl ether (Fraction 4), into separate K-D flasks.

     7.3.5  Concentrate the eluates by  standard K-D techniques using the
water bath at about 85*C  (75'C for  Fraction 4).  Adjust the final volume
to whatever volume is required (1-10 mL).  Analyze by gas chromatography.

7.4  Nitroaromatics and isophorone;

     7.4.1  Reduce the sample extract volume to 2 mL prior to cleanup.
     7.4.2   Prepare a  slurry  of   10  g
chloride/hexane  (1:9)  (v/v)  and   place
chromatographic  column.   Tap the column
cm of  anhydrous  sodium sulfate to   the
about  2 mL/min.
 activated  Florisil  in methylene
 the  Florisil   into a 10-mrn I.D.
 to settle the  Florisil and add 1
top.   Adjust the elution rate to
      7.4.3   Just  prior to  exposure   of   the   sodium   sulfate  layer to the
 air,  quantitatively  transfer the  sample   extract onto the column  using an
 additional  2 mL  of   hexane   to   complete the  transfer.   Just  prior to
 exposure  of the sodium sulfate layer to  the air, add  30 mL  of methylene
 chloride/hexane (1:9)   (v/v)  and  continue   the  elution  of the column.
 Discard the eluate.

      7.4.4   Next, elute  the column  with   30  mL   of acetone/methylene
 chloride  (1:9)  (v/v)   into  a 500-mL  K-D  flask  equipped   with a  10-mL
 concentrator tube.   Concentrate   the collected fraction, while exchanging
 the  solvent to   hexane.    To exchange   the solvent,  reduce the elution
 solvent to  about  10  mL.  Add 50  mL of  hexane, a fresh boiling chip, and
 return the  reassembled K-D apparatus to  the  hot water bath.   Adjust  the
                              3620 - 5
                                                     Revision       0
                                                     Date  September  1986

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                         TABLE 1

      DISTRIBUTION OF CHLORINATED PESTICIDES,  PCBs,
      AND HALOETHERS INTO FLORISIL COLUMN FRACTIONS
Parameter
                                   Percent Recovery by Fraction3
               1
Aldrin
a-BHC
/7-BHC
5-BHC
7-BHC
Chlordane
4,4'-DDD
4,4'-DDE
4,4'-DDT
Dieldrin
Endosulfan I
Ensosulfan II
Endosulfan sulfate
Endrln
Endrin aldehyde
Haloethers
Heptachlor
Heptachlor epoxide
Toxaphene
PCB-1016
PCB-1221
PCB-1232
PCB-1242
PCB-1248
PCB-1254
PCB-1260
100
100
97
98
100
100
99
98
100
0
37
0
0
4
0
R
100
100
96
97
97
95
97
103
90
95









100
64
7 91
0 106
96
68 26






4




aEluant composition:
Fraction 1-6% ethyl  ether In hexane
Fraction 2 - 15% ethyl  ether in hexane
Fraction 3 - 50% ethyl  ether 1n hexane
R = Recovered  (no percent recovery data presented).

SOURCE:  U.S.  EPA and FDA data.
                        3620 - 6
                                               Revision      0
                                               Date  September  1986

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                              TABLE 2

           DISTRIBUTION OF ORGANOPHOSPHOROUS PESTICIDES
                  INTO FLORISIL COLUMN FRACTIONS
                                      Percent Recovery by Fraction*
Parameter
Azinophos methyl
Bolstar (Sulprofos)
Chlorpyrifos
Coumaphos
Demeton
Diazinon
Dichlorvos
Dimethoate

ND
>80
NR
100

NR
ND

ND

NR

100
NR
ND
20
ND

NR


NR
ND
80
ND





ND
Disulfoton 25-40
EPN
Ethoprop
Fensulfothion
Fenthion
Malathion
Merphos
Mevinphos
Monochrotophos
Naled
Parathion
Parathion methyl
Phorate
Ronnel
Stirophos (Tetrachlorvinphos)
Sulfotepp
TEPP
Tokuthion (Prothiofos)
Trichloronate
aEluant composition: Fraction
Fraction
Fraction
Fraction

V
ND
R

V
ND
ND
NR


0-62
>80
ND
V
ND
>80
>80
1 - 200
2 - 200
3 - 200
4 - 200
>80
V
ND
R
5
V
ND
ND
NR
100
100


ND
V
ND


mL of
mL of
mL of
mL of

V
ND

95
V
ND
ND
NR




ND

ND


6% ethyl
15% ethyl
50% ethyl
100% ethyl


ND



ND
ND





ND

ND


ether in hexane
ether in hexane
ether in hexane
ether
R = Recovered  (no percent  recovery  information presented)  (U.S.  FDA).
NR = Not recovered  (U.S. FDA).
V = Variable recovery  (U.S.  FDA).
ND = Not determined.

SOURCE:  U.S.  EPA and  FDA  data.
                              3620 -  7
                                                     Revision       0
                                                     Date   September  1986

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    final volume of the cleaned-up extract to whatever volume is required
    (1-10 ml).  Compounds that elute in this fraction are:

                   2,4-Dinitrotoluene
                   2,6-Dinitrotoluene
                   Isophorone
                   Nitrobenzene.

    Analyze by gas chromatography.

    7.5  Chlorinated  hydrocarbons;

         7.5.1  Reduce  the  sample extract  volume  to  2 ml prior to cleanup.
    The  extract solvent must be  hexane.

         7.5.2  Place 12  g  of   Florisil   into  a  10-mm  I.D. chromatographic
    column.   Tap  the  column to  settle  the  Florisil  and  add 1 to 2  cm of
    anhydrous sodium  sulfate to  the  top.

         7.5.3  Preelute  the column  with 100  ml of  petroleum ether.  Discard
    the  eluate  and, just  prior to exposure of the  sodium  sulfate layer to the
    air,  quantitatively   transfer   the  sample  extract   to  the  column  by
    decantation and subsequent petroleum ether washings.   Discard the eluate.
    Just prior to exposure  of   the   sodium  sulfate  layer to  the air,  begin
    eluting  the column with 200  ml   of petroleum ether and collect the eluate
    in a 500-mL K-D   flask  equipped  with a  10-mL concentrator tube.  This
    fraction  should contain all  of  the chlorinated hydrocarbons:

                2-Chloronaphthalene
                 1,2-Dichlorobenzene
                1,3-Dichlorobenzene
                1,4-Dichlorobenzene
                Hexachlorobenzene
                Hexachlorobutadiene
                Hexachlorocyclopentadiene
                Hexachloroethane
                 1,2,4-Trichlorobenzene.

          7.5.4 Concentrate the  fraction,  using   hexane  to prewet the column.
    When the apparatus is cool,  remove  the Snyder column and  rinse  the  flask
    and  its  lower joint into  the  concentrator  tube with hexane.  Adjust the
     final  volume  of  the cleaned-up  extract to whatever volume  is  required
     (1-10  ml).  Analyze by gas  chromatography.


8.0  QUALITY  CONTROL

     8.1   Refer to Chapter  One   for  specific   quality control  procedures and
Method 3600 for cleanup procedures.

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


                                  3620 - 8
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     8.3  For sample extracts that are cleaned up using this method,  the
associated quality control samples should also be processed through this
cleanup method.


9.0  METHOD PERFORMANCE

     9.1  Table 1 Indicates the distribution of chlorinated pesticides, PCB's,
and haloethers in various Florisll column fractions.

     9.2  Table 2 indicates the distribution of organophosphorous pesticides
in various Florisil column fractions.
10.0  REFERENCES

1.  Gordon, A.J. and R.A. Ford, The Chemist's Companion:  A Handbook of
Practical Data, Techniques, and References  (New York;John Wiley & Sons,
Inc.), pp. 372, 374, and 375,  1972.

2.  Floridin of ITT System, Florisil:   Properties, Application, Bibliography,
Pittsburgh, Pennsylvania, 5M381DW.

3.  Mills, P.A., "Variation of Florisil Activity; Simple Method for Measuring
Absorbent Capacity and  its use in Standardizing Florisil Columns," Journal of
the Association of Official Analytical  Chemists, 51., 29, 1968.

4.  U.S. Food  and Drug  Association, Pesticides Analytical Manual  (Volume  1),
July  1985.

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.
                                   3620 - 9
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                            METHOD 3620

                      FLORISIL COLUMN CLEANUP
7.1.1
       Reduce
     volume of
 •ample extract
      to 2 mL
7.1.2
        Place
       Florisll
 into chromato-
graphic column:
 add anhydrous
•odium sulfate
                                                    7.2.1
         Reduce
       volume of
   sample extract
        to 2 mL
                                                    7.2.2
           Put
         Florlsll
  Into chrometo-
  graphic column:
   add anhydrous
  sodium sulfate
7.1.3| Preelute
        column
   Hlth hexane:
transfer sample
  extract:  add
      hexane
                                                 7.2.3
Preelute column with
ethyl ether/pentane:
transfer ex- tract:
    add pentane
7.1.4
  Elute column
   with ethyl
ether in hexane
                                                    7.2.4
    Elute column
     with ethyl
   •ther/pentane
7.1.41

   Concentrate
    fraction:
 adjust volume:
    analyze
  7.2.5
       I Elute
     column with
    acetone/ethyl
      ether into
        flask
    o
      0
                       3620 - 10
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                                                  Date   September 1986

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                                            METHOD 3630

                                      FLORISIL  COLUMN CLEANUP
                                            (Continued)
                                Q
                   OrganochlorIne
             pesticides,  haloethers
             and ornanoohDsnhorous
          Reduce
        volume of
    cample extract
         tO Z mL
7.3.2
              Nltroaromatlcs
              and Isophorone
    Add Florlsll to
    chromatographlc
      column;  add
   anhydrous medium.
 sulfate then hexane:
    discard eluate
                                     Chlorinated
                                    hydrocaroons
                                    Reduce
                                  volume  of
                              sample extract
                                   to Z mL
          Reduce
        volume of
    sample extract
         to Z mL
7.3.3  Adjust
     I  sample
extract volume:
  transfer to
 column:  rinse
  with  hexane
                         7.5.2
                                                   7.4.2
                                                                                o
                                                 Put Florisil slurry
                                                  in chromatographlc
                                                    " column:  add
                                                   anhydrous sodium
                                                       sulfate
                           Place Florlsll in
                            chromatographic
                              column: add
                           anhydrous sodium
                                sulfate
  	1  Drain
         column:
     elute column
     4 times  into
   separate flasks
   7.3.5
                                                   7.4.3
                                                                                7.3.6
     Add
   methenol
to fraction:
concentrate
                              Transfer sample
                           extract  onto column:
                               add  methylene
                             Chloride/hexane:
                              discard eluate
                         7.5.3
Preelute column with
   petroleum ether;
   transfer sample
  •xtract to column:
   discard eluate
     Concentrate
    luates: adjust
       volume
                                                   7.4.4
                                                  Elute column with
                                                  acetone/ methylene
                                                  chloride:  exchange
                                                  solvent to hexane
   7.5.41

      Concentrate
       fraction:
     adjust final
        volume
                                                   7.4.41

                                                      Concentrate
                                                       fraction:
                                                     adjust final
                                                        volume
      G>
                                        3620 - 11
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                                                                  Date  September  1986

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                                 METHOD 3630

                             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 and derivatized
phenolic compounds.


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   performed  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 I.D.; 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

                                  3630 - 1
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                                                         Date  September 1986

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     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-Dam'sh (K-D) apparatus:
          4.3.1   Concentrator tube:  10-mL,  graduated  (Kontes K-570050-1025 or
     equivalent).  Ground-glass  stopper  Is  used  to  prevent evaporation of
     extracts.
          4.3.2   Evaporation  flask:      500-mL   (Kontes   K-570001-0500   or
     equivalent).  Attach to concentrator tube with springs.
          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).
     4.4  Muffle furnace.
     4.5  Reagent bottle:  500-mL.
     4.6  Water   bath;     Heated,  with  concentric  ring   cover,  capable   of
temperature control (+5*C).  The bath should be used 1n a  hood.
     4.7  Boiling chips:  Solvent extracted, approximately iO/40 mesh (silicon
carbide or equivalent).
     4.8  Erlenmeyer flasks;  50- and 250-mL.
5.0  REAGENTS
     5.1  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.
     5.2  Sodium sulfate (ACS):   Granular,  anhydrous  (purified by heating at
400°C for 4 hr in  a shallow tray).
     5.'3  Eluting  solvents;     Cyclohexane,   hexane,  2-propanol,  toluene,
methylene chloride, pentane  (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.
                                  3630 - 2
                                                         Revision
                                                         Date  September 1986

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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.    Add 1 to 10 ml of the
     sample extract (in methylene chloride) and  a boiling chip to a clean K-D
     concentrator tube.  Add 4 ml  of cyclohexane and attach a two-ball micro-
     Snyder. column.  Prewet the column  by adding 0.5 ml of methyl ene chloride
     to the top.  Place  the  micro-K-D  apparatus  on a boiling (100'C) 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 to 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 the liquid
     reaches 0.5 ml, remove the K-D  apparatus  and allow it to drain and cool
     for at least 10 min.  Remove  the micro-Snyder column and rinse its lower
     joint into the concentrator  tube  with  a minimum amount of cyclohexane.
     Adjust the extract volume to about 2 m!_.

          7.1.2  Prepare a slurry of 10 g of activated silica gel in methylene
     chloride and place this into  a  10-mm  I.D. 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
     elutlons 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
     1s  required  (1-10 ml).   Proceed  with  HPLC  or GC analysis.  Components
     that elute 1n  this fraction are:

                    Acenaphthene
                    Acenaphthylene
                    Anthracene
                    Benzo(a)anthracene
                    Benzo(a)pyrene
                    Benzo(b)f1uoranthene
                    Benzo(ghi)perylene
                    Benzo(k)f1uoranthene
                    Chrysene
                    Dibenzo(a,h)anthracene
                    Fluoranthene
                    Fluorene
                                   3630 - 3
                                                          Revision
                                                          Date   September  1986

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                    Indeno(l,2,3-cd)pyrene
                    Naphthalene
                    Phenanthrene
                    Pyrene
     7.2   Derivatized  phenols;

          7.2.1   This  silica  gel
     extracts that have  undergone
     described  in Method 8040.
cleanup  procedure  is  performed on sample
pentafluorobenzyl  bromide derivatization as
          7.2.2  Place 4.0  g   of  activated   silica   gel   into   a   10-mm  I.D.
     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,  pi pet 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).
8.0  QUALITY CONTROL

     8.1  Refer to Chapter  One  for
Method 3600 for cleanup procedures.
   specific  quality control procedures and
     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
phenolic derivatives using this method.
       information  on   the  fractionation of
                                  3630 - 4
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                                                         Date  September 1986

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10.0  REFERENCES

1.  Gordon, A.J.,  and  R.A.  Ford,  The  Chemist's  Companion;  A Handbook of
Practical Data, Techniques, and  References,(NewYork:John Wiley & Sons,
Inc.), pp. 372, 374, and 375, 1972.

2.  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.
                                   3630 - 5
                                                          Revision
                                                          Date   September 1986

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TABLE 1.  SILICA GEL FRACTIONATION OF PFBB DERIVATIVES

                                         Percent Recovery by Fraction1

Parameter                           1           23
2-Chlorophenol
2-Nitrophenol
Phenol
2, 4-Dimethyl phenol
2, 4-Dichl orophenol
2,4, 6-Tri chl orophenol
4-Chl oro-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.
                                   3630 -  6
                                                          Revision
                                                         Date  September  1986

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                               METHOD 3630

                           SILICA GEL CLEANUP
 7.1
       Exchange
  extract solvent to
 cyclonexane:  distill
  using mlcro-Snyder
    column:  adjust
    extract volume
       to 2 mL
   7.1.8
                       Polynuclear
                        aromatic
                       hydrocarbon
                      7.2.11Do penta-
                           I  fluoro-
                       benzyl bromide
                       derlvatlzatlon
                         on sample
                       extract (8040)
           Put
          silica
    gel.  methylene
   chloride slurry
    In chromato-
   grapnlc column
                                                    7.2.2
                      Place activated
                       silica gel  in
                      chromatographic
                   column:  add anhydrous
                      sodium sulfate
   7.1.8
           Elute
         methylene
     chloride:  add
        anhydrous
    •odium sulfate
7.1.3
                                                       7.2.3
                             Preelute
                              column
                         with hexane:
                        pipet hexane
                         solution on
                        column:  elute
 Preelute column with
   pentane:  transfer
 •xtract onto column;
  elute with pentane
                                                       7.2.4
                                                               Elute
                                                              column
                          with hexane
                          solutions:
                           analyze
                        (Method 6040)
   7.1.41

          Elute
    with nethylcne
       chloride/
        pentane
   7.1.4]

      Concentrate
       fraction;
    adjust volume:
       analyze
Analyze
 by GC
 (Method
 6040)
                          3630  - 7
                                                     Revision       0
                                                     Date   September  1986

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                                 METHOD 3640

                           GEL-PERMEATION CLEANUP
1.0  SCOPE AND APPLICATION

     1.1  Gel-permeation chromatography (GPC)  is  a  size exclusion procedure
using organic solvents and  hydrophobic  gels  in  the separation of synthetic
macromolecules  (Gordon  and  Ford).    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 greater than those of the
molecules to be separated (Shugar, et al.).

     1.2  General  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 (Shugar, et al.).

     1.3  Specific application;  This method  includes guidance for cleanup of
sample extracts containing the compounds  listed  1n Tables 2-1 through 2-9 of
Chapter 2.


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  to  be  analyzed.   Elutlon is
effected with a suitable sol vent(s) and the product 1s 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
method detection limit before this method is performed on actual samples.

     3.2  More extensive procedures than those  outlined  1n this method may be
necessary for reagent purification.


4.0  APPARATUS

     4.1  Gel  permeation  chromatography   system;     (Analytical   Biochemical
Laboratories, Inc. GPC  autoprep  Model  1002A  or  equivalent).  An automated
system of this type is  not   required;  however, if  not used, equivalency  of an
alternative  system must be shown.

          4.1.1  Chromatographtc  column;   600-  to  700-mm  x  25-mm I.D.  glass
     column  fitted for  upward flow  operation.

          4.1.2  B1o-beads S-X3:   70  g per column.


                                   3640 - 1
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          4.1.3  Pump:   Capable of constant  flow  of   0.1  to  5  mL/m1n  at  up  to
     100 psi.
          4.1.4  Injector:   With 5-mL loop.
          4.1.5  Ultraviolet detector:   254-nm (optional).
          4.1.6  Strip-chart recorder:   (optional).
          4.1.7  Syringe:   10-mL with Luerlok fitting.
          4.1.8  Syringe filter holder and filter:   BioRad "Prep Disc"  sample
     filter #  343-0005 and 5-um size filters or equivalent.
     4.2  Beakers;  400-mL.

5.0  REAGENTS   -
     5.1  Methylene chloride;  Pesticide quality or equivalent.
     5.2  GPC  calibration solutions;
          5.2.1  Corn oil:  200 mg/mL in methylene chloride.
          5.2.2  B1s(2-ethylhexyl)phthaiate  and  pentachlorophenol  solution:
     4.0 mg/mL 1n methylene chloride.
          5.2,3  Mix the corn oil with  the  phthalate/phenol solution 1f a UV
     detector  is used.  The concentrations should remain the same.

6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING
     6.1  See  the introductory  material  to  this  chapter, Organic Analytes,
Section 4.1i
                                           \
7.0  PROCEDURE
     7.1  Packing the column;   Place approximately 70 g of Bio Beads SX-3 1n a
400-mL beaker.Cover thebeads  with  methylene chloride; allow the beads to
swell overnight  (before packing the  columns).    Transfer the swelled beads to
the column and start pumping solvent  through   the column, from bottom to top,
at 5.0 mL/min.  After approximately  1 hr, adjust  the  pressure on the column to
7-10 ps1 and pump an additional 4  hr  to  remove air from the column.  Adjust
the column pressure periodically as  required  to  maintain 7-10 psi.  (See the
instrument manual for  more  details  on  packing  the  column.)  The pressure
should not be  permitted to exceed 25 psi.
     7.2  Calibration of the   column;    The  column  can either be calibrated
manually by gravimetric/GC/FID  techniques  or   automatically if a recording UV
detector with  a flow through cell is available.
                                  3640 - 2
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                                                         Date  September 1986

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          7.2.1   Manual  calibration:   Load  5  mL   of  the  corn oil  solution  into
     sample loop No.  1  and 5 mL of the phthalate-phenol  solution  into  loop
     No.  2.  Inject the  corn  oil   and  collect  10-mL fractions  (i.e.,  change
     fractions at 2-min intervals)   for  36  min.  Inject  the  phthalate-phenol
     solution and collect 15 mL fractions for 60 min.   Determine the  corn oil
     elution pattern  by evaporation of each  fraction to dryness  followed  by  a
     gravimetric determination of the  residue.    Analyze  the  phthalate-phenol
     fractions by GC/FID using  a  DB-5  capillary  column, a  UV  spectrophoto-
     meter, or a GC/MS  system.    Plot  the concentration  of each component in
     each fraction versus total  eluant  volume   (or time) from  the injection
     points.  Choose  a  dump time  which  allows   £ 85% removal  of the  corn oil
     and  ]> 85% recovery of the bis(2-ethylhexyl)phthalate.  Choose the collect
     time to extend at  least  10  min  after  the  elution of pentachlorophenol.
     Wash the column  with methylene chloride   at  least 15  min  between  samples.
     Typical parameters selected are:    Dump time,  30 min  (150 mL);  collect
     time, 36 min (180  mL); and wash time,  15 min (75 mL).

          7.2.2  Automated calibration:  The  column  can also  be  calibrated by
     the  use of a 254-nm detector  in  place  of gravimetric and GC analyses of
     fractions.   Use  the  corn  oil/phthalate/phenol  mixture   when using  a UV
     detector.  Load  5  mL into sample  loop  No.  1.  Use the  same criteria for
     choosing dump time and collect time as in the manual  calibration.

          7.2.3  The  SX-3 Bio Beads column  may   be  reused for several months,
     even if discoloration occurs.  Recalibrate the  system once a week.

     7.3   GPC Extract Cleanup;  The extract  must be in  methylene chloride or,
primarily methylene chloride.  All other solvents must be  concentrated to  1 mL
and diluted to  10.0  mL  with  methylene  chloride.    Prefilter  or  load all
extracts  via the filter  holder  to  avoid   particulates that  might cause  flow
stoppage  or damage the valve.  Load one 5.0 mL aliquot of  the extract  onto the
GPC column.  Do not apply  excessive  pressure when  loading.   Purge the sample
loading tubing thoroughly  with  solvent  between  extracts.   After especially
dirty extracts, run a GPC blank  (methylene chloride)  to check for carry-over.
Process the extracts using the  dump,  collect,  and  wash parameters determined
from the  calibration,  and  collect  the  cleaned  extracts  in 400-mL beakers
tightly covered with aluminum  foil.
     NOTE:  Half of the 10.0 mL extract is  lost during the loading of the GPC.
     Therefore,  divide  the   sample  size   by  two   when   calculating analyte
     concentration.

     7.4  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 required final
     volume.
8.0  QUALITY CONTROL

     8.1  Refer to Chapter  One  for  specific  quality control procedures and
Method 3600 for cleanup procedure.
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     8.2  The analyst should demonstrate that  the compound(s) of interest are
being quantitatively recovered before applying this method to actual samples.

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

     9.1  Refer to the determinative methods for performance data.


10.0  REFERENCES

1.  Gordon, A.J.,  and  R.A.  Ford,  The  Chemist's  Companion;  A Handbook of
Practical Data. Techniques, and  References(NewYork:John Wiley & Sons,
Inc.) pp. 372, 374, and 375, 1972.

2.  ShugarG.J., et  al.,  Chemical Technician's Ready Reference Handbook, 2nd
ed. (New York:  McGraw-Hill Book Co.) pp. 764-766, 1981.

3.  Wise, R.H., D.F. Bishop,  R.T. Williams, and B.M. Austern,  "Gel  Permeation
Chromatography in  the  GC/MS  Analysis  of  Organics  in  Sludges," U.S.  EPA,
Municipal Environmental Research Laboratory, Cincinnati, Ohio 45268.

4.  U.S.  EPA  Contract  Laboratory  Program,  Statement  of  Work for Organic
Analysis, Revision, July 1985.
                                   3640 - 4
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                                                          Date   September 1986

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                              METHOD 3640

                        GEL-PERMEATION CLEANUP
7. 1
Be
adjust
Pack
CO lumn
with Bio
ads SX-3;
pressure
7.2.1
  Manually  calibrate
by GC/FIO using OB-S
  capillary column:
Uv spectrophotometer
 or GC/MS to analyze
     fractions
   7.2.1
     Select dump.
     collect,  ana
     wash  times
                       Manual
                      alIbrat ion
           Automated
          calibration
                       7.2.2 Calibrate
                              using  o
 Calibrate
   column?
   UV detector
 ana corn oil/
   phthalate/
phenol mixture
                                                             Select
                                                              dump.
                                                        collect, and
Dilute with
 metnylene
 chloride
   wash times:
   recalibrate
   once a  week
                         Load extract onto GPC
                          column and process:
                             purge  column
                           between  extracts
                             7.4
                              Concentrate
                                extract:
                                analyze
                                V- -  -  -
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                                                    Date  September  1986

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                                 METHOD 3650

                         ACID-BASE PARTITION CLEANUP
1.0  SCOPE AND APPLICATION

     1.1  Method 3650 was formally Method  3530  in the second edition of this
manual.

     1.2  This  is  a  liquid-liquid  partitioning  method  to  separate  acid
analytes from base/neutral analytes using pH  adjustment.   It may be used for
cleanup of petroleum waste prior to alumina cleanup.


2.0  SUMMARY OF METHOD

     2.1  The solvent extract is  shaken  with  water  that is strongly basic.
The acid analytes partition  into  the  aqueous  layer, whereas, the basic and
neutral compounds stay in the  organic  solvent.  The base/neutral fraction is
concentrated and is ready for further cleanup, if necessary, or analysis.  The
aqueous layer is  acidified  and  extracted  with  an  organic  solvent.  This
extract is concentrated and then ready for analysis for the acid analytes.
3.0  INTERFERENCES

     3.1  A reagent blank should  be  performed  for  the compound 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
necessary for reagent purification.
   outlined  in  this  method may be
4.0  APPARATUS AND MATERIALS

     4.1  Separatory funnel;   125-mL, with Teflon stopcock.

     4.2  Drying column;  20-mm  I.D.  Pyrex chromatographic column; with Pyrex
glass wool at bottom and a  Teflon stopcock.
     NOTE:   Fritted glass   discs  are  difficult to decontaminate after highly
     contaminated extracts  have  been  passed  through.   Columns without frits
     may be  purchased.  Use  a  small  pad  of  Pyrex glass wool to retain the
     adsorbent.  Prewash the  glass wool pad  with 50 mL of acetone followed by
     50 mL of elution  solvent prior to packing the column with adsorbent.
      4.3   Kuderna-Danish  (K-D)  apparatus;

           4.3.1   Concentrator tube:    10-mL,
      equivalent).  Ground-glass   stopper  is
      extracts.
 graduated  (Kontes K5700-1025 or
used  to  prevent  evaporation of
                                   3650 - 1
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          4.3.2  Evaporation flask:     500-mL   (K-570001-0500  or  equivalent).
     Attach to concentrator tube with  springs.

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

          4.3.4  Snyder  column:    Two-ball   micro  (Kontes  K569001-0219  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-cap.

     4.7  pH Indicator paper;  pH range Including the desired extraction pH.

     4.8  Erlenmeyer flask;  125-mL.


5.0  REAGENTS

     5.1  Reagent water;    Reagent  water  1s  defined  as  water  1n which an
interferent is not observed at the  method detection limit of the compounds of
interest.

     5.2  Sodium hydroxide  solution ION:   (ACS) 40 g NaOH 1n reagent water and
dilute to 100 ml.

     5.3  Sodium sulfate;   (ACS)  Granular,  a'nhydrous  (purified by heating at
400*C for 4 hr in a shallow tray).

     5.4  Sulfuric acid solution  (1:1):  Slowly add 50 ml ^04 (sp. gr.  1.84)
to 50 ml of reagent water.

     5.5  Solvents;    Acetone,  methanol,  ethyl  ether,  methylene  chloride
(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   Place  10 mL of the extract or  organic liquid waste to be cleaned up
into the  separatory funnel.
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                                                         Date  September 1986

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     7.2  Add 20 ml of methylene chloride to the separatory  funnel.

     7.3  Add 20 ml of reagent water  and  adjust  the pH to 12-13 with  sodium
hydroxide.

     7.4  Seal and shake  the  separatory  funnel  for  1-2   min 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.

     7.5  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 of the size of  the  solvent  layer,  the analyst must employ mechanical
techniques to complete the  phase  separation.   The optimum technique depends
upon the sample, and may include  stirring, filtration of the emulsion through
glass wool, centrifugation, or other physical methods.

     7.6  Separate the aqueous phase  and  transfer  it to a 125-mL Erlenmeyer
flask.  Repeat  the extraction  two  more  times  using fresh 20 ml portions of
reagent water pH 12-13.  Combine the aqueous extracts.

     7.7  At  this point the  analytes  will  be  in  the organic and/or in the
aqueous phase.   Organic  acids  and  phenols  will  be  in the aqueous phase,
whereas, base/neutral  analytes  will  be   in  the  organic  solvent.   If the
analytes are  in the aqueous phase  only, discard the organic phase and proceed
to  Paragraph  7.8.   If  the  analytes  are  in   the organic phase,  discard the
aqueous phase  and proceed to Paragraph 7.10.

     7.8  Transfer the aqueous phase to  a clean  separatory  funnel.  Adjust the
aqueous layer to a pH  of  1-2  with  sulfuric   acid.   Add 20 ml of methylene
chloride  to  the separatory funnel  and shake   for 2 min.  Allow the solvent to
separate  from the  aqueous  phase  and   collect  the   solvent in an Erlenmeyer
flask.

     7.9  Add  a second  20 ml  volume  of methylene chloride to the separatory
funnel  and re-extract at pH  1-2  a  second  time, combining  the extracts in the
Erlenmeyer flask.  Perform a third extraction in the  same manner.

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

     7.11  Dry  the extracts by  passing them through a  drying column containing
about  10  cm  of anhydrous sodium sulfate.  Collect the  dried extract  in the K-D
concentrator.   Rinse  the Erlenmeyer  flask  which contained  the solvent extract
and the column  with 20 ml  of  methylene chloride to  complete the quantitative
transfer.

     7.12  Add  one or two boiling  chips   to  the flask and  attach a three-ball
macro-Snyder column.    Prewet   the  Snyder  column  by  adding  about  1  ml of
methylene  chloride to the top of the column.  Place the  K-D apparatus on  a hot
                                   3650  - 3
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                                                          Date   September  1986

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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 with
hot vapor.   Adjust  the  vertical  position  of  the  apparatus and the water
temperature as required to complete  the  concentration  in 15-20 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 from the  water  bath  and allow it to drain and cool
for at least 10 min.   Remove  the  Snyder  column and rinse the flask and its
lower joints into the concentrator tube with 1-2 ml of extraction solvent.

     7.13  Add another one or two  boiling  chips to the concentrator tube and
attach a two-ball micro-Snyder column.  Prewet  the column by adding 0.5 ml of
methylene chloride to the top of the column.  Place the K-D apparatus in a hot
water bath (95°-100*C) so that the  concentrator tube is partially immersed in
the hot water.  Adjust the  vertical  position  of the apparatus and the water
temperature as required to complete  the  concentration  in  5-10 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 the liquid reaches
0.5 ml, remove the K-D apparatus  and  allow  it  to drain for at least 10 min
while cooling.  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 ml with solvent.

     7^14  The acid  fraction is now  ready  for analysis.  If the base/neutral
extract is to  undergo  further   cleanup  by  the  Alumina  Column Cleanup for
Petroleum Waste  (Method 3611), the  extract  must  be exchanged to hexane.  To
the 1-mL  base/neutral  extract,  5  ml  of  hexane   should  be added  (solvent
exchanged), and  this mixture then  reconcentrated  to   1 ml using the micro-KD
apparatus.  If no  further cleanup  of  the base/neutral  extract  is required, it
is also ready for  analysis.

                                                  )•

8.0- QUALITY CONTROL

     8.1   Refer  to Chapter   One   for   specific  quality control procedures and
Method 3600 for  cleanup procedures.

     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   be   processed  through this  cleanup
method.
.9.0  METHOD PERFORMANCE

      9.1   Refer to the determinative  methods  for  performance  data.


 10.0  REFERENCES

      10.1  None required.

                                   3650 - 4
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                                                          Date   September 1986

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                                         METHOD 3650

                                 ACID-BASE PARTITION CLEANUP
 7. 1
        Place
       extract
     or organic
   liquid waste
into separatory
      funnel
 7.2
 Add methylene
   chloride
 7.3
                                                                              7.5
                                                         Complete
                                                          phase
                                                       separatIon
                                                  with mechanical
                                                       techniques
                                Separate
                                aqueous
                           phase:  Repeat
                          extract  twice:
                         combine aqueous
                              extracts
  Add reagent
     water;
   adjust  pH
                           7.7
   Discard
aqueous phase
 7.4
 Seal  and  snake
   •eparatory
     f unne1
 7.5
        Allow
    separation
    or organic
    layer  from
   water phase
   o
                                            On 1 y    s	V
                                           organic/  Which phase  ^v^
                                          •	  	analytes In?  ^
                                           Only
                                                                              7.7
                             Discard
                          organic  phase
                                Trans fer
                                aqueous
                               phase  to
                           clean funnel:
                              adjust  pH
                          7.6  I   Add
                              Imethylene
                              chloride:
                         shake:  separate
                         and collect In
                                flask
   o
7.9
    I  Perform
     two more
  extractions;
     combine
    extracts
                                     3650 - 5
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                                                                Date   September 1986

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                  METHOD 36SO
          AGIO-BASE PARTITION CLEANUP
                   (Continued)
    7. 10
    Assemble K-O
    concentrator
   7. 11
   Dry and collect
   extracts In K-D
    concentrator
   7 .
     Concentrate
   extract to 1  ml
      using K-O
      apparatus
7. 13
 Concentrate extract
 to O.5 ml uElno K-O
  apparatus:  adjust
    final volume
     Is  further
  extraction needed
      for base-
      neutral?
       Use
  Methoo 3611:
change extract
   to hexane
       Analyze
      fractions
            3650  - 6
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                                       Date   September 1986

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                                 METHOD 3660

                               SULFUR CLEANUP
1.0  SCOPE AND APPLICATION

     1.1  Elemental sulfur is encountered  in many sediment samples (generally
specific to different areas in the country),  marine algae,  and some industrial
wastes.  The solubility of sulfur  in  various solvents is  very similar to the
organochlorine  and  organophosphorous   pesticides;   therefore,   the  sulfur
interference follows along with  the  pesticides through the normal extraction
and cleanup techniques.   In  general,  sulfur  will usually elute entirely in
Fraction 1 of the Florisil cleanup (Method 3620).

     1.2  Sulfur will be  quite  evident  in  gas  chromatograms obtained from
electron capture detectors, flame photometric detectors operated in the sulfur
or phosphorous mode, and  Coulson  electrolytic  conductivity detectors in the
sulfur mode.  If the  gas  chromatograph  is operated at the normal conditions
for pesticide analysis, the sulfur interference can completely mask the region
from the solvent peak through Aldrin.

     1.3  Three techniques for the  elimination  of sulfur are detailed within
this method: (1) the use of copper powder; (2) the use of mercury; and
(3) the use of  tetrabutylamrnonium-sulfite.  Tetrabutylamrnonium-sulfite causes
the least amount of degradation  of  a  broad  range of pesticides and organic
compounds, while copper  and  mercury  may  degrade  organophosporous and some
organochlorine pesticides.


2.0  SUMMARY OF METHOD

     2.1  The sample to undergo cleanup  is mixed with either copper, mercury,
or tetrabutylammonium  (TBA)-sulfite.  The mixture is shaken and the extract is
removed from the sulfur cleanup reagent.


3.0  INTERFERENCES

     3.1  Removal  of sulfur  using copper;

          3.1.1  The copper  must be   very  reactive;   therefore, all oxides of
     copper must be  removed  so that  the  copper  has  a shiny, bright appearance.

          3.1.2  The sample   extract must   be   vigorously  agitated  with the
     reactive  copper for  at  least one minute.


4.0  APPARATUS AND MATERIALS

     4.1  Mechanical shaker  or mixer;  Such  as  the  Vortex  Genie.

     4.2   Pi pets;   Disposable,  Pasteur  type.

                                   3660  - 1
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     4.3  Centrifuge tubes;  Calibrated,  12-mL.

     4.4  Glass bottles or vials;    10-mL  and 50-mL,  with Teflon-lined screw-
caps.


5.0  REAGENTS

     5.1  Reagent water;   Reagent  water  Is  defined  as  water  1n which an
interferent is not observed at the  method detection limit of the compounds of
interest.

     5.2  Nitric acid;  Dilute.

     5;3  Acetone, hexane, 2-propanol;   Pesticide quality or equivalent.

     5.4  Copper powder;  Remove oxides  by  treating with dilute nitric acid,
rinse with distilled water to  remove  all  traces of acid, rinse with acetone
and dry under a stream of  nitrogen.  (Copper, fine granular Mallinckrodt 4649
or equivalent).

     5.5  Mercury;  Triple distilled.

     5.6  Tetrabutylammonium  (TBA)-sulfite   reagent;      Dissolve   3.39  g
tetrabutylammonium  hydrogen  sulfate  in  100  ml  reagent  water.  To remove
impurities, extract this solution three  times  with 20-mL portions of hexane.
Discard the  hexane  extracts,  and  add  25  g  sodium  sulfite  to the water
solution.   Store  the  resulting  solution,  which  is  saturated with sodium
sulfite, in an amber bottle with  a Teflon-lined screw-cap.  This solution can
be stored at room temperature for at least one month.


6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

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

     7.1  Removal of sulfur using copper;

          7.1.1  Concentrate the  sample  to  exactly  1.0-mL  in the Kuderna-
     Danish tube.

          7.1.2  If the  sulfur  concentration  is  such  that crystallization
     occurs, centrifuge to settle  the  crystals,  and  carefully draw off the
     sample extract with a disposable  pi pet  leaving the excess sulfur in the
     K-D tube.  Transfer the extract to a calibrated centrifuge tube.

          7.1.3  Add approximately 2 g of cleaned copper powder (to the 0.5 mL
     mark) to the centrifuge tube.  Mix  for  at least 1 min on the mechanical
     shaker.

                                  3660 - 2
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         7.1.4  Separate the  extract  from  the  copper  by  drawing off the
    extract with a disposable pipet and transfer to a clean vial.  The volume
    remaining still represents 1.0 ml of extract.
         NOTE:  This separation  is  necessary to prevent further degradation
         of the pesticides.

    7.2  Removal of sulfur using mercury;

         NOTE:  Mercury  is a highly  toxic  metal and therefore, must be used
         with great care.  Prior to using mercury, it is recommended that the
         analyst  become  acquainted   with   proper   handling  and  cleanup
         techniques associated with this metal.

         7.2.1  Concentrate the sample extract to exactly 1.0 ml.

         7.2.2  Pipet  1.0 ml of the extract into a clean concentrator tube or
    Teflon-sealed vial.

         7.2.3  Add one  to  three  drops  of  mercury  to  the vial and seal.
    Agitate the contents of the vial for 15-30 sec.  Prolonged shaking  (2 hr)
    may  be required.   If so, use a mechanical shaker.

         7.2.4  Separate the   sample  from  the  mercury  by  drawing off the
    extract with a disposable  pipet and transfer to a clean vial.

    7.3  Removal of sulfur using TBA-sulfite;

         7.3.1  Concentrate the sample extract to exactly 1.0 ml.

         7.3.2  Transfer the 1.0 ml  to  a  50-mL  clear glass bottle or vial
    with a Teflon-lined  screw-cap.  Rinse  the concentrator tube with 1 ml of
    hexane, adding the rinsings to the 50-mL bottle.

         7.3.3  Add  1.0  ml TBA-sulfite reagent   and  2 ml 2-propanol, cap the
    bottle, and shake  for at least  1  min.    If  the sample  is colorless or if
    the  initial   color  is  unchanged,  and   if  clear crystals  (precipitated
    sodium  sulfite)  are  observed,  sufficient  sodium  sulfite is present.  If
    the  precipitated  sodium sulfite  disappears,  add more  crystalline  sodium
    sulfite  in  approximately  100-mg  portions  until  a  solid residue remains
    after  repeated  shaking.

          7.3.4  Add  5  ml distilled  water  and  shake  for at  least  1  min.  Allow
    the  sample  to  stand for 5-10  min.     Transfer the hexane  layer (top)  to  a
     concentrator  tube  and  use  the  K-D  technique  to  concentrate  the extract to
     1.0  ml.

     7.4   Analyze  the  cleaned   up   extracts   by   gas  chromatography  (see  the
determinative  methods,  Section  4.3  of this  chapter).
                                  3660 - 3
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8.0  QUALITY CONTROL

     8.1  Refer to Chapter  One  for  specific  quality control procedures and
Method 3600 for cleanup procedures.

     8.2  All  reagents  should  be  checked  prior  to  use  to  verify  that
interferences do not exist.
9.0  METHOD PERFORMANCE

     9.1  Table 1 indicates the effect  of  using copper and mercury to remove
sulfur on the recovery of certain pesticides.


10.0  REFERENCES

1.  Loy, E.W., private communication.

2.  Goerlitz, D.F. and L.M.  Law, Bulletin for Environmental Contamination and
Toxicology, 6, 9  (1971).

3.  U.S.  EPA  Contract  Laboratory  Program,  Statement  of  Work for Organic
Analysis, Revision, July 1985.
                                   3660 - 4
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                                                          Date   September  1986

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Table 1.  EFFECT OF MERCURY AND COPPER ON PESTICIDES
 Pesticide
                                         Percent Recovery9 using;
Mercury
Copper
Aroclor 1254
Lindane
Heptachlor
Aldrin
Heptachlor epoxide
DDE
DDT
BHC
Dieldrin
Endrin
Chi orobenzi late
Malathion
Diazinon
Parathion
Ethion
Trithion
97.10
75.73
39.84
95.52
69.13
92.07
78.78
81.22
79.11
70.83
7.14
0.00
0.00
0.00
0.00
0.00
104.26
94.83
5.39
93.29
96.55
102.91
85.10
98.08
94.90
89.26
0.00
0.00
0.00
0.00
0.00
0.00
a  Percent  recoveries  cited  are  averages  based  on duplicate analyses for all
compounds  other   than  for  Aldrin  and  BHC.    For  Aldrin,  four  and three
determinations were averaged  to  obtain  the  result  for mercury and copper,
respectively.  Recovery of  BHC  using  copper  is based on one analysis.
                                   3660 - 5
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                                                          Date   September  1986

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                                         METHOD 3660

                                       SULFUR CLEANUP
                                                         Start
                                            Copper
                                                                    TBA-sulfItc
                          7.1.1
7.1.3
 Centrifuge and
draw off sample
    extract
                            Concentrate
                           sample extract
                                                    7.2.1
                                                            Mercury
 Concentrate
sample extract
                                                    7.2.8
                                                                             7.3.1
  Concentrate
sample extract
      Plpet
 extract Into
 concentrator
 tube or vial
                                Transfer
                               extract  to
                               centr1fuge
                                 tube
                                                    7.2.3
                                                                             7.3.2
      Transfer
     extract  to
   glass bottle
      or vial
 Add mercury;
   agitate
                              0
                                                                             7.3.3
       Add
TBA-sulflte  and
   2-propano 1:
      shake
                            O
                                      3660  - 6
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                                         METHOD  3660

                                       SULFUR  CLEANUP
                                         (Continued)
    o
7.1.3
    o
   Add copper
  powder;  mix
                          7.2.4
Separate sample
 from mercury
7.1.4
    Separate
  •xtract from
     copper
Add more sodium
 sulflte:  shake
                               distilled
                           water; . shake:
                              let stand:
                             concentrate
                               •extract
                                    3660 - 7
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4.3  DETERMINATION OF ORGANIC ANALYTES

     4.3.1  GAS CHROMATOGRAPHIC METHODS
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                                 METHOD 8000

                             GAS CHROMATOGRAPHY
1.0  SCOPE AND APPLICATION

     1.1  Gas chromatography is a quantitative analytical  technique useful  for
organic compounds capable  of  being  volatilized  without being decomposed or
chemically rearranged.  Gas  chromatography  (GC),   also  known as vapor phase
chromatography (VPC),  has  two  subcategories  distinguished  by:   gas-solid
chromatography  (GSC),  and  gas-liquid  chromatography  (GLC)   or  gas-liquid
partition chromatography (GLPC).  This  last  group is the most commonly used,
distinguished by type of column adsorbent or packing.

     1.2  The gas chromatographic methods are  recommended for use only by, or
under the close supervision of, experienced residue analysts.


2.0  SUMMARY OF METHOD

     2.1  Each organic analytical method  that  follows provides a recommended
technique for extraction,  cleanup,  and  occasionally,  derivatization of the
samples to be analyzed.  Before the prepared sample  is introduced into the GC,
a procedure for standardization must be followed to  determine the recovery and
the limits of  detection   for  the  analytes  of  interest.   Following sample
introduction into the GC,  analysis proceeds with a comparison of sample values
with standard values.   Quantitative  analysis is achieved through integration
of peak area or measurement of peak height.


3.0  INTERFERENCES

     3.1  Contamination by carryover  can  occur  whenever high-level and  low-
level  samples are   sequentially   analyzed.    To  reduce carryover, the sample
syringe or purging  device  must   be   rinsed  out  between samples with reagent
water  or  solvent.   Whenever  an   unusually concentrated sample  is encountered,
it should be followed by an analysis  of a solvent blank or of reagent water to
check  for cross contamination.   For  volatile samples  containing  large amounts
of water-soluble materials, suspended  solids,   high boiling compounds or  high
organohalide levels,  it may be  necessary  to  wash  out the  syringe or purging
device with a detergent solution,  rinse  it with distilled water, and then dry
it in  a 105°C oven  between analyses.


4.0  APPARATUS AND  MATERIALS

     4.1  Gas chromatograph;    analytical  system  complete  with  gas chromato-
graph   suitable  for on-column    injections  and  all  required  accessories,
including detectors,  column supplies,  recorder,  gases,  and syringes.  A  data
system for measuring peak  height  and/or peak areas is  recommended.
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     4.2  Gas chromatographic columns;  See the specific determinative method.
Other  packedorcapillary(open-tubular)    columns  may  be  used  if  the
requirements of Section 8.6 are met.


5.0  REAGENTS

     5.1  See the specific determinative method for the reagents needed.


6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

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


7.0  PROCEDURE

     7.1  Extraction:  Adhere to  those  procedures specified in the referring
determinative method.

     7.2  Cleanup and separation;  Adhere to those procedures specified in the
referring determinative method.

     7.3  The recommended gas chromatographic columns and operating conditions
for the instrument are specified in the referring determinative method.

     7.4  Calibration;

          7.4.1  Establish gas chromatographic operating parameters equivalent
     to  those   indicated  in  Section  7.0  of  the  determinative  method of
     interest.   Prepare calibration   standards  using the procedures indicated
     in Section  5.0 of the  determinative  method  of interest.  Calibrate the
     chromatographic   system  using   either  the  external  standard technique
     (Section 7.4.2) or the internal  standard technique  (Section 7.4.3).

          7.4.2  External standard calibration procedure:

               7.4.2.1  For  each  analyte  of  interest,   prepare calibration
          standards at  a  minimum  of  five  concentration  levels  by adding
          volumes of one or  more  stock   standards  to  a volumetric flask and
          diluting to  volume with an  appropriate solvent.   One  of the  external
          standards should be at a  concentration  near, but above, the method
          detection limit.  The other  concentrations should correspond to the
          expected range of  concentrations  found  in   real samples or should
          define the working range of the detector.

               7.4.2.2  Inject each calibration  standard   using the technique
          that will be  used  to  introduce  the  actual  samples into the gas
          chromatograph (e.g, 2-  to  5-uL  injections,  purge-and-trap, etc.).
          Tabulate peak height or  area  responses  against the mass injected.
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The results can be  used  to  prepare  a  calibration curve for each
analyte.  Alternatively, for  samples  that  are introduced into the
gas chromatograph using a syringe,  the  ratio of the response to the
amount injected, defined  as  the  calibration  factor  (CF), can be
calculated for each analyte at  each standard concentration.  If the
percent relative standard deviation (%RSD) of the calibration factor
is less than  20%  over  the  working  range,  linearity through the
origin can be assumed,  and  the  average  calibration factor can be
used in place of a calibration curve.


     Calibration factor =      Total Area of Peak*
                          Mass injected (in nanograms)

*For multiresponse pesticides/PCBs use the total area of all  peaks
 used for quantitation.

     7.4.2.3  The working  calibration  curve  or calibration factor
must be verified on each working day by the injection of one or more
calibration standards.  The  frequency  of verification is dependent
on the detector.  Detectors,  such as the electron capture detector,
that operate  in  the  sub-nanogram  range  are  more susceptible to
changes in detector response caused by GC column and sample effects.
Therefore, more frequent  verification  of calibration is necessary.
The flame ionization detector  is  much  less sensitive and requires
less frequent verification.  If  the response for any analyte varies
from the predicted response  by  more  than  +15%, a new calibration
curve must be prepared for that analyte.

                          R, - Rp
     Percent Difference = -*—*—- x 100
                             Kl
where:

     R! = Calibration  Factor from first analysis.

     R2 = Calibration  Factor from succeeding analyses.

7.4.3   Internal standard calibration procedure:

     7.4.3.1  To  use  this approach,  the   analyst must select one or
more internal standards that  are   similar in analytical behavior to
the compounds of   interest.    The  analyst must  further demonstrate
that the measurement  of  the  internal  standard  is  not affected by
method  or  matrix  interferences.    Due   to  these   limitations, no
internal  standard applicable to all samples can be suggested.

     7.4.3.2  Prepare calibration   standards  at  a   minimum of  five
concentration levels  for each analyte   of  interest by adding volumes
of one  or more  stock standards  to   a volumetric   flask.  To  each
calibration  standard,  add a  known  constant  amount   of one or  more
internal  standards and dilute to  volume with an appropriate solvent.
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     One of the standards should  be  at a concentration near,  but above,
     the. method  detection  limit.    the  other  concentrations  should
     correspond to the  expected  range  of  concentrations found In real
     samples or should define the working range of the detector.

          7.4.3.3  Inject  each  calibration   standard  using  the  same
     Introduction technique that will  be  applied  to the actual samples
     (e.g, 2- to  5-uL  injection,  purge-and-trap,  etc.).  Tabulate the
     peak height or  area  responses  against  the  concentration of each
     .compound and Internal standard.  Calculate response factors (RF) for
     each compound as follows:

                         RF = (AsC1s)/(A1sCs)

     where:  .

          As  = Response for the analyte to be measured.

          Ais = Response for the internal standard.

          C}s = Concentration of the internal standard, ug/L.

          Cs  = Concentration of the analyte to be measured, ug/L.

     If the RF value over the  working  range is constant  «20% RSD), the
     RF can be assumed to be  invariant,  and  the average RF can be used
     for calculations.  Alternatively, the results  can be used to plot a
     calibration curve of response ratios, As/Afs versus RF.

          7.4.3.4  The working calibration curve  or  RF must be verified
     on each working day by  the  measurement  of one or more calibration
     standards.   The  frequency  of  verification  is  dependent  on the
     detector.  Detectors, such  as  the  electron capture detector, that
     operate in the sub-nanogram range are more susceptible  to  changes 1n
     detector  response  caused   by   GC    column  and  sample effects.
     Therefore, more frequent  verification  of calibration  is  necessary.
     The  flame ionization detector   is  much  less sensitive and requires
     less frequent verification.   If  the response for any analyte varies
     from the predicted  response  by  more   than  +15%, a  new calibration
     curve must be prepared  for that compound.

 7.5 Retention time windows;

     7.5.1   Before establishing   windows,  make   sure  the  GC   system 1s
 within optimum operating conditions.  Make three  injections  of  all  single
 component  standard  mixtures   and   multiresponse products   (I.e.,  PCBs)
 throughout  the  course  of  a   72-hr  period.    Serial  injections over less
 than a 72-hr period  result  in  retention  time windows  that  are  too  tight.

     7.5.2   Calculate   the   standard deviation   of   the   three  absolute
.retention times  for  each  single   component  standard.   For  multiresponse
 products,  choose  one   major   peak  from  the  envelope   and  calculate the
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standard deviation of the three retention  times for that peak.   The peak
chosen  should  be  fairly  immune  to  losses  due  to  degradation  and
weathering in samples.

          7.5.2.1  Plus or minus  three  times  the standard deviation of
     the absolute retention  times  for  each  standard  will  be used to
     define the retention  time  window;  however,  the experience of the
     analyst should weigh heavily 1n the interpretation of chromatograms.
     For multiresponse products (i.e., PCBs),  the analyst should use the
     retention time window but  should  primarily  rely on pattern recog-
     nition.

          7.5.2.2  In those  cases  where  the  standard  deviation for a
     particular standard  is  zero,  the  laboratory  must substitute the
     standard deviation of a close eluting, similar compound to develop a
     valid retention time window.

     7.5.3  The laboratory must calculate retention time windows for each
standard on each GC column  and  whenever  a  new GC column  1s Installed.
The data must be retained by the laboratory.

7.6  Gas chromatographic analysis:

     7.6.1  Introduction of organic compounds   into the gas  chromatograph
varies  depending on the  volatility  of  the compound.  Volatile organlcs
are primarily introduced by purge-and-trap (Method 5030).  However, there
are limited applications where  direct   injection  is acceptable.  Use of
Method  3810  or  3820  as  a  screening  technique  for  volatile organic
analysis may be valuable with some sample matrices to prevent overloading
and  contamination  of  the  GC   systems.    Semi volatile   organlcs  are
introduced by direct  injection.

     7.6.2  The appropriate detector(s)  is given  in the specific method.

     7.6.3  Samples are analyzed  in  a  set  referred  to as an analysis
sequence.  The sequence  begins  with   instrument calibration followed by
sample  extracts interspersed with  multilevel calibration standards.  The
sequence  ends  when  the  set  of  samples   has  been   injected  or when
qualitative and/or quantitative QC criteria  are exceeded.

     7.6.4  Direct  Injection:   Inject 2-5  uL of  the sample  extract using
the solvent flush technique.  Smaller  (1.0-uL)  volumes can be Injected 1f
automatic devices  are  employed.     Record   the  volume  injected  to the
nearest 0.05  uL and the  resulting peak  size  in  area  units or peak height.

      7.6.5   If the  responses   exceed   the   linear   range  of the system,
dilute  the  extract  and   reanalyze.     It  is ,recommended  that extracts be
diluted so  that all peaks  are on  scale.  Overlapping peaks are  not  always
evident  when  peaks    are  off    scale.       Computer   reproduction  of
chromatograms, manipulated to  ensure  all   peaks  are on  scale over  a  100-
fold  range,  are acceptable  1f   linearity   is  demonstrated. Peak  height
measurements  are  recommended over  peak area integration  when overlapping
peaks  cause  errors  in area Integration.

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         7.6.6   If  peak  detection   is   prevented   by   the  presence  of
     interferences,  further cleanup is required.

         7.6.7   Examples of chromatograms for  the  compounds of interest are
     frequently  available in the  referring analytical method.

         7.6.8   Calibrate the  system   immediately  prior  to  conducting any
     analyses  (see  Paragraph 7.4).  A  midlevel standard must also be  injected
     at  intervals specified in  the  method   and   at  the  end of the  analysis
     sequence.   The  calibration   factor   for  each analyte to be quantitated,
     must not  exceed a  15% difference when compared to  the initial standard of
     the analysis sequence.  When this   criteria  is exceeded, inspect  the GC
     system to   determine  the   cause   and   perform  whatever  maintenance is
     necessary (see  Section   7.7)  before  recalibrating  and proceeding with
     sample analysis.     All   samples  that   were  injected   after   the  sample
     exceeding the  criteria must  be reinjected.

         7.6.9   Establish daily  retention time windows for each  analyte.  Use
     the absolute retention time  for   each  analyte   from  Section 7.6.8  as the
     midpoint  of the window for  that  day.     The daily retention time  window
     equals the  midpoint +  three  times  the standard  deviation  determined  1n
     Section 7.5.

               7.6.9.1   Tentative identification  of   an analyte  occurs  when  a
         peak from a  sample   extract   falls   within   the  daily  retention time
         window.  Normally,  confirmation is  required:   on a  second  GC column;
         by  GC/MS  if   concentration    permits;   or by   other   recognized
          confirmation  techniques.   Confirmation   may  not be necessary  if the
          composition  of  the  sample   matrix  is well established  by prior
          analyses.

               7.6.9.2   Validation  of  GC system  qualitative  performance:  Use
          the midlevel  standards  interspersed throughout the  analysis sequence
          (Paragraph 7.6.8)   to  evaluate  this  criterion.     If  any  of the
          standards fall outside  their dally  retention  time window,  the  system
          is out of control.   Determine   the   cause  of the problem  and correct
          it (see Section 7.7).

     7.7  Suggested chromatography   system maintenance;  Corrective measures
may require any one or more  of the  following  remedial  actions.

          7.7.1  Packed columns:   For  instruments  with injection  port  traps,
     replace the demister trap,  clean,  and deactivate the  glass  injection port
     insert or replace with   a  cleaned  and   deactivated  insert.  Inspect  the
     injection end of the column  and remove any foreign material  (broken glass
     from the rim of the column or  pieces  of septa).   Replace  the glass wool
     with fresh deactivated glass wool.    Also,  it may be necessary to remove
     the first few millimeters of the packing material  if any discoloration  1s
     noted, also swab out the  Inside  walls   of  the column  if any residue  1s
     noted. , If these procedures fail  to eliminate the degradation  problem,  It
     may be necessary  to  deactivate  the  metal  injector body (described  1n
     Section 7.7.3) and/or repack/replace the column.


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     7.7.2  Capillary columns:  Clean  and deactivate the glass Injection
port insert or replace with a  cleaned and deactivated insert.   Break off
the first few inches, up to one  foot,  of the injection port side of the
column.   Remove  the  column  and  solvent  backflush  according  to the
manufacturer's instructions.  If  these  procedures fail to eliminate the
degradation problem, it may be necessary to deactivate the metal injector
body and/or replace the column.

     7.7.3  Metal Injector  body:    Turn  off  the  oven  and remove the
analytical column when oven has cooled.   Remove the glass injection port
insert (instruments  with  off-column  injection  or  Grob).    Lower the
injection port temperature to  room  temperature.   Inspect the injection
port and remove any noticeable foreign material.

          7.7.3.1  Place a beaker beneath the injector port inside the GC
     oven.  Using a wash bottle,  serially rinse the entire inside of the
     injector port with acetone and then toluene; catching the rinsate in
     the beaker.

          7.7.3.2   Prepare a  solution of  deactivating agent (Sylon-CT or
     equivalent) following manufacturer's  directions.    After all metal
     surfaces inside the injector  body  have been thoroughly  coated with
     the deactivation  solution,  serially  rinse  the   injector body with
     toluene, methanol.acetone, and  hexane.   Reassemble  the injector and
     replace the GC  column.

7.8 Calculations;

     7.8.1   External  standard  calibration:     The   concentration  of each
analyte  in  the  sample   may   be  determined   by   calculating  the amount of
standard  purged  or  injected,   from    the peak   response,   using  the
calibration curve   or   the   calibration   factor determined  in  Paragraph
7.4.2.   The concentration of a  specific  analyte is calculated  as  follows:

Aqueous  samples;
      Concentration (ug/L)  =  [(Ax) (A) (Vt) (D)]/[(AS) OWVs)]

 where:

      Ax = Response for the analyte  in   the   sample,   units may  be  in  area
           counts or peak height.

      A   = Amount of standard injected  or  purged,  ng.

      As = Response for the external  standard,  units  same  as  for Ax.

      V-j = Volume of extract  injected,   uL.    For  purge-and-trap analysis,
           Vj  is not applicable and  therefore = 1.

      D   = Dilution factor, if dilution was   made on the sample prior to
           analysis.  If no dilution was made,  D = 1,  dimensionless.

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     Vt = Volume of total extract,  uL.   For purge-and-trap analysis,  Vt
          is not.applicable and therefore = 1.
     Vs = Volume of sample extracted or purged,  mL.
Nonaqueous samples;
     Concentration (ng/g) = [(Ax)(A)(Vt)(D)]/[(AS)(V^(W)]
where:
     W  = Weight of sample extracted or purged,  g.  The wet weight or dry
          weight may be used, depending upon the specific applications of
          the data.
     AXI ASl A, vti DI ancl vi have the same definition as for aqueous
          samples.
     7.8.2  Internal standard calibration:  For each analyte of interest,
the concentration of that analyte in the sample is calculated as follows:
Aqueous samples;
     Concentration (ug/L) =  [(Ax)(C1s)(D)]/[(A1s)(RF)(Vs)]
where:
     Ax =   Response of the analyte being  measured,  units may be in area
            counts or peak height.
     Cis =  Amount of internal standard  added  to extract or volume purged,
            ng.
     D  =   Dilution factor,  if a dilution was made on the sample prior to
            analysis.   If no  dilution was made, D  = 1, dimensionless.
     A-JS =  Response of the internal standard, units same  as  Ax.
     RF  =  Response  factor   for analyte,  as  determined   in  Paragraph
            7.4.3.3.
     Vs =   Volume of water extracted or purged, ml.
Nonaqueous  samples;
     Concentration  (ug/kg) =  [(As)(Cis)(D)]/[(Ais)(RF)(Ws)]
where:
     Ws =   Weight of sample  extracted,  g.    Either  a dry  weight or wet
            weight may be used, depending upon the  specific application of
            the  data.
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          As. Cis, D, A-js, and RF have the same definition as for aqueous
                samples.


8.0  QUALITY CONTROL

     8.1  Each laboratory that uses  these  methods  is  required to operate a
formal quality control  program.    The  minimum  requirements of this program
consist of ah initial  demonstration  of  laboratory capability and an ongoing
analysis of  spiked  samples  to  evaluate  and  document  quality  data.  The
laboratory  must  maintain  records  to  document  the  quality  of  the  data
generated.    Ongoing  data  quality  checks  are  compared  with  established
performance  criteria  to  determine  if  the  results  of  analyses  meet the
performance characteristics of  the  method.    When  results of sample spikes
indicate atypical method performance, a quality control check standard must be
analyzed to confirm that the measurements were performed in an in-control mode
of operation.

     8.2  Before  processing  any  samples,  the  analyst  should demonstrate,
through the analysis of  a  reagent  water  blank, that interferences from the
analytical system, glassware, and reagents are under control.  Each time a set
of samples is extracted or  there  is  a  change  in reagents, a reagent water
blank  should  be  processed   as   a  safeguard  against  chronic  laboratory
contamination.  The blank samples should  be carried through all stages of the
sample preparation and measurement steps.

     8.3  For each analytical  batch   (up  to  20  samples),  a reagent blank,
matrix spike  and  matrix  spike  duplicate/duplicate  must  be  analyzed  (the
frequency of the  spikes may   be  different for different monitoring programs).
The blank and spiked  samples  must be   carried through  all stages of the  sample
preparation  and measurement steps.

      8.4  The experience  of  the  analyst  performing  gas  chromatography  is
invaluable to  the   success   of  the   methods.     Each  day  that  analysis  is
performed, the daily calibration   sample   should   be evaluated to determine  if
the chromatographic  system  is  operating   properly.    Questions  that  should  be
asked  are:   Do the peaks  look  normal?;  Is  the  response obtained comparable  to
the response from previous  calibrations?    Careful examination of the standard
chromatogram can  indicate whether  the   column   is  still  good, the  injector  is
leaking,  the injector septum  needs  replacing,  etc.   If any changes  are made  to
the system  (e.g,  column  changed),  recalibration  of the system must  take place.

      8.5  Required  Instrument QC;

          8.5.1   Section  7.4  requires   that   the  %RSD   vary   by  <20%  when
      comparing calibration  factors  to   determine  if  a  five point  calibration
      curve  is  linear.

          8.5.2   Section 7.4  sets  a   limit  of  +15% difference  when  comparing
      daily  response  of a given   analyte   versus   the initial  response.   If the
      limit  is  exceeded,  a new standard curve must  be prepared.
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          8.5.3  Section 7.5  requires  the  establishment  of  retention time
     wi ndows.

          8.5.4  Paragraph  7.6.8  sets  a   limit  of  +15%  difference  when
     comparing the initial response of  a  given analyte versus any succeeding
     standards analyzed during an analysis sequence.

          8.5.5  Paragraph 7.6.9.2 requires  that  all succeeding standards in
     an analysis sequence must  fall  within  the  daily retention time window
     established by the first standard of the sequence.

     8.6  To  establish  the  ability  to  generate  acceptable  accuracy  and
precision, the analyst must perform the following operations.

          8.6.1  A  quality  .(QC)   check   sample   concentrate  is  required
     containing each analyte of interest.  The QC check sample concentrate may
     be prepared  from  pure  standard  materials  or  purchased  as certified
     solutions.    If  prepared  by   the  laboratory,  the  QC  check  sample
     concentrate must be  made  using  stock  standards prepared independently
     from those used for calibration.

               8.6.1.1  The concentration of  the  QC check sample concentrate
          is  highly   dependent   upon   the   analytes  being  investigated.
          Therefore, refer  to  Method  3500,  Section  8.0  for  the required
          concentration of the QC check sample concentrate.

          8.6.2  Preparation of QC check samples:

               8.6.2.1  Volatile organic  analytes  (Methods  8010,  8020, and
          8030):  The QC check sample is  prepared  by adding 200 uL of the QC
          check sample concentrate  (Section 8.6.1) to 100 ml of reagent water.

               8.6.2.2  Semivolatile  organic  analytes   (Methods  8040, 8060,
          8080, 8090, 8100, and 8120):TheQCcheck  sample is prepared by
          adding 1.0 ml of the QC   check sample concentrate  (8.6.1) to  each of
          four 1-L aliquots of reagent water.

          8.6.3  Four aliquots of the well-mixed  QC  check  sample are analyzed
     by the same procedures  used   to  analyze  actual samples  (Section  7.0 of
     each of  the methods).    For   volatile organics, the preparation/analysis
     process  is purge-and-trap/gas  chromatography.  For semi volatile organics,
     the  QC check samples  must  undergo   solvent extraction  (see Method 3500)
     prior  to chromatographic analysis.

          8.6.4  Calculate  the average recovery  (7)   in ug/L,  and the standard
     deviation of the  recovery  (s)  in  ug/L,  for each  analyte  of interest using
     the  four results.

     '     8.6.5   For  each   analyte   compare   s  and   K  with  the  corresponding
     acceptance criteria  for precision   and   accuracy,  respectively, given the
     QC Acceptance  Criteria Table   at  the   end   of   each of  the  determinative
     methods.  If s and  7  for  all   analytes of  interest  meet the acceptance


                                  8000 - 10
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                                                          Date  September 1986

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     criteria,  the  system  performance  is  acceptable  and analysis of actual
     samples  can  begin.  If   any   individual  s exceeds the precision limit or
     any  individual 7  falls  outside  the  range  for accuracy, then the system
     performance  is unacceptable  for that analyte.
          NOTE:   The large number of   analytes  in  each of the QC Acceptance
          Criteria  Tables present a  substantial  probability that one or more
          will  fail at least one  of  the acceptance criteria when all analytes
          of  a  given method  are determined.

          8.6.6  When  one or more of the  analytes tested fail at least one of
     the  acceptance criteria, the analyst  must  proceed according to Section
     8.6.6.1  or 8.6.6.2.

               8.6.6.1  Locate and correct   the  source  of  the  problem and
          repeat the  test  for all analytes of  interest beginning with Section
          8.6.2.

               8.6.6.2  Beginning with  Section  8.6.2,  repeat  the test only for
          those analytes that  failed   to   meet  criteria.    Repeated failure,
          however,  will  confirm a general problem with the  measurement system.
          If this occurs,  locate   and   correct   the   source of the problem and
          repeat the  test  for all compounds of  interest beginning with Section
          8.6.2.

     8.7   The laboratory must, on an  ongoing  basis,  spike  at  least one  sample
per analytical  batch  (maximum  of  20   samples   per  batch)  to  assess  accuracy.
For laboratories analyzing  one to ten   samples   per  month,  at  least one  spiked
sample per month is required.

          8.7.1  The  concentration of   the   spike   in the  sample   should be
determined as follows:

               8.7.1.1  If,  as in compliance  monitoring, the  concentration of
          a  specific  analyte  in  the  sample  is   being  checked   against  a
          regulatory concentration limit,  the spike  should  be  at that limit or
          1 to 5 times higher  than  the background  concentration determined  in
          Section 8.7.2, whichever concentration  would be larger.

               8.7.1.2  If the  concentration  of  a  specific   analyte  in the
          sample is  not  being  checked  against  a  limit  specific  to that
          analyte,  the spike should   be  at  the  same concentration  as  the QC
          check sample (8.6.2) or  1   to  5  times   higher  than  the  background
          concentration determined in  Section   8.7.2, whichever concentration
          would be larger.

               8.7.1.3  For  semivolatile organics,  it  may   not  be  possible  to
          determine  the  background   concentration   levels  prior   to  spiking
          (e.g., maximum holding times  will   be  exceeded).     If  this  is  the
          case,  the  spike  concentration   should   be   (1)   the   regulatory
          concentration limit, if any;  or,  if  none (2) the larger of either 5
          times higher than  the  expected  background  concentration or the  QC
          check sample concentration (Section 8.6.2).


                                  8000 - 11
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                                                         Date  September 1986

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         8.7.2  Analyze  one  unspiked  and  one  spiked  sample  aliquot  to
    determine percent recovery of each of the spiked compounds.

              8.7.2.1  Volatile organlcs;  Analyze one 5-mL sample aliquot to
         determine the background  concentration  (B)  of  each  analyte.  If
         necessary, prepare a new QC check sample concentrate  (Section 8.6.1)
         appropriate for the background concentration 1n the sample.  Spike a
         second 5-mL  sample  aliquot  with  10  uL  of  the   QC check sample
         concentrate and   analyze  it  to  determine  the concentration after
         spiking  (A) of each analyte.  Calculate each percent  recovery (p) as
         100(A -  B)%/T, where T is the known true value of the spike.


              8.7.2.2  Semi volatile organics;    Analyze  one  sample aliquot
          (extract of 1-Lsample)to  determine the background concentration
          (B)  of each analyte.   If  necessary,  prepare a new  QC check sample
         concentrate   (Section   8.6.1)    appropriate   for    the  background
         concentration  in  the  sample.  Spike a  second  1-L sample aliquot  with
          1.0  mL  of  the   QC   check   sample  concentrate  and  analyze   it  to
         determine the  concentration  after   spiking   (A)   of each analyte.
         Calculate each percent recovery  (p) as 100(A  - B)%/T, where T  is the
          known  true  value  of  the  spike.

         8.7.3   Compare  the percent  recovery   (p)   for each analyte with the
     corresponding criteria presented   in  the   QC   Acceptance Criteria  Table
    ifound  at  the  end of each   of  the  determinative  methods.   These acceptance
     criteria  were calculated  to  include  an allowance for  error in  measurement
     of both the  background   and   spike   concentrations,  assuming a spike  to
     background  ratio of 5:1.   This  error  will  be  accounted  for  to the  extent
     that the  analyst's  spike  to background  ratio  approaches 5:1.   If spiking
     was  performed   at   a   concentration   lower  than   the   QC  check  sample
     concentration (8.6.2), the analyst   must   use   either   the  QC acceptance
     criteria  presented  in   the Tables,   or optional   QC acceptance criteria
     calculated  for the  specific   spike  concentration.   To  calculate optional
     acceptance  criteria  for   the  recovery of  an  analyte:    (1)  Calculate
     accuracy  (x1)  using   the  equation   found  1n   the  Method   Accuracy and
     Precision as  a  Function   of   Concentration   Table   (appears  at the  end  of
     each determinative  method),  substituting   the  spike concentration (T) for
     C; (2) calculate overall  precision  (S1)   using  the  equation  in the same
     Table, substituting x1 for 7;  (3)  calculate the range for recovery  at the
     spike  concentration  as (lOOx'/T)  + 2.44(100S'/T)%.

          8.7.4   If any  individual  p   falls  outside  the  designated  range for
     recovery, that  analyte  has   failed   the   acceptance  criteria.    A  check
     standard   containing   each analyte   that   failed   the   criteria  must  be
     analyzed  as described  in  Section  8.8.

     8.8  If any analyte fails the acceptance  criteria  for recovery in Section
8.7, a QC check  standard containing   each analyte that  failed must  be prepared
and analyzed.
     NOTE:   The  frequency for   the  required  analysis   of a QC check standard
     will depend upon  the number  of analytes  being  simultaneously  tested, the


                                  8000 - 12
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    complexity of the  sample matrix,  and  the performance of the laboratory.
    If the entire list of analytes given  in a method must be measured in the
    sample in Section  8.7, the  probability  that  the analysis of a QC check
    standard will be required is high.    In  this case the QC check standard
    should be routinely analyzed with the spiked sample.

          8.8.1   Preparation of the QC check standard:  For volatile organics,
    add  10 uL of the QC check  sample concentrate  (Section 8.6.1 or 8.7.2) to
    5 ml of reagent water.  For  semi volatile  organics, add 1.0 ml of the QC
    check sample concentrate   (Section  8.6.1  or  8.7.2)  to  1 L of reagent
    water. The QC check   standard  needs  only  to  contain the analytes that
    failed criteria in the  test  in   Section  8.7.    Prepare  the QC check
    standard for analysis  following   the  guidelines  given  in Method 3500
     (e.g., purge-and-trap, extraction,  etc.).

          8.8.2   Analyzed  the QC  check standard to  determine the concentration
    measured  (A) of each  analyte.    Calculate  each  percent recovery  (ps) as
     100  (A/T)%,  where  T  is the true  value of the standard  concentration.

          8.8.3   Compare  the percent  recovery   (ps)   for each analyte with  the
     corresponding QC  acceptance  criteria  found  in   the  appropriate Table in
     each of  the  methods.   Only  analytes  that  failed the  test  in  Section  8.7
     need to  be  compared  with   these   criteria.     If the  recovery  of any  such
     analyte  falls  outside  the  designated   range,  the laboratory  performance
     for that  analyte  is  judged to  be out of  control, and  the problem  must be
     immediately identified and corrected.   The  result for that  analyte in  the
     unspiked  sample  is   suspect  and   may   not  be  reported   for regulatory
     compliance  purposes.

     8.9  As  part of the  QC  program  for  the laboratory,  method  accuracy for
each matrix studied must  be  assessed  and  records must be maintained.  After
the analysis  of  five spiked samples  (of  the  same matrix type)  as in  Section
8.7, calculate the average percent recovery   (p)  and the standard  deviation of
the percent recovery   (sp).    Express  the   accuracy  assessment  as a  percent
recovery  interval from JJ - 2sn to  p  +   2sp.     If  JJ = 90% and sp =  10%,  for
example,   the accuracy  interval  is  expressed  as 70-110%.   Update  the  accuracy
assessment for each analyte on a  regular  basis  (e.g. after each five to ten
new accuracy measurements).

     8.10  To determine acceptable accuracy and precision  limits for surrogate
standards the following procedure should be  performed.

          8.10.1  For  each sample analyzed,   calculate the percent recovery of
          cuvifnnal'o in tho camnlo
each surrogate in the sample
          8.10.2  Once a minimum of  thirty  samples  of  the same matrix have
     been analyzed, calculate the  average  percent  recovery (p) and standard
     deviation of the percent recovery (s) for each of the surrogates.

          8.10.3  For a given matrix,  calculate  the  upper and lower control
     limit for method performance for each surrogate standard.  This should be
     done as follows:
                                  8000 - 13
                                                         Revision
                                                         Date  September 1986

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               Upper  Control  Limit  (UCL) = p + 3s
               Lower  Control  Limit  (LCL) = p - 3s

          8.10.4   For aqueous and soil  matrices, these laboratory established
     surrogate  control  limits  should,  if  applicable,  be  compared with the
     control  limits listed   in  Tables  A  and  B  of  Methods  8240 and 8270,
     respectively.  The  limits given  in  these methods are multi-laboratory
     performance  based limits for soil  and aqueous samples, and therefore, the
     single-laboratory limits established in Paragraph 8.10.3 must fall within
     those given  in Tables  A and B  for  these matrices.

          8.10.5   If  recovery is not  within limits,  the following is required.

               •   Check to   be  sure  there  are  no errors  in calculations,
                  surrogate solutions  and  internal  standards.   Also, check
                  instrument performance.

               •   Recalculate the data  and/or  reanalyze  the extract if any  of
                  the above checks  reveal a problem.

               •   Reextract and reanalyze the  sample if none of the above are
                  a problem or flag the data as  "estimated  concentration."

          8.10.6   At   a  minimum,   each  laboratory   should update  surrogate
     recovery limits  on a matrix-by-matrix  basis,  annually.

     8.11  It is   recommended  that  the   laboratory adopt additional  quality
assurance practices  for use with this method.   The specific practices  that are
most productive depend upon the needs of   the  laboratory  and the  nature of the
samples.  Field duplicates  may  be  analyzed   to  assess  the  precision of the
environmental measurements.  When   doubt   exists  over  the  Identification of a
peak on the chromatogram,  confirmatory  techniques  such  as gas chromatography
with a dissimilar column, specific element  detector, or mass spectrometer must
be used.  Whenever possible,  the  laboratory  should  analyze standard reference
materials and participate in relevant performance evaluation studies.


9.0  METHOD PERFORMANCE

     9.1  The  method  detection  limit  (MDL)   is  defined  as  the  minimum
concentration of a   substance   that  can  be  measured  and  reported with  99%
confidence that the  value is above zero.   The MDL concentrations listed in  the
referring analytical   methods   were  obtained  using  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  Refer to the  determinative  method  for specific method performance
information.
                                  8000 - 14
                                                         Revision      0
                                                         Date  September 1986

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10.0  REFERENCES

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

2.  U.S. EPA  40  CFR  Part  136,  Appendix  B.  "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.

3.  U.S.  EPA  Contract  Laboratory  Program,  Statement  of  Work for Organic
Analysis, July 1985, Revision.
                                   8000 -  15
                                                          Revision
                                                         Date  September  1986

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                                            METHOD BOOO

                                        GAS CHROMATOGRAPHY
    7.1
   	1 Refer to
     determinative
        method for
        extraction
        procedure
                          7.4.3
    Select Internal
   standards having
  similar behavior  to
compounds of interest
    7.2
           Refer
         to deter-
   minative method
   for cleanup and
       separation
       procedures
7.4.1
                             7.4.3.2
                                                                                7.4.2.1
                                                              Prepare
                                                                              calibration
                                                                             standards  for
                                                                            each parameter
                                                                              of Interest
        Prepare
      calIbratIon
       standards
    Establish gas
    chromatograph
operating parameters;
 prepare calibration
      standards
                             7.4.3.3
                                                                             7.4.2
                                                                          Inject  calibration
                                                                          standard: prepare
                                                                          calibration curve
                                                                        or calibration  factor
          Inject
       colIbratIon
        standards;
      calculate HF
o
                             7.4.3.4
                                                                                7.4.2.3
                                                                            Verify  working
                                                                             cal IbratIon
                                                                            curve each day
                             Verify working
                               calIbration
                               curve or  RF
                                each day
                                                        7.5
                                Calculate
                             retention tlmo
                                 windows
                                                          O
                                        8000 -  16
                                                                   Revision       p
                                                                   Date  September  1986

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              METHOD 8000

           GAS CHROMATOGRAPH

               (Continued)
                                                      o
7.6.1
Use
Method
3810 or 3880
as screening
technique.
If necessary

7.6.1
into
mate
purge
(Met


Introduce
compounds
gas chro-
>graph by
•-and-trap
hod 5030)


volatile ^S 7.6.1 ^s^emlvolat 1 le
}S Type of ^\
* Vorganlc compound?>? *
7.6.1
Introduce
compounds Into
gas chromato-
graph by direct
Injection

7.6.4
extr
sol\
t
recc


Inject
sample
•act using
'ent flush
.echnlque;
>rd volume


Does response
exceed linear
   range of
   system?
                                                      chromatography
                                                           system
                                                        maintenance
                                                          If needed
Dilute extract
and reanalyze
                                                      Calculate
                                                  concentration of
                                                 each analyte. using
                                                 appropriate  formula
                                                 for matrix and typa
                                                    of standard
 Is peak deten-
tlon prevented by
  Interference?
                              Do  further
                               cleanup
                                                   7.6.8
                                                         Calibrate
                                                          system
                                                       Immediately
                                                         prior  to
                                                         analyses
                                                   7.6.9
                                                         Establish
                                                         dally
                                                   retention time
                                                     windows for
                                                     each analyte
           8000 - 17
                                      Revision       p
                                      Date   September  1986

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                                 METHOD 8010

                        HALOGENATED VOLATILE ORGANICS
1.0  SCOPE AND APPLICATION

     l.i  Method 8010  1s  used  to  determine  the  concentration  of various
volatile halogenated organic compounds.   Table 1 Indicates compounds that may
be analyzed by this  method  and  lists  the  method  detection limit for each
compound 1n reagent water.  Table 2 lists the practical  quantisation 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 analyzed
using direct injection or purge-and-trap  (Method 5030).  Ground water samples
must be analyzed using Method 5030.   A temperature program 1s used 1n the gas
chromatograph to separate the organic  compounds.   Detection is achieved by a
halogen-specific detector (HSD).

     2.2  The method provides an optional  gas chromatographic column that may
be helpful 1n resolving the analytes from interferences that may occur 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 field sample blank prepared
from 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 detector, analytical
     columns, recorder, gases, and syringes.  A  data system for measuring peak
     heights and/or peak  areas is  recommended.
                                   8010 -  1
                                                         Revision
                                                         Date  September 1986

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TABLE 1.  CHROMATOGRAPHIC CONDITIONS AND METHOD DETECTION. LIMITS  FOR
          HALOGENATED VOLATILE ORGANICS                     '•;:.,.'
Compound
Benzyl chloride
Bi s (2-chl oroethoxy)methane
Bi s (2-chl oroi sopropyl ) ether
Bromobenzene
Bromodi chl oromethane
Bromoform
Bromomethane
Carbon tetrachloride
Chl oroacetal dehyde
Chl orobenzene
Chloroethane
Chloroform
1-Chlorohexane
2-Chl oroethyl vinyl ether
Chl oromethane
Chloromethylmethyl ether
Chlorotoluene
Di bromochl oromethane
Dibromomethane
1 , 2-D1 chl orobenzene
1 , 3-Di chl orobenzene
1,4-Di chl orobenzene
Di chl orodi f 1 uoromethane
1,1-Di chl oroethane
1,2-Dichloroethane
1,1-Di chl oroethyl ene
trans-1 , 2-Di chl oroethyl ene
Di chl oromethane
1 , 2-D1 chl oropropane
trans-1 , 3-D1 chl oropropyl ene
1,1,2, 2-Tetrachl oroethane
1,1,1, 2-Tetrachl oroethane
Tetrachl oroethyl ene
1 , 1 , 1-Tri chl oroethane
1,1, 2-Tri chl oroethane
Tr1 chl oroethyl ene
Tri chl orof 1 uoromethane
Tri chl oropropane
Vinyl chloride
Retentlo
(ml
Col. 1




13.7
19.2

13.0

24.2
3.33
10.7

18.0
1.50


16.5

34.9
34.0
35.4

9.30
11.4
8.0
10.1

14.9
15.2
21.6

21.7
12.6
16.5
15.8
7.18

2.67
in time M
n) det
	 i
• • "• • • '•• • " ' ' I
Col. 2 (
•-.•-;•
...,-..." ; ; ' •• •_
•-• ••:. .: -. ,-i'i

14.6
M9.2 . .>:-
' • '• .'•','.
14.4
- ••»; •. •! : '••'',
18.8, •• » ,
8.68
12.1


5.28


16.6

23.5
22.4
22.3

12.6
15.4
7.72
9.38

16.6
16.6


15.0
13.1
18.1
13.1


5.28
ethod
ectlon
1m1ta
ug/L)
\-;\-'

: " /. ' •

0.10
,0.20
, -.
0.12
• 5
0.25
0.52
0.05

0.13
0.08


0.09

0.15
0.32
0.24

0.07
0.03
0.13
0.10

0.04
0.34
0.03

0.03
0.03
0.02
0.12


0.18
   a  Using  purge-and-trap method (Method 5030)
                                   8010 - 2
                                                          Revision      0
                                                          Date  September 1986

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2.  DETERMINATION OF PRACTICAL QUANTITATION LIMITS (PQL)  FOR VARIOUS
    MATRICES3


trlx                                                    Factor*5
 water                                                     10
vel soil                                                   10
m1sc1ble liquid waste                                     500
evel soil and sludge                                     1250
ter mlsdble waste                                       1250
Sample PQLs are highly  matrix-dependent.    The  PQLs listed herein are
rovided for guidance and may not always be achievable.

PQL = [Method detection limit (Table 1)] X [Factor (Table 2)].  For non-
queous samples, the factor 1s on a wet-weight basis.
                             8010 -  3
                                                    Revision       0
                                                    Date   September  1986

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          4.1.2   Columns:

              4.1.2.1   Column  1:   8-ft  x  O.l-1n  I.D.  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  I.D.  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  (HSD).

     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;  10-,  50-, 100-,  500-, and 1,000-mL  with a  ground-
glass stopper.

     4.5  Microsyringe;  10-, 25-uL with a 0.006-in I.D. needle  (Hamilton  702N
or equivalent) and a 100-uL.


5.0  REAGENTS

     5.1  Reagent water;  Reagent  water  is  defined  as  a water in which an
interferent is  not  observed  at  the  method  detection  limit  (MDL) of the
parameters of interest.

     5.2  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 of
the toxicity of these materials should be prepared in a hood.

          5.2.1  Place about 9.8 mL of methanol  in a 10-mL tared ground-glass-
     stoppered volumetric flask.  Allow  the  flask to stand, unstoppered, for
     about 10 min or until all   alcohol-wetted surfaces have dried.  Weigh the
     flask to the nearest 0.1 mg.

          5.2.2  Add the assayed  reference material, as described below.

               5.2.2.1  Liquids:  Using a  100-uL 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.

               5.2.2.2  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
                                  8010 -  4
                                                          Revision      0
                                                          Date  September 1986

-------
         meniscus.  Slowly  Introduce the reference standard above the surface
         of  the  liquid.   The  heavy  gas  rapidly dissolves 1n 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.

         5.2.3   Reweigh, dilute  to  volume, stopper, and then mix by inverting
     the  flask several times.   Calculate  the concentration in micrograms per
     microliter  (ug/uL) from the  net gain  in weight.  When compound purity 1s
     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.

         5.2.4   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.

         5.2.5   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.

     5.3   Secondary  dilution   standards:     Using  stock   standard solutions,
prepare 1n  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.

     5.4  Calibration standards;   Calibration  standards   at  a minimum of five
concentration levels are prepared in 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  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.

          5.4.1  Do not inject more than 20  uL  of alcoholic  standards  into  100
     ml of reagent water.

          5.4.2  Use  a  25-uL   Hamilton   702N   microsyringe  or  equivalent
      (variations in  needle  geometry  will   adversely  affect  the ability  to
     deliver reproducible volumes of methanolic standards  into water).

          5.4.3  Rapidly  inject  the  alcoholic    standard  into  the  filled
     volumetric flask.  Remove the needle as fast as possible after injection.

                                  8010 - 5
                                                         Revision      0
                                                         Date  September 1986

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          5.4.4  Mix aqueous  standards   by   inverting   the   flask  three times
     only.

          5.4.5  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).

          5.4.6  Never use pipets  to dilute  or  transfer  samples or aqueous
     standards.

          5.4.7  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.

     5.5  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  (Paragraph 5.6)  have  been
used successfully as  internal  standards,  because  of their generally unique
retention times.

          5.5.1  Prepare  calibration   standards   at   a   minimum  of  five
     concentration levels   for  each  parameter  of  interest  as described in
     Section 5.4.

          5.5.2  Prepare a  spiking  solution  containing  each of the internal
     standards  using the procedures described in  Sections 5.2 and 5.3.  It is
     recommended  that  the  secondary  dilution  standard  be  prepared  at a
     concentration of   15   ug/mL  of  each  internal   standard  compound.   The
     addition  of 10 uL  of   this  standard  to  5.0 ml of sample or calibration
     standard  would be  equivalent to 30 ug/L.

          5.5.3  Analyze each calibration  standard  according to Section 7.0,
     adding  10  uL  of   internal  standard  spiking  solution  directly to the
     syringe.

     5.6  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
water blank  with surrogate  halocarbons.   A combination of bromochloromethane,
2-bromo-l-chloropropane, and  1,4-dichlorobutane   is  recommended to encompass
the range of the temperature program used in this method.  From stock standard
solutions prepared as in Section  5.2,  add  a  volume  to give 750 ug of each
surrogate to 45 ml of   reagent  water  contained   in a  50-mL  volumetric flask,
mix, and  dilute to volume  for a concentration  of  15 ng/uL.    Add 10 uL 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  (Paragraph 5.5.2).


                                  8010 - 6
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                                                         Date  September 1986

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     5.7  Methanol:  pesticide quality or  equivalent.    Store away from other
solvents.
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-level  contaminated  soils  and
sediments.  For  medium-level  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:  Set helium gas  flow  at 40 mL/min flow rate.  Set
     column temperature at 45*C for 3 min; then program an 8*C/min temperature
     rise to 220*C and hold for 15 min.

          7.2.2  Column 2:  Set helium gas  flow  at 40 mL/min flow rate.  Set
     column temperature at 50*C for 3  min; then program a 6*C/min temperature
     rise to 170'C and hold for 4 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  Calibration  must   take   place   using   the   same   sample
     introduction method  that  will  be  used  to   analyze actual samples  (see
     Paragraph 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 Paragraph 7.4.1.1).  If  the internal standard calibration  technique
     is used,  add  10  uL  of  internal  standard to the sample prior to purging.

               7.4.1.1   Direct injection;   In very  limited applications  (e.g.,
          aqueous process wastes) direct  injection  of  the sample into  the GC
          system with a  10-uL syringe may be appropriate.  The detection limit
          is very  high   (approximately   10,000  ug/L)  therefore,  it is  only
                                   8010 - 7
                                                          Revision
                                                         Date  September  1986

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          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
     time windows,  and identification criteria.   Include a mid-level 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  Calculation of concentration   is  covered  in  Section  7.8 of
     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 reagent water.    The   dilution  must be performed on a
     second aliquot of the sample which   has   been  properly sealed and  stored
     prior to use.


8.0  QUALITY CONTROL

     8.1  Refer to Chapter  One  for  specific  quality  control  procedures  and
Method 8000 for gas chromatographic  procedures.   Quality control  to ensure  the
proper operation of the purge-and-trap device is covered in Method  5030.

     8.2  Mandatory quality control   to   validate   the  GC  system operation 1s
found in Method 8000, Section 8.6.

          8.2.1  The quality control  check  sample   concentrate  (Method 8000,
     Section 8.6) should contain each parameter of interest at a  concentration
     of 10 ug/mL 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, Section 8.10).
                                  8010 - 8
                                                         Revision      0
                                                         Date  September 1986

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                                                                            i
      00
      o
      H-»
      o

      I

      ID
 O 73
 DJ tt>
 r+ <
 fT> _i.
CO O
O> 3
ft)

CT
                                                     Column: 1% SP-1000 on Carbopacfc-B
                                                     Program: 46»C 3 Minute*. 8°/MinuM to 220°C
                                                     Detector:  Hall 700 A Electrolytic Conductivity
                                                                                                                                       1
                                                                                                                                       s
                                                                                                                                       o
                                                                                                                          e
                                                                                                                          o
                                                                                                                          «M
8     10     12     14     16     18      20     22     24


                           RETENTION TIME (MINUTES)
                                                                                                     26
28
30
32
34
36
00
                                                   Figure 1.  Gas Chromatogram of halogenated volatile organic*.

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          8.3.1   If recovery  is  not  within^limits,  the  following  is  required.

               •   Check to be  sure  there   are   no  errors   in  calculations,
                  surrogate solutions   and   internal  standards.   Also,  check
                  instrument  performance.

               •   Recalculate the data and/or reanalyze  the  extract if any of
                  the above checks reveal  a  problem.

               •   Reextract and  reanalyze  the sample   if none of the above are
                  a problem or flag the data as "estimated concentration."


9.0  METHOD PERFORMANCE

     9.1  This method  was  tested  by  20  laboratories  using reagent water,
drinking water,  surface water, and  three  industrial  wastewaters spiked at six
concentrations over  the  range   8.0-500  ug/L.    Single  operator precision,
overall precision, and method accuracy  were  found  to be directly related to
the concentration of the parameter  and  essentially independent of the sample
matrix.  Linear equations  to  describe  these  relationships 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., and J.J.  Lichtenberg,  J. Amer. Water Works Assoc., 66(12),
pp. 739-744, 1974.

2.  Bellar, T.A., and  J.J. Lichtenberg, "Semi-Automated Headspace Analysis of
Drinking  Waters  and  Industrial   Waters   for  Purgeable  Volatile  Organic
Compounds," in Van Hall, ed.,  Measurement  of Organic Pollutants in Water and
Wastewater, ASTM STP 686, pp. 108-129, 1979.

3.  Development and Application of  Test Procedures for Specific Organic Toxic
Substances in  Wastewaters:    Category  11  -  Purgeables  and  Category 12 -
Acrolein, Acrylonitrile, and Dichlorodifluoromethane,  Report for EPA Contract
68-03-2635 (in preparation).

4.  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.  Provost, L.P.  and  R.S.   Elder, "Interpretation of Percent Recovery Data,"
American Laboratory, 15, pp.   58-63, 1983.

6.  "EPA  Method   Validation  Study   23,  Method  601 (Purgeable  Halocarbons),"
Report  for EPA Contract  68-03-2856  (in preparation).
                                  8010 -  10
                                                         Revision
                                                         Date  September 1986

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TABLE 3.  CALIBRATION AND QC ACCEPTANCE CRITERIA3
Parameter
Bromodi chl oromethane
Bromoform
Bromome thane
Carbon tetrachloride
Chlorobenzene
Chloroethane
2-Chloroethyl vinyl ether
Chloroform
Chloromethane
Di bromochl oromethane
1,2-Di chlorobenzene
1,3-Di Chlorobenzene
1,4-Di chlorobenzene
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
trans-l,2-Dichloroethene
1,2-Di chl oropropane
cis-l,3-Dichloropropene
trans-l,3-Dichloropropene
Methylene chloride
1, 1,2,2-Tetrachloroethane
Tetrachloroethene
1,1, 1-Tri chl oroethane
1,1, 2-Tri chl oroethane
Trichloroethene
Tri chl orof 1 uoromethane
Vinyl chloride
Range
for Q
(ug/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
14.8-25.2
12.8-27.2
12.8-27.2
15.5-24.5
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
(ug/L)
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
5.2
7.3
7.3
4.0
9.2
5.4
4.9
3.9
4.2
6.0
5.7
Range
for 7
(ug/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
10.1-29.9
6.2-33.8
6.2-33.8
7.0-27.6
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
44-156
22-178
22-178
25-162
8-184
26-162
41-138
39-136
35-146
21-156
28-163
      Q = Concentration measured  in QC check sample, in ug/L.
      s = Standard deviation of four recovery measurements, in ug/L.
      7 = Average recovery  for four recovery measurements, in ug/L.
      P, Ps  =  Percent  recovery measured.
      D = Detected;  result  must be greater than zero.
      aCriteria from  40   CFR  Part  136   for  Method  601  and were calculated
      assuming  a QC check  sample concentration of 20 ug/L.
                                   8010 -  11
                                                          Revision       0
                                                          Date  September  1986

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TABLE 4.  METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION3
Parameter
Bromodi chl oromethane
Bromoform
Bromomethane
Carbon tetrachloride
Chlorobenzene
Chloroethane
2-Chloroethyl vinyl etherb
Chloroform
Chl oromethane
Di bromochl oromethane
1 , 2-Di chl orobenzene
1 , 3-Di chl orobenzene
1 , 4-Di chl orobenzene
1, 1-Di chloroethane
1, 2-Di chloroethane
1,1-Dichloroethene
trans-1, 2-Di chl oroethene
1 , 2-Di chl oropropane*5
ci s-1 , 3-Di chl oropropeneb
trans-1, 3-Di chl oropropene^
Methylene chloride
1,1, 2, 2-Tetrachl oroethene
Tetrachl oroethene
1,1, 1-Tri chl oroethane
1,1,2-Tri chloroethane
Trichloroethene
Trichlorofluoromethane
Vinyl chloride
Accuracy, as
recovery, x1
(ug/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
l.OOC
l.OOC
l.OOC
0.91C-0.93
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, sr'
(ug/L)
0.117+0.04
0.127+0.58
0.287+0.27
0.157+0.38
0.157-0.02
0.147-0.13
0.207
0.137+0.15
0.287-0.31
0.117+1.10
0.207+0.97
0.147+2.33
0.157+0.29
0.087+0.17
0.117+0.70
0.217-0.23
0.117+1.46
0.137
0.187
0.187
0.117+0.33
0.147+2.41
0.147+0.38
0.157+0.04
0.137-0.14
0.137-0.03
0.157+0.67
0.137+0.65
Overal 1
precision,
S1 (ug/L)
0.207+1.00
0.217+2.41
0.367+0.94
0.207+0.39
0.187+1.21
0.177+0.63
0.357
0.197-0.02
0.527+1.31
0.247+1.68
0.137+6.13
0.267+2.34
0.207+0.41
0.147+0.94
0.157+0.94
0.297-0.04
0.177+1.46
0.237
0.327
0.327
0.217+1.43
0.237+2.79
0.187+2.21
0.207+0.37
0.197+0.67
0.237+0.30
0.267+0.91
0.277+0.40
     x1  =  Expected  recovery  for  one  or  more  measurements  of  a  sample
            containing a concentration of C, in ug/L.
     sr' =  Expected  single analyst  standard  deviation  of measurements at an
            average concentration of 7, in ug/L.
     S1  =  Expected  interlaboratory standard  deviation  of measurements at an
            average concentration found of 7, in ug/L.
     C   =  True value for the concentration, in ug/L.
     7   =  Average recovery found for measurements of samples containing a
            concentration of C, in ug/L.
     aFrom  40 CFR Part 136 for Method 601.
     ^Estimates based upon the performance in a single laboratory.
                                  8010 - 12
                                                         Revision      0
                                                         Date  September 1986

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                                   METHOD 6010

                          WALOGENATED VOLATILE ORGANICS
        Start
 7. 1
 Introduce compounds
       Into gas
   chromatograph by
 direct Injection or
    purge-ano-trap
    (Method 5O30)
                                                       7.4.4
       Record
  volume  purged
or Injected  and
    peak  sizes
    7.2
       Set gas
    chromatograph
      condition
    7.3
                                                       7.4.5
     Calculate
  concentration
  (Section  7.6.
   Method BOOO)
o
      Cal lorate
      (refer to
     Method BOOO)
7 . J. 1
  Introduce volatile
  compounds Into gas
   chromatograph by
    Method 5030 or
   direct Injection
7.4.2
S<
In M«
for
sequc
Follow
sctlon 7.6
•thod 6000
analys Is
nee. etc .
                                                                                7.4.6
                          Analyze using
                            second GC
                             column
                                                                                7.4.7
                          Dilute second
                            aliquot of
                              •ample
                                        8010 - 13
                                                                  Revision        0
                                                                  Date  September 1986

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                                 METHOD 8015

                      NONHALOGENATED VOLATILE  ORGANICS
1.0  SCOPE AND APPLICATION

     1.1  Method 8015  is  used  to  determine  the  concentration   of various
nonhalogenated volatile organic compounds.     Table  1  indicates the compounds
that may be investigated by this method.


2.0  SUMMARY OF METHOD

     2.1  Method  8015  provides   gas   chromatographic  conditions  for  the
detection of certain nonhalogenated  volatile  organic compounds.  Samples may
be analyzed using direct  injection  or  purge-and-trap (Method 5030).  Ground
water samples must be analyzed by Method  5030.  A temperature program is used
in the gas chromatograph  to  separate  the  organic  compounds.  Detection is
achieved by a flame ionization detector (FID).

     2.2  If interferences are  encountered,  the  method provides an optional
gas chromatographic column that may be  helpful in resolving the analytes from
interferences that may occur and for analyte confirmation.


3.0  INTERFERENCES

     3.1  Refer to 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 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:  8-ft x 0.1-in I.D. stainless steel or glass
          column  packed  with  1%  SP-1000   on  Carbopack-B   60/80  mesh  or
          equivalent.


                                  8015 - 1
                                                         Revision      0	
                                                         Date   September 1986

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TABLE 1.  NONHALOGENATED VOLATILE ORGANICS
Aery1 amide
Diethyl ether
Ethanol
Methyl ethyl ketone  (MEK)
Methyl isobutyl ketone  (MIBK)
Paraldehyde (trimer  of  acetal.dehyde)
                                   8015 - 2
                                                          Revision      0
                                                          Date  September 1986

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               4.1.2.2  Column 2:  6-ft x 0.1-in I.D.  stainless steel  or glass
          column packed with n-octane  on  Porasil-C 100/120 mesh  (Durapak)  or
          equivalent.

          4.1.3  Detector:  Flame ionization (FID).

     4.2  Sample  introduction  apparatus:    Refer  to  Method  5030  for the
appropriate equipment for sample introduction purposes.

     4.3  Syringes;  A 5-mL  Luerlok  glass  hypodermic  and a 5-mL,  gas-tight
with shutoff valve.

     4.4  Volumetric flask;  10-, 50-, 100-, 500-,  and 1,000-mL with  a ground-
glass stopper.

     4.5  Microsyringe;  10- and 25-uL  with  a 0.006-in I.D. needle  (Hamilton
702N or equivalent) and a 100-uL.


5.0  REAGENTS

     5.1  Reagent water;  Reagent  water  is  defined  as  a water in which an
interferent is  not  observed  at  the  method  detection  limit  (MDL) of the
analytes of interest.

     5.2  Stock standards;  Stock solutions may be prepared from pure standard
materials or purchased as   certified   solutions.    Prepare stock standards in
methanol using assayed liquids.

          5.2.1  Place about 9.8 mL of methanol in a 10-mL tared ground-glass-
     stoppered volumetric  flask.  Allow   the  flask to stand,  unstoppered, for
     about  10 min  or until  all   alcohol-wetted  surfaces have dried.  Weigh the
     flask  to the  nearest  0.1 mg.

          5.2.2  Using a  100-uL  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.

          5.2.3  Reweigh,  dilute to volume,  stopper, and then  mix by  inverting
     the flask  several times.    Calculate  the  concentration  in micrograms per
     microliter  (ug/uL) 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.

          5.2.4  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.

          5.2.5  Standards  must  be   replaced   after   6  months,  or  sooner if
     comparison with check  standards  indicates  a problem.


                                  8015 - 3
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     5.3  Secondary dilution standards:    Using stock standard solutions,  pre-
pare in methanol  secondary  dilution  standards,   as  needed,  that contain the
compounds of  interest,   either  singly   or  mixed  together.     The secondary
dilution standards should be prepared  at concentrations such  that the aqueous
calibration standards prepared in Section  5.4  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.

     5.4  Calibration standards;  Calibration  standards  at a minimum of five
concentration levels are prepared in 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 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.

          5.4.1  Do not inject more than 20 uL of alcoholic standards into
     100 ml of reagent water.

          5.4.2  Use  a  25-uL   Hamilton   702N  microsyringe  or  equivalent
      (variations in  needle  geometry  will  adversely  affect  the ability to
     deliver reproducible volumes of methanolic standards into water).

          5.4.3  Rapidly  inject  the  alcoholic    standard  into  the  filled
     volumetric  flask.  Remove the needle as fast as possible after injection.

          5.4.4  Mix aqueous   standards  by  inverting  the  flask three  times
     only.

          5.4.5   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).

          5.4.6   Never  use  pipets   to  dilute  or  transfer samples or  aqueous
      standards.

          5.4.7   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.

      5.5 •Internal  standards  (if internal   standard  calibration  is  used);  To
 use  this.approach,  the  analyst must  select  one or more inter$l  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.
                                   8015 - 4
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          5.5.1  Prepare  calibration    standards    at    a   minimum  of   five
     concentration levels  for  each   parameter of   interest   as  described  in
     Section 5.4.

          5.5.2  Prepare a spiking  solution   containing  each  of  the internal
     standards using the procedures described in   Sections  5.2  and 5.3.   It  is
     recommended  that  the  secondary  dilution   standard   be   prepared   at a
     concentration of  15  ug/mL  of  each  internal  standard   compound.  The
     addition of 10 uL of  this  standard  to  5.0 ml of  sample or calibration
     standard would be equivalent to 30 ug/L.

          5.5.3  Analyze each calibration  standard   according  to  Section  7.0,
     adding 10  uL  of  internal  standard  spiking   solution   directly  to the
     syringe.

     5.6  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
water blank with one or  two  surrogate compounds  recommended to encompass the
range of  temperature  program  used  in  this  method.     From stock standard
solutions prepared as in Section  5.2,  add  a  volume  to  give 750 ug  of  each
surrogate to 45 mL of  reagent  water  contained   in a 50-mL volumetric  flask,
mix, and dilute to volume for a concentration  of  15 ng/uL.  Add 10 uL  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 (Paragraph 5.5.2).

     5.7  Methanol;  pesticide quality or  equivalent.   Store  away from other
solvents.

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-level  contaminated  soils  and
sediments.  For  medium-level  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:  Set helium gas  flow  at 40 mL/min flow rate.  Set
     column temperature  at 45°C for 3  min; then program an 8*C/min temperature
     rise to 220*C and hold for 15 min.
                                   8015 -  5
                                                         Revision
                                                         Date  September 1986

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          7.2.2  Column 2:   Set  helium  gas   flow  at 40 mL/min flow  rate.  Set
     column temperature at  50*C  for 3   min;  then  program  a 6*C/min temperature
     rise to 170*C and hold for  4 min.

     7.3  Calibration:    Refer    to   Method   8000   for proper calibration
techniques.
          7.3.1  Calibration  must
     introduction method that  will
     Section 7.4.1).
take   place   using   the   same  sample
be  used  to  analyze actual  samples (see
          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 uL 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  uL  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 ug/L);
          therefore, it is  only  permitted  when  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
     time windows, and identification criteria.   Include a mid-level  standard
     after each group of 10 samples in the analysis sequence.

          7.4.3  Record the sample volume purged or injected and the resulting
     peak sizes (in area units or peak heights).
          7.4.4  Calculation of concentration  is  covered  in
     Method 8000.
                           Section 7.8 of
          7.4.5   If analytical interferences are suspected, or for the purpose
     of confirmation, analysis using the second GC column is recommended.

          7.4.6   If the response for a  peak  is off-scale, prepare a dilution
     of the sample with reagent water.    The  dilution must be performed on a
     second-aliquot of the sample  which  has  been properly sealed and stored
     prior to  use.                    :
                                  8015 - 6
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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, Section 8.6.

     8.3  Calculate surrogate standard  recovery  on  all  samples, blanks, and
spikes.   Determine  if  recovery  is  within  limits  (limits  established by
performing QC procedure outlined in Method 8000, Section 8.10).

          8.3.1  If recovery is not within limits, the following is required.

               •  Check to  be  sure  there  are  no  errors  in calculations,
                  surrogate solutions  and  internal  standards.   Also,  check
                  instrument performance.

               •  Recalculate the data and/or reanalyze  the extract if any of
                  the above checks reveal a problem.

               •  Reextract and reanalyze the sample  if none of the above are
                  a problem or flag the data as "estimated concentration."


9.0  METHOD PERFORMANCE

     9.1  The accuracy and precision obtained will be determined by the sample
matrix, sample introduction technique, and calibration procedures used.

     9.2  Specific method  performance   information  will  be   provided   as  it
becomes available.
 10.0   REFERENCES

 1.  Bellar,  T.A.,  and J.J.   Lichtenberg,  J. Amer. Water Works Assoc., 66(12),
 pp. 739-744,  1974.

 2.  Bellar,  T.A.,  and   J.J.   Lichtenberg, Semi-Automated Headspace Analysis of
 Drinking   Waters   and   Industrial   Waters   for   Purgeable  Volatile  Organic
 Compounds,  in Van  Hall,  ed.,   Measurement  of  Organic  Pollutants in Water and
 Wastewater,  ASTM STP 686,  pp.  108-129,  1979.

 3.  Development and Application  of  Test Procedures  for Specific Organic Toxic
 Substances in Wastewaters:    Category 11  -  Purgeables   and  Category 12  -
 Acrolein,  Acrylonitrile,  and  Dichlorodifluoromethane,   Report for EPA Contract
 68-03-2635 (in preparation).
                                   8015 -  7
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                                                          Date  September  1986

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                                         METHOD 8015

                              NONrlALDGENATEw VOLATILE ORSASICS
       Stai-t
7. 1
Introduce compcunos
      into gas
  cnromatograeh by
direct Injection o.~
   purge-ano-t-sp
   (Method 503C;
   7 .S
      Set gas
      oTiatog~e
     condition
   7.3
     Cal ibrste
      (refe- tc
    Metnoc BCOO!
 Introduce volatile
 compojnos Into gas
  ch"-ornBtogf'Bch by
   Method 503C o-
  dlrect Injection
         Follow
      Section 7.6
   In Methoo 6000
     for- analysis
   sequence,  etc.
                          o
o
       Record
  volume purged
or injected and
    peak sizes
                                                      7.4.4
                           Calculate
                        concentration
                         (Section 7.6.
                         Method 6000)
                              O
                                                                                7.4.5
                                                 Analyze  using
                                                   second  GC
                                                    column
                                                                      Yes
                      /              VI V
                      Is response for X.
                      • peak off-scale?
                                                                                7.4.6
                                                 Dilute  second
                                                   aliquot  of
                                                     •ample
                                     8015 -  8
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                                                                 Date   September  1986

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                                 METHOD 8020

                         AROMATIC VOLATILE ORGANICS
1.0  SCOPE AND APPLICATION

     1.1  Method 8020  1s  used  to  determine  the  concentration  of various
aromatic volatile organic compounds.  Table 1 indicates compounds which may be
determined by this  method  and  lists  the  method  detection  limit for each
compound In reagent water.    Table  2  lists the practical  quantitation limit
(PQL) 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 analyzed using direct injection
or purge-and-trap (Method  5030).    Ground  water  samples must be determined
using Method 5030.  A temperature program  is used in the gas chromatograph to
separate the organic compounds.   Detection  is achieved by a photo-ionization
detector (PID).

     2.2   If interferences are  encountered,  the  method provides an optional
gas  chromatographic column that may be  helpful 1n 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 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.
                                   8020 - 1
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                                                          Date  September  1986

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TABLE 1.  CHROMATOGRAPHIC CONDITIONS AND METHOD DETECTION LIMITS FOR AROMATIC
          VOLATILE ORGANICS



Compound
Benzene
Chloroberizene
1,4-Dichlorobenzene
1 , 3-Di chl orobenzene
1 , 2-Di chl orobenzene
Ethyl Benzene
Toluene
Xylenes
Retention
(m1n)

Col. 1
3.33
9.17
16.8
18.2
25.9
8.25
5.75

time


Col. 2
2.75
8.02
16.2
15.0
19.4
6.25
4.25

Method
detection
11m1ta
(ug/L)
0.2
0.2
0.3
0.4
0.4
0.2
0.2

    a Using purge-and-trap method  (Method 5030).
TABLE 2.  DETERMINATION OF  PRACTICAL QUANTITATION  LIMITS  (PQL)  FOR VARIOUS
          MATRICES3


    Matrix                                                     Factorb
Ground water                                                      10
Low-level  soil                                                    10
Water miscible  liquid  waste                                      500
High-level  soil  and  sludge                                      1250
Non-water  miscible waste                                        1250
      aSample  PQLs  are  highly   matrix-dependent.     The   PQLs  listed  herein  are
      provided for  guidance  and may  not  always  be  achievable.

      bPQL  = {Method  detection  limit (Table  1)] X  [Factor (Table 2)].   For non-
      aqueous  samples,, the factor  is on  a wet-weight basis.
                                   8020 T-  2
                                                          Revision
                                                         Date  September  1986

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          4.1.2  Columns:

               4.1.2.1  Column 1:  6-ft  x  0.082-in I.D.  #304 stainless steel
          or glass column  packed  with  5%  SP-1200  and   1.75% Bentone-34 on
          100/120 mesh Supelcort or equivalent.

               4.1.2.2  Column 2:  8-ft x 0.1-in I.D. stainless steel  or glass
          column packed with 5% 1,2,3-Tris(2-cyanoethoxy)propane on 60/80 mesh
          Chromosorb W-AW or equivalent.

          4.1.3  Detector:  Photoionization  (PID)   (h-Nu   Systems, Inc. Model
     PI-51-02 or equivalent).

     4.2  Sample  introduction  apparatus;    Refer  to  Method  5030   for the
appropriate equipment for sample introduction purposes.

     4.3  Syringes:  A 5-mL  Luerlok  glass  hypodermic  and a 5-mL, gas-tight
with shutoff valve.

     4.4  Volumetric flask:  10-, 50-, 100-, 500-,  and 1,000-mL with a ground-
glass stopper.

     4.5  Microsyringe:  10- and 25-uL  with  a 0.006-in I.D. needle (Hamilton
702N or equivalent) and a 100-uL.


5.0  REAGENTS

     5.1  Reagent water;  Reagent  water  is  defined  as  a water in which an
interferent is  not  observed  at  the  method  detection  limit   (MDL) of the
parameters of interest.

     5.2  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.

          5.2.1  Place about 9.8  mL of  methanol in a  10-mL tared ground-g5!ass-
     stoppered volumetric  flask.  Allow  the  flask  to stand, unstoppered, for
     about 10 min  or  until  all   alcohol-wetted  surfaces have dried.  Weigh the
     flask to the  nearest  0.1  mg.

          5.2.2  Using a  100-uL  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.

          5.2.3  Reweigh,  dilute  to volume, stopper,  and then mix  by inverting
     the flask several times.    Calculate  the  concentration in micrograms per
     microliter  (ug/uL)  from the  net  gain  in weight.  When compound purity is
     assayed  to be 96% or  greater,  the  weight may  be used without correction
                                  8020 -  3
                                                         Revision
                                                         Date  September 1986

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     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.

          5.2.4  Transfer the  stock  standard   solution  into a  Teflon-sealed
     screw-cap bottle.  Store, with minimal headspace,  at 4*C and protect from
     light. •'•

          5.2.5  All standards must be replaced   after   6 months, or sooner if
     comparison with check standards indicates  a problem.

     5.3  Secondary dilution standards;   Using  stock  standard solutions, pre-
pare in methanol secondary  dilution  standards,  as   needed, that contain  the
compounds of  interest,   either  singly  or  mixed together.    The secondary
dilution standards, should be prepared  at concentrations such that the aqueous
calibration standards prepared in Paragraph 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.

     5.4  Calibration standards:  Calibration  standards  at a minimum of five
concentration levels are prepared in 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 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.

          5.4.1  Do not inject more than 20 uL of alcoholic standards into 100
     ml of reagent water.

          5.4.2  Use  a  25-uL   Hamilton   702N  microsyringe  or  equivalent
      (variations in  needle  geometry  will  adversely  affect  the ability to
     deliver reproducible volumes of methanolic standards into water).

          5.4.3  Rapidly  inject  the  alcoholic   standard  into  the   filled
     volumetric  flask.  Remove the needle  as fast as possible after injection.

          5.4.4  Mix aqueous   standards  by  inverting  the  flask three times
     only.

          5.4.5- 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).
                                  8020 - 4
                                                         Revision
                                                         Date  September 1986

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          5.4.6  Never use pipets  to  dilute  or  transfer samples  or aqueous
     standards.

          5.4.7  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.

     5.5  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
compound,  alpha,alpha,alpha-trifluorotoluene   recommended   for   use  as  a
surrogate spiking compound (Paragraph  5.6)  has  been used successfully as an
internal standards.

          5.5.1  Prepare  calibration   standards   at   a   minimum  of  five
     concentration levels  for  each  parameter  of  interest  as described in
     Section 5.4.

          5.5.2  Prepare a spiking  solution  containing  each of the internal
     standards using the procedures described in  Sections 5.2 and 5.3.  It is
     recommended  that  the  secondary  dilution  standard  be  prepared  at a
     concentration of  15  ug/mL  of  each  internal  standard  compound.  The
     addition of 10 uL of  this  standard  to  5.0 mL of sample or calibration
     standard would be equivalent to 30 ug/L.

          5.5.3  Analyze each calibration  standard  according to Section 7.0,
     adding 10  uL  of  internal  standard  spiking  solution  directly to the
     syringe.

     5.6  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
water blank with surrogate compounds  (e.g, alpha.alpha,alpha-trifluorotoluene)
recommended to encompass the  range  of  the  temperature program used in this
method.  From  stock  standard  solutions  prepared  as  in  Section 5.2, add a
volume to give 750 ug of each surrogate to 45 mL of reagent water contained in
a 50-mL volumetric flask, mix, and dilute to volume for a concentration of
15 ng/uL.  Add 10 uL 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  (Paragraph 5.5.2).

     5.7  Methanol;  pesticide quality or  equivalent.   Store  away from other
solvents.
                                  8020 - 5
                                                         Revision      0
                                                         Date  September 1986

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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  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-level  contaminated  soils  and
sediments.  For  medium-level  soils  or  sediments, methanollc extraction, as
described 1n Method 5030, may be necessary prior to purge-and-trap analysis.

     7.2  Gas chromatography conditions (Recommended);

          7.2.1  Column  1:  Set helium gas  flow  at 36 mL/m1n flow rate.  The
     temperature  program  sequences  are  as  follows:    For  lower  boiling
     compounds, operate  at 50'C isothermal for  2 min; then program at 6*C/m1n
     to 90*C and hold until  all  compounds  have  eluted.  For higher boiling
     range of compounds, operate at 50*C Isothermal for 2 m1n; then program at
     3*C/min to 110'C and  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:  Set helium gas  flow  at 30 mL/min flow rate.  The
     temperature program sequence 1s as  follows:   40*C Isothermal for 2 min;
     then 2°C/min to 100'C and hold  until  all compounds have eluted.  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  aromatlcs  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.
                                   8020 - 6
                                                          Revision
                                                          Date   September  1986

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    7.4  Gas chromatographlc 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 uL 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 uL syringe may be appropriate.  The detection limit
         is very high  (approximately   10,000  ug/L);  therefore,   it is only
         permitted when 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  of  Method  8000  for instructions on the
    analysis  sequence,  appropriate  dilutions,   establishing daily retention
    time windows,  and  identification criteria.    Include a mid-level standard
    after  each group of 10  samples  1n 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  Section  7.8  of
     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 reagent water.     The  dilution  must  be performed ion 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 1n  Method  5030.

     8.2  Mandatory quality control   to  validate   the  GC  system operation  is
found in Method 8000,  Section 8.6.
                                  8020 - .7
                                                         Revision      0
                                                         Date  September 1986

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                                                                                Column: 5% SP-1200/1.75% Bentone34
                                                                                Program: 60<>C-2 Minutes. 6°C/Min. to 90°C
                                                                                Detector: Photoionization
                                                                                Sample: 0.40 jig/I Standard Mixture
     oo
     o
     ro
     o
     oo
Ql  (V
rf <
(/) O
(t> =3
O
(D
                                                6        8        10       12       14

                                                          RETENTION TIME (MINUTES)
16
18
20
22
00
0>
                                Figure 1. Chromatogram of aromatic volatile organics (column 1 conditions).

-------
                                  Column:  5% 1.2.3-Trii (2-Cyanoetrtoxy)
                                  Propane on Chromosorb—W
                                  Program:  40°C-2 Minutei 2OC/Min. to 100«C
                                  Detector: Photoionization
                                  Samplt: 2.0 MB/1 Standard Mixture
                        8          12         16

                       RETENTION TIME (MINUTES)
20
24
Figure 2. Chromatogram of aromatic volatile organics (column 2 conditions).
                        8020  - 9
                                                   Revision       Q
                                                   Date   September 1986

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          8.2.1  The quality control   check  sample  concentrate (Method 8000,
     Section 8.6) should contain each parameter of Interest at a concentration
     of 10 ug/mL 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, Section 8.10).

          8.3.1  If recovery is not within limits, the following is required.

               •  Check to  be  sure  there  are  no  errors  in calculations,
                  surrogate solutions  and  internal  standards.   Also, check
                  instrument performance.

               •  Recalculate the data and/or reanalyze  the extract if any of
                  the above checks reveal a problem.

               •  Reextract and reanalyze the sample  if none of the above are
                  a problem or flag the data as "estimated concentration."


9.0  METHOD PERFORMANCE

     9.1  This method  was  tested  by  20  laboratories  using reagent water,
drinking water,  surface water, and  three industrial wastewaters spiked at six
concentrations over  the  range  2.1-500  ug/L.    Single  operator precision,
overall precision, and method accuracy  were  found  to be directly related to
the concentration of the parameter  and  essentially independent of the sample
matrix.  Linear  equations   to  describe  these  relationships 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.,  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.
                                  8020 -  10
                                                          Revision      0
                                                          Date  September  1986

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3.  Dowty, B.J., S.R. Antolne, 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.  Provost, L.P., and R.S. Elder,  ."Interpretation of Percent Recovery Data,"
American Laboratory,  15, pp. 58-63, 1983.
                                   8020 - 11
                                                          Revision
                                                          Date  September 1986

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TABLE 3.  CALIBRATION AND QC ACCEPTANCE CRITERIA3
Parameter
Benzene
Chl orobenzene



1 , 2-Di chl orobenzene
1 , 3-Di chl orobenzene
1 , 4-D1 chl orobenzene
Ethyl benzene
Toluene
,

Range
for Q
(ug/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
(ug/L)
4.1
3.5
5.8
5.0
5.5
6.7
4.0
Range
for 7
(ug/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, PS
t V \
\ /
39-150
55-135
37-154
50-141
42-143
32-160
46-148
     Q = Concentration measured 1n QC check sample, 1n ug/L.

     s = Standard deviation of four recovery measurements, In ug/L.

     7 = Average recovery for four recovery measurements, 1n ug/L.

     P, Ps = Percent recovery measured.

     aCr1ter1a are from 40 CFR  Part  136  for  Method 602 and were calculated
assuming a QC check sample concentration of 20 ug/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.
                                   8020 -  12
                                                          Revision
                                                         Date  September  1986

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TABLE 4.  METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION


Parameter
Benzene
Chlorobenzene
1 , 2-D1 chl orobenzene
1,3-01 chlorobenzene
1 , 4-D1 chl orobenzene
Ethyl benzene
Toluene
Accuracy, as
recovery, x1
(ug/L)
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 Overall
precision, sr'
(ug/L)
0.097+0.59
0.097+0.23
0.177-0.04
0.157-0.10
0.157+0.28
0.177+0.46
0.097+0.48
precision,
S1 (ug/L)
0.217+0.56
0.177+0.10
0.227+0.53
0.197+0.09
0.207+0.41
0.267+0.23
0.187-0.71
     x1  = Expected  recovery  for  one  or  more  measurements  of  a  sample
           containing a concentration of C, in ug/L.

     sr' = Expected single analyst  standard  deviation  of measurements at an
           average concentration of 7, 1n ug/L.

     S1  = Expected interlaboratory standard  deviation  of measurements at an
           average concentration found of 7, in ug/L.

     C   = True value for the concentration, in ug/L.

     7   = Average recovery found for measurements of samples containing a
           concentration of C, 1n ug/L.
                                   8020 -  13
                                                         Revision      0
                                                         Date  September 1986

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                                          METHOD B020

                                  AROMATIC VOLATILE ORGANICS
 7. J
                                                          Q
 Introduce compounds
       Into gas
   chromatograph by
 direct Injection or
    purge-ano-trap
    (Method 5030)
    7.2
                                                       7.4.4
       Record
  volume purged
or injected and
    peak sizes
       Set gas
    chromatosraph
      condition
    7.3
                                                       7.4.5
     Calculate
  concentration
  (Section 7.6.
   Method BOOO)
   o
      Calibrate
      (refer tc
     Method 6000!
7.4.1
                                                                      Yes
'              \.' B
 Are analytically.
 Interferences
  suspected?
                                                                                7.4.6
  Introduce volatile
  compounds into gas
   chromatooraph by
    Method 5030 or
   direct injection
   7.4.8
          Follow
       Section 7.6
    in Method BOOO
      for analysis
    sequence,  etc.
Analyze using
  second GC
   column
                           Dilute  second
                             aliquot  of
                               sample
                                     8020 -  14
                                                                Revision       0
                                                                Date  September  1986

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                                 METHOD 8030

                    ACROLEIN.  ACRYLONITRILE. ACETONITRILE
1.0  SCOPE AND APPLICATION

     1.1  Method 8030 is used to  determine the concentration of the following
three volatile organic compounds:

          Acrolein (Propenal)
          Acrylonltrile
          Acetonltrile

     1.2  Table 1 lists chromatographlc conditions and method detection limits
for acrolein and acrylonitrlle in reagent  water.  Table 2 lists the practical
quantisation limit (PQL) for other matrices.


2.0  SUMMARY OF METHOD

     2.1  Method  8030  provides   gas   chromatographlc  conditions  for  the
detection of the three 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.   A temperature program is used 1n the gas
chromatograph to separate the organic  compounds.   Detection 1s achieved by a
flame ionization detector (FID).

     2.2  The method provides an optional  gas chromatographlc column that may
be helpful  in resolving the  analytes from interferences that may occur and for
analyte confirmation.


3.0  INTERFERENCES

     3.1  Refer to Methods 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 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 height and/or peak area  1s recommended.

                                   8030 - 1
                                                         Revision      0
                                                         Date  September 1986

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TABLE 1.  CHROMATOGRAPHIC CONDITIONS AND METHOD DETECTION LIMITS

                                         Retention time            Method
                                              (m1n)               detection
                                                                   I1m1ta
Compound                               Col.  1Col.  2         (ug/L)
Acroleln                                 10.6         8.2            0.7
Acrylon1tr1le                            12.7         9.8            0.5
     a Based on using purge-and-trap, Method 5030.
TABLE 2.  DETERMINATION OF PRACTICAL QUANTITATION LIMITS (PQL) FOR VARIOUS
          MATRICES3


    Matrix                                                    Factorb


Ground water                                                     10
Low-level soil                                                   10
Water mlsdble  liquid waste                                     500
High-level  soil  and  sludge                                     1250
Non-water mlsdble waste                                       1250


     aSample  PQLs are highly  matrix-dependent.    The  PQLs  listed herein are
provided for  guidance and may not always be achievable.

     bPQL = .[Method  detection limit  (Table 1)] X  [Factor (Table 2)].  For non-
aqueous samples, the factor 1s on a wet-weight basis.
                                  8030 - 2
                                                         Revision
                                                         Date  September 1986

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          4.1.2  Columns:

               4.1.2.1  Column 1:   10-ft x  2-mm I.D.  stainless  steel or glass
          packed with Porapak-QS (80/100 mesh)  or equivalent.

               4.1.2.2  Column 2:   6-ft x O.l-1n I.D.  stainless  steel or glass
          packed with Chromosorb 101 (60/80 mesh)  or equivalent.

          4.1.3  Detector:  Flame 1on1zat1on (FID).

     4.2  Sample  Introduction  apparatus;    Refer  to  Method   5030   for the
appropriate equipment for sample Introduction purposes.

     4.3  Syringes:  A 5-mL  Luerlok  glass  hypodermic  and a 5-mL, gas-tight
with shutoff valve.

     4.4  Volumetric flask;  10-, 50-, 100-, 500-, and 1,000-mL with  a  ground-
glass stopper.

     4.5  Microsyringe;  10- and 25-uL  with  a 0.006-1n I.D. needle  (Hamilton
702N or equivalent) and a 100-uL.


5.0  REAGENTS

     5.1  Reagent water;  Reagent  water   1s  defined  as  a water 1n which an
interferent  isnotoEserved   at  the  method  detection  limit  (MDL) of the
parameters of  interest.

     5.2  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  acroleln  and  acrylonitrlle are
lachrymators,  primary dilutions of these compounds   should  be prepared in a
hood.

          5.2.1   Place  about  9.8 ml of reagent  water  1n a 10-mL tared ground-
     glass-stoppered  volumetric flask.     For   acrolein  standards the reagent
     water must  be adjusted to  pH  4-5 using hydrochloric add  (1:1)  or sodium
     hydroxide (10 N),  if necessary.   Weigh the flask  to the nearest 0.1 mg.

          5.2.2   Using  a  100-uL syringe,  Immediately   add two or more drops of
     assayed reference  material to the  flask;  then reweigh.  The liquid must
     fall directly into the water  without contacting the neck of the flask.

          5.2.3   Reweigh,  dilute to volume, stopper, and then mix by Inverting
     the  flask several  times.   Calculate  the  concentration 1n mlcrograms per
     microllter  (ug/uL) from  the net  gain  1n weight.  When compound purity 1s
     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.
                                   8030 - 3
                                                          Revision
                                                          Date   September  1986

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          5.2.4  Transfer the  stock  standard   solution   Into a Teflon-sealed
     screw-cap bottle.   Store,  with minimal  headspace,  at 4*C and protect  from
     light.

          5.2.5  Prepare fresh standards dally.

     5.3  Secondary dilution standards;   Using  stock standard solutions,  pre-
pare In reagent water  secondarydTTution  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 Paragraph 5.4  will bracket the working range
of the analytical system.  Secondary  dilution standards should be stored with
minimal headspace for volatlles and should  be checked frequently for signs of
degradation or evaporation,  especially  just  prior  to preparing calibration
standards from them.

     5.4  Calibration standards;  Calibration  standards  at a minimum of five
concentration levels are prepared in 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 concentrations
found in real samples or  should  define  the  working  range of the GC.  Each
standard should contain each analyte for  detection  by this method.  In order
to prepare accurate aqueous standard solutions,  the following precautions must
be observed.

          5.4.1  Use  a  25-uL   Hamilton   702N  microsyrlnge  or  equivalent
     (variations in  needle  geometry  will  adversely  affect  the ability to
     deliver reproducible volumes of standards into water).

          5.4.2  Never use plpets  to  dilute  or  transfer samples or aqueous
     standards.

          5.4.3  These standards must be prepared daily.

     5.5   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 1s not
affected by method or matrix Interferences.   Because of these  limitations, no
Internal standard can be suggested that is applicable to all  samples.

           5.5.1  Prepare  calibration   standards   at   a    minimum  of  five
     concentration  levels   for  each   parameter  of  interest  as described 1n
     Section 5.4.

           5.5.2  Prepare a  spiking  solution  containing  each  of the internal
     standards using the procedures described 1n  Sections  5.2  and  5.3.   It is
     recommended  that   the secondary dilution  standard   be   prepared  at a
     concentration  of   15   ug/mL   of   each   internal   standard   compound.  The
     addition of 10 uL of   this  standard   to   5.0  ml  of sample or  calibration
     standard would be equivalent  to  30 ug/L.


                                   8030 - 4
                                                          Revision      0
                                                          Date  September  1986

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          5.5.3  Analyze each calibration  standard  according to Section 7.0,
     adding 10  uL  of  Internal   standard  spiking  solution  directly to the
     syringe.

     5.6  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
water blank with one or  two  surrogate  compounds (e.g., compounds similar in
analytical behavior to the analytes of  interest but which are not expected to
be  present  in  the  sample)  recommended  to  encompass  the  range  of  the
temperature program  used  in  this  method.    From  stock standard solutions
prepared as in Section 5.2, add a  volume  to give 750 ug of each surrogate to
45 ml of reagent water contained in  a 50-mL volumetric flask, mix, and dilute
to volume for a  concentration  of  15  ng/uL.    Add  10 uL 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  (Paragraph 5.5.2).


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-level  contaminated  soils  and
sediments.    For  high-level   soils  or  sediments,  methanollc 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:  Set helium gas  flow  at 30 mL/m1n flow rate.  Set
      column temperature  at 110*C  for 1.5 m1n; then heat as rapidly as possible
      to 150*C and hold for 20  min.

          7.2.2   Column  2:  Set helium gas  flow  at 40 mL/min flow rate.  Set
      column temperature  at 80*C for 4  min;  then program at 50*C/m1n to 120°C
      and hold for 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   Calibration   must  take   place   using   the    same  sample
      introduction method that  will  be  used  to  analyze actual  samples  (see
      Section  7.4.1).
                                   8030 - 5
                                                          Revision
                                                          Date   September 1986

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         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 chromatographlc 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 1s used, add
    10 uL of the Internal standard to the sample prior to purging.

               7.4.1.1  Direct Injection:   In very limited applications  (e.g.,
         aqueous process wastes), direct Injection  of the sample  Into  the GC
         system with a 10 uL syringe may be appropriate.  The detection limit
         Is very high  (approximately   10,000  ug/L);  therefore,   1t 1s  only
         permitted when 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  of  Method  8000  for  Instructions  on the
     analysis  sequence,  appropriate   dilutions,   establishing daily retention
     time windows,  and  identification  criteria.    Include a mid-level  standard
     after  each group of 10  samples  in the  analysis  sequence.

         7.4.3  Table  1   summarizes    rthe   estimated   retention   times   and
     detection  limits  for  a  number  of organic compounds  analyzable using  this
     method.   Figure  1  illustrates  the  chromatographlc  separation  of acrolein
     and  of acrylonitrile  using  Column 1.

         7.4.4  Record the  sample volume purged or  injected  and  the resulting
     peak sizes (in area  units or peak heights).

         7.4.5  Calculation of  concentration   is  covered   in  Section  7.8 of
     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  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.
                                  8030 - 6
                                                         Revision      0
                                                         Date  September 1986

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  Column: Porapak-QS
  Program. 110°C for 1.5 mm. rapidly
         healed to 150°C
  Detector: Flame lonization
  1.6
30
45
60
7.5
9.0
10.5
120,  135
150
                 RETENTION TIME. MtN.
Figure 1.  Gas  chromatogram of acroleln  and  acrylonltrlle.
                        8030 - 7
                                               Revision       0
                                               Date   September 1986

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     8.2  Procedures to check  the  GC  system  operation  are found 1n Method
8000, Section 8.6.

          8.2.1  The quality control  check  sample  concentrate (Method 8000,
     Section 8.6) should contain each parameter of Interest at a concentration
     of 25 ug/mL 1n reagent water.

          8.2.2  Table 3 Indicates the  calibration and QC acceptance criteria
     for this method.  Table 4  gives single laboratory accuracy and precision
     for the analytes of Interest.  The contents of both Tables should be used
     to evaluate a  laboratory's  ability  to  perform and generate acceptable
     data by this method.

     8.3  Calculate surrogate standard  recovery  on  all samples,  blanks, and
spikes.   Determine  If  recovery  1s  within  limits  (limits  established by
performing QC procedure outlined 1n Method 8000, Section 8.10).

          8.3.1  If recovery 1s not within limits, the following 1s required.

               •  Check to  be  sure  there  are  no  errors  1n calculations,
                  surrogate solutions  and  Internal  standards.   Also, check
                  Instrument performance.

               •  Recalculate the data and/or reanalyze  the extract 1f any of
                  the above checks  reveal a problem.

               •  Reextract and reanalyze the sample  1f none of the above are
                  a problem or flag the data as "estimated concentration."


9.0  METHOD  PERFORMANCE

     9.1   In  a   single  laboratory,   the  average  recoveries  and   standard
deviations presented  1n  Table  4  were  obtained  using  Method   5030.   Seven
replicate  samples were analyzed at  each spike level.

     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.  Uchtenberg,  J.  Amer. Water Works  Assoc.,  66(12),
pp.  739-744, 1974.

2.   Bellar,  T.A.  and  J.J.  Uchtenberg,   "Semi-Automated Headspace Analysis  of
Drinking   Waters and  Industrial   Waters   for   Purgeable   Volatile   Organic
Compounds,"  1n Van  Hall, ed.,  Measurement  of  Organic  Pollutants  1n Water and
Wastewater,  ASTM STP  686,  pp.  108-129, 1979.
                                   8030 - 8
                                                          Revision
                                                          Date  September  1986

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3.  Development and Application of Test  Procedures for Specific Organic Toxic
Substances in Wastewaters, Category 11:  Purgeables and Category 12: Acrolein,
Acrylonitrile, and Dichlorodifluoromethane, Report for EPA Contract 68-03-2635
(in preparation).

4.  Going, J.,  et  al.,  Environmental  Monitoring  Near  Industrial  Sites -
Acrylonitrile, Office  of  Toxic  Substances,  U.S.  EPA,  Washington, DC, EPA
560/6-79-003, 1979.

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

6.  Provost, L.P. and R.S.  Elder,  "Interpretation of Percent Recovery Data,"
American Laboratory, lj>, pp. 58-63, 1983.

7.  Kerns, E.H., et al. "Determination  of Acrolein and Acrylonitrile in Water
by Heated Purge  and  Trap  Technique,"  U.S. Environmental Protection Agency,
Environmental Monitoring and Support Laboratory, Cincinnati, Ohio 45268, 1980.

8.  "Evaluation of Method 603," Final  Report  for EPA Contract 68-03-1760 (in
preparation).
                                   8030 - 9
                                                          Revision
                                                          Date  September 1986

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TABLE 3.  CALIBRATION AND QC ACCEPTANCE CRITERIA3
Parameter
Acrolein
Acrylonitrile
Range
for Q
(ug/L).
45.9-54.1
41.2-58.8
Limit
for S
(ug/L)
4.6
9.9
Range
for 7
(ug/L)
42.9-60.1
33.1-69.9
Range
P. PS
(%)
88-118
71-135
     Q = Concentration measured in QC check sample, in ug/L.

     S = Standard deviation of four recovery measurements, in ug/L.

     7 = Average recovery for four recovery measurements, in ug/L.

     P, Ps = Percent recovery measured.

     Criteria from  40  CFR  Part  136  for  Method  603  and were calculated
     assuming a QC check sample concentration of 50 ug/L.
 TABLE 4.  SINGLE  LABORATORY ACCURACY AND PRECISION
Parameter
Acrolein





Acrylonitrile





Spi ke
cone.
(ug/L)
5.0
50.0
5.0
50.0
5.0
100.0
5.0
50.0
20.0
100.0
10.0
100.0
Average
recovery
(ug/L)
5.2
51.4
4.0
44.4
0.1
9.3
4.2
51.4
20.1
101.3
9.1
104.0
Standard
deviation
(ug/L)
0.2
0.7
0.2
0.8
0.1
1.1
0.2
1.5
0.8
1.5
0.8
3.2
Average
percent
recovery
104
103
80
89
2
9
84
103
100
101
91
104
Sample
matrix3
RW
RW
POTW
POTW
IW
IW
RW
RW
POTW
POTW
IW
IW
 aRW   =  Reagent  water.
  POTW =  Prechlorination  secondary  effluent  from  a municipal  sewage treatment
          plant.
  IW   =  Industrial  wastewater containing  an unidentified  acrolein reactant.
                                   8030 - 10
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                                                          Date   September  1986

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                                        METHOD 8030

                           ACROLEIN. ACRYLONITRILE. ACETONITRILE
 7.1
 Introduce compounas
       Into B>S
   chromatograph by
 direct Injection or
    purge-ana-tr,ap
     (Method S030)
o
    7 .Z
       Set gas
    chromatograph
      condition
    7.3
      Calibrate
      (refer to
     Method BOOO)
7.4.1
  Introduce volatile
  compounds Into gas
   chromatograph by
    Method SO3O or
   direct Injection
   7.4.2
          Follow
       Section 7.6
    In Method 8000
      for analysis
    •eguence.  etc.
       O
       Record
  volume purged
or Injected and
    peak sizes
                           Calculate
                        concentration
                        (Section 7.6.
                         Method BOOO)
                       Are analytical
                       Interferences
                        suspected?
                                                 Analyze using
                                                   second GC
                                                    column
                      la response  for
                     a peak off-acale?
                                                 Dilute second
                                                   aliquot of
                                                    sample
                                     8030 -  11
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                                                               Date  September 1986

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                                 METHOD 8040

                                   PHENOLS
1.0  SCOPE AND APPLICATION

     1.1  Method 8040  1s  used  to  determine  the  concentration  of various
phenolic compounds.  Table 1 Indicates  compounds that may be analyzed by this
method and lists  the  method  detection  limit  for  each compound 1n reagent
water.   Table  2  lists  the  practical  quantltatlon  limit  (PQL) for other
matrices.
2.0  SUMMARY OF METHOD

     2.1  Method  8040  provides   gas   chromatographic  conditions  for  the
detection of phenolic compounds.  Prior to analysis, samples must be extracted
using appropriate techniques (see Chapter  Two  for  guidance).  Both neat and
diluted organic liquids   (Method  3580,  Waste  Dilution)  may  be analyzed by
direct Injection.  A 2- to  5-uL  sample  1s Injected Into a gas chromatograph
using the solvent  flush  technique,  and  compounds  in  the  GC effluent are
detected by a  flame 1on1zat1on detector (FID).

     2.2  Method 8040 also provides  for the preparation of pentafluorobenzyl-
bromlde  (PFB)  derivatives,  with  additional  cleanup  procedures for electron
capture gas chromatography.    This  1s  to  reduce  detection  limits of some
phenols and to aid the analyst 1n the elimination of interferences.


3.0  INTERFERENCES

     3.1  Refer to Methods 3500, 3600, and 8000.

     3.2  Solvents,  reagents, glassware, and  other sample processing hardware
may   yield    discrete    artifacts    and/or   elevated   baselines   causing
misinterpretation  of  gas  chromatograms.     All  these  materials  must  be
demonstrated  to  be  free from  interferences,  under  the  conditions of the
analysis, by   running  method  blanks.    Specific  selection  of reagents and
purification  of solvents  by distillation 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

                                  8040 - 1
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                                                          Date   September  1986

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TABLE 1.  FLAME IONIZATION GAS CHROMATOGRAPHY OF PHENOLS

                                                                  Method
                                         Retention time          Detection
Compound                                      (min)            limit (ug/L)


2-sec-Butyl-4,6-dinitrophenol (DNBP)
4-Chloro-3-methylphenol                        7.50                  0.36
2-Chlorophenol                                 1.70                  0.31
Cresols (methyl phenols)
2-Cyclohexyl-4,6-di ni trophenol
2,4-Dichlorophenol                             4.30                  0.39
2,6-Dichlorophenol
2,4-Dimethylphenol                             4.03                  0.32
2,4-Dinitrophenol                             10.00                 13.0
2-Methyl-4,6-dinitrophenol                    10.24                 16.0
2-Nitrophenol                                  2.00                  0.45
4-N1trophenol                                 24.25                  2.8
Pentachlorophenol                             12.42                  7.4
Phenol                                         3.01                  0.14
Tetrachlorophenols
Trichlorophenols
2,4,6-Trichlorophenol                          6.05                  0.64
TABLE 2.   DETERMINATION  OF  PRACTICAL  QUANTITATION  LIMITS  (PQL)  FOR VARIOUS
           MATRICES3


     Matrix ,                                                   Factorb


Ground  water                                                      10
Low-level  soil  by sonication with GPC cleanup                   670
High-level  soil  and  sludges by sonication                    10,000
Non-water  miscible waste      '                              100,000


      aSample  PQLs are highly  matrix-dependent.     The  PQLs listed herein are
      provided for guidance  and may not always be achievable.

      bPQL  = [Method  detection limit (Table 1)] X [Factor (Table 2)].  For non-
      aqueous  samples, the factor is on a wet-weight basis.
                                   8040 - 2
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                                                          Date  September 1986

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    accessories,  Including detectors,  column  supplies, recorder, gases, and
    syringes.  A  data  system  for  measuring peak areas and/or peak heights is
    recommended.

          4.1.2  Columns:

              4.1.2.1   Column for underivatized phenols:   1.8-m x 2.0-iron  I.D.
          glass column  packed  with 1%   SP-1240DA on  Supelcoport 80/100 mesh or
          equivalent.

              4.1.2.2   Column for derivatlzed  phenols:     1.8-m  x  2-mm  I.D.
          glass column  packed   with  5%  OV-17  on Chromosorb W-AW-DMCS  80/100
          mesh or  equivalent.


          4.1.3  Detectors:     Flame  lonization   (FID)   and electron capture
     (ECD).

    4.2  Reaction vial;  20-mL, with  Teflon-lined cap.

    4.3  Volumetric flask;   10-,  50-,  and 100-mL, ground-glass stopper.

    4.4  Kuderna-Danish (K-D) apparatus;

          4.4.1  Concentrator tube:  10-mL,  graduated (Kontes K-570050-1025 or
    equivalent).   Ground-glass  stopper   is  used   to prevent evaporation of
    extracts

          4.4.2   Evaporation   flask:       500-mL    (Kontes  K-570001-500 or
    equivalent).   Attach to concentrator tube with  springs.

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

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

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

     4.6  Water  bath;    Heated,   with  concentric  ring  cover,   capable  of
temperature control (+5*C).  The bath should be used 1n a hood.

     4.7  Microsyringe;  10-uL.

     4.8  Syringe;  5-mL.
5.0  REAGENTS

     5.1  Solvents:  Hexane,  2-propanol,  and  toluene  (pesticide quality or
equivalent)^


                                  8040 - 3
                                                         Revision      0
                                                         Date  September 1986

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     5.2  Derlvatization reagent;  Add 1  ml pentafluorobenzyl  bromide and  1  g
18-crown-6-ether to a 50-mL  volumetric  flask  and  dilute  to volume with 2-
propanol.   Prepare fresh weekly.   This  operation  should be carried out in  a
hood.  Store at 4'C and protect from light.

          5.2.1  Pentafluorobenzyl   bromide  (alpha-Bromopentafluorotoluene):
     97% minimum purity.
          NOTE:  This chemical is a lachrymator.

          5.2.2  18-crown-6-ether     (1,4,7,10,13,16-Hexaoxacyclooctadecane):
     98% minimum purity.
          NOTE:  This chemical is highly toxic.

     5.3  Potassium carbonate;   (ACS) Powdered.

     5.4  Stock standard solutions;

          5.4.1  Prepare stock standard  solution  at  a concentration of 1.00
     ug/uL by dissolving 0.0100 g  of assayed reference material in 2-propanol
     and diluting to volume in a  10-mL  volumetric flask.  Larger volumes can
     be used at the  convenience  of  the  analyst.    When compound purity is
     assayed to be 96% or greater,  the  weight can be used without correction
     to calculate  the  concentration  of  the  stock  standard.  Commercially
     prepared stock standards can  be  used  at  any concentration if they are
     certified by the manufacturer or by an independent source.

          5.4.2  Transfer  the   stock  standard  solutions  into Teflon-sealed
     screw-cap bottles.  Store at 4°C and protect from light.  Stock standards
     should be checked  frequently  for  signs  of degradation or evaporation,
     especially just prior to preparing calibration standards from them.

          5.4.3  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
concentrationlevelsshouldbe  prepared  through  dilution  of  the  stock
standards with 2-propanol.  One  of  the  concentration  levels should be at a
concentration near, but  above,  the  method  detection  limit.  The remaining
concentration levels should correspond to the expected range of concentrations
found   in   real  samples  or  should  define  the  working   range  of  the GC.
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 as  described  in Paragraph  5.5.


                                  8040  - 4
                                                          Revision      0
                                                          Date  September 1986

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          5.6.2  To each calibration standard,  add   a  known  constant  amount of
     one or more Internal standards, and dilute to  volume  with  2-propanol.

          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  (Tf  necessary),  and  analytical  system   and the
effectiveness of the method in dealing with each sample matrix by spiking each
sample, standard, and reagent water  blank  with phenolic  surrogates  (e.g., 2-
fluorophenol and 2,4,6-tribromophenol) recommended  to  encompass the range of
the temperature program used in  this  method.    Method 3500, Section 5.3.1.1,
details instructions  on  the  preparation  of  acid  surrogates.   Deuterated
analogs of analytes should not  be  used as surrogates for gas chromatographic
analysis due to coelution problems.


6.0  SAMPLE COLLECTION,  PRESERVATION, AND HANDLING

     6.1  See the  introductory  material  to  this  chapter, Organic Analytes,
Section 4.1.  Extracts must be  stored under refrigeration and analyzed within
40 days of extraction.


7.0  PROCEDURE

     7.1  Extraction:

          7.1.1  Refer to Chapter Two for guidance on choosing the appropriate
     extraction procedure.   In general, water samples are extracted at a pH of
     less than or  equal  to 2 with methylene chloride, using either Method 3510
     or 3520.  Solid samples are  extracted  using either Method 3540 or 3550.
     Extracts obtained from  application of  either  Method 3540 or 3550 should
     undergo Acid-Base Partition Cleanup,  using Method 3650.

          7.1.2  Prior to gas chromatographic analysis, the extraction solvent
     must be exchanged to 2-propanol.    The  exchange 1s performed during the
     micro  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 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
          95-100'C.  Remove  the  Snyder  column  and  rinse  the flask and its
          lower joint  into the concentrator tube with 1-2 mL of 2-propanol.  A
          5-mL syringe  is  recommended   for this   operation.    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 2-
          propanol to  the  top.  Place   the K-D apparatus on the water bath so
          that the concentrator tube  1s  partially immersed in the hot water.
                                   8040  -  5
                                                          Revision      0
                                                          Date  September  1986

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         Adjust  the  vertical  position  of  the  apparatus  and  the  water
         temperature, as required, to complete concentration 1n 5-10 m1n.  At
         the proper  rate  of  distillation  the  balls  of  the  column will
         actively chatter,  but  the  chambers  will  not  flood.    When the
         apparent volume of liquid reaches  2.5  ml, remove the K-D apparatus
         and allow 1t  to  drain  and  cool  for  at  least  10  m1n.  Add an
         additional 2 ml of 2-propanol ,  add  one or two clean boiling chips
         to the concentrator tube, and  resume concentrating as before.  When
         the apparent  volume  of  liquid  reaches  0.5  ml,  remove  the K-D
         apparatus and allow 1t to drain and cool for at least 10 m1n.

               7.1.2.3  Remove  the  mlcro-Snyder  column  and  rinse Its  lower
         joint Into  the   concentrator  tube  with  a  minimum  amount  of 2-
         propanol.   Adjust  the  extract  volume  to  1.0  ml.   Stopper the
         concentrator  tube  and  store   refrigerated   at  4*C  1f  further
         processing will  not be performed  Immediately.   If the extract will
         be  stored  longer than   two  days,   1t  should  be  transferred to  a
         Teflon-sealed screw-cap  vial.    If   the  extract requires  no further
         der1vat1zat1on   or    cleanup,   proceed   with  gas  chromatographlc
         analysis.

     7.2 Gas chromatography  conditions  (Recommended);

          7.2.1  Column  for underlvatlzed  phenols:     Set nitrogen gas flow at
     30 mL/m1n flow rate.     Set   column   temperature   at 80*C  and  Immediately
     program an 8*C/m1n  temperature   rise   to  150*C;  hold until  all  compounds
     have eluted.

          7.2.2  Column  for derlvatlzed  phenols:  Set  5% methane/95% argon gas
     flow at 30 mL/m1n  flow rate.   Set column temperature at  200'C  Isothermal.

     7.3  Calibration;     Refer   to   Method   8000   for  proper  calibration
techniques"^Use Table  1  and  especially   Table 2 for guidance on  selecting the
lowest point on the calibration curve.

          7.3.1  The procedure for  Internal   or external   calibration  may be
     used  for  the  underlvatlzed phenols.     Refer  to  Method  8000   for  a
     description of  each  of  these   procedures.     If der1vat1zat1on  of the
     phenols 1s required,  the method  of  external  calibration  should  be used by
     Injecting five or more  levels   of   calibration   standards  that have also
     undergone der1vat1zat1on and  cleanup  prior to  Instrument calibration.

     7.4  Gas chromatographlc analysis;

          7.4.1  Refer to Method  8000.    If the Internal standard  calibration
     technique 1s used,  add 10 uL  of   Internal  standard to the sample prior to
     Injection.

          7.4.2  Phenols are to be determined  on a gas chromatograph equipped
     with a flame 1on1zat1on detector  according  to the conditions  listed  for
     the 1% SP-1240DA column (Paragraph   7.2.1).  Table 1  summarizes estimated
                                  8040 - 6
                                                         Revision      0
                                                         Date  September 1986

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retention times and sensitivities that  should be achieved by this method
for  clean  water  samples.    Practical   quantltation  limits  for other
matrices are list 1n Table 2.

     7.4.3  Follow Section 7.6  In  Method  8000  for Instructions on the
analysis sequence,  appropriate  dilutions,   establishing daily retention
time windows, and Identification criteria.   Include a mid-level  standard
after each group of 10 samples 1n the analysis sequence.

     7.4.4  An example of a  GC/FID  chromatogram  for certain phenols is
shown in Figure 1.    Other  packed  or capillary (open-tubular)  columns,
chromatographic conditions, or detectors may  be used if the requirements
of Section 8.2 are met.

     7.4.5  Record the  sample  volume  injected  and  the resulting peak
sizes (in area units or peak heights).

     7.4.6  Using either the  Internal  or external calibration procedure
(Method 8000), determine the identity and quantity of each component peak
1n the sample chromatogram  which  corresponds  to the compounds used for
calibration purposes.  See  Section  7.8  of  Method 8000 for calculation
equations.

     7.4.7   If peak detection using  the  SP-1240DA column with the flame
ionization detector is prevented by  interferences, PFB derivatives of the
phenols should  be  analyzed  on   a  gas  chromatograph   equipped with an
electron  capture  detector  according  to  the   conditions  listed for the 5%
OV-17 column  (Paragraph  7.2.2).  The derivatizatlon and  cleanup procedure
is outlined  in Sections  7.5   through 7.6.    Table 3  summarizes estimated
retention times for derivatives  of  some  phenols using  the  conditions of
this method.

     7.4.8   Figure 2  shows a GC/ECD chromatogram  of  PFB derivatives of
certain phenols.

     7.4.9   Record  the   sample   volume  Injected  and  the resulting  peak
sizes  (in area  units  or  peak heights).

     7.4.10     Determine the identity and quantity of each component  peak
in the  sample chromatogram  which   corresponds   to the  compounds  used for
calibration  purposes.  The method   of external  calibration should  be  used
 (see Method  8000   for guidance).    The  concentration  of the Individual
compounds In the  sample  is calculated as  follows.

     Concentration  (ug/L)  =  [(A)(Vt)(B)(D)]/[(Vt)(X)(C)(E)]

where:

   A  = Mass  of underivatlzed  phenol represented   by area  of peak  in  sample
      chromatogram, determined  from calibration  curve   (see Method  8000
      Paragraph  7.4.2),  ng.
                              8040 - 7
                                                     Revision       0
                                                     Date   September  1986

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        Column: 1% SP-1240DA on Supelcoport
        Program: 80°C 0 Minutes 8°/Minute to 150°C
        Detector: Flame lonization
     8      12      16      20
      RETENTION TIME (MINUTES)
24      28
Figure 1. Gas chromatogram of phenols.
  8040 - 8
                          Revision       o
                          Date  September 1986

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TABLE 3.  ELECTRON CAPTURE GAS CHROMATOGRAPHY OF PFB DERIVATIVES
Parent compound
Retention
  time
  (m1n)
                       Method
                      detection
                     limit (ug/L)
4-Chloro-2-methylphenol
2-Chlorophenol
2,4-D1chlorophenol
2,4-01methyl phenol
2,4-D1n1trophenol
2-Methy1-4,6-d1nltrophenol
2-N1trophenol
4-N1trophenol
Pentachlorophenol
Phenol
2,4,6-TH chlorophenol
 4.8
 3.3
 5.8
 2.9
46.9
36.6
 9.1
14.0
28.8
 1.8
 7.0
                            1.8
                            0.58
                            0.68
                            0.63
                            0.77
                            0.70
                            0.59
                            2.2
                            0.58
                                   8040 - 9
                                                          Revision       0
                                                          Date  September 1986

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                Column: S% OV-17 on Qiromowrb W-AW
                Temperature: 200°C
                Detector: Electron Capture
     (M CN
1
         8      12      16     20      24      28

             RETENTION TIME (MINUTES)
                                            32
Figure 2. Gas chromatogram of PFB derivativas of phanols.
                    8040 - 10
                                            Revision       0
                                            Date  September 1986

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      Vt  =  Total  amount  of column  eluate  or  combined fractions from which Vj
           was  taken,  uL.

       B  =  Total  volume  of hexane  added in  Paragraph  7.5.5, ml.

       D  =  Total  volume  of 2-propanol  extract prior to der1vat1zat1on, mL.

      Vj  =  Volume injected, uL.

       X  =  Volume of  water  extracted,   ml,  or  weight  of  nonaqueous  sample
           extracted,  g, from Section  7.1.    Either   the dry or wet weight of
           the nonaqueous sample  may   be  used,  depending  upon  the  specific
           application of the data.

       C  =  Volume of hexane sample  solution  added   to  cleanup column (Method
           3630,,  Section 7.2), ml.

       E  =  Volume of  2-propanol  extract  carried  through  derivatization  in
           Paragraph 7.5.1, ml.

     7.5   Derivatization;  If interferences  prevent   measurement  of peak area
during analysis of theextract  by  flame  ionization gas chromatography,  the
phenols  must  be   derivatized   and    analyzed   by   electron   capture  gas
chromatography.

          7.5.1  Pipet a   1.0-mL  aliquot  of  the  2-propanol  stock standard
     solution or of the sample extract into a glass  reaction  vial.  Add 1.0  ml
     derivatization reagent   (Paragraph  5.3).     This  amount  of  reagent  1s
     sufficient to derivatize a solution whose  total  phenolic content does not
     exceed 0.3 mg/mL.

          7.5.2  Add approximately 3 mg of potassium carbonate to  the solution
     and shake gently.

          7.5.3  Cap the mixture and heat it for  4  hr at 80*C in a hot water
     bath.

          7.5.4  Remove the solution from the  hot  water bath and allow it to
     cool.                 -    	       .

          7.5.5  Add 10 ml hexane  to  the  reaction vial and shake vigorously
     for 1 min.  Add 3.0   ml  distilled,  deionized water to the reaction vial
     and shake for 2 min.

          7.5.6  Decant the organic  layer  into  a  concentrator tube and cap
     with a glass stopper.  Proceed with cleanup procedure.

     7.6  Cleanup;

          7.6.1  Cleanup  of the derivatized  extracts takes place using Method
     3630  (Silica Gel Cleanup), in which specific instructions for cleanup of
     the derivatized phenols  appear.

                                   8040 - 11
                                                          Revision      0
                                                         Date  September 1986

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          7.6.2  Following column cleanup,   analyze  the samples using GC/ECD,
     as described starting 1n Paragraph 7.4.7.


8.0  QUALITY CONTROL

     8.1  Refer  to  Chapter  One  for  specific  quality  control  procedures.
Quality control to validate sample extraction is covered in Method 3500 and in
the extraction method used.  If  extract  cleanup was performed, follow the QC
in Method 3600 and in the specific cleanup method.

     8.2  Procedures to check  the  GC  system  operation  are found 1n Method
8000, Section 8.6.

          8.2.1  The quality control  check  sample  concentrate (Method 8000,
     Section 8.6) should contain each  analyte  of interest at a concentration
     of 100 ug/mL 1n 2-propanol.

          8.2.2  Table 4 indicates the  calibration and QC acceptance criteria
     for this  method.    Table  5  gives  method  accuracy  and  precision as
     functions of concentration  for the analytes.  The contents of both Tables
     should be used to evaluate  a laboratory's ability to perform and generate
     acceptable data by this method.

     8.3  Calculate surrogate standard  recovery  on  all samples, blanks, and
spikes.  Determine 1f  the   recovery   is  within  limits  (limits established by
performing QC procedures outlined in Method 8000, Section 8.10).

          8.3.1   If recovery 1s  not within limits, the following is required.

               •  Check to   be   sure   there  are  no  errors  1n calculations,
                  surrogate  solutions  and  internal  standards.   Also, check
                  Instrument performance.

               •  Recalculate the data and/or reanalyze  the extract  if any of
                  the above  checks reveal a problem.

               •  Reextract  and  reanalyze the sample  if none of the  above are
                  a problem  or flag the data as  "estimated concentration."


9.0  METHOD PERFORMANCE

     9.1  The method  was  tested  by  20  laboratories  using  reagent water,
drinking water,  surface water, and  three industrial wastewaters spiked at six
concentrations over the range  12  to  450  ug/L.   Single operator precision,
overall precision, and method accuracy were  found  to  be directly related to
the  concentration of the   analyte  and essentially  Independent of the sample
matrix.     Linear  equations  to describe  these relationships  for a flame
ionization  detector are presented in Table 5.
                                   8040 -  12
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                                                          Date   September  1986

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     9.2  The accuracy and precision obtained  will  be affected by the sample
matrix, sample-preparation technique, and calibration procedures used.


10.0  REFERENCES

1.  Development and Application of Test  Procedures for Specific Organic Toxic
Substances In Wastewaters.  Category 3 - Chlorinated Hydrocarbons and Category
8 - Phenols.  Report for EPA Contract 68-03-2625 (in preparation).

2.  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.

3.  "Determination of Phenols in Industrial and Municipal Wastewaters," Report
for EPA Contract 68-03-2625  (in preparation).

4.  "EPA Method Validation Study  Test  Method  604  (Phenols)," Report for EPA
Contract 68-03-2625 (1n preparation).

5.  Kawarahara,  F.K.  "Microdetermination  of   Derivatives  of  Phenols  and
Mercaptans  by  Means  of  Electron  Capture  Gas  Chromatography," Analytical
Chemistry, 40, 1009, 1968.

6.  Provost, L.P. and R.S.   Elder,   "Interpretation  of Percent  Recovery Data,"
American Laboratory, 15, pp. 58-63,  1983.

7.  Burke, J.A.,  "Gas  Chromatography   for   Pesticide  Residue  Analysis; Some
Practical  Aspects,"  Journal   of    the  Association of  Official  Analytical
Chemists, 48,  1037, 1965.
                                   8040 -  13
                                                          Revision
                                                          Date  September 1986

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TABLE 4.  QC ACCEPTANCE CRITERIA3
Parameter
4-Chloro-3-methyl phenol
2-Chlorophenol
2,4-D1chlorophenol
2,4-01 methyl phenol
4, 6-D1 n1 tro-2-methyl phenol
2,4-D1n1trophenol
2-N1trophenol
4-N1trophenol
Pentachlorophenol
Phenol
2,4,6-Trlchlorophenol
Test
cone.
(ug/L)
100
100
100
100
100
100
100
100
100
100
100
Limit
for s
(ug/L)
16.6
27.0
25.1
33.3
25.0
36.0
22.5
19.0
32.4
14.1
16.6
Range
for 7
(ug/L)
56.7-113.4
54.1-110.2
59.7-103.3
50.4-100.0
42.4-123.6
31.7-125.1
56.6-103.8
22.7-100.0
56.7-113.5
32.4-100.0
60.8-110.4
Range
P, PS
(%)
99-122
38-126
44-119
24-118
30-136
12-145
43-117
13-110
36-134
23-108
53-119
     s = Standard deviation of four recovery measurements, In. ug/L.

     7 = Average recovery for four recovery measurements, 1n ug/L.

     P, Ps = Percent recovery measured.

     aCr1ter1a from 40 CFR Part 136 for  Method 604.  These criteria are based
directly upon the method performance  data  1n  Table 5.  Where necessary, the
limits for recovery have been broadened  to assure applicability of the limits
to concentrations below those used to develop Table 5.
                                  8040  -  14
                                                          Revision      0
                                                          Date  September  1986

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TABLE 5.  METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION3
Parameter
4-Chl oro-3-methyl phenol
2-Chlorophenol
2,4-D1chlorophenol
2,4-D1methylphenol
4, 6-D1n1tro-2-methyl phenol
2,4-D1n1trophenol
2-Nttrophenol
4-N1trophenol
Pentachlorophenol
Phenol
2,4,6-Trlchlorophenol
Accuracy, as
recovery, x1
(ug/L)
0.87C-1.97
0.83C-0.84
0.81C+0.48
0.62C-1.64
0.84C-1.01
0.80C-1.58
0.81C-0.76
0.46C+0.18
0.83C+2.07
0.43C+0.11
0.86C-0.40
Single analyst
precision, sr'
(ug/L)
0.117-0.21
0.187+0.20
0.177-0.02
0.307-0.89
0.157+1.25
0.277-1.15
0.157+0.44
0.177+2.43
0.227-0.58
0.207-0.88
0.107+0.53
Overal 1
precision,
S' (ug/L)
0.167+1.41
0.217+0.75
0.187+0.62
0.257+0.48
0.197+5.85
0.297+4.51
0.147+3.84
0.197+4.79
0.237+0.57
0.177+0.77
0.137+2.40
     x1  = Expected  recovery  for  one  or  more  measurements  of  a  sample
           containing a concentration of C, 1n ug/L.
     sr' = Expected single analyst  standard  deviation  of measurements at an
           average concentration of 7, 1n ug/L.
     S1  = Expected Interlaboratory standard  deviation  of measurements at an
           average concentration found of 7, in ug/L.
     C   = True value for the concentration, in ug/L.
     7   = Average recovery found for measurements of samples containing a
           concentration of C, in ug/L.
     aFrom 40 CFR Part  136 for Method 604.
                                   8040  -  15
                                                         Revision      0
                                                         Date  September  1986

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                                          METHOD  BO4O

                                            PHENOLS
c
 7.1.1
        Choose
       ' appro-
 priate extract-
  Ion procedure
     (refer to
    Chapter 2)
                          Use method of
                      external calibration
                       by Injecting >/- 5
                      levels of calibration
                           standards
 7.1.2
        Exchange
        extract-
   Ion solvent to
     2—propanol
    during micro
   K-O procedures
  7.2
     Set gas
  chromatography
   conditions
  7.3
        Refer to
     Method 8OOO
     for proper
     calibration
     techniques
      Is
derIvatlzatlon
  of phenols
  required?
  Perform GC
analysis (see
 Method 8OOO)
     0
                                       8040 - 16
                                                                  Revision       0
                                                                  Date • September 1986

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 METHOD 6O4O

   PHENOLS
  (Continued]
      Do
interferences
prevent peak
  detection
Cleanup using
 Method 3630
      Record
 sample volume
  injected ana
   peak sizes
   Prepare
derlvatlzetion
  identity and
   quantity of
       each
component peak
 Analyze PFB
 derivatives
using GC/CCD
  Calculate
concentration
           8040 -  17
                                      Revision       Q
                                      Date   September 1986

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                                 METHOD 8060

                              PHTHALATE ESTERS
1.0  SCOPE AND APPLICATION

     1.1  Method 8060  is  used  to  determine  the  concentration  of various
phthalate esters.  Table 1 indicates  compounds that may be determined by this
method and lists  the  method  detection  limit  for  each compound in reagent
water.   Table  2  lists  the  practical  quantitation  limit  (PQL) for other
matrices.
2.0  SUMMARY OF METHOD

     2.1  Method  8060  provides   gas   chromatographic  conditions  for  the
detection of ppb levels of  phthalate  esters.    Prior to use of this method,
appropriate sample extraction techniques must be  used.  Both neat and diluted
organic liquids  (Method  3580,  Waste  Dilution)  may  be  analyzed by direct
injection.  A 2-  to  5-uL  aliquot  of  the  extract  is  injected into a gas
chromatograph (GC) using the solvent flush  technique, and compounds in the GC
effluent are  detected  by  an  electron  capture  detector  (ECD)  or a flame
ionization detector (FID).  Ground water samples should be determined by ECD.

     2.2  The method provides a second  gas chromatographic column that may be
helpful in resolving the analytes  from  interferences  that may occur and for
analyte confirmation.


3.0  INTERFERENCES

     3.1  Refer to Methods 3500, 3600, and 8000.

     3.2  Phthalate esters contaminate many   types  of products commonly found
in the  laboratory.  The  analyst  must  demonstrate that no phthalate residues
contaminate the sample or  solvent   extract   under the conditions of analysis.
Plastics, in particular, must  be  avoided because phthalates are  commonly  used
as plasticizers and  are  easily  extracted   from  plastic materials.  Serious
phthalate contamination may  result at  any  time if consistent quality control
is not  practiced.

     3.3  Solvents, reagents,  glassware, and  other sample processing hardware
may   yield   discrete    artifacts    and/or   elevated   baselines   causing
misinterpretation  of  gas   chromatograms.      All  these  materials  must  be
demonstrated to   be  free  from  interferences,  under the  conditions  of the
analysis, by analyzing  method blanks.    Specific   selection of reagents and
purification of solvents by  distillation in all-glass systems may be  required.

     3.4   Interferences coextracted  from  samples  will vary considerably  from
source  to  source,  depending  upon  the  waste  being sampled.  Although general
cleanup techniques are recommended as part  of  this method,  unique  samples may
require additional cleanup.


                                  8060 - 1
                                                         Revision      0
                                                         Date  September 1986

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TABLE 1.  RETENTION TIME AND DETECTION LIMIT INFORMATION FOR PHTHALATE ESTERS

                                Retention time (m1n)      Method detection
                                                            limit (ug/L)
Compound                         Col. la    Col. 2D        ECD        FID
Benzyl butyl phthalate
B1 s (2-ethyl hexyl Jphthal ate
D1-n-butyl phthalate
D1 ethyl phthalate
Dimethyl phthalate
D1-n-octyl phthalate
*6.94
*8.92
8.65
2.82
2.03
*16.2
**5.11
**10.5
3.50
1.27
0.95
**8.0
0.34
2.0
0.36
0.49
0.29
3.0
15
20
14
31
19
31
     aColumn 1:  Supelcoport 100A120  mesh  coated with 1.5% SP-2250/1.95% SP-
     2401 packed 1n a 180-cm x 4-mrn  I.D.  glass column with carrier gas at 60
     mL/m1n flow rate.  Column temperature  1s 180*C, except where * Indicates
     220*C.  Under these conditions the  retention  time of Aldrln 1s 5.49 m1n
     at 180*0 and 1.84 mln at 220'C.

     bColumn 2:  Supelcoport 100/120 mesh with 3% OV-1 1n a 180-cm x 4-mm I.D.
     glass column with carrier gas at 60 mL/m1n flow rate.  Column temperature
     1s 200*C, except where **  Indicates  220*C.   Under these conditions the
     retention time of Aldrln 1s 3.18 m1n at 200'C and 1.46 m1n at 220*C.
TABLE 2.  DETERMINATION OF PRACTICAL QUANTITATION LIMITS  (PQL) FOR VARIOUS
          MATRICES*


    Matrix                                                    Factor0


Ground water                                                      10
Low-level soil  by  sonlcation with GPC  cleanup                    670
High-level  soil  and  sludges by  sonlcatlon                     10,000
Non-water mlsclble waste                                     100,000


     aSample  PQLs  are highly  matrix-dependent.     The   PQLs listed  herein  are
     provided for  guidance and  may  not always  be  achievable.

     DPQL = [Method  detection limit (Table 1)] X  [Factor (Table  2)].   For non-
     aqueous  samples, the factor 1s on a wet-weight basis.
                                   8060 -  2
                                                          Revision
                                                          Date   September  1986

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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  4-mm  I.D. glass column packed with
          1.5%  SP-2250/1.95%   SP-2401   on   Supelcoport   100/120  mesh  or
          equivalent.
               4.1.2.2  Column 2:  1.8-m x  4-mm  I.D. glass column packed with
          3% OV-1 on Supelcoport 100/120 mesh or  equivalent.
          4.1.3  Detectors:  Flame ionlzation (FID) or electron capture  (ECD).
     4.2  Volumetric flask;  10-, 50-, and 100-mL, ground-glass stopper.
     4.3  Kuderna-Danish  (K-D) apparatus;
          4.3.1  Concentrator tube;   10-mL, graduated  (Kontes K-570050-1025 or
     equivalent).  Ground-glass  stopper  1s  used  to  prevent evaporation of
     extracts
   •*
          4.3.2  Evaporation   flask;      500-mL   (Kontes   K-570001-500  or
     equivalent).  Attach  to concentrator tube with springs.
          4.3.3  Snyder column:    Three-ball  macro   (Kontes K-503000-0121 or
     equivalent).
          4.3.4  Snyder   column:    Two-ball  micro   (Kontes  K-569001-0219 or
     equivalent).
     4.4  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  Microsyringe;   10-uL.
     4.7  Syringe;   5-mL.
     4.8  Vials;  Glass,  2- and  20-mL capacity with  Teflon-lined  screw cap.
                                   8060 - 3
                                                          Revision
                                                          Date  September 1986

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5.0  REAGENTS

     5.1  Solvents;    Hexane,    acetone,   Isooctane  (2,2,4-trlmethylpentane)
(pesticide quality or equivalent).

     5.2  Stock standard solutions:

          5.2.1  Prepare stock standard solutions  at  a concentration of 1.00
     ug/uL by dissolving 0.0100 g  of  assayed reference material  in isooctane
     and diluting to volume in a  10-mL  volumetric flask.  Larger volumes can
     be used at the  convenience  of  the  analyst.    When compound purity is
     assayed to be 96% or greater,  the  weight can be used without correction
     to calculate  the  concentration  of  the  stock  standard.  Commercially
     prepared stock standards can  be  used  at  any concentration if they are
     certified by the manufacturer or by an independent source.

          5.2.2  Transfer  the  stock  standard  solutions  into Teflon-sealed
     screw-cap bottles.  Store at 4'C and protect from light.  Stock standards
     should be checked  frequently  for  signs  of degradation or evaporation,
     especially just prior to preparing calibration standards from them.

          5.2.3  Stock standard solutions must be  replaced after one year, or
     sooner if comparison with check standards indicates a problem.

     5.3  Calibration standards:  Calibration  standards  at a minimum of five
concentrationlevelsshouldbe  prepared  through  dilution  of  the  stock
standards with isooctane.   One  of  the  concentration  levels should be at a
concentration near, but  above,  the  method  detection  limit.  The remaining
concentration levels should correspond to the expected range of concentrations
found   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.

     5.4  Internal standards (if  internal  standard  calibration is used);  To
use this approach, the analyst must select one or more internal standards that
are similar in analytical behavior to  the compounds of interest.  The analyst
must further demonstrate that the measurement  of the internal standard is not
affected by method or matrix interferences.   Because of these limitations, no
internal standard  can be suggested that is applicable to all samples.

          5.4.1  Prepare  calibration   standards   at   a   minimum  of  five
     concentration  levels  for   each  analyte  of  interest  as  described in
     Paragraph 5.3.

          5.4.2  To each calibration standard, add  a known constant amount of
     one or more internal standards, and dilute to volume with Isooctane.

          5.4.3  Analyze each calibration standard according to Section 7.0.

     5.5  Surrogate standards;  The analyst  should monitor the performance of
the extraction, cleanup(when  used),  and  analytical  system and the effec-
tiveness of  the method   in  dealing  with  each  sample matrix by spiking each


                                   8060 - 4
                                                         Revision      0
                                                         Date  September  1986

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sample, standard, and reagent water  blank  with  one or two surrogates (e.g.,
phthalates that are not expected to be In the sample) recommended to encompass
the range of  the  temperature  program  used  1n  this  method.   Method 3500,
Section 5.3.1.1,  details  Instructions  on  the  preparation  of base/neutral
surrogates.  Deuterated analogs of  analytes  should not be used  as surrogates
for gas chromatographlc analysis due to coelutlon problems.


6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

     6.1  See the Introductory  material  to  this  chapter, Organic Analytes,
Section 4.1.  Extracts must be  stored under refrigeration and analyzed within
40 days of extraction.


7.0  PROCEDURE

     7.1  Extraction;

          7.1.1  Refer to Chapter Two  for guidance on choosing the appropriate
     extraction  procedure.    In  general,  water  samples  are  extracted at a
     neutral, or as  1s, pH  with  methylene chloride, using either Method 3510
     or 3520.  Solid samples  are extracted using either Method 3540 or 3550.

          7.1.2  Prior to gas chromatographlc analysis, the extraction solvent
     must be exchanged to hexane.    The  exchange 1s performed during the K-D
     procedures  listed 1n all  of   the extraction   methods.   The exchange 1s
     performed  as  follows.

                7.1.2.1   Following  K-D  of the methylene chloride extract  to
           1 mL  using the macro-Snyder  column,   allow the apparatus to  cool and
          drain  for  at least  10 m1n.

                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  1s partially   Immersed   1n  the hot water.   Adjust
           the vertical position of the apparatus and the water temperature, as
           required,  to complete concentration 1n 5-10 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 1t to drain and
           cool  for at least  10 m1n.    The extract will be handled differently
           at this  point, depending on   whether   or   not cleanup  1s needed.  If
           cleanup  is not required,  proceed   to   Paragraph  7.1.2.3.  If cleanup
           is needed, proceed  to Paragraph  7.1.2.4.

                7.1.2.3   If cleanup of  the  extract  1s not  required, remove the
           Snyder column  and   rinse  the   flask   and   Its   lower joint  Into the
           concentrator tube   with   1-2 mL   of   hexane.     A   5-mL  syringe 1s
           recommended for this operation.  Adjust the extract  volume to


                                   8060 -  5
                                                         Revision      0
                                                          Date   September  1986

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          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,  1t  should  be
          transferred  to a   Teflon-sealed  screw-cap  vial.   Proceed with gas
          chromatographlc analysis.

              7.1.2.4 If cleanup  of  the  extract  1s  required, remove the
          Snyder  column and  rinse  the  flask  and  Its  lower joint Into the
          concentrator tube  with  a minimum  amount  of hexane.  A 5-mL syringe
          1s recommended for this operation.   Add a clean boiling chip to the
          concentrator tube  and attach a two-ball mlcro-Snyder column.  Prewet
          the column by adding about  0.5 ml  of  hexane to the top.  Place the
          m1cro-K-D  apparatus  on  the   water   bath    (80°C)  so  that  the
          concentrator tube  1s partially  Immersed  1n  the  hot water.  Adjust
          the vertical position of the apparatus and the water temperature, as
          required,  to complete concentration 1n 5-10 m1n.   At the proper rate
          of distillation the balls of  the  column will actively chatter, but
          the chambers will  not   flood.    When  the apparent volume of liquid
          reaches 0.5  ml, remove  the  K-D  apparatus  and  allow 1t to drain and
          cool "for at  least  10 mln.

               7.1.2.5  Remove the mlcrb-Snyder  column and  rinse the flask and
          Its  lower joint  Into the  concentrator  tube  with 0.2 ml of hexane.
          Adjust  the extract volume to  2.0  ml  and proceed  with either Method
          3610  or 3620.

     7.2  Gas   chromatpgraphy  conditions   (Recommended);     The   analysis  for
phthalate esters  mayBeconductedusing   eitheraflame  1on1zat1on  or  an
electron capture detector.   The  ECD may,  however,  provide substantially better
sensitivity.

          7.2.1  Column 1:   Set 5% methane/95%   argon   carrier gas  flow  at  60
     mL/m1n flow rate.  Set column temperature  at 180*C Isothermal.

          7.2.2  Column 2:   Set 5% methane/95%   argon   carrier gas  flow at  60
     mL/m1n flow rate.  Set column temperature  at 200*C Isothermal.

     7.3  Calibration;    Refer   to    Method   8000   for  proper  calibration
techniquesTUse Table 1 and especially  Table  2 for guidance on selecting the
lowest point on the calibration curve.

          7.3.1  The  procedure for  Internal   or  external   calibration  may be
     used.    Refer   to  Method  8000  for  a  description  of  each   of  these
     procedures.

          7.3.2  If cleanup 1s performed  on  the  samples,  the analyst  should
     process a series  of  standards   through  the  cleanup procedure and then
     analyze the samples by GC.     This  will  confirm elutlon patterns and the
     absence of interferents from the reagents.
                                  8060 - 6
                                                         Revision      0
                                                         Date  September 1986

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    7.4  Gas chromatographlc analysis;

         7.4.1  Refer to Method 8000.    If the Internal standard calibration
    technique 1s used, add  10 uL of  Internal standard to the sample prior to
    Injection.

         7.4.2  Follow Section 7.6   1n  Method  8000  for Instructions on the
    analysis sequence,  appropriate  dilutions,  establishing dally retention
    time windows,  and Identification criteria.   Include a mid-level standard
    after  each  group of 10  samples 1n the analysis sequence.

         7.4.3  Examples of GC/ECD  chromatograms  for  phthalate esters are
    shown  In Figures 1 and  2.

         7.4.4  Record the  sample   volume  Injected  and  the resulting peak
    sizes  (1n area units or peak heights).

         7.4.5  Using either the  Internal  or external calibration procedure
     (Method 8000),  determine the Identity  and  quantity of each analyte peak
    1n  the  sample chromatogram.    See  Section  7.8  of  Method  8000 for
    calculation equations.

         7.4.6   If peak detection  and   Identification  are  prevented due to
     interferences, the hexane  extract may undergo cleanup using either Method
     3610 or  3620.

     7.5 Cleanup;

         7.5.1   Proceed with   either Method   3610  or  3620,  using the 2-mL
     hexane extracts obtained  from  Paragraph  7.1.2.5.

          7.5.2:    Following cleanup,  the extracts  should be  analyzed by GC, as
     described  1n  the previous  paragraphs and  1n Method  8000.


8.0  QUALITY CONTROL

     8.1  Refer  to  Chapter  One  for  specific   quality   control  procedures.
Quality control  to validate sample extraction 1s  covered 1n  Method 3500  and 1n
the extraction method utilized.  If  extract cleanup was performed,  follow the
QC in Method 3600 and in the specific cleanup method.

     8.2  Procedures to check  the  GC  system  operation   are found In  Method
8000, Section 8.6.

          8.2.1  The quality control   check  sample  concentrate (Method 8000,
     Section 8.6)  should contain  each  analyte  of  Interest at the following
     concentrations 1n acetone:    butyl  benzyl   phthalate,  10 ug/mL;  b1s(2-
     ethylhexyl) phthalate, 50 ug/mL; d1-n-octyl   phthalate, 50 ug/mL;  and any
     other phthalate, 25 ug/mL.
                                  8060 - 7
                                                         Revision
                                                         Date  September 1986

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          -Column: 1.5%SP-2250+
                   1.95% SP-2401 on Suptlcoport
           Temperature: 180°C
           Detector:  Electron Capture
                            3
                            I
                            £
      0    2    4    6    8    10   12

         RETENTION TIME (MINUTES)


Figure 1. Gas chromatogram of phthalates (example 1).
         8060 - 8
                                  Revision       p
                                  Date  September 1986

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     Column:  1.5% SP-2250+
             1.95% SP-2401 on Sopeleoport
     Ttmptraturt: 18C
     Otttctor: Eltctron Capture
   0       4       8       12      16

           RETENTION TIME (MINUTES)


Figure 2. Gas chromatogram of phthalates (example 2).
                     8060 - 9
                                              Revision       o
                                              Date  September 1986

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          8.2.2  Table 3 Indicates the  calibration and QC acceptance criteria
     for this  method.    Table  4  gives  method  accuracy  and  precision as
     functions of concentration for the analytes of Interest.  The contents of
     both Tables should be used to  evaluate a laboratory's ability to perform
     and generate acceptable data by this method.

     8.3  Calculate surrogate standard  recovery  on  all  samples, blanks,  and
spikes.  Determine if  the  recovery  is  within limits (limits established by
performing QC procedures outlined 1n Method 8000, Section  8.10).

          8.3.1  If recovery is not within limits, the following is required.

               •  Check to  be  sure  there  are  no  errors  in calculations,
                  surrogate solutions  and  Internal  standards.   Also, check
                  instrument performance.

               •  Recalculate the data and/or reanalyze  the extract if any of
                  the above checks reveal a problem.

               •  Reextract and reanalyze the sample  if none of the above are
                  a problem or flag the data as  "estimated concentration."


9.0  METHOD PERFORMANCE

     9,1  The method  was  tested  by  16  laboratories  using  reagent water,
drinking water, surface water, and  three industrial wastewaters spiked at six
concentrations over the range  0.7  to  106  ug/L.  Single operator precision,
overall precision, and method accuracy  were  found  to be directly related to
the concentration of  the  analyte  and  essentially  independent of the sample
matrix.    Linear  equations  to  describe  these  relationships  for  a flame
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 1n Wastewaters.  Category 1  - Phthalates.  Report for EPA Contract
68-03-2606 (in preparation).

2.  "Determination of  Phthalates  in  Industrial  and Municipal Wastewaters,"
EPA-600/4-81-063,   U.S.   Environmental   Protection   Agency,   Environmental
Monitoring and Support  Laboratory, Cincinnati,  Ohio 45268, October  1981.

3.  Burke, J.A.   "Gas  Chromatography  for  Pesticide  Residue  Analysis;  Some
Practical  Aspects,"  Journal  of   the  Association  of   Official  Analytical
Chemists, 48,  1037, 1965.
                                   8060  -  10
                                                          Revision
                                                          Date  September  1986

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4.  "EPA Method Validation Study  16,  Method  606 (Phthalate Esters)," Report
for EPA Contract 68-03-2606 (in preparation).

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

6.  Provost, L,,P. and R.S.  Elder,   "Interpretation of Percent Recovery Data,"
American Laboratory, 15, pp. 58-63,  1983.
                                   8060 - 11
                                                          Revision
                                                          Date  September 1986

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TABLE 3.  QC ACCEPTANCE CRITERIA3


Parameter
B1 s (2-ethy 1 hexy 1 ) phthal ate
Butyl benzyl phthal ate
D1-n-butyl phthal ate
01 ethyl phthal ate
Dimethyl phthal ate
D1-n-octyl phthal ate
Test
cone.
(ug/L)
50
10
25
25
25
50 .
Limit
for s
(ug/L)
38.4
4.2
8.9
9.0
9.5
13.4
Range
for 7
(ug/L)
1.2-55.9
5.7-11.0
10.3-29.6
1.9-33.4
1.3-35.5
D-50.0
Range
P, Ps
(%)
D-158
30-136
23-136
D-149
D-156
D-114
     s = Standard deviation of four recovery measurements, In ug/L.

     7 = Average recovery for four recovery measurements, in ug/L.

     PI PS = Percent recovery measured.

     D = Detected; result must be greater than zero.

     aCr1ter1a from 40 CFR Part  136 for  Method 606.  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.
                                   8060  -  12
                                                          Revision
                                                          Date   September  1986

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TABLE 4.  METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION3
Parameter
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Di ethyl phthalate
Dimethyl phthalate
Di-n-octyl phthalate
Accuracy, as
recovery, x1
(ug/L)
0.53C+2.02
0.82C+0.13
0.79C+0.17
0.70C+0.13
0.73C+0.17
0.35C-0.71
Single analyst
precision, sr'
(ug/L)
0.807-2.56
0.267+0.04
0.237+0.20
0.277+0.05
0.267+0.14
0.387+0.71
Overall
precision,
S1 (ug/L)
0.737-0.17
0.257+0.07
0.297+0.06
0.457+0.11
0.447+0.31
0.627+0.34
     x1  = Expected  recovery  for  one  or  more  measurements  of  a  sample
           containing a concentration of C, in ug/L.

     sr' = Expected single analyst  standard  deviation  of measurements at an
           average concentration of 7, in ug/L.

     S1  = Expected interlaboratory standard  deviation  of measurements at an
           average concentration found of 7, in ug/L.

     C   = True value for the concentration, in ug/L.

     7   = Average recovery found for measurements of samples containing a
           concentration of C, in ug/L.

     aCriteria from 40 CFR Part 136 for Method 606.
                                  8060  -  13
                                                         Revision      0
                                                         Date  September 1986

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                                         METHOD B060

                                      PHTHALATE ESTERS
7.1.1
       Choose
    appropriate
    extraction
     procedure
(see Chapter 2)
7.1.2
       Exchange
       extract-
 ion solvent to
       hexane
   during micro
 K-O procedure;:
 7.3
    Set gas
 chromatography
  conditions
 7.3
       Refer to
    Method 8000
    for proper
    calibration
    techniques
                                                       0
                                                    7.4
  Perform GC
analysis (see
 Method 8000)
                                                                             7.5.1
                            Cleanup
                          using Method
                         361O or 3630)
 Is identifica-
tion G detection
  prevented  by
   interfer-
     ences

        "No
                          7.3.21
                                Process
                                •  aeries
                             of  standards
                          through cleanup
                              procedure:
                            analyze by  GC
                                     8060 -  14
                                                               Revision       0
                                                               Date  September  1986

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                                 METHOD 8080

                     ORGANOCHLORINE PESTICIDES AND PCBs
1.0  SCOPE AND APPLICATION

     1.1  Method 8080  is  used  to  determine  the  concentration  of various
organochlorine pesticides and  polychlorinated  biphenyls  (PCBs).     Table 1
indicates compounds that may be determined by this method and lists the method
detection limit for  each  compound  in  reagent  water.     Table  2 lists the
practical quantitation limit (PQL) for other matrices.


2.0  SUMMARY OF METHOD

     2.1  Method  8080  provides   gas   chromatographic  conditions  for  the
detection of ppb levels 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-uL 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 a halogen-
specific detector  (HSD).

     2.2  The sensitivity of  Method  8080  usually  depends  on  the level 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, Fieri si 1 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  (Section  3.5, in  particular), 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
mlcrocoulometrlc or  electrolytic conductivity detector.
                                   8080  -  1
                                                          Revision      0
                                                          Date  September  1986

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TABLE 1.  GAS CHROMATOGRAPHY OF PESTICIDES AND PCBsa
Compound
Aldrin
a-BHC
/J-BHC
ff-BHC
7-BHC (Llndane)
Chlordane (technical)
4,4'-DDD
4, 4 '-DDE
4, 4 '-DDT
Dieldrin
Endosulfan I
Endosulfan II
Endosulfan sulfate
Endrln
Endrln aldehyde
Heptachlor
Heptachlor epoxlde
Methoxychlor
Toxaphene
PCB-1016
PCB-1221
PCB-1232
PCB-1242
PCB-1248
PCB-1254
PCB-1260
Retention
Col. 1
2.40
1.35
1.90
2.15
1.70
e
7.83
5.13
9.40
5.45
4.50
8.00
14.22
6.55
11.82
2.00
3.50
18.20
e
e
e
e
e
e
e
e
time (m1n)
Col. 2
4.10
1.82
1.97
2.20
2.13
e
9.08
7.15
11.75
7.23
6.20
8.28
10.70
8.10
9.30
3.35
5.00
26.60
e
e
e
e
e
e
e
e
Method
Detection
limit (ug/L)
0.004
0.003
0.006
0.009
0.004
0.014
o.oii
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
     aU.S.  EPA.     Method   617.      Organochlorlde  Pesticides  and  PCBs,
Environmental Monitoring and Support Laboratory, Cincinnati, Ohio 45268.
     e  =  Multiple peak response.
     nd = not determined.
                                  8080 - 2
                                                         Revision
                                                         Date  September 1986

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TABLE 2.  DETERMINATION OF PRACTICAL QUANTITATION LIMITS (PQL)  FOR VARIOUS
          MATRICES3


    Matrix                                                    Factorb
Ground water                                                     10
Low-level soil by sonlcatlon with GPC cleanup                   670
High-level soil and sludges by sonlcatlon                    10,000
Non-water misdble waste                                    100,000


     aSample PQLs are highly  matrix-dependent.    The  PQLs listed herein are
     provided for guidance and may not always be achievable.

     bPQL = [Method detection limit (Table 1)] X [Factor (Table 2)].  For non-
     aqueous samples, the factor 1s on a wet-weight basis.
                                   8080  - 3
                                                         Revision
                                                         Date  September 1986

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4.0  APPARATUS AND MATERIALS

     4.1  Gas chromatograph;

          4.1.1  Gas  Chromatograph:    Analytical  system  complete  with gas
     chromatograph  suitable  for   on-column   Injections  and  all  required
     accessories, including detectors,  column  supplies, recorder, gases, and
     syringes.  A data system for  measuring peak 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-mrn I.D. glass column or
          equivalent.

               4.1.2.2  Column 2:  Supelcoport  (100/120  mesh) coated with 3%
          OV-1 in a 1.8-m x 4-mm I.D. glass column or equivalent.

          4.1.3  Detectors:  Electron capture   (ECD) or halogen specific  (HSD)
      (i.e., electrolytic conductivity detector).

     4.2  Kuderna-Danish (K-D) apparatus;

          4.2.1  Concentrator tube:  10-mL, graduated (Kontes K-570050-1025 or
     equivalent),.  Ground-glass  stopper  Is  used  to  prevent evaporation of
     extracts

          4.2.2  Evaporation   flask:      500-mL   (Kontes   K-570001-500  or
     equivalent).  Attach to concentrator tube  with springs.

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

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

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

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

     4.5  Volumetric  flasks;  10-, 50-, and 100-mL, ground-glass stopper.

      4.6  Microsyrlnge;  10-uL.

      4.7  Syri nge;   5-mL.

      4.8  Vials;  Glass, 2-, 10-,  and  20-mL capacity with  Teflon-lined  screw
 cap.
                                   8080 - 4
                                                          Revision
                                                          Date   September 1986

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5.0  REAGENTS

     5.1  Solvents;   Hexane,  acetone,   toluene,   Isooctane (2,2,4-trlmethyl-
pentane) (pestlcTcfe quality or equivalent).

     5.2  Stock standard solutions:

          5.2.1  Prepare stock standard solutions at a concentration of
     1.00 ug/uL  by  dissolving  0.0100  g  of  assayed  reference material  in
     Isooctane and diluting to volume  1n  a  10-mL volumetric flask.  A small
     volume of toluene may be  necessary  to  put some pesticides 1n solution.
     Larger volumes can be  used  at  the  convenience  of  the analyst.  When
     compound purity 1s assayed to be  96%  or greater, the weight can be used
     without correction to calculate the  concentration of the stock standard.
     Commercially prepared stock standards can be used at any concentration 1f
     they are certified by the manufacturer or by an independent source.

          5.2.2  Transfer  the  stock  standard  solutions  into Teflon-sealed
     screw-cap bottles.  Store at 4*C and protect from light.  Stock standards
     should be checked  frequently  for  signs  of degradation or evaporation,
     especially just prior to preparing calibration standards from them.

          5.2.3  Stock standard solutions must be  replaced after one year, or
     sooner if comparison with check standards Indicates a problem.

     5.3  Calibration standards:  Calibration  standards  at a minimum of five
 concentration levelsforeach  parameter  of  interest  are prepared through
 dilution of the stock  standards  with  Isooctane.    One of the concentration
 levels  should be at a  concentration  near,  but  above, the method detection
 limit.  The remaining concentration  levels  should correspond to the expected
 range of concentrations found  in  real  samples  or should define the working
 range of the GC.   Calibration solutions  must be replaced after six months, or
 sooner, 1f comparison with check standards indicates a problem.

     5.4  Internal  standards  (if internal  standard  calibration is used);  To
 use  this approach,  the analyst must select one or more internal standards that
 are  similar in analytical behavior to  the compounds of Interest.  The analyst
 must further demonstrate that the measurement  of the  Internal standard  1s not
 affected by method or matrix interferences.   Because of these limitations, no
 internal standard  can be suggested that is applicable  to all samples.

          5.4.1  Prepare  calibration   standards   at   a   minimum  of five
     concentration  levels   for  each  analyte  of  Interest  as  described in
     Paragraph 5.3.

          5.4.2  To each calibration standard, add  a  known constant amount of
     one or more internal standards, and dilute to volume with Isooctane.

          5.4.3  Analyze each calibration  standard according to Section  7.0.
                                   8080 - 5
                                                          Revision       0
                                                          Date  September 1986

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     5.5  Surrogate standards;  The analyst  should monitor the performance  of
the extraction, cleanup(when  used),   and  analytical   system and the effec-
tiveness of the method  1n  dealing  with  each  sample  matrix by spiking each
sample, standard, and reagent water  blank with pesticide surrogates.   Because
GC/ECD data are much  more  subject  to  Interference than GC/MS,  a secondary
surrogate 1s to  be  used  when  sample  Interference  Is  apparent.  D1butyl -
chlorendate (DBC) 1s also subject  to  add  and base degradation.   Therefore,
two surrogate standards are added  to  each  sample; however,  only one need  be
calculated for recovery.   DBC  1s  the  primary  surrogate and should be used
whenever possible.  However,  1f  DBC  recovery  1s low  or compounds Interfere
with DBC, then  the  2,4,5,6-tetrachloro-meta-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.  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 chromatographlc  analysis,  the extraction solvent
     must  be  exchanged  to  hexane.    The exchange  1s 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   1n   the hot  water.   Adjust
           the vertical  position of the apparatus and the water temperature, as
           required,  to  complete concentration  in 5-10 m1n.  At the  proper rate
           of  distillation  the balls of  the  column will actively  chatter,  but
           the chambers  will  not   flood.    When  the apparent volume of liquid
           reaches 1  mL,  remove the K-D  apparatus   and  allow it  to drain  and
           cool for at least 10 min.

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               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  1s recommended for  this operation.  Adjust the extract
          volume   to  10.0  ml.    Stopper  the  concentrator  tube  and store
          refrigerated  at 4*C,   1f  further  processing  will not be performed
          Immediately.   If the  extract will be stored longer than two days, 1t
          should  be transferred to  a  Teflon-sealed  screw-cap vial.  Proceed
          with  gas  chromatographlc  analysis   1f  further  cleanup  1s  not
          required.

     7.2   Gas chromatography  conditions  (Recommended);

          7.2.1  Column 1:  Set 5% methane/95% argon carrier gas flow at
     60 mL/m1n  flow rate.     Column  temperature  1s  set at 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:  Set 5% methane/95% argon carrier gas flow at
     60 ml_/m1n  flow rate.  Column  temperature held Isothermal at 200*C.  When
     analyzing  for the  low molecular  weight  PCBs  (PCB  1221-PCB 1248), 1t 1s
     advisable  to set  the oven  temperature to 140*C.

          7.2.3  When  analyzing  for  most  or   all  of  the  analytes  1n this
     method,  adjust the oven  temperature and  column gas  flow so that 4,4'-DDT
     has  a retention  time  of  approximately 12 m1n.

     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-level standard.
     Inject this prior to beginning Initial  or dally  calibration.

     7.4  Gas chromatographlc analysis;

          7.4.1  Refer to Method 8000.     If the Internal standard calibration
     technique Is used, add 10 uL of  Internal  standard to  the  sample prior to
     injection.

          7.4.2  Follow Section 7.6  1n  Method   8000   for  Instructions on the
     analysis sequence,  appropriate  dilutions,  establishing  daily retention
     time windows, and Identification criteria.    Include a mid-level  standard
     after each group of 10 samples in the analysis sequence.
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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 Paragraph 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-level 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 Section  7.7  of  Method 8000.  Calculate percent
breakdown as follows:

% breakdown     Total DDT degradation peak area (DDE + ODD)   ,nn
for 4,4'-DDT  "    Total DDT peak area (DDT + DDE + ODD)    * iuu

% breakdown
for Endrin
Total endrin degradation peak area  (endrin aldehyde + endrin ketone)  1QO
 Total endrin peak area  (endrin + endrin aldehyde + endrin ketone)
     7.4.6  Record the  sample  volume  injected  and  the resulting peak
sizes  (in area units or peak heights).

     7.4.7  Using either the  internal  or external calibration procedure
(Method 8000), determine the identity and quantity of each component peak
in the sample chromatogram  which   corresponds  to the compounds used for
calibration purposes.

     7.4.8  If peak  detection  and   identification  are  prevented due to
interferences, the   hexane  extract may  need  to  undergo cleanup  using
Method 3620.  The resultant extract(s)  may  be  analyzed  by GC directly or
may undergo further  cleanup to remove Sulfur using Method  3660.

7.5  Cleanup;

     7.5.1  Proceed  with Method  3620,  followed  by,  if  necessary, Method
3660,  using the  10-mL  hexane extracts obtained  from  Paragraph 7.1.2.3.

     7.5.2  Following  cleanup, the  extracts  should   be  analyzed  by GC, as
described in  the previous  paragraphs and  in  Method  8000.

7.6  Calculations  (exerpted from U.S. FDA,  PAM):

      7.6.1  Calculation of Certain  Residues:  Residues  which  are mixtures
of two or more  components  present problems  in measurement.  When they are
found  together,  e.g.,   toxaphene and  DDT,   the   problem of  quantitation
becomes even  more difficult.    In  the following  sections  suggestions are
offered for handling toxaphene,  chlordane,   PCB,   DDT,  and BHC.  A column
10%  DC-200 stationary   phase   was  used   to   obtain   the chromatograms in
Figures 6-9.
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   Column: 1.5% SP-225CK
          1.95% SP-2401 on Suptlcopon
   Ttmptraturi: 200°C
   Ofttetor: Eltctron Capture
o
00
    u
   •X
 VJ
       4          8         12
          RETENTION TIME (MINUTES)
16
  Figure 1. Gas ehromatogram of pesticides.
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       Column: 1.5*8?-2250*
               1.95* SP-2401 on Suptleopon
       Ttmptrtture 2t)C°C
       Drttctor: Electron Capiurt
     I     <     I      t
                                      •	I
04          8          12         16
         RETENTION TIME (MINUTES)
    Figure 2. Gas chromatogram of chlordane.
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                  Column: 1.5% 9-2250+
                         1J5% SP-2401 on Suptlcopon
                  T0mptfituri: 200°C
                  Dmctor: Eltctron Cioturt
         10        14        18
      RETENTION TIME (MINUTES)
22
26
Figure 3. Gas chromatogram of toxaphene.
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Column: 1.5\SP-2250»
       1.95% SP 2401 en Suptlcepon
Ttmperaturt: 200°C
Otttctor: Eltcrron CtPturt
         6          10          14         18
           RETENTION TIME (MINUTES)
22
    Figure 4. Gas chromatogrim of PCS-1254.
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Column: 1.5* SP-2250*
       1.95% SP-2401 on Suptlcooon
Ttrnpcraturf: 200°C
iDtUCtor: Electron Capture
               10       14        18
             RETENTION TIME (MINUTES)
22
26
       Figure 5. Gas chromatogram of PCB-1260.
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    J..L
Fig, 6—Baseline construction for some typical gas chromatographlc peaks.
a, symmetrical separated flat baseline; b and c. overlapping flat baseline;
d, separated (pen does not return to baseline between peaks); e, separated
sloping baseline; f,  separated (pen goes below  baseline between peaks);
g. «- andy-BHC sloping baseline; h, «-.£-. and Y-BHC sloping baseline;
1, chlordane  flat baseline; j.  heptachlor and heptachlor epoxlde super-
imposed  on chlordane;  k, chair-shaped peaks, unsymmetrtcal peak; 1,
p,p'-DDT superimposed on toxaphene.
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Fig. 7a—Baseline construction for multiple residues with standard
                        toxaphene.
      \l
   Fig, 7b—Baseline construction for multiple residues with toxa-
             phene, DOE and o.p'-, and p.p'-DDT.
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 Fig. 8a—Baseline construction for multiple residues:  standard toxaphene.
Fig. 8b—Baseline construction for multiple residues: rice bran with BHC,
                  toxaphene, DOT, and methoxychlor.
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            Fig. 9a—Baseline construction for multiple residues:  standard chlordane.
Fig. 9b—Baseline construction for multiple residues:  rice bran with chlordane, toxaphene, and DOT.
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     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  sample  size  so that toxaphene major
peaks are 10-30%  full-scale  deflection  (FSD);  (b)  inject a toxaphene
standard that is  estimated  to  be  within  +10  ng  of  the sample;  (c)
construct the baseline of standard  toxaphene between it extremities;  and
(d) construct the baseline under  the  sample, using the distances of the
peak troughs to baseline on the  standard  as  a guide (Figures 7, 8,  and
9).  This procedure  is  made  difficult  by  the  fact that the relative
heights and widths  of  the  peaks  in  the  sample  will probably not be
identical to the standard.    A  toxaphene  standard that has been passed
through a Florisil column will show  a  shorter retention time for peak X
and an enlargement of peak Y.

     7.6.3  Toxaphene and DDT:   If  DDT  is present, it will superimpose
itself on toxaphene peak V.  To determine the approximate baseline of the
DDT, draw a line connecting the trough  of  peaks U and V with the trough
of peaks W and X and  construct  another line parallel to this line which
will just cut the top of peak  W   (Figure 61).  This procedure was tested
with ratios of standard toxaphene-DDT  mixtures  from 1:10 to 2:1 and the
results of added and calculated DDT and toxaphene by the "parallel lines"
method of baseline  construction were  within  10% of the actual values in
all cases.

          7.6.3.1   A  series of  toxaphene   residues  have been calculated
     using total peak area for comparison   to the standard and also using
     area of the last four peaks   only  in  both sample and standard.  The
     agreement between the results obtained  by the  two methods justifies
     the  use of the latter  method  for calculating  toxaphene  in  a sample
     where the early  eluting  portion  of   the toxaphene chromatogram is
     interfered with  by other substances.

          7.6.3.2   The    baseline   for   methoxychlor   superimposed  on
     toxaphene  (Figure 8b) was constructed  by overlaying the  samples on  a
     toxaphene standard of  approximately   the  same  concentration  (Figure
     8a)  and viewing  the  charts against a lighted background.

     7.6.4   Chlordane  is  a  technical  mixture  of at  least   11 major
components   and  30  or   more   minor  ones.    Gas  chromatography-mass
spectrometry and nuclear  magnetic  resonance  analytical techniques have
been applied to the elucidation  of  the  chemical  structures  of  the many
chlordane constituents.   Figure 9a  is  a chromatogram of standard chlor-
dane.   Peaks E and  F  are  responses to trans-  and  cis-chlordane,  respec-
tively.   These are  the  two  major components of technical chlordane, but
the  exact percentage  of each  in  the technical  material  1s not completely
defined  and  is not  consistent from batch to batch.  Other labelled peaks
in Figure 9a are  thought to  represent:     A, monochlorinated adduct of
pentachlorocyclopentadiene   with   cyclopentadiene;    B,    coelution  of
heptachlor  and a-chlordene;  C,  coelution of /?-chlordene and  7-chlordene;
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D, a chlordane analog; G, coelutlon  of cis-nonachlor and "Compound K,"  a
chlordane Isomer.  The right "shoulder"  of  peak  F is  caused by trans-
nonachlor.

          7.6.4.1  The GC  pattern  of  a  chlordane  residue  may differ
     considerably from that of the  technical standard.  Depending on the
     sample substrate and its history,  residues of chlordane can consist
     of almost  any  combination  of:    constituents  from the technical
     chlordane;  plant  and/or  animal   metabolities;  and  products  of
     degradation caused  by  exposure  to  environmental  factors such as
     water and sunlight.  Only  limited information is available on which
     residue GC patterns are likely to  occur in which samples types, and
     even this information may not be applicable to a situation where the
     route of exposure is unusual.  For example, fish exposed to a recent
     spill of  technical  chlordane  will  contain  a residue drastically
     different from a  fish  whose  chlordane  residue was accumulated by
     Ingestion of  smaller  fish  or  of  vegetation,  which  in turn had
     accumulated  residues  because  chlordane  was  in  the  water  from
     agricultural runoff.

          7.6.4.2  Because  of  this  Inability  to  predict  a chlordane
     residue GC pattern, it is not  possible to prescribe a single method
     for  the quantitation of chlordane  residues.  The analyst must judge
     whether or not the  residue's  GC  pattern is sufficiently similar to
     that of a technical chlordane  reference  material to use the latter
     as a reference standard for quantitation.

          7.6.4.3  When  the chlordane  residue does not  resemble technical
     chlordane,   but    instead   consists   primarTTy   of    Individual,
     identifiable peaks,  quantitate   each   peak  separately   against the
     appropriate reference materials  and  report the  Individual residues.
     (Reference  materials  are  available   for  at   least   11  chlordane
     constituents, metabolites or degradation products which may occur in
     the  residue.)

          7.6.4.4  When  the GC pattern  of   the residue resembles  that of
     technical chlordane, quantitate  chlordane  residues by  comparing the
     total area  of  the  chlordane  chromatogram  from  peaks  A through  F
     (Figure 9a) in   the sample  versus  the  same   part of the standard
     chromatogram.  Peak G may be obscured in a sample by the  presence of
     other  pesticides.     If  G  is   not  obscured,   include  it  in the
     measurement for  both standard and sample.  If the  heptachlor  epoxide
     peak is relatively  small, include it  as part of the total chlordane
     area for   calculation  of  the   residue.    If   heptachlor  and/or
     heptachlor  epoxide  are  much  out  of   proportion  as   in Figure 6j,
     calculate these  separately and subtract  their areas from total area
     to give a corrected chlordane  area.    (Note that octachlor epoxide,
     metabolite  of  chlordane,  can   easily  be  mistaken  for heptachlor
     epoxide on  a nonpolar GC column.)
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         7.6.4.5  To  measure   the   total   area   of   the  chlordane
    chromatogram, proceed as 1n Section  7.6.2  on toxaphene.  Inject an
    amount  of  technical  chlordane   standard  which  will  produce  a
    chromatogram  1n which peaks E and  F are approximately the same size
    as  those  In  the   sample  chromatograms.    Construct  the baseline
    beneath the standard from the beginning of peak A to the end of peak
    F as shown 1n Figure 9a.    Use the distance from the trough between
    peaks E and F to the baseline 1n the chromatogram of the standard to
    construct the baseline 1n the chromatogram of the sample.  Figure 9b
    shows how  the  presence  of  toxaphene  causes  the  baseline under
    chlordane to  take an upward angle.   When  the size of peaks E and F
    1n  standard and sample chromatograms are the same, the distance from
    the trough  of  the peaks  to  the  baselines  should  be the same.
    Measurement of chlordane area should  be  done by total peak area 1f
    possible.
         NOTE:  A comparison  has  been  made  of  the  total peak area
         Integration method and the addition  of peak heights method for
         several  samples containing chlordane.    The peak heights A, B,
         C, D,  E, and F were  measured  1n millimeters from peak maximum
         of each  to the baseline  constructed under the total chlordane
         area and were  then added  together.   These results obtained by
         the two  techniques are too close  to  Ignore this method of  "peak
         height  addition"  as   a  means   of calculating  chlordane.  The
         technique  has  Inherent difficulties  because  not  all the  peaks
         are  symmetrical and  not all  are  present   in the  same ratio 1n
         standard and  1n sample.    This  method  does  offer  a means of
         calculating  results  1f  no   means of  measuring   total  area 1s
         practical.

     7.6.5   Polychlorlnated blphenyls  (PCBs):    Quant1tat1on of residues
of PCB Involves  problems similar  to those encountered 1n  the quantltatlon
of toxaphene,  Strobane,  and  chlordane:     1n   each  case,  the chemical  1s
made up of  numerous  compounds  and  so  the chromatograms  are multi-peak;
also 1n each case the chromatogram  of  the residue  may not match  that of
the standard.

          7.6.5.1  Mixtures of PCB of various  chlorine contents were sold
     for many years 1n the U.S.  by  the Monsanto  Co.  under the tradename
     Aroclor (1200 series and 1016).   Though these Aroclors are no longer
     marketed,  the PCBs remain 1n  the environment and are sometime found
     as residues  1n foods,  especially fish.

          7.6.5.2  PCB residues are quantltated  by  comparison to one  or
     more of  the  Aroclor  materials,  depending   on the chromatographlc
     pattern of the residue.  A  choice  must be made as to which  Aroclor
     or mixture of Aroclors will   produce  a chromatogram most  similar to
     that of the  residue.   This  may  also Involve a judgment  about what
     proportion of  the  different  Aroclors  to  combine  to produce the
     appropriate  reference material.
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              7.6.5.3  Quantltate PCB  residues  by  comparing  total area or
         height of residue  peaks  to  total  area  of  height  of peaks from
         appropriate Aroclor(s) reference materials.    Measure total area or
         height response from  common  baseline  under  all  peaks.  Use only
         those peaks from sample  that  can be attributed to chloroblphenyls.
         These peaks  must  also  be  present  1n  chromatogram  of reference
         materials.  Mixture  of  Aroclors  may  be  required to provide best
         match of GC patterns of sample and reference.

         7.6.6  DDT:  DDT found 1n  samples  often consists of both o,p'- and
    p,p'-DDT.  Residues of  DDE  and  TDE  are  also frequently present.  Each
    Isomer of DDT and Its   metabolites  should  be quantltated using the pure
    standard of that compound and reported as such.

         7.6.7  Hexachlorocyclohexane   (BHC,  from  the  former name, benzene
    hexachlorlde):  Technical grade  BHC  1s  a cream-colored amorphous solid
    with a very characteristic musty  odor;  1t  consists of a mixture of six
    chemically distinct Isomers and  one or more heptachloro-cyclohexanes and
    octachloro-cyclohexanes.

              7.6.7.1  Commercial BHC preparations  may  show a wide variance
         1n the percentage  of  Individual  Isomers  present.  The elimination
         rate of the Isomers fed to rats  was  3 weeks for the a-, 7-, and 6-
         Isomers and 14 weeks for the  /Msomer.   Thus 1t may be possible to
         have any  combination  of  the  various  Isomers  1n  different food
         commodities.   BHC found  1n  dairy  products  usually  has a large
         percentage of /Msomer.

              7.6.7.2   Individual  Isomers  (a, 0, 7, and 6) were Injected Into
         gas chromatographs equipped with flame  1on1zat1on, m1crocoulometr1c,
         and electron capture detectors.     Response   for  the four Isomers 1s
         very nearly the   same  whether flame  1on1zat1on  or m1crocoulometr1c
         GLC  1s   used.     The  a-,  7-,  and dMsomers  show  equal electron
         affinity.  /J-BHC  shows a   much weaker  electron affinity compared to
         the others  Isomers.

               7.6.7.3   Quantltate  each  Isomer   (a,  /f,  7,  and 6) separately
          against  a standard of  the respective   pure  Isomer, using a  GC  column
         which  separates  all  the  Isomers  from one  another.


8.0  QUALITY CONTROL

     8.1  Refer  to  Chapter  One   for  specific  quality   control  procedures.
Quality control  to validate sample extraction 1s covered  In Method  3500  and  1n
the extraction method utilized.   If  extract cleanup was  performed,  follow  the
QC In Method 3600 and 1n the specific  cleanup method.

     8.2  Mandatory quality control   to  evaluate  the  GC  system operation  1s
found 1n Method 8000,  Section 8.6.
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          8.2.1  The quality control   check   sample   concentrate  (Method 8000,
     Section 8.6)  should contain  each  single-component  parameter of  interest
     at the following concentrations   in  acetone:    4,4'-DDD,  10 ug/mL; 4,4'-
     DDT,  10 ug/mL;  endosulfan  II,   10  ug/mL;   endosulfan sulfate,  10 ug/mL;
     endrin, lOug/mL; and any other  single-component  pesticide, 2 ug/mL.   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 ug/mL
     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, Section 8.10).

          8.3.1  If recovery is not within limits, the following  is required.

               •  Check to  be  sure  there   are  no  errors  in  calculations,
                  surrogate solutions  and  Internal  standards.    Also, check
                  instrument performance'.

               •  Recalculate the data and/or reanalyze  the extract if any  of
                  the above checks reveal a problem.

               •  Reextract and reanalyze the sample  if none of the above are
                  a problem or flag the data as "estimated concentration."

     8.4  GC/MS confirmation;  Any compounds confirmed by two columns may also
be confirmed by GC/MSifthe  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/uL  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.


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9.0  METHOD PERFORMANCE

     9.1  The method  was  tested  by  20  laboratories  using  reagent water,
drinking water, surface water, and  three Industrial wastewaters spiked at six
concentrations.  Concentrations used 1n the  study  ranged from 0.5 to 30 ug/L
for single-component pesticides and from  8.5  to 400 ug/L for multl-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 1on1zat1on detector are presented 1n 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 1n  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 1n Sediments and F1sh Tissue," Environmental Monitoring and Support
Laboratory, Cincinnati, OH 45268, October 1980.

3.  Pressley, T.A., and  J.E.  Longbottom,   "The  Determination of Organohallde
Pesticides and PCBs 1n 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  1n   Industrial  and  Municipal
Wastewaters, U.S. Environmental  Protection  Agency,"  Environmental Monitoring
and Support Laboratory, Cincinnati, OH 45268,  EPA-600/4-82-023, June 1982.

5.  GoerlUz,  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   Chromatographlc  Science,  11, 366,
1973.

8.  Millar, J.D., R.E.  Thomas and  H.J. Schattenberg,   "EPA Method  Study  18,
Method 608:   Organochlorlne   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.


                                   8080 - 23
                                                          Revision      0
                                                          Date  September 1986

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10.  Provost, L.P. and R.S. Elder,  "Interpretation of Percent Recovery Data,"
American Laboratory, 15, pp. 58-63, 1983.

11.  U.S. Food and Drug  Administration,  Pesticide Analytical Manual, Vol. 1,
June 1979.

12.  Sawyer, L.D., JAOAC, 56, 1015-1023  (1973), 61 272-281 (1978), 61 282-291
(1978).

13.  Official Methods of Analysis  of  the  Association of Official Analytical
Chemists, 12th Edition; Changes   1n  Methods,  JAOAC  61, 465-466  (1978), Sec.
29.018.
                                   8080  -  24
                                                          Revision
                                                          Date   September  1986

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TABLE 3.  QC ACCEPTANCE CRITERIA3
Parameter
Aldrln
a-BHC
fl-BHC
ff-BHC
7-BHC
Chlordane
4,4'-DDD
4, 4 '-DDE
4,4'-DDT
D1eldr1n
Endosulfan I
Endosulfan II
Endosulfan Sulfate
Endrln
Heptachlor
Heptachlor epoxlde
Toxaphene
PCB-1016
PCB-1221
PCB-1232
PCB-1242
PCB-1248
PCB-1254
PCB-1260
Test
cone.
(ug/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
(ug/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
/ /
' tonge
/ /for 7
(ug/L)
/i! 08-2. 24
/ /. 98-2. 44
(U. 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
/ (V \
\ /
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,  1n  ug/L.
      7 = Average recovery for four recovery measurements,  1n ug/L.
      P,  Ps = Percent recovery measured.
      D = Detected; result must be greater than  zero.
      aCriter1a from 40 CFR Part 136 for   Method 608.   These criteria are based
 directly upon the method performance  data  1n   Table  4.   Where necessary,  the
 limits for recovery have been broadened   to assure applicability of  the limits
 to concentrations below those used to develop Table 4.
                                   8080 - 25
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                                                          Date  September 1986

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TABLE 4.  METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION3


Parameter
Aldrin
a-BHC
/J-BHC
5-BHC
7-BHC
Chlordane
4,4'-DDD
4,4'-DDE
4,4'-DDT
Dleldrin
Endosulfan
Endosulfan
Endosulfan
Endrin
Heptachlor
Heptachlor
Toxaphene
PCB-1016
PCB-1221
PCB-1232
PCB-1242
PCB-1248
PCB-1254
PCB-1260
x' =

sr' =

S1 =
Accuracy, as
recovery, x1
(ug/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
I 0.97C+0.04
II 0.93C+0.34
Sulfate 0.89C-0.37
0.89C-0.04
0.69C+0.04
epoxide 0.89C+0.10
0.80C+1.74
0.81C+0.50
0.96C+0.65
0.91C+10.79
0.93C+0.70
0.97C+1.06
0.76C+2.07
0.66C+3.76
Single analyst Overall
precision, sr' precision,
(ug/L)
0.167-0.04
0.137+0.04
0.227+0.02
0.187+0.09
0.127+0.06
0.137+0.13
0.207-0.18
0.137+0.06
0.177+0.39
0.127+0.19
0.107+0.07
0.417-0.65
0.137+0.33
0.207+0.25
0.067+0.13
0.187-0.11
0.097+3.20
0.137+0.15
0.297-0.76
0.217-1.93
0.117+1.40
0.177+0.41
0.157+1.66
0.227-2.37
S1 (ug/L)
0.207-0.01
0.237-0.00
0.337-0.95
0.257+0.03
0.227+0.04
0.187+0.18
0.277-0.14
0.287-0.09
0.317-0.21
0.167+0.16
0.187+0.08
0.477-0.20
0.247+0.35
0.247+0.25
0.167+0.08
0.257-0.08
0.207+0.22
0.157+0.45
0.357-0.62
0.317+3.50
0.217+1.52
0.257-0.37
0.177+3.62
0.397-4.86
Expected recovery for one or more measurements of a sample
containing a concentration of C, 1n
Expected single analyst standard
average concentration of 7, in ug/L
Expected interlaboratory standard
ug/L.
deviation of
•
deviation of

measurements at an

measurements at an
           average concentration  found of 7, in ug/L.

      C    = True value  for the concentration, in ug/L.

      7    = Average recovery found for measurements of samples containing a
           concentration of C,  in ug/L.
                                  8080 - 26
                                                         Revision      0
                                                         Date  September 1986

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                                         METHOD aoao

                              ORGANOCHLORINE PESTICIDES C PCBa
                                                       o
7.1.1
     I Choose
    appropriate
    axtractlon
     procedure
(see Chapter a)
7.1.8
                                                     7.4
    Perform GC
  analysis (see
   Method 8OOO)
       Exchange
       extract-
 ion solvent to
       hexone
   during micro
 K-D procedures
                                                                             7.5.1
 7.Z
    Set gas
 chromatography
  conditions
 7.3
       Refer to
    Method BOOO
    for proper
    calibration
    techniques
     Is peak
detection £ Iden-
   tification
     prevent-
       ed?
    Cleanup
 using Method
3630 and 3660
If necessary
                             Methods of
                           calculation of
                        toxaphena. chlordane.
                        PCS. DOT. and 6HC are
                           handled In this
                             section
7.3.21
     I Prime or
     deactivate
     GC column
 prior to dally
   calibration
    O
                                     8080 -  27
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                                                               Date  September  1986

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                                 METHOD 8090

                      NITROAROMATICS AND CYCLIC KETONES
1.0  SCOPE AND APPLICATION

     1.1  Method 8090  is  used  to  determine  the  concentration  of various
nitroaromatic and cyclic ketone compounds.    Table 1 indicates compounds that
may be determined by this method and lists the method detection limit for each
compound in reagent water.    Table  2  lists the practical  quantisation limit
(PQL) for other matrices.


2.0  SUMMARY OF METHOD

     2.1  Method  8090  provides   gas   chromatographic  conditions  for  the
detection of ppb levels of  nitroaromatic  and cyclic ketone compounds.  Prior
to use of this method, appropriate  sample extraction techniques must be used.
Both neat and diluted  organic  liquids   (Method  3580, Waste Dilution) may be
analyzed by direct injection.  A 2- to 5-uL aliquot of the extract is injected
into a gas chromatograph  (GC) using the solvent flush technique, and compounds
in the GC effluent are  detected  by  an  electron capture detector (ECD) or a
flame ionization detector  (FID).    The  dinitrotoluenes are determined using
ECD, whereas the other compounds amenable  to this method are determined using
FID.

     2.2  If interferences  prevent  proper  detection  of  the  analytes, the
method may also be performed on extracts  that have undergone cleanup.


3.0  INTERFERENCES

     3.1  Refer to Method 3500, 3600, and 8000.

     3.2  Solvents,  reagents, glassware,  and other  sample-processing  hardware
may   yield   discrete    artifacts    and/or   elevated   baselines    causing
misinterpretation of gas  chromatograms.    All  of  these  materials  must be
demonstrated to  be   free from   interferences,   under the  conditions of the
analysis, by analyzing   method  blanks.    Specific   selection  of  reagents and
purification of  solvents by distillation  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.
                                   8090  -  1
                                                          Revision       0
                                                          Date  September  1986

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TABLE 1.  GAS CHROMATOGRAPHY OF NITROAROMATICS AND ISOPHORONE

                                Retention time (m1n)      Method detection
                                                            Unit (ug/L)
Compound                         Col. la    Col. 2b        ECD        FID
Isophorone
Nitrobenzene
2,4-D1n1trotoluene
2,6-D1n1trotoluene
D1 nitrobenzene
Naphthoqulnone
4.49
3.31
5.35
3.52


5.72
4.31
6.54
4.75


15.7
13.7
0.02
0.01


5.7
3.6
-
-


  aColumn 1:  Gas-Chrom  Q  (80/100  mesh)  coated  with 1.95% QF-1/1.5% OV-17
packed 1n a 1.2-m x 2-mm or  4-mm  I.D.  glass column.  A 2-mm I.D. column and
nitrogen gas at 44 mL/min flow  rate were used when determining isophorone and
nitrobenzene by GC/FID.  The  column  temperature was held Isothermal at 85°C.
A 4-mm I.D. column and  10%  methane/90%  argon  carrier gas at 44 mL/m1n flow
rate were used when  determining  the  dinltrotoluenes  by GC/ECD.  The column
temperature was held Isothermal at 145°C.

  bColumn 2:  Gas-Chrom Q (80/100 mesh) coated with 3% OV-101 packed 1n a 3.0-
m x 2-mm or 4-mm I.D. glass  column.   A 2-mm I.D. column and nitrogen carrier
gas  at  44  mL/m1n  flow  rate  were  used  when  determining  Isophorone and
nitrobenzene by GC/FID.  The column  temperature was held isothermal at 100'C.
A 4-mm I.D. column and  10%  methane/90%  argon  carrier gas at 44 mL/min flow
rate were  used  to  determine  the  dinltrotoluenes  by  GC/ECD.   The column
temperature was held Isothermal at 150°C.
TABLE 2.  DETERMINATION OF  PRACTICAL QUANTITATION LIMITS  (PQL)  FOR VARIOUS
          MATRICES*


    Matrix                                                     Factorb


Ground  water                                                      10
Low-level soil  by  sonication  with  GPC  cleanup                    670
High-level  soil  and  sludges by sonication                     10,000
Non-water miscible waste                                     100,000


      aSample  PQLs  are highly   matrix-dependent.     The  PQLs listed  herein  are
      provided for  guidance  and may not always  be  achievable.

      Multiply the  Method  Detection   Limits   in  Table  1   by  the Factor to
      determine the PQL for  each analyte in the matrix to be  analyzed.
                                   8090 - 2
                                                          Revision
                                                          Date  September 1986

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4.0  APPARATUS AND MATERIALS

     4.1  Gas chromatograph;

          4.1.1  Gas  chromatograph:    Analytical   system  complete  with gas
     chromatograph  suitable  for   on-column   injections  and  all  required
     accessories, including detectors,  column  supplies, recorder, gases, and
     syringes.  A data system for  measuring peak areas and/or peak heights is
     recommended.

          4.1.2  Columns:

               4.1.2.1  Column 1:  1.2-m x 2- or 4-mrn I.D. glass column packed
          with  1.95%  QF-1/1.5%  OV-17  on   Gas-Chrom  Q  (80/100  mesh)  or
          equivalent.

               4.1.2.2  Column 2:  3.0-m x 2- or 4-mm I.D. glass column packed
          with 3% OV-101 on Gas-Chrom Q (80/100 mesh) or equivalent.

          4.1.3  Detectors:  Flame ionization (FID) or electron capture (ECD).

     4.2  Kuderna-Danish (K-D) apparatus;

          4.2.1  Concentrator tube:  10-mL, graduated (Kontes K-570050-1025 or
     equivalent).  Ground-glass  stopper  is  used  to  prevent evaporation of
     extracts

          4.2.2  Evaporation   flask:      500-mL   (Kontes   K-570001-500  or
     equivalent).  Attach to concentrator tube with springs.

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

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

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

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

     4.5  Volumetric  flasks;  10-, 50-, and  100-mL, ground-glass stopper.

     4.6  Microsyringe:  10-uL.

     4.7  Syri nge;   5-mL.

     4.8  Vials;  Glass, 2-, 10-,  and  20-mL capacity with Teflon-lined  screw
 cap.
                                   8090 -  3
                                                          Revision
                                                          Date   September 1986

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5.0  REAGENTS

     5.1  Solvents;  hexane, acetone (pesticide quality or equivalent.)

     5.2  Stock standard solutions;

          5.2.1  Prepare stock standard solutions  at  a concentration of 1.00
     ug/uL by dissolving 0.0100 g of  assayed reference material  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.

          5.2.2  Transfer  t;.:  stock  standard  solutions  into Teflon-sealed
     screw-cap bottles.  Store at 4*C and protect from light.  Stock standards
     should be checked  frequently  for  signs  of degradation or evaporation,
     especially just prior to preparing calibration standards from them.

          5.2.3  Stock  standard solutions must be  replaced after one year, or
     sooner  1f comparison with check standards indicates a problem.

     5.3  Calibration standards;   Calibration  standards  at a minimum of five
 concentration levels are prepared  through dilution of the stock standards with
 hexane.  One of the  concentration  levels   should be at a concentration near,
 but  above, the method   detection   limit.     The  remaining concentration levels
 should  correspond  to   the  expected  range  of  concentrations  found 1n real
 samples or should  define the working  range  of  the GC.  Calibration solutions
 must be replaced   after six  months,  pr  sooner  1f  comparison with a check
 standard indicates a problem.

     5.4  Internal standards  (if internal  standard  calibration is used);  To
 use  this approach, the  analyst must select one or more internal standards that
 are  similar  in analytical behavior to  the compounds of Interest.  The analyst
 must further demonstrate that the  measurement  of the internal standard is not
 affected by  method or matrix  interferences.    Because of these limitations, no
 internal standard  can be suggested that is applicable to all samples.

          5.4.1  Prepare  calibration   standards   at   a   minimum  of  five
     concentration levels   for  each  parameter  of  Interest  as described 1n
     Paragraph 5.3.

          5.4.2  To each calibration standard, add  a known constant amount of
     one or  more internal standards, and dilute  to volume with hexane.

          5.4.3  Analyze each calibration standard according to Section 7.0.

     5.5  Surrogate standards;  The analyst   should monitor the performance of
 the  extraction, cleanup(when  used),  and   analytical   system and the effec-
 tiveness of  the method   1n  dealing  with  each   sample matrix by  spiking each
                                   8090 -  4
                                                          Revision       0
                                                          Date   September  1986

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sample, standard, and reagent water blank with one or two surrogates (e.g.,  2-
fluoroblphenyl) recommended to encompass the  range of the temperature program
used 1n this method.   Method  3500,  Section 5.3.1.1, details Instructions  on
the preparation of base/neutral  surrogates.    Deuterated analogs of analytes
should not be  used  as  surrogates  for  gas  chromatographlc analysis due  to
coelutlon problems.


6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

     6.1  See the Introductory  material  to  this  chapter, Organic Analytes,
Section 4.1.  Extracts must be  stored under refrigeration and analyzed within
40 days of extraction.


7.0  PROCEDURE

     7.1  Extraction;

          7.1.1  Refer to Chapter Two for guidance on choosing the appropriate
     extraction  procedure.   In general,  water  samples  are extracted at a pH
     between 5 to  9 with methylene  chloride, using either Method 3510 or 3520.
     Solid  samples  are extracted using  either Method  3540 or 3550.

          7.1.2  Prior to gas  chromatographlc analysis,  the extraction solvent
     must be exchanged to hexane.     The  exchange is performed during the  K-D
     procedures  listed in all  of the extraction  methods.   The exchange may be
     performed 1n  one of two ways,  depending on the data requirements.  If  the
     detection limits cited  1n Table 1 must be  achieved,  the exchange should
     be performed  as  described starting 1n   Section 7.1.4.  If these detection
      limits are  not necessary,  solvent exchange is performed as  outlined 1n
     Section 7.1.3.

          7.1.3  Solvent exchange  when   detection  limits  In  Table 1  are  not
      required:

               7.1.3.1   Following  K-D of the methylene  chloride extract to
          1 mL using the macro-Snyder column,   allow  the apparatus  to cool  and
          drain  for at  least 10 m1n.

               7.1.3.2  Momentarily remove  the  Snyder   column,   add  50 mL of
          hexane,  a new  boiling  chip,   and  reattach the macro-Snyder column.
          Concentrate the  extract  using 1   mL  of hexane to  prewet the Snyder
          column.   Place the  K-D   apparatus on   the  water  bath  so that  the
          concentrator tube  1s partially  Immersed  1n   the hot water.  Adjust
          the  vertical position of the  apparatus  and  the water temperature, as
          required, to complete concentration  1n  5-10 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 1t to drain  and
          cool for at least  10 min.    The  extract will  be handled  differently
                                   8090 - 5
                                                          Revision
                                                          Date  September 1986

-------
    at this point, depending on  whether  or  not cleanup 1s needed.  If
    cleanup 1s riot required, proceed  to  Paragraph 7.1.3.3.  If cleanup
    1s needed, proceed to  Paragraph 7.1.3.4.

          7.1.3.3  If cleanup of the extract  1s not required, remove the
    Snyder column and  rinse  the  flask  and  Its  lower joint Into the
    concentrator tube  with  1-2  ml  of  hexane.    A  5-mL  syringe 1s
    recommended for this operation.  Adjust the extract volume to
    10.0  ml.  Stopper  the concentrator  tube and store refrigerated at
    4*C 1f further processing will not be performed Immediately.  If the
    extract  will  be  stored  longer   than  two  days,  it  should  be
    transferred to a  Teflon-sealed  screw-cap  vial.   Proceed with gas
    chromatographlc analysis.

          7.1.3.4  If cleanup  of  the  extract  1s  required, remove the
    Snyder column and  rinse  the  flask  and  Its  lower joint Into the
    concentrator tube with a minimum  amount  of hexane.  A 5-mL syringe
    1s recommended for this operation.   Add a clean boiling chip to the
    concentrator tube and  attach a two-ball 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 concen-
    trator 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  0.5  ml,  remove the K-D   apparatus  and allow it to  drain and
    cool  for at  least  10 min.

          7.1.3.5  Remove  the  micrp-Snyder column  and  rinse  the  flask and
     Its  lower joint  Into  the   concentrator   tube  with  0.2  ml of  hexane.
    Adjust the extract  volume to  2.0. ml  and proceed with Method 3620.

     7.1.4  Solvent exchange when  detection  limits listed  In Table 1 must
be achieved:

          7.1.4.1  Following K-D  of the methylene  chloride  extract to
     1 ml using the macro-Snyder  column,   allow the  apparatus  to cool  and
     drain for at least  10 min.

          7.1.4.2  Remove  the  Snyder column   and   rinse  the  flask  and  Its
     lower joint Into  the  concentrator   tube  with   1-2 mL of  methylene
     chloride.   A 5-mL syringe  1s  recommended  for this operation.  Add
     1-2 mL of hexane,  a clean boiling  chip, and  attach  a two-ball micro-
     Snyder column.   Prewet the column  by  adding  0.5  mL of  hexane to  the
     top.   Place the micro-K-D  apparatus  on the  water  bath (60-65'C)  so
     that the concentrator tube is  partially  immersed  1n  the  hot water.
     Adjust  the  vertical   position  of   the  apparatus  and  the  water
     temperature,  as required,  to complete concentration in  5-10 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   0.5   mL,  remove  the  K-D  apparatus
     and allow it to drain and cool  for at  least  10  min.

                             8090 - 6
                                                    Revision      0
                                                    Date September  1986

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               7.1.4.3  Remove the mlcro-Snyder column and rinse the flask and
          Its lower joint Into the concentrator  tube with a minimum amount of
          hexane.  The volume of the  extract  should be adjusted to 1.0 ml 1f
          the extract will  be analyzed  without  cleanup.  If the extract will
          require cleanup,  adjust the volume  to  2.0 ml with hexane.  Stopper
          the concentrator  tube  and  store  refrigerated  at  4*C 1f further
          processing will not be performed  Immediately.   If the extract will
          be stored longer  than  two  days,  1t  should  be  transferred to a
          Teflon-sealed screw-cap vial.    Proceed  with  either gas chromato-
          graphlc analysis or with cleanup, as necessary.

     7.2  Gas chromatography conditions  (Recommended);   The determination of
dinitrotoluenesshouldbe  performedusingGC/ECD.    All  other compounds
amenable to this method are to be analyzed by GC/FID.

          7.2.1  Column 1:   Set  10%  methane/90%  argon  carrier gas flow at
     44 ml_/m1n flow rate.  For a 2-mm I.D. column, set the temperature at 85*C
     Isothermal.   For  a  4-mm  I.D.  column,  set  the  temperature at 145*C
     isothermal.

          7.2.2  Column 2:   Set  10%  methane/90%  argon  carrier gas flow at
     44 mL/m1n flow rate.   For  a  2-mm  I.D.  column, set the temperature at
     100°C Isothermal.  For a 4-mm  I.D.  column, set the temperature at 150*C
     Isothermal.

     7.3  Calibration;    Refer   to   Method   8000  for  proper  calibration
techniques"!  Use Table 1 and especially  Table 2 for guidance on selecting the
lowest point on the calibration curve.

          7.3.1  The procedure for  Internal  or external standard calibration
     may be used.  Refer to  Method  8000   for  a description of each of these
     procedures.

          7.3.4  If cleanup is performed  on  the  samples,  the analyst should
     process a series  of  standards   through  the   cleanup  procedure and  then
     analyze the samples by GC.    This  will confirm elution patterns and the
     absence of  interferents  from the  reagents.

     7.4  Gas  chromatographic analysis;

          7.4.1  Refer to Method 8000.     If  the  internal standard calibration
     technique  1s  used,  add  10  uL of   internal standard to  the  sample prior  to
     injection.

          7.4.2  Follow  Section  7.6   in   Method   8000   for  Instructions on the
     analysis  sequence,  appropriate   dilutions,   establishing  daily retention
     time windows, and identification  criteria.    Include a mid-level standard
     after  each  group  of 10   samples   in   the analysis  sequence when using FID
     and after each group of  5   samples   in   the analysis  sequence  when  using
     ECD.
                                   8090  -  7
                                                         Revision      0
                                                         Date  September 1986

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          7.4.3  An example  of  a  GC/FID  chromatogram   for  nitrobenzene and
     isophorone 1s shown 1n Figure  1.     Figure   2   1s an example of  a GC/ECD
     chromatogram of the dlnltrotoluenes.

          7.4.4  Record the  sample  volume  Injected and  the  resulting peak
     sizes (1n area units or peak heights).

          7.4.5  Using either the  Internal  or external  calibration procedure
     (Method 8000), determine the Identity  and  quantity of each analyte peak
     in  the  sample  chromatogram.    See  Section   7.8   of  Method   8000 for
     calculation equations.

          7.4.6  If peak detection  and  Identification   are  prevented due  to
     interferences, the hexane extract may undergo cleanup using Method 3620.

     7.5  Cleanup;

          7.5.1  Proceed with  Method  3620,  using   the   2-mL hexane  extracts
     obtained from either Paragraph 7.1.3.5 or 7.1.4.3.

          7.5.2  Following cleanup, the extracts should   be analyzed by GC,  as
     described 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 1s covered 1n Method 3500 and  1n
the extraction method utilized.  If  extract cleanup was performed,  follow the
QC in Method 3600 and 1n the specific cleanup method.

     8.2  Procedures to check  the  GC  system  operation  are found  1n Method
8000, Section 8.6.

          8.2.1  The quality control  check  sample  concentrate (Method  8000,
     Section 8.6) should contain each  parameter  of  interest in acetone at a
     concentration of 20  ug/mL  for  each  dinitrotoluene  and  100 ug/mL for
     isophorone and nitrobenzene.

          8.2.2  Table  3 Indicates the  calibration and QC acceptance criteria
     for this  method.    Table  4  gives  method  accuracy  and  precision as
     functions of concentration  for the, analytes of Interest.  The contents of
     both Tables should be used  to  evaluate a laboratory's ability to perform
     and generate acceptable data by this  method.

     8.3  Calculate surrogate  standard  recovery  on  all  samples, blanks,  and
spikes.  Determine  if   the   recovery  is   within limits  (limits  established by
performing  QC  procedures outlined  in Method 8000, Section  8.10).
                                  8090 - 8
                                                         Revision      0
                                                         Date  September 1986

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             COLUMN: 1.5% OV-17 +1.95% QF-1
                      ON GAS CHROM Q
             TEMPERATURE: 85°C.
             DETECTOR: FLAME IONIZATION
            24   6    8   10  12
            RETENTION TIME-MINUTES
Figure 1. Gas chromatogram of nitrobenzene and isophorone.
                     8090 - 9
                                           Revision      Q
                                           Date  September 1986

-------
          COLUMN: 1.5% OV-17 4-1.95% QM
                   ON GAS CHROM Q
          TEMPERATURE: 145°C.
          DETECTOR: ELECTRON  CAPTURE
             3
             g
             O

             z
             o
             to
                  Ul
                  Z
O
O
K
I
o
V
fN
I
               u
           2468
      RETENTION TIME-MINUTES
Figure 2. Gas chromatogram of dinitrotoluenes.

                  8090  - 10
                                        Revision      0
                                        Date  September  1986

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          8.3.1   If recovery is not within  limits,  the  following  1s  required.

               •   Check to  be  sure  there  are  no errors   1n  calculations,
                  surrogate solutions  and   Internal  standards.   Also,  check
                  Instrument performance.

               •   Recalculate the data and/or reanalyze  the  extract 1f any of
                  the above checks reveal  a problem.

               •   Reextract and reanalyze  the sample  1f none of the above are
                  a problem or flag the data as "estimated concentration."


9.0  METHOD PERFORMANCE

     9.1  The method  was  tested  by  18  laboratories  using  reagent water,
drinking water,  surface water, and  three industrial wastewaters spiked at six
concentrations over the range  1.0  to  515  ug/L.  Single operator precision,
overall precision, and method accuracy  were  found  to be directly related to
the concentration of the parameter  and  essentially independent of the sample
matrix.    Linear  equations  to  describe  these  relationships  for  a flame
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  4  -   Nitroaromatics and Isophorone,'
Report  for EPA Contract 68-03-2624  (in preparation).

2.  "Determination  of  Nitroaromatics   and    Isophorone  in  Industrial  and
Municipal  Wastewaters,"    EPA-600/4-82-024,    U.S.  Environmental  Protection
Agency, Environmental  Monitoring  and  Support  Laboratory,  Cincinnati,  Ohio
45268,  June 1982.

3.  Burke, J.A.   "Gas  Chromatography  for  Pesticide  Residue  Analysis;  Some
Practical  Aspects,"  Journal  of   the  Association  of  Official  Analytical
Chemists, 48, 1037,  1965.

4.  "EPA  Method   Validation   Study   19,   Method  609   (Nitroaromatics  and
Isophorone)," Report for  EPA  Contract 68-03-2624  (in preparation).

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

6.  Provost, L.P.  and  R.S.   Elder,   "Interpretation of Percent Recovery Data,"
American  Laboratory, 1J>,  pp.  58-63,  1983.
                                   8090  -  11
                                                          Revision       0
                                                          Date   September  1986

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TABLE 3.  QC ACCEPTANCE CRITERIA3


Parameter
2,4-D1n1trotoluene
2,6-Dinitrotoluene
Isophorone
Nitrobenzene
Test
cone.
(ug/L)
20
20
100
100
Limit
for s
(ug/L)
5.1
4.8
32.3
33.3
Range
for 7
(ug/L)
3.6-22.8
3.8-23.0
8.0-100.0
25.7-100.0
Range
P, PS
00
6-125
8-126
D-117
6-118
     s = Standard deviation of four recovery measurements, in ug/L.
     7 = Average recovery for four^recovery measurements, in ug/L.
     P, Ps = Percent recovery measured.
     D = Detected; result must be greater than zero.
     aCriteria from 40 CFR Part 136 for  Method 609.  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.
                                  8090 - 12
                                                         Revision
                                                         Date  September 1986

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TABLE 4.  METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION
Parameter
2,4-D1n1trotoluene
2,4-D1n1trotoluene
Isophorene
Nitrobenzene
Accuracy, as
recovery, x1
(ug/L)
0.65C+0.22
0.66C+0.20
0.49C+2.93
0.60C+2.00
Single analyst
precision, sr'
(ug/L)
0.207+0.08
0.197+0.06
0.287+2.77
0.257+2.53
Overal 1
precision,
S1 (ug/L)
0.377-0.07
0.367-0.00
0.467+0.31
0.377-0.78
     x1  = Expected  recovery  for  one  or  more  measurements  of  a  sample
           containing a concentration of C, 1n ug/L.

     sr' = Expected single analyst  standard  deviation  of measurements at an
           average concentration of 7, 1n ug/L.

     S1  = Expected Interlaboratory standard  deviation  of measurements at an
           average concentration found of 7, 1n ug/L.

     C   = True value for the concentration, 1n ug/L.

     7   = Average recovery found for measurements of samples containing a
           concentration of C, 1n ug/L.
                                  8090  -  13
                                                         Revision
                                                         Date  September 1986

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                                         METHOD BO9O

                              NITROAROMATICS AND CYCLIC  KETONES
                          7.1.1
                                 Choose
                               extract Ion
                           procedure from
                               Chapter Z
7.1.3
       Rinse
   with hexane:
 re—concentrate
    to .5 mL:
 adjust to Z mL
7. 1.3
                     Yes
                           Are the  MOL
                            In table  Z
                             required?
                           Concentrate  to
                           1 mL using K-D
                             apparatus
                                          Yes
IB cleanup
 required?
 Cleanup using
  Method 362O

7. 1.3
Into cor
tor tut
hexane:
to 1


Rinse
flash
icentra-
>e with
adjust
10 mL
                             0
                                                   7.1.4
                              Rinse
                           with hexane:
                          concetrate to
                        .5 ml using K-D
                                                      Is cleanup
                                                      .required?
                                                                   Yes

7.1.4



Adjust volume
to
1 mL
                                                                             7.1.4
Adjust volume
   to Z mL
                                                                             7.1.41
                                                  Cleanup using
                                                   Method 362O
                                     8090  - 14
                                                                Revision       p
                                                                Date   September 1986

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           METHOD 8090

NITROAROMATXCS AND CYCLIC KETONES
           (Continued)
          7.S
          Set  GC column
            operating
            conditions
          7.3
          Calibrate  (see
           Method BOOO)
          7.4
               Perform
             GC analysis
             (see Method
               aoooi
       (      Stop       J
    8090  - 15
                              Revision       0
                              Date  September  1986

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                                 METHOD 8100

                      POLYNUCLEAR AROMATIC HYDROCARBONS
1.0  SCOPE AND APPLICATION

     1.1  Method 8100  is  used  to  determine  the  concentration  of certain
polynuclear aromatic hydrocarbons (PAH).  Table 1 Indicates compounds that may
be determined by this method.

     1.2  The packed column gas  chromatographic  method described here cannot
adequately resolve the  following  four  pairs  of  compounds:  anthracene and
phenanthrene;  chrysene   and   benzo(a)anthracene;  benzo(b)fluoranthene  and
benzo(k)fluoranthene; and  dibenzo(a,h)anthracene  and indeno(l,2,3-cd)pyrene.
The use of a capillary column instead  of the packed column, also described 1n
this method, may adequately resolve  these  PAHs.  However, unless the purpose
of the  analysis  can  be  served  by  reporting  a  quantitative  sum  for an
unresolved PAH pair, either liquid chromatography  (Method 8310) or gas chroma-
tography/mass spectroscopy (Method 8270) should be used for these compounds.


2.0  SUMMARY OF METHOD

     2.1  Method  8100  provides   gas   chromatographlc  conditions  for  the
detection of ppb levels of  certain  polynuclear aromatic hydrocarbons.  Prior
to use  of this method, appropriate   sample extraction techniques must be used.
Both neat and diluted  organic   liquids  (Method   3580, Waste Dilution) may be
analyzed by direct  injection.  A 2-  to  5-uL aliquot of the  extract 1s Injected
Into a  gas chromatograph  (GC) using  the solvent  flush technique, and compounds
1n the  GC effluent  are detected  by a flame lonization detector  (FID).

     2.2  If  interferences   prevent proper   detection  of  the  analytes  of
interest, the method may   also   be   performed  on  extracts  that have undergone
cleanup using silica gel  column  cleanup  (Method  3630).


3.0  INTERFERENCES

     3.1  Refer  to  Methods 3500, 3600,  and 8000.

     3.2  Solvents,  reagents, glassware, and   other sample  processing hardware
may   yield   discrete     artifacts     and/or    elevated    baselines   causing
misinterpretation of gas chromatograms.    All   of  these  materials must be
demonstrated to  be free from  interferences,  under  the  conditions of the
analysis, by analyzing   method   blanks.    Specific   selection  of reagents and
purification of  solvents  by  distillation 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.


                                   8100 - 1
                                                         Revision      0
                                                          Date   September  1986

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TABLE 1.  GAS CHROMATOGRAPHY OF POLYNUCLEAR AROMATIC HYDROCARBONS3

Compound                                    Retention time (m1n)
Acenaphthene
Acenaphthylene
Anthracene
Benzo (a) anthracene
Benzo(a)pyrene
Benzo b fluoranthene
Benzo J fluoranthene
Benzo k fluoranthene
Benzo (ghl)perylene
Chrysene
10
10
15
20
29
28

28
38
24
.8
.4
.9
.6
.4
.0

.0
.6
.7
D1benz(a,h)acr1d1ne
D1benz(a,J)acr1d1ne
Dlbenzo(a,h)anthracene                              36.2
7H-D1benzo(c,g)carbazole
D1benzo(a,e)pyrene
D1benzo(a,h)pyrene
Dlbenzo(a,1)pyrene
Fluoranthene                                        19.8
Fluorene                                            12.6
Indeno(l,2,3-cd)pyrene                              36.2
3-Methy1cholanthrene
Naphthalene                                          4.5
Phenanthrene                                        15.9
Pyrene                                              20.6
     aResults obtained  using Column  1,
                                   8100 - 2
                                                          Revision
                                                          Date   September 1986

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4.0  APPARATUS AND MATERIALS

     4.1  Gas chromatograph;

          4.1.1  Gas  chromatograph:    Analytical   system  complete  with gas
     chromatograph  suitable  for   on-column   injections  and  all  required
     accessories, Including detectors,  column  supplies,  recorder,  gases, and
     syringes.  A data system for  measuring peak areas and/or peak heights 1s
     recommended.

          4.1.2  Columns:

               4.1.2.1  Column 1:  1.8-m x  2-mm I.D. glass column packed with
          3% OV-17 on Chromosorb W-AW-DCMS (100/120 mesh)  or equivalent.

               4.1.2.2  Column 2:   30-m  x  0.25-mm  I.D.  SE-54 fused silica
          capillary column.

               4.1.2.3  Column 3:   30-m  x  0.32-mm  I.D.  SE-54 fused silica
          capillary column.

          4.1.3  Detector:  Flame 1on1zat1on (FID).

     4.2  Volumetric flask;  10-, 50-, and 100-mL,  ground-glass stopper.

     4.3  Microsyringe;  10-uL.


5.0  REAGENTS

     5.1  Solvents:    Hexane,   Isooctane  (2,2,4-trlmethylpentane) (pesticide
quality or equivalent).

     5.2  Stock  standard solutions;

          5.2.1  Prepare stock standard solutions  at  a concentration of 1.00
     ug/uL by  dissolving 0.0100  g  of  assayed reference material 1n Isooctane
     and diluting to volume 1n a 10-mL  volumetric  flask.  Larger  volumes can
     be used at  the  convenience of  the  analyst.    When compound purity 1s
     assayed to  be 96% or  greater,  the  weight can  be used without correction
     to calculate  the   concentration  of  the  stock  standard.  Commercially
     prepared  stock standards can  be  used  at  any concentration  1f they are
     certified by the manufacturer or by an  independent source.

          5.2.2  Transfer   the   stock  standard  solutions  into  Teflon-sealed
     screw-cap bottles.  Store at 4*C and  protect  from light.  Stock standards
     should be checked   frequently  for  signs  of degradation or evaporation,
     especially  just prior to preparing calibration  standards  from  them.

          5.2.3  Stock  standard  solutions  must be  replaced after one year, or
     sooner  1f comparison  with check  standards Indicates  a problem.
                                   8100 - 3
                                                          Revision
                                                         Date  September  1986

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     5.3  Calibration standards;  Calibration  standards   at a minimum of five
concentrationlevelsshouldbe  prepared  through  dilution  of  the  stock
standards with isooctane.   One  of  the  concentration  levels should be at a
concentration near, but  above,  the  method  detection  limit.  The remaining
concentration levels should correspond to the expected range of concentrations
found in real samples or should  define  the  working  range of the GC.  Cali-
bration solutions must be replaced  after  six months, or sooner if comparison
with a check standard indicates a problem.

     5.4  Internal standards (if internal  standard  calibration is used);  To
use this approach, the analyst must select one or more internal standards that
are similar in analytical behavior to  the compounds of interest.  The analyst
must further demonstrate that the measurement  of the internal standard is not
affected by method or matrix interferences.   Because of these limitations, no
internal standard can be suggested that is applicable to all samples.

          5.4.1  Prepare  calibration   standards   at   a   minimum  of  five
     concentration  levels  for  each  analyte  of  interest  as  described in
     Paragraph 5.3.

          5.4.2  To each calibration standard, add  a known constant amount of
     one or more internal standards, and dilute to volume with isooctane.

          5.4.3  Analyze each calibration standard according to Section 7.0.

     5.5  Surrogate standards;  The analyst  should monitor the performance of
the  extraction,cleanup(when   used),   and   analytical  system  and  the
effectiveness of the method in dealing with each sample matrix by spiking each
sample, standard, and reagent water blank with one or two surrogates (e.g., 2-
fluorobiphenyl and 1-fluoronaphthalene) recommended  to encompass the range of
the temperature program used in  this  method.   Method 3500, Section 5.3.1.1,
details  instructions   on   the   preparation   of  base/neutral  surrogates.
Deuterated analogs of  analytes  should  not  be  used  as  surrogates for gas
chromatographic analysis due to coelution problems.


6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

     6.1  See the  introductory  material  to  this  chapter, Organic Analytes,
Section 4.1.  Extracts must be  stored under refrigeration and must be analyzed
within 40 days of  extraction.


7.0  PROCEDURE

     7.1  Extraction;

          7.1.1   Refer to  Chapter  Two for guidance  on  choosing the appropriate
     extraction procedure.    In general,  water  samples   are   extracted  at  a
     neutral pH with methylene  chloride,  using  either  Method 3510 or  3520.
     Solid samples are extracted using  either Method  3540 or  3550.   To achieve
     maximum sensitivity with  this method, the extract must be concentrated to
     1 mL.

                                   8100 - 4
                                                         Revision      0
                                                         Date  September  1986

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     7.2  Gas  chromatography  conditions  (Recommended);

          7.2.1   Column 1:  Set  nitrogen   carrier  gas  flow at 40-mL/m1n flow
     rate.  Set  column temperature  at  100*C for  4 m1n; then program  at 8*C/min
     to a final  hold at 280*C.

          7.2.2   Column 2:  Set  helium  carrier gas  at  20-cm/sec  flow rate.
     Set column  temperature at  35*C  for  2  m1n;   then  program at 10*C/min  to
     265'C and hold for 12  m1n.

          7.2.3   Column 3:  Set  helium  carrier gas  at  60 cm/sec  flow rate.
     Set column  temperature at  35*C  for  2  m1n;   then  program at 10'C/min  to
     265*C and hold for 3 m1n.

     7.3  Calibration;    Refer   to  Method   8000   for   proper calibration
techniques.

          7.3.1   The procedure  for  Internal  or external  standard calibration
     may be used.  Refer to  Method  8000   for  a description  of  each of these
     procedures.

          7.3.2  If cleanup 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
     Injection.

          7.4.2  Follow Section 7.6  1n  Method  8000  for instructions  on  the
     analysis sequence,  appropriate  dilutions,  establishing dally retention
     time windows, and Identification criteria.    Include  a mid-level standard
     after each group of 10 samples 1n the analysis sequence.

          7.4.3  Record the  sample  volume  Injected  and  the  resulting  peak
     sizes (in area units or peak heights).

          7.4.4  Using either the  internal  or external calibration procedure
     (Method 8000), determine the Identity and quantity of each  component peak
     in the sample chromatogram  which  corresponds  to the compounds used for
     calibration purposes.   See  Section  7.8  of  Method 8000 for calculation
     equations.

          7.4.5  If peak detection  and  identification  are  prevented due to
     interferences, the extract may undergo cleanup using Method 3630.

     7.5  Cleanup;

          7.5.1  Proceed with  Method  3630.     Instructions  are given  in this
     method for exchanging the solvent of the extract to hexane.

                                  8100 - 5
                                                         Revision       0
                                                         Date  September 1986

-------
          7.5.2  Following cleanup,  the extracts should  be analyzed by GC,  as
     described 1n the previous paragraphs and 1n Method 8000.


8.0  QUALITY CONTROL

     8.1  Refer  to  Chapter  One  for  specific  quality  control procedures.
Quality control to validate sample extraction 1s covered 1n Method 3500 and in
the extraction method utilized.  If  extract cleanup was performed, follow the
QC in Method 3600 and in the specific cleanup method.

     8.2  Procedures to check  the  GC  system  operation  are found in Method
8000, Section 8.6.

          8.2.1  The quality control  check  sample  concentrate  (Method 8000,
     Section 8.6) should contain each  analyte at the following concentrations
     in acetonltrile:    naphthalene,  100  ug/mL;  acenaphthylene, 100 ug/mL;
     acenaphthene, 100 ug/mL;  fluorene,  100  ug/mL; phenanthrene, 100 ug/mL;
     anthracene, 100 ug/mL; benzo(k)flubranthene,  5  ug/mL; and  any other PAH
     at 10 ug/mL.

          8.2.2  Table 2  indicates the   calibration and QC acceptance  criteria
     for this  method.    Table  3  gives  method  accuracy  and   precision as
     functions of concentration  for the  analytes of interest.  The contents of
     both Tables should be  used  to  evaluate a  laboratory's ability to perform
     and generate acceptable  data by this method.

     8.3  Calculate  surrogate  standard   recovery  on  all  samples,  blanks, and
spikes.  Determine if  the  recovery   is  within limits  (limits established by
performing QC  procedures  outlined in Method 8000, Section  8.10).

          8.3.1  If  recovery  is  not   within  limits, the  following procedures
     are required.

                •  Check to  be  sure   there  are  no  errors   1n  calculations,
                  surrogate solutions  and   internal   standards.    Also,  check
                  instrument  performance.

                •  Recalculate the data and/or reanalyze  the extract if any of
                  the above checks  reveal a problem.

                •  Reextract and  reanalyze the sample   if none  of  the above are
                  a  problem or flag the  data as  "estimated concentration."


9.0  METHOD  PERFORMANCE

     9.1  The  method was  tested   by   16   laboratories  using reagent water,
drinking water,  surface water, and  three industrial wastewaters  spiked at  six
concentrations over  the range 0.1  to  425  ug/L.   Single operator precision,
overall precision, and method accuracy  were  found  to  be directly related to
                                   8100 - 6
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                                                          Date  September  1986

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the concentration of the  analyte  and  essentially  independent of the sample
matrix.    Linear  equations  to  describe  these  relationships  for  a flame
ionization detector are presented in Table 3.

     9.2  This method has been  tested  for  linearity  of spike recovery from
reagent  water  and  has   been   demonstrated   to  be  applicable  over  the
concentration range from 8 x MDL  to  800  x MDL with the following exception:
benzo(ghi)perylene recovery at 80  x  and  800  x  MDL  were low (35% and 45%,
respectively).

     9.3  The accuracy and precision obtained will be determined by the sample
matrix, sample-preparation technique, and calibration procedures used.

10.0  REFERENCES

1.  "Development and Application of Test Procedures for Specific Organic Toxic
Substances in Wastewaters.  Category 9 - PAHs," Report for EPA Contract 68-03-
2624 (in preparation).

2.  Sauter, A.D., L.D. Betowski, T.R. Smith, V.A. Strickler, R.G. Beimer,
B.N. Colby, and J.E. Wilkinson,  "Fused  Silica Capillary Column GC/MS for the
Analysis of Priority Pollutants," Journal of HRC&CC 4, 366-384, 1981.

3.  "Determination of  Polynuclear  Aromatic  Hydrocarbons  in  Industrial and
Municipal  Wastewaters,"    EPA-600/4-82-025,   U.S.   Environmental   Protection
Agency, Environmental  Monitoring  and  Support   Laboratory,  Cincinnati, Ohio
45268,  September 1982.

4.  Burke, J.A.  "Gas  Chromatography  for   Pesticide Residue  Analysis; Some
Practical  Aspects,"   Journal   of    the  Association   of  Official   Analytical
Chemists, 48,  1037,  1965.

5.  "EPA  Method  Validation   Study   20,   Method 610  (Polynuclear  Aromatic
Hydrocarbons)," Report for  EPA Contract 68-03-2624  (in preparation).

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

7.  Provost,  L.P. and  R.S.  Elder,   "Interpretation of Percent  Recovery Data,"
American  Laboratory,  lj>,  pp.  58-63,  1983.
                                   8100 - 7
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                                                          Date   September  1986

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TABLE 2.  QC ACCEPTANCE CRITERIA3
Parameter
Acenaphthene
Acenaphthylene
Anthracene
Benzo (a) anthracene
Benzo(a)pyrene
Benzo (b) f 1 uoranthene
Benzo (ghi ) peryl ene
Benzo (k)fl uoranthene
Chrysene
Dibenzo (a, h) anthracene
Fl uoranthene
Fluorene
Indeno (1 , 2 , 3-cd) pyrene
Naphthalene
Phenanthrene
Pyrene
Test
cone.
(ug/L)
100
100
100
10
10
10
10
5
10
10
10
100
10
100
100
10
Limit
for s
(ug/L)
40.3
45.1
28.7
4.0
4.0
3.1
2.3
2.5
4.2
2.0
3.0
43.0
3.0
40.7
37.7
3.4
Range
for 7
(ug/U
D-105.7
22.1-112.1
11.2-112.3
3.1-11.6
0.2-11.0
1.8-13.8
D-10.7
D-7.0
D-17.5
0.3-10.0
2.7-11.1
D-119
1.2-10.0
21.5-100.0
8.4-133.7
1.4-12.1
Range
P. PS
(%)
D-124
D-139
D-126
12-135
D-128
6-150
D-116
D-159
D-199
D-110
14-123
D-142
D-116
D-122
D-155
D-140
     s = Standard deviation of four recovery measurements, 1n ug/L.

     7 = Average recovery for four recovery measurements, in ug/L.

     P, Ps = Percent recovery measured.

     D = Detected; result must be greater than zero.

     Criteria from 40 CFR Part 136 for  Method 610.  These criteria are based
directly upon the method performance  data  1n  Table 3.  Where necessary, the
limits for recovery have been broadened  to assure applicability of the limits
to concentrations below those used to develop Table 3.
                                  8100 - 8
                                                         Revision
                                                         Date  September 1986

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TABLE 3.  METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION
Parameter
Acenaphthene
Acenaphthylene
Anthracene
Benzo (a) anthracene
Benzo (a) pyrene
Benzo (b) f 1 uoranthene
Benzo (ghi)perylene
Benzo (k) f 1 uoranthene
Chrysene
Dlbenzo (a, h) anthracene
Fl uoranthene
Fluorene
Ideno (1 , 2 , 3-cd) pyrene
Naphthalene
Phenanthrene
Pyrene
Accuracy, as
recovery, x1
(ug/L)
0.52C+0.54
0.69C-1.89
0.63C-1.26
0.73C+0.05
0.56C+0.01
0.78C+0.01
0.44C+0.30
0.59C+0.00
0.77C-0.18
0.41C-0.11
0.68C+0.07
0.56C-0.52
0.54C+0.06
0.57C-0.70
0.72C-0.95
0.69C-0.12
Single analyst
precision, sr'
(ug/L)
0.397+0.76
0.367+0.29
0.237+1.16
0.287+0.04
0.387-0.01
0.217+0.01
0.257+0.04
0.447-0.00
0.327-0.18
0.247+0.02
0.227+0.06
0.447-1.12
0.297+0.02
0.397-0.18
0.297+0.05
0.257+0.14
Overall
precision,
S1 (ug/L)
0.537+1.32
0.427+0.52
0.417+0.45
0.347+0.02
0.537-0.01
0.387-0.00
0.587+0.10
0.697+0.10
0.667-0.22
0.457+0.03
0.327+0.03
0.637-0.65
0.427+0.01
0.417+0.74
0.477-0.25
0.427-0.00
     x1  = Expected  recovery  for  one  or  more  measurements  of  a  sample
           containing a concentration of C, in ug/L.

     sr' = Expected single analyst  standard  deviation  of measurements at an
           average concentration of 7, in ug/L.

     S1  = Expected interlaboratory standard  deviation  of measurements at an
           average concentration found of 7, in ug/L.

     C   = True value for the concentration, in ug/L.

     7   = Average recovery found for measurements of samples containing a
           concentration of C, in ug/L.
                                   8100 - 9
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                                                          Date   September  1986

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                                        METHOD 8100

                              POLYNUCLEAR AROMATIC HYDROCARBONS
7.1.1
       Choose
     »  appro-
priate  extract-
 Ion procedure
    (refer to
   Chapter 2)
 7.2
    Set gas
 chromatography
  conditions
                         7.3.21
                              I  Process
                               series  of
                               •tanaards
                         through cleanup
                             procedures
.Do  GC analysis
   (refer to
  Method 8000)
 7.3
       Refer to
    Method 8000
    for proper
    calibration
    techniques
    Q
                                                                            7.5. 1
                            Do cleanup
                           using Method
                              3630
                                     8100  - 10
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                                                                Date  September 1986

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                                 METHOD 8120

                          CHLORINATED HYDROCARBONS
1.0  SCOPE AND APPLICATION

     1.1  Method 8120  1s  used  to  determine  the  concentration  of certain
chlorinated hydrocarbons.  Table 1  indicates compounds that may be determined
by this method and  lists  the  method  detection  limit  for each compound in
reagent water.  Table 2 lists the practical quantitation limit (PQL) for other
matrices.
2.0  SUMMARY OF METHOD

     2.1  Method  8120  provides   gas   chromatographic  conditions  for  the
detection of ppb levels 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-uL aliquot  of the extract 1s Injected Into a gas
chromatograph  (GC) using the solvent flush  technique, and compounds 1n the GC
effluent are detected by an electron capture detector (ECD).

     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
                                   8120 - 1
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                                                          Date  September  1986

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TABLE 1.  GAS CHROMATOGRAPHY OF CHLORINATED HYDROCARBONS
Compound
Retention time (nrin)
 Col. 1     Col.  2
   nd = not determined.
   a!50°C column temperature.
   bl65°C column temperature.
   C100*C column temperature.
  Method
Detection
limit (ug/L)
Benzal chloride
Benzotri chloride
Benzyl chloride
2-Chl oronaphthal ene
1 , 2-Di chl orobenzene
1 , 3-Di chl orobenzene
1 , 4-Di chl orobenzene
Hexachl orobenzene
Hexachl orobutadi ene
Hexachl orocycl ohexane
Hexachl orocycl opentadi ene
Hexachl oroethane
Tetrachlorobenzenes
1,2, 4-Tri chl orobenzene
Pentachlorohexane


2.7a
6.6
4.5
5.2
5.6a
7.7

nd
4.9

15.5



3.6°
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

                                  8120 - 2
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                                                         Date  September 1986

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TABLE 2.  DETERMINATION OF PRACTICAL QUANTITATION LIMITS (PQL) FOR VARIOUS
          MATRICES3


    Matrix                                                    Factorb
Ground water                                                     10
Low-level soil by sonication with GPC cleanup                   670
High-level soil and sludges by sonication                    10,000
Non-water miscible waste                                    100,000


     aSample PQLs are highly  matrix-dependent.    The  PQLs listed herein are
provided for guidance and may not always be achievable.

     bPQL = [Method detection limit (Table 1)] X [Factor (Table 2)].  For non-
aqueous samples, the factor is on a wet-weight basis.
                                   8120 - 3
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                                                          Date  September  1986

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     accessories,  Including detectors,  column  supplies, recorder, gases, and
     syringes.  A  data  system  for  measuring peak areas and/or peak heights 1s
     recommended.
          4.1.2  Columns:
              4.1.2.1   Column 1:  1.8-m x  2-mm I.D. 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-mrn I.D. 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-Dam'sh (K-D) apparatus;
          4.2.1  Concentrator tube:   10-mL, graduated  (Kontes  K-570050-1025 or
     equivalent).   Ground-glass  stopper   is  used   to  prevent  evaporation of
     extracts
          4.2.2  Evaporation   flask:      500-mL    (Kontes    K-570001-500  or
     equivalent).   Attach  to concentrator  tube  with  springs.
          4.2.3  Snyder column:   Three-ball   macro  (Kontes  K-5Q3000-0121 or
     equivalent).
          4.2.4  Snyder  column:    Two-ball  micro   (Kontes   K-569001-0219 or
     equivalent).
     4.3  Boiling  chips;  Solvent extracted,  approximately  10/40 mesh (silicon
carbide or equivalent).
     4.4  Water  bath;     Heated,  with  concentric   ring  cover,  capable of
temperature control  (+5*C).   The bath should be used in a hood.
     4.5  Volumetric flasks;  10-,  50-, and 100-mL,  ground-glass stopper.
     4.6  Microsyrlnge;  10-uL.
     4.7  Syri nge;   5-mL.
     4.8  Vials;  Glass, 2-,  10-,  and  20-mL capacity with Teflon-Hned screw
cap.
5.0  REAGENTS
     5.1  Solvents;     hexane,   isooctane,   acetone  (pesticide  quality  or
          equivalent).
                                  8120 - 4
                                                         Revision
                                                         Date  September 1986

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     5.2  Stock standard solutions;

          5.2.1  Prepare stock standard  solutions  at  a  concentration of
     1.00 ug/uL  by  dissolving  0.0100   g   of   assayed  reference material  in
     isooctane and diluting to  volume  in   a   10-mL  volumetric  flask.   Larger
     volumes can be used at  the  convenience   of   the  analyst.  When compound
     purity is assayed to be 96%  or  greater,   the weight  can be used without
     correction  to  calculate  the   concentration  of  the  stock  standard.
     Commercially prepared stock standards  can  be  used  at any concentration  if
     they are certified by the manufacturer or  by  an  independent source.

          5.2.2  Transfer  the  stock  standard solutions   into Teflon-sealed
     screw-cap bottles.  Store at 4*C and protect  from  light.  Stock standards
     should be checked  frequently  for  signs   of degradation or evaporation,
     especially just prior to preparing calibration standards from them.

          5.2.3  Stock standard solutions must  be   replaced after one year,  or
     sooner if comparison with check standards  indicates a  problem.

     5.3  Calibration standards;  Calibration   standards at a minimum of five
concentrationlevelsshouldbe  prepared through  dilution   of  the   stock
standards with isooctane.   One  of  the concentration  levels  should be at a
concentration near, but  above,  the  method detection  limit.  The remaining
concentration levels should correspond to the expected  range of  concentrations
found  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.

     5.4  Internal standards (if internal  standard  calibration is used);  To
use this approach, the analyst must select  one  or  more  internal  standards that
are similar in analytical behavior to  the  compounds  of interest.  The analyst
must further demonstrate that the measurement   of  the internal  standard  is not
affected by method or matrix interferences.   Because of these  limitations,  no
internal standard can be suggested that is  applicable to all  samples.

          5.4.1  Prepare  calibration   standards    at   a   minimum   of  five
     concentration  levels  for  each  analyte   of  interest  as  described in
     Paragraph 5.3.

          5.4.2  To each calibration standard,  add  a known constant  amount of
     one or more internal standards, and dilute to volume with  isooctane.

          5.4.3  Analyze each calibration standard according to Section  7.0.

     5.5  Surrogate standards;  The analyst  should monitor the performance of
the  extraction,cleanup(when   used),   and   analytical  system  and  the
effectiveness  of the method  in dealing with each  sample matrix by spiking each
sample,  standard,  and  reagent water  blank  with  one or two surrogates  (e.g.,
chlorinated   hydrocarbons  that  are  not   expected  to  be  in  the  sample)
recommended to encompass the   range  of  the  temperature program used 1n this
method.  Method 3500,  Section  5.3.1.1, details  instructions on the preparation
of base/neutral surrogates.  Deuterated  analogs of analytes should not be used
as surrogates  for  gas  chromatographic analysis  due to coelution problems.


                                  8120 - 5
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                                                         Date  September  1986

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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.  Extracts must be  stored under refrigeration and analyzed within
40 days of extraction.


7.0  PROCEDURE

     7.1  Extraction;

          7.1.1  Refer to Chapter Two for guidance on choosing the appropriate
     extraction procedure.   In  general,  water  samples  are  extracted at a
     neutral, or as 1s, pH  with  methylene chloride, using either Method 3510
     or 3520.  Solid samples are extracted using either Method 3540 or 3550.

          7.1.2  Prior to gas chromatographlc analysis, the extraction solvent
     must be exchanged to hexane.    The  exchange 1s performed during the K-D
     procedures listed 1n all  of  the  extraction  methods.   The exchange 1s
     performed as follows.

               7.1.2.1  Following K-D  of  the  methylene  chloride extract to
          1-mL using the macro-Snyder column,  allow the apparatus to cool and
          drain for at least 10 min.

               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 1s partially  immersed  in  the hot water.  Adjust
          the vertical position of the apparatus and the water temperature, as
          required, to complete concentration 1n 5-10 m1n.  At the proper rate
          of distillation the balls of  the  column will actively chatter, but
          the chambers will not  flood.    When  the apparent volume of liquid
          reaches 1 mL, remove the  K-D  apparatus  and  allow it to drain and
          cool for at  least 10 min.    The extract will be handled differently
          at this point, depending on  whether  or  not cleanup is needed.  If
          cleanup is not required, proceed  to  Paragraph 7.1.2.3.  If cleanup
          1s needed, proceed to Paragraph 7.1.2.4.

               7.1.2.3 If cleanup of the extract  is not required, remove the
          Snyder column and  rinse  the  flask  and  Its  lower joint  into the
          concentrator tube  with  1-2  mL  of  hexane.    A  5-mL  syringe is
          recommended  for this operation.  Adjust the extract volume to
          10.0 mL.  Stopper  the  concentrator  tube and  store refrigerated at
          4*C 1f further processing will not be performed Immediately.  If the
          extract  will  be  stored   longer   than  two   days,  it  should  be
          transferred  to a  Teflon-sealed  screw-cap  vial.   Proceed  with gas
          chromatographlc analysis.
                                   8120 - 6
                                                          Revision       0
                                                          Date   September  1986

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              7.1.2.4   If cleanup  of  the  extract  1s  required, remove the
         Snyder column  and  rinse  the  flask  and  Its  lower joint Into the
         concentrator tube with a minimum  amount  of hexane.  A 5-mL syringe
         1s  recommended for this operation.   Add a clean boiling chip to the
         concentrator tube and attach a two-ball mlcro-Snyder column.  Prewet
         the column  by  adding about 0.5 ml  of  hexane to the top.  Place the
         m1cro-K-D apparatus on the  water  bath  (80*C)  so that the concen-
         trator tube 1s partially  Immersed  1n  the  hot  water.  Adjust the
         vertical  position of  the  apparatus  and  the water temperature, as
         required, to complete concentration 1n 5-10 m1n.  At the proper rate
         of  distillation the balls of  the  column will actively chatter, but
         the chambers will not  flood.    When  the apparent volume of liquid
         reaches  0.5 ml, remove the K-D  apparatus  and allow 1t to drain and
         cool for at least 10 m1n.

               7.1.2.5   Remove the mlcro-Snyder column and rinse the flask and
          Its lower joint Into the  concentrator  tube  with  0.2 ml of hexane.
         Adjust  the  extract  volume to  2.0 ml and proceed with Method 3620.

     7.2 Gas chromatography  conditions (Recommended);

          7.2.1  Column  1:  Set  5% methane/95% argon carrier  gas flow at
     25 mL/m1n flow rate.   Set   column temperature at 65*C  Isothermal, unless
     otherwise specified (see Table  1).

          7.2.2  Column  2:  Set  5% methane/95% argon carrier  gas flow at
     25 mL/min flow rate.   Set   column temperature at 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 1s performed  on  the   samples,  the  analyst should
     process a series  of  standards   through  the  cleanup  procedure and then
     analyze the samples by GC.    This   will  validate  elutlon patterns  and  the
     absence of Interferents  from the  reagents.

     7.4  Gas chromatographlc analysis;

          7.4.1  Refer to Method 8000.     If the Internal  standard calibration
     technique Is  used,  add 10 uL of  Internal  standard  to the sample prior to
     Injecting.

          7.4.2  Follow Section 7.6  1n  Method   8000   for Instructions on  the
     analysis sequence,   appropriate  dilutions,   establishing dally retention
     time windows, and  identification criteria.    Include a mid-level  standard
     after each group of 10 samples in the analysis sequence.


                                  8120 - 7
                                                         Revision       0
                                                         Date  September 1986

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          7.4.3   Examples  of  GC/ECD  chromatograms  for  certain chlorinated
     hydrocarbons are  shown  1n Figures 1 and 2.

          7.4.4   Record  the  sample  volume  Injected  and  the resulting peak
     sizes (in area  units or peak  heights).

          7.4.4   Using either the  Internal  or external calibration procedure
     (Method  8000),  determine the  Identity and quantity of each component peak
     1n  the sample chromatogram  which  Corresponds  to the compounds  used for
     calibration  purposes.   See  Section  7.8  of  Method 8000 for calculation
     equations.

          7.4.5   If  peak detection  and   Identification  are  prevented due  to
     interferences,  the  hexane extract may undergo cleanup using  Method 3620.

     7.5  Cleanup;

          7.5.1   Proceed with  Method  3620   using  the  2-mL  hexane  extracts
     obtained from Paragraph 7.1.2.5.

          7.5.2   Following cleanup,  the  extracts  should  be  analyzed by GC,  as
     described in the previous  paragraphs and 1n  Method  8000.


8.0  QUALITY CONTROL

     8.1  Refer  to  Chapter  One  for .specific   quality   control  procedures.
Quality control  to validate sample extraction is  covered in  Method 3500 and in
the extraction method utilized.    If  extract cleanup was performed,  follow the
QC in Method 3600 and 1n the specific cleanup method.

     8.2  Procedures to check  the  GC  system  operation   are found in Method
8000, Section 8.6.

          8.2.1  The quality control  check  sample  concentrate (Method 8000,
     Section 8.6) should contain  each  parameter  of interest at the following
     concentrations 1n acetone:    hexachloro-substituted hydrocarbon, 10 ug/mL;
     and  any other chlorinated hydrocarbon,  100 ug/mL.

          8.2.2  Table 3 indicates the  calibration and QC acceptance criteria
     for  this  method.    Table   4  gives  method  accuracy  and  precision as
     functions of concentration for the analytes of interest.  The contents of
     both Tables should be  used to  evaluate a laboratory's ability to perform
     and  generate acceptable data by this method.

     8.3  Calculate surrogate standard  recovery  on  all  samples, blanks, and
spikes.   Determine if  the  recovery  is  within limits (limits established by
performing QC procedures outlined in Method 8000, Section 8.10).
                                  8120 - 8
                                                         Revision
                                                         Date  September 1986

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                    Column: 1.5% OV-1+1.5% OV-225 on Gas Chrom Q
                    Ttmptraturt: 75°C
                    Dtttctor: Eltctron Capture
                       4         8        12       16
                         RETENTION TIME (MINUTES)
20
Figure 1. Gas chromatogram of chlorinated hydrocarbons (low molecular weight compounds).
                            8120 - 9
                                                     Revision       o
                                                     Date  September 1986

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1

I





























g
«>
1
I''
?
0
i

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          8.3.1  If recovery 1s  not  within  limits,  the  following procedures
     are required.

               •  Check to  be  sure  there  are  no  errors  in calculations,
                  surrogate solutions  and  internal  standards.   Also,  check
                  Instrument performance.

               •  Recalculate the data and/or reanalyze  the extract if any of
                  the above checks reveal  a problem.

               •  Reextract and reanalyze the sample  if none of the above are
                  a problem or flag the data as "estimated concentration."


9.0  METHOD PERFORMANCE

     9.1  The method  was  tested  by  20  laboratories  using  reagent water,
drinking water, surface water, and  three industrial wastewaters spiked at six
concentrations over the range  1.0  to  356  ug/L.  Single operator precision,
overall precision, and method accuracy  were  found  to be directly related to
the concentration of the parameter  and  essentially independent of the sample
matrix.    Linear  equations  to  describe  these  relationships  for  a flame
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.  Provost, L.P.  and  R.S.   Elder,   "Interpretation of Percent  Recovery Data,"
American  Laboratory,  15,  pp. 58-63,  1983.

7.   "Determination of  Chlorinated   Hydrocarbons   in   Industrial and  Municipal
Wastewaters,"  Report  for  EPA Contract 68-03-2625  (in  preparation).

                                  8120 -  11
                                                          Revision      0
                                                          Date   September  1986

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TABLE 3.  QC ACCEPTANCE CRITERIA3


Parameter
2-Chloronaphthalene
1,2-Dichlorobenzene
1 , 3-Di chl orobenzene
1,4-Dichlorobenzene
Hexachl orobenzene
Hexachl orobutadl ene
Hexachl orocycl opentadl ene
Hexachl oroethane
1,2, 4-Tr1 chl orobenzene
Test
cone.
(ug/L)
100
100
100
100
10
10
10
10
100
Limit
for s
(ug/L)
37.3
28.3
26.4
20.8
2.4
2.2
2.5
3.3
31.6
Range
for 7
(ug/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, 1n ug/L.
     7 = Average recovery for four recovery measurements, 1n ug/L.
     P, Ps = Percent recovery measured.
     D = Detected; result must be greater than zero.
     aCHter1a from 40 CFR Part 136 for  Method 612.  These criteria are based
directly upon the method performance  data  1n  Table 4.  Where necessary, the
limits for recovery have been broadened  to assure applicability of the limits
to concentrations below those used to develop Table 4.
                                   8120 - 12
                                                          Revision       0
                                                          Date   September  1986

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Table 4.  METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION3


Parameter
Chloronaphthalene
1 , 2-D1 chl orobenzene
1 , 3-Di chl orobenzene
1 , 4-Di chl orobenzene
Hexachl orobenzene
Hexachlorobutadlene
Hexachl orocycl opentadi enea
Hexachl oroethane
1,2, 4-Tri chl orobenzene
Accuracy, as
recovery, x1
(ug/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 Overall
precision, sr'
(ug/L)
0.287-1.17
0.227-2.95
0.217-1.03
0.167-0.48
0.147+0.07
0.187+0.08
0.247
0.237+0.07
0.237-0.44
precision,
S1 (ug/L)
0.387-1.39
0.417-3.92
0.497-3.98
0.357-0.57
0.367-0.19
0.537-0.12
0.507
0.367-0.00
0.407-1.37
     x1  = Expected  recovery  for  one  or  more  measurements  of  a  sample
           containing a concentration of C, in ug/L.
     sr' = Expected single analyst  standard  deviation  of measurements at an
           average concentration of 7, in ug/L.
     S1  = Expected interlaboratory standard  deviation  of measurements at an
           average concentration found of 7, in ug/L.
     C   = True value for the concentration, in ug/L.
     7   = Average recovery found for measurements of samples containing a
           concentration of C, in ug/L.
     Estimates based upon the performance in a single laboratory.
                                   8120 -  13
                                                         Revision      0
                                                         Date  September 1986

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                                         METHOD BISO

                                  CHLORINATED HYDROCARBONS
                                                       0
7.1.1
     '  Choose
    appropriate
    extraction
     procedure
(see Chapter 2)
                                                    7 .
  Perform GC
analysis (see
 Method 8000)
7.1.2
       Exchange
       extract-
 Ion solvent to
       hexane
    during K—0
    procedures
 7.2
    Set gas
 chromatography
  conditions
                                                                            7.5.1
                            Cleanup
                          using Method
                              3E20
7
	 1 Refer to
Method 6OOO
for proper
calibration
techniques
                         7.3.2
                                Process
                                a series
                            of standards
                         through cleanup
                             procedure:
                           analyze by GC
                                     8120 -  14
                                                                Revision       0
                                                                Date   September 1986

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                                 METHOD 8140

                         ORGANOPHOSPHORUS PESTICIDES
1.0  SCOPE AND APPLICATION

     1.1  Method 8140 Is a gas  chromatographic  (GC)  method used to  determine
the concentration of various organosphosphorus  pesticides.   Table 1  Indicates
compounds that may be determined by this method and lists the method  detection
limit for each  compound  in  reagent  water.    Table  2  lists the  practical
quantisation limit (PQL) for other matrices.

     1.2  When Method 8140  is  used  to  analyze unfamiliar samples, compound
identifications should be  supported  by  at  least two additional qualitative
techniques if mass spectroscopy  1s  not  employed.   Section 8.4 provides gas
chromatograph/mass  spectrometer   (GC/MS)   criteria   appropriate   for  the
qualitative confirmation of compound identifications.


2.0  SUMMARY OF METHOD

     2.1  Method  8140  provides   gas   chromatographic  conditions  for  the
detection of ppb  levels  of  organophosphorus  pesticides.  Prior to analysis,
appropriate sample extraction techniques must be  used.  Both neat and diluted
organic liquids   (Method  3580,  Waste  Dilution)  may  be  analyzed by direct
injection.  A 2-  to  5-uL  aliquot  of  the  extract  is  injected into a gas
chromatograph, and compounds in  the  GC  effluent  are  detected with a flame
photometric or thermionic detector.

     2.2  If interferences are encountered   in  the  analysis, Method 8140 may
also be performed on extracts  that  have   undergone cleanup using Method 3620
and/or Method 3660.


3.0  INTERFERENCES

     3.1  Refer to Methods 3500  (Section 3.5, in particular), 3600, and 8000.

     3.2  The use of Florisll 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   organophosphorous  pesticides 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%.
                                   8140 - 1
                                                          Revision      0
                                                          Date  September  1986

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TABLE 1.  GAS CHROMATOGRAPHIC CONDITIONS AND METHOD DETECTION  LIMITS  FOR
          ORGANOPHOSPHOROUS PESTICIDES3
Compound
Azlnphos methyl
Bolstar
Chlorpyrlfos
Coumaphos
Demeton-0
Demeton-S
Diazlnon
Dichlorvos
Disulfoton
Ethoprop
Fensulfothlon
Fenthion
Merphos
Mevlnphos
Naled
Parathlon methyl
Phorate
Ronnel
Stlrophos (Tetrachlorvlnphos)
Tokuthion (Prothiofos)
Trlchloronate
GC K
col umn°
la
la
2
la
la
la
2
lb, 3
la
2
la
la
2
lb
3
2
la
2
lb, 3
la
la
Retention
time
(m1n) i
6.80
4.23
6.16
11.6
2.53
1.16
7.73
0.8, 1.50
2.10
3.02
6.41
3.12
7.45
2.41
3.28
3.37
1.43
5.57
8.52, 5.51
3.40
2.94
Method
detection
limit (ug/L)
1.5
0.15
0.3
1.5
0.25
0.25
0.6
0.1
0.20
0.25
1.5
0.10
0.25
0.3
0.1
0.03
0.15
0.3
5.0
0.5
0.15
     Development of  Analytical  Test  Procedures  for  Organic Pollutants in
     Wastewater; Report  for  EPA Contract 68-03-2711 (in preparation).

     b$ee Sections 4.2.1 and 7.2  for column descriptions and conditions.
                                  8140 - 2
                                                         Revision      0
                                                         Date  September 1986

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TABLE 2.  DETERMINATION OF PRACTICAL QUANTITATION LIMITS (PQL) FOR VARIOUS
          MATRICES3


    Matrix                                                   Factorb
Ground water                                                     10
Low-level soil by sonlcation with GPC cleanup                   670
High-level soil and sludges by sonication                    10,000
Non-water miscible waste                                    100,000


     aSample PQLs are highly  matrix-dependent.    The  PQLs listed herein are
     provided for guidance and may not always be achievable.

     bPQL = [Method detection limit (Table 1)] X [Factor (Table 2)].  For non-
     aqueous samples, the factor is on a wet-weight basis.
                                  8140 - 3
                                                         Revision
                                                         Date  September  1986

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     3.3  Use of a  flame  photometric  detector  1n  the phosphorus mode will
minimize  Interferences  from  materials   that  do  not  contain  phosphorus.
Elemental sulfur, however,  may  Interfere  with  the determination of certain
organophosphorus pesticides by flame  photometric  gas chromatography.  Sulfur
cleanup using Method 3660 may alleviate this Interference.

     3.4  A  halogen-specific  detector  (I.e.,  electrolytic  conductivity or
mlcrocoulometric) Is very selective  for the halogen-containing pesticides and
1s recommended for use with dlchlorvos, naled, and stlrophos.


4.0  APPARATUS AND MATERIALS

     4.1  Gas   chrpmatograph;      Analytical   system   complete   with  gas
chromatograph suitable for on-column  Injections and all required accessories,
Including detectors, column supplies, recorder,  gases,  and syringes.  A data
system for measuring peak areas and/or peak heights 1s recommended.

          4.1.1  Columns:

               4.1.1.1  Column la and Ib:    1.8-m  x  2-mm I.D. glass, packed
          with 5% SP-2401 on Supelcoport, 100/120 mesh (or equivalent).

               4.1.1.2  Column 2:  1.8-m x 2-mm I.D. glass, packed with 3% SP-
          2401 on Supelcoport, 100/120 mesh (or equivalent).

               4.1.1.3  Column 3:  50-cm x l/8-1n O.D. Teflon, packed with 15%
          SE-54 on Gas Chrom Q, 100/120 mesh  (or equivalent).

          4.1.2  Detectors:  The following  detectors  have proven effective 1n
     analysis for the analytes listed 1n Table  1 and  were used to develop the
     accuracy and precision statements  1n Section 9.0.

               4.1.2.1  Phosphorus-specific:      Nitrogen/Phosphorus    (N/P),
          operated  1n phosphorus-sensitive mode.

               4.1.2.2  Flame  Photometric  (FPD):     FPD   1s more  selective for
          phosphorus than  the  N/P.

               4.1.2.3  Halogen-specific:       Electrolytic    conductivity  or
          mlcrocoulometric.   These   are  very  selective  for those  pesticides
          containing halogen  substituents.

     4.2 Balance;  analytical,  capable of  accurately weighing  to  the  nearest
 0.0001  g.

     4.3 Vials;  Amber glass,  10-   to  15-mL  capacity with Teflon-Hned screw-
 cap.

     4.4 Kuderna-Danlsh  (K-D)  apparatus;

          4.4.1   Concentrator tube:   10-mL, graduated (Kontes K-570050-1025 or
     equivalent).   Ground-glass  stopper  is   used   to  prevent  evaporation of
     extracts

                                  8140  - 4
                                                          Revision       0
                                                         Date  September  1986

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          4.4.2  Evaporation   flask:       500-mL    (Kontes    K-570001-500  or
     equivalent).  Attach to concentrator tube with  springs.

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

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

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

     4.6  Water  bath;    Heated,  with  concentric   ring  cover,  capable  of
temperature control (+5°C).  The bath should be used 1n a hood.

     4.7  Mlcrosyrlnge;  10-uL.

     4.8  Syringe;  5-mL.

     4.9  Volumetric flasks;  10-, 50-, and*100-mL,  ground-glass stopper.


5.0  REAGENTS

     5.1  Solvents:    Hexane,   acetone,  Isooctane  (2,2,4-trimethylpentane)
(pesticide quality or equivalent).

     5.2  Stock  standard solutions;

          5.2.1  Prepare stock  standard solutions by accurately weighing about
     0.0100 g of pure  material.    Dissolve  the  material in hexane or other
     suitable solvent  and  dilute  to  volume  in  a  10-mL volumetric flask.
     Larger volumes can  be  used  at  the  convenience  of  the  analyst.   If
     compound purity 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 1f
     they are certified by the  manufacturer or by an independent source.

          5.2.2  Transfer  the   stock  standard  solutions  into Teflon-sealed
     screw-cap bottles.  Store  at 4*C  and protect  from light.   Stock standard
     solutions should  be  checked  frequently  for signs  of   degradation or
     evaporation, especially   just  prior  to  preparing calibration standards
     from them.

          5.2.3  Stock standard solutions must be   replaced after one year, or
     sooner  if comparison with check standards Indicates a problem.

     5.3  Calibration  standards;   Calibration  standards  at  a minimum of five
concentration  levels  for each  parameter  of  Interest should be prepared through
dilution of  the  stock   standards  with   Isooctane.    One of  the concentration
levels should  be at   a  concentration  near,   but   above, the method detection
                                   8140 - 5
                                                          Revision
                                                         Date  September  1986

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limit.  The remaining concentration  levels  should correspond to the  expected
range of concentrations found  1n  real   samples  or should define the working
range of the GC.  Calibration standards   must be replaced after six months,  or
sooner 1f comparison with check standards Indicates a problem.

     5.4  Internal standards (1f Internal  standard  calibration 1s used);   To
use this approach, the analyst must select one or more Internal standards that
are similar 1n analytical behavior to  the compounds of Interest.  The analyst
must further demonstrate that the measurement  of the Internal standard 1s not
affected by method or matrix Interferences.   Because of these limitations,  no
Internal standard can be suggested that 1s applicable to all samples.

          5.4.1  Prepare  calibration   standards   at   a   minimum  of  five
     concentration levels  for  each  parameter  of  Interest  as described 1n
     Paragraph 5.3.

          5.4.2  To each calibration standard, add  a known constant amount of
     one or more Internal standards, and dilute to volume with hexane or other
     suitable solvent.

          5.4.3  Analyze each calibration  standard according to Section 7.0.
                                                       i
     5.5  Surrogate standards;  The analyst  should monitor the performance of
the  extraction,cleanup(when   used),   and   analytical  system  and  the
effectiveness of the method  1n dealing with each sample matrix by spiking each
sample, standard, and  reagent water  blank with  one or two surrogates  (e.g.,
organophosphorous  pesticides  not  expected  to  be  present  in  the sample)
recommended to encompass the range  of  the  temperature program used 1n this
method.  Deuterated analogs  of analytes  should  not be used as surrogates for
gas chromatographic analysis due to coelution problems.


6.0  SAMPLE COLLECTION,  PRESERVATION, AND  HANDLING

      6.1  See the introductory  material   to  this  chapter, Organic Analytes,
Section 4.1.  Extracts must  be  stored under refrigeration and analyzed within
40 days of extraction.


7.0   PROCEDURE

      7.1   Extraction;

           7.1.1   Refer to Chapter  Two for  guidance on  choosing the  appropriate
      extraction  procedure.    In  general,  water   samples   are  extracted at a
      neutral, or as  1s,  pH   with   methylene  chloride,  using  either  Method 3510
      or 3520.   Solid  samples are extracted using  either  Method 3540 or 3550.

           7.1.2  Prior to gas  chromatographic  analysis,  the  extraction solvent
      may be  exchanged to hexane.   This   Is recommended if  the detector used is
      halogen-specific.  The exchange  1s  performed  during  the K-D procedures
      listed  in  all  of the   extraction  methods.    The exchange 1s performed as
      follows.

                                   8140 - 6
                                                          Revision     0
                                                          Date  September 1986

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              7.1.2.1  Following K-D of the methylene chloride extract to
         1 ml using the macro-Snyder column,  allow the apparatus to cool and
         drain for at least 10 m1n.

              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 1s partially  Immersed  1n  the hot water.  Adjust
         the vertical position of the apparatus and the water temperature, as
         required, to complete concentration 1n 5-10 m1n.  At the proper rate
         of distillation the balls of  the  column will actively chatter, but
         the chambers will not  flood.    When  the apparent volume of liquid
         reaches 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 Us
         lower joint Into the concentrator  tube with 1-2 ml of hexane.   A
         5-mL syringe  1s recommended  for  this operation.  Adjust the extract
         volume  to  10.0  ml.    Stopper   the  concentrator  tube  and  store
         refrigerated  at 4*C  1f  further   processing  will  not be performed
         Immediately.  If the extract will  be stored longer than two days, 1t
         should  be  transferred  to  a  Teflon-sealed  screw-cap vial.  Proceed
         with  gas   chromatographlc   analysis   1f   further  cleanup  1s not
         required.

     7.2 Gas chromatography conditions  (Recommended);

         7.2.1   Column la:  Set  helium  carrier  gas  flow at 30 mL/m1n flow
     rate.   Column  temperature 1s  set  at   150*C for  1 m1n  and then programmed
     at 25*C/m1n  to  220'C and  held.

         7.2.2   Column Ib:  Set nitrogen   carrier gas flow at 30 mL/m1n flow
     rate.   Column  temperature  1s  set  at   170*C for  2 m1n  and then programmed
     at 20*C/m1n  to  220*C and  held.

         7.2.3   Column 2:   Set   helium  carrier   gas  at 25 mL/m1n flow  rate.
     Column temperature Is  set   at   170*C   for  7  m1n  and then programmed at
     !0*C/m1n  to  250*C  and  held.

         7.2.4   Column 3:   Set  nitrogen  carrier  gas at 30 mL/m1n flow  rate.
     Column temperature 1s  set   at   100*C   and  then  Immediately programmed at
     25*C/m1n  to  200*C  and  held.

     7.3 Calibration;     Refer    to   Method   8000   for   proper   calibration
techniques^Use  Table  1  and especially  Table  2 for  guidance  on  selecting the
lowest point on  the calibration  curve.

          7.3.1   The procedure for  Internal  or   external   calibration may be
     used.     Refer  to  Method   8000  for   a   description   of  each   of  these
     procedures.
                                  8140 - 7
                                                         Revision      0
                                                         Date  September 1986

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          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 Interferents from the reagents.

     7.4   Gas chromatographlc analysis;

          7.4.1   Refer to  Method 8000.    If the Internal  standard calibration
     technique 1s used, add  10 uL of  Internal standard  to the sample prior to
     injection.

          7.4.2   Follow Section 7.6   1n  Method  8000  for instructions on the
     analysis sequence,  appropriate  dilutions,  establishing dally  retention
     time windows, and Identification criteria.   Include  a mid-level standard
     after each group  of 10  samples  in the  analysis  sequence.

          7.4.3   Examples  of chromatograms   for   various  organophosphorous
     pesticides are shown  1n Figures  1 through 4.

          7.4.4   Record  the   sample   volume  injected  and the  resulting peak
     sizes (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  Section  7.8 of Method 8000  for calculation
     equations.

          7.4.6  If peak detection  and   identification   are   prevented  due  to
     interferences, the hexane extract may   undergo  cleanup using Method 3620.
     The resultant extract(s) may  be  analyzed   by   GC directly  or may undergo
     further cleanup to remove sulfur using Method  3660.

     7.5  Cleanup:

          7.5.1   Proceed with Method 3620,   followed  by,  if  necessary,  Method
     3660, using  the 10-mL hexane  extracts  obtained  from Paragraph 7.1.2.3.

          7.5.2  Following cleanup,  the  extracts should   be analyzed  by  GC,  as
     described 1n the previous paragraphs  and in Method  8000.


8.0  QUALITY CONTROL

     8.1  Refer  to  Chapter  One   for  specific quality  control  procedures.
Quality control  to validate  sample extraction 1s covered in Method 3500  and  in
the extraction method utilized.   If  extract cleanup was performed,  follow  the
QC in Method 3600 and 1n the specific cleanup method.

     8.2  Procedures to check  the  GC   system  operation  are  found  in  Method
8000, Section 8.6.
                                  8140 - 8
                                                         Revision
                                                         Date  September 1986

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                        Column: 5% SP-2401 on Suptlcoport
                        Temperature: 170°C 7 Minutts. then
                                    1 (PC/Minute to 250°C
                        Detector: Phosphorus-Specific Flame Photometric
                    45678
                     RETENTION TIME (MINUTES)
10
11
12
Figure 1. Gas chromatogram of organophosphorus pesticides (Example 1).
                      8140 - 9
                                                Revision       p
                                                Date  September  1986

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    Column: 3% SP-2401
    Program: 170°C 7 Minutes. 10°C/Minute
           t6250°C
    Detector: Phosphorus/Nitrogen
                                                              1
                 765432
                        RETENTION TIME (MINUTES)
Figure 2. Gas chromatogram of organophosphorus pesticides (Example 2).
                    8140 - 10
                                              Revision       0
                                              Date  September  1986

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Column: 15% SE-54 on Gas Chrom Q
Temperature: 100°C Initial, then
            25°C/Minute to 200°C
Detector: Hall Electrolytic Conductivity-Oxidative Mode
                 8
7654321
   RETENTION TIME (MINUTES)
   Figure 3. Gas chromatogram of organophosphorus pesticides (Example 3).
                           8140  - 11
                                                     Revision       0
                                                     Date   September  1986

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                Column: 5% SP-2401 on Supelcoport
                Temperature: 170°C 2 Minutes, then 20°C/Minute to 220°C
                Detector: Phosphorus-Specific Flame Photometric
                 3456
                  RETENTION TIME (MINUTES)
Figure 4. Gas chromatogram of organophosphorus pesticides (Example 4).
                           8140 - 12
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                                                     Date   September  1986

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          8.2.1  Select a representative  spike   concentration  for  each  analyte
     to be measured.    The  quality  control  check  sample  concentrate  (Method
     8000,  Section  8.6)  should  contain   each  analyte   In  acetone  at   a
     concentration 1,000  times  more  concentrated   than   the  selected  spike
     concentration.

          8.2.2  Table 3 Indicates Single  Operator  Accuracy and Precision for
     this method.  Compare  the  results   obtained  with  the  results given  in
     Table 3 to determine if the data quality 1s acceptable.

     8.3  Calculate surrogate standard  recovery  on  all  samples, blanks, and
spikes.  Determine if  the  recovery  1s   within limits (limits established  by
performing QC procedures outlined in Method 8000,  Section  8.10).

          8.3.1  If recovery is  not  within  limits, the  following procedures
     are required.

               •  Check to  be  sure  there  are  no  errors  in calculations,
                  surrogate solutions  and  Internal  standards.   Also,  check
                  instrument performance.

               •  Recalculate the data and/or reanalyze  the extract 1f any  of
                  the above checks reveal a problem.

               •  Reextract and reanalyze the sample  if none of the above are
                  a problem or flag the data as "estimated concentration."

     8.4  GC/MS confirmation;

          8.4.1  GC/MS techniques should  be  judiciously  employed to support
     qualitative identifications made with  this  method.   The GC/MS operating
     conditions and procedures  for  analysis  are  those  specified in Method
     8270.

          8.4.2  When  available,  chemical  ionization  mass  spectra  may be
     employed to aid in  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 and
     additional cleanup.


9.0  METHOD  PERFORMANCE

     9.1  Single-operator  accuracy and  precision   studies  have been conducted
using  spiked wastewater  samples.   The  results of  these studies  are presented
in Table  3.
                                  8140 -  13
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                                                         Date  September  1986

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10.0  REFERENCES

1.  Pressley, T.A. and J.E. Longbottom, "The Determination of Organophosphorus
Pesticides in Industrial and Municipal Wastewater: Method 614," U.S. EPA/EMSL,
Cincinnati, OH, EPA-600/4-82-004, 1982.

2.  Burke, J.A.,  "Gas  Chromatography  for  Pesticide  Residue Analysis; Some
Practical  Aspects,"    Journal  of  the  Association  of  Official Analytical
Chemists 48, 1037, 1965.

3.  U.S. EPA, "Analysis of  Volatile  Hazardous Substances by GC/MS: Pesticide
Methods Evaluation," Letter Reports 6,  12A,  and 14, EPA Contract 68-03-2697,
1982.

4.  U.S.   EPA,  "Method   622,  Organophosphorous  Pesticides,"  Environmental
Monitoring and Support  Laboratory, Cincinnati, OH 45268.
                                   8140-14
                                                          Revision
                                                          Date  September 1986

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TABLE 3.  SINGLE-OPERATOR ACCURACY AND PRECISION3
Parameter
Azinphos methyl
Bolstar
Chlorpyrifos
Coumaphos
Demeton
Dlazinon
Dlchlorvos
Dlsulfoton
Ethoprop
Fensulfothlon
Fenthion
Merphos
Mevinphos
Naled
Parathlon methyl
Phorate
Ronnel
Stlrophos
Tokuthlon
Trlchloronate
Average
recovery
72.7
64.6
98.3
109.0
67.4
67.0
72.1
81.9
100.5
94.1
68.7
120.7
56.5
78.0
96.0
62.7
99.2
66.1
64.6
105.0
Standard
deviation
/ (V \
\ /
18.8
6.3
5.5
12.7
10.5
6.0
7.7
9.0
4.1
17.1
19.9
7.9
7.8
8.1
5.3
8.9
5.6
5.9
6.8
18.6
Spl ke Number
range of
(ug/L) analyses
21-250
4.9-46
1.0-50.5
25-225
11.9-314
5.6
15.6-517
5.2-92
1.0-51.5
23.9-110
5.3-64
1.0-50
15.5-520
25.8-294
0.5-500
4.9-47
1.0-50
30.3-505
5.3-64
20
17
17
18
17
17
7
16
17
18
17
17
18
16
16
21
17
18
16
17
3
 Information taken from Reference 4.
                                  8140 - 15
                                                         Revision      0
                                                         Date  September 1986

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                                         METHOD 8140

                                  ORGANOPHOSPHOBUS PESTICIDES
(    s"rt    )
                                                    0
 7.1.1
      »  Choose
     appropriate
     extraction
      procedure
 (see Chapter 2)
                                                     7.4
                                                   Perform GC
                                                 analysis (see
                                                  Method 80001
 7.1.31
        Exchange
        extract-
  ion solvent to
        hexane
     during K-D
     procedures
  7.2
     Set gas
  chromatography
   conditions
                                                                         7.S.II

                                                                               Cleanup
                                                                            using Method
                                                                           3630 and 3360
                                                                            If necessary
7
IM^H
	 < Refer to
Method 8000
for proper
calibration
techniques
                          7.3.2
                                 Process
                                 a aeries
                             of standards
                          through cleanup
                              procedure:
                            analyze by GC
    Is
 cleanup
necessary?
                                    8140 -  16
                                                               Revision       0
                                                               Date   September 1986

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                                 METHOD 8150

                           CHLORINATED HERBICIDES
1.0  SCOPE AND APPLICATION

     1.1  Method 8150 1s  a  gas  chromatographic  (GC)  method for determining
certain chlorinated acid herbicides.  Table  1 indicates compounds that may be
determined by this  method  and  lists  the  method  detection  limit for each
compound in reagent water.    Table  2  lists the practical  quantitation limit
(PQL) for other matrices.

     1.2  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.

     1.3  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 chroma-
tographic 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
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.
                                   8150 - 1
                                                          Revision
                                                         Date  September  1986

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TABLE 1.  CHROMATOGRAPHIC CONDITIONS AND DETECTION LIMITS FOR CHLORINATED
          HERBICIDES

                                    Retention time (m1n)a        Method
                                                                detection
Compound
2,4-D
2,4-DB
2,4,5-T
2,4,5-TP (Sllvex)
Dalapon
Oicamba
Dlchloroprop
Dinoseb
MCPA
MCPP
Col. la
2.0
4.1
3.4
2.7
-
1.2
-
-
-
—
Col.lb

-
-
-
-
-
4.8
11.2
4.1
3.4
Col. 2 Col. 3
1.6
-
2.4
2.0
5.0
1.0
-
-
-
— —
limit (ug/L)
1.2
0.91
0.20
0.17
5.8
0.27
0.65
0.07
249
192
     aColumn conditions are given 1n Sections 4.1 and 7.4.
 TABLE  2.   DETERMINATION  OF  PRACTICAL  QUANTITATION  LIMITS  (PQL)  FOR  VARIOUS
           MATRICES3


     Matrix                                                    Factorb
 Ground water                    .                           .      10
 Low-level  soil  by sonlcatlon with GPC cleanup                   670
 High-level  soil  and sludges by sonlcatlon                     10,000
 Non-water mlsdble waste                                    100,000


      aSample PQLs are highly  matrix-dependent.     The  PQLs listed  herein  are
      provided for guidance and may not always be achievable.

      bPQL = [Method detection limit (Table 1)]  X [Factor (Table 2)].   For non-
      aqueous samples, the factor 1s on a wet-weight basis.
                                   8150 - 2
                                                          Revision
                                                          Date   September  1986

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     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;    Analytical  system  complete  with gas chroma-
tograph  suitable  for  on-column  injections  and  all  required accessories,
including detectors, column supplies, recorder,  gases,  and syringes.  A data
system for measuring peak areas and/or peak heights 1s recommended.

          4.1.1  Columns:

               4.1.1.1  Column la and Ib:    1.8-m  x  4-mm I.D. glass, packed
          with 1.5% SP-2250/1.95%  SP-2401  on  Supelcoport  (100/120 mesh) or
          equivalent.

               4.1.1.2  Column 2:  1.8-m x 4-mm I.D. glass, packed with 5% 0V-
          210 on Gas Chrom Q  (100/120 mesh) or equivalent.

               4.1.1.3  Column 3:  1.98-m x  2-mm I.D. glass, packed with 0.1%
          SP-1000 on 80/100 mesh Carbopack C or equivalent.

          4.1.2  Detector:  Electron capture (ECD).

     4.2  Erlenmeyer flasks;  250-  and  500-mL Pyrex, with 24/40 ground-glass
joint.

     4.3  Beaker;   500-mL.

     4.4  Diazomethane generator;   Refer  to  Section   7.3 to  determine which
method of diazomethane generation  should be  used  for a particular application.

          4.4.1  Dlazald kit:   recommended   for the  generation  of diazomethane
     using  the procedure given   in Section  7.3.2  (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 1n Figure 1.   The procedure for
     use  of this type of generator is given  1n Section  7.3.3.

     4.5  Vials;  Amber  glass,  10- to   15-mL  capacity with Teflon-lined  screw
cap.


                                   8150 -  3
                                                         Revision      0
                                                         Date  September  1986

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                                                                                                 glass tubing
                               nitrogen
     CO
     i—>
     01
     o

     I

     •t*
rubber stopper

O 50
a» n
rt- <
a> ->•
00 O
(V 3
O
rt
(D
                                                 tube 1
                                               tube 2
oo
01
                                               Figure 1.  Dlazomethane generator.

-------
     4.6  Separatory funnel;  2-L, 125-mL,  and 60-mL.

     4.7  Drying column;   400-mm  x  20-mm  I.D.  Pyrex chromatographlc 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 elutlon solvent prior to packing the column with adsorbent.

     4.8  Kuderna-Dam'sh (K-D) apparatus;

          4.8.1  Concentrator tube:  10-mL, graduated  (Kontes K-570050-1025 or
     equivalent).  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.

          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).

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

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

     4.11  Microsyringe;   10-uL.

     4.12  Wrist shaker;   Burrell Model 75 or equivalent.

     4.13  Glass wool;  Pyrex, add washed.

     4.14  Balance;     Analytical,  capable  of  accurately  weighting   to the
nearest 0.0001 g.

     4.15  Syri nge;   5-mL.

     4.16  Glass rod.
 5.0   REAGENTS

      5.1   Reagent water;   Reagent   water  1s   defined   as   a water  in which an
 interferent 1s not observed at the method  detection  limit  of each parameter of
 interest.
                                   8150 - 5
                                                          Revision
                                                          Date   September  1986

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     5.2  Sulfuric add solution;

          5.2.1  (1:1)  (v/v)  - slowly add 50 ml  ^804 (sp.  gr.  1.84)  to  50 ml
     of reagent water.

          5.2.2  (1:3)  (v/v)  - slowly add 25 mL  H2So4 (sp.  gr.  1.84)  to  75 ml
     of reagent water.

     5.3  Hydrochloric  acid;    (ACS),   (1:9)   (v/v)   -  add  one  volume of
concentrated HC1 to 9 volumes of reagent water.

     5.4  Potassium hydroxide solution;   37% aqueous solution (w/v).  Dissolve
37 g ACS grade potassium hydroxide pellets in reagent water and dilute to
100 ml.

     5.5  Carbitol (D1ethyle,.c glycol monoethyl ether):  (ACS), available from
Aldrlch Chemical Co.

     5.6  Solvents;

          5.6.1  Acetone,  methanol,   ethanol,   methylene  chloride,  hexane
     (pesticide quality or equivalent).

          5.6.2  D1ethyl ether:   Pesticide  quality  or  equivalent.  Must be
     free of peroxides, as indicated  by  EM Quant test strips  (available from
     Scientific  Products  Co.,  Cat.   No.  P1126-8,  and  other  suppliers).
     Procedures recommended  for  removal  of   peroxides  are provided with the
     test strips.  After cleanup, 20  ml ethanol preservative must be added to
     each liter of ether.

     5.7  Sodium sulfate;  (ACS) granular, acidified, anhydrous. Heat treat in
a shallow tray at 400'C for  a  minimum  of 4 hr to remove phthalates and other
interfering organic  substances.  Alternatively,  heat  16 hr at 400-500'C in a
shallow tray or Soxhlet extract with methylene chloride for 48  hr.  Acidify by
slurrying 100 g sodium sulfate  with  enough   diethyl  ether to just cover the
solid;  then add  0.1   ml  of concentrated  sulfuric  acid and mix thoroughly.
Remove  the ether under a vacuum.  Mix 1  g of  the resulting solid with 5 ml of
reagent water and measure the pH of  the mixture.   It must be below a pH of 4.
Store at 130*C.

     5.8  N-Methyl-N-nitroso-p-toluenesulfonamide (Diazald):    (ACS) available
from Aldrich Chemical  Co.

     5.9  Silicic acid;  chromatographlc  grade,  nominal  100  mesh.  Store at
130*C.

     5.10  Stock  standard solutions;  Stock  standard  solutions  can be prepared
from pure standard materials or purchased as certified solutions.

          5.10.1   Prepare  stock   standard   solutions  by  accurately weighing
     about 0.0100 g  of pure  acids.   Dissolve the material in pesticide quality
     diethyl ether and dilute to volume   1n  a 10-mL  volumetric flask.   Larger


                                   8150 - 6
                                                          Revision      0
                                                          Date   September  1986

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     volumes can be used  at   the   convenience  of  the  analyst.   If compound
     purity 1s  certified at 96%  or  greater,  the  weight can be used without
     correction  to  calculate  the   concentration  of  the  stock  standard.
     Commerically prepared stock standards  can be used at any concentration if
     they are certified by the manufacturer or by an independent source.

          5.10.2  Transfer the  stock  standard  solutions  Into Teflon-sealed
     screw-cap  bottles.  Store at  4'C  and  protect from  light.  Stock standard
     solutions  should  be  checked  frequently  for  signs  of  degradation or
     evaporation, especially   just  prior  to  preparing calibration standards
     from them.

          5.10.3  Stock standard solutions  must  be  replaced after 1 year, or
     sooner if  comparison with check standards  indicates a problem.

     5.11  Calibration standards:   Calibration  standards at a minimum  of five
concentration levels for each parameter of interest  should be prepared  through
dilution of the stock standards  with  diethyl  ether.   One of the  concentration
levels should be at  a  concentration  near,   but   above, the method detection
limit.  The remaining concentration  levels  should  correspond to the expected
range of concentrations found  1n  real  samples   or should define the  working
range of the GC.  Calibration solutions  must be  replaced after  six months, or
sooner if comparison with check standards indicates  a  problem.

     5.12   Internal standards (if internal  standard  calibration  is used):  To
use this approach, the analyst must select one or more internal  standards that
are similar 1n analytical behavior to  the compounds of Interest.  The  analyst
must further demonstrate  that the measurement  of the internal  standard is not
affected by method or matrix  interferences.   Because of these limitations,  no
internal standard can be  suggested that is applicable to all  samples.

          5.12.1  Prepare  calibration  standards   at   a    minimum  of  five
     concentration levels  for  each  parameter  of  Interest  as described 1n
     Paragraph 5.11.

          5.12.2  To each calibration standard, add a known  constant amount of
     one or more internal standards, and dilute to volume with diethyl  ether.

          5.12.3  Analyze each  calibration standard according to Section 7.0.

     5.13   Surrogate standards;   The analyst should monitor the performance of
the  extraction,  cleanup(when   used),   and   analytical   system  and  the
effectiveness of the method in  dealing with each sample matrix by spiking each
sample,  standard, and  reagent water blank with one or two 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 1n this
method.  Deuterated analogs of  analytes  should  not be used as surrogates for
gas chromatographlc analysis  due  to coelutlon problems.
                                  8150 - 7
                                                         Revision      0
                                                         Date  September 1986

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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.  Extracts must be  stored under refrigeration and analyzed within
40 days of extraction.


7.0  PROCEDURE

     7.1  Preparation of solid samples;

          7.1.1  Extraction:

               7.1.1.1  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
          with concentrated HC1 and monitor the  pH for 15 min with occasional
          stirring.  If necessary, add additional  HC1 until  the pH remains at
          2.

               7.1.1.2  Add 20 mL acetone  to  the  flask and mix the contents
          with the wrist shaker for 20  min.    Add 80 mL diethyl ether to the
          same flask and shake  again  for  20  min.    Decant the extract and
          measure the volume of solvent recovered.

               7.1.1.3  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 min and
          the acetone-ether extract decanted.

               7.1.1.4  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.

               7.1.1.5  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 min 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
          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.

          7.1.2  Hydrolysis:

               7.1.2.1  Add 30 mL of  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 min.

                                  8150 - 8
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     7.1.2.2  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.

7.1.3  Solvent cleanup:

     7.1.3.1  Adjust the pH to 2 by  adding 5 ml cold (4'C) sulfurlc
acid (1:3) to the separatory  funnel.    Be  sure to check the pH at
this point.  Extract the herbicides  once  with 40 ml and twice with
20 ml of diethyl ether.  Discard the aqueous phase.

     7.1.3.2  Combine ether extracts  in  a  125-mL Erlenmeyer flask
containing 1.0 g of acidified anhydrous sodium sulfate.  Stopper and
allow the extract to  remain  1n  contact  with the acidified sodium
sulfate.    If  concentration  and  esterification  are  not  to  be
performed  immediately,   store   the   sample   overnight   1n  the
refrigerator.

     7.1.3.3  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.

     7.1.3.4  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   1s  bathed   in  vapor.     Adjust the vertical
position of  the apparatus  and the water  temperature,  as required, to
complete the concentration  in   15-20  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   from   the  water bath  and  allow  it to
drain  and  cool  for at  least  10  min.

     7.1.3.5  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   min. When  the  apparent
volume of the  liquid reaches 0.5  ml_,  remove the micro-K-D  from the
                         8150 - 9
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     bath and allow 1t 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 dlethyl  ether.
     Proceed to Section 7.3 for esterlflcation.

7.2  Preparation of liquid samples;,

     7.2.1  Extraction:

          7.2.1.1  Mark the water  mlnlscus   on  the  side  of the sample
     container for later determination of sample volume.  Pour the entire
     sample Into a 2-liter separatory funnel  and check the pH with wide-
     range pH paper.  Adjust  the  pH  to  less than 2 w1th,sulfur1c acid
     (1:1).

          7.2.1.2  Add 150 ml  of  diethyl  ether  to  the sample bottle,
     seal, and shake for 30 sec to rinse the walls.  Transfer the solvent
     wash to the separatory funnel and  extract the sample by shaking the
     funnel for 2 min with  periodic  venting to release excess pressure.
     Allow the organic  layer  to  separate  from  the  water layer for a
     minimum of 10 min.  If the emulsion interface between layers 1s 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.

          7.2.1.3  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.)

     7.2.2   Hydrolysis:

           7.2.2.1  Add  one or two   clean  boiling   chips   and   15 ml of
     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
     m1n, continue  heating for a  total  of 60 min,  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  min.

           7.2.2.2   Transfer the  solution  to   a  60-mL separatory funnel
     using 5-10 ml  of reagent  water.     Wash  the  basic solution twice by
     shaking for 1  min with 20-mL portions  of  diethyl ether.  Discard the
     organic phase.   The  herbicides remain  in  the  aqueous phase.


                              8150 - 10
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7.2.3  Solvent cleanup:

     7.2.3.1  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 min.  Drain the aqueous  layer into a 250-mL Erlenmeyer flask, and
pour the organic  layer  into  a  125-mL Erlenmeyer flask containing
about 0.5 g  of  acidified  sodium  sulfate.   Repeat the extraction
twice more  with  10-mL  aliquots  of  diethyl  ether, combining all
solvent in the 125-mL flask.  Allow the extract to remain in  contact
with the sodium sulfate for approximately 2 hr.

     7.2.3.2  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.

     7.2.3.3  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  1n  vapor.    Adjust the vertical
position of the apparatus and the water temperature, as required, to
complete the concentration in 15-20  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  from  the water bath and allow  it to
drain and cool for at  least 10 min.

     7.2.3.4  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   min.  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.

      7.2.3.5  Determine  the original  sample   volume  by  refilling  the
sample bottle to the mark   with   water and  transferring to a  1-liter
graduated cylinder.  Record the  sample volume to  the nearest  5  mL.
                         8150 - 11
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7.3  Esterification;

     7.3.1  Two methods may be  used  for the generation of diazomethane:
the bubbler method (set up shown in Figure 1) and the Dlazald 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 1s
safer to use than the Dlazald  kit  procedure.  The Dlazald kit method 1s
good for large quantities of samples needing esterification.  The Dlazald
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:
     CAUTION:  Diazomethane 1s 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 1n the presence of
        solid materials such as copper powder, calcium chloride, and
        boiling chips.

     7.3.2  Dlazald kit method:   Instructions for preparing diazomethane
are provided with the generator kit.

          7.3.2.1  Add 2 mL of diazomethane solution and let sample stand
     for  10 min with occasional swirling.

          7.3.2.2   Rinse inside wall of ampule with several hundred uL of
     d1ethyl ether.   Allow  solvent  to  evaporate spontaneously at room
     temperature to about 2 mL.

          7.3.2.3   Dissolve the residue in  5  mL  of  hexane.  Analyze by
     gas  chromatography.

     7.3.3  Bubbler method:    Assemble  the  diazomethane  bubbler  (see
Figure 1).

          7.3.3.1   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 Dlazald  to  the  second  test  tube.  Immediately place  the exit
     tube Into  the concentrator  tube  containing  the   sample  extract.
                              8150 - 12
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         Apply nitrogen flow (10  mL/m1n)  to bubble dlazomethane through the
         extract for  10  m1n  or  until  the  yellow  color  of dlazomethane
         persists.  The amount  of  Dlazald  used 1s sufficient for esterifl-
         catlon of approximately three  sample  extracts.  An additional 0.1-
         0.2 g  of  Dlazald  may  be  added  (after  the  Initial  Dlazald 1s
         consumed) to extend the  generation  of  the dlazomethane.  There 1s
         sufficient KOH present 1n the original solution to perform a maximum
         of approximately 20 m1n of total esterlflcation.

              7.3.3.2  Remove  the  concentrator  tube  and  seal  1t  with a
         Neoprene or Teflon stopper.  Store at room temperature 1n a hood for
         20 mln.

              7.3.3.3  Destroy any unreacted dlazomethane by adding 0.1-0.2 g
         silicic add 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  1f   further   processing   will   not   be  performed
         Immediately.  It   1s  recommended  that  the  methylated extracts be
         analyzed  Immediately to minimize   the trans-ester1f1cat1on and  other
         potential reactions that may occur.  Analyze  by gas chromatography.

     7.4 Gas  chromatography conditions  (Recommended);

         7.4.1   Column  la:  Set  5% methane/95%   argon  carrier gas  flow at  70-
     mL/m1n flow rate.  Column  temperature  Is  set  at  185'C  Isothermal.

          7.4.2   Column  Ib:  Set  5% methane/95%   argon  carrier gas  flow at  70-
     mL/mln flow rate.   Column  temperature  1s   set at 140*C  for  6 m1n  and then
     programmed  at  !0*C/m1n  to  200*C  and held.

          7.4.3   Column  2:   Set  5%  methane/95%  argon carrier gas at  70-mL/m1n
     flow rate.   Column  temperature  1s set  at  185*C  Isothermal.

          7.4.4   Column  3:   Set   nitrogen  (ultra-high   purity)  carrier gas at
     25-mL/m1n flow  rate.     Column   temperature  Is  set   at   100°C  and then
     Immediately programmed  at  10*C/min  to  150*C  and  held.

     7.5  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.

          7.5.1   The  procedure  for  Internal  or  external   calibration may be
     used.     Refer  to   Method  8000  for  a   description   of   each   of these
     procedures.

          7.5.2   The  following  gas  chromatographic columns  are  recommended  for
     the compounds indicated:
                                  8150 - 13
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                                                         Date  September 1986

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          Parameter           Column

          Dicamba             la,2
          2,4-D               la,2
          2,4,5-TP            la,2
          2,4,5-T             la,2
          2,4-DB              la
          Dalapon             3
          MCPP                Ib
          MCPA                Ib
          Dichloroprop        Ib
          Dinoseb             Ib
7.6  Gas chromatographic analysis;

     7.6.1  Refer to Method 8000.    If the Internal  standard calibration
technique Is used, add 10 uL of  Internal  standard to the sample prior to
Injection.

     7.6.2  Follow Section 7.6  1n  Method  8000  for Instructions on the
analysis sequence,  appropriate  dilutions,  establishing dally retention
time windows, and Identification criteria.   Include a mid-level standard
after each group of 10 samples 1n the analysis sequence.

     7.6.3  Examples   of   chromatograms   for   various   chlorophenoxy
herbicides are shown 1n Figures 2 through 4.

     7.6.4  Record the  sample  volume  Injected  and  the resulting peak
sizes (in area units or peak heights).

     7.6.5  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.

     7.6.6  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, Section 7.8 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.

     7.6.7  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.
                             8150 -  14
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                                                    Date  September 1986

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Column: 1.5% SP-2250/1.95% SP-2401 on Supelcopon (100/120 Mesh)
Ttmperature: Isothtrmal at 185°C
Detector: Electron Capture
          _L
          0      12345
            RETENTION TIME (MINUTES)
  Figure 2.  Gas chomatogram of chlorinated herbicides.
                       8150 - 15
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   Column: 1.5% SP-2260/1.95% SP-2401 on Supelcoport (100/120 Mesh)
   Program: 140°C for 6 Mm, 10°C/Mmute to 200°C
   Detector: Electron Capture
          466
          RETENTION TIME (MINUTES)
10
12
Figure 3. Gas chromatogram of chlorinated herbicides.
                8150 - 16
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                                          Date   September 1986

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             J
                    Column: 0.1% SP-1000 on 80/100 Mtsh Ccrbopak C
                    Program: 100°C, 10°C/Min to 160°C
                    Dttictor: Electron Capture
                          o
             0246
          RETENTION TIME (MINUTES)
Figure 4. Gas chromatogram of dalapon, column 3.
                         8150 - 17
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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 1n Method 3500 and 1n
the extraction method utilized.  If  extract cleanup was performed, follow the
QC in Method 3600 and in the specific cleanup method.

     8.2  Procedures to check  the  GC  system  operation  are found in Method
8000, Section 8.6.

          8.2.1  Select a representative spike concentration for each compound
     {add 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.

          8.2.2  Table 3 Indicates Single  Operator Accuracy and Precision for
     this method.  Compare  the  results  obtained  with  the results given 1n
     Table 3 to determine if the data quality 1s acceptable.

     8.3  Calculate  surrogate  standard  recovery  on  all samples, blanks, and
spikes.  Determine if  the  recovery  1s  within limits  (limits established by
performing QC procedures outlined in Method 8000, Section 8.10).

          8.3.1   If  recovery is  not  within  limits, the following procedures
     are required.

                •  Check to  be  sure  there  are  no  errors  in calculations,
                  surrogate solutions   and  internal  standards.   Also, check
                  instrument performance.

                •  Recalculate  the data  and/or reanalyze  the extract 1f any of
                  the above checks reveal a problem.

                •  Reextract and  reanalyze the sample  if none of the above are
                  a  problem or flag the data as  "estimated  concentration."

     8.4  GC/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.
                                   8150 - 18
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9.0  METHOD PERFORMANCE

     9.1  In a  single  laboratory,  using  reagent  water  and effluents from
publicly owned treatment  works  (POTW),  the  average recoveries presented in
Table 3 were obtained.  The  standard  deviations of the percent recoveries of
these measurements are also included in Table 3.
10.0  REFERENCES

1.  U.S. EPA, National  Pollutant  Discharge  Elimination  System, Appendix A,
Fed. Reg., 38, No. 75, Pt.  II, Method for Chlorinated Phenoxy Acid Herbicides
in Industrial Effluents, Cincinnati, Ohio, 1971.

2.  Goerlitz, D.G., and W.L. Lamar,  "Determination of Phenoxy Acid Herbicides
in Water by  Electron Capture  and  Mlcrocoulometric 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 133 for EPA Contract No. 68-
03-2697.  Available from  U.S.   Environmental Protection Agency,  Environmental
Monitoring and  Support Laboratory, Cincinnati,  Ohio 45268.

6.  McNair,  H.M.  and  E.J.  BonelH,  "Basic  Chromatography,"  Consolidated
Printing, Berkeley, California,  p. 52, 1969.

7.  Elchelberger, J.W., L.E. Harris,  and  W.L.  Budde,  "Reference Compound to
Calibrate Ion Abundance Measurement  1n Gas Chromatography-Mass Spectrometry,"
Analytical Chemistry, 47, 995, 1975.

8.  Glaser,  J.A.  et.al.,  "Trace   Analysis  for  Wastewaters,"  Environmental
Science & Technology, _15, 1426,  1981.

9.  U.S.  EPA, "Method  615.  The Determination  of  Chlorinated  Herbicides 1n
Industrial and  Municipal  Wastewater,"  Environmental  Monitoring and Support
Laboratory,  Cincinnati, Ohio, 45268, June 1982.
                                   8150 - 19
                                                          Revision
                                                          Date   September 1986

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TABLE 3.  SINGLE-OPERATOR ACCURACY AND PRECISION3
Parameter
2,4-D


Dalapon


2,4-DB


Dlcamba


Dlchlorprop


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
(ug/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
     aAll   results   based   upon    seven   replicate   analyses.     Ester1f1cation
 performed  using  the bubbler method.   Data  obtained  from reference  9.

     DW = Reagent water
     MW = Municipal  water
                                   8150 ->20
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                                                          Date  September  1986

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                            METHOD B1SO

                      CHLORINATED HERBICIDES
7.2.1
Extract 3 times
  with diethyl
     ether
                 Lloulo
                           	v   Solid
                           Type of sample xvvsample
                          for preparation    	'
                                                    7. > . 1
     Extract
    sample 3
  times with
 acetone ana
diethyl ether
7.2.1
    Combine
    extracts
7.2.2
                                                    7.1.1
  Combine
  extracts
   Do solvent
    cleanup
7.2.3
                                                    7.1.1.5
       Allow
       layers
 to separate:
  re-extract
 and discard
aqueous phase
  Proceed with
   hydrolysis
                                                    7.1.2
 Oo solvent
  cleanup
                                                    7.1.3
                                                     Proceed with
                                                      hydrolysis
                              o
                              8150 - 21
                                                        Revision        0
                                                        Date  September 1986

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                                         METHOD 81SO

                                   CHLORINATED HERBICIDES
                                         (Continued)
7.3.3
       Assemble
   dlazomethane
       bubbler:
      generate
   dlazometnane
                                                    7 .3.2
       Prepare
   dlazometnane
     according
       to Kit
   Instructions
                           7.4
                               Set  gas
                           chromatography
                             conditions
                           7.5
                              Cal Ibrate
                            according  to
                             Method  8000
                          7.5.3
                                                   7.6.7
                                                                              7.6
                          Analyze by GC
                             (refer to
                           Method BOOO)
       Process
      series of
      standards
through system.
      cleanup
                                Choose
                            GC  column  for
                           compound to be
                               analyzed
                                    8150 - 22
                                                               Revision       0
                                                               Date   September 1986

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4.3  DETERMINATION OF ORGANIC ANALYTES

     4.3.2  GAS CHROMATOGRAPHIC/MASS SPECTROMETRIC METHODS
                                   FOUR - 10
                                                          Revision
                                                          Date   September  1986

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                                 METHOD 8240

         GAS CHROMATOGRAPHY/MASS SPECTROMETRY FOR VOLATILE ORGANICS


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.

     1.2  Method 8240 can be used  to quantify most volatile organic compounds
that have boiling points below 200'C [vapor pressure is approximately equal to
mm Hg @ 25°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  practical  quantitation  limit  (PQL)  of  Method  8240  for an
individual compound is approximately  5  ug/kg  (wet weight) for soil/sediment
samples, 0.5 mg/kg (wet weight) for  wastes,   and 5 ug/L for ground water (see
Table 2).  PQLs 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 inter-
pretation 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
spectrometer operating parameters, are given.


                                  8240 -  1
                                                          Revision      0
                                                          Date  September  1986

-------
TABLE 1.  RETENTION TIMES AND CHARACTERISTIC IONS FOR VOLATILE COMPOUNDS
Retention
Compound Time (m1n)
Acetone
Acroleln
Acrylom'trile
Benzene
Bromochloromethane (I.S.)
Bromodi chl oromethane
4-Bromofluorobenzene (surr.)
Bromoform
Bromomethane
2-Butanone
Carbon dlsulflde
Carbon tetrachloride
Chlorobenzene
Chlorobenzene-ds (I.S.)
Chlorodlbromomethane
Chloroethane
2-Chloroethyl vinyl ether
Chloroform
Chl oromethane
Dlbromomethane
l,4-D1chloro-2-butane
Dlchlorodlfluoromethane
l,l-D1chloroethane
1,2-Dlchloroethane
1,2-01 chl oroethane-d4 (surr.)
1,1-Dlchloroethene
trans-l,2-D1chloroethene
1 , 2-D1 chl oropropane
c1s-l,3-D1chloropropene
trans-l,3-D1chloropropene
1,4-01 fluorobenzene (I.S.)
Ethanol
Ethyl benzene
Ethyl methacrylate
2-Hexanone
lodomethane
Methylene chloride
4-Methyl -2-pentanone
Styrene
1,1,2,2-Tetrachloroethane
Tetrachloroethene
Toluene
Toluene-dg (surr.)
__
—
—
17.0
9.3
14.3
28.3
19.8
3.1
—
—
13.7
24.6
—
—
4.6
18.6
11.4
2.3
—
—
—
—
10.1
12.1
9.0
10.0
15.7
15.9
17.2
19.6
—
26.4
—
—
—
6.4
—
—
22.1
22.2
23.5
— —
Primary Ion
43
56
53
78
128
83
95
173
94
72
76
117
112
117
129
64
63
83
50
93
75
85
63
62
65
96
96
63
75
75
114
31
106
69
43
142
84
43
104
83
164
92
98
Secondary Ion(s)
58
55, 58
52, 51
52, 77
49, 130,
85, 129
174, 176
171, 175,
96, 79
57, 43
78
119, 121
114, 77
82, 119
208, 206
66, 49
65, 106
85, 47
52, 49
174, 95
53, 89
87, 50,
65, 83
64, 98
102
61, 98
61, 98
62, 41
77, 39
77, 39
63, 88
45, 27,
91
41, 39,
58, 57,
127, 141
49, 51,
58, 100
78, 103
85, 131,
129, 131,
91, 65
70, 100




51


252













101









46

99
100

86


133
166


                                   8240 - 2
                                                          Revision       0
                                                          Date   September  1986

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TABLE 1. - Continued
                               Retention
Compound                       Time (min)     Primary Ion    Secondary Ion(s)

1,1,1-Trichloroethane            13.4              97           99, 117
1,1,2-Trichloroethane            17.2              97           83,  85,  99
Trichloroethene                  16.5             130           95,  97, 132
Trichlorofluoromethane            8.3             101          103,  66
1,2,3-Trichloropropane           —                75          110,  77, 61
Vinyl acetate                    —                43           86
Vinyl chloride                    3.8              62           64,  61
Xylene                           —               106           91
                                   8240 - 3
                                                          Revision       0
                                                          Date   September  1986

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TABLE 2.  PRACTICAL QUANTITATION LIMITS (PQL) FOR VOLATILE ORGANICSa

                                                           Practical
                                                          Quant1tat1on
                                                            L1m1tsb
Volatiles
1. Chloromethane
2. Bromomethane
3. Vinyl Chloride
4. Chloroethane
5. Methyl ene Chloride
6. Acetone
7. Carbon D1sulf1de
8. 1,1-Dichloroethene
9. 1,1-01 chloroethane
10. trans-l,2-D1chloroethene
11. Chloroform
12. 1,2-Di chloroethane
13. 2-Butanone
14. I,l,l-Tr1 chloroethane
15. Carbon Tetrachloride
16. Vinyl Acetate
17. Bromodl chloromethane
18. 1,1,2,2-Tetrachloroethane
19. 1,2-Dichloropropane
20. trans-l,3-D1chloropropene
21. Trlchloroethene
22. Dibromochloromethane
23. I,l,2-Tr1 chloroethane
24. Benzene
25. cis-l,3-Dichloropropene
26. 2-Chloroethyl Vinyl Ether
27. Bromoform
28. 2-Hexanone
29. 4-Methyl-2-pentanone
30. Tetrachloroethene
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
78-93-3
71-55-6
56-23-5
108-05-4
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
110-75-8
75-25-2
591-78-6
108-10-1
127-18-4
Ground water
ug/L
10
10
10
10
5
100
5
5
5
5
5
5
100
5
5
50
5
5
5
5
5
5
5
5
5
10
5
50
50
5
Low Soil /Sediment
ug/Kg
10
10
10
10
5
100
5
5
5
5
5
5
100
5
5
50
5
5
5
5
5
5
5
5
5
10
5
50
50
5
                                   8240 - 4
                                                          Revision      0
                                                          Date  September 1986

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TABLE 2. - Continued
                                                           Practical
                                                          Quantitation
                                                            L1mitsb
                                                Ground water   Low Soil/Sediment
   Volatiles                     CAS Number        ug/L              ug/Kg
31.
32.
33.
34.
35.
Toluene
Chlorobenzene
Ethyl Benzene
Styrene
Total Xylenes
108-88-3
108-90-7
100-41-4
100-42-5

5
5
5
5
5
5
5
5
5
5
aSample PQLs are highly matrix-dependent.  The PQLs listed herein are provided
for guidance and may not always be achieveable.  See the following information
for further guidance on matrix-dependent PQLs.
       listed  for  soil /sediment  are  based  on  wet  weight.  Normally data is
 reported on a dry weight basis; therefore, PQLs will be higher, based on the
 % moisture in each  sample.
          Other Matrices;                             Factor1

      Water miscible liquid waste                        50
      High-level  soil  & sludges                         125
      Non-water miscible waste                         500


      *PQL = [PQL for  ground water  (Table  2)]   X [Factor].   For non-aqueous
      samples,  the factor  is on  a  wet-weight basis.
                                   8240 - 5
                                                          Revision
                                                          Date  September 1986

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     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
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 field blank prepared from
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-level  and low-level
samples are analyzed sequentially.   Whenever an unusually concentrated sample
is analyzed, it should be followed  by  the analysis of reagent water to check
for cross-contamination.    The  purge-and-trap  system  may require extensive
bake-out and cleaning after a high-level 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-gasing
from the plumbing ahead of the  trap  account  for the majority of contamination
problems.  The analytical system must  be demonstrated to be free  from contam-
ination under the conditions  of   the  analysis  by running  laboratory reagent
blanks.  The use of  non-TFE  plastic  coating, non-TFE  thread sealants, or flow
controllers with rubber components  in the purging device  should be avoided.


4.0  APPARATUS AND MATERIALS

     4.1  Microsyringes;  10-uL, 25-uL,  100-uL,  250-uL,  500-uL, and 1,000 uL.
These  syringes shouldbe  equipped  with  a  20-gauge   (0.006-in  I.D.) needle
                                  8240 - 6
                                                         Revision      0
                                                         Date  September 1986

-------
having a length sufficient to extend from  the  sample Inlet  to  within  1  cm of
the glass frit 1n 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), 1f applicable
to the purging device.

     4.3  Syringe;  5-mL, gas-tight with shutoff valve.

     4.4  Balance;  Analytical, capable of accurately weighing 0.0001 g,  and a
top-loading balance capable of weighing 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 Uner.

     4.6  Volumetric flasks;   10-mL  and  100-mL,  class   A  with ground-glass
stoppers.

     4.7  Vials;  2-mL, for GC autosampler.

     4.8  Spatula;  Stainless steel.

     4.9  Disposable pi pets;  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  1s  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  1s
      recommended  that  1.0 cm  of   methyl  si 11 cone-coated packing be  inserted  at
     the  inlet  to extend the  life of  the   trap   (see Figure  2).   If 1t  Is  not
      necessary  to analyze   for  dichlorodifluoromethane or other f1uorocarbons
     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
                                   8240 - 7
                                                          Revision       0
                                                          Date  September  1986

-------
         OPTIONAL
         FOAM TRAP
>pfi«-	 Exit V

       V-14m,
14 Inch 0. D. Exit
     10 mm Glass Frit
     Medium Porosity
14 Inch 0. D.
                                    mm 0. D.
                                 Inlet Vt Inch 0. D.
                                   Sample Inlet
                                   2-Way Syringe Valve
                                  17 cm, 20 Gauge Syringe Needle
                                   6 mm 0. D. Rubber Septum
                                        mm 0. D.
                                        Inlet
                                        14 Inch 0. D.
                                        1/16 Inch 0. D.
                                        Stainless Steel
                                                           13x Molecular
                                                           Sieve Purge
                                                           Gas Filter
                                                           Purge Gas
                                                           Flow Control
                           Figure 1. Purging chamber.
                          8240 -  8
                                                      Revision        p
                                                      Date   September 1986

-------
            Packing Procedure
Construction
 Glass Wool   S mm

   Grade 15       |
   Silica Gel    8cm
     Tenax    15cm
 3%OV-1   1cm;
 Glass Wool   5 mm
             Compression
             Fitting Nut
             and Ferrules
             14 Ft. 7Ii/Foot
             Resistance Wire
             Wrapped Solid
               Thermocouple/
               Controller
               Sensor
                   Electronic
                   Temperature
                   Control and
                   Pyrometer
                                                      Tubing 25cm
                                                      0.105 In. I.D.
                                                      0.125 In.O.D.
                                                      Stainless Steel
                   Trap Inlet
Figure 2.  Trap packings and construction to include desorb capability for Method 8240.
                             8240 -  9
                                                          Revision        0
                                                          Date   September  1986

-------
and the polymer Increased to fill   the  entire trap.   Before Initial  use,
the trap should be conditioned overnight at 180*C by  backflushlng with an
Inert gas flow of at  least  20  ml/mln.    Vent the  trap effluent to the
room, not to the analytical column.   Prior to dally  use, the trap should
be conditioned for 10 mln at  180*C  with  backflushlng.  The trap may be
vented to the analytical  column  during dally 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 1n 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.li.5.2   Methyl  sllicone 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.

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.  I.D.   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  sec 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 accep-
table  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


                              8240 -  10
                                                     Revision      0
                                                     Date  September  1986

-------
 CARRIER GAS FLOW CONTROL
PRESSURE REGULATOR
PURGE GAS
FLOW CONTROL
 13X MOLECULAR
 SIEVE FILTER
                       LIQUID INJECTION PORTS
                            /           ^ COLUMN OVEN
                             1 "non ' ,__ CONFIRMATORY COLUMN
                                          TO DETECTOR
                                          *—ANALYTICAL COLUMN

                               OPTIONAL 4-PORT COLUMN
                               SELECTION VALVE
                                 TRAP INLET
                                  x RESISTANCE WIRE
                                  	  CHEATER CONTROL
                                    TRAP 'OFF*
                                     arc
                                     PURGING
                                     DEVICE
                                         Nott:ALL LINES BETWEEN
                                             TRAP AND GC
                                             SHOULD BE HEATED
                                             TO 80*C
   Figure 3. Schematic of purge-and-trap device — purge mode for Method 8240.
             CARRIER GAS
                 CONTROL
      REGULATOR
TOR.     I
-*M
                       LIQUID INJECTION PORTS
PURGE GAS  ._\,
FLOW CONTROL] 4
             *-A
              _iL
 Kl MOLECULAR 5
     SIEVE FILTER   ^
                                /,
                                           COLUMN OVEN
                                  n p n
                                 '  U' J
            r	CONFIRMATORY CCLU.'.IX

     nnnn-I^100^010"
. ,.-u.-'jL'U  {  ^-ANALYTICAL COLUMN
 \OPTIONAL 4-PORT COLUMN
                                  SELECTION VALVE
                            6-PORT TRAP INLET
                                     PURGING
                                     DEVICE
                                                     CONTROL
                                             Note:
                                             ALL LINES BETWEEN
                                             TRAP AND GC
                                             SHOULD BE HEATED
                                             TO 30°C.
    Figure 4. Schematic of purge-and-trap device — desorb mode for Method 8240.
                          8240  -  11
                                                   Revision       0
                                                   Date   September 1986

-------
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
                                   8240 - 12
                                                          Revision       0
                                                          Date   September  1986

-------
     glass-lined materials  are  recommended.     Glass   can   be deactivated  by
     sllanlzing with dlchlorodimethylsllane.

          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 1n any EICP
     between specified time or scan-number limits.  The most recent version  of
     the EPA/NIH Mass Spectral Library should also be available.


5.0  REAGENTS

     5.1  Stock solutions:  Stock solutions may be prepared  from pure standard
materials or purchased as certified  solutions.   Prepare stock standard solu-
tions in methanol, using assayed liquids or gases, as appropriate.

          5.1.1  Place about 9.8  ml  of  methanol  in  a  10-mL tared ground-
     glass-stoppered volumetric flask.  Allow the flask to stand,  unstoppered,
     for about 10 min or until  all alcohol-wetted surfaces  have dried.  Weigh
     the flask to the nearest 0.1 mg.

          5.1.2  Add the assayed reference material, as described below.

               5.1.2.1  Liquids;  Using a  100-uL 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.

               5.1.2.2  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 stan-
          dard 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
           (186600).  Attach Teflon  tubing  to   the  side-arm  relief valve and
          direct  a  gentle  stream of gas  into  the  methanol meniscus.

          5.1.3   Reweigh,  dilute to volume, stopper, and  then  mix by inverting
      the flask  several  times.   Calculate the concentration  in micrograms per
      microliter (ug/uL)  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 1f they  are
      certified  by the manufacturer or by an  independent source.
                                   8240 - 13
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          5.1.4  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.

          5.1.5  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, or sooner 1f comparison with check standards indicates a problem.

     5.2  Secondary  dilution  standards;     Using  stock  standard solutions,
prepare in methanol secondarydilution  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.

     5.3  Surrogate standards;   The surrogates  recommended are  toluene-dg,
4-bromofluorobenzene, and l,2-dichloroethane-d4.   Other  compounds may be used
as surrogates, depending upon  the  analysis  requirements.   A stock surrogate
solution in methanol should be  prepared  as  described  in  Section 5.1, and a
surrogate standard spiking solution  should  be  prepared  from the stock at a
concentration of 250  ug/10  ml  in  methanol.     Each sample undergoing GC/MS
analysis must be spiked with 10 uL  of the surrogate spiking solution prior to
analysis.

     5.4  Internal standards:  The  recommended  internal standards are bromo-
chloromethane, 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 5.1 and 5.2.   It  is recommended that the secondary dilution standard
should be prepared at a  concentration  of  25 ug/mL of each internal standard
compound.  Addition of  10 uL  of  this  standard  to 5.0  ml of sample or cali-
bration standard would  be the equivalent of 50 ug/L.

     5.5  4-Bromofluorobenzene (BFB) standard:   A standard solution containing
25 ng/uL of BFB in methanol should be prepared.

     5.6  Calibration standards;  Calibration  standards   at a minimum of five
concentration  levels should be prepared  from  the secondary dilution of stock
standards  (see Sections 5.1  and  5.2).    Prepare  these solutions in reagent
water.  One of the concentration levels should be at a concentration near,  but
above, the method detection  limit.   The remaining concentration levels should
correspond to  the expected range  of  concentrations  found in real samples or
should 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).    Store  for one week only in a
vial with  no  headspace.                 \

     5.7   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,


                                   8240 -  14
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trlchloroethene, chlorobenzene, toluene,  and benzene.    The standard should be
prepared in methanol, with  each  compound  present  at a concentration of 250
ug/10.0 ml.

     5.8  Great care must be taken  to  maintain the Integrity of all standard
solutions.  It is recommended that  all  standards be stored at -10'C to -20'C
in screw-cap amber bottles with Teflon liners.

     5.9  Reagent water;  Reagent water is defined as water in which an inter-
ferent is not observed at the  method  detection limit (MDL) of the parameters
of interest.

          5.9.1  Reagent water may be generated by passing tap water through a
     carbon filter bed  containing  about  453  g  of activated carbon (Calgon
     Corp., Filtrasorb-300 or equivalent).

          5.9.2  A water purification system  (Millipore Super-Q or equivalent)
     may be used to  generate reagent water.

          5.9.3  Reagent water may also  be   prepared  by boiling water for 15
     min.  Subsequently, while maintaining  the  temperature at 90*C, bubble a
     contaminant-free inert gas through the water  for 1 hr.  While it is still
     hot, transfer the water to a  narrow-mouth screw-cap bottle and seal with
     a Teflon-lined  septum and cap.

     5.10  Methanol;  Pesticide quality or equivalent.  Store apart  from other
solvents.
 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 uL 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
 ug/L);  therefore, it is only permitted when  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).
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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 min.
Column temperature program:   8'C/niin.
Final column temperature:     220'C.
Final column holding time:    15 min.
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-bromof1uorobenzene  (2-uL
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.    Add  5.0  ml  of reagent water  to the
-purging device.  The reagent water is added to the purging device using  a
5-mL glass  syringe fitted with  a  J15-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-uL or 25-uL  micro-
syringe equipped with  a long needle  (Paragraph 4.1), take a volume  of the
secondary  dilution solution  containing   appropriate concentrations  of the
calibration standards  (Paragraph 5;6).     Add  the aliquot of calibration
solution  directly  to the reagent water in  the purging device by inserting
the needle  through the  sample   inlet.    When discharging the contents of
the micro-syringe, be  sure that  the  end   of  the syringe needle is well
beneath the surface of  the reagent water.    Similarly,  add 10 uL  of the
internal  standard  solution  (Paragraph   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.
                              8240 - 16
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                                                     Date  September 1986

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     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 = (AxCis)/(AlsCx)

where:

      Ax   = Area of the characteristic ion for the compound being
             measured.

      Ajs  = 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 check for
 degradation caused  by contaminated  lines   or   active sites 1n  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  quantisation  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  may improve  bromoform  response.

          7.2.8.3   Tetrachloroethane   and   1,1-dichloroethane;     These
     compounds are  degraded bycontaminated  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).
                              8240 - 17
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     %RSD = -- x 100
              Y
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
(x1  - x]
  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-Di chloroethene,
          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-hr shift.

      7.3.2  The  initial calibration  curve  (Section 7.2) for  each compound
of interest must be checked  and verified  once  every 12 hr 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   (Paragraph 7.3.3) and CCC  (Paragraph
7.3.4).

      7.3.3  System  Performance  Check Compounds   (SPCCs):    A  system
performance check must be made each  12 hr.   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 Bromo-
form).   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.


                             8240 -  18
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     7.3.4  Calibration  Check  Compounds  (CCCs):      After  the  system
performance check 1s met,  CCCs  listed  1n  Paragraph  7.2.9 are used to
check the validity of  the  Initial  calibration.    Calculate the percent
difference using:


                     RFT - RFr
      % Difference = — i  — - x 100
where:

     RFj = 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 sec from  the last check calibration (12 hr), the
chromatographlc 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  (ECD);  and   extraction   of the
      sample with hexadecane and analysis  of   the  extract  on a  GC with a
      FID  and/or an  ECD  (Method 3820).
                              8240 - 19
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     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  1n Paragraph
7.2.1.

     7.4.1.4  BFB  tuning  criteria   and  dally  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/m1n on the  purge-and-trap  device.    Optimize  the flow rate to
provide the best response for  chloromethane and bromoform, 1f 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, 1f
there 1s 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  1s  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 1s  needed from a syringe, 1t must be
analyzed within  24 hr.    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-t
     o  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  reagent  wate
      r to be  added to  the  volumetric  flask  selected and  add slightly
      less than  this quantity of  reagent water to the  flask.

           7.4.1.7.3  Inject the  proper aliquot of samples from the sy
      ringe  prepared  in Paragraph  7.4.1.6   into  the flask.  AHquots
      of less  than  1-mL are  not   recommended.   Dilute the sample to
      the  mark with  reagent water.    Cap the flask,  Invert,  and shake
      three times.   Repeat  above  procedure  for additional dilutions.
                         8240 - 20
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          7.4.1.7.4 Fill  a 5-mL syringe with the diluted sample as  1
     n Paragraph 7.4.1.6.

     7.4.1.8  Add 10.0 uL  of  surrogate spiking solution (Paragraph
5.3) and 10 uL of Internal standard spiking solution (Paragraph 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  uL of the surrogate spiking
solution to 5 ml of  sample  1s  equivalent to a concentration of 50
ug/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
min 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 6C/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 m1n.  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  reagent water  (or methanol followed
by reagent water)  to  avoid  carryover  of pollutant compounds into
subsequent analyses.

     7.4.1.13  After desorbing the sample for 4 min, recondition the
trap by returning the purge-and-trap device to the purge mode.  Wait
15  sec; then close the syringe  valve  on the purging device to begin
gas  flow  through  the   trap.    The   trap  temperature   should  be
maintained at 180*C.  Trap temperatures up  to 220*C may be employed;
however, the higher temperature will   shorten the useful life  of the
trap.  After approximately 7 min,  turn off the  trap heater and open
the  syringe valve to  stop the  gas  flow through  the  trap.   When cool,
the  trap is ready  for the next  sample.

      7.4.1.14   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 quantltation  1s allowed only when there are
sample  interferences  with   the primary   ion.    When   a   sample  1s
analyzed that  has  saturated  Ions from  a compound, this  analysis must
be  followed   by a   blank  reagent  water   analysis.     If the blank
                         8240 - 21
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     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  uL of the matrix
     spike solution  (Paragraph  5.7)   to   the  5  ml  of  sample purged.
     Disregarding any dilutions, this is equivalent to a concentration of
     50 ug/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-misclble liquids:

          7.4.2.1   Water-miscible  liquids are   analyzed   as water samples
     after first diluting them at  least 50-fold with  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 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 reagent water by   adding at  least 20  uL,  but not
     more than 100-uL 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 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-level  method (0.005-1  mg/kg)  or the high-level method
    mg/kg).

          7.4.3.1  Low-level  method;     This   is  designed   for  samples
     containing individualpurgeable  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-level method  is based  on
     purging a  heated  sediment/soil   sample   mixed   with  reagent  water
     containing  the  surrogate  and  internal  standards.    Analyze  all
     reagent blanks  and  standards  under   the  same  conditions  as  the
     samples.   See Figure 5 for an illustration of a  low soils impinger.

               7.4.3.1.1  Use a 5-g sample   if the expected concentration
          is <0.1  mg/kg  or  a  1-g  sample  for expected concentrations
          between 0.1 and 1 mg/kg.
                             8240 - 22
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                                                    Date  September 1986

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  PURGE INLET FITTING
 SAMPLE OUTLET FITTING       11
3" » 6mm 0 D GLASS TUBING
                                     SEPTUM
                                        CAP
             40ml VIAL
      Figure 5.  Low Soils  Inpinger
                    8240 - 23
                                         Revision     0
                                         Date  September 1986

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     7.4.3.1.2  The  GC/MS  system  should  be  set  up  as  1n
Paragraphs 7.4.1.2-7.4.1.4.  This  should  be done prior to the
preparation of  the  sample  to  avoid  loss  of volatlles from
standards and samples.   A  heated purge calibration curve must
be prepared  and  used  for  the  quantltation  of  all samples
analyzed with the  low-level  method.    Follow the Initial and
dally 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  reagent  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
(Paragraph 5.3) and internal  standard solution (Paragraph 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  ug/kg  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 Paragraph  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   moisture    of    the
soil/sediment sample.   This   includes  waste   samples that  are
amenable to moisture   determination.   Other   wastes  should be
reported on a wet-weight basis.   Immediately after  weighing  the
sample,  weigh  (to  0.1  g) 5-10  g  of  additional  sediment/soil
into a  tared  crucible.     Dry  the  contents   of  the  crucibles
overnight  at  105*C.   Allow to  cool  in  a  desiccator and reweigh
the dried  contents.   Concentrations of  individual  analytes will
be reported  relative  to the dry  weight  of sediment.


   * mn,-ctiire  -  grams  of sample - grams  of dry  sample    ,nn
   * moisture  -             grams  Qf  sample             x luu


     7.4.3.1.6  Add   the   spiked  reagent  water  to  the  purge
device,  which  contains   the  weighed   amount  of  sample,  and
connect the  device to the  purge-and-trap  system.
     NOTE:   Prior  to   the   attachment  of the  purge device,  the
     procedures in Paragraphs   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 min.

                    8240 - 24
                                           Revision       0
                                           Date  September 1986

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          7.4.3.1.8  Proceed  with  the   analysis  as  outlined  in
     Paragraphs 7.4.1.11-7.4.1.16.   Use  5  mL  of the same reagent
     water as in the reagent blank.    If saturated peaks occurred or
     would occur if  a  1-g  sample   were analyzed, the medium-level
     method must be followed.

          7.4.3.1.9  For low-level sediment/soils  add  10 uL of the
     matrix spike solution  (Paragraph  5.7)   to  the  5 ml of water
     (Paragraph 7.4.3.1.3).    The  concentration  for  a 5-g sample
     would be equivalent to 50 ug/kg of each  matrix spike standard.

     7.4.3.2  High-level 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.  An aliquot of
the extract  is  added  to  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.

          7.4.3.2.1  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
     waste 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 moisture of the sample using the procedure in Paragraph
     7.4.3.1.5.  For waste that  is  soluble  in methanol, 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, 1t must
     be calibrated prior to use.  P1pet 10.0 mL of methanol into the
     vial and  mark  the  bottom  of  the  meniscus.    Discard this
     solvent.)

          7.4.3.2.2  Quickly add 9.0 ml of methanol;  then add  1.0 ml
     of the surrogate spiking solution  to  the vial.  Cap and  shake
     for  2 min.
          NOTE:  Steps  7.4.3.2.1  and  7.4.3.2.2  must be performed
           rapidly  and without interruption to avoid  loss of volatile
          organics.  These  steps  must  be performed  in a laboratory
           free  from  solvent  fumes.

           7.4.3.2.3   Pipet  approximately  1 ml of  the  extract to a GC
     vial  for  storage,  using a  disposable pipet.   The  remainder may
     be  disposed  of.     Transfer   approximately   1  mL  of reagent
     methanol  to a separate  GC  vial   for  use as the  method  blank for
     each set  of samples.    These  extracts  may  be  stored  at  4'C 1n
     the  dark,  prior to analysis.    The addition  of  a 100-uL aliquot
     of each of these   extracts  1n   Paragraph  7.4.3.2.6 will  give a
     concentration  equivalent  to   6,200  ug/kg   of each  surrogate
     standard.
                         8240 -  25
                                                Revision
                                               Date  September  1986

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     7.4.3.2.4  The  GC/MS  system  should  be  set  up  as  1n
Paragraphs 7.4.1.2-7.4.1.4.  This  should  be done prior to the
addition of the methanol  extract to reagent water.

     7.4.3.2.5  Table 4 can be used  to determine the volume of
methanol extract to  add  to  the  5  ml  of  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-level analysis to determine
the appropriate volume.    If  the  sample  was  submitted as a
medium-level sample, start  with  100  uL.   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  reagent  water.    Replace  the  plunger and
compress the water to vent  trapped  air.  Adjust the volume to
4.9 ml.  Pull the plunger  back  to  5.0 ml to allow volume for
the addition of the sample  extract  and  of standards.  Add 10
uL of internal  standard  solution.    Also  add  the volume of
methanol extract determined 1n Paragraph 7.4.3.2.5 and a volume
of methanol solvent  to  total  100  uL  (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  water/methanol  sample  into the purging
chamber.

     7.4.3.2.8  Proceed  with  the   analysis  as  outlined  in
Paragraphs  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  uL  of methanol to  simulate
the sample  conditions.

     7.4.3.2.9  For  a   matrix    spike    1n   the medium-level
sediment/soil  samples,  add   8.0   ml   of methanol,   1.0   ml of
surrogate  spike solution  (Paragraph 5.3),  and 1.0 ml of  matrix
spike  solution  (Paragraph  5.7)  as in Paragraph 7.4.3.2.2.   This
results in a   6,200  ug/kg concentration  of each matrix spike
standard when  added to  a 4-g   sample.    Add  a 100-uL  aliquot of
this  extract  to 5  ml   of  water   for  purging (as per Paragraph
7.4.3.2.6).
                    8240 - 26
                                           Revision
                                           Date  September 1986

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TABLE 4.  QUANTITY OF METHANOL EXTRACT REQUIRED FOR ANALYSIS OF MEDIUM-LEVEL
          SOILS/SEDIMENTS

                Approximate                         Volume of
            Concentration Range                  Methanol  Extract3

              500-10,000 ug/kg                         100 uL
            1,000-20,000 ug/kg                          50 uL
            5,000-100,000 ug/kg                         10 uL
           25,000-500,000 ug/kg               100 uL of 1/50 dilution b


     Calculate appropriate dilution  factor  for concentrations exceeding this
table.

     aThe volume of methanol added  to  5  mL  of water being purged should be
kept constant.  Therefore, add to the 5-mL syringe whatever volume of methanol
is necessary to maintain a volume of 100 uL added to the syringe.

     ''Dilute an aliquot of  the  methanol  extract  and  then  take 100 uL for
analysis.
                                  8240 - 27
                                                         Revision
                                                         Date  September  1986

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7.5  Data Interpretation;

     7.5.1  Qualitative analysis:

          7.5.1.1  An  analyte  (e.g.,  those   listed  1n  Table  1)   1s
     Identified by comparison of the  sample  mass spectrum with the mass
     spectrum of a standard of the suspected compound (standard reference
     spectrum).  Mass spectra  for  standard reference should be obtained
     on the user's 6C/MS within the same 12 hours as the sample analysis.
     These standard reference spectra may be obtained through analysis of
     the calibration standards.  Two criteria must be satisfied to verify
     identification:  (1)  elutlon  of  sample  component  at the same GC
     relative retention  time  (RRT)  as  those  of the standard component;
     and  (2) correspondence  of  the  sample  component  and the standard
     component mass spectrum.

               7.5.1.1.1  The sample component RRT must compare within
          +0.06 RRT units of  the  RRT  of  the standard component.  For
          reference, the standard must be  run  within  the same 12 hr as
          the sample.   If  coelutlon  of Interfering  components prohibits
          accurate assignment of the  sample  component. RRT from the total
          1on chromatogram, the  RRT should be assigned by using extracted
          1on current   profiles  for  Ions   unique  to  the  component of
          Interest.

               7.5.1.1.2  (1)  All  Ions  present   1n the  standard mass
          spectra at a  relative  Intensity greater than 10%  (most abundant
          1on  1n the spectrum equals  100%   must be present 1n the  sample
          spectrum).   (2) The relative  Intensities  of Ions specified 1n
           (1) must agree within  plus  or  minus 20%  between the standard
          and  sample spectra.   (Example:  For an 1on  with an abundance of
          50%  1n the standard spectra, the corresponding  sample abundance
          must be between 30  and 70 percent.

          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  1on) should be present  1n the sample
      spectrum.

      (2)  The  relative Intensities  of the   major ions should  agree within
      +20%.   (Example:     For  an  1on  with   an   abundance   of 50% 1n  the
      standard  spectrum, the   corresponding   sample   ion  abundance  must  be
      between 30 and 70%).

      (3)  Molecular ions  present  1n  the   reference  spectrum should be
      present 1n the sample spectrum.
                              8240 - 28
                                                     Revision      0
                                                     Date  September 1986

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(4)  Ions present 1n the  sample  spectrum  but not 1n the reference
spectrum should be reviewed for possible background contamination or
presence of coelutlng compounds.

(5)  Ions present 1n the  reference  spectrum  but not In the sample
spectrum should be reviewed for possible subtraction from the sample
spectrum because  of  background  contamination  or coelutlng 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 quantifi-
cation of that compound  will   be  based on the Integrated abundance
from the EICP  of  the  primary characteristic ion.  Quantification
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  1n the sample as follows:

Water  and Water-Mi scible Waste;

                            (AJ(IS)
 concentration  (ug/L) =  (A )(RF)(V  )

where:

     Ax  = Area  of characteristic  ion for compound being  measured.

      Is  = Amount  of  Internal  standard  injected  (ng).

           Area  of characteristic  ion for the  Internal standard.
      RF  = Response factor for compound  being measured  (Paragraph
              7.2.7).

      V0  = Volume of water purged  (ml),  taking  Into  consideration
            any dilutions made.
                         8240 - 29
                                                Revision
                                                Date  September 1986

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TABLE 5.  VOLATILE INTERNAL STANDARDS WITH CORRESPONDING ANALYTES ASSIGNED
          FOR QUANTITATION
Bromochloromethane

Acetone
Acrolein
Acrylonitrile
Bromomethane
Carbon disulflde
Chloroethane
Chloroform
Chioromethane
Di chlorodi f1uoromethane
1,1-Dichloroethane
1,2-Dichloroethane
1,2-Di chloroethane-d4  (surrogate)
1,1-Dichloroethene
trans-1,2-Di chloroethene
lodomethane
Methylene chloride
Trichlorofluoromethane
Vinyl chloride
1,4-Difluorobenzene

Benzene
Bromodichloromethane
Bromoform
2-Butanone
Carbon tetrachloride
Chlorodibromomethane
2-Chloroethyl vinyl ether
Dibromomethane
1,4-Di chloro-2-butene
1,2-Di chloropropane
ci s-1,3-Di chloropropene
trans-1,3-Di chloropropene
1,1,1-Tri chloroethane
1,1,2-Tri chloroethane
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-ds (surrogate)
                             1,2,3-Trichloropropane
                             Xylene
                                   8240 - 30
                                                          Revision      0
                                                          Date  September 1986

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         Sediment/Soil, Sludge, and Waste;

          High-level:

                                    (Aj(Is)(Vt)
          concentration (ug/kg) =  (AIS)(RF)(VI)(WS)
          Low-level:
                                     (AX)(IS)
          concentration  (ug/kg) =  (AU)(RF)(WS)

         where:

              Ax»  !s» A1s» RF = same as for water.

              Vt   =  volume of total extract  (uL)  (use 10,000 uL or a factor
                     of this when dilutions are made).

              Vi   =  volume of extract  added  (uL)  for purging.

              Ws   =  weight of sample extracted or purged  (g).  The wet weight
                     or dry weight  may  be  used,  depending upon the specific
                     applications of the data.

                 7.5.2.3   Sediment/soil samples   are  generally  reported  on  a
           dry weight basis, while  sludges  and   wastes  are reported on a wet
           weight basis.    The   %   moisture   of   the  sample  (as calculated In
           Paragraph  7.4.3.1.5)  should  be  reported  along with  the data 1n
           either Instance.

                 7.5.2.4   Where  applicable, an   estimate  of concentration for
           noncallbrated   components   1n   the  sample   should   be  made.    The
           formulas given above  should   be  used  with  the following  modifica-
           tions:   The  areas   Ax   and  Ais   should  be  from  the   total 1on
           chromatograms, and  the  RF  for the   compound  should  be assumed  to be
           1.  The concentration obtained should be  reported  Indicating
           (1) that the value  1s  an   estimate  and (2)  which  Internal  standard
           was used to  determine   concentration.    Use  the  nearest internal
           standard free of interferences.

                 7.5.2.5  Report results without correction for recovery  data.
           When duplicates and spiked  samples   are   analyzed,  report all  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  requirements of this  program
consist of an initial  demonstration   of  laboratory  capability and  an  ongoing


                                  8240  - 31
                                                         Revision       0
                                                         Date  September 1986

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analysis of  spiked  samples  to  evaluate  and  document  quality  data.   The
laboratory  must  maintain  records  to  document  the  quality  of  the  data
generated.    Ongoing  data  quality  checks  are  compared  with  established
performance  criteria  to  determine  1f  the  results  of  analyses  meet the
performance characteristics of  the  method.    When  results of sample spikes
Indicate atypical method performance, a quality control  check standard must be
analyzed to confirm that the measurements were performed In an 1n-control  mode
of operation.

     8.2  Before  processing  any  samples,  the  analyst  should demonstrate,
through the analysis of  a  reagent  water  blank, that interferences from the
analytical system, glassware, and reagents are under control.  Each time a set
of samples 1s extracted or  there  1s  a  change  1n reagents, a reagent water
blank  should  be  processed   as   a  safeguard  against  chronic  laboratory
contamination.  The blank samples should  be carried through all stages of the
sample preparation and measurement steps.

     8.3  The  experience  of  the   analyst   performing  GC/MS  analyses  is
invaluable to  the  success  of  the  methods.    Each  day  that  analysis 1s
performed, the daily calibration standard  should be evaluated to determine if
the chromatographic system is  operating  properly.   Questions that should be
asked are:  Do the peaks look  normal?; Is the response obtained comparable to
the response from previous calibrations?   Careful examination of the standard
chromatogram can Indicate whether the column is still useable, the Injector is
leaking, the Injector septum needs replacing, etc.  If any changes are made to
the system (e.g, column changed), recalibration of the system must take place.

     8.4  Required instrument QC is found  in the following section:

          8.4.1  The GC/MS system must be  tuned to meet the BFB specifications
     in Section  7.2.2.

          8.4.2  There must be an initial  calibration  of the GC/MS system as
     specified in 7.2.

          8.4.3  The GC/MS system  must  meet  the  SPCC criteria  specified 1n
     7.3.3 and the CCC criteria  in 7.3.4,  each 12 hr.

     8.5  To  establish   the  ability  to   generate   acceptable   accuracy  and
precision, the analyst must perform  the  following operations.

          8.5.1  A  quality   (QC)    check    sample    concentrate   is   required
     containing  each analyte  at  a concentration   of  10  ug/mL  in methanol.  The
     QC  check sample concentrate may  be prepared  from  pure  standard materials
     or  purchased  as certified  solutions.    If prepared by the  laboratory, the
     QC  check sample concentrate must  be   made  using stock  standards  prepared
     independently  from  those used  for calibration.

          8.5.2   Prepare a  QC check  sample to contain  20  ug/L  of each analyte
     by  adding 200  uL of QC  check   sample  concentrate  to  100  mL of reagent
     water.
                                   8240 - 32
                                                          Revision      0
                                                          Date  September  1986

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          8.5.3   Four 5-mL  allquots  of  the  well-mixed  QC  check sample are
     analyzed  according  to  the  method  beginning  1n Section 7.4.1.

          8.5.4   Calculate  the  average recovery  (7)   in ug/L, and  the  standard
     deviation of the recovery  (s)   in  ug/L,  for each analyte  using  the four
     results.

          8.5.5   For each  analyte   compare   s   and   7 with  the corresponding
     acceptance  criteria for precision  and  accuracy, respectively,  found  in
     Table 6.   If s and  7  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
     7 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.

          8.5.6   When one or more of the  analytes  tested fail at  least one  of
     the acceptance criteria, the analyst   must  proceed according  to  Paragraph
     8.5.6.1 or 8.5.6.2.

               8.5.6.1  Locate  and  correct  the source   of   the   problem and
          repeat the test for all analytes beginning  with Section  8.5.2.

               8.5.6.2  Beginning with Section  8.5.2, repeat  the test only for
          those analytes that  failed  to   meet   criteria.    Repeated failure,
          however, will  confirm a general  problem with the measurement system.
          If this occurs, locate  and  correct   the   source of the problem and
          repeat the test for all compounds of  interest beginning  with Section
          8.5.2.

     8.6  The laboratory must,  on an ongoing  basis,  analyze  a reagent blank, a
matrix spike, and a matrix spike duplicate/duplicate  for  each analytical batch
(up to a maximum of  20  samples/batch)   to assess  accuracy.   For  laboratories
analyzing one to ten samples per  month,  at least  one spiked sample  per month
is required.
          8.6.1  The concentration  of
     determined as follows:
the  spike  in  the  sample  should be
               8.6.1.1  If, as in compliance  monitoring, the concentration of
          a  specific  analyte  in  the  sample  is  being  checked  against a
          regulatory concentration limit, the spike should be at that limit or
          1 to 5 times higher  than the background concentration determined in
          Section 8.6.2, whichever concentration would be larger.

               8.6.1.2  If the  concentration  of  a  specific  analyte in the
          sample is not  being  checked  against  a  specific limit, the spike
          should be at 20 ug/L  or  1  to  5  times higher than the background
          concentration determined in  Section  8.6.2, whichever concentration
          would be larger.
                                  8240 - 33
                                                         Revision      0
                                                         Date  September 1986

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TABLE 6.  CALIBRATION AND QC ACCEPTANCE CRITERIA3
Parameter
Benzene
Bromodi chl oromethane
Bromoform
Bromomethane
Carbon tetrachloride
Chlorobenzene
2-Chloroethyl vinyl ether
Chloroform
Chl oromethane
01 bromochl oromethane
1,2-01 chlorobenzene
1,3-01 chlorobenzene
1 , 4-01 chl orobenzene
l,l-D1chloroethane
1,2-Dichloroethane
1,1-01 chl oroethene
trans-1, 2-01 chl oroethene
1 , 2-01 chl oropropane
cis-l,3-Di chl oropropene
trans-1 , 3-01 chl oropropene
Ethyl benzene
Methylene chloride
1,1,2,2-Tetrachloroethane
Tetrachl oroethene
Toluene
1,1,1-Trlchloroethane
1,1, 2-Tr1 chl oroethane
Trlchloroethene
Tr1 chl orof 1 uoromethane
Vinyl chloride
Range
for Q
(ug/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
0-44.8
13.5-26.5
0-40.8
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
(ug/L)
6.9
6.4
5.4
17.9
5.2
6.3
25.9
6.1
19.8
6.1
7.1
5.5
7.1
5.1
6.0
9.1
5.7
13.8
15.8
10.4
7.5
7.4
7.4
5.0
4.8
4.6
5.5
6.6
10.0
20.0
Range
for 7
(ug/L)
15.2-26.0
10.1-28.0
11.4-31.1
0-41.2
17.2-23.5
16.4-27.4
0-50.4
13.7-24.2
0-45.9
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
0-41.0
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
0-43.5
Range
P, Ps
CO
37-151
35-155
45-169
0-242
70-140
37-160
0-305
51-138
0-273
53-149
18-190
59-156
18-190
59-155
49-155
0-234
54-156
D-210
0-227
17-183
37-162
0-221
46-157
64-148
47-150
52-162
52-150
71-157
17-181
0-251
     Q  =  Concentration measured  In QC check sample, 1n ug/L.
     s  =  Standard deviation of four recovery measurements, 1n ug/L.
     7  =  Average recovery  for four recovery measurements, in ug/L.
     p, ps  =  Percent  recovery measured.
     0  =  Detected;  result  must be greater than zero.

     Criteria  from  40  CFR  Part  136  for  Method  624  and were calculated
 assuming  a  QC check sample concentration of 20 ug/L.  These criteria are based
 directly  upon the method performance  data  1n  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.
                                   8240 - 34
                                                          Revision       0
                                                          Date  September  1986

-------
         8.6.2  Analyze one 5-mL sample  aliquot  to determine the background
    concentration  (B) of each analyte.   If necessary, prepare a new QC check
    sample  concentrate  (Section  8.5.1)   appropriate  for  the  background
    concentration  In the sample.  Spike  a second 5-mL sample aliquot with 10
    uL of the QC check  sample  concentrate  and  analyze 1t to determine the
    concentration  after spiking  (A) of  each analyte.  Calculate each percent
    recovery  (p) as  100(A-B)%/T,  where  T  1s  the  known  true value of the
    spike.

         8.6.3  Compare the percent recovery   (p)  for  each analyte with the
    corresponding  QC acceptance  criteria found  1n Table 6.  These acceptance
    criteria  were  calculated  to  Include an allowance for error  in measurement
    of both the background   and  spike  concentrations,  assuming a spike to
    background  ratio of 5:1.   This  error  will be acounted for to the extent
    that the  analyst's  spike  to  background  ratio approaches 5:1.  If spiking
    was  performed  at a  concentration  lower than 20 ug/L, the analyst must use
    either  the  QC  acceptance  criteria presented  1n  Table 6,  or optional QC
    acceptance  criteria calculated  for the  specific  spike concentration.  To
    calculate optional  acceptance criteria  for  the  recovery  of an analyte:
     (1)  Calculate  accuracy   (x1)   using  the equation  found  in  Table 7,
    substituting  the spike  concentration   (T)  for  ,C;  (2) calculate overall
    precision (S1) using  the  equation in   Table 7,  substituting x1 for 7;  (3)
    calculate the range for recovery   at  the  spike  concentration  as  (lOOx'/T)
    + 2.44(100S'/T)%.

          8.6.4   If any individual  p  falls  outside   the designated  range  for
     recovery, that analyte  has   failed   the   acceptance  criteria.   A  check
     standard  containing   each  analyte   that  failed  the   criteria must be
     analyzed as described in  Section  8.7.

     8.7   If any analyte falls the  acceptance criteria  for  recovery  1n  Sectln
8.6, a QC check standard containing  each analyte  that failed  must be prepared
and analyzed.
     NOTE:   The  frequency  for  the  required   analysis  of  a  QC  check standard
    will depend upon the  number  of analytes  being  simultaneously tested,  the
     complexity of the sample matrix,   and  the performance  of the laboratory.
     If the entire list of analytes in  Table  6 must be  measured in  the  sample
     in Section 8.6, the probability that  the analysis  of  a  QC  check standard
     will be required is high.  In  this   case the  QC check  standard  should be
     routinely analyzed with the spiked sample.

          8.7.1   Prepare the QC check standard by  adding 10  uL of the QC  check
     sample concentrate (Section 8.5.1  or  8.6.2)   to  5 ml of reagent  water.
     The QC check standard  needs  only  to  contain  the  analytes that  failed
     criteria in the test in Section 8.6.

          8.7.2  Analyze the QC check  standard to determine the concentration
     measured (A)  of each analyte.    Calculate  each precent recovery (ps)  as
     100 (A/T)%, where T is the true value of the standard  concentration.
                                  8240 - 35
                                                         Revision
                                                         Date  September 1986

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TABLE 7.  METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION3
Parameter
Benzene
Bromodl chl oromethane
Bromoform
Bromomethane
Carbon tetrachlorlde
Chlorobenzene
Chloroethane
2-Chloroethyl vinyl ether3
Chloroform
Chl oromethane
D1 bromochl oromethane
1 , 2-D1 chl orobenzene*5
1 , 3-D1 chl orobenzene
1 , 4-D1 chl orobenzene'3
1,1-01 chloroethane
1,2-D1 chloroethane
1,1-01 chl oroethene
trans-1 , 2 , -D1 chl oroethene
1 , 2-D1 chl oropropane3
c1s-l,3-D1chloropropene3
trans-1 , 3-D1 chl oropropene3
Ethyl benzene
Methylene chloride
1,1,2,2-Tetrachloroethane
Tetrachl oroethene
Toluene
1,1, 1-Trl chl oroethane
1,1, 2-Tr1 chl oroethane
Tr1 chl oroethene
Tr1 ch 1 orof 1 uoromethane
Vinyl chloride
Accuracy, as
recovery, x'
(ug/L)
0.93C+2.00
1.03C-1.58
1.18C-2.35
l.OOC
1.10C-1.68
0.98C+2.28
1.18C+0.81
l.OOC
0.93C+0.33
1.03C-1.81
1.01C-0.03
0.94C+4.47
1.06C+1.68
0.94C+4.47
1.05C+0.36
1.02C+0.45
1.12C+0.61
1.05C+0.03
l.OOC
l.OOC
l.OOC
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
Single analyst
precision, sr'
(ug/L)
0.267-1.74
0.157+0.59
0.127+0.34
0.437
0.127+0.25
0.167-0.09
0.147+2.78
0.627
0.167+0.22
0.377+2.14
0.177-0.18
0.227-1.45
0.147-0.48
0.227-1.45
0.137-0.05
0.177-0.32
0.177+1.06
0.147+0.09
0.337
0.387
0.257
0.147+1.00
0.157+1.07
0.167+0.69
0.137-0.18
0.157-0.71
0.127-0.15
0.147+0.02
0.137+0.36
0.337-1.48
0.487
Overall
precision,
S' (ug/L)
0.257-1.33
0.207+1.13
0.177+1.38
0.587
0.117+0.37
0.267-1.92
0.297+1.75
0.847
0.187+0.16
0.587+0.43
0.177+0.49
0.307-1.20
0.187-0.82
0.307-1.20
0.167+0.47
0.217-0.38
0.437-0.22
0.197+0.17
0.457
0.527
0.347
0.267-1.72
0.327+4.00
0.207+0.41
0.167-0.45
0.227-1.71
0.217-0.39
0.187+0.00
0.127+0.59
0.347-0.39
0.657
      x1   =     Expected recovery for  one   or  more  measurements  of  a  sample
      containing a concentration  of C,  in ug/L.
      sr'  =     Expected single analyst standard  deviation of measurements at
      an  average concentration  of 7,  in ug/L.
      S'   =     Expected Interlaboratory standard  deviation of measurements at
      an  average concentration  found  of 7,  in ug/L.
      C   =     True value for  the concentration,  in  ug/L.
      7 =  Average recovery  found  for measurements  of   samples  containing a
      concentration of C,  in ug/L.

      3Est1mates based upon the performance In a single laboratory.
      bDue to chromatographic  resolution   problems,  performance  statements for
      these Isomers are based upon the  sums of their  concentrations.
                                   8240 - 36
                                                          Revision       0
                                                          Date   September  1986

-------
          8.7.3  Compare the percent recovery  (ps)   for each analyte with the
     corresponding QC acceptance criteria  found  In  Table  6.   Only analytes
     that failed the  test  1n  Section  8.6  need  to  be compared with these
     criteria.   If  the  recovery  of  any  such  analyte  falls  outside the
     designated range, the laboratory  performance  for that analyte 1s judged
     to be out of control, and  the problem must be immediately Identified and
     corrected.  The result for that analyte 1n the unspiked sample 1s suspect
     and may not be reported for regulatory compliance purposes.

     8.8  As part of the QC  program  for  the laboratory, method accuracy for
each matrix studied must be  assessed  and  records must be maintained.  After
the analysis of five spiked samples  (of  the  same matrix) as 1n Section 8.6,
calculate the average percent recovery  (J5)  and the standard deviation of the
percent recovery (sn).  Express the  accuracy assessment as a percent recovery
interval from JJ - 2sp to p + 2sp.   If  p = 90% and sp = 10%, for example, the
accuracy interval is expressed as 70-110%.  Update the accuracy assessment for
each analyte on a regular  basis  (e.g.  after  each  five to ten new accuracy
measurements).

     8.9  To determine acceptable accuracy  and precision limits for surrogate
standards the following procedure should be performed.

          8.9.1  For each sample analyzed,  calculate  the percent recovery of
     each surrogate in the sample.

          8.9.2  Once a minimum of  thirty  samples of the  same matrix have been
     analyzed,  calculate  the  average  percent  recovery   (p)  and   standard
     deviation of the percent recovery  (s)  for each of the surrogates.

          8.9.3  For  a given  matrix,   calculate  the  upper and lower control
     limit  for method performance for  each surrogate  standard.  This  should be
     done as  follows:

          Upper  Control  Limit  (UCL) =  p +  3s
          Lower  Control  Limit  (LCL) =  p -  3s

          8.9.4   For aqueous  and  soil   matrices, these  laboratory established
     surrogate control  limits   should,   if  applicable,   be  compared  with the
     control  limits listed  1n  Table 8.   The limits  given 1n  Table  8 are multi-
     laboratory  performance based   limits   for  soil   and aqueous  samples, and
     therefore,  the single-laboratory   limits  established  in  Paragraph 8.9.3
     must fall within those given  in Table 8  for these matrices.

          8.9.5   If recovery  1s  not  within   limits,  the following procedures
     are required.

                •   Check to  be  sure  there  are  no   errors  in calculations,
                   surrogate  solutions   and  Internal   standards.    Also, check
                   instrument  performance.

                •   Recalculate the data and/or reanalyze   the extract 1f any of
                   the above checks  reveal  a problem.


                                  8240 - 37
                                                          Revision       0
                                                          Date   September 1986

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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


4-Bromofluorobenzene                    86-115                 74-121
l,2-D1chloroethane-d4                   76-114                 70-121
Toluene-d8                              88-110                 81-117
                                  8240 - 38
                                                         Revision
                                                         Date  September 1986

-------
               •  Reextract and reanalyze the sample  1f none of the above are
                  a problem or flag the data as "estimated concentration."

          8.9.6  At  a  minimum,  each   laboratory  should  update  surrogate
     recovery limits on a matrlx-by-matrix basis,  annually.

     8.10  It 1s  recommended  that  the  laboratory  adopt additional  quality
assurance practices for use with this method.  The specific practices that are
most productive depend upon the needs of  the laboratory and the nature of the
samples.  Field duplicates  may  be  analyzed  to  assess the precision of the
environmental measurements.  When  doubt  exists  over the identification of a
peak on the chromatogram,  confirmatory  techniques such as gas chromatography
with  a  dissimilar  column  or  a  different  lonization  mode  using  a mass
spectrometer must be used.   Whenever  possible, the laboratory should analyze
standard  reference  materials   and   participate   in  relevant  performance
evaluation studies.
9.0  METHOD PERFORMANCE

     9.1  The  method  detection  limit  (MDL)   1s  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  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 reagent water,
drinking water,  surface  water,  and  Industrial  wastewaters  spiked  at six
concentrations over the range 5-600  ug/L.  Single operator precision, overall
precision, and method  accuracy  were  found  to  be  directly  related to the
concentration of the analyte and essentially  Independent of the sample matrix.
Linear equations to describe these relationships are presented 1n Table 7.


10.0  REFERENCES

1.  U.S. EPA 40 CFR Part  136,  "Guidelines Establishing Test Procedures for the
Analysis of Pollutants Under   the  Clean  Water  Act, Method 624," October 26,
1984.

2.  U.S. EPA   Contract   Laboratory   Program,  Statement  of  Work  for Organic
Analysis,  July 1985,  Revision.

3.  Bellar, T.A.,  and J.J.  Lichtenberg,   J.   Amer. 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.
                                   8240 - 39
                                                          Revision      0
                                                          Date  September 1986

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5.  Budde, W.L. and J.W.  Elchelberger,  "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  1n  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.  Elchelberger, Unpublished report, October 1980.

8.  Provost, L.P. and R.S.  Elder,  "Interpretation of Percent Recovery Data,"
American  Laboratory, 15, pp. 58-63, 1983.

9.  "Interlaboratory Method Study for  EPA Method 624-Purgeables," Final Report
for EPA Contract 68-03-3102.

10.   "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.
                                   8240 - 40
                                                          Revision
                                                          Date  September 1986

-------
                      METHOD 8240

GAS CHROMATOGRAPHY/MASS SPECTROMETRY FOR VOLATILE ORGANICS
                                  Direct
                                  inject ion

7. a st
cone
use appr
purge-*
proc

7.2
Purge-an
trap
:t GC/MS
jer-otlng
lltlons;
•oprlate
ind-trap
edure


Calculate
Response
Factors for
5 SPCC's

7.3
f
call
usini
one


erf orm
dally
Dratlon
SPCC ' s
CCC'e
                       o
                 8240 - 41
                                          Revision       0
                                          Date  September  1986

-------
                                         METHOD 6240

                 GAS CHROMATOGRAPHY/MASS SPECTROMETRY FOR VOLATILE ORGANICS
                                         ICont Inuea)
                  Water
                 mlsclble
                 1loulos
                Sediment/
                  soil
                            Select GC/MS
                           method for the
                           waste matrix
Dilute at leact
   SOX with
 reagent water
                           Screen sample
                           using  Methods
                           3810 or 382O
                                                           IG
                                                     concentration
                                                         mg/teg?
   sample using
Methods 3810 or
   3820:  dilute
   if necessary
                          7.4.1 Introduce
                                  sample
                            and standards
                              into GC by
                           purge-and-trap
                                 method
                                                    and High-level
                                                    purge-and-trao
                                                         method
                                response
                            xceed initial
                            calibration
 Dilute sample
  Interference:
  decontaminate
     system if
     necessary
    Do ions
   saturate?
                                  8240 -  42
                                                             Revision        p
                                                             Date  September 1986

-------
                      METHOD 6240

GAS CHROMATOGHAPHY/MASS SPECTROMETRY FOR VOLATILE ORGANICS
                      (Continued)
                       o
7.5 ]
by cc
the
and i
mass

7.S
Ct
concer
of
Ider
ant

Identify
inalytes
loipar ing
; sample
standard
spectra

ilculate
itrat ion
each '
itif ied
ilyte

7.S |
Report results
                   (     Stop      J
                 8240  - 43
                                          Revision       0
                                          Date  September 1986

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                                 METHOD 8250

       GAS CHROMAT06RAPHY/MASS SPECTROMETRY FOR SEMIVOLATILE ORGANICS;
                           PACKED COLUMN TECHNIQUE


1.0  SCOPE AND APPLICATION

     1.1  Method 8250 1s used to  determine the concentration of semi volatile
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.

     1.2  Method 8250 can be used to quantify most neutral, acidic, and basic
organic compounds that are soluble 1n methylene chloride and capable of being
eluted without  derivatlzation  as  sharp  peaks  from  a gas chromatographic
packed column.   Such  compounds  include  polynuclear aromatic hydrocarbons,
chlorinated hydrocarbons  and  pesticides,  phthalate  esters, organophosphate
esters,  nltrosamlnes,  haloethers,  aldehydes,  ethers,  ketones,  anilines,
pyridines,  quinolines,  aromatic  nitro  compounds,  and  phenols, including
m'trophenols.  See Table 1 for  a  11st 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 oxldative 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 endrln are subject  to  decomposition.   Neutral extraction should be
performed if these compounds  are  expected  and  are not being determined by
Method 8080.  Hexachlorocyclopentadlene  is  subject to thermal decomposition
1n the Inlet of the gas chromatograph, chemical reaction in acetone solution,
and photochemical  decomposition.    N-nltrosodimethyl amine  is  difficult to
separate from the solvent under the chromatographic conditions described.
N-n1trosod1phenylamine decomposes in the gas chromatographic Inlet and cannot
be separated from diphenylamine.  Pentachlorophenol, 2,4-d1nitrophenol,
4-nitrophenol,  4,6-dinitro-2-methylphenol,  4-chloro-3-methylphenol, benzole
acid, 2-nitroaniline, 3-n1troan1line,  4-chloroan1line, and benzyl  alcohol are
subject to erratic chromatographic behavior,  especially   1f the GC system 1s
contaminated with high boiling material.

     1.4  The  practical  quantltation  limit    (PQL)   of Method 8250  for
determining an  individual compound 1s   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  ug/L  for  ground   water  samples  (see Table 2).   PQLs
will be  proportionately  higher for   sample  extracts that  require  dilution to
avoid  saturation  of  the  detector.

     1.5  This  method 1s restricted   to  use  by or under the  supervision of
analysts  experienced  1n  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.
                                   8250 - 1
                                                          Revision       0
                                                          Date   September  1986

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TABLE 1.  CHROMATOGRAPHIC CONDITIONS, METHOD DETECTION LIMITS, AND
          CHARACTERISTIC IONS FOR SEMIVOLATILE COMPOUNDS
,1
Retention
Compound Time (m1n)
Acenaphthene
Acenaphthene-djo (I.S.)
Acenaphthylene
Acetophenone
Aldrln
Aniline
Anthracene
4-Aminob1 phenyl
Aroclor-1016b
Aroclor-1221b
Aroclor-1232b
Aroclor-1242b
Aroclor-1248b
Aroclor-1254b
Aroclor-1260b
Benzidine3
Benzole add
Benzo (a) anthracene
Benzo (b) f 1 uoranthene
Benzo (k) f 1 uoranthene
Benzo (g , h , 1 ) pery 1 ene
Benzo(a)pyrene
Benzyl alcohol
a-BHCa
£-BHC
5-BHC
7-BHC (Lindane)a
B1 s (2-chl oroethoxy)methane
B1s (2-chl oroethyl) ether
B1 s (2-chl orol sopropy 1 ) ether
B1 s (2-ethyl hexyl ) phthal ate
4-Bromophenyl phenyl ether
Butyl benzyl phthal ate
Chlordaneb
4-Chloroanillne
1-Chloronaphthalene
2-Chl oronaphthal ene
4-Chloro-3-methyl phenol
2-Chlorophenol
4-Chlorophenyl phenyl ether
Chrysene
Chrysene-di2 (I.S.)
4,4'-DDD
4,4'-DDE
17.8
—
17.4
—
24.0
—
22.8
18-30
15-30
15-32
15-32
12-34
22-34
23-32
28.8
—
31.5
34.9
34.9
45.1
36.4
—
21.1
23.4
23.7
22.4
12.2
8.4
9.3
30.6
21.2
29.9
19-30
—
—
15.9
13.2
5.9
19.5
31.5
—
28.6
27.2
Method
detection
limit (ug/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
5.6
Primary
Ion
154
164
152
105
66
93
178
169
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
246
Secondary
Ion(s)
153, 152
162, 160
151, 153
77, 51
263, 220
66, 65
176, 179
168, 170
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
248, 176
                                   8250 - 2
                                                          Revision       0
                                                          Date  September 1986

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TABLE 1.  - Continued
Retention
Compound Time (m1n)
4,4'-DDT
D1benz(a,j)acridine
D1 benz (a, h) anthracene
Dlbenzofuran
D1-n-butylphthalate
1 , 3-D1 chl orobenzene
1 , 4-Di chl orobenzene
l,4-D1chlorobenzene-d4 (I.S.)
1 , 2-D1 chl orobenzene
3,3'-D1chlorobenz1d1ne
2 , 4-D1 chl orophenol
2,6-Dichlorophenol
D1eldr1n
Diethylphthalate
p-Di methyl ami noazobenzene
7 , 12-Di methyl benz (a) anthracene
a- , a-D1 methyl phenethy 1 ami ne
2,4-D1methylphenol
Dimethylphthalate
4 , 6-Di ni tro-2-methy 1 phenol
2,4-Dinitrophenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Diphenylamine
1 , 2-D1 pheny 1 hydrazl ne
Di-n-octylphthalate
Endosulfan Ia
Endosulfan IIa
Endosulfan sulfate
Endrin*
Endrln aldehyde
Endrin ketone
Ethyl methanesulfonate
Fluoranthene
Fluorene
2-Fluorobi pheny 1 (surr.)
2-Fluorophenol (surr.)
Heptachlor
Heptachlor epoxide
Hexachl orobenzene
Hexachl orobutadi ene
Hexachl orocycl opentadi ene*
Hexachl oroethane
Indeno (1 , 2 , 3-cd) pyrene
29.3
—
43.2
—
24.7
7.4
7.8
—
8.4
32.2
9.8
—
27.2
20.1
—
—
—
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
Method
detection
limit (ug/L)
4.7
—
2.5
—
2.5
1.9
4.4
—
1.9
16.5
2.7
—
2.5
1.9
—
—
—
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
Primary
Ion
235
279
278
168
149
146
146
152
146
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
Secondary
Ion(s)
237, 165
280, 277
139, 279
139
150, 104
148, 111
148, 111
150, 115
148, 111
254, 126
164, 98
164, 98
263, 279
177, 150
225, 77
241, 257
91, 42
107, 121
194, 164
51, 105
63, 154
63, 89
63, 89
168, 167
105, 182
167, 43
339, 341
339, 341
387, 422
82, 81
345, 250
67, 319
109, 97
101, 203
165, 167
171
64
272, 274
355, 351
142, 249
223, 227
235, 272
201, 199
138, 227
                                   8250 - 3
                                                          Revision      0
                                                          Date  September 1986

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TABLE 1.  - Continued
Retention
Compound Time (m1n)
Isophorone
Methoxychlor
3-Methyl chol anthrene
Methyl methanesulfonate
2-Methyl naphthal ene
2-Methyl phenol
4-Methyl phenol
Naphthalene
Naphthal ene-ds (I.S.)
1-Naphthylamlne
2-Naphthylamine
2-Nitroan1l1ne
3-N1troan11ine
4-Nitroaniline
Nitrobenzene
Nitrobenzene-ds (surr.)
2-Nitrophenol
4-Nitrophenol
N-N1 troso-di -n-butyl ami ne
N-Ni trosodimethyl ami nea
N-Ni trosodi phenyl ami nea
N-Ni troso-di -N-propyl ami ne
N-Ni trosopi peri dine
Pentachl orobenzene
Pentachl oroni trobenzene
Pentachl orophenol
Perylene-di2 (I.S.)
Phenacetin
Phenanthrene
Phenanthrene-djo (I.S.)
Phenol
Phenol -ds (surr.)
2-P1coline
Pronamide
Pyrene
Terphenyl-dj4 (surr.)
1, 2, 4, 5-Tetrachl orobenzene
2,3,4, 6-Tetrachl orophenol
2,4,6-Tribromophenol (surr.)
1,2, 4-Tri chl orobenzene
2, 4, 5-Trichl orophenol
2, 4, 6-Tri chl orophenol
Toxaphene"
11.9
—
—
—
—
—
—
12.1
—
—
—
—
—
—
11.1
—
6.5
20.3
—
—
20.5
—
—
—
—
17.5
—
—
22.8
—
8.0
—
—
—
27.3
—
—
—
—
11.6
—
11.8
25-34 ,
Method
detection
limit (ug/L)
2.2
—
—
—
—
—
—
1.6
—
—
—
—
—
—
1.9
—
3.6
2.4
—
—
1.9
—
—
—
—
3.6
—
—
5.4
—
1.5
—
—
• —
1.9
—
—
—
—
1.9
—
2.7
Primary
Ion
82
227
268
80
142
108
108
128
136
143
143
65
138
138
77
82
139
139
84
42
169
70
42
250
295
266
264
108
178
188
94
99
93
173
202
244
216
232
330
180
196
196
159
Secondary
Ion(s)
95, 138
228
253, 267
79, 65
141
107, 79
107, 79
129, 127
68
115, 116
115, 116
92, 138
108, 92
108, 92
123, 65
128, 54
109, 65
109, 65
57, 41
74, 44
168, 167
130, 42
114, 55
252, 248
237, 142
264, 268
260, 265
109, 179
179, 176
94, 80
65, 66
42, 71
66, 92
175, 145
200, 203
122, 212
214, 218
230, 131
332, 141
182, 145
198, 200
198, 200
231, 233
aSee Section 1.3
^These compounds are mixtures of various Isomers.
                                  8250 - 4
                                                         Revision      0
                                                         Date  September 1986

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TABLE 2.  DETERMINATION OF PRACTICAL QUANTITATION LIMITS (PQL) FOR VARIOUS
           MATRICES3


    Matrix                                                    Factor^
Ground water                                                     10
Low-level soil by sonication with GPC cleanup                   670
High-level soil and sludges by sonication                    10,000
Non-water miscible waste                                    100,000


     aSample PQLs are highly  matrix-dependent.    The  PQLs listed herein are
     provided for guidance and may not always be achievable.

     bPQL = [Method detection limit (Table 1)] X [Factor (Table 2)].  For non-
     aqueous samples, the factor is on a wet-weight basis.
                                  8250 - 5
                                                          Revision
                                                         Date  September  1986

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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-level and low-
level 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 I.D.
          stainless or  glass,packedwith  3%SP-2250-DB  on 100/120 mesh
          Supelcoport or  equivalent.

               4.1.2.2  For acid compound detection;   2-m  x 2-mm I.D. glass,
          packed  with  1%SP-1240-DAon100/120  mesh  Supelcoport  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 uL 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
                                   8250 -  6
                                                         Revision      0
                                                         Date  September  1986

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     TABLE 3.   DFTPP KEY IONS  AND  ION  ABUNDANCE CRITERIA a

   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


   a J.W. Elchelberger, I.E. Harris,  and  W.L.  Budde. "Reference Compound to
Calibrate Ion Abundance Measurement 1n Gas Chromatography-Mass Spectrometry",
Analytical Chemistry, 47, 995 (1975).
                                  8250 - 7
                                                         Revision
                                                         Date  September 1986

-------
     used.   GC-to-MS  Interfaces  constructed  entirely of glass oY* glass-lined
     materials  are  recommended.   Glass  may be deactivated by silanlzlng with
     d1chlorodimethyls1lane.

          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 1on abundances versus time or scan
     number.  This   type  of   plot  1s 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-uL.
5.0  REAGENTS

     5.1  Stock standard solutions (1.00  ug/uL):    Standard solutions can be
prepared from pure standard materials or purchased as certified solutions.

          5.1.1  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  1s 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.

          5.1.2  Transfer the  stock  standard  solutions  Into Teflon-sealed
     screw-cap bottles.  Store at 4*C and protect from light.  Stock standard
     solutions should  be  checked  frequently  for  signs  of degradation or
     evaporation, especially just  prior  to  preparing calibration standards
     from them.                                    ',

          5.1.3  Stock standard solutions  must  be  replaced  after  1 yr or
     sooner if comparison  with  quality  control  check  samples Indicates a
     problem.

     5.2  Internal standard solutions;    The  internal standards recommended
are 1,4-d1chlorobenzene-d4,naphthalene-dg,  acenaphthene-diQi phenanthrene-
dio. chrysene-di2, and perylene-di2.  Other compounds may be used as internal
standards as long  as  the  requirements  given  1n  Paragraph 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.
                                  8250 - 8
                                                         Revision      0
                                                         Date  September 1986

-------
Most of the compounds are also soluble 1n small  volumes of methanol,  acetone,
or toluene, except for  perylene-dj2«    The  resulting solution will  contain
each standard at a concentration  of  4,000  ng/ul.  Each 1-mL sample extract
undergoing analysis should be  spiked  with  10  uL  of the Internal  standard
solution, resulting in a concentration of 40 ng/uL of each internal  standard.
Store at 4*C or less when not being used.

     5.3  GC/MS tuning standard;  A methylene chloride solution containing
50 ng/uL oT  decaf1uorotriphenylphosphine  (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.

     5.4  Calibration standards;  Calibration standards  at a minimum of five
concentration levels 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 1n 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 1n Table  1  may  be included).  Each 1-mL aliquot of
calibration standard should be  spiked  with  10  uL 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 dally calibration standard should be prepared weekly
and stored at 4*C.

     5.5  Surrogate  standards;    The  recommended  surrogate  standards are
phenol-ds, 2-f1uorophenol,274,6-tribromophenol,  nitrobenzene-ds, 2-fluoro-
biphenyl, and p-terphenyl-dj4.    See  Method  3500  for  the instructions on
preparing the surrogate standards.   Determine what concentration should be  1n
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.

     5.6  Matrix spike  standards;    See  Method  3500  for  instructions on
preparing the matrix spike standard.   Determine what  concentration should be
1n 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.


6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

     6.1   See the  Introductory  material  to  this chapter, Organic Analytes,
Section  4.1.
                                   8250 - 9
                                                          Revision      0
                                                          Date   September  1986

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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                                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 uL syringe  may
     be appropriate.  The detection  limit is very high (approximately 10,000
     ug/L); therefore, it is only permitted where concentrations in excess of
     10,000 ug/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
          Organophosphorous pesticides          3620, 3640
          Petroleum waste                       3611, 3650
          All priority pollutant base,
              neutral, and acids                3640

     aMethod  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;

     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 uL
     Carrier  gas:  Helium at 30 mL/min
                                  8250 - 10
                                                         Revision
                                                         Date  September 1986

-------
Conditions for base/neutral analysis (3% SP-2250-DB):

     Initial column temperature and hold time:  50*C for 4 m1n
     Column temperature program:  50-300*C at 8*C/m1n
     Final column temperature hold:  300*C for 20 m1n

Conditions for add analysis (1% SP-1240-DA):

     Initial column temperature and hold time:  70*C for 2 m1n
     Column temperature program:  70-200*C at 8*C/m1n
     Final column temperature hold:  200*C for 20 m1n

          7.3.1  Each  GC/MS  system  must  be  hardware-tuned  to  meet  the
     criteria 1n 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%.  Benz1d1ne and
     pentachlorophenol should be present  at  their  normal responses, and no
     peak tailing should be visible.  If degradation 1s excessive and/or poor
     chromatography Is noted, the  Injection port may require cleaning.

          7.3.2  The Internal   standards  selected  In  Paragraph  5.1 should
     permit most of the  components  of  Interest  1n  a chromatogram to have
     retention times of 0.80-1.20  relative   to one of the  Internal standards.
     Use  the  base peak 1on from the  specific  Internal standard as the primary
     1on  for  quantltatlon  (see  Table 1).  If Interferences are noted, use the
     next  most   Intense   1on   as    the  quantltatlon   1on,   I.e.,   for  1,4-
     d1chlorobenzene-d4 use m/z 152  for quantltatlon.

           7.3.3   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  1n  Table 1).
     Calculate response factors (RFs) for each compound as follows:

                  RF =  (AxC1s)/(A1sCx)

     where:

           Ax   =  Area of  the  characteristic  Ion  for  the  compound being
                 measured.

           Ais =  Area of  the  characteristic  1on  for  the  specific Internal
                  standard.

           Cx   =  Concentration of the compound being measured  (ng/uL).

           Cjs =  Concentration of the specific Internal  standard  (ng/uL).
                                   8250 - 11
                                                          Revision
                                                          Date  September 1986

-------
     7.3.4  The average RF should be  calculated for each compound.   The
percent relative standard deviation (%RSD  =  100[SD7RF]) 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 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.

7.4  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-hr shift.

     7.4.2  A  calibration   standard(s)   at   mid-level  concentration
containing all semi volatile analytes, including all required surrogates,
must be performed every  12-hr  during  analysis.   Compare the response
factor data from the  standards  every  12-hr  with the  average response
factor from the initial  calibration  for  a  specific Instrument as per
SPCC  (Paragraph 7.4.3) and CCC  (Paragraph 7.4.4) criteria.

     7.4.3  System  Performance  Check  Compounds   (SPCCs):    A  system
performance check must be made during  every  12  hr  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  1n  Table 4  are used to check the
validity of the initial  calibration.   Calculate the percent  difference
using:
                             8250 -  12
                                                    Revision      0
                                                    Date  September 1986

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TABLE 4.  CALIBRATION CHECK COMPOUNDS
Base/Neutral Fraction                     Add Fraction
Acenaphthene                              4-Chloro-3-methylphenol
1,4-D1chlorobenzene                       2,4-D1chlorophenol
Hexachlorobutadi ene                       2-N1trophenol
N-Ni troso-d1-n-phenylamine                Phenol
D1-n-Octy1phthalate                       Pentachlorophenol
Fluoranthene                              2,4,6-Trlchlorophenol
Benzo(a)pyrene
                                  8250 -  13
                                                         Revision
                                                         Date  September 1986

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                    RFj - RF
     % Difference = —   — - x 100
where:

      RFj = average response factor from Initial calibration.

      RFC = response factor from current verification check standard.

If the percent  difference  for  any  compound  1s  greater  than 20, the
laboratory  should  consider  this  a  warning  limit.    If  the percent
difference for each CCC  1s  less  than  30%,  the Initial calibration 1s
assumed to be valid.  If  the  criterion 1s not met (>30% difference) for
any one CCC, corrective action MUST  be taken.  Problems similar to those
listed under SPCCs could affect  these  criterion.    If no source of the
problem can be determined after  corrective  action has been taken, a new
five-point calibration MUST be  generated.    This  criterion MUST be met
before sample analysis begins.

      7.4.5  The Internal standard responses  and  retention times 1n 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 sec from the last check calibration  (12 hr), the
chromatographlc system must  be  Inspected  for malfunctions and correc-
tions 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  dally 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 1s 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.

      7.5.2  Spike the  1-mL extract obtained  from  sample preparation with
10 uL of the  Internal  standard solution just prior to analysis.

      7.5.3  Analyze the  1-mL  extract  by   GC/MS using  the appropriate
column   (as   specified  in  Paragraph  4.1.2).    The  recommended GC/MS
operating  conditions to  be used  are  specified  in  Paragraph 7.3.

      7.5.4  If the  response for  any  quantltatlon  1on  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/uL  of each  Internal standard  1n
the  extracted volume..   The diluted extract must be reanalyzed.
                              8250 - 14
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                                                     Date  September 1986

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     7.5.5  Perform all  qualitative  and  quantitative  measurements as
described 1n Paragraph 7.6.   Store  the extracts at 4*C, protected from
light 1n screw-cap vials equipped with unplerced Teflon-lined septa.

7.6  Data Interpretation:

     7.6.1  Qualitative analysis:

          7.6.1.1  An  analyte   (e.g.,  those   listed  1n  Table  1)  1s
     Identified by comparison of the  sample  mass spectrum with the mass
     spectrum of a standard of the suspected compound  (standard reference
     spectrum).  Mass  spectra for  standard reference compounds should be
     obtained on the user's GC/MS within  the same 12 hours as the sample
     analysis.  These  standard reference  spectra may be obtained through
     analysis  of  the calibration  standards.    Two  criteria  must be
     satisfied to verify Identification:  (1) elutlon of sample component
     at the  same  GC  relative  retention  time  (RRT)  as  the standard
     component; and  (2) correspondence  of  the  sample component and the
     standard component mass spectrum.

               7.6.1.1.1   The sample component RRT must compare within
          +0.06 RRT units of  the  RRT  of  the standard component.  For
          reference, the standard must be  run  within the same 12 hrs as
          the sample.  If  coelutlon  of Interfering components prohibits
          accurate assignment of the sample  component RRT from the  total
          1on chromatogram, the  RRT should be assigned by using extracted
          1on current  profiles  for  ions  unique  to  the  component of
          interest.

               7.6.1.1.2   All ions present  1n  the standard mass spectra
          at a relative  intensity greater  than 10% (most abundant  ion  1n
          the  spectrum  equals  100%  must  be  present  in  the   sample
          spectrum.

               7.6.1.1.3   The relative intensities  of   Ions specified  in
          Paragraph  7.6.1.1.2 must agree within plus or minus 20% between
          the standard and sample spectra.  (Example:  For an ion with  an
          abundance  of 50% in   the  standard  spectra,  the corresponding
          sample abundance must  be between 30 and 70 percent.

          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   (e.g.,    for   EPA   Contract   Laboratory  Program
     requirements, up  to 20 substances of greatest  apparent  concentration
     not  listed   in  the   Hazardous  Substance   List   must be tentatively
     identified).  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  spectra with   the nearest library  searches will
                              8250 - 15
                                                     Revision      0
                                                     Date  September 1986

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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 1n sample the spectrum.

(4)  Ions present 1n  the  sample  spectrum but not 1n the reference
spectrum should be reviewed for possible background contamination or
presence of coelutlng compounds.

(5)  Ions present 1n  the  reference  spectrum but not in the sample
spectrum should be reviewed for possible subtraction from the sample
spectrum because  of  background  contamination  or coelutlng 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  quantltatlon
of that  compound will be based  on  the Integrated abundance  from the
EICP of  the   primary  characteristic  1on.    Quantltatlon 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;

                           (Ax)(IJ(Vt)
  concentration (ug/L) = -TT—WRF\ /v
                                   o

 where:

      Ax   =  Area    of    characteristic    ion    for   compound  being
            measured.

      Is   =  Amount  of  Internal  standard  Injected  (ng).
                         8250 - 16
                                                Revision
                                                Date   September  1986

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TABLE 5.  SEMIVOLATILE INTERNAL STANDARDS WITH CORRESPONDING ANALYTES
          ASSIGNED FOR QUANTITATION
1,4-Di chlorobenzene-d4
Naphtha!ene-dg
Acenaphthene-dio
Aniline
Benzyl alcohol
Bi s(2-chloroethyl)ether
Bi s(2-chl oroi sopropyl)ether
2-Chlorophenol
1,3-Di chlorobenzene
1,4-Di chlorobenzene
1,2-Di chlorobenzene
Ethyl methanesulfonate
2-Fluorophenol  (surr.)
Hexachloroethane
Methyl methanesulfonate
2-Methylphenol
4-Methylphenol
N-Ni trosodlmethylami ne
N-Ni troso-di-n-propy1 ami ne
Phenol
Phenol-de  (surr.)
2-P1coline
Acetophenone
Benzoic acid
Bi s(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-dg  (surr.)
2-Nitrophenol
N-Ni troso-di-n-butylami ne
N-Nitrosopiperidine
1,2,4-Trichlorobenzene
Acenaphthene
Acenaphthylene
1-Chloronaphthalene
2-Chloronaphthalene
4-Chlorophenyl
  phenyl ether
Dibenzofuran
Diethyl phthalate
Dimethyl phthalate
2,4-Dinitrophenol
2,4-Di ni trotoluene
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
                                   8250 - 17
                                                          Revision      0
                                                          Date  September 1986

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TABLE 5.  SEMIVOLATILE INTERNAL STANDARDS WITH CORRESPONDING ANALYTES
          ASSIGNED FOR QUANTITATION  (Continued)
Phenanthrene-dio
Chrysene-di2
Perylene-dj2
4-Am1nob1phenyl
Anthracene
4-Bromophenyl phenyl ether
D1-n-butyl phthalate
4,6-Din1tro-2-methylphenol
D1phenylamine
1,2-D1phenylhydrazlne
Fluoranthene
Hexachlorobenzene
N-N1trosodlphenylamine
Pentachlorophenol
Pentachloronltrobenzene
Phenacetln
Phenanthrene
Pronamlde
Benz1d1ne
Benzo(a)anthracene
B1s(2-ethy1hexyl)phthalate
Butyl benzylphthalate
Chrysene
3,3'-D1chlorobenzld1ne
p-D1methyl aminoazobenzene
Pyrene
Terphenyl-dj4 (surr.)
Benzo(b)fluor-
  anthene
Benzo(k)fluor-
  anthene
Benzo(g,h,1)
  perylene
Benzo(a)pyrene
D1benz(a,j)acr1d1ne
D1benz(a,h)
  anthracene
7,l2-D1methylbenz-
  (a)anthracene
D1-n-octylphthalate
Indeno(l,2,3-cd)
  pyrene
3-Methylchol-
 anthrene
(surr.) = surrogate
                                   8250 - 18
                                                          Revision      0
                                                          Date  September 1986

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     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 uL.     If  half the base/neutral extract and
           half the add extract are  combined,  Vt =  2,000.

     AJS = Area of characteristic Ion for the Internal  standard.

     RF  = Response factor for  compound   being measured  (Paragraph
           7.3.3).

     V0  = Volume of water extracted  (ml_).

     Vj  = Volume of extract Injected (uL).


Sediment/Soil Sludge (on a dry-weight basis)  and Waste (normally  on
a wet-weight basis;

                             (AJU.MVJ
 concentration (ug/kg) = (AIS)(RF)(VI)(WS)(D)

where:

     Ax» Is* Vt! Ais, RF, V^ = same as for water.

     Ws = weight of sample extracted or diluted 1n  grams.

     D =  (100 -  % moisture 1n sample)/100, or 1 for a wet-weight
          basis.
     7.6.2.3  Where applicable,  an  estimate  of concentration for
noncallbrated  components  1n  the  sample  should  be  made.   The
formulas given above should  be  used  with the following modifica-
tions:  The areas Ax and Ajs should be from the total 1on chromato-
grams and the RF for the compound  should  be assumed to be 1.  The
concentration obtained should be  reported  Indicating (1) that the
value 1s an estimate and   (2)  which  Internal standard was used to
determine concentration.   Use the nearest Internal standard free of
Interferences.

     7.6.2.4  Report results without  correction for recovery data.
When duplicates  and spiked samples  are  analyzed, report all data
obtained with the sample results.

     7.6.2.5  Quantisation of   multlcomponent   compounds   (e.g.,
Aroclors)   is  beyond  the  scope   of  Method  8270.    Normally,
quantltatlon  is  performed  using a GC/ECD by Method 8080.
                         8250 - 19
                                               Revision      0
                                               Date  September  1986

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8.0  QUALITY CONTROL

     8.1  Each laboratory.that uses  these  methods  is required to operate a
formal quality control program.    The  minimum  requirements of this program
consist of an initial demonstration  of  laboratory capability and an ongoing
analysis of spiked  samples  to  evaluate  and  document  quality  data.   The
laboratory  must  maintain  records  to  document  the  quality  of  the  data
generated.    Ongoing  data  quality  checks  are  compared  with established
performance criteria  to  determine  if ', the  results  of  analyses  meet the
performance characteristics of the  method.    When  results of sample spikes
indicate atypical method performance,  a  quality control check standard  must
be analyzed to confirm that the  measurements were performed in an 1n-control
mode of operation.

     8.2  Before processing  any  samples,  the  analyst  should demonstrate,
through the analysis of a  reagent  water  blank, that interferences from the
analytical system, glassware, and reagents  are  under  control.  Each time a
set of samples is extracted or there is a change in reagents, a reagent water
blank  should  be  processed  as   a  safeguard  against  chronic  laboratory
contamination.  The blank samples should be carried through all stages of the
sample preparation and measurement steps.

     8.3  The  experience  of  the   analyst  performing  GC/MS  analyses  1s
invaluable to  the  success  of  the  methods.'    Each  day  that analysis is
performed, the daily calibration standard should be evaluated to determine if
the chromatographic system is operating  properly.   Questions that should be
asked are:  Do the peaks look normal?; Is the response obtained comparable to
the response from previous calibrations?  Careful examination of the standard
chromatogram can Indicate whether the  column  is still good, the Injector 1s
leaking, the injector septum needs replacing,  etc.   If any changes are made
to the system (e.g, column  changed),  recalibration  of the system must take
place.

     8.4  Required instrument QC is found 1n the following section:

          8.4.1  The  GC/MS  system  must   be   tuned   to  meet  the  DFTPP
     specifications  in Section 7.3.1 and 7.4.1.

          8.4.2  There must be an initial  calibration of the GC/MS system as
     specified in 7.3.

          8.4.3  The GC/MS system must  meet  the  SPCC criteria specified 1n
     7.4.3 and the CCC criteria in 7.4.4, each 12 hr.

     8.5  To  establish  the   ability  to  generate  acceptable  accuracy and
precision, the analyst must perform the; following operations.

          8.5.1  A   quality   (QC)   check   sample   concentrate   is  required
     containing  each  analyte at a concentration  of  100 ug/mL  in acetone.  The
     QC check sample  concentrate may  be prepared from pure  standard materials
     or purchased as  certified solutions.   If prepared by the  laboratory, the
                                  8250 - 20
                                                         Revision      0
                                                         Date  September 1986

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    QC check  sample  concentrate must  be  made using stock standards prepared
    independently  from  those  used for calibration.

          8.5.2   Using a pipet, prepare QC check samples at a concentration of
    100  ug/L  by  adding  1.00 ml of QC check sample concentrate to each of four
    1-L  aliquots of  reagent water.

          8.5.3   Analyze the   well-mixed  QC  check  samples  according to the
    method beginning in Section 7.1 with extraction of the samples.

          8.5.4   Calculate the average recovery  (7)  in ug/L, and the standard
    deviation of the recovery (s)  in ug/L, for  each analyte of  interest using
    the  four  results.

          8.5.5   For  each  analyte   compare   s   and  7  with the corresponding
    acceptance  criteria for   precision   and  accuracy, respectively, found  in
    Table 6.   If s and   7  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 7 falls outside  the   range  for accuracy, then the system
    performance is unacceptable  for that analyte.
          NOTE:   The  large number  of analytes in Table 6  present a  substantial
          probability  that  one   or more  will   fail  at least   one  of the
          acceptance   criteria when all   analytes  of   a given   method  are
          analyzed.

          8.5.6  When one or more  of the   analytes tested fail at  least one  of
     the  acceptance criteria,  the   analyst  must  proceed according to Section
    8.5.6.1 or 8.5.6.2.

               8.5.6.1  Locate and  correct  the  source   of  the   problem and
          repeat the  test for all   analytes of  interest beginning with Section
          8.5.2.

               8.5.6.2  Beginning  with  Section  8.5.2,  repeat the test only for
          those analytes that  failed  to  meet  criteria.  Repeated failure,
          however,  will  confirm  a  general  problem  with the measurement system.
          If this occurs, locate   and  correct   the   source of the  problem and
          repeat the test for all  compounds of  interest beginning with Section
          8.5.2.

     8.6  The laboratory must, on  an ongoing  basis,  analyze a  reagent blank,  a
matrix spike,  and a matrix spike/duplicate  for each  analytical  batch  (up  to a
maximum of 20 samples/batch)  to  assess  accuracy.  For  laboratories analyzing
one to ten  samples  per  month,   at  least  one  spiked   sample  per month  is
required.

          8.6.1  The concentration  of  the  spike  in  the   sample  should  be
determined as follows:

               8.6.1.1   If, as in compliance   monitoring, the  concentration  of
          a   specific   analyte  in  the  sample  is   being  checked  against a
          regulatory concentration limit, the spike  should be  at that limit  or

                                  8250 - 21
                                                         Revision       0
                                                         Date   September 1986

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TABLE 6.  QC ACCEPTANCE CRITERIA3
Parameter
Acenaphthene
Acenaphthylene
AldHn
Anthracene
Benzo a) anthracene
Benzo bjfluoranthene
Benzo kjfluoranthene
Benzo ajpyrene
Benzo (ghl)perylene
Benzyl butyl phthalate
/7-BHC
5-BHC
B1s 2-chloroethyl) ether
Bis 2-chloroethoxy)methane
B1s 2-chloro1sopropyl) ether
B1 s (2-ethy 1 hexyl ) phthal ate
4-Bromophenyl phenyl ether
2-Chl oronaphthal ene
4-Chlorophenyl phenyl ether
Chrysene
4, 4 '-ODD
4,4'-DDE
4, 4 '-DDT
Dlbenzo (a, h) anthracene
Dl-n-butyl phthalate
1 , 2-D1 chl orobenzene
1 , 3-D1 chl orobenzene
1,4-01 chl orobenzene
3,3'-D1chlorobenz1d1ne
Dleldrln
D1 ethyl phthalate
Dimethyl phthalate
2,4-D1n1trotoluene
2,6-D1n1trotoluene
01 -n-octyl phthal ate
Endosulfan sulfate
Endrln aldehyde
Fluoranthene
Fluorene
Heptachlor
Heptachlor epoxlde
Hexachl orobenzene
Hexach 1 orobutadl ene
Hexachl oroethane
Test
cone.
(ug/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
100
Limit
for s
(ug/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
(ug/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
                                   8250 - 22
                                                          Revision      0
                                                          Date  September  1986

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TABLE 6.  QC ACCEPTANCE CRITERIA3 - Continued
Parameter
Indeno (1, 2 ,3-cd)pyrene
Isophorone
Naphthalene
Nitrobenzene
N-N1 troso-d1 -n-propyl ami ne
PCB-1260
Phenanthrene
Pyrene
1,2,4-Trlchlorobenzene
4-Chl oro-3-methyl phenol
2-Chlorophenol
2,4-Chlorophenol
2,4-01 methyl phenol
2,4-D1n1trophenol
2-Methyl -4, 6-d1 n1 trophenol
2-N1trophenol
4-N1 trophenol
Pentachlorophenol
Phenol
2,4,6-Trlchlorophenol
Test
cone.
(ug/L)
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
Limit
for s
(ug/L)
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
Range
for 7.
(ug/L)
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
Range
P, Ps
(%)
D-171
21-196
21-133
35-180
D-230
D-164
54-120
52-115
44-142
22-147
23-134
39-135
32-119
D-191
D-181
29-182
D-132
14-176
5-112
37-144
      s  =  Standard deviation  of four recovery measurements,  1n  ug/L.

      7  =  Average recovery for four recovery measurements,  1n ug/L.

      p, ps = Percent recovery measured.

      D  =  Detected;  result must be greater than  zero.

      aCn'ter1a 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.
                                   8250 - 23
                                                          Revision
                                                          Date  September 1986

-------
         1 to 5 times higher  than the background concentration determined 1n
         Section 8.6.2, whichever concentration would be larger.

              8.6.1.2  If the  concentration  of  a  specific  analyte in the
         sample is  not  being  checked  against  a  limit  specific  to that
         analyte, the spike should be at 100 ug/L or 1 to 5 times higher than
         the background concentration determined  in Section 8.6.2, whichever
         concentration would be larger.

              8.6.1.3  If it 1s  impractical  to  determine background levels
         before spiking (e.g., maximum  holding  times will be exceeded), the
         spike concentration should  be  at  (1) the regulatory concentration
         limit, if any; or, if none  (2)  the larger of either 5 times higher
         than the expected background concentration or 100 ug/L.

         8.6.2  Analyze  one  sample  aliquot  to  determine  the  background
     concentration  (B) of each analyte.   If necessary, prepare a new QC check
     sample  concentrate   (Section  8.5.1)   appropriate  for  the  background
     concentration  in the sample.  Spike  a second sample aliquot with 1.00 mL
     of  the QC  check  sample  concentrate  and  analyze  it  to determine the
     concentration  after spiking  (A) of  each analyte.  Calculate each percent
     recovery  (p) as 100(A-B)%/T,  where  T  is  the  known  true value of the
     spike.

         8.6.3   Compare the percent recovery   (p)  for  each analyte with the
     corresponding  QC acceptance  criteria found  In Table 6.  These acceptance
     criteria  were  calculated  to  include an allowance for error  1n measurement
     of  both  the  background   and  spike  concentrations,   assuming a spike to
     background  ratio of 5:1.   This  error  will  be accounted  for to the extent
     that the  analyst's  spike  to  background  ratio approaches 5:1.   If  spiking
     was performed  at a  concentration   lower  than   100  ug/L, the analyst must
     use either  the QC  acceptance  criteria  presented  in Table  6,  or optional
     QC  acceptance  criteria calculated   for  the specific spike  concentration.
     To  calculate optional  acceptance  criteria  for the  recovery  of  an analyte:
     (1)  Calculate  accuracy   (x1)   using   the  equation   found  in  Table  7,
     substituting the  spike  concentration   (T)   for  C;  (2)  calculate  overall
     precision (S1)  using  the  equation  in   Table 7,  substituting x1  for 7;  (3
     calculate the  range  for recovery   at  the  spike  concentration as  (lOOx'/T
     + 2.44(100S'/T)%.

          8.6.4   If any individual  p  falls  outside  the designated  range for
     recovery, that analyte  has   failed  the   acceptance   criteria.    A  check
     standard  containing   each  analyte  that   failed   the  criteria   must  be
     analyzed as described 1n  Section  8.7.

     8.7  If any analyte fails the acceptance  criteria  for  recovery 1n  Section
8.6, a QC check  standard containing  each  analyte that  failed must  be prepared
and analyzed.
     NOTE:   The  frequency  for  the  required  analysis   of  a QC  check standard
     will depend upon  the  number  of analytes  being  simultaneously  tested,  the
     complexity  of the  sample  matrix,  and  the  performance of the laboratory.
                                  8250 - 24
                                                         Revision      0
                                                         Date  September 1986

-------
TABLE 7.  METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION3
Parameter
Acenaphthene
Acenaphthylene
Aldrin
Anthracene
Benzo (a) anthracene
Chloroethane
Benzo (b) f 1 uoranthene
Benzo (k) f 1 uoranthene
Benzo(a)pyrene
Benzo (ghi ) pery 1 ene
Benzyl butyl phthalate
0-BHC
5-BHC
Bi s (2-chl oroethyl ) ether
Bi s (2-chl oroethoxy) methane
Bi s (2-chl orol sopropyl ) ether
B1 s (2-ethyl hexyl )phthal ate
4-Bromophenyl phenyl ether
2-Chl oronaphthal ene
4-Chlorophenyl phenyl ether
Chrysene
4,4'-DDD
4,4'-DDE
4,4'-DDT
Dibenzo(a,h)anthracene
Di-n-butyl phthalate
l,2-D1chlorobenzene
1 , 3-Di chl orobenzene
1 , 4-D1 chl orobenzene
3 , 3 ' -Di chl orobenzi d1 ne
Dieldrin
Di ethyl 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
Hexachl orobutadi ene
Hexachl oroethane
Accuracy, as
recovery, x1
(ug/L)
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
Single analyst
precision, sr'
(ug/L)
0.157-0.12
0.247-1.06
0.277-1.28
0.217-0.32
0.157+0.93
0.147-0.13
0.227+0.43
0.197+1.03
0.227+0.48
0.297+2.40
0.187+0.94
0.207-0.58
0.347+0.86
0.357-0.99
0.167+1.34
0.247+0.28
0.267+0.73
0.137+0.66
0.077+0.52
0.207-0.94
0.287+0.13
0.297-0.32
0.267-1.17
0.427+0.19
0.307+8.51
0.137+1.16
0.207+0.47
0.257+0.68
0.247+0.23
0.287+7.33
0.207-0.16
0.287+1.44
0.547+0.19
0.127+1.06
0.147+1.26
0.217+1.19
0.127+2.47
0.187+3.91
0.227-0.73
0.127+0.26
0.247-0.56
0.337-0.46
0.187-0.10
0.197+0.92
0.177+0.67
Overall
precision,
S1 (ug/L)
0.217-0.67
0.267-0.54
0.437+1.13
0.277-0.64
0.267-0.21
0.177-0.28
0.297+0.96
0.357+0.40
0.327+1.35
0.517-0.44
0.537+0.92
0.307+1.94
0.937-0.17
0.357+0.10
0.267+2.01
0.257+1.04
0.367+0.67
0.167+0.66
0.137+0.34
0.307-0.46
0.337-0.09
0.667-0.96
0.397-1.04
0.657-0.58
0.597+0.25
0.397+0.60
0.247+0.39
0.417+0.11
0.297+0.36
0.477+3.45
0.267-0.07
0.527+0.22
1.057-0.92
0.217+1.50
0.197+0.35
0.377+1.19
0.637-1.03
0.737-0.62
0.287-0.60
0.137+0.61
0.507-0.23
0.287+0.64
0.437-0.52
0.267+0.49
0.177+0.80
                                   8250 - 25
                                                          Revision       0
                                                          Date   September  1986

-------
TABLE 7.  METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION3 -
           Continued
Parameter
Indeno (1 , 2 , 3-cd) py rene
Isophorone
Naphthalene
Nitrobenzene
N-N1 troso-d1 -n-propy 1 ami ne
PCB-1260
Phenanthrene
Pyrene
1,2, 4-Tr1 chl orobenzene
4-Chl oro-3-methyl phenol
2-Chlorophenol
2,4-D1chlorophenol
2, 4-D1methyl phenol
2,4-D1n1trophenol
2-Methyl -4, 6-d1 n1 trophenol
2-N1trophenol
4-N1 trophenol
Pentachlorophenol
Phenol
2,4,6-Trichlorophenol
Accuracy, as
recovery, x'
(ug/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, sr'
(ug/L)
0.297+1.46
0.277+0.77
0.217-0.41
0.197+0.92
0.277+0.68
0.357+3.61
0.127+0.57
0.167+0.06
0.157+0.85
0.237+0.75
0.187+1.46
0.157+1.25
0.167+1.21
0.387+2.36
0.107+42.29
0.167+1.94
0.387+2.57
0.247+3.03
0.267+0.73
0.167+2.22
Overal 1
precision,
S' (ug/L)
0.507-0.44
0.337+0.26
0.307-0.68
0.277+0.21
0.447+0.47
0.437+1.82
0.157+0.25
0.157+0.31
0.217+0.39
0.297+1.31
0.287+0.97
0.217+1.28
0.227+1.31
0.427+26.29
0.267+23.10
0.277+2.60
0.447+3.24
0.307+4.33
0.357+0.58
0.227+1.81
     x1  = Expected  recovery  for  one  or • more  measurements  of  a  sample
           containing a concentration of C, 1n ug/L.
                                        -i-      '
     sr' = Expected single analyst  standard  deviation  of measurements at an
           average concentration of 7, 1n ug/L.

     S1  = Expected Interlaboratory standard  deviation  of measurements at an
           average concentration found of 7, 1n ug/L.

     C   = True value for the concentration, 1n ug/L.

     7   = Average recovery found for measurements of samples containing a
             concentration of C, in ug/L.
                                  8250 - 26
                                                         Revision      0
                                                         Date  September 1986

-------
     If the entire  11st of analytes  1n  Table 6 must be measured 1n the sample
     1n Section  8.6,  the probability that  the analysis of a QC check standard
     will  be  required 1s high.   In   this  case the QC check standard should be
     routinely analyzed with  the spiked sample.

          8.7.1   Prepare the  QC check  standard   by  adding  1.0  ml of the QC
     check sample concentrate  (Section  8.5.1  or  8.6.2)  to  1 L of reagent
     water.   The QC check   standard  needs   only  to contain the analytes  that
     failed criteria in the test 1n  Section  8.6.

          8.7.2   Analyzed  the QC check standard to determine the concentration
     measured (A) of each  analyte.     Calculate   each percent  recovery  (Ps) as
     100  (A/T)%, where T  1s the true value of the standard  concentration.

          8.7.3   Compare  the  percent recovery  (Ps)   for each  analyte with the
     corresponding QC acceptance criteria   found  In  Table 6.  Only analytes
     that failed the  test  1n  Section  8.6  need   to   be  compared with  these
     criteria.    If  the   recovery  of  any   such  analyte   falls  outside the
     designated  range, the laboratory   performance   for that analyte  1s judged
     to be out  of control,  and  the problem must  be  Immediately Identified and
     corrected.   The result for that analyte in  the  unspiked sample  1s  suspect
     and may not be reported  for regulatory compliance  purposes.

     8.8  As part of the  QC  program  for   the laboratory,  method  accuracy for
each matrix studied must  be  assessed  and  records  must be maintained.   After
the analysis of five spiked samples  (of  the  same  matrix) as in  Section 8.6,
calculate the average percent recovery  (p)   and the standard  deviation of the
percent recovery (sp).  Express the  accuracy assessment as a  percent  recovery
Interval  from p - 2sp to  p + 2sp.   If  p  = 90%  and sp  = 10%,  for  example, the
accuracy Interval is expressed as 70-110%.   Update  the  accuracy assessment for
each analyte on a regular  basis  (e.g.   after  each  five  to  ten  new accuracy
measurements).

     8.9  To determine acceptable accuracy  and  precision limits for surrogate
standards the following procedure should be performed.

          8.9.1  For each sample analyzed,   calculate  the percent recovery of
     each surrogate  1n the sample.

          8.9.2  Once a minimum of  thirty samples of the same matrix have been
     analyzed,   calculate  the  average  percent  recovery  (P)  and  standard
     deviation  of  the percent  recovery (s)  for each of the surrogates.

          8.9.3  For a given   matrix,  calculate  the  upper and lower control
     limit for  method performance for each  surrogate standard.  This should be
     done as follows:

                Upper Control  Limit  (UCL) =  P + 3s
                Lower Control  Limit  (LCL) =  P - 3s
                                   8250 - 27
                                                          Revision
                                                          Date   September 1986

-------
          8.9.4   For  aqueous  and   soil  matrices, these laboratory established
     surrogate control  limits  should,  if  applicable,  be  compared with the
     control  limits listed  in Table 8.  The limits given in Table 8 are multi-
     laboratory  performance based  limits  for   soil  and aqueous samples, and
     therefore,  the single-laboratory   limits   established  in  Paragraph 8.9.3
     must fall within those given  in Table 8 for these matrices.

          8.9.5   If recovery  is not  within  limits, the following procedures
     are required.

               •  Check to  be  sure  there  are no errors   in calculations,
                  surrogate solutions   and   internal  standards.   Also, check
                  instrument  performance.

               •  Recalculate the  data  and/or reanalyze  the  extract  1f any  of
                  the above checks reveal  a  problem.

               •  Reextract and reanalyze  the sample  if none of the  above are
                  a problem or flag  the data as "estimated  concentration."

          8.9.6  At  a  minimum,   each    laboratory  should  update   surrogate
     recovery limits  on a matrlx-by-matrix basis, annually.

     8.10  It is  recommended  that   the  laboratory  adopt additional  quality
assurance practices for use with this method.   The  specific practices that are
most productive depend upon the needs of  the  laboratory and  the nature of the
samples.  Field duplicates may  be   analyzed   to  assess  the precision of the
environmental measurements.  When   doubt  exists  over the  identification  of a
peak on the chromatogram,  confirmatory  techniques such as gas chromatography
with a dissimilar column  or  mass  spectrometry  using other ionization modes
must be used.    Whenever  possible,   the  laboratory  should analyze standard
reference  materials  and  participate    in  relevant  performance  evaluation
studies.
9.0  METHOD PERFORMANCE

     9.1  Method 8250 was  tested  by  15  laboratories  using reagent water,
drinking water,  surface  water,  and  Industrial  wastewaters  spiked at six
concentrations over the range  5-1,300  ug/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.
                                  8250 - 28
                                                         Revision      0
                                                         Date  September 1986

-------
TABLE 8.  SURROGATE SPIKE RECOVERY LIMITS FOR WATER AND SOIL/SEDIMENT SAMPLES

                                     Low/Medium                Low/Medium
   Surrogate Compound                   Water                 Soil/Sediment


Nitrobenzene-ds                        35-114                    23-120
2-Fluorobiphenyl                       43-116                    30-115
p-Terphenyl-di4                        33-141                    18-137

Phenol-d6                              10-94                     24-113
2-Fluorophenol                         21-100                    25-121
2,4,6-Tribromophenol                   10-123                    19-122
                                  8250 - 29
                                                         Revision
                                                         Date  September  1986

-------
2.  U.S. EPA  Contract  Laboratory  Program,  Statement  of  Work  for Organic
Analysis, July 1985, Revision.

3.  Provost, L.P. and R.S.  Elder,  "Interpretation of Percent Recovery Data,"
American Laboratory, lj>, 58-63, 1983.

4.  Elchelberger, J.W., L.E. Harris,  and  W.L.  Budde, "Reference Compound to
Calibrate Ion Abundance  Measurement  1n  Gas Chromatography-Mass Spectrometry
Systems," Analytical Chemistry, 47, 995-1000, 1975.

5.  "Method Detection Limit for Methods 624  and 625," Olynyk, P., W.L. Budde,
and J.W. Elchelberger, Unpublished report, October 1980.

6.  "Interlaboratory Method Study for EPA Method 625-Base/Neutrals, Adds, and
Pesticides," Final Report for  EPA. Contract 68-03-3102  (1n preparation).

7.  Burke, J.A.   "Gas  Chromatography  for   Pesticide  Residue  Analysis; Some
Practical  Aspects,"  Journal  of   the  Association   of  Official  Analytical
Chemists, 48, 1037, 1965.
                                   8250 - 30
                                                          Revision
                                                          Date  September 1986

-------
                           METHOD easo

 GAS CMROMATOGRAPHY/MASS SPECTROMETRY FOR SEMIVOLATILE  ORGANICS:

                     PACKED COLUMN TECHNIQUE
7. t
Prepare ••tuple
 using Method
 3540 or 3SSO
                                                    7. 1
Prepare sample
 using Method
 3510 or 3520
                          7.1  |

                              Prepare
                           •ample  using
                           Method  3540.
                           3SSO  or 3580
                          7.2
                         Cleanup  extract
                          7.3
                               Set GC/MS
                              operating
                          conditions ana
                         perform  initial
                            calibration
                       7.4
                       Perform daily GC/MS
                         calibration -1th
                       SPCCs  ana CCC» prior
                          to  analysis of
                             samples
                            o
                   8250 -  31
                                              Revision        0
                                              Date  September 1986

-------
                                           METHOD 8250

                 GAS CMROMATOGRAPHY/MASS SPECTROMETRY FOR SEMIVOLATILE ORCANICS:

                                     PACKED COLUMN TECHNIQUE
                                           (Continued)
      o
  7.5.1
    0
         Screen
         extract
     on GC/FID or
  GC/PIO to elim-
   inate too-high
    concentration
7.5
7.6. 1
       Identify
       analyte
   by comparing
 the sample and
  standard mass
       spectra
 Analyze extract by
    GC/MS using
  silicone-coated
   fused—s ilica
 capillary column
                                                                               7.6.2
      Calculate
  concentration
      of each
    identified
      analyte
   Does  response
   exceed initial
    calibration
      curve
      range
                                                                               7.6.2.4
Report results
                                                                              f     Stop       J
                                       8250 - 32
                                                                  Revision       o
                                                                  Date   September 1986

-------
                                    METHOD  8260
&
         GAS CHROMATOGRAPHY/MASS SPECTROMETRY FOR VOLATILE
*                         CAPILLARY  COLUMN TECHNIQUE
S'v^
 l!o- 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
                   Benzene
                   Bromobenzene
                   Bromochloromethane
                   Bromodichloromethane
                   Bromoform
                   Bromomethane
                   n-Butylbenzene
                   sec-Butyl benzene
                   tert-Butylbenzene
                   Carbon tetrachloride
                   Chlorobenzene
                   Chloroethane
                   Chloroform
                   Chloromethane
                   2-Chlorotoluene
                   4-Chlorotoluene
                   Di bromochloromethane
                   1,2-Dibromo-3-chloropropane
                   1,2-Dibromoethane
                   Dibromomethane
                   1,2-Dichlorobenzene
                   1,3-Dichlorobenzene
                   1,4-Dichlorobenzene
                   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
                   1,1-Dichloropropene
                   Ethyl benzene
                   Hexachlorobutadiene

                                     8260  -  1
                                                    CAS No.
                                                     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
                                                    156-69-4
                                                    156-60-5
                                                     78-87-5
                                                    142-28-9
                                                    594-20-7
                                                    563-58-6
                                                    100-41-4
                                                     87-68-3
                                                                  Revision 1
                                                                  December 1988

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               Analyte                             CAS No.a


               Isopropylbenzene                     98-82-8
               p-Isopropyltoluene                   99-87-6
               Methylene chloride                   75-09-2
               Naphthalene                          91-20-3
               n-Propylbenzene                     103-65-1
               Styrene                             100-42-5
               1,1,1,2-Tetrachloroethane           630-20-6
               1,1,2,2,-Tetrachloroethane           79-34-5
               Tetrachloroethene                   127-18-4
               Toluene                             108-88-3
               T,2.3-Trichlorobenzene               87-61-6
               1,2,4-Trichlorobenzene              120-82-1
               1,1,1-Trichloroethane                71-55-6
               1,f,2-Trichloroethane                79-00-5
               Trichloroethene                      79-01-6
               Trichlorofluoromethane               75-69-4
               1,2,3-Trichloropopane •               96-18-4
               1,2,4-Trimethylbenzene               95-63-6
               1,3,5-Trimethylbenzene              108-67-8
               Vinyl  chloride                      75-01-4
               o-Xylene                            95-47-6
               m-Xylene                           108-38-3
               p-Xylene                           106-42-3


               aChemical Abstract  Services  Registry Number.

    1.2  Method 8260 can be  used  to quantify 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  practical  quantitation  limit  (PQL)  of  Method 8260  for  an
individual compound  is  approximately  5 ug/kg  (wet  weight)  for soil/sediment
samples, 0.5 mg/kg (wet weight) for wastes,  and 5 ug/L for ground water (see
Table 3). PQLs 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.

                                  8260  -  2                       Revision 1
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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 diretly  to a  large bore capillary  or cryofocussed  on  a capillary
precolumn  before  being  flash  evaporated  to  a  narrow  bore capillary  for
anaylsis. 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 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 quantified 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.  Analyse? of calibration  and reagent  blanks provide  information
about the presence of contaminants.  When potential  interfering peaks  are noted
in blanks, the  analyst  should change  the purge gas source and regenerate the
molecular  sieve  purge  gas  filter  (Figure  1).  Subtracting  blank values  from
sample results is not permitted.  If reporting values not corrected  for blanks
result  in  what the  laboratory  feels  is a  false  positive for a sample,  this
should be fully explained in text  accompanying the uncorrected data.

    3.2  Interfering contamination  may occur  when  a  sample containing low
concentrations of  volatile  organic  compounds  is analyzed immediately after a
sample  containing  high  concentrations  of volatile  organic  compounds.  The
preventive technique is rinsing of the purging apparatus and  sample  syringes
with  two portions  of 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 levels  of compounds being  determined,  it may be
necessary  to .wash  the  purging device  with   a  soap  solution, rinse  it  with
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

                                  8260 - 3                        Revision  1
                                                                 December  1988

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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  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
    contain  the following amounts  of absorbents: 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

                                  8260 - 4                       Revision 1
                                                                 December 1988

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    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:  uncharaceristic recoveries of surrogates, especially toluene-ds;
    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-Di phenyl ene  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.

    4.2  Heater or  heated oil   bath  - Should  be  capable  of maintaining  the
purging chamber to within laC over  the  temperature range  of  ambient to  100°C.

    4.3  Gas chromatography/mass spectrometer/data system

         4.3.1   The  GC must be  capable of temperature programming and 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  subambient  oven  controller may
    be required. 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
    Step 8.2.4 can be achieved.

         4.3.2  Gas   chromatographic  column  1  -  60  m  x 0.75  mm  i.d. VOCOL
    (Supelco)  wide bore capillary column with 1.5 urn film thickness. The  flow
    rate  of helium  carrier gas   is  established at  15 mL/min.  The  column
    temperature is held  for 5  minutes  at 10"C,  then programmed  to  160°C at
    6°C/min,  and held  until   all  expected  compounds  have  eluted.  A sample
    chromatogram obtained with  this column is presented  in  Figure 5.

         4.3.3   Gas   chromatographic  column  2 -  30  m x 0.53  mm  i.d.  DB-624
    wide-bore (J&W Scientific)  column with 3  urn  film thickness.

                                 8260  - 5                      Revision  1
                                                                December  1988

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          4.3.3.1   Cryogenic  cooling  -  Helium  carrier  gas  flow  is
     15 mL/min.  The column  temperature  is held for  5 minutes at 10°C, then
     programmed  to 1608C at 6"C/min. A sample  chromatogram obtained with
     this column is presented  in  Figure 6.

          4.3.3.2   Non-cryogenic  cooling  -  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  interst.  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.  The  column  temperature   is  held  for  2  minutes  at  458C,  then
     programmed  to  200°C  at  8°C/min,  and held  for 6 minutes.  A sample
     chromatogram  is  presented   in  Figure  7.  A trap  preheated  to  1508C
     prior  to  trap desorption   is  required  to   provide  adequate
     chromatography of the  gas analytes.

     4.3.4  Gas  chromatographic column  3  - 30 m  x  0.32 mm  i.d.  fused
silica capillary column  coated with Durabond DB-5  (J&W Scientific) with a
1 urn  film  thickness.  Helium carrier gas flow is  4 mL/min.  The column  is
maintained  at  10°C  for  5 minutes,  then  programmed  at  6°C/min for
10 minutes  then 15°C/min   for 5  minutes  to 1458C.  A sample chromatogram
obtained with this column  is presented  in  Figure 8.

     4.3.5  Mass  spectrometer - Mass  spectral  data  are  obtained  with
electron impact  ionization  at  a  nominal  electron energy of  70 eV.  The mass
spectrometer must be  capable  of  scanning  from  35 to  300  amu  every
2 seconds or less  and must  produce  a mass  spectrum  that meets all  criteria
in Table 4 when 50 ng of  4-bromofluorobenzene  is introduced into 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.  Injector  temperature  should be  200-225°C and
transfer line temperature,  250-3008C.   This  includes,  but is not  limited
to quadrupole,  magnetic, ion trap,  time of fight,  and  mixed  analyzer  (i.e.
combined analyzers such  as  magnetic and quadrupole)  mass  spectrometers.

     4.3.6  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  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 i.d.).
                              8260 -  6                        Revision  1
                                                             December  1988

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         4.3.7  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
    NBS/EPA Mass Spectral  Library should also be available.

    4.4  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.

         4.4.1  Under a  stream of  liquid  nitgrogen, the  temperature  of the
    fused   silica  in  the interface  is maintained  at   -1508C  during  the
    cryofocussing step. 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.

    4.5  Microsyringes - 10,  25, 100,  250,  500,  and 1,000-uL.

    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,   capable  of accurately weighing 0.0001 g, and  a
top-loading balance  capable of  weighing  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.

5.0 REAGENTS

    5.1  Methanol, CHsOH.   Pesticide quality  or  equivalent, demonstrated to be
free of analytes. Store apart from other solvents.

    5.2  Reagent Tetraglyme  -  Reagent tetraglyme is  defined as tetraglyme in
which interference  is not  observed  at the method  detection limit  of  compounds
of interest.

    CAUTION: Glycolethers  are  suspected  carcinogens.   All  solvent  handling
             should be done  in  a hood while  using proper  protective  equipment
             to minimize exposure to liquid and  vapor.

                                  8260 - 7                        Revision  1
                                                                 December 1988

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         5.2.1  Tetraglyme (tetraethylene glycol  dimethyl  ether, Aldrich #17,
    240-5 or equivalent), CsHisOs. 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).

    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.

         5.2.2  In order  to  demonstrate that  all  interfering  volatiles have
    been  removed  from  the   tetraglyme, a  water/tetraglyme   blank  must  be
    analyzed.

    5.3  Polyethylene  glycol, reagent   grade.  Free of interferences  at the
detection limit of the analytes.

    5.4  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.

    5.5  Hydrochloric  acid  (1:1),  HCL.  Carefully  add  a measured  volume of
concentrated HCL to an equal  volume of water.

    5.6  ASTM Type II  Water (ASTM Dll93-77 (1983)).  All references to  water in
the method  refer  to ASTM Type II unless otherwise specified. Must be free of
interferents at the method detection  limit (MDL) of the analytes  of  interest.
ASTM Type II water is  further purified by any of the following techniques:

         5.6.1  Water may  be  generated  by passing  tap water through  a  carbon
    filter  bed  containing about  450 g  of  activated carbon   (Calgon  Corp.,
    Filtrasorb-300 or equivalent).

         5.6.2  A water  purification  system  (Millipore  Milli-Q  Plus with the
    Organex-Q cartridge or equivalent) may be used  to  generate water.

         5.6.3  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.  While it  is still
    hot, transfer the water to a narrow-mouth screw-cap  bottle and seal  with  a
    Teflon lined septum and cap.

                                  8260 - 8                       Revision  1
                                                                 December  1988

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    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 0.1  mg.

         5.7.2  Add the assayed reference material,  as  described below.

              5.7.2.1   Liquids - Using a 100-uL  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  Gasses  -  To prepare  standards  for any compounds  that
         boil  below 308C  (e.g. bromomethane, chloroethane, chloromethane,  or
         vinyl  chloride),  fill  a 5-mL  valved  gas-tight syringe  with the
         reference standard to the 5.0-mL mark.  Lower the  needle to 5 mm  above
         the methanol meniscus. Slowly introduce the reference standard  above
         the surface of the liquid. The heavy gas will  rapidly dissolve  in the
         methanol. Standards  may  also be prepared  by  using a lecture  bottle
         equipped  with a  Hamilton  Lecture  Bottle  Septum  (#86600). Attach
         Teflon tubing to the side arm relief valve and direct a gentle  stream
         of gas into the methanol  meniscus.

         5.7.3  Reweigh, dilute to Volume, stopper,  and then  mix  by inverting
    the  flask several   times.  Calculate  the concentration in micrograms per
    micro!iter  (ug/uL)  from the net gain  in weight.  When compound  purity  is
    assayed to be 90% 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.                                                I

         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-chloroethylvinyl ether and  styrene may need  to  be prepared more
    frequently.  All  other  standards  must be  replaced after  six months,  or
    sooner  if  comparison  with check  standards  indicates  a problem.  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.

    5.8  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

                                  8260 -  9                      Revision 1
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degradation  or  evaporation,  especially  just  prior to  preparing  calibration
standards from them.  Store  in a  vial with no headspace for one week only.

    5.9  Surrogate standards  -  The surrogates  recommended  are  toluene-ds,
4-bromofluorobenzene,  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  Step  5.7,  and  a
surrogate  standard spiking  solution should be prepared  from the stock  at  a
concentration of  50-250  ug/10  ml  in  methanol.  Each sample  undergoing  GC/MS
analysis must be spiked with 10 uL of the surrogate spiking solution prior to
analysis.

    5.10 Internal  standards  -  The  recommended  internal  standards  are
chlorobenzene-ds,   1, 4-dif1uorobenzene,  1, 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 Steps 5.7 and  5.8.  It is  recommended that
the  secondary, dilution  standard  should be prepared  at a  concentration  of
25  ug/mL  of  each internal  standard  compound.   Addition  of 10  uL  of this
standard to  5.0 ml of sample  or calibration standard  would  be the equivalent
of 50 ug/L.

    5.11 4-Bromofluorobenzene (BFB) standard -  A  standard solution containing
25 ng/uL of BFB in methanol  should be  prepared.

    5.12 Calibration  standards  -  Calibration  standards  at a  minimum of five
concentration levels  should be  prepared from the  secondary  dilution of stock
standards  (see  Steps  5.7  and 5.8). Prepare these  solutions  in  water. One of
the  concentration  levels  should  be at  a concentration  near, but  above,  the
method  detection  limit.  The remaining concentration levels  should correspond
to the  expected range of concentrations found  in  real  samples 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  ug/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.
                                 8260 - 10                   .    Revision  1
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6.0 SAMPLE COLLECTION, PRESERVATION,  AND HANDLING

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

7.0 PROCEDURE

    7.1  Direct injection -  In very  limited appliations  (e.g. aqueous  process
wastes) direct  injection of  the  sample into  the  GC/MS system with  a 10 uL
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 ug/L); therefore, it is only permitted when  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 using  the  same  solvent  (e.g.
water)  for  standards  as  the sample  matrix  (bypassing the  purge-and-trap
device).

    7.2  Initial calibration for purge-and-trap procedure
               t
         7.2.1  Each  GC/MS system must  be hardware-tuned to  meet  the  criteria
    in Table 4  for  a  50 ng  injection or purging of 4-bromofluorobenzene  (2 uL
    injection  of  the BFB  standard).   Analyses  must  not  begin  until  these
    criteria are met.

         7.2.2  Assemble a purge-and-trap device that  meets  the specification
    in Step  4.1. 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 minutes while backflushing  at  180'C  with the column  at 220°C.

         7.2.3  Connect  the purge-and-trap device  to  a gas  chromatograph.

         7.2.4  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 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  uL of  internal  standard.
    Then transfer the contents to a purging  device.

         7.2.5  Carry  out  the purge-and-trap  analysis procedure  as  described
    in Step 7.4.1.

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     7.2.6  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 (Step 7.5.2).
The RF is calculated as  follows:

     RF =  (AxCis)/(AisCx)

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.

     Cx  = Concentration of the  compound being measured.

     7.2.7  The  average  RF must  be  calculated  for  each compound  and
recorded on  Form  VI  (see  Chapter  One).  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-tetrachlor.oethane,  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
occurences are:

           7.2.7.1  Chloromethane  -  This   compound  is the  most  likely
     compound to be lost if the  purge  flow  is  too  fast.

           7.2.7.2  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.

           7.2.7.3  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.

     7.2.8  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  on  Form VI   (see Chapter One).
The percent RSD is calculated  as follows:


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                                                            December 1988

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          %RSD =  SD  13 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.
                   N        - 2
          SD  =       (x  - x)*
                  1-1 -R-T-T-
                                              •
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.

If  the CCCs  are not  required  analytes  by the permit,  then  all   required
analytes must meet the 30% RSD criterion.

    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 4  before  sample  analysis begins.
    These criteria must be demonstrated each 12-hour shift.

         7.3.2   The  initial  calibration  curve  (Step 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 (Step 7.3.3)  and CCC (Step 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
    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 degration,  injection port inlet
    contamination,  contamination  at  the  front  end  of  the  analytical  column,
    and active sites in the column or chromatographic system.

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     7.3.4  Calibration Check Compounds  (CCCs)  -  After the  system
performance check is  met, CCCs  listed  in Step 7.2.8 are used to check the
validity  of the  initial  calibration. Calculate  the  percent difference
using the following equation:
% Difference = -— ----- -  x  100
                          - RF


                         RF
                           ,

 where:

      RFj = 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.

     7.3.5  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
chromatograhic system must be  inspected for malfunctions and  corections
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  (BCD), and extraction  of the  sample with

                             8260 - 14                       Revision  1
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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 analyses.

     7.4.1.3  Set up the GC/MS system as outlined  in Step 4.3.

     7.4.1.4  BFB  tuning  criteria  and  daily  GC/MS  calibration
criteria must be met (Step 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 Step 7.2.7)-.

     7.4.1.6  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 VGA 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 water to be
     added  to  the  volumetric  flask selected  and  add  slightly  less
     than this quantity of water to the flask.

          7.4.1.7.3   Inject  the  proper  aliquot of  samples from  the
     syringe prepared  in Step  7.4.1.6   into the  flask. Aliquots  of
     less  than  1 ml are  not recommended.   Dilute  the  sample  to  the
     mark with water.  Cap the flask, invert,  and  shake three times.
     Repeat above procedure  for additional  dilutions.


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          7.4.1.7.4   Fill  a 5-mL syringe with the  diluted  sample  as
     in Step  7.4.1.6.

7.4.1.8.  Compositing  samples prior to GC/MS analysis

          7.4.1.8.1   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.

          7.4.1.8.2   The  samples must  be cooled at  4°C  during  this
     step to  minimize volatilization  losses.

          7.4.1.8.3   Mix  well  and draw  out  a  5  ml  aliquot  for
     analysis.

          7.4.-1.8.4    Follow  sample  introduction,  purging,  and
     desorption steps described  in the method.

          7.4.1.8.5    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.

     7.4.1.9   Add 10.0  uL  of  surrogate  spiking solution  (Step  5.9)
and 10 uL  of  internal  standard  spiking  solution (Step 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  ug/L  of each
surrogate standard.

     7.4.1.10 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.

     7.4.1.11 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.

     7.4.1.12 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  Step  7.4.1.13.  The conditions for  using  narrow  bore
columns are described in Step  7.4.1.14.

     7.4.1.13 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.

          7.4.1.13.1   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

                        8260 -  16                      Revision 1
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     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 or  25  ml portions  of 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.

          7.4.1.13.2    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.

          7.4.1.13.3   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.

     7.4.1.14    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.

          7.4.1.14.1  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).  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  or 25 ml
     portions  of 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.

          7.4.1.14.2    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


                        8260  - 17                       Revision  1
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          flow through the trap. When  the  trap is cool,  the  next  sample
          can  be  analyzed.

          7.4.1.15  If the  initial  analysis  of the  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 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.

          7.4.1.16  For matrix  spike analysis,  add  10  uL of the  matrix
     spike solution  (Step  5.13) to  the 5  mL of sample purged. Disregarding
     any dilutions,  this  is  equivalent to  a concentration of 50 ug/L of
     each matrix  spike standard.

          7.4.1.17  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 Steps  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  water.

          7.4.2.2  Initial  and  serial  dilutions  can be  prepared  by
     pipeting  2 mL  of the  sample  to a 100-mL  volumetric  flask and diluting
     to  volume with  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 water  by  adding  at least 20 uL, but not  more than
     100-uL 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 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-Jevel   method  (0.005-1  mg/kg)  or  the high-level  method
(> 1 mg/kg).

          7.4.3.1  Low-level  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-level  method is  based on  purging a

                             8260 - 18                      Revision 1
                                                            December 1988

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heated sediment/soil  sample mixed with 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.

          7.4.3.1.1   Use a 5 g sample  if  the  expected concentration
     is  <  0.1 mg/kg  or a  1 g  sample for expected  concentrations
     between 0.1  and  1  mg/kg.

          7.4.3.1.2   The GC/MS system  should  be set  up  as  in  Steps
     7.4.1.3-7.4.1.4. 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-
     level  methoxl.  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  (Step 5.9)  and  internal  standard
     solution (Step  5.10) 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  ug/kg 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 Step
     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  moisture  of  the
     soil/sediment  sample.  This  includes  waste  samples  that  are
     amenable to moisture  determination.  Other  wastes  should  be
     reported on a wet-weight  basis.  Immediately  after weighing the
     sample, weigh  (to  0.1 g) 5-10  g of additional sediment/soil into
     a tared crucible.  Dry  the  contents  of  the crucibles  overnight at
     105°C.  Allow  to  cool   in a desiccator  and  reweigh  the  dried
     contents. Concentrations of  individual  analytes will be reported
     relative to the dry weight of  sediment.

                     grams of sample -  grams of  dry sample
        % moisture  =	  x 100
                               grams  of sample

          7.4.3.1.6   Add the  spiked  water to the  purging device,
     which  contains  the weighed  amount  of sample,  and  connect  the
     device to the  purge-and-trap system.

                        8260 - 19                      Revision 1
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     NOTE:   Prior  to  the  attachment  of  the  purge  device,  the
            procedures  in  Steps 7.4.3.1.4  and  7.4.3.1.6  must  be
            performed rapidly and without interruption to avoid loss
            of volatile brganics. These steps must be performed in a
            laboratory  w°ee—&f  solvent  vapors.   There must  be  no
            solvents brought into the  lab  other than those used for
            extracting samples for  volatiles  or dissolving volatile
            standards  (i.e.  methanol ,  etc.).    It  is  highly
            recommended that GC and  GC/MS analysis  for pesticides and
            semivolatiles  be performed in  a  different  room to avoid
            high background  levels of  methylene  chloride  and  hexane.

          7.4.3.1.7   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.

          7.4.3.1.8  Proceed with the  analysis  as outlined in Steps
     7.4.1.12-7.4.1.17.  Use  5 ml of the  same water as in the  blank.
     If saturated peaks occurred  or  would occur if a 1 g sample were
     analyzed, the medium-level method  must be followed.

          7.4.3.1.9  For  low-level  sediment/soils,  add  10 uL  of the
     matrix spike  solution  (Step 5.7)  to  the  5 ml of  water  (Step
     7.4.3.1.3).  The  concentration  for  a  5  g  sample would  be
     equivalent to 50 ug/kg  of each  matrix  spike standard.

     7.4.3.2  High-level  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 tetraglyme or possibly polyethylene glycol   (PEG). An aliquot of
the extract  is  added  to 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.

          7.4.3.2.1  | 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
     moisture of  the sample using  the  procedure in Step  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.  Cap
     and shake for 2 minutes.

                        8260 - 20                       Revision 1
                                                        December 1988

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on
Vti
              NOTE:   Steps 7.4.3.2.1 and 7.4.3.2.2 must be performed rapidly
                     and  without  interruption  to avoid  loss of  volatile
                      jrganics. These steps must be performed in a laboratory
                           from  solvent vapors.   There must be  no  solvents
                     brought  into  the  lab  other  than  those  used  for
                     extracting samples for volatiles or dissolving volatile
                     standards  (i.e.  methanol,  etc.).    It  is  highly
                     recommended that  GC  and  GC/MS  analysis  for pesticides
                     and  semivolatiles  be  performed in a  different room to
                     avoid high  background  levels  of methylene chloride and
                     hexane.

                   7.4.3.2.3   Pipet  approximately 1 ml of the extract to a GC
              vial  for storage, using a disposable pipet. The remainder may be
              disposed. 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 uL aliquot of each of these
              extracts in  Step 7.4.3.2.6 will give  a  concentration equivalent
              to 6,200 ug/kg  of each surrogate standard.

                   7.4.3.2.4   The  GC/MS system should  be  set  up  as  in Steps
              7.4.1.3-7.4.1.4. This  should  be  done prior  to  the  addition of
              the solvent  extract to water.

                   7.4.3.2.5   The  following  information  can  be  used  to
              determine the  volume  of solvent  extract to add to  the 5 ml of
              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-level analysis to
              determine the appropriate volume.  If the sample was  submitted as
              a  medium-level   sample,  start  with  100 uL.  All  dilutions must
              keep  the  response  of the  major constituents  (previously
              saturated peaks) in  the upper half of  the linear range of the
              curve.

                QUANTITY OF EXTRACT  REQUIRED FOR ANALYSIS OF
                             HIGH-LEVEL SAMPLES

         ApproximateVolume of
     Concentration Range                        Extract3


         500- 10,000 ug/kg                       100 uL
       1,000- 20,000 ug/kg                        50 uL
       5,000-100,000 ug/kg                        10 uL
      25,000-500,000 ug/kg              100 uL of 1/50 dilution^


Calculate appropriate dilution factor for concentrations exceeding this  table.


                                 8260 -  21                      Revision  1
                                                               December  1988

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a The volume of  solvent  added to 5 mi  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  uL  added to the syringe.

b Dilute an aliquot of the solvent extract  and then take  100 uL for analysis.

                  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  uL  of internal standard solution; then
             add 10 uL of the surrogate  spiking  solution.  Also add the  volume
             of solvent  extract determined  in Step  7.4.3.2.5  and a volume of
             extraction  or dissolution  solvent  to  total 100 uL (excluding
             solvent 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 water/solvent  sample into  the purging chamber.

                  7.4.3.2.8  Proceed with  the  analysis as outlined  in Steps
             7.4.1.12-7.4.1.17.  Analyze all  blanks on the same  instrument as
             that used for the  samples. The standards and blanks should also
             contain  100 uL  of the  dilution solvent to  simulate  the  sample
             conditions.

                  7.4.3.2.9  For  a  matrix  spike  in  the  medium-level
             sediment/soil  samples,  add  8.0  ml  of methanol,  1.0  ml  of
             surrogate spike  solution (Step  5.9), and 1.0 ml of matrix spike
             solution  (Step  5.13)   as  in   Step  7.4.3.2.2.  This  results in  a
             6,200  ug/kg concentration  of  each  matrix  spike standard when
             added to  a  4 g  sample. Add a  100  uL aliquot of this extract to
             5 ml of water for purging  (as per Step  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  analytical  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 Jf  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  or within one scan of each  other.
              Selection  of a  peak  by  a  data  system  target  compound  search

                                 8260 - 22                       Revision  1
                                                                 December  1988

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     routine  where  the  search  is based  on  the  presence  of a
     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
     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.

                        8260 - 23                       Revision 1
                                                       December 1988

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     (4)  Ions  present  in  the  sample  spectrum  but not  in  the
reference  spectrum  should  be reviewed for  possible  background
contamination or presence  of  coeluting compounds.

     (5)  Ions  present  in the  reference spectrum but  not in  the
sample spectrum should be reviewed for possible subtraction from the
sample  spectrum because  of background  contamination or  coeluting
peaks.  Data  system library reduction programs  can  sometimes  create
these discrepancies.

     Computer  generated  library  search routines  should not  use
normalization routines that would  misrepresent the library or unknown
spectra when compared to each other. Only after visual comparison of
sample  with the  nearest  library  searches   will  the  mass spectral
interpretation specialist  assign a  tentative  identification.

7.5.2  Quantitative analysis

     7.5.2.1  When a compound has  been identified, the  quantification
of that compound will  be  based  on the integrated abundance from the
EICP  of the  primary characteristic ion. Quantification  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).

     7.5.2.2   Calculate the  concentration  of  each  identified
analyte in the sample as follows:

Water and Water-Miscible Waste

                            (AX)(IS)
  concentration (ug/L) = TT—T75pT7n-y

 where:

      Ax  = Area of characteristic ion for compound  being
            measured.

      Is  = Amount of internal  standard  injected  (ng).

      ATS = Area of characteristic ion for the  internal standard-

      RF  = Response factor for compound  being measured (Step 7.2.6).

      V0  = Volume of  water  purged  (ml), taking into consideration
            any dilutions made.

 Sediment/Soil, Sludge,  and Waste
                        8260 - 24                       Revision 1
                                                        December 1988

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           High-level:

                                    (AJ(Is)(Vt)
           concentration (ug/kg) = (AT'TTRFTIVTyiiTJ

           Low-level:

                                    (AX)(IS)
           concentration (ug/kg) = (AT~y(RF)(W"T

          where:

               AX>  Is> AiS, RF =  Same  as  in  water  and  water-miscble waste
                                 above.

               v"t   = Volume of total extract  (uL) (use 10,000 uL or a factor
                     of this when dilutions are made).

               Vj   = Volume of extract added (uL) for  purging.

               Ws   = Weight of sample extracted or purged (g). The wet weight
                     or dry  weight  may be used, depending upon the specific
                     applications of the data.

              7.5.2.3   Sediment/soil  samples  are generally reported  on a dry
         weight basis,  while  sludges and wastes are reported on a wet weight
         basis. The % moisture of the sample (as calculated in  Step 7.4.3.1.5)
         should be  reported along with the data in either  instance.

              7.5.2.4   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 Ais  should  be  from the  total  ion  chromatograms, and the
         RF for the compound  should be  assumed to be  1. The  concentration
         obtained   should  be  reported  indicating (1)  that  the value  is an
         estimate  and  (2) which internal  standard was used  to  determine
         concentration.   Use  the  nearest  internal   standard  free  of
         interferences.

              7.5.2.5   Report  results  without  correction for recovery data.
         When  duplicates  and  spiked  samples  are analyzed,  report  all  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  requirements  of  this  program
consist of  an initial  demonstration  of laboratory capability and an  ongoing
analysis  of  spiked samples  to  evaluate  and  document quality data.  The
laboratory must  maintain records to document the  quality  of  the  data
generated.  Ongoing data quality checks are  compared with  established
performance  criteria  to  determine  if  the  results  of analyses  meet the
                                 8260  - 25                      Revision  1
                                                                December  1988

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performance  characteristics  of the  method.  When  results of  sample spikes
indicate atypical  method performance,  a  quality  control check  standard must be
analyzed to confirm that the measurements  were performed  in  an in-control mode
of operation.

    8.2   Before  processing  any samples,  the  analyst  should  demonstrate,
through  the analysis  of  a calibration  blank,  that  interferences  from the
analytical system, glassware, and reagents are under control. Each time a set
of  samples  is  extracted  or there  is a  change  in  reagents,  a  reagent blank
should be  processed  as  a safeguard against chronic laboratory contamination.
The  blanks  should be  carried through  all  stages of  sample  preparation and
measurement.

    8.3  The experience of the analyst performing GC/MS analyses  is  invaluable
to the success of the methods.  Each day that analysis  is performed,  the daily
calibration  standard should be  evaluated  to determine if the chromatographic
system  is  operating properly.  Questions  that  should  be asked are:   Do the
peaks  look  normal?  Is  the  response obtained comparable  to the response  from
previous calibrations?   Careful  examination of the standard  chromatogram can
indicate  whether  the column  is  still  useable,  the  injector  is  leaking, the
injector  septtum needs  replacing, etc. If  any changes  are  made to the  system
(e.g. column changed),  recalibration of the system must take place.

    8.4  Required instrument QC

         8.4.1  The GC/MS system must be  tuned  to meet the  BFB specifications
    in Step  7.2.1.

         8.4.2  There must  be an initial  calibration  of the GC/MS  system  as
    specified in Step 7.2.

         8.4.3  The  GC/MS  system  must meet  the SPCC criteria  specified  in
    Step 7.3.3 and the CCC criteria in Step 7.3.4,  each 12  hours.

    8.5 To establish the ability to generate acceptable accuracy  and  precision
on water samples,  the analyst must  perform the  following  operations.

         8.5.1  A  quality  control  (QC)  reference   sample  concentrate  is
    required containing each  analyte  at a  concentration  of  10  ug/mL  in
    methanol. The  QC reference  sample  concentrate  may be  prepared  from  pure
    standard materials or purchased as certified solutions.  If prepared  by the
    laboratory, the  QC  reference sample concentrate must be made using  stock
    standards prepared independently from those  used for  calibration.

         8.5.2   Prepare  a  QC  reference  sample to  contain  20 ug/L of each
    analyte  by adding 200  uL of QC reference sample concentrate to  100 ml  of
    water. For the low level 25 mL  a sample, spike at 5 ug/L.

         8.5.3  Four 5 ml aliquots  (or 25  ml for  low  level)  of the  well-mixed
    QC reference sample are analyzed according  to the method beginning in  Step
    7.4.1.
                                  8260  -  26                       Revision 1
                                                                 December 1988

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         8.5.4  Calculate  the average percent  recovery (R) and  the  standard
    deviation of  the percent recovery  (SR),  for  the results.  Ground  water
    background corrections  must  be made before R and RR calculation.

         8.5.5  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 results  obtained  in Step 8.5.4 to  the single  laboratory recovery
    and precision data. If the  results  are not  comparable,  review potential
    problem  areas  and repeat   the  test.  Results  are  comparable  if  the
    calculated percent  relative standard deviation (RSD)  does  not  exceed 2.6
    times the single laboratory  RSD  or 20%,  whichever is greater and the mean
    recovery  lies  within  the   interval  R ±  3S  or  R ±  30%,  which  ever is
    greater.

         8.5.6  When one or more of the analytes  tested fail  at least one of
    the  acceptance  criteria,  the analyst  must  proceed  according  to  Step
    8.5.6.1 or 8.5.6.2.

              8.5.6.1  Locate and correct the source of the problem and repeat
         the test for all  analytes beginning with  Step 8.5.2.

              8.5.6.2  Beginning with Step  8.5.2, repeat  the  test  only for
         those  analytes  that   failed  to meet criteria.  Repeated  failure,
         however, will  confirm  a general  problem with the measurement system.
         If  this  occurs,   locate and  correct  the  source  of the  problem and
         repeat the  test  for all compounds  of interest  beginning  with  Step
         8.5.2. -

    8.6  The laboratory must, on an  ongoing  basis, analyze a blank and spiked
replicates for each analytical  batch  (up to  a maximum of 20 samples/batch) to
assess  accuracy.   For soil  and waste samples  where detectable  amounts of
organics are present, replicate samples  may  be appropriate in place of spiked
replicates.  For laboratories analyzing one to  ten  samples per month,  at  least
one spiked sample per month is required.

         8.6.1  The  concentration  of the  spike in  the sample  should be
    determined as follows:

              8.6.1.1  If,  as in compliance monitoring, the concentration  of  a
         specific analyte   in  the sample is being checked against a regulatory
         concentration  limit, the  spike  should  be at that  limit  or 1  to   5
         times  higher  than  the  background  concentration  determined  in  Step
         8.6.2, whichever  concentration would be larger.

              8.6.1.2  If  the concentration  of a  specific  analyte  in a water
         sample  is  not being  checked  against a specific limit,  the   spike
         should be at 20 ug/L (or 5 ug/L for low level) or  1 to  5 times higher
         than the background  concentration determined  in Step 8.6.2, whichever
         concentration  would  be  larger.  For other matrices,  the recommended
         spiking concentration  is 10 times the  PQL.
                                 8260 - 27                      Revision 1
                                                                December 1988

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         8.6.2   Analyze  one  5 ml sample aliquot  (or  25  ml for low  level)  to
    determine  the  background  concentration  (B)  of each  analyte.  If necessary,
    prepare a  new  QC  check sample concentrate (Step 8.5.1) appropriate for the
    background  concentration  in the sample. Spike a second 5 ml  (or 25 ml for
    low  level)  sample  aliquot  with  10 ui  of  the   QC reference  sample
    concentrate and analyze  it  to  determine  the concentration after  spiking
    (A)  of each analyte. Calculate each percent  recovery  (p)  as  100(A-B)%/T,
    where T is  the known  true value of the spike.

              8.6.2.1  Compare the percent recovery (Ri)  for each  analyte with
         QC acceptance criteria established  from the analyses of laboratory
         control  standards  (Step 8.5).  Monitor  all  data  from dosed  samples.
         Analyte recoveries must fall within the established control limits.

              8.6.2.2  If recovery  is  not  within  limits,  the following
         procedures are  required.

                   8.6.2.2.1  Check  to  be   sure  there  are no  errors  in
              calculations,   matrix  spike  solutions, and  internal  standards.
              Also,' check instrument performance.

                   8.6.2.2.2  Recalculate  the  data  and/or  reanalyze  the
              extract  if any  of the above checks reveal  a problem.

                   8.6.2.2.3  If the checks in 8.6.2.2.1 reveal no errors, the
              recovery problem  encountered with  the dosed sample  is judged to
              be  matrix-related,  non  system-related.  The result for  that
              analyte in  the unspiked  sample  is  labeled  suspect/matrix  to
              inform   the  user  that  the  results are  suspect due  to matrix
              effects.

    8.7  As part  of  the QC  program  for the  laboratory,  method  accuracy for
each matrix studied must be assessed and records must be maintained. After the
analysis, of five spiked  samples  (of the  same matrix) as in Step 8.6, calculate
the average percent  recovery (p)  and the  standard deviation of  the percent
recovery (sp).  Express the accuracy assessment as a percent recovery interval
from p  - 2sp to  p +  2sp. If p = 90% and  Sp  =  10%,  for  example,  the accuracy
interval  is  expressed as  70-110%.  Update the  accuracy  assessment  for each
analyte on a  regular  basis  (e.g.  after  each five  to  ten  new  accuracy
measurements).

    8.8  To determine acceptable accuracy and  precision  limits  for surrogate
standards the  following  procedure should be performed.

         8.8.1   For each sample analyzed,  calculate the  percent  recovery of
    each surrogate in the sample.

         8.8.2  Once  a minimum  of  thirty samples of the  same matrix have been
    analyzed,  calculate the  average  percent  recovery (p)  and  standard
    deviation  of the  percent  recovery  (sp) for each of the surrogates.
                                 8260 - 28                      Revision 1
                                                                December 1988

-------
         8.8.3   For a  given matrix,  calculate  the  upper  and lower  control
    limit for method performance for each surrogate  standard. This  should  be
    done as  follows:

         Upper  Control  Limit (UCL) = p + 3sp
         Lower  Control  Limit (LCL) = p - 3sp

         8.8.4   For aqueous  and  soil  matrices,  these  laboratory  established
    surrogate  control  limits  should,  if  applicable,  be  compared with  the
    control  limits listed in Table 9.  The limits given  in  Table  9 are multi-
    laboratory  performance  based limits  for soil  and  aqueous samples,  and
    therefore,   the  single-laboratory  limits  established  in  Step 8.8.3  must
    fall within those  given  in  Table 9 for these matrices.

         8.8.5   If recovery  is  not within limits, the following procedures are
    required.
                                                                           "•
                  Check  to   be  sure there  are  no errors  in calculations,
                  surrogate  solutions  and internal  standards.  Also,  check
                  instrument performance.

                  Recalculate the data  and/or reanalyze  the extract  if any  of
                  the  above  checks reveal a problem.

                  Reextract  and reanalyze  the sample if none  of the above are
                  a problem or  flag  the data  as  "estimated concentration."

         8.9.6   At a minimum, each laboratory should update surrogate recovery
    limits on a matrix-by-matrix basis, annually.

    8.10 It  is recommended that  the laboratory  adopt  additional  quality
assurance practices for use with this  method. The specific practices that are
most productive depend upon the needs  of the  laboratory and the nature of the
samples.  Field duplicates  may  be  analyzed  to assess  the precision  of the
environmental   measurements.  When doubt exists  over the identification  of a
peak on  the  chromatogram,  confirmatory techniques  such  as  gas chromatography
with  a  dissimilar column  or a different  ionization  mode  using  a  mass
spectrometer must  be  used.   Whenever possible,  the  laboratory should analyze
standard reference  materials and  participate  in  relevant   performance
evaluation studies.

    8.11 In recognition of the rapid advances occurring  in  chromatography, the
an'alyst  is  permitted  to  modify GC  columns,  GC conditions,   or  detectors  to
improve  the  separations  or  lower  the cost  of  measurements.  Each  time such
modifications  to  the  method are made,  the analyst  is  required  to repeat the
procedure in Step 8.4.

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.

                                 8260 - 29                      Revision 1
                                                                December 1988
'0

-------
    9.2  This method  has been  tested  in  a single  laboratory using  spiked
water. Using a wide-bore capillary column,  water  was  spiked  at  concentrations
between 0.5  and  10 ug/L. Single  laboratory  accuracy  and  precision data  are
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 ug/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.
2.


3.


4.
5.
6.



7.


8.


9.



10.
Methods for the Determination of Organic Compounds  in  Finished  Drinking
Hater and  Raw  Source  Water Method 524.2; U.S.  Environmental  Protection
                                           Environmental  Monitoring  and
     Agency.
     Support
        Office  of
        Laboratory:
Research  Development.
Cincinnati,  OH  1986.
U.S.  EPA  Contract  Laboratory Program,  Statement of  Work for  Organic
Analysis,  July 1985,  Revision.
Bell'ar,  T.A.;  Lichtenberg, J.J.
739-744.
                                  Amer. Water Works Assoc.  1974,  66(12).
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.

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.

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, 4_7,  995-1000.

Olynyk, P.; Budde,  W.L.; Eichelberger,  J.W.  "Method  Detection  Limit  for
Methods 624 and 625";  Unpublished report, October 1980.

Provost,  L.P.;  Elder R.S. "Interpretation  of Percent Recovery  Data";
American Laboratory 1983, 1_5,  58-63.

Non  Cryogenic   Temperatures  Program and  Chromatogram,  Private
Communications;  Myron  Stephenson  and Frank Allen,  EPA  Region IV
Laboratory,  Athens,  GA.

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,
1987; SW-846;  955-001-00000-1.
                                 8260 - 30
                                                           Revision 1
                                                           December 1988

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

12.   1985 Annual Book  of ASTM  Standards.  Vol.  11.01;  "Standard  Specification
     for Reagent Water";  ASTM:  Philadelphia,  PA, 1985;
     D1193-77.
                                 8260 - 31                       Revision 1
                                                                 December 1988

-------
                            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-Dichloroethane
Methyl ene chloride
trans- 1,2-Di chl oroethene
1,1-Dichloroethane
2,2-Dichloropropane
cis- 1,2-Di chl oroethene
Chloroform
Bromochl oromethane
1 , 1 , 1-Trichloroethane
Carbon tetrachloride
1,1-Dichloropropene
Benzene
1,2-Dichloroethane
Trichloroethene
1,2-Dichloropropane
Bromodi chl oromethane
Dibromomethane
Toluene
1 , 1 , 2-Tri chloroethane
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-Tetrachloroethane
Bromobenzene
Column ]
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
18.95
RETENTION TIME
(minutes)
1* Column 2°
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
15.86
Column 3
..
2.07
2.12
2.26
2.31
2.42
3.08
3.32
3.48
4.10
4.43
4.42
4.58
4.54
5.09
5.18
5.18
5.29
5.29
6.07
6.20
6.39
6.27
7.36
8.07
8.21
8.20
8.39
--

9.33
9.41
9.44
9.56
9.56
10.32
10.33
10.48

11.38
11.35
MDLd
(ug/L)
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
0.03
                            8260 - 32
Revision 1
December 1988

-------
                                 TABLE 1.
                                (Continued)
    ANALYTE
         RETENTION TIME          MDLd
           (minutes)              (ug/L)
Column la   Column 2b  Column 3C
1,2,3-Trichloropropane
n-Propyl benzene
2-Chlorotoluene
1 , 3 , 5-Tri methyl benzene
4-Chlorotoluene
tert-Butyl benzene
1, 2, 4-Tri methyl benzene
sec-Butyl benzene
p-Isopropyl toluene
1 ,3-Dichlorobenzene
1,4-Dichlorobenzene
n-Butyl benzene
1,2-Dichlorobenzene
1 , 2-Di bromo-3-chl oropropane
1,2, 4-Tri chlorobenzene
Hexachlorobutadiene
Naphthalene
1, 2, 3-Tri chlorobenzene
19.02
19.06
19.34
19.47
19.50
20.28
20.34
20.79
21.20
21.22
21.55
22.22
22.52
24.53
26.55
26.99
27.17
27.78
16.23
16.41
16.42
16.90
16.72
17.57
17.70
18.09
18.52
18.14
18.39
19.49
19.17
21.08
23.08
23.68
23.52
24.18
11.40
--
11.57
--
12.08
--
--
--
--
13.16
13.27
--
14.10
--
--
--
--
--
0.32
0.04
0.04
0.05
0.06
0.14
0.13-
0.13
0.12
0.12
0.03
0.11
0.03
0.26
0.04
0.11
0.04
0.03
INTERNAL STANDARDS/SURROGATES

4-Bromof1uorobenzene
18.63
15.71
11.22
aColumn  1  -  60 m  x 0.75  mm  i.d.  VOCOL  capillary.  Hold  at  10°C  for
5 minutes,  then program to 160°C at 6°/min.

^Column  2  -  30  m  x  0.53  mm  i.d.  DB-624  wide-bore  capillary  using
cryogenic oven.  Hold at  10°C  for 5  minutes,  then program  to  160°C  at
6°/min.

cColumn 3 -  30  m x  0.53  mm  i.d.  DB-624 wide-bore capillary, cooling  GC
oven to ambient temperatures.  Hold at  45°C  for 2  minutes,  then program to
200"C at 8°/min and hold for 6 minutes.

     based on a 25 mL sample volume.
                                 8260  - 33
                                 Revision 1
                                 December 1988

-------
                            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
Tri chl orof 1 uoromethane
1,1-Dichloroethene
Methylene chloride
trans- 1,2-Di chl oroethene
1,1-Dichloroethane
cis -1,2-Di chl oroethene
2,2-Dichloropropane
Chloroform
Bromochloromethane
1 , 1, 1 -Tri chloroethane
1,2-Dichloroethane
1,1-Bichloropropene
Carbon tetrachloride
Benzene
1,2-Dichloropropane
Trichloroethene
Dibromomethane
Bromodi chloromethane
Toluene
1 , 1 , 2-Tri chl oroethane
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-Trichloropropane
Isopropyl 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
(ug/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
                            8260 - 34
Revision 1
December 1988

-------
                                  TABLE 2.
                                 (Continued)
    ANALYTE
RETENTION TIME
 (minutes)
Column 3a
MDI_b
(ug/L)
Bromobenzene
2-Chlorotoluene
n-Propyl benzene
4-Chlorotoluene
1 , 3, 5-Trimethyl benzene
tert-Butyl benzene
1,2,4-Trimethylbenzene .
sec-Butyl benzene
1,3-Dichlorobenzene
p-Isopropyltoluene
1,4-Dichlorobenzene
1,2-Dichlorobenzene
n-Butyl benzene
l,2-Dibromo-3-chloropropane
1,2,4-Trichlorobenzene
Naphthalene
Hexachlorobutadiene
1,2,3-Trichlorobenzene
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
aColumn 3 - 30 m x 0.32 mm i.d. DB-5 capillary with urn film thickness.

bMDL based on a 25 ml sample volume.
                                  8260 -  35
                                 Revision  1
                                 December  1988

-------
                                  TABLE 3.
            PRACTICAL QUANTITATION LIMITS FOR VOLATILE ANALYTESa
                                            Practical
                                          Quantitation
                                             Limits
                                 Ground water   Low Soil/Sedimentb
                                    ug/L              ug/kg
Volume of water purged             5 mL  25 mL

All analytes in Table 1            5     1
aPractical Quantitation  Limit  (PQL) - The  lowest  level that  can  be reliably
achieved  within  specified limits  of  precision and  accuracy during  routine
laboratory operating  conditions.  The  PQL 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 PQL analyte level  is selected for the  lowest
non-zero  standard  in  the calibration curve.  Sample  PQLs are  highly  matrix-
dependent.  The  PQLs  listed herein  are  provided for  guidance  and  may   not
always be achieveable. See  the  following information  for further guidance  on
matrix-dependent PQLs.
       listed  for soil/sediment  are  based  on  wet  weight.  Normally  data  is
reported on  a  dry weight basis; therefore, PQLs will  be  higher,  based on the
% moisture in each sample.
        Other Matrices:                             Factor0

    Water miscible liquid waste                        50
    High-level soil and sludges                       125
    Non-water miscible waste                          500


CPQL  = [PQL  for low  soil  sediment  (Table  3)]  X  [Factor].  For  non-aqueous
samples, the factor is on a wet-weight basis.
                                  8260  -  36                       Revision 1
                                                                 December 1988

-------
                               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
                               8260  -  37                       Revision 1
                                                              December 1988

-------
                              TABLE 5.
     CHARACTERISTIC MASSES  (M/Z)  FOR  PURGEABLE ORGANIC COMPOUNDS
Analyte
  Primary
Characteristic
    Ion
  Secondary
Characteristic
    Ion(s)
Benzene
Bromobenzene
Bromochl oromethane
Bromod i chl oromethane
Bromoform
Bromomethane
n-Butyl benzene
sec-Butyl benzene
tert-Butyl benzene
Carbon tetrachloride
Chlorobenzene
Chloroethane
Chloroform
Chl oromethane
2-Chlorotoluene
4-Chlorotoluene
l,2-Dibromo-3-chloropropane
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-l,2-Dichloroethene
trans-l,2-Dichloroethene
1,2-Dichloropropane
1 ,3-Dichloropropane
2,2-Dichloropropane
1,1-Dichloropropene
Ethyl benzene
Hexachlorobutadiene
Isopropyl benzene
p-Isopropyltoluene
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
126
91
75
129 '
107
93
146
146
146
85
63
62
96
96
96
63
76
77
75
91
225
105
119
84
128
120
104
131
8260 - 38

77,158
49,130
-85,127
175,254 >
96
92,134 -
134
91,134
119
77,114
66
85
52
126
126
155,157
127
109,188
95,174
111,148
111,148
111,148
87
65,83
98
61,63
61,98
61,98
112
78
97
110,77
106
223,227
120
134,91
86,49 .
-
120
78
133,119
Revision 1
                                                             December 1988

-------
                                  TABLE  5.
                                (Continued)
                                    •  Primary              Secondary
                                    Characteristic       Characteristic
    Analyte                             Ion                  Ion(s)
1,1,1 , 2-Tetrachl oroethane
Tetrachloroethene
Toluene
1,2,3-Trichlorobenzene
1 ,2,4-Trichlorobenzene
1,1,1-Trichloroethane
1,1,2-Trichloroethane
Trichloroethene
Trichlorofluoromethane
1,2,3-Trichloropropane
1 , 2 , 4-Tri methyl 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
131,85
168,129
91
182,145
182,145
99,61
97, "85
130,132
103
77
120
120
64
91
91
91
INTERNAL STANDARDS/SURROGATES

4-Bromofluorobenzene                     95                  174,176
Dibromofluoromethane                    113
Toluene-da                               98
Pentafluorobenzene                      168
1,4-Difluorobenzene                     114
Chlorobenzene-ds                        117
l,4-Dichlorobenzene-d4                  152
                                 8260 - 39                       Revision 1
                                                                 December 1988

-------
                                  TABLE 6.
           VOLATILE  INTERNAL  STANDARDS  WITH  CORRESPONDING  ANALYTES
                          ASSIGNED FOR  QUANTITATION
Pentafluorobenzene

Acetone
Acrolein
Acrylonitrile
Bromochloromethane
Bromomethane
2-Butanone
Carbon disulfide
Chloroethane
Chloroform
Chloromethane
Di chlorodi f1uoromethane
1,1-Dichloroethane
1,1-Dichloroethene
cis-1,2-Dichloroethene
trans-1,2-Dichloroethene
2,2-Dichloropropane
lodomethane
Methylene chloride
1,1,1-Trichloroethane
Tri chlorof1uoromethane
Vinyl acetate
Vinyl chloride

Chlorobenzene-ds

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-Di chloropropane
1,1-Dichloropropene
cis-l,3-Dichloropropene
trans-1,3-Dichloropropene
4-Methyl-2-pentanone
Toluene
Toluene-ds (surrogate)
1,1,2-Trichloroethane
Trichloroethene

1.4-Dichlorobenzene-d4

Bromobenzene
n-Butylbenzene
sec-Butyl benzene
tert-Butylbenzene
2-Chlorotoluene
4-Chlorotoluene
1,2-Dibromo-3-chloropropane
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Hexachlorobutadiene
Isopropyl benzene
p-Isopropyltoluene
Naphthalene
n-Propylbenzene
1,1,2,2-Tetrachloroethane
1,2,3-Trichlorobenzene
1,2,4-Trichlorobenzene
1,2,3-Trichloropropane
1,2,4-Trimethylbenzene
1,3,5-Trimethyl benzene
                                  8260 - 40
                        Revision 1
                        December 1988

-------
                         TABLE 7.
SINGLE LABORATORY ACCURACY AND PRECISION DATA FOR VOLATILE
    ORGANIC COMPOUNDS IN WATER DETERMINED WITH A WIDE-
                   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
l,2-Dibromo-3-chloropropane
Di bromochl oromethane
1,2-Dibromoethane
Dibromomethane
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Di chl orod i f 1 uoromethane
1, 1-Dichlorobenzene
1,2-Dichlorobenzene
1,1-Dichloroethene
cis-l,2-Dichloroethene
trans -1,2-Di chl oroethene
1,2-Dichloropropane
1,3-Dichloropropane
2,2-Dichloropropane
1,1-Dichloropropene
Ethyl benzene
Hexachlorobutadiene
Isopropyl benzene
p-Isopropyltoluene
Cone. Number
Range, of
ug/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
- 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
- JO
- 10
- 10
- 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
Recovery
%
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
Standard Percent
,a Deviation Rel . Std.
of Recovery0 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
5.7
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
                       8260  -  41
Revision 1
December 1988

-------
                                    TABLE 7.
                                   (Continued)
Analyte
Cone.
Range,
ug/L
Number
of
Samples
Standard
Recovery,3 Deviation
% of Recovery*5
Percent
Rel. Std.
Dev.
Methylene chloride
Naphthalene
n-Propylbenzene
Styrene
1,1,1,2-Tetrachloroethane
1,1,2,2-Tetrachloroethane
Tetrachloroethene
Toluene
1,2,3-Trichlorobenzene
1,2,4-Trichlorobenzene
1,1,1-Trichloroethane
1,1,2-Trichloroethane
Trichloroethene
Tri chlorof1uoromethane
1,2,3-Trichloropropane
1,2,4-Trimethylbenzene
1,3,5-Trimethylbenzene
Vinyl chloride
o-Xylene
m-Xylene
p-Xylene
0.1
0.1
0.1
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
- 10
-100
- 10
-100
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 31
- 10
- 10
30
31
31
39
24
30
24
18
18
18
18
18
24
24
16
18
23
18
18
31
18
 95
104
100
102
 90
 91
 89
102
109
108
 98
104
 90
 89
108
 99
 92
 98
103
 97
104
 5.0
 8.6
 5.8
 7.3
 6.1
 5.7
 6.0
 8.1
 9.4
 9.0
  .9
  .6
 6.5
 7.2
15.6
 8.0
 6.8
 6.5
 7.4
 6.3
 8.0
7,
7.
 5.3
 8.2
 5.8
 7.2
 6.8
 6.3
 6.8
 8.0
 8.6
 8.3
 8.1
 7.
 7.
 8.
14.
 8.1
 7.4
 6.7
 7.2
 6.5
 7.7
.3
.3
,1
.4
Recoveries were calculated using internal standard method. Internal standard
 was fluorobenzene.

^Standard deviation was calculated by pooling data form three levels.
                                  8260 -  42
                        Revision  1
                        December  1988

-------
                    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
Bromodichlorome thane
Bromoform
Bromomethane
n-Butyl benzene
sec-Butyl benzene
tert-Butyl benzene
Carbon tetrachloride
Chlorobenzene
Chloroethane
Chloroform
Chloromethane
2-Chlorotoluene
4-Chlorotoluene
1 , 2-Dibromo-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-l,2-Dichloroethene
trans-l,2-Dichloroethene
1,2-Dichloropropane
1,3-Dichloropropane
2, 2 -Di chl oropropane
1, 1-Dichloropropene
Ethyl benzene
Hexachlorobutadiene
Isopropyl benzene
p-Isopropyl toluene
Cone.
ug/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
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
Recovery,3
%
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
i 100
! 95
1 100
: 98
96
99
99
102
99
100
102
113
Standard
Deviation
of Recovery*5
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
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
                  8260 - 43
Revision 1
December 1988

-------


TABLE 8.



(Continued)

Analyte
Methylene 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-Tri chl oroethane
Trichloroethene
Tri chl orofl uoromethane
1,2,3-Trichloropropane
1, 2, 4-Trimethyl benzene
1 , 3 , 5-Trimethyl benzene
Vinyl chloride
o-Xylene
m-Xylene
p-Xylene
Cone.
ug/L
0.5
0.5
0.5
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
7
7
7
Recovery,3
%
97
98
99
96
100
100
96
100
102
91
100
102
104
97
96
96
101
104
106
106
97
Standard
Deviation
of Recovery^
13.0
7.2
6.6
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.
13.4
7.3
6.7
19.8
4.7
1*2.0
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.
                                 8260  - 44
Revision 1
December 1988

-------
                            MINI-COLUMN TEST RESULTS
                    50
                    40
                2   30
               o
               z
               o
                    20
                    10
                           CARBORUNDUM GAC 830
                            TETRACHLOROETHVLEN6

       TRICHLOROETHYLENE


             /

              I


            1.1.1-TRICHLORO

            ETHANE	r—7

              '        '  /
                                IOOO          2000         3000


                                      WATER TREATED (ml)
                        4000
Define:
          Controlling VOC



          Carbon  Usaye based on:



               Carbon usage (lbs/1,000 gal)
= W x 8461.5

  V
                wherr.-  W = weight of carbon  (0.1  gin)

                      V = volume treated  (ml)



          Preliminary Process Design
                                      -12-

-------
                                  TABLE 9.
     SURROGATE  SPIKE  RECOVERY  LIMITS FOR WATER AND SOIL/SEDIMENT SAMPLES
                                 Low/Medium              Low/Medium
    Surrogate Compound             Water                 Soil/Sediment
4-Bromofluorobenzenea            86-115                   74-121
Dibromofluoromethane3            86-118                   80-120
Toluene-da*                      88-110                   81-117
aSingle laboratory data for. guidance only.
                                 8260  - 45                       Revision 1
                                                                 December 1988

-------
                                 METHOD 8270

       GAS CHROMATOGRAPHY/MASS SPECTROMETRY FOR SEMIVOLATILE ORGANICS;
                         CAPILLARY COLUMN TECHNIQUE


1.0  SCOPE AND APPLICATION

     1.1  Method 8270 1s used to  determine the concentration of semi volatile
organic  compounds  1n  extracts  prepared  from  all   types  of  solid waste
matrices, soils, and ground water.  Direct  injection  of a sample may be used
in limited applications.

     1.2  Method 8270 can be used to quantify most neutral,  acidic,  and basic
organic compounds that are soluble 1n 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,  nitrosamlnes,
haloethers,  aldehydes,  ethers,  ketones,  anilines,   pyridines, quinolines,
aromatic nitro compounds, and phenols,  Including  nltrophenols.  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.    Benzldine  can  be  subject to oxldative 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 1n acetone solution, and photochemical decomposition.
N-nitrosod1methyl amine is difficult to  separate  from  the solvent under the
chromatographic conditions described.    N-nitrosod1phenylam1ne decomposes in
the gas chromatographic  Inlet  and  cannot  be separated from diphenylamlne.
Pentachlorophenol,    2,4-dinitrophenol,     4-n1trophenol,    4,6-din1tro-2-
methylphenol,  4-chloro-3-methylphenol,  benzole   acid,  2-n1troan1line,  3-
nltroaniUne, 4-chloroan1line,  and  benzyl  alcohol   are  subject to erratic
chromatographic behavior, especially 1f  the  GC  system 1s contaminated with
high boiling material.

     1.4  The  practical  quantltatlon  limit    (PQL)    of  Method  8270  for
determining an individual compound 1s  approximately rmg/kg  (wet weight) for
soil/sediment samples, 1-200 mg/kg for wastes  (dependent on matrix and method
of preparation), and 10  ug/L for  ground  water  samples (see Table 2).  PQLs
will be proportionately  higher  for  sample  extracts that require dilution to
avoid saturation of the  detector.

     1.5  This method  1s restricted  to  use  by  or under the  supervision of
analysts experienced 1n  the  use  of gas chromatograph/mass spectrometers and
skilled 1n the interpretation of mass spectra.   Each analyst must demonstrate
the ability to generate  acceptable results with this method.


                                  8270 - 1
                                                         Revision      0
                                                         Date  September 1986

-------
TABLE 1.  CHARACTERISTIC IONS FOR SEMIVOLATILE COMPOUNDS
Retention
Compound Time (m1n)
Acenaphthene
Acenaphthene-dio (I.S.)
Acenaphthylene
Acetophenone
Aldrin
Aniline
Anthracene
4-Aminobiphenyl
Aroclor-1016
Aroclor-1221
Aroclor-1232
Aroclor-1242
Aroclor-1248
Aroclor-1254
Aroclor-1260
Benzidine
Benzole acid
Benzo (a) anthracene
Benzo (b) f 1 uoranthene
Benzo (k)fl uoranthene
Benzo (g,h,i)peryl ene
Benzo(a)pyrene
Benzyl alcohol
a-BHC
/J-BHC
5-BHC
7-BHC (Lindane)
Bi s (2-chl oroethoxy) methane
Bi s (2-chl oroethy 1 ) ether
Bi s (2-chl oroi sopropyl ) ether
Bi s (2-ethyl hexyl ) phthal ate
4-Bromophenyl phenyl ether
Butyl benzyl phthal ate
Chlordane
4-Chloroaniline
1-Chl oronaphthal ene
2-Chl oronaphthal ene
4-Chloro-r3-methyl phenol
2-Chlorophenol
4-Chlorophenyl phenyl ether
Chrysene
Chrysene-di2 (I.S.)
4,4'-DDD
4,4'-DDE
15.13
15.05
14.57
7.96a
—
5.68
19.77
19.18a
—
—
--
—
—
—
—
23.87
9.38
27.83 .
31.45
31.55
41.43
32.80
6.78
—
— . ;
—
;
9.23
5.82
7.22
28.47
18.27
26.43
—
10.08
13.65a
13.30
11.68
5.97
16.78
27.97
27.88
—
!
Primary Ion
154
164
152
105
66
93
178
169
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
246
Secondary Ion(s)
153, 152
162, 160
151, 153
77, 51
263, 220
66, 65
176, 179
168, 170
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
248, 176
                                  8270 -  2
                                                         Revision      0
                                                         Date  September  1986

-------
TABLE 1.  CHARACTERISTIC IONS FOR SEMIVOLATILE COMPOUNDS (Continued)
Retention
Compound Time (m1n)
4,4'-DDT
D1benz(a,j)acr1d1ne
D1 benz (a , h) anthracene
Dlbenzofuran
D1 -n-butyl phthal ate
1,3-Dichlorobenzene
1 , 4-D1 chl orobenzene
l,4-D1chlorobenzene-d4 (I.S.)
1,2-01 chl orobenzene
3,3'-D1chlorobenz1d1ne
2,4-D1chlorophenol
2,6-D1chlorophenol
D1eldr1n
D1 ethyl phthal ate
p-D1 methyl ami noazobenzene
7 , 12-D1methy 1 benz (a) anthracene
a- , a-D1 methyl phenethy 1 ami ne
2, 4-D1methyl phenol
Dimethyl phthal ate
4 , 6-D1 n1 tro-2-methy 1 phenol
2,4-D1m'trophenol
2,4-D1n1trotoluene
2,6-D1n1trotoluene
Dlphenylamlne
1 , 2-D1 pheny 1 hydrazl ne
D1 -n-octyl phthal ate
Endosulfan I
Endosulfan II
Endosulfan sulfate
Endrln
Endrln aldehyde
Endrln ketone
Ethyl methanesulfonate
Fluoranthene
Fluorene
2-Fluorob1phenyl (surr.)
2-Fluorophenol (surr.)
Heptachlor
Heptachlor epoxlde
Hexachl orobenzene
Hexachl orobutadl ene
Hexachl orocycl opentadl ene
Hexachl oroethane
Indeno(l,2,3-cd)pyrene
— —
32.55a
39.82
15.63
21.78
6.27
6.40
6.35
6.85
27.88
9.48
10.05a
—
16.70
24.48a
29.54a
9.51a
9.03
14.48
17.05
15.35
15.80
14.62
17.54a
—
30.48
—
—
—
—
—
—
5.33a
23.33
16.70
—
—
—
—
18.65
10.43
12.60
7.65
39.52
Primary Ion
235
279
278
168
149
146
146
152
146
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
Secondarylon(s)
237, 165
280, 277
139, 279
139
150, 104
148, 111
148, 111
150, 115
148, 111
254, 126
164, 98
164, 98
263, 279
177, 150
225, 77
241, 257
91, 42
107, 121
194, 164
51, 105
63, 154
63, 89
63, 89
168, 167
105, 182
167, 43
339, 341
339, 341
387, 422
82, 81
345, 250
67, 319
109, 97
101, 203
165, 167
171
64
272, 274
355, 351
142, 249
223, 227
235, 272
201, 199
138, 227
                                   8270 - 3
                                                          Revision      0
                                                          Date  September 1986

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TABLE 1.  CHARACTERISTIC IONS FOR SEMIVOLATILE COMPOUNDS  (Continued)
Retention
Compound Time (m1n)
Isophorone
Methoxychlor
3-Methyl chol anthrene
Methyl methanesulfonate
2-Methyl naphthal ene
2-Methy 1 phenol (o-cresol )
4-Methyl phenol (p-cresol)
Naphthalene
Naphthal ene-dg (I.S.)
1-Naphthylamine
2-Naphthylamine
2-Nitroaniline
3-N1troan1line
4-Nitroan1l1ne
Nitrobenzene
Nitrobenzene-ds (surr.)
2-N1trophenol
4-N1trophenol
N-N1 troso-di -n-butyl ami ne
N-N1trosod1 methyl ami ne
N-Ni trosodi phenyl ami ne
N-Ni trosodi propy 1 ami ne
N-N1 trosopi peri di ne
Pentachl orobenzene
Pentachloronitrobenzene
Pentachlorophenol
Perylene-dj2 (I.S.)
Phenacetin
Phenanthrene
Phenanthrene-dio (I.S.)
Phenol
Phenol-ds (surr.)
2-P1coline
Pronamide
Pyrene
Terphenyl-dj4 (surr.)
1,2, 4, 5-Tetrachl orobenzene
2,3,4,6-Tetrachlorophenol
2,4,6-Tribromophenol (surr.)
1, 2, 4-Trichl orobenzene
2,4,5-Trichlorophenol
2,4,6-Trichlorophenol
Toxaphene
8.53
—
31.14a
4.32a ;
11.87
7.22
7.60
9.82
9.75
15.80a
16.00a
13.75
15.02
16.90
7.87
__ i
8.75
15.80
10.99a
—
17.17
7.55
—
15.64a
19.47a
19.25
33.05
18.59a
19.62
19.55
5.77
—
3.75a
19.61a
24.02
—
13.62a
16.09a
—
9.67
13.00
12.85
--
Primary Ion
82
227
268
80
142
108
108
128
136
143
143
65
138
138
77
82
139
139
84
42
169
70
42
250
295
266
264
108
178
188
94
99
93
173
202
244
216
232
330
180
196
196
159
Secondarylon(s)
95, 138
228
253, 267
79, 65
141
107, 79
107, 79
129, 127
68
115, 116
115, 116
92, 138
108, 92
108, 92
123, 65
128, 54
109, 65
109, 65
57, 41
74, 44
168, 167
42, 101, 130
114, 55
252, 248
237, 142
264, 268
260, 265
109, 179
179, 176
94, 80
65, 66
42, 71
66, 92
175, 145
200, 203
122, 212
214, 218
230, 131
332, 141
182, 145
198, 200
198, 200
231, 233
 I.S.  =  internal  standard
 surr. = surrogate

 Estimated  retention  times.
                                  8270 - 4
                                                         Revision      0
                                                         Date  September 1986

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TABLE 2.  PRACTICAL QUANTITATION LIMITS (PQL) FOR SEMIVOLATILE ORGANICS**
                                              Practical Quantisation
                                                      Limits*
Ground Water
Semlvolatlles
Phenol
b1s(2-Chloroethyl) ether
2-Chlorophenol
1 , 3-Di chl orobenzene
1 , 4-Di chl orobenzene
Benzyl Alcohol
1 , 2-D1 chl orobenzene
2-Methylphenol
b1 s (2-Chl oroi sopropyl )
ether
4-Methyl phenol
N-Ni troso-DI -N-propy 1 ami ne
Hexachloroethane
Nitrobenzene
Isophorone
2-Nitrophenol
2, 4-Di methyl phenol
Benzole Add
bis(2-Chloroethoxy)
methane
2,4-Dichlorophenol
1,2, 4-Tri chl orobenzene
Naphthalene
4-Chloroaniline
Hexachl orobutadi ene
4-Chl oro-3-methy 1 phenol
2-Methyl naphthal ene
Hexach 1 orocycl opentadi ene
2,4,6-Trichlorophenol
2,4,5-Trichlorophenol
CAS Number
108-95-2
111-44-4
95-57-8
541-73-1
106-46-7
100-51-6
95-50-1
95-48-7

39638-32-9
106-44-5
621-64-7
67-72-1
98-95-3
78-59-1
88-75-5
105-67-9
65-85-0

111-91-1
120-83-2
120-82-1
91-20-3
106-47-8
87-68-3
59-50-7
91-57-6
77-47-4
88-06-2
95-95-4
ug/L
10
10
10
10
10
20
10
10

10
10
10
10
10
10
10
10
50

10
10
10
10
20
10
20
10
10
10
10
Low Soil /Sediment1
ug/Kg
660
660
660
660
660
1300
660
660

660
660
660
660
660
660
660
660
3300

660
660
660
660
1300
660
1300
660
660
660
660
                                   8270 - 5
                                                          Revision       0
                                                          Date   September  1986

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TABLE 2.  PRACTICAL QUANTITATION LIMITS (PQL) FOR SEMIVOLATILE ORGANICS**
          (Continued)

                                              Practical  Quantisation
                                                      Limits*
Ground Water
SemlvolatHes
2-Chloronaphthalene
2-Nitroan1Hne
Dimethyl phthalate
Acenaphthylene
3-N1troanil1ne
Acenaphthene
2,4-D1n1trophenol
4-N1trophenol
Dlbenzofuran
2,4-D1nitrotoluene
2,6-D1n1trotoluene
D1 ethyl phthalate
4-Chlorophenyl phenyl
ether
Fluorene
4-N1troan1l1ne
4 , 6-D1 n1 tro-2-methyl phenol
N-N1 trosodl phenyl ami ne
4-Bromophenyl phenyl ether
Hexachlorobenzene
Pentachlorophenol
Phenanthrene
Anthracene
D1 -n-buty 1 phthal ate
Fluoranthene
Pyrene
Butyl benzyl phthalate
3,3'-D1chlorobenz1d1ne
Benzo (a) anthracene
b1 s (2-ethyl hexy 1 ) phthal ate
CAS Number
91-58-7
88-74-4
131-11-3
208-96-8
99-09-2
83-32-9
51-28-5
100-02-7
132-64-9
121-14-2
606-20-2
84-66-2

7005-72-3
86-73-7
100-01-6
534-52-1
86-30-6
101-55-3
118-74-1
87-86-5
85-01-8
120-12-7
84-74-2
206-44-0
129-00-0
85-68-7
91-94-1
56-55-3
117-81-7
ug/L
10
50
10
10
50
10
50
50
10
10
10
10

10
10
50
50
10
10
10
50
10
10
10
10
10
10
20
10
10
Low Soil /Sediment1
ug/Kg
660
3300
660
660
3300
660
3300
3300
660
660
660
660

660
660
3300
3300
660
660
660
3300
660
660
660
660
660
660
1300
660
660
                                   8270 - 6
                                                          Revision       0
                                                          Date   September  1986

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TABLE 2.  PRACTICAL QUANTITATION LIMITS (PQL) FOR SEMIVOLATILE ORGANICS**
          (Continued)

                                              Practical  Quantisation
                                                      Limits*
Semi-Volatiles
                                          Ground Water   Low Soil/Sediment1
CAS Number
ug/L
ug/Kg
Chrysene
Di-n-octyl phthalate
Benzo (b) f 1 uoranthene
Benzo (k) f 1 uoranthene
Benzo(a)pyrene
Indeno(l,2,3-cd)pyrene
Di benz (a , h) anthracene
Benzo (g , h , i ) peryl ene
218-01-9
117-84-0
205-99-2
207-08-9
50-32-8
193-39-5
53-70-3
191-24-2
10
10
10
10
10
10
10
10
660
660
660
660
660
660
660
660 r
*PQLs listed for soil/sediment  are  based  on  wet  weight.  Normally data is
reported on a dry weight basis, therefore, PQLs will be higher based on the
% moisture in each sample.  This is  based on a 30-g sample and gel permeation
chromatography cleanup.
**Sample  PQLs  are   highly  matrix-dependent.    The  PQLs
provided  for guidance  and may not always be achleveable.
                               listed  herein are
         Other Matrices

      Medium-level  soil and sludges  by sonicator
      Non-water-miscible waste
                           Factor1

                              7.5
                             75
           = [PQL for Ground Water (Table 2)]  X  [Factor].
                                   8270 - 7
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                                                          Date   September  1986

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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-level and low-
level samples are  sequentially  analyzed.    To  reduce carryover, the sample
syringe must  be  rinsed  out  between  samples  with  solvent.    Whenever an
unusually concentrated sample 1s  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.  The  capillary  column should be directly coupled to
     the source.

          4.1.2  Column:  30-m  x  0.25-mm  I.D.   (or  0.32-mm I.D.) 1-um film
     thickness silicon-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 decafluorotriphenylphosphlne  (DFTPP)
     which  meets all of the criteria 1n Table  3 when 1 uL 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
     the duration  of the  chromatographic  program.   The  computer  must  have
                                   8270 - 8
                                                          Revision      0
                                                          Date  September 1986

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TABLE 3.  DFTPP KEY IONS AND ION ABUNDANCE CRITERIA3

   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

   3J.W.  Eichelberger,  I.E.  Harris,  and  W.L.  Budde. "Reference Compound to
Calibrate Ion Abundance Measurement  1n Gas Chromatography-Mass Spectrometry",
Analytical Chemistry, 47, 995  (1975).
                                   8270 - 9
                                                          Revision
                                                          Date   September 1986

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     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-uL.


5.0  REAGENTS

     5.1  Stock standard solutions (1.00  ug/uL):     Standard solutions can  be
prepared from pure standard materials or purchased as certified  solutions.

          5.1.1  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.

          5.1.2  Transfer  the  stock  standard  solutions  into Teflon-sealed
     screw-cap bottles.  Store at 4*C  and protect from light.   Stock standard
     solutions should  be  checked  frequently  for  signs  of  degradation  or
     evaporation, especially  just  prior  to  preparing calibration standards
     from them.

          5.1.3  Stock standard  solutions  must  be  replaced  after  1 yr or
     sooner  if  comparison  with  quality  control  check  samples Indicates a
     problem.

     5.2  Internal standard solutions;   The internal standards recommended are
l,4-dichlorobenzene-d4,naphthalene-ds,  acenaphthene-djo,  phenanthrene-dio,
chrysene-di2, and perylene-di2.    Other compounds  may  be  used as internal
standards as long  as  the  requirements  given  in  Paragraph  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  1n small volumes of methanol, acetone,
or toluene,  except for perylene-di2.  The resulting solution will contain each
standard at  a  concentration  of  4,000 ng/uL.    Each  1-mL  sample extract
undergoing analysis should  be  spiked   with  10   uL  of the internal standard
solution, resulting  in a  concentration of  40 ng/uL of each internal standard.
Store at 4*C or  less  when  not being used.

     5.3  GC/MS  tuning standard;  A methylene chloride solution containing
50 ng/uL of  decaf1uorotriphenylphosphlne  (DFTPP)  should  be  prepared.  The
                                  8270 -  10
                                                         Revision      0
                                                         Date  September 1986

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standard should also contain 50 ng/uL each of 4,4'-DDT,  pentachlorophenol,  and
benzldlne to verify Injection port Inertness and GC column performance.   Store
at 4*C or less when not being used.

     5.4  Calibration standards;  Calibration  standards  at a minimum of five
concentration levels 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  uL  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 dally  calibration standard should be prepared weekly
and stored at 4°C.

     5.5  Surrogate  standards;    The  recommended  surrogate  standards  are
phenol-ds,2-fluorophenol,  2,4,6-tribromophenol,  nitrobenzene-ds, 2-fluoro-
biphenyl, and  p-terphenyl-di4.    See  Method  3500  for  the Instructions on
preparing the surrogate standards.   Determine what concentration should be in
the blank extracts  after   all T 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.

      5.6  Matrix   spike  standards;    See  Method  3500  for  Instructions on
preparing the matrix spike standard.     Determine what  concentration  should be
1n  the blank extracts  after all  extraction,  cleanup, and concentration steps.
Inject this concentration  Into  the  GC/MS  to determine recovery of  surrogate
standards 1n all blanks, spikes,  and  sample  extracts.  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
                                   8270 - 11
                                                          Revision       0
                                                          Date  September  1986

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          7.1.1  Direct  Injection:    In  very  limited  applications   direct
     Injection of the sample Into the GC/MS system with a 10 uL syringe may  be
     appropriate.  The  detection  limit  1s  very  high (approximately 10,000
     ug/L); therefore, 1t 1s only  permitted where concentrations 1n excess  of
     10,000 ug/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
          Organochlorlne pesticides & PCBs      3620, 3640,  3660
          Nltroaromatlcs and cyclic ketones     3620, 3640
          Polynuclear aromatic hydrocarbons     3611, 3630,  3640
          Haloethers                            3620, 3640
          Chlorinated hydrocarbons              3620, 3640
          Organophosphorous pesticides          3620, 3640
          Petroleum waste                       3611, 3650
          All priority pollutant base,
              neutral, and adds                3640

     aMethod 8040  Includes  a  der1vat1zat1on  technique  followed  by GC/ECD
     analysis,  1f  Interferences are encountered on GC/FID.

     7.3   Initial  calibration;  The recommended GC/MS operating conditions:

     Mass  range:   35-500  amu           ;
     Scan  time:  1 sec/scan            !
     Initial column temperature and hold time:  40*C for 4 m1n
     Column temperature program:   40-270*C  at  !0*C/m1n
     Final column  temperature  hold:   270*C  (until benzo[g,h,1]perylene
                                      has eluted)
     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  uL
     Carrier gas:  Hydrogen at 50  cm/sec or helium  at  30 cm/sec.

           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 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.   It may also be necessary
     to break  off  the first 6-12 in.  of the capillary  column.

                                   8270 - 12
                                                         Revision      0
                                                         Date  September 1986

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     7.3.2  The  Internal  standards  selected  1n  Paragraph  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  1,4-
dichlorobenzene-d4 use m/z 152 for quantitation.

     7.3.3  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).
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)/(AisCx)

where:

     Ax  = Area of the characteristic ion for the compound being
           measured.

     AIS = Area of the characteristic 1on for the specific internal
            standard.

     Cx  = Concentration of the compound being measured (ng/uL).

     C^s = Concentration of the specific internal standard (ng/uL).


     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-dinitrophenol;
and 4-nitrophenol.  The  minimum acceptable average RF  for these  compounds
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.
                              8270 - 13
                                                     Revision      0
                                                     Date  September  1986

-------
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                       R1C                               DATA: 51BHS680736 fcl     SCANS  2*8 TO 2700
                       38/07/86  6:26:38                  CHLI: 51BHS680786 13
                       SHMPLE: BASE ACID STD,2U-/20rtG--Ul.
                       COMDS.:
                       RuNCE: G   1,2788  LABEL: N  8, 4.0  OUnN: A  U, 1.8 J 8  BASE: U 28,  3
                RIC
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                                                   16:48
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                                                                                                                        13S523.
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                         Figure  1.  Gas chromatogram of  base/neutral  and add  calibration standard.

-------
TABLE 4.  CALIBRATION CHECK COMPOUNDS
Base/Neutral Fraction                     Add Fraction
Acenaphthene                              4-Chloro-3-methy1 phenol
1,4-01chlorobenzene                       2,4-Dichlorophenol
Hexachlorobutadiene                       2-N1trophenol
N-Ni troso-di-n-pheny1 ami ne                Phenol
01-n-octy1phthalate                       Pentachlorophenol
Fluoranthene                              2,4,6-Trichlorophenol
Benzo(a)pyrene
                                  8270 -  15
                                                         Revision
                                                         Date  September  1986

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7.4  Dally 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-hr shift.

     7.4.2  A   calibration   standard(s)    at   mid-level  concentration
containing all semi volatile analytes,  including all required surrogates,
must be performed  every  12-hr  during  analysis.   Compare the response
factor data from  the  standards  every  12-hr  with the average response
factor from the initial calibration for  a specific instrument as per the
SPCC (Paragraph 7.4.3) and CCC  (Paragraph 7.4.4) criteria.

     7.4.3  System  Performance  Check  Compounds   (SPCCs):    A  system
performance check must be made  during  every  12  hr 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  - RF
   =
   RF
                             r
      % Difference  = —  - - X  100
                           i

where:

      RFj  =  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 calibration MUST be generated.    This   criterion MUST be met
before  sample analysis begins.
                              8270 - 16
                                                     Revision
                                                     Date   September  1986

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     7.4.5  The Internal standard  responses  and  retention times 1n 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 sec from  the last check calibration (12 hr), 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 dally
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  uL 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) si 11 cone-coated  fused-sH1ca capillary  column.  The volume  to be
Injected should  ideally contain  100 ng of  base/neutral and  200 ng of add
surrogates  (for  a   1 uL   Injection).     The   recommended GC/MS operating
conditions  to  be used are specified  in  Paragraph 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/uL  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  Paragraph  7.6.    Store  the   extracts at 4*C,  protected from
 light  1n  screw-cap  vials  equipped with  unpierced Teflon-lined  septa.

 7.6  Data  Interpretation;

      7.6.1   Qualitative analysis:

           7.6.1.1   An   analyte  (e.g.,   those    listed   in   Table  1)  is
      identified  by  comparison  of the   sample  mass spectrum with  the mass
      spectrum of a  standard of the suspected compound  (standard reference
      spectrum).  Mass  spectra   for  standard reference  should  be  obtained
      on the user's  GC/MS  within  the  same  12 hours as the sample analysis.
      These standard reference  spectra  may be obtained  through  analysis of
      the  calibration standards.   Two criteria  must be  satisfied to verify
      identification:  (1)  elution  of  sample  component  at  the same GC
      relative retention time   (RRT)   as  the  standard  component;  and  (2)
      correspondence of the  sample  component   and the  standard component
      mass spectrum.
                              8270 - 17
                                                     Revision      0
                                                     Date  September 1986

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          7.6.1.1.1   The  sample  component  RRT must compare within
     +0.06 RRT units of   the  RRT  of  the  standard component.  For
     reference,  the  standard must be  run  within the same 12 hrs as
     the  sample.   If  coelutlon  of Interfering components prohibits
     accurate assignment  of the  sample  component RRT from the total
     ion  chromatogram,  the RRT should be assigned by using extracted
     ion  current   profiles for  ions   unique  to  the  component of
     interest.

          7.6.1.1.2   All  ions present   in  the standard mass spectra
     at a relative intensity greater  than 10%  (most abundant ion in
     the   spectrum  equals 100% must  be  present  in   the  sample
     spectrum.

          7.6.1.1.3   The  relative  intensities  of   ions specified in
     Paragraph 7.6.1.1.2  must agree within plus or minus  20% between
     the  standard and sample  spectra.   (Example:  For an  ion with an
     abundance of 50%  in  the   standard   spectra,  the  corresponding
     sample abundance must be between 30  and 70 percent.

     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.  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 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 1n  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.
                        8270 - 18
                                               Revision      0
                                               Date  September 1986

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7.6.2  Quantitative analysis:

     7.6.2.1  When a compound has  been Identified,  the quantltatlon
of that compound will be based  on the Integrated abundance from the
EICP of the  primary  characteristic  1on.     Quantltatlon 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
1n the sample as follows:

Water:
                          (Ax)(Is)(Vt)
 concentration (ug/L) = (A
where:

     Ax  = Area   of   characteristic   1on   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 uL.    If  half  the base/neutral extract and
           half  the add extract are combined, Vt = 2,000.

     A^s = Area  of characteristic 1on for the Internal standard.

     RF  = Response factor  for  compound  being measured  (Paragraph
           7.3.3).

     V0  = Volume of water extracted  (ml).

     \l\  = Volume of extract  Injected  (uL).

 Sed1ment/Spn Sludge  (on a dry-weight  basis) and Waste  (normally on
 a wet-weight basis;

                              (AJ(IS)(V )
  concentration  (ug/kg)  =  (A.S)(RF)(V.)(W$)(D)

  where:

       AXI  Is»  Vti Ais*  RF'  vi  = same  as  ^or water-

       Ws  =  weight of  sample  extracted or diluted in  grams.

       D =  (100 - % moisture  In sample)/100, or 1 for a  wet-weight
             basis.

                         8270 -  19
                                               Revision       0
                                                Date   September  1986

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TABLE 5.  SEMIVOLATILE INTERNAL STANDARDS WITH CORRESPONDING ANALYTES
          ASSIGNED FOR QUANTITATION
1,4-D1chlorobenzene-d4
Naphthalene-ds
Acenaphthene-djo
Aniline
Benzyl alcohol
Bi s(2-chloroethyl)ether
Bi s(2-chloroi sopropyl)ether
2-Chlorophenol
1,3-Di chlorobenzene
1,4-Dichlorobenzene
1,2-Di chlorobenzene
Ethyl methanesulfonate
2-Fluorophenol (surr.)
Hexachloroethane
Methyl methanesulfonate
2-Methylphenol
4-Methylphenol
N-N1trosodlmethyl amine
N-N1 troso-d1-n-propylamine
Phenol
Phenol-ds  (surr.)
2-P1col1ne
Acetophenone
Benzole acid
B1s(2-chloroethoxy)methane
4-Chloroanil1ne
4-Chloro-3-methy1 phenol
2,4-Dichlorophenol
2,6-Dichlorophenol
a,a-Dimethyl -
  phenethylamine
2,4-Dimethyl phenol
Hexachlorobutadi ene
Isophorone
2-Methylnaphthalene
Naphthalene
Nitrobenzene
Nitrobenzene-ds (surr.)
2-N1trophenol
N-N1 troso-'d1 -n-butyl ami ne
N-N1trosop1per1d1ne
1,2,4-Tri chlorobenzene
Acenaphthene
Acenaphthylene
1-Chloronaphthal ene
2-Chloronaphthalene
4-Chlorophenyl
  phenyl ether
Dibenzofuran
Diethyl phthalate
Dimethyl phthalate
2,4-Dinitrophenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Fluorene
2-Fluorob1phenyl
  (surr.)
Hexachlorocyclo-
  pentadlene
l-Naphthylam1ne
2-Naphthylam1ne
2-Nitroan1l1ne
3-Nitroan1line
4-N1troan1line
4-N1trophenol
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
                                   8270 - 20
                                                          Revision      0
                                                          Date   September 1986

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TABLE 5.  SEMIVOLATILE INTERNAL STANDARDS WITH CORRESPONDING ANALYTES
          ASSIGNED FOR QUANTITATION  (Continued)
Phenanthrene-dio
Chrysene-di2
Perylene-dj2
4-Amlnoblphenyl
Anthracene
4-Bromophenyl phenyl ether
Di-n-butyl phthalate
4,6-Di ni tro-2-methy1 phenol
Diphenylamine
1,2-Di phenylhydrazi ne
Fluoranthene
Hexachlorobenzene
N-Ni trosodi phenylami ne
Pentachlorophenol
Pentachloroni trobenzene
Phenacetin
Phenanthrene
Pronamide
Benzidine
Benzo(a)anthracene
Bi s(2-ethylhexyl)phthalate
Butyl benzylphthalate
Chrysene
3,3'-Di chlorobenzidi ne
p-Dimethylaminoazobenzene
Pyrene
Terphenyl-di4 (surr.)
Benzo(b)fluor-
  anthene
Benzo(k)fluor-
  anthene
Benzo(g,h,i)
  perylene
Benzo(a)pyrene
Dibenz(a,j)acridine
D1benz(a,h)
  anthracene
7,12-Dimethylbenz-
  (a)anthracene
D1-n-octy1phthalate
Indeno(l,2,3-cd)
  pyrene
3-Methylchol-
 anthrene
 (surr.) = surrogate
                                   8270 - 21
                                                          Revision      0
                                                          Date  September 1986

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               7.6.2.3  Where applicable,   an  estimate  of  concentration  for
          noncallbrated components 1n the  sample should be made.   The formulas
          given above should be  used  with  the following modifications:   The
          areas Ax and AIS 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  Report results without  correction  for recovery data.
          When duplicates and  spiked  samples  are  analyzed, report all  data
          obtained with the sample results.

               7.6.2.5  Quantisation   of   multicomponent   compounds  (e.g.,
          Aroclors)  1s  beyond  the   scope   of   Method  8270.    Normally,
          quantltation is performed using a GC/ECD by Method 8080.


8.0  QUALITY CONTROL

     8.1  Each laboratory that uses  these  methods  1s   required to operate a
formal quality control  program.    The  minimum  requirements of this program
consist of an Initial  demonstration  of  laboratory capability and an ongoing
analysis of spiked samples to evaluate  and document quality data.  The labor-
atory must maintain records  to  document  the  quality of the data generated.
Ongoing data quality checks are compared with established performance criteria
to determine 1f the results  of  analyses meet the performance characteristics
of the  method.    When  results  of  sample  spikes   indicate atypical method
performance, a quality control check standard must be  analyzed to confirm that
the measurements were performed in an 1n-control mode  of  operation.

     8.2  Before  processing  any  samples,  the  analyst  should demonstrate,
through the analysis of  a  reagent  water  blank, that Interferences from the
analytical system, glassware, and reagents are under control.  Each time a set
.of samples 1s extracted or  there  is  a  change  in reagents, a reagent water
blank  should  be  processed   as   a  safeguard  against  chronic  laboratory
contamination.  The blank  samples should  be carried through all stages of the
sample preparation and measurement steps.

     8.3  The  experience  of  the   analyst   performing GC/MS  analyses  is
Invaluable to  the  success  of  the  methods.    Each day  that  analysis is
performed, the daily calibration standard   should be evaluated to determine if
the chromatographic system is  operating  properly.    Questions that  should be
asked are:  Do the peaks  look  normal?; Is  the  response obtained comparable to
the response from previous calibrations?    Careful examination of the standard
chromatogram can  indicate  whether the   column   is  still  good, the  injector is
leaking,  the injector  septum  needs  replacing,  etc.   If any changes  are  made to
the system  (e.g,  columnichanged), recalibration  of the system must  take place.
                                   8270 - 22
                                                          Revision       0
                                                          Date   September  1986

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     8.4  Required Instrument QC Is  found  1n  the  following  sections:

          8.4.1  The  GC/MS  system    must   be    tuned   to  meet  the  DFTPP
     specifications in Section 7.3.1 and 7.4.1.

          8.4.2  There must be an initial   calibration   of  the  GC/MS  system as
     specified in 7.3.

          8.4.3  The GC/MS system must meet  the  SPCC criteria specified 1n
     7.4.3 and the CCC criteria in 7.4.4,  each 12 hr.

     8.5  To  establish  the  ability  to   generate  acceptable  accuracy   and
precision, the analyst must perform the following operations.

          8.5.1  A  quality   (QC)   check    sample   concentrate  is   required
     containing each analyte at a concentration  of 100 ug/mL 1n acetone.   The
     QC check sample concentrate may  be prepared from pure standard  materials
     or purchased as certified solutions.    If prepared by the laboratory, the
     QC check sample concentrate must  be   made using stock standards prepared
     independently from those used for calibration.

          8.5.2  Using a pipet, prepare QC check samples at a concentration of
     100 ug/L by adding 1.00 ml of QC check sample concentrate to each of four
     1-L aliquots of reagent water.

          8.5.3  Analyze the  well-mixed  QC  check  samples  according to the
     method beginning in Section 7.1 with extraction of the samples.

          8.5.4  Calculate the average recovery  (X)  in ug/L, and the standard
     deviation of the recovery  (s)  in ug/L, for each analyte of interest using
     the four  results.

          8.5.5  For each  analyte  compare  s  and  7.  with the corresponding
     acceptance criteria for  precision   and  accuracy, respectively, found 1n
     Table 6.  If s and 7  for  all analytes meet the acceptance criteria, the
     system performance  1s   acceptable   and  analysis  of  actual samples can
     begin.   If any individual s exceeds  the precision limit or any individual
     7  falls outside the range  for  accuracy,  then the system performance 1s
     unacceptable for that analyte.
          NOTE:  The  large number of analytes in Table 6 present a substantial
          probability  that   one  or  more  will  fail  at  least  one  of the
          acceptance  criteria  when  all   analytes  of  a  given  method  are
          analyzed.

          8.5.6  When one or  more of the  analytes tested fall at least one of
     the acceptance criteria, the   analyst  must  proceed according to Section
     8.5.6.1  or 8.5.6.2.

               8.5.6.1  Locate  and  correct  the  source  of  the  problem and
          repeat  the  test  for all   analytes of interest beginning with Section
          8.5.2.
                                   8270 - 23
                                                         Revision      0
                                                         Date  September 1986

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TABLE 6.  QC ACCEPTANCE CRITERIA3
Parameter
Acenaphthene
Acenaphthylene
Aldrin
Anthracene
Benzo (a) anthracene
Benzo (b) f 1 uoranthene
Benzo (k) f 1 uoranthene
Benzo(a)pyrene
Benzo (ghl)perylene
Benzyl butyl phthalate
/J-BHC
5-BHC
B1 s (2-chl oroethyl ) ether
B1 s (2-chl oroethoxy)methane
B1 s (2-chl orol sopropyl ) ether
Bi s (2-ethy 1 hexy 1 ) phthal ate
4-Bromophenyl phenyl ether
2-Chloronaphthalene
4-Chlorophenyl phenyl ether
Chrysene
4,4'-DDD
4, 4 '-DDE
4,4'-DDT
Dibenzo (a, h) anthracene
D1-n-butyl phthalate
l,2-D1chl orobenzene
1 , 3-D1 chl orobenzene
l,4-D1chl orobenzene
3,3'-D1chlorobenz1d1ne
D1eldr1n
Dlethyl phthalate
Dimethyl phthalate
2,4-D1n1trotoluene
2,6-D1m'trotoluene
D1-n-octyl phthal ate
Endosulfan sulfate
Endrin aldehyde
Fl uoranthene
Fluorene
Heptachlor
Heptachlor epoxide
Hexachl orobenzene
Hexachl orobutadl ene
Hexachl oroethane
Test
cone.
(ug/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
100
Limit
for s
(ug/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 7
(ug/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
                                   8270 - 24
                                                          Revision       0
                                                          Date   September  1986

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TABLE 6.  QC ACCEPTANCE CRITERIA3 - Continued
Parameter
Indeno(l,2,3-cd)pyrene
Isophorone
Naphthalene
Nitrobenzene
N-N1 trosodl -n-propy 1 ami ne
PCB-1260
Phenanthrene
Pyrene
1,2,4-Trichlorobenzene
4-Chl oro-3-methyl phenol
2-Chlorophenol
2,4-Chlorophenol
2,4-01 methyl phenol
2,4-D1m'trophenol
2-Methyl -4 , 6-dl n1 trophenol
2-N1trophenol
4-N1 trophenol
Pentachlorophenol
Phenol
2,4,6-Trlchlorophenol
Test
cone.
(ug/L)
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
Limit
for s
(ug/L)
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
Range
for 7
(ug/L)
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
Range
P, Ps
(X)
D-171
21-196
21-133
35-180
D-230
D-164
54-120
52-115
44-142
22-147
23-134
39-135
32-119
D-191
D-181
29-182
D-132
14-176
5-112
37-144
      s  =  Standard deviation  of  four  recovery measurements, 1n ug/L.

      7  =  Average recovery  for four recovery measurements,  1n ug/L.

      p, ps  =  Percent  recovery measured.

      D  =  Detected;  result  must  be greater  than  zero.

      3Cr1ter1a from 40 CFR Part 136  for  Method 625.   These criteria  are  based
 directly  on the method  performance   data   1n   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.
                                   8270 - 25
                                                          Revision
                                                          Date  September 1986

-------
               8.5.6.2  Beginning with Section 8.5.2,  repeat the test only for
          those analytes that  failed  to  meet  criteria.    Repeated failure,
          however, will confirm a general problem with the  measurement system.
          If this occurs, locate  and  correct  the  source of the problem and
          repeat the test for all compounds of Interest beginning with Section
          8.5.2.

     8.6  The laboratory must, on an ongoing basis, analyze a reagent blank,  a
matrix spike, and a matrix spike duplicate/duplicate for each analytical  batch
(up to a maximum of  20  samples/batch)  to assess accuracy.  For laboratories
analyzing one to ten samples per  month,  at least one spiked sample per month
1s required.

          8.6.1  The concentration  of  the  spike  1n  the  sample  should be
     determined as follows:

               8.6.1.1  If, as 1n compliance  monitoring, the concentration of
          a  specific  analyte  1n  the  sample  1s  being   checked  against a
          regulatory concentration limit, the spike should  be at that limit or
          1 to 5 times higher  than the background concentration determined 1n
          Section 8.6.2, whichever concentration would be larger.

               8.6.1.2  If the  concentration  of  a  specific  analyte 1n the
          sample 1s  not  being  checked  against  a  limit  specific  to that
          analyte, the spike should be at 100 ug/L or 1 to  5 times higher than
          the background concentration determined  1n Section 8.6.2, whichever
          concentration would be larger.

               8.6.1.3  If 1t Is  Impractical  to  determine background levels
          before spiking (e.g., maximum  holding  times will be exceeded), the
          spike concentration should  be  at   (1) the regulatory concentration
          limit, 1f any; or, 1f none   (2)  the larger of either 5 times higher
          than the expected background concentration or  100 ug/L.

          8.6.2  Analyze  one  sample  aliquot  to  determine  the  background
     concentration  (B) of each analyte.   If necessary, prepare a new QC check
     sample  concentrate   (Section  8.5.1)   appropriate  for  the  background
     concentration  1n  the sample.  Spike  a second sample aliquot with 1.00 ml
     of the QC  check  sample  concentrate  and  analyze  1t  to determine the
     concentration  after spiking  (A) of  each  analyte.   Calculate each percent
     recovery  (p) as 100(A-B)%/T,  where  T  Is  the  known  true value of the
     spike.       .

          8.6.3  Compare the percent recovery   (p)  for  each analyte with the
     corresponding  QC  acceptance criteria found  1n Table 6.  These acceptance
     criteria were  calculated to Include an allowance for error 1n measurement
     of both the  background  and  spike  concentrations,   assuming a spike to
     background ratio  of 5:1.  This error  will be accounted for to the extent
     that the analyst's  spike to background  ratio approaches 5:1.  If spiking
     was performed  at  a  concentration   lower   than  100  ug/L, the analyst must
     use either the QC acceptance  criteria  presented 1n Table 6, or optional
     QC acceptance  criteria calculated   for  the specific spike concentration.
     To calculate optional acceptance  criteria for the recovery of an analyte:

                                  8270 4- 26
                                                         Revision      0
                                                         Date  September 1986

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     (1)   Calculate  accuracy  (x1)   using  the  equation  found  1n  Table 7,
     substituting the spike  concentration  (T)  for  C;  (2)  calculate overall
     precision (S1) using the equation 1n  Table 7,  substituting x1  for X;  (3)
     calculate the range for recovery  at the spike  concentration as (lOOx'/T)
     + 2.44(100S'/T)%.

          8.6.4  If any Individual p  falls  outside  the designated range for
     recovery, that analyte  has  failed  the  acceptance  criteria.   A check
     standard  containing  each  analyte  that  failed  the  criteria  must be
     analyzed as described 1n Section 8.7.

     8.7  If any analyte fails the acceptance criteria for recovery in Section
8.6, a QC check standard containing  each analyte that failed must be prepared
and analyzed.
     NOTE:  The frequency for  the  required  analysis  of a QC check standard
     will depend upon the number  of analytes being  simultaneously tested, the
     complexity of the sample matrix,  and  the performance of the laboratory.
     If the entire list of analytes in  Table 6 must be measured in the sample
     1n Section 8.6, the probability that  the analysis of a QC check standard
     will be required is high.  In  this  case the QC check standard should be
     routinely analyzed with the spiked sample.

          8.7.1  Prepare the QC check  standard  by  adding  1.0  ml of the QC
     check sample concentrate  (Section  8.5.1  or  8.6.2)  to  1 L of reagent
     water.  The QC check  standard  needs  only  to contain the analytes that
     failed criteria in the test in Section 8.6.

          8.7.2  Analyzed the QC check standard to determine the concentration
     measured  (A) of each analyte.    Calculate  each percent recovery  (ps) as
     100  (A/T)%, where T is the true value of  the standard concentration.

          8.7.3  Compare the percent recovery   (ps)  for each analyte with the
     corresponding QC acceptance criteria  found  in  Table  6.  Only analytes
     that failed the  test  1n  Section  8.6   need  to  be compared with these
     criteria.   If  the  recovery  of  any  such  analyte  falls  outside the
     designated  range, the laboratory  performance  for that analyte  is judged
     to  be out of  control, and  the problem must be Immediately  Identified and
     corrected.  The analytical result for that analyte  1n the  unspiked sample
     1s  suspect  and may  not be reported for regulatory compliance purposes.

     8.8 As  part  of the QC  program  for  the laboratory, method accuracy for
each matrix  studied must be  assessed  and  records must be maintained.  After
the analysis  of  five  spiked  samples   (of  the   same matrix) as  in Section  8.6,
calculate the average percent  recovery   (JJ)  and the  standard deviation of the
percent  recovery (sp).   Express the   accuracy  assessment as a percent recovery
interval  from p  -  2sp to p + 2sp.    If  p = 90% and sp =  10%, for example, the
accuracy interval  is  expressed as 70-110%.  Update  the accuracy assessment for
each analyte on  a  regular  basis   (e.g.   after each   five  to ten new accuracy
measurements).                                              >   .

     8.9  To determine  acceptable accuracy   and precision  limits for surrogate
standards the following  procedure should  be performed.


                                   8270 - 27
                                                          Revision       0
                                                          Date   September  1986

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TABLE 7.  METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION3
Parameter
Acenaphthene
Acenaphthylene
Aldrln
Anthracene
Benzo (a) anthracene
Chloroethane
Benzo (b) fl uoranthene
Benzo (k)fl uoranthene
Benzo(a)pyrene
Benzo (ghi)perylene
Benzyl butyl phthalate
/7-BHC
5-BHC
Bis(2-chloroethyl) ether
B1 s (2-chl oroethoxy) methane
Bi s (2-chl orol sopropyl ) ether
B1 s (2-ethy 1 hexy 1 ) phthal ate
4-Bromophenyl phenyl ether
2-Chloronaphthalene
4-Chlorophenyl phenyl ether
Chrysene
4,4'-DDD
4,4'-DDE.
4,4'-DDT
Dibenzo (a, h) anthracene
Dl-n-butyl phthalate
1,2-Dichl orobenzene
1 , 3-Di chl orobenzene
l,4-D1chlorobenzene
3,3'-D1chlorobenzid1ne
Dleldrin
D1 ethyl phthalate
Dimethyl phthalate
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Di -n-octyl phthal ate
Endosulfan sulfate
Endrln aldehyde
Fl uoranthene
Fluorene
Heptachlor
Heptachlor epoxide
Hexachl orobenzene
Hexachl orobutadi ene
Hexachl oroethane
Accuracy, as
recovery, x'
(ug/L)
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
Single analyst
precision, sr'
(ug/L)
0.157-0.12
0.247-1.06
0.277-1.28
0.217-0.32
0.157+0.93
0.147-0.13
0.227+0.43
0.197+1.03
0.227+0.48
0.297+2.40
0.187+0.94
0.207-0.58
0.347+0.86
0.357-0.99
0.167+1.34
0.247+0.28
0.267+0.73
0.137+0.66
0.077+0.52
0.207-0.94
0.287+0.13
0.297-0.32
0.267-1.17
0.427+0.19
0.307+8.51
0.137+1.16
0.207+0.47
0.257+0.68
0.247+0.23
0.287+7.33
0.207-0.16
0.287+1.44
0.547+0.19
0.127+1.06
0.147+1.26
0.217+1.19
0.127+2.47
0.187+3.91
0.227-0.73
0.127+0.26
0.247-0.56
0.337-0.46
0.187-0.10
0.197+0.92
0.177+0.67
Overall
precision,
S1 (ug/L)
0.217-0.67
0.267-0.54
0.437+1.13
0.277-0.64
0.267-0.21
0.177-0.28
0.297+0.96
0.357+0.40
0.327+1.35
0.517-0.44
0.537+0.92
0.307+1.94
0.937-0.17
0.357+0.10
0.267+2.01
0.257+1.04
0.367+0.67
0.167+0.66
0.137+0.34
0.307-0.46
0.337-0.09
0.667-0.96
0.397-1.04
0.657-0.58
0.597+0.25
0.397+0.60
0.247+0.39
0.417+0.11
0.297+0.36
0.477+3.45
0.267-0.07
0.527+0.22
1.057-0.92
0.217+1.50
0.197+0.35
0.377+1.19
0.637-1.03
0.737-0.62
0.287-0.60
0.137+0.61
0.507-0.23
0.287+0.64
0.437-0.52
0.267+0.49
0.177+0.80
                                   8270 - 28
                                                          Revision       0
                                                          Date   September  1986

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TABLE 7.  METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION3 -
           Continued
Parameter
Indeno(l , 2, 3-cd)pyrene
Isophorone
Naphthalene
Nitrobenzene
N-Ni trosodi -n-propyl ami ne
PCB-1260
Phenanthrene
Pyrene
1,2, 4-TH chl orobenzene
4-Chloro-3-methyl phenol
2-Chlorophenol
2,4-Dichlorophenol
2, 4-Dimethyl phenol
2,4-D1nitrophenol
2-Methyl -4 , 6-di ni trophenol
2-Nitrophenol
4-Ni trophenol
Pentachlorophenol
Phenol
2,4,6-Trichlorophenol
Accuracy, as
recovery, x1
(ug/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, sr'
(ug/L)
0.297+1.46
0.277+0.77
0.217-0.41
0.197+0.92
0.277+0.68
0.357+3.61
0.127+0.57
0.167+0.06
0.157+0.85
0.237+0.75
0.187+1.46
0.157+1.25
0.167+1.21
0.387+2.36
0.107+42.29
0.167+1.94
0.387+2.57
0.247+3.03
0.267+0.73
0.167+2.22
Overall
precision,
S1 (ug/L)
0.507-0.44
0.337+0.26
0.307-0.68
0.277+0.21
0.447+0.47
0.437+1.82
0.157+0.25
0.157+0.31
0.217+0.39
0.297+1.31
0.287+0.97
0.217+1.28
0.227+1.31
0.427+26.29
0.267+23.10
0.277+2.60
0.447+3.24
0.307+4.33
0.357+0.58
0.227+1.81
     x1   =  Expected   recovery   for  one  or  more  measurements  of  a  sample
            containing a  concentration of C, in ug/L.

     sr'  =  Expected  single  analyst  standard  deviation  of measurements at an
            average concentration of 7, in ug/L.

     S1   =  Expected  interlaboratory standard  deviation  of measurements at an
            average concentration found of 7, in ug/L.

     C    =  True  value for the  concentration, in ug/L.

     7    =  Average recovery found for measurements of samples containing a
              concentration  of  C, in ug/L.
                                   8270 - 29
                                                          Revision       0
                                                          Date   September  1986

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         8.9.1  For each sample analyzed,  calculate  the percent recovery of
    each surrogate 1n the sample.

         8.9.2  Once a minimum of thirty samples of the same matrix have been
    analyzed,  calculate  the  average  percent  recovery   (P)  and  standard
    deviation of the percent recovery  (s) for each of the surrogates.

         8.9.3  For a given  matrix,   calculate  the  upper and lower control
    limit  for method performance for each surrogate standard.  This should be
    done as  follows:

              Upper Control  Limit  (UCL) = p + 3s
              Lower Control  Limit  (LCL) = p - 3s

         8.9.4  For aqueous  and  soil  matrices, these  laboratory established
    surrogate control  limits   should,  if  applicable,  be  compared with the
    control  limits  listed  1n Table  8.  The limits given 1n  Table 8 are multi-
    laboratory performance based   limits  for   soil   and  aqueous samples, and
    therefore, the  single-laboratory   limits  established  in  Paragraph  8.9.3
    must  fall within  those given in Table 8 for these matrices.

          8.9.5   If  recovery  is  not within   limits,  the  following procedures
    are required.

               •   Check to  be   sure there  are no   errors  in  calculations,
                  surrogate solutions   and   Internal   standards.    Also,  check
                  instrument  performance.

               •   Recalculate the data  and/or  reanalyze  the extract  if  any  of
                  the  above checks  reveal  a  problem.

               •   Reextract and reanalyze  the  sample   1f none  of  the  above are
                  a  problem or flag the data  as  "estimated concentration."

          8.9.6   At   a  minimum,   each    laboratory   should  update  surrogate
     recovery limits on a matrix-by-matrix basis,  annually.

     8.10  It 1s   recommended  that  the   laboratory   adopt additional quality
assurance practices  for use with this method.   The  specific practices that are
most productive  depend upon the needs of   the  laboratory and the  nature  of the
samples.  Field  duplicates   may  be  analyzed   to  assess  the  precision  of the
environmental measurements.   When  doubt   exists  over the Identification of a
peak on the chromatogram,  confirmatory  techniques  such as gas chromatography
with a dissimilar column, specific  element detector,  or  mass spectrometer must
be used.  Whenever possible,   the laboratory  should  analyze standard  reference
materials and participate in  relevant performance evaluation studies.
                                  8270 - 30
                                                         Revision
                                                         Date  September 1986

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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-ds                        35-114                    23-120
2-Fluorobiphenyl                       43-116                    30-115
p-Terphenyl-di4                        33-141                    18-137

Phenol-d6                              10-94                     24-113
2-Fluorophenol                         21-100                    25-121
2,4,6-Tribromophenol                   10-123                    19-122
                                  8270 - 31
                                                         Revision
                                                         Date  September  1986

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9.0  METHOD PERFORMANCE

     9.1  Method 8250  was  tested  by  15  laboratories  using reagent water,
drinking water,  surface  water,  and  Industrial  wastewaters  spiked  at six
concentrations over the  range  5-1,300  ug/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.  Provost, L.P. and R.S.  Elder,  "Interpretation of Percent Recovery Data,"
American Laboratory, 1J5, 58-63, 1983.

4.  Eichelberger, J.W., L.E. Harris,  and  W.L.  Budde, "Reference Compound to
Calibrate Ion Abundance  Measurement  1n  Gas Chromatography-Mass Spectrometry
Systems," Analytical Chemistry, 47, 995-1000, 1975.

5.  "Method Detection Limit for Methods 624  and 625," Olynyk, P., W.L. Budde,
and J.W. Eichelberger, Unpublished report, October  1980.

6.  "Interlaboratory Method Study for EPA Method 625-Base/Neutrals, Adds, and
Pesticides," Final  Report  for EPA Contract 68-03-3102  (1n preparation).

7.  Burke, J.A.   "Gas  Chromatography  for   Pesticide  Residue   Analysis; Some
Practical  Aspects,"  Journal   of   the  Association   of  Official  Analytical
Chemists, 48,  1037,  1965.
                                   8270 - 32
                                                          Revision
                                                          Date   September 1986

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                           METHOD 8270

 GAS CMROMATOGRAPHY/MASS SPECTROMETRY FOR SEMIVOUATILE ORGANICS:

                   CAPILLARY COLUMN TECHNIQUE
7. 1
Prepare cample
 using Method
 3540 or 3550
                                                   7. 1
Prepare cample
 using Method
 3510 or 3520
                               Prepare
                           cample  using
                           Method  3540.
                           3550 or 3560
                          7.2
                         Cleanup  extract
                          7.3
                               Set  GC/MS
                              operating
                          conditions and
                         perform initial
                            calibration
                       7.4
                       Perform dally GC/MS
                         calibration with
                       SPCCc  and  CCCc prior
                          to  analyclc of
                             camples
                            o
                    8270 - 33
                                              Revision        0
                                              Date  September 1986

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                                           METHOD 8270

                 GAS CHRONATOGRAPHY/MASS  SPECTHOMETRY FOR SEMIVOLATILE ORGANICS:

                                   CAPILLARY  COLUMN TECHNIQUE
                                           (Continued)
  7.5. 1
                                                                                  o
         Screen
         extract
     on GC/FIO or
  GC/PIO to elim-
   inate too-high
    concentration
7.5
7.6.1
       Identify
	>  enalyte
   by comparing
 the cample and
  standard mase
       spectra
 Analyze extract  by
    GC/HS using
  silIcone-coated
   fueed-sillea
 capillary column
                                                                               7.6.2
      Calculate
  concentration
      of  each
    Identified
      analyte'
   Does  response
   exceed Initial
                                                                               7.6.2.4
                                                                              Report results
                                                                             f     Stop       J
                                       8270  - 34
                                                                  Revision       o
                                                                  Date  September 1986

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                                 METHOD 8280

              THE ANALYSIS OF POLYCHLORINATED DIBENZO-P-DIOXINS
                      AND POLYCHLORINATED DIBENZOFURANS
1.0  SCOPE AND APPLICATION

     1.1  This method is appropriate for  the determination of tetra-,  penta-,
hexa-, hepta-,  and  octachlorinated  dibenzo-p-dioxins  (PCDD's)  and dibenzo-
furans  (PCDF's)  in  chemical  wastes  including  still   bottoms,   fuel  oils,
sludges, fly ash, reactor residues, soil and water.

     1.2  The sensitivity  of  this  method  is  dependent  upon  the level  of
interferents within a given matrix.  Proposed quantification levels for target
analytes were 2 ppb in soil samples, up to 10 ppb in other solid wastes and
10 ppt in water.  Actual values  have  been shown to vary by homologous series
and, to a lesser degree, by individual  isomer.  The total detection limit for
each CDD/CDF homologous  series  is  determined  by  multiplying the detection
limit of a given isomer within that series by the number of peaks which can  be
resolved under the gas chromatographic conditions.

     1.3  Certain   2,3,7,8-substituted   congeners   are   used   to  provide
calibration and method  recovery  information.    Proper  column selection and
access to reference isomer  standards,  may  in  certain cases, provide isomer
specific data.    Special  instructions  are  included  which measure 2,3,7,8-
substituted congeners.

     1.4  This method is recommended for use only by analysts experienced with
residue analysis and skilled in mass spectral analytical  techniques.

     1.5  Because of the extreme toxicity of these compounds, the analyst must
take necessary precautions to prevent  exposure  to  himself, or to others,  of
materials known or believed to  contain  PCDD's or PCDF's.  Typical infectious
waste incinerators  are  probably  not  satisfactory  devices  for disposal  of
materials highly contaminated with PCDD's or PCDF's.  A laboratory planning to
use these compounds should prepare a disposal plan to be reviewed and approved
by EPA's Dioxin Task Force (Contact  Conrad  Kleveno, WH-548A, U.S. EPA, 401 M
Street S.W., Washington,  D.C.  20450).    Additional  safety instructions are
outlined in Appendix B.


2.0  SUMMARY OF THE METHOD

     2.1  This procedure uses  a  matrix-specific  extraction, analyte-specific
cleanup,  and   high-resolution   capillary   column   gas  chromatography/low
resolution mass spectrometry  (HRGC/LRMS) techniques.

     2.2  If   interferents  are  encountered,  the  method  provides  selected
cleanup procedures to aid  the analyst  in their elimination.  The analysis flow
chart is shown  in  Figure 1.
                                  8280 - 1
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                                                         Date  September 1986

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                      Complex
                       Waste
                      Sample
                            (1)  Add Internal  Standards:  13C12-PCDD's
                                 and I3C12-PCDF's.
                            (2)  Perform matrix-specific extraction.
                      Sample
                      Extract
                            (1)  Wash with 20% KOH
                            (2)  Wash with 5% Nad
                            (3)  Wash with cone. H2S04
                            (4)  Wash with 5% NaCl
                            (5)  Dry extract
                            (6)  Solvent exchange
                            (7)  Alumina column
                  60% CH2Cl2/hexane
                     Fraction
                            (1)  Concentrate eluate
                            (2)  Perform carbon column cleanup
                            (3)  Add recovery standard(s)-13C12-l,2,3,4-TCDD
                  Analyze by GC/MS
Figure 1.  Method 8280 flow chart for sample extraction and cleanup as
 used for the analysis of PCDD's and PCDF's 1n complex waste samples.
                          8280 - 2
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                                                  Date   September  1986

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3.0  INTERFERENCES

     3.1  Solvents, reagents, glassware, and  other sample processing hardware
may  yield  discrete  artifacts  and/or  elevated  baselines  which  may cause
misinterpretation of chromatographic data.    All  of  these materials must be
demonstrated to be free from interferents  under the conditions of analysis by
running laboratory method blanks.

     3.2  The use of  high  purity  reagents  and  solvents  helps to minimize
interference problems.  Purification of  solvents by distillation in all glass
systems may be required.

     3.3  Interferents co-extracted  from  the  sample  will vary considerably
from source to source,  depending  upon  the industrial process being sampled.
PCDD's and PCDF's  are  often  associated  with  other interfering chlorinated
compounds such as  PCB's and polychlorinated diphenyl ethers which may be found
at concentrations  several orders of magnitude higher than that of the analytes
of interest.   Retention  times  of  target  analytes  must  be verified using
reference standards.   These   values  must  correspond  to  the retention time
windows established  in  Section  6-3.    While  certain cleanup techniques are
provided as part of  this method, unique  samples may require additional cleanup
techniques to achieve  the  method  detection  limit   (Section 11.6) stated in
Table 8.

     3.4  High resolution capillary columns are  used  to resolve as many PCDD
and  PCDF isomers as  possible;  however,   no  single column  is  known to resolve
all  of  the isomers.

     3.5  Aqueous  samples cannot  be  aliquoted  from  sample  containers.  The
entire  sample must be  used and the sample container washed/rinsed out with the
extracting solvent.


4.0  APPARATUS AND MATERIALS

     4.1  Sampling equipment  for discrete or composite sampling;

          4.1.1  Grab  sample  bottle—amber  glass,  1-liter or 1-quart  volume.
     French or Boston  Round  design is recommended.  The container must be acid
     washed and  solvent  rinsed before use to minimize  interferences.

          4.1.2  Bottle  caps—threaded  to screw  onto the  sample bottles.  Caps
     must be  lined with  Teflon.  Solvent washed  foil,  used  with the  shiny side
     toward the  sample,  may  be  substituted  for  Teflon   if  the sample  is not
     corrosive.  Apply tape  around cap  to completely seal cap  to bottom.

          4.1.3  Compositing  equipment—automatic    or    manual   compositing
     system.  No tygon  or   rubber  tubing  may  be  used,  and the  system must
     incorporate glass sample containers for  the collection of  a  minimum of
     250 ml_.  Sample containers  must be kept refrigerated after  sampling.

     4.2  Water  bath—heated,  with    concentric   ring    cover,   capable  of
 temperature  control  (+2°C).   The bath  should be  used in a hood.

                                  8280  - 3
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4.3  Gas chromatograph/mass spectrometer data system;

     4.3.1  Gas chromatograph:  An  analytical  system with a temperature-
programmable gas  chromatograph  and  all  required accessories Including
syringes, analytical columns, and gases.

     4.3.2  Fused silica capillary  columns  are  required.   As shown 1n
Table 1, three columns  were  evaluated  using a column performance check
mixture   containing   1,2,3,4-TCDD,   2,3,7,8-TCDD,   1,2,3,4,7   PeCDD,
1,2,3,4,7,8-HxCDD, 1,2,3,4,6,7,8-HpCDD, OCDD, and 2,3,7,8-TCDF.

The columns include the  following:     (a) 50-m CP-Sil-88 programmed 60°-
190' at 20*/minute, then 190*-240* ,at 5°/minute; (b) DB-5  (30-m x 0.25-mm
I.D.; 0.25-um film thickness) programmed  170° for 10 minutes, then 170*-
320* at  SVminute,  hold  at  320°C  for  20  minutes;   (c) 30-m SP-2250
programmed 70°-320° at  lO'/minute.     Column/conditions  (a) provide good
separation of 2,3,7,8-TCDD from the other TCDD's at the expense of longer
retention times for higher homologs.    Column/conditions  (b) and (c) can
also  provide  acceptable  separation   of  2,3,7,8-TCDD.    Resolution of
2,3,7,8-TCDD from the other  TCDD's  is  better  on column  (c), but column
(b) is  more  rugged,  and   may  provide  better  separation  from certain
classes of interferents.  Data presented in  Figure 2 and  Tables 1 to 8 of
this  Method    were  obtained  using   a  DB-5  column  with  temperature
programming described in  (b)  above.   However, any capillary  column which
provides  separation  of  2,3,7,8-TCDD   from   all  other TCDD  isomers
equivalent to that  specified in Section 6.3 may be used;  this  separation
must be demonstrated and  documented   using  the performance  test mixture
described 1n Paragraph 6.3.

     4.3.3  Mass  spectrometer:  A,low  resolution instrument is  specified,
utilizing 70  volts   (nominal)  electron  energy   in   the electron  impact
lonization mode.   The system must  be  capable of  selected ion  monitoring
(SIM) for at least  11 ions  simultaneously,   with a  cycle  time of 1  sec or
less.   Minimum  integration  time for SIM  is 50  ms per  m/z.   The  use of
systems  not capable of monitoring  11 ions  simultaneously  will  require the
analyst  to make multiple  injections.

     4.3.4  GC/MS .Interface:   Any   GC-to-MS   interface  that gives an
acceptable calibration  response   for   each  analyte   of   interest  at the
concentration   required   and  achieves   the  required   tuning performance
criteria  (see  Paragraphs   6.1.-6.3)  may be used.    GC-to-MS  interfaces
constructed of  all  glass   or  glass-lined  materials are  required.  Glass
can be  deactivated  by   silanizing  with  dichlorodimethylsilane.   Inserting
a  fused  silica  column directly   into   the  MS source is recommended;  care
must be  taken not to expose the end of the column  to the  electron beam.

     4.3.5  Data  system:   A  computer   system  must  be Interfaced  to the
mass spectrometer.  The system must allow for the  continuous acquisition
and storage on  machine-readable media  of all data  obtained throughout the
duration  of the chromatographic program.   The computer must have software
that can  search any GC/MS data  file for  ions of  a  specific  mass and can
plot such ion abundances  versus  time   or  scan number.  This  type of  plot
                              8280 - 4
                                                     Revision
                                                     Date   September  1986

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     1s defined as an Selected Ion Current Profile (SICP).   Software must also
     be able to integrate the  abundance,   1n any SICP,  between specified time
     or scan number limits.

     4.4  Pipets-Disposable,  Pasteur,  150-mm   long   x  5-mrn  I.D.  (Fisher
Scientific Company, No. 13-678-6A, or equivalent).

          4.4.1  Pipet,  disposable,  serological  10-mL  (American Scientific
     Products No.  P4644-10,  or  equivalent)  for  preparation  of the carbon
     column specified in Paragraph 4.19.

     4.5  Amber glass bottle (500-mL, Teflon-lined screw-cap).

     4.6  Reacti-vial 2-mL,  amber  glass  (Pierce  Chemical  Company).  These
should be silanized prior to use.

     4.7  500-mL Erlenmeyer flask (American Scientific Products Cat. No. f4295
500fO) fitted with Teflon stoppers  (ASP No. S9058-8, or equivalent).

     4.8  Wrist Action Shaker (VWR  No. 57040-049, or equivalent).

     4.9  125-mL  and  2-L  Separatory  Funnels   (Fisher  Scientific  Company,
No. 10-437-5b, or equivalent).

     4.10   500-mL  Kuderna-Danish  fitted with a 10-mL concentrator tube and
3-ball Snyder column  (Ace Glass No.  6707-02, 6707-12, 6575-02, or equivalent).

     4.11   Teflon  boiling chips  (Berghof/American Inc., Main  St., Raymond, New
Hampshire 03077, No.  15021-450,   or  equivalent).    Wash with hexane prior to
use.

     4.12   300-mm  x 10.5-mm glass   chromatographlc  column fitted  with  Teflon
stopcock.

     4.13   15-mL  conical   concentrator   tubes    (Kontes   No.  K-288250,  or
equivalent).

     4.14   Adaptors  for concentrator  tubes   (14/20  to  19/22)  (Ace Glass No.
9092-20, or equivalent).

     4.15   Nitrogen  blowdown  apparatus  (N-Evap  (reg.  trademark)  Analytical
Evaporator    Model    111,     Organomation   Associates   Inc.,   Northborough,
Massachusetts or  equivalent).     Teflon   tubing connection   to  trap  and gas
regulator  is  required.

     4.16   Microflex conical  vials  2.0-mL (Kontes K-749000, or equivalent).

     4.17   Filter paper (Whatman No. 54,   or equivalent).   Glass fiber filters
or glass wool  plugs  are also  recommended.

     4.18   Solvent reservoir  (125-mL)  Kontes;     (special  order item)  12.5-cm
diameter,  compatible with  gravity carbon  column.


                                   8280 -  5
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                                                          Date   September 1986

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     4.19  Carbon column (gravity  flow);    Prepare carbon/silica gel packing
material bymlx1ng5percent  (byweight)  active  carbon  AX-21 (Anderson
Development Co., Adraln,  Michigan),  pre-washed  with  methanol  and dried Iji
vacuo at 110'C and 95 percent (by  weight)  Silica gel (Type 60, EM reagent 70
to 230 mesh, CMS No. 393-066)  followed  by  activation of the mixture at 130*
for 6 hr.  Prepare a  10-mL  disposable  serologlcal plpet by cutting off each
end to achieve a  4-1n.  column.    F1re  polish  both ends; flare 1f desired.
Insert a glass-wool plug at one end and pack with 1 g of the carbon/siHca gel
mixture.  Cap the packing with a glass-wool plug.  (Attach reservoir to column
for addition of solvents).

     Option:  Carbon column (HPLC):  A  sllanlzed glass HPLC column (10 mm x 7
cm), or equivalent, which  contains  1  g  of  a  packing prepared by mixing 5
percent (by weight) active  carbon  AX-21,   (Anderson Development Co., Adrian,
Michigan), washed with methanol and  dried   in  vacuo at 110*C, and 95 percent
(by weight)  10  urn  silica  (Spherisorb  S10W  from  Phase Separations, Inc.,
Norwalk, Connecticut).  The mixture must  then be stirred and sieved through a
38-um screen (U.S. Sieve  Designation  400-mesh, American Scientific Products,
No. S1212-400, or equivalent) to remove any  clumps.1

     4.20  HPLC pump with loop  valve  (1.0  ml)  Injector  to  be used 1n the
optional carbon column cleanup procedure.

     4.21  Dean-Stark trap, 5-  or  10-mL  with  T  joints, (Fisher Scientific
Company, No. 09-146-5, or equivalent) condenser and 125-mL flask.

     4.22  Continuous liquid-liquid extractor (Hershberg-Wolfe type, Lab Glass
No. LG-6915; or equivalent.).

     4.23  Roto-evaporator, R-110.   Buchi/Brinkman   - American Scientific No.
E5045-10; or equivalent.               ;


5.0  REAGENTS

     5.1  Potassium hydroxide  (ASC):  20 percent  (w/v) in distilled water.

     5.2  Sulfuric acid  (ACS),  concentrated.

     5.3  Methylene   chloride,  hexane,  benzene,  petroleum   ether,  methanol,
trldecane,  Isooctane, toluene,  cyclohexane.   Distilled   1n  glass or  highest
available purity.

     5.4  Prepare  stock  standards   in  a   glovebox  from  concentrates  or  neat
materials.  The  stock solutions (50 ppm)   are   stored in the  dark  at 4*C, and
checked  frequently for  signs   of   degradation   or evaporation,  especially  Just
prior to  the preparation of working standards.
 1    The  carbon  column  preparation  and   use   is adapted  from W. A.  Korfmacher,
 L. G.  Rushing,  D.  M. Nestorick,  H.  C.  Thompson, Jr.,  R.  K. Mltchum, and J. R.
 Kominsky,   Journal  of  High   Resolution  Chromatography and  Chromatography
 Communications, 8,  12-19 (1985).

                                  8280  - 6
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                                                         Date  September  1986

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     5.5  Alumina, neutral, Super 1,  Woelm,   80/200  mesh.    Store in a sealed
container at room temperature in a desiccator over self-indicating silicafgel.

     5.6  Prepurified nitrogen gas.

     5.7  Anhydrous sodium  sulfate  (reagent  grade):    Extracted  by manual
shaking with several portions of hexane and dried at 100*C.

     5.8  Sodium chloride - (analytical reagent), 5 percent (w/v) in distilled
water.
6.0  CALIBRATION

     6.1  Two types of calibration procedures are required.  One type, initial
calibration, is required  before  any  samples  are  analyzed  and is required
intermittently throughout sample analyses  as  dictated  by results of routine
calibration procedures described below.   The other type, routine calibration,
consists  of  analyzing   the   column   performance   check  solution  and  a
concentration calibration solution of 500  ng/mL  (Paragraph 6.2).  No samples
are to be analyzed until acceptable calibration as described in Paragraphs 6.3
and 6.6 is demonstrated and documented.

     6.2  Initial calibration;

          6.2.1     Prepare multi-level calibration  standards2 keeping one of
the recovery standards and the  internal standard at fixed concentrations (500
ng/mL).    Additional   internal   standards   (13Ci2-OCDD  1,000  ng/mL)  are
recommended when quantification of  the  hepta-  and octa-isomers is required.
The use of separate  internal  standards  for  the PCDF's is also recommended.
Each calibration standard should contain the following compounds:

2,3,7,8-TCDD,
1,2,3,7,8-PeCDD      or any available   2,3,7,8,X-PeCDD  isomer,
1,2,3,4,7,8-HxCDD    or any available   2,3,7,8,X,Y-HxCDD isomer,
1,2,3,4,6,7,8-HpCDD  or any available   2,3,7,8,X,Y,Z-HpCDD isomer,

2,3,7,8-TCDF
l,2,3,7,8,PeCDF      or any available   2,3,7,8,X-PeCDF  isomer,
1,2,3,4,7,8-HxCDF    or any available   2,3,7,8,X,Y,HxCDF  isomer,
1,2,3,4,6,7,8-HpCDF  or any available   2,3,7,8,X,Y,Z-HpCDF isomer,

     OCDD,  OCDF,  13C12-2,3,7,8-TCDD,  i3Ci2-l,2,3,4-TCDD  and 13C12-OCDD.
 2    *3Ci2-labeled analytes are  available  from Cambridge  Isotope  Laboratory,
  Woburn,  Massachusetts.   Proper quantification   requires  the  use  of a  specific
  labeled  isomer for each congener to  be  determined.   When labeled PCDD's  and
  PCDF's of each homolog  are  available,   their  use will be  required consistent
  with the technique of isotopic dilution.
                                   8280 - 7
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                                                          Date  September 1986

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Recommended concentration levels for  standard  analytes  are 200,  500,  1,000,
2,000', and 5,000 ng/mL.  These values  may be adjusted in order to  insure that
the  analyte  concentration  falls  within  the  calibration  range.     Two uL
injections of calibration  standards  should  be  made.    However,  some GC/MS
instruments may require the use of  a 1-uL injection volume; if this injection
volume is used then  all  injections  of  standards, sample extracts and blank
extracts must also be made at  this injection volume.  Calculation  of relative
response factors is described in Paragraph 11.1.2.  Standards must  be analyzed
using the  same  solvent  as  used  in  the  final  sample  extract.   A wider
calibration range is  useful  for  higher  level  samples  provided  it can be
described within  the  linear  range  of  the  method,  and the identification
criteria defined in Paragraph 10.4 are  met.   All standards must be stored in
an isolated  refrigerator  at  4°C  and  protected  from  light.   Calibration
standard solutions must be replaced routinely after six months.

     6.3  Establish operating parameters for  the GC/MS system; the instrument
should be tuned to meet  the  isotopic  ratio  criteria  listed in Table 3 for
PCDD's and PCDF's.   Once  tuning  and  mass  calibration procedures have been
completed, a column performance  check  mixture^ containing the isomers listed
below should be injected into the GC/MS system:

TCDD      1,3,6,8; 1,2,8,9; 2,3,7,8; 1,2,3,4; 1,2,3,7; 1,2,3,9
PeCDD     1,2,4,6,8; 1,2,3,8,9
HxCDD     1,2,3,4,6,9; 1,2,3,4,6,7
HpCDD     1,2,3,4,6,7,8; 1,2,3,4,6,7,9
OCDD      1,2,3,4,6,7,8,9

TCDF      1,3,6,8; 1,2,8,9             ;
PeCDF     1,3,4,6,8; 1,2,3,8,9
HxCDF     1,2,3,4,6,8; 1,2,3,4,8,9
HpCDF     1,2,3,4,6,7,8; 1,2,3,4,7,8,9
OCDF      1,2,3,4,6,7,8,9

     Because of the known  overlap  between the late-eluting tetra-isomers and
the early-eluting penta-isomers  under  certain  column  conditions, it may be
necessary to perform two  injections  to  define the TCDD/TCDF and PeCDD/PeCDF
elution windows, respectively.   Use  of  this  performance check mixture will
enable the following parameters to be  checked:   (a) the retention windows for
each of the homologues,  (b)  the  GC  resolution of 2,3,7,8-TCDD and 1,2,3,4-
TCDD, and  (c) the relative ion abundance criteria listed for PCDD's and PCDF's
in Table 3.  GC column performance  should be checked daily for resolution and
peak shape using this  check mixture.

     The chromatographic peak separation between 2,3,7,8-TCDD and 1,2,3,4-TCDD
must be resolved with  a valley of £25 percent, where

          Valley Percent =  (x/y)  (100)

     x = measured as  in Figure 2
     y = the peak height of 2,3,7,8-TCDD
 3     Performance  check  mixtures   are   available   from Brehm  Laboratory, Wright
 State  University,  Dayton,  Ohio.

                                   8280 - 8
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                                                         Date   September  1986

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     It is the  responsibility  of  the  laboratory  to  verify the  conditions
suitable for maximum resolution of  2,3,7,8-TCDD  from all  other TCDD Isomers.
The peak representing 2,3,7,8-TCDD should be labeled and Identified  as such on
all chromatograms.

     6.4  Acceptable  SIM  sensitivity  1s  verified  by  achieving   a minimum
s1gnal-to-no1se ratio of 50:1  for  the  m/z  320 1on of 2,3,7,8-TCDD obtained
from Injection of the 200 ng/mL calibration standard.

     6.5  From  Injections  of  the  5  calibration  standards,  calculate the
relative response factors  (RRF's)  of  analytes  vs. the appropriate Internal
standards, as described in  Paragraph  11.1.2.   Relative response factors for
the hepta- and octa-chlorinated CDD's and CDF's are to be calculated using the
corresponding 13Ci2-octachlorinated standards.

     6.6  For each analyte calculate the  mean relative response factor (RRF),
the standard  deviation,  and  the  percent  relative  standard deviation from
triplicate determinations of   relative  response  factors for each calibration
standard solution.

     6.7  The  percent  relative  standard  deviations   (based  on  triplicate
analysis) of  the  relative   response  factors  for  each calibration standard
solution should not  exceed 15  percent.     If this condition is not satisfied,
remedial action should be taken.

     6.8  The Laboratory must  not  proceed  with  analysis  of samples before
determining and documenting acceptable calibration with the criteria  specified
in Paragraphs 6.3 and 6.7.

     6.9  Routine calibration;

          6.9.1   Inject  a  2-uL  aliquot   of  the   column  performance  check
     mixture.  Acquire at least five data   points  for  each GC peak and use  the
     same data acquisition time for each of the ions being monitored.
          NOTE:   The same  data  acquisition  parameters  previously used to
                  analyze concentration  calibration  solutions  during initial
                  calibration  must be used   for the performance check  solution.
                  The column performance  check  solution  must  be  run at  the
                  beginning and end  of  a   12  hr  period.   If the contractor
                  laboratory    operates   during    consecutive   12-hr periods
                  (shifts), analysis of the  performance  check solution at  the
                  beginning of each  12-hr period and  at the end of the final
                  12-hr period is  sufficient.

     Determine and   document   acceptable   column   performance  as described in
     Paragraph 6.3.

           6.9.2   Inject  a 2-uL aliquot of  the  calibration  standard  solution at
     500  ng/mL at the  beginning  of   a   2-hr   period.  Determine and document
     acceptable   calibration   as   specified   in    Paragraph   6.3,   I.e.,   SIM
     sensitivity  and relative 1on abundance  criteria.  The measured RRF's of
                                   8280 - 9
                                                          Revision      0
                                                          Date  September 1986

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     .all  analytes must be within +30 percent of the mean values  established  by
     Initial analyses of the callBratlon standard solutions.


7.0  QUALITY CONTROL

     7.1  Before processing any samples,  the analyst must demonstrate through
the  analysis  of  a  method  blank   that  all  glassware  and   reagents  are
interferent-free at the  method  detection  limit  of  the matrix of Interest.
Each time a set of samples is  extracted,  or there is a change  in reagents, a
method  blank  must   be   processed   as   a   safeguard  against  laboratory
contamination.

     7.2  A laboratory "method blank" must  be  run along with each analytical
batch (20 or fewer samples).  A  method blank is performed by executing all  of
the specified extraction and cleanup  steps,  except for the introduction of a
sample.  The method blank  is  also  dosed  with  the Internal standards.  For
water samples, one liter of deionized and/or distilled water should be used as
the method blank.  Mineral  oil  may  be  used  as  the method blank for other
matrices.

     7.3  The laboratory will  be  expected  to analyze performance evaluation
samples as provided by the EPA on  a periodic basis throughout the course of a
given project.   Additional  sample  analyses  will  not  be  permitted if the
performance criteria are not achieved.    Corrective  action must be taken and
acceptable performance must be demonstrated before sample analyses can resume.

     7.4  Samples may be split  with  other  participating  labs on a periodic
basis to ensure  interlaboratory consistency.   At  least one sample per set of
24 must be  run in duplicate to determine  Intralaboratory precision.

     7.5  Field  duplicates  (Individual  samples taken from the same location at
the  same   time)  should  be  analyzed  periodically  to  determine  the total
precision (field and lab).

     7.6  Where  appropriate, "field blanks"  will  be   provided to monitor  for
possible cross-contamination of  samples  in   the  field.   The typical "field
blank" will consist of uncontaminated soil  (background  soil taken off-site).

     7.7  GC  column performance  must   be  demonstrated Initially and verified
prior to analyzing any sample 1n   a  12-hr  period.  The GC column performance
check solution   must  be  analyzed under  the  same  chromatographic and mass
spectrometric conditions used for  other samples and standards.

     7.8  Before using  any  cleanup  procedure,   the   analyst  must process a
series of   calibration  standards   (Paragraph  6.2)  through  the procedure to
validate elution patterns and the  absence of interferents from reagents.  Both
alumina column and carbon column performance must  be checked.  Routinely check
the 8 percent CH2Cl2/hexane eluate of  environmental extracts from the alumina
column for  presence of target analytes.
     NOTE:  This fraction is intended to  contain  a high level of Interferents
            and  analysis near the  method  detection limit may not be possible.


                                   8280  -  10
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8.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

     8.1  Grab and composite samples  must  be  collected In glass containers.
Conventional sampling practices must  be  followed.    The  bottle must not be
prewashed  with  sample  before  collection.    Composite  samples  should  be
collected 1n glass containers.    Sampling  equipment  must  be free of tygon,
rubber tubing, other potential sources  of  contamination which may absorb the
target analytes.

     8.2  All samples must be  stored  at  4*C,  extracted  within 30 days and
completely analyzed within 45 days of collection.


9.0  EXTRACTION AND CLEANUP PROCEDURES

     9.1  Internal standard addition.  Use a sample aliquot of 1 g to 1,000 mL
(typical sample size requirements  for  each  type  of  matrix are provided 1n
Paragraph 9.2) of the chemical  waste  or  soil  to be analyzed.  Transfer the
sample to a tared  flask  and  determine  the  weight  of  the sample.  Add an
appropriate quantity of 13Ci2-2,3,7,8-TCDD, and any other material which is to
be used as an  internal  standard,   (Paragraph  6.2).    All samples should be
spiked with at least  one   internal  standard, for example, 13Ci2-2,3,7,8-TCDD,
to give a concentration of  500 ng/mL 1n the final concentrated extract.  As an
example, a  10 g sample concentrated  to  a  final volume of 100 uL requires the
addition of 50 ng of 13Ci2-2,3,7,8-TCDD,  assuming 100% recovery.  Adoption of
different   calibration  solution    sets    (as   needed  to  achieve  different
quantification limits  for different   congeners)  will  require a change 1n the
fortification level.    Individual   concentration  levels  for each  homologous
series must be specified.

     9.2   Extraction

           9.2.1   Sludge/fuel  oil.   Extract  aqueous sludge  samples by refluxlng
     a  sample  (e.g.  2  g) with 50   mL  of   toluene  (benzene) in a 125-mL  flask
     fitted with  a  Dean-Stark water  separator.   Continue  refluxlng  the sample
     until  all  the   water   has  been  removed.     Cool   the  sample,  filter the
     toluene  extract through   a   fiber  filter,   or   equivalent,  into  a 100-mL
     round  bottom flask.   Rinse  the filter with  10  mL of  toluene, combine the
     extract  and  rinsate.   Concentrate  the   combined solution to near dryness
     using  a  rotary evaporator at  50'C.     Use   of an inert  gas to concentrate
     the  extract  is also permitted.   Proceed  with  Step 9.2.4.

           9.2.2   Still  bottom.     Extract   still   bottom  samples  by  mixing a
     sample (e.g.,  1.0 g)  with 10   mL  of   toluene  (benzene) 1n a small beaker
     and  filtering  the solution  through a glass  fiber  filter (or equivalent)
     into  a 50-mL round bottom flask.   Rinse the  beaker and filter  with  10 mL
     of toluene.  Concentrate the  combined   toluene solution to near dryness
     using  a  rotary evaporator at   50*C while connected  to  a  water  aspirator.
     Proceed  with Step 9.2.4.
                                   8280 - 11
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     9.2.3>  Fly ash.  Extract fly  ash  samples by placing a sample (e.g.
10 g) and an equivalent amount  of  anhydrous sodium sulfate 1n a Soxhlet
extraction apparatus charged with 100 ml of toluene (benzene) and extract
for 16 hr using a three cycle/hour schedule.  Cool and filter the toluene
extract through a glass  fiber  filter  paper  Into a 500-mL round bottom
flask.  Rinse the filter with 5  ml of toluene.  Concentrate the combined
toluene solution to  near  dryness  using  a  rotary  evaporator at 50*C.
Proceed with Step 9.2.4.

     9.2.4  Transfer the  residue  to  a  125-mL  separatory funnel using
15 ml of hexane.  Rinse  the  flask  with two 5-mL allquots of hexane and
add the rinses to  the  funnel.    Shake  2  min  with  50  ml of 5% NaCl
solution, discard the aqueous layer and proceed with Step 9.3.

     9.2.5  Soil.  Extract soil samples by placing the sample (e.g. 10 g)
and  an  equivalent  amount  of  anhydrous  sodium  sulfate  in  a 500-mL
Erlenmeyer flask fitted with a teflon stopper.  Add 20 ml of methanol and
80 ml of petroleum Aether, in that order, to the flask.  Shake on a wrist-
action shaker for two hr.  The solid portion of sample should mix freely.
If a smaller soil  aliquot  1s  used,  scale  down the amount of methanol
proportionally.

          9.2.5.1  Filter the  extract  from  Paragraph  9.2.5  through a
     glass funnel  fitted  with  a  glass  fiber  filter  and filled with
     anhydrous  sodium  sulfate   Into   a   500-mL  Kuderna-Danish  (KD)
     concentrator fitted with a 10-mL  concentrator  tube.   Add 50 mL of
     petroleum ether to  the  Erlenmeyer  flask,  restopper  the flask and
     swirl the sample gently, remove the stopper  carefully and decant the
     solvent through the funnel as above.  Repeat this procedure with two
     additional 50-mL  aliquots  of  petroleum  ether.    Wash the sodium
     sulfate 1n the funnel with two additional  5-mL portions of petroleum
     ether.

          9.2.5.2  Add a Teflon  or   PFTE  boiling  chip  and a three-ball
     Snyder column  to the KD  flask.   Concentrate in a 70*C  water  bath to
     an  apparent volume of  10 mL.    Remove  the  apparatus  from the  water
     bath and  allow it to cool for 5  min.

          9.2.5.3   Add 50 mL  of  hexane  and   a  new boiling  chip to the KD
      flask.  Concentrate in  a water bath  to  an apparent  volume of 10 mL.
      Remove the  apparatus from the  water   bath  and  allow to cool  for 5
     min.

          9.2.5.4   Remove and Invert  the Snyder  column and rinse  1t down
      Into the  KD with two 1-mL  portions  of hexane.  Decant the  contents
      of  the KD and concentrator  tube   into   a 125-mL separatory  funnel.
      Rinse  the KD  with  two   additional   5-mL portions of  hexane,  combine.
      Proceed with  Step  9.3.

      9.2.6  Aqueous samples:   Mark the  water  meniscus on the  side of the
 1-L sample  bottle  for   later  determination   of  the  exact  sample  volume.
                              8280 - 12
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                                                     Date   September  1986

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    Pour the entire sample  (approximately  1-L) Into a 2-L separatory funnel.
    Proceed with Step 9.2.6.1.
         NOTE:  A continuous liquid-liquid extractor may  be used 1n 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  1s  encountered  using  a separatory
                funnel.   Add  60  ml  of  methylene  chloride  to the sample
                bottle,  seal,  and  shake  for  30  sec  to  rinse  the Inner
                surface.  Transfer the solvent  to the extractor.  Repeat the
                sample bottle  rinse with an  additional 50- to 100-mL portion
                of methylene chloride  and  add  the  rinse to the extractor.
                Add 200  to  500 ml  of  methylene  chloride to the distilling
                flask;   add sufficient   reagent   water  to  ensure  proper
                operation,  and extract for 24 hr.  Allow to cool, then detach
                the distilling flask.    Dry  and  concentrate the extract as
                described 1n Paragraphs  9.2.6.1  and  9.2.6.2.  Proceed with
                Paragraph 9.2.6.3.

               9.2.6.1  Add  60  ml  methylene  chloride  to  the sample bottle,
         seal  and shake  30  sec  to  rinse  the  Inner surface.  Transfer the
         solvent to the  separatory funnel  and  extract the sample by shaking
         the funnel for  2 min  with periodic venting.  Allow the organic layer
         to separate from the  water phase  for  a  minimum of 10 m1n.  If the
         emulsion Interface between layers 1s  more than one-third the volume
         of the solvent  layer, the  analyst must employ mechanical techniques
         to complete the phase separation.  Collect the methylene chloride
          (3 x  60  ml)   directly  into  a  500-mL Kuderna-Danish concentrator
          (mounted with   a   10-mL  concentrator  tube)  by  passing the sample
         extracts through a filter funnel packed with a glass wool plug and
         5 g of anhydrous sodium sulfate.   After the third extraction, rinse
         the sodium  sulfate with an additional 30 ml of methylene chloride to
         ensure quantitative  transfer.

               9.2.6.2   Attach  a Snyder column  and concentrate the extract on
          a water  bath  until the apparent  volume  of the  liquid  reaches 5 ml.
          Remove the  K-D apparatus  and allow  it to drain and cool  for at least
          10 min.   Remove the  Snyder  column,   add 50 ml hexane,  re-attach the
          Snyder column  and  concentrate   to   approximately  5  ml.    Add a new
          boiling  chip  to the  K-D   apparatus  before proceeding with the  second
          concentration  step.

          Rinse the  flask and  the  lower joint with 2  x  5 ml hexane and combine
          rinses with extract  to  give  a  final  volume  of  about  15  ml.

               9.2.6.3   Determine  the  original  sample   volume  by  refilling  the
          sample  bottle to the mark and   transferring  the  liquid  to a 1,000-mL
          graduated cylinder.   Record  the  sample   volume  to the  nearest 5  ml.
          Proceed  with  Paragraph  9.3.

     9.3  In  a 250-mL Separatory  funnel,   partition  the solvent  (15 ml hexane)
against 40 ml of  20  percent   (w/v)   potassium  hydroxide.   Shake for 2 m1n.
                                  8280 - 13
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                                                         Date  September 1986

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Remove and discard the aqueous layer  (bottom).   Repeat the  base washing  until
no color 1s visible 1n the  bottom  layer  (perform base washings a maximum of
four times).   Strong  base  (KOH)  1s  known  to degrade certain PCDD/PCDF's,
contact time must be minimized.

     9.4  Partition the solvent (15  ml  hexane)   against  40  ml of 5 percent
(w/v) sodium chloride.  Shake  for  2  m1n.   Remove and discard aqueous  layer
(bottom).
     NOTE:  Care  should  be  taken  due  to  the  heat  of neutralization and
     hydratlon.

     9.5  Partition the solvent (15 ml  hexane)  against 40 ml of concentrated
sulfuric acid.   Shake  for  2  min.    Remove  and  discard the aqueous  layer
(bottom).  Repeat the acid  washings  until  no  color  is visible in the add
layer.   (Perform acid washings a maximum of four times.)

     9.6  Partition the  extract  against  40  ml  of  5  percent (w/v) sodium
chloride.  Shake for 2 min.    Remove  and discard the aqueous layer (bottom).
Dry the organic layer by pouring  through a funnel containing anhydrous sodium
sulfate into a 50-mL round bottom  flask,  wash the separatory funnel with two
15-mL portions of hexane,  pour  through  the  funnel,  and combine the hexane
extracts.  Concentrate  the  hexane  solution  to  near  dryness with a rotary
evaporator  (35°C water bath), making  sure  all traces of toluene are removed.
(Use of  blowdown  with  an  inert  gas  to  concentrate  the  extract 1s also
permitted).

     9.7  Pack a gravity column (glass 300-mm x 10.5-mm), fitted with a Teflon
stopcock, in the following manner:

     Insert a glass-wool plug  into the bottom  of the column.  Add a 4-g layer
of sodium sulfate.  Add a 4-g  layer of Woelm super 1 neutral alumina.  Tap the
top of the column gently.  Woelm super 1 neutral alumina need not be activated
or cleaned prior to use but should be stored 1n a sealed desiccator.  Add a 4-
g layer of sodium sulfate to cover  the  alumina.   Elute with 10 ml of hexane
and close the stopcock just prior to  the exposure of the sodium sulfate layer
to air.  Discard the eluant.   Check the column for channeling.  If channeling
1s present discard the column.  Do not tap a wetted column.

     9.8  Dissolve the residue from Step 9.6  in  2 ml of hexane and apply the
hexane solution to the top of  the  column.   Elute with  enough hexane  (3-4 mL)
to complete the transfer of the sample  cleanly to the surface of the  alumina.
Discard  the eluant.

          9.8.1   Elute with 10 ml of  8   percent   (v/v) methylene  chloride in
      hexane.   Check  by GC/MS  analysis  that  no  PCDD's or PCDF's are eluted in
      this  fraction.   See  Paragraph 9.9.1.

           9.8.2   Elute the  PCDD's and  PCDF's from   the  column with  15  ml of 60
      percent  (v/v) methylene  chloride  in hexane  and collect this fraction  in a
      conical  shaped  (15-mL) concentrator tube.
                                   8280 - 14
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                                                          Date   September  1986

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    9.9  Carbon column cleanup:

         Prepare a carbon column as described in Paragraph 4.18.

         9.9.1  Using a  carefully  regulated  stream  of nitrogen (Paragraph
    4.15),  concentrate  the  8  percent  fraction  from  the  alumina column
    (Paragraph 9.8.1) to about 1 ml.  Wash the sides of the tube with a small
    volume of hexane  (1 to 2 ml) and  reconcentrate to about 1 ml.  Save this
    8 percent concentrate for  GC/MS  analysis  to  check for breakthrough of
    PCDD's and PCDF's.  Concentrate the 60 percent fraction (Paragraph 9.8.2)
    to about 2 to 3   ml.    Rinse  the carbon with 5 ml cyclohexane/methylene
    chloride (50:50 v/v) 1n the  forward  direction  of  flow and then 1n the
    reverse direction of flow.  While still  1n the reverse direction of flow,
    transfer the sample concentrate to  the  column  and  elute with 10 ml of
    cyclohexane/methylene  chloride   (50:50  v/v)   and  5  ml  of  methylene
    chloride/methanol/benzene  (75:20:5, v/v).    Save  all  above eluates and
    combine  (this fraction may be  used as a  check on column efficiency).  Now
    turn  the column over  and  1n  the  direction  of  forward  flow elute the
    PCDD/PCDF fraction with 20 ml  toluene.
          NOTE:  Be sure no carbon  fines are  present 1n the eluant.

          9.9.2  Alternate carbon column cleanup.  Proceed as in Section 9.9.1
    to obtain the 60  percent  fraction   re-concentrated  to  400 uL which is
    transferred to an HPLC   Injector loop   (1  ml).    The injector  loop 1s
    connected to the  optional  column  described   in Paragraph 4.18.  Rinse the
    centrifuge tube with  500  uL  of hexane  and  add  this   rinsate to the
    injector loop.     Load  the  combined concentrate  and  rlnsate onto the
    column.   Elute the column  at 2 mL/m1n, ambient temperature, with 30 ml of
    cyclohexane/methylene chloride 1:1  (v/v).  Discard the eluant.  Backflush
    the  column with 40  ml  toluene   to   elute   and collect PCDD's and PCDF's
     (entire   fraction).     The  column  1s    then  discarded  and  30  ml  of
    cyclohexane/methylene chloride 1:1  (v/v)  is pumped through a new column
    to prepare  it  for the next sample.

          9.9.3   Evaporate the  toluene fraction  to   about  1   ml on a rotary
    evaporator  using  a water  bath  at   50*C.   Transfer to a 2.0-mL Reacti-vial
    using a  toluene   rinse  and  concentrate  to the desired  volume  using  a
    stream of  N2-  The  final  volume  should be  100 uL  for soil samples  and
    500  uL for sludge,  still   bottom,  and   fly  ash samples; this is provided
    for  guidance,  the correct volume   will   depend on the  relative concentra-
    tion of  target  analytes.   Extracts which are determined to  be outside the
    calibration  range for individual   analytes   must  be diluted or a  smaller
    portion  of the  sample must be   re-extracted. Gently  swirl  the solvent on
     the  lower portion of  the  vessel   to  ensure complete dissolution of the
     PCDD's and PCDF's.

     9.10  Approximately 1  hr before  HRGC/LRMS  analysis,  transfer  an  aliquot
of the extract to  a  micro-vial   (Paragraph   4.16).     Add to  this  sufficient
recovery standard (13Cj2l,2,3,4-TCDD)  to  give  a  concentration of  500 ng/mL.
(Example:  36 uL aliquot of  extract  and   4 uL of recovery standard  solution.
Remember to adjust the final  result  to  correct for this  dilution.   Inject  an
appropriate aliquot (1 or 2 uL) of the sample into the GC/MS  instrument.


                                  8280 - 15
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                                                         Date  September 1986

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10.0  GC/MS ANALYSIS

     10.1  When toluene Is employed as the final  solvent use of a bonded phase
column from Paragraph 4.3.2 is  recommended.   Solvent exchange Into trldecane
1s required for other liquid phases or nonbonded columns (CP-S11-88).
     NOTE:  Chromatographlc conditions must be adjusted to account for solvent
            boiling points.

     10.2  Calculate response factors for  standards  relative to the Internal
standards, 13Ci2-2,3.7,8-TCDD  and  13Ci2-OCDD  (see  Section  11).    Add the
recovery standard (l3Ci2-l,2,3,4-TCDD) to the samples prior to Injection.  The
concentration of the recovery standard in  the sample extract must be the same
as that in the calibration standards used to measure the response factors.

     10.3  Analyze samples with selected 1on monitoring, using all of the ions
listed 1n Table 2.  It is recommended  that the GC/MS run be divided into five
selected 1on monitoring sections, namely:   (1) 243, 257,, 304, 306, 320, 322,
332, 334, 340, 356, 376   (TCDD's,  TCDF's,  13Ci2-labeled Internal and recovery
standards, PeCDD's, PeCDF's, HxCDE);  (2)  277,  293,  306, 332, 338, 340, 342,
354, 356, 358, 410  (peCDD's,  PeCDF's,  HpCDE);   (3)  311, 327, 340, 356, 372,
374, 376, 388, 390, 392,  446,   (HxCDD's,   HxCDF's,  OCDE);  (4) 345, 361, 374,
390, 406, 408, 410, 422,  424,  426,  480  (HpCDD's, HpCDF's,  NCDE) and (5) 379,
395, 408, 424, 442,  444,  458,  460,  470,  472, 514  (OCDD, OCDF,  13Ci2-OCDD,
DCDE).  Cycle  time not  to  exceed   1  sec/descriptor.  It Is  recommended that
selected  ion monitoring section  1   should  be  applied  during   the GC  run to
encompass the  retention window  (determined  in Paragraph 6.3) of the  first- and
last-elutlng tetra-chlorinated isomers.   If a  response 1s observed  at m/z 340
or  356, then the  GC/MS   analysis  must   be repeated; selected ion monitoring
section 2 should then  be applied   to  encompass  the retention  window  of the
first- and last-eluting penta-chlorinated Isomers.   HxCDE,  HpCDE,  OCDE, NCDE,
DCDE, are abbreviations for  hexa-,   hepta-, octa-, nona-, and decachlorinated
dlphenyl  ether, respectively.

     10.4  Identification criteria for PCDD's and PCDF's;

          10.4.1  All  of the   characteristic  ions,  i.e.  quantltation ion,
     confirmation ions, listed in Table   2  for   each  class of PCDD and PCDF,
     must be present in the  reconstructed  ion chromatogram.  It is desirable
     that the  M  -  COC1  ion   be   monitored  as  an  additional  requirement.
     Detection limits will be based  on quantltation ions within  the molecules
     1n cluster.

          10.4.2  The maximum  intensity  of  each  of  the  specified charac-
     teristic  ions must coincide within 2 scans or 2 sec.

          10.4.3  The relative intensity  of the selected, isotopic  ions  within
     the  molecular  ion cluster of a  homologous series of PCDD's of  PCDF's must
     lie  within the  range specified  in Table 3.

          10.4.4  The GC  peaks assigned to  a given homologous  series must have
     retention times within  the  window  established  for   that  series  by the
     column performance solution.


                                  8280 -  16
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     10.5  Quantltate the PCDD and  PCDF  peaks  from the response relative to
the appropriate Internal standard.    Recovery  of each Internal  standard)  vs.
the recovery standard must be greater than 40 percent.  It Is recommended that
samples with recoveries of less than 40 percent or greater than 120 percent be
re-extracted and re-analyzed.
     NOTE:  These  criteria  are  used  to  assess  method  performance;   when
            properly applied, Isotope  dilution  techniques are Independent of
            Internal standard recovery.

In those  circumstances  where  these  procedures  do  not  yield a definitive
conclusion, the use  of  high  resolution  mass  spectrometry or HRGC/MS/MS 1s
suggested.


11.0  CALCULATIONS

      NOTE:  The relative response  factors  of  a  given  congener within any
             homologous series  are  known  to  be  different.    However, for
             purposes of these  calculations,  1t  will  be assumed that every
             congener within a  given  series  has  the same relative response
             factor.  In order to  minimize  the  effect of this assumption on
             risk   assessment,   a   2,3,7,8-substltuted   Isomer   that   1s
             commercially  available  was  chosen  as  representative  of each
             series.  All relative  response   factor  calculations for a given
             homologous series are based on that compound.

      11.1   Determine the concentration of  Individual  Isomers of tetra-, penta,
and  hexa-CDD/CDF according to  the equation:


           Concentration, ng/g  =
 where:
      QJS   =   ng  of  Internal  standard   13Ci2-2,3,7,8-TCDD,  added to the sample
              before extraction.

        G   =   g of sample  extracted.

       As   =   area of quantltatlon  1on  of  the compound of  Interest.

      Ajs   =   area of quantltatlon   1on  (m/z   334)  of  the  Internal standard,
              13Ci2-2,3,7,8-TCDD.

      RRF   =   response factor  of   the  quantltatlon  1on  of the  compound of
              Interest relative to  m/z  334 of 13Ci2-2,3,7,8-TCDD.

      NOTE:   Any  dilution   factor   Introduced   by  following  the  procedure 1n
             Paragraph 9.10 should  be applied to this calculation.
                                   8280 - 17
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                                                          Date   September  1986

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         .1.1.1.1  Determine the concentration of  Individual  isomers  of hepta-
     CDD/CDF and the concentration of OCDD and OCDF according to the  equation:

                                    Q1s x As
          Concentration,  ng/g  -  G x     x RRF
where:
     Qls  =  n9 °f Internal standard  13Ci2-OCDD,   added  to the, sample before
             extraction.

       G  =  g of sample extracted.

      As  =  area of quantitatlon 1on of the compound of Interest.

     A^s  =  area of quantitatlon  Ion  (m/z  472)   of  the Internal  standard,
             13C12-OCDD.

     RRF  =  response factor  of  the  quantitatlon  ion  of  the  compound of
             Interest relative to m/z 472 of 13Ci2-OCDD.

     NOTE:  Any dilution  factor  introduced  by  following  the  procedure 1n
            Paragraph 9.10 should be applied to this calculation.

          11.1.2  Relative response factors are calculated using data obtained
     from the analysis of  multi -level  calibration standards according to the
     equation:                                                         f
          RRF =   *  *   'J
                 A1s x  Ls
where:

      AS  =  area of quantitatlon ion of the, compound of Interest.

     Ajs  =  area of quantisation  ion  of   the  appropriate internal standard
             (m/z 334 for 13C12-2,3,7,8-TCDD; m/z 472 for 13C12-OCDD).

     Cis  =  concentration of the appropriate internal standard,
             13C12-2,3,7,8-TCDD or 13C12-OCDD)

      Cs  =  concentration of the compound of interest.

          11.1.3  The concentrations  of  unknown  isomers  of  TCDD  shall be
     calculated using the mean RRF determined for 2,3,7,8-TCDD.

          The concentrations of unknown  Isomers  of PeCDD shall be calculated
     using the  mean  RRF  determined  for   1,2,3,7,8-PeCDD  or  any available
     2,3,7,8,X-PeCDD isomer.
                                  8280 - 18
                                                         Revision
                                                         Date  September 1986

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     The concentrations of unknown  Isomers  of HxCDD shall  be calculated
using the mean  RRF  determined  for  1,2,3,4,7,8-HxCDD  or any available
2,3,7,8,-X,Y-HXCDD Isomer.

     The concentrations of unknown  Isomers  of HpCDD shall  be calculated
using the mean RRF  determined  for  1,2,3,4,6,7,8-HpCDD or any available
2,3,7,8,X,Y,Z-HpCDD Isomer.

     The concentrations of unknown  Isomers  of  TCDF shall  be calculated
using the mean RRF determined for 2,3,7,8-TCDF.

     The concentrations of unknown  isomers  of PeCDF shall  be calculated
using the  mean  RRF  determined  for  1,2,3,7,8-PeCDF  or  any available
2,3,7,8,X-PeCDF isomer.

     The concentrations of unknown  Isomers  of HxCDF shall  be calculated
using the  mean  RRF  determined  for  1,2,4,7,8-HxCDF  or  any available
2,3,7,8-X,Y-HxCDF isomer.

     The concentrations of unknown  Isomers  of HpCDF shall  be calculated
using the mean RRF  determined  for  1,2,3,4,6,7,8-HpCDF or any available
2,3,7,8,X,Y,Z-HpCDF Isomer.

     The concentration of the  octa-CDD  and octa-CDF shall  be calculated
using the mean RRF determined for each.

     Mean relative response factors  for  selected  PCDD's and PCDF's are
given 1n Table 4.

     11.1.4  Calculate  the  percent  recovery,  Ris,  for  each Internal
standard 1n the sample extract, using the equation:
     "1s    Ars X RFr X Q,s

where:

     Ars   =  Area of quantitation ion  (m/z 334) of the recovery standard,
             13Ci2-l,2,3,4-TCDD.

     Qrs   =  n9  °f  recovery   standard,  13Ci2-l,2,3,4-TCDD,  added  to
             extract.

The  response factor  for   determination  of   recovery is calculated using
data obtained  from the analysis  of  the multi-level calibration standards
according  to the equation:


     DF    A1s  x  Crs
        r ~  A  x C
        r     Ars x Lis
                              8280 -  19
                                                    Revision
                                                    Date  September 1986

-------
     where:

          Crs  =  Concentration of the recovery standard,  13Ci2-1.2,3,4-TCDD.

          11.1.5  Calculation of  total   concentration  of  all  Isomers within
     each homologous series of PCDD's and PCDF's.

     Total concentration  =  Sum of the concentrations of the Individual
     of PCDD's or PCDF's     PCDD or PCDF Isomers

     11.4  Report results In  nanograms  per  gram;   when duplicate and spiked
samples are reanalyzed, all data obtained should be  reported.

     11.5  Accuracy and Precision.    Table  5  gives  the  precision data for
revised Method 8280 for  selected  analytes  1n  the  matrices shown.  Table 6
lists recovery data for the same analyses.  Table 2  shows the linear range and
variation of  response  factors  for  selected  analyte  standards.    Table 8
provides the method detection limits as measured 1n  specific sample matrices.

     11.6  Method Detection  Limit.    The  Method  Detection  Limit  (MDL) is
defined as the minimum concentration of  a  substance that can be measured and
reported with 99  percent  confidence  that  the  value  Is  above  zero.  The
procedure used to determine the  MDL  values  reported in Table 8 was obtained
from Appendix  A  of  EPA  Test  Methods  manual,   EPA-600/4-82-057 July 1982,
"Methods  for  Organic   Chemical   Analysis   of   Municipal  and  Industrial
Wastewater."

     11.7  Maximum Holding Time  (MHT).   Is  that  time  at which a 10 percent
change 1n the analyte  concentration  (Ctio)  occurs  and the precision of the
method of  measurement  allows  the  10  percent  change  to  be statistically
different from the 0 percent change  (Cto) at the 90 percent confidence level.
When  the  precision  of  the   method  1s  not  sufficient  to  statistically
discriminate a 10 percent change  1n  the concentration from 0 percent change,
then the maximum holding time  1s  that  time  where the percent change in the
analyte concentration  (Ctn) is   statistically different than the concentration
at 0 percent change  (Cto) ancl greater than 10 percent change at the 90 percent
confidence level.
                                   8280 -; 20
                                                         Revision      0
                                                         Date  September  1986

-------
TABLE 1.  REPRESENTATIVE GAS CHROMATOGRAPH RETENTION  TIMES*  OF  ANALYTES
Analyte
2,3,7,8-TCDF
2,3,7,8-TCDD
1,2,3,4-TCDD
1, 2,3,4, 7-PeCDD
1, 2,3,4,7, 8-HxCDD
1,2,3,4,6,7,8-HpCDD
OCDD
50-m
CP-Sil-88
25.2
23.6
24.1
30.0
39.5
57.0
NM
30-m
DB-5
17.8
17.4
17.3
20.1
22.1
24.1
25.6
3—m
SP-2250
26.7
26.7
26.5
28.1
30.6
33.7
NM
*Retent1on time in min, using temperature programs shown below.
NM  =  not measured.
Temperature Programs;
          CP-Sil-88           60°C-190'C at 20'/m1n; 190'-240° at 5Vm1n.
          DB-5                170*, 10 min; then at 8°/min to 320'C, hold
          30 m x 0.25 mm      at 320*C 20 min (until OCDD elutes).
          Thin film  (0.25 urn)
          SP-2250             70'-320» at lOVminute.
                            Column Manufacturers
CP-S11-88            Chrompack, Incorporated, Bridgewater, New Jersey
DB-5,                J  and   W   Scientific,   Incorporated,  Rancho  Cordova,
                     California
SP-2250              Supelco,     Incorporated,     Bellefonte,    Pennsylvania
                                   8280 - 21
                                                         Revision
                                                         Date  September 1986

-------
                   TABLE 2.   IONS SPECIFIED3 FOR SELECTED ION MONITORING
                           FOR  PCDD'S AND  PCDF'S
                       Quantitation
                            ion
                  Confirmation
                      ions
        M-COC1
PCDD'S
13Cj2-Tetra
Tetra
Penta
Hexa
Hepta
Octa
13Ci2-Octa
PCDF's
Tetra
Penta
Hexa
Hepta
Octa

334
322
356
390
424
460
472

306
340
374
408
444

332
320
354;358
388; 392
422; 426
458
470

304
338; 342
372; 376
406; 410
442

__ _
257
293
327
361
395


243
277
311
345
379
alons at m/z 376 (HxCDE), 410 (HpCDE), 446 (OCDE), 480 (NCDE) and 514 (DCDE)
 are also included in the scan monitoring sections (1) to (5), respectively.
 See Paragraph 10.3.
  TABLE 3.  CRITERIA FOR ISOTOPIC RATIO MEASUREMENTS FOR PCDD'S AND PCDF'S
                        Selected ions (m/z)
                               Relative intensity
PCDD's

Tetra
Penta
Hexa
Hepta
Octa

PCDF's
320/322
358/356
392/390
426/424
458/460
0.65-0.89
0.55-0.75
0.69-0.93
0.83-1.12
0.75-1.01
Tetra
Penta
Hexa
Hepta
Octa
304/306
342/340
376/374
410/408
442/444
0.65-0.89
0.55-0.75
0.69-0.93
0.83-1.12
0.75-1.01
                                  8280 - 22
                                                         Revision      0
                                                         Date  September  1986

-------
     TABLE 4.  MEAN RELATIVE RESPONSE FACTORS OF CALIBRATION STANDARDS
Analyte
2,3,7,8-TCDD
1,2,3,7,8-PeCDD
1,2,3,4,7,8-HxCDD
l,2,3,4,6,7,8-HpCDDb
OCDDb
2,3,7,8-TCDF
1,2,3,7,8-PeCDF
1,2,3,4,7,8-HxCDF
l,2,3,4,6,7,8-HpCDFb
OCDFb
13Ci2-2t3,7,8-TCDD
13Ci2-l,2,3,4-TCDD
13C12-OCDD
RRFa
1.13
0.70
0.51
1.08
1.30
1.70
1.25
0.84
1.19
1.57
1.00
0.75
1.00
RSD%
(n = 5)
3.9
10.1 ^
6.6
6.6
7.2
8.0
8.7
9.4
3.8
8.6
-
4.6
-
Quantltatlon 1on
(•/z)
322
356
390
424
460
306
340
374
444
408
334
334
472
aThe RRF value is the mean of the five determinations made.  Nominal  weights
 injected were 0.2, 0.5, 1.0, 2.0 and 5.0 ng.

bRRF values for these analytes were determined relative to 13Ci2-OCDD.  All
 other RRF's were determined relative to 13Ci2-2,3,7,8-TCDD.

Instrument Conditions/Tune - GC/MS system was tuned as specified in
                             Paragraph 6.3.  RRF data was acquired under
                             SIM control, as specified in Paragraph 10.3.

GC Program - The GC column temperature was programmed as specified in
             Paragraph 4.3.2(b).
                                  8280 - 23
                                                         Revision
                                                         Date  September 1986

-------
TABLE 5.  PRECISION DATA FOR REVISED METHOD 8280
Compound
2,3,7,8-TCDD




1,2,3,4-TCDD




1,3,6,8-TCDD



•
1,3,7,9-TCDD




1,3,7,8-TCDD




1,2,7,8-TCDD




1,2,8,9-TCDD




Analyte
Matrix3
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
level (ng/g)
Native
NDb
378
ND
ND
487
ND
ND
ND
38.5
ND
ND
ND
ND
19.1
227
ND
ND
ND
58.4
ND
ND
ND
ND
16.0
422
ND
ND
: ND
2.6
ND
ND
ND
ND
ND
ND
Native
+ spike
5.0
378
125
46
487
5.0
25.0
125
38.5
2500
2.5
25.0
125
19.1
2727
2.5
25.0
125.0
58.4
2500
5.0
25.0
125
16.0
2920
5.0
25.0
125
2.6
2500
5.0
25.0
125
46
2500
N
4
4
4
2
4
3
4
4
4
4
4
4
4
2
2
4
4
4
2
2
4
4
4
4
2
4
4
4
3
2
4
4
4
2
2
Percent
RSD
4.4
2.8
4.8
-
24
1.7
1.1
9.0
7.9
-
7.0
5.1
3.1
-
-
19
2.3
6.5
_
-
7.3
1.3
5.8
3.5
-
7.7
9.0
7.7
23
-
10
0.6
1.9
-
_
                    8280 - 24
                                            Revision      0
                                            Date  September  1986

-------
TABLE 5  (Continued)
Compound
1,2,3,4, 7-PeCDD




1,2,3,7,8-PeCDD




1,2,3,4,7,8-HxCDD




1,2,3,4,6,7,8-HpCDD




1,2,7,8-TCDF




1,2,3,7,8-PeCDF




1,2,3,4,7,8-HxCDF




Analyte
Matrix3
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge0
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom3
clay
soil
sludge
fly ash
still bottom
level (ng/g)
Native
NO
ND
ND
25.8
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
8760
ND
ND
ND
ND
ND
7.4
ND
ND
ND
ND
ND
25600
ND
ND
13.6
24.2
ND
Native
+ spike
5.0
25.0
125
25.8
2500
5.0
25.0
125
46
2500
5.0
25.0
125
46
2500
5.0
25.0
8780
-
-
5.0
25.0
125
7.4
2500
5.0
25.0
125
46
28100
5.0
25.0
139
24.2
2500
N
4
4
4
2
2
4
4
4
2
2
4
4
4
2
2
4
4
4
-
-
4
4
4
3
2
4
4
4
2
2
4
4
4
4
2
Percent
RSD
10
2.8
4.6
6.9
-
25
20
4.7
-
-
38
8.8
3.4
-
-
_
-
-
-
-
3.9
1.0
7.2
7.6
-
6.1
5.0
4.8
.
-
26
6.8
5.6
13.5
-
       8280 - 25
                              Revision       0
                              Date  September 1986

-------
                            TABLE 5.   (Continued)


Compound
OCDF




Analyte

Matrix3
clay
soil
sludge
fly ash
still bottom
level (ng/g)
Native Percent
Native + spike N RSD
ND ...
ND -
192 317 4 3.3
ND -
ND -
amatr1x types:
 clay:  pottery clay.
 soil:  Times Beach,  Missouri,  soil  blended  to  form a homogeneous sample.
This sample was analyzed as  a  performance evaluation sample for the Contract
Laboratory Program (CLP)  in  April  1983.    The  results  from EMSL-LV and 8
contract laboratories using  the  CLP  protocol  were  305.8 ng/g 2,3,7,8-TCDD
with a standard deviation of 81.0.
 fly ash:  ash from a municipal incinerator; resource recovery ash No. 1.
 still bottom:  distillation bottoms (tar) from 2,4-dichlorophenol production.
sludge:    sludge  from  cooling   tower  which  received  both  creosote  and
pentachl orophenol i c wastewaters .
Cleanup of clay, soil and fly ash samples was through alumina column only.
(Carbon column not used.)
    - not detected at concentration injected (final volume 0.1 mL or greater).
GEst1mated concentration out of calibration range of standards.
                                  8280 - 26
                                                         Revision
                                                         Date  September 1986

-------
TABLE 6.  RECOVERY DATA FOR REVISED METHOD 8280
Compound
2,3,7,8-TCDD




1,2,3,4-TCDD




1,3,6,8-TCDD




1,3,7,9-TCDD




1,3,7,8-TCDD




1,2,7, 8-TCDD




1,2,8,9-TCDD




Matrix3
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
Nat1veb
(ng/g)
ND
378
ND
ND
487
ND
ND
ND
38.5
ND
ND
ND
ND
19.1
227
ND
ND
ND
58.4
ND
ND
ND
ND
16.0
615
ND
ND
ND
2.6
ND
ND
ND
ND
ND
ND
Sp1kedc
level
(ng/g)
5.0
-
125
46
-
5.0
25.0
125
46
2500
2.5
25.0
125
46
2500
2.5
25.0
125
46
2500
5.0
25.0
125
46
2500
5.0
25.0
125
46
2500
5.0
25.0
125
46
2500
Mean
percent
recovery
61.7
-
90.0
90.0
-
67.0
60.3
73.1
105.6
93.8
39.4
64.0
64.5
127.5
80.2
68.5
61.3
78.4
85.0
91.7
68.0
79.3
78.9
80.2
90.5
68.0
75.3
80.4
90.4
88.4
59.7
60.3
72.8
114.3
81.2
                    8280 - 27
                                           Revision       0
                                           Date   September  1986

-------
TABLE 6.  (Continued)
Compound
1,2,3,4,7-PeCDD




1,2,3,7,8-PeCDD




1,2,3, 4,7,8-HxCDD




1,2,3,4,6,7,8-HpCDD




2,3,7,8-TCDD
(C-13)



1,2,7,8-TCDF




1,2,3,7,8-PeCDF




Matrix3
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
•— • * — j
soil
sludge^
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
Nativeb
(ng/g)
< ND
ND
ND
25.8
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
8780
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
7.4
ND
ND
ND
! ND
ND
25600
Spikedc
level
(ng/g)
5.0
25.0
125
46
2500
5.0
25.0
125
46
2500
5.0
25.0
125
46
2500
5.0
25.0
125
•i

5.0
25.0
125
46
2500
5.0
25.0
125
46
2500
5.0
25.0
125
46
2500
Mean
percent
recovery
58.4
62.2
79.2
102.4
81.8
61.7
68.4
81.5
104.9
84.0
46.8
65.0
81.9
125.4
89.1
ND
ND

-
-
64.9
78.8
78.6
88.6
69.7
65.4
71.1
' 80.4
90.4
104.5
57.4
64.4
84.8
105.8
_
       8280 - 28
                              Revision       0
                              Date   September 1986

-------
                            TABLE  6.   (Continued)

Compound
1,2,3,4,7,8-HxCDF




OCDF





Matrix3
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
Nat1veb
(ng/g)
ND
ND
13.6
24.2
ND
ND
ND
192
ND
ND
Spikedc
level
(ng/g)
5.0
25.0
125
46
2500
_
-
125
-
-
Mean
percent
recovery
54.2
68.5
82.2
91.0
92.9
_
-
86.8
-
-
amatn'x types:
clay:  pottery clay.
soil:  Times Beach, Missouri soil blended  to form a homogeneous sample.  This
sample was  analyzed  as  a  performance  evaluation  sample  for the Contract
Laboratory Program  (CLP)  In  April  1983.    The  results  from EMSL-LV and 8
contract laboratories using  the  CLP  protocol  were  305.8 ng/g 2,3,7,8-TCDD
with a standard deviation of 81.0.
fly ash:  ash from  a municipal incinerator:  resource recovery ash No. 1.
still bottom:  distillation bottoms (tar) from 2,4-dichlorophenol production.
sludge:    sludge   from  cooling   tower  which  received  both  creosote  and
pentachlorophenol wastewaters.
The clay, soil and  fly ash  samples  were subjected to alumina column cleanup,
no carbon column was used.
bFinal volume of concentrate 0.1 mL  or greater, ND means below quantification
limit, 2 or more samples analyzed.
cAmount of analyte  added to sample, 2 or more samples analyzed.
^Estimated concentration out of calibration range of standards.
                                  8280 - 29
                                                         Revision      0
                                                         Date  September 1986

-------
          TABLE 7.   LINEAR RANGE AND VARIATIOIN OF RESPONSE FACTORS
Analyte Linear range tested (pg) n&
l,2,7,8-TCDFa
2,3,7,8-TCDDa
2,3,7,8-TCDF
50-6000
50-7000
300-4000
8
7
5
Mean RF
1.634
0.721
2.208
%RSD
12.0
11.9
7.9
aResponse factors for these analytes were calculated using 2,3,7,8-TCDF as the
Internal standard.  The response  factors for 2,3,7,8-TCDF were calculated vs.
13Ci2-l,2,3,4-TCDD.

DEach value of n represents a different concentration level.
                                  8280 - 30
                                                         Revision
                                                         Date  September 1986

-------
   TABLE 8.  METHOD DETECTION LIMITS OF   C12 - LABELED PCDD'S and PCDF'S

             IN REAGENT WATER (PPT) AND ENVIRONMENTAL SAMPLES (PPB)
1 ^-Labeled
Analyte
2,3,7,8-TCDD
i,2,3,7,8-PeCDD
1,2,3,6,7,8-HxQDD
1,2,3,4,6,7,8-HpCDD
OCDD
2,3,7,8-TCDF
1,2,3,7,8-PeCDF
1,2,3,4,7,8-ttcCDF
Reagent
Water3
0.44
1.27
2.21
2.77
3.93
0.63
1.64
2.53
Missouri
Soi?
0.17
0.70
1.25
1.87
2.35
0.11
0.33
0.83
rs»
Ash
0.07
0.25
0.55
1.41
2.27
0.06
0.16
0.30
Industrial
Sludge0
0.82
1.34
2.30
4.65
6.44
0.46
0.92
2.17
Still-d
Bottom
1.81
2.46
6.21
4.59
10.1
0.26
1.61
2.27
Fuel
Oil*
0.75
2.09
5.02
8.14
23.2
0.48
0.80
2.09
Fuel Oil/
Sawdust
0.13
0.18
0.36
0.51
1.48
0.40
0.43
2.22
.Sample size 1 ,000 mL.
 Sample size 10 g.
.Sample size 2 g.
 Sample size 1 g.
Note:  The final sample-extract volume was 100 uL for all samples.

Matrix types used in MDL Study:

     - Reagent water:  distilled, deionized laboratory water.
     - Missouri soil:  soil blended to form a homogeneous sample.
     - Fly-ash:  alkaline ash recovered from the electrostatic precipitator of
       a coal-burning power plant.
     - Industrial sludge:  sludge from  cooling tower which received creosotic
       and pentachlorophenolic wastewaters.  Sample  was ca. 70 percent water,
       mixed with oil and sludge.
     - Still-bottom:    distillation  bottoms  (tar)  from  2,4-dichlorophenol
       production.
     - Fuel oil:  wood-preservative solution from the modified Thermal Process
       tanks.  Sample  was  an  oily  liquid  (>90  percent oil) containing no
       water.
     - Fuel oil/Sawdust:  sawdust was obtained  as a very fine powder from the
       local lumber yard.   Fuel  oil  (described  above)  was  mixed at the 4
       percent (w/w) level.

Procedure used for the Determination  of  Method Detection Limits was obtained
from "Methods  for  Organic  Chemical  Analysis  of  Municipal  and Industrial
Wastewater" Appendix A, EPA-600/4-82-057,  July  1982.   Using this procedure,
the method detection  limit  is  defined  as  the  minimum  concentration of a
substance that can be measured  and  reported  with 99 percent confidence that
the value is above zero.
                                  8280 - 31
                                                         Revision      0	
                                                         Date  September 1986

-------
           lOO.On
   00
   ro
   oo
   o
   to
   po
O 73
cu n>
00 O
fD 3
O
IT
ft)
vo
00
                15:00
18:00        21:00

         Retention Time
24:00
27:00
                        Figure 2.  Mass Chromatogram of Selected PCDD and PCDF Congeners.

-------
                             METHOD easo

POLYCHLORINATEO OIBENZO-P-DIOXIINS AND POLYCHLOHINATED OIBENZONFUHANS
(      Start      )
         Q
  6. 1
 Perform Initial
 calibration on
  GC/MS system
  6.9
                                                      10.2
          Calculate
          response
        factors for
         standards
   Do routine
   calibration
                                                      10.3
           Analyze
        samples  with
        selected ion
         monitoring
  S.Z
 	1  Extract
    •ample using
    appropriate
  method for the
   waste matrix
  9.9 |

       Prepare
  carbon column:
     do  carbon
  column cleanup
      10. S
     Quantitate  PCOO
      and PCOF peaks
Yes
    o
      11.01

         Determine
      concentrations
        •nd  report
         results
                                                   f     Stop      J
                                   8280 -  33
                                                             Revision       0
                                                             Date  September  1986

-------
                                 APPENDIX A

                    SIGNAL-TO-NOISE DETERMINATION METHODS
MANUAL DETERMINATION

     This method corresponds to a manual determination of the S/N from a GC/MS
signal, based on the measurement of  Its  peak height relative to the baseline
noise.  The procedure is composed of  four steps as outlined below.  (Refer to
Figure 1 for the following discussion).

     1.   Estimate the peak-to-peak noise (N) by tracing the two lines (EI and
          £2) defining the noise envelope.   The lines should pass through the
          estimated statistical mean  of  the  positive  and the negative peak
          excursions as shown in Figure 1.  In addition, the signal offset (0)
          should be set high enough such that negative-going noise (except for
          spurious negative spikes) is  recorded.

     2.   Draw the  line   (C)  corresponding  to  the  mean  noise between the
          segments defining the noise envelope.

     3.   Measure the height of the GC/MS  signal   (S) at the apex of the peak
          relative to the  mean noise C.   For noisy GC/MS signals, the average
          peak height should be measured from the estimated mean apex signal D
          between £3 and,£4.

     4.   Compute-the S/N.

     This method of  S/N   measurement   1s  a  conventional, accepted method of
 noise  measurement in analytical chemistry.
                           s

 INTERACTIVE COMPUTER GRAPHICAL METHOD

     This method calls  for the  measurement  of  the  GC/MS peak  area using the
 computer data  system and Eq.  1:
                                    A/t
                         S/N  = Aj/2t +  A  /2t
 where t is the elution time window  (time   interval,  t2~t2,  at  the  base  of  the
 peak used to measure the peak area A).    (Refer to  Figure  2,  for the  following
 discussion).

      AI and Ar correspond to the areas   of  the noise level  1n  a region  to  the
 left (AI) and to the right (Ar)  of the  GC  peak of Interest.
                                 8280 - A - 1
                                                          Rev'i s 1 on       0
                                                          Date September  1986

-------
     The procedure to determine the S/N 1s  as  follows:

     1.    Estimate the average negative  peak   excursions   of the  noise  (I.e.,
          the low segment-E2-of  the  noise envelope).     Line £3 should  pass
          through the estimated statistical mean   of the  negative-going noise
          excursions.  As stated earlier,  1t   1s  Important to have the  signal
          offset  (0)  set  high  enough such  that negative-going  noise  1s
      ;    recorded.

     2.    Using the cross-hairs  of  the video display terminal, measure the
          peak area (A) above  a  baseline   corresponding  to the mean negative
          noise value (£3) and between the  time t\ and  t£  where the GC/MS  peak
          Intersects the baseline,  £3.  Make note  of the time width t=t2-tj.

     3.    Following a similar procedure  as described  above, measure the  area
          of the noise 1n a region to  the   left (AI) and  to the right (Ar)  of
          the GC/MS signal using a time window twice the size of t, that 1s,
          2 x t.

     The analyst must sound  judgement  1n   regard  to  the proper  selection  of
Interference-free regions  1n  the  measurement  of  Aj and  Ar.     It  1s not
recommended to perform these noise measurements  (Aj and Ar) 1n remote regions
exceeding ten time widths (lot).

     4.    Compute the S/N using Eq. 1.

     NOTE:  If the noise does not occupy  at  least 10  percent of the vertical
            axis  (I.e., the noise envelope  cannot be defined accurately),  then
            1t 1s necessary to  amplify  the  vertical   axis so that the noise
            occupies 20 percent of the terminal display (see Figure 3).
                                8280 - A - 2
                                                         Revision
                                                         Date  September 1986

-------
                               FIGURE CAPTIONS

Figure 1.  Manual determination of S/N.
           The peak height (S) Is measured between the mean noise (lines C and
           D).  These mean  signal  values  are  obtained  by tracing the line
           between the baseline average noise extremes, Ej and £?,  and between
           the apex average noise  extremes,  £3  and  £4,  at the  apex of the
           signal.  Note,  1t  Is  Imperative  that the Instrument's Interface
           amplifier electronlc's zero  offset  be  set  high enough such that
           negative-going baseline noise 1s recorded.

Figure 2.  Interactive determination of S/N.
           The peak area (A) 1s  measured  above the baseline average negative
           noise £2 and between times ti  and  t2.  The noise 1s obtained from
           the areas AI and Ar measured  to  the  left and to the right of the
           peak of Interest using time windows Tj and Tr (Ti=Tr=2t).

Figure 3.  Interactive determination of S/N.
           A) Area measurements  without  amplification  of the vertical axis.
           Note that  the  noise  cannot  be  determined  accurately by visual
           means.   B)  Area  measurements  after  amplification  (10X) of the
           vertical axis so  that  the  noise  level occupies approximately 20
           percent of the display, thus enabling a better visual estimation of
           the baseline noise, Ej, £2, and C.
                                 8280 - A -  3
                                                         Revision      0
                                                         Date  September  1986

-------
    00
    ro
    oo
    o
O 73
01 n
r+ <
(0 -*
  (ft

OO O
0> 3
a
CT
a>
(O
00
100-,



 90-



 80-



 70-



 60-



 50-



 40-



 30-


 20-



 10-
                                                      E3

                                                       I
                                                      E4
                                          117
                                    N
                                               = 19.5
                 20:00
                22:00
26:00
28:00
30:00
                                          Figure 1.  Manual Determination of S/N.

-------
100
 90-
 80-
 70-
 60-
 50-
 40-
 30-
 20-
 10-
  0
                   = 558.10
                          iv
                                14.7
=75.88
Ar = 88.55
         25:30  26:00 26:30
               27:00   27:30 28:00
                      17 sec.
          Figure 2.  Interactive Determination of S/N.
                      8280 - A - 5
                                        Revision     p
                                        Date  September 1986

-------
100-
 90-
 80-
 70-
 60-
 60-
 40-
 30-
 20-
 10-
  0-
                   A = 686.41
      = 17.18
Ar= 13.32
  26:30  26:00 36:30  27:00 27:30 28:00
                   A = 706.59
                        Ar = 41.88
  26:30  26:00  26:30  27:00  27:30  28:00
Figure 3.  Interactive Determination of S/N.
             8280 - A - 6
                                   Revision      0
                                   Date  September 1986

-------
                                 APPENDIX B

        RECOMMENDED SAFETY AND HANDLING PROCEDURES FOR PCDD'S/PCDF'S


     1.  The human toxicology  of  PCDD/PCDF  1s  not well  defined at present,
although the 2,3,7,8-TCDD Isomer has been found to be acnegenlc,  carcinogenic,
and teratogenlc in the course of  laboratory animal studies.  The 2,3,7,8-TCDD
1s a solid at room temperature, and  has a relatively low vapor pressure.  The
solubility of this compound 1n water 1s only about 200 parts-per-tr1H1on,  but
the solubility 1n various organic  solvents  ranges from about 0.001 perent to
0.14 percent.  The physical properties  of  the 135 other tetra- through octa-
chlorinated PCDD/PCDF have not been  well established, although 1t 1s presumed
that the physical properties of these congeners are generally similar to those
of the 2,3,7,8-TCDD Isomer.  On  the  basis of the available toxlcologlcal  and
physical property data for TCDD, this compound,  as well as the other PCDD and
PCDF, should be handled only  by  highly  trained personnel who are thoroughly
versed 1n the appropriate procedures, and who understand the associated risks.

     2.  PCDD/PCDF and samples  containing these are handled using essentially
the same techniques as  those  employed  1n handling radioactive or Infectious
materials.  Well-ventilated, controlled-access  laboratories are required,  and
laboratory personel entering these laboratories should wear appropriate safety
clothing, Including disposable coveralls,  shoe  covers,  gloves, and face and
head masks.  During analytical operations  which  may give rise to aerosols or
dusts,  personnel  should  wear  respirators  equipped  with  activated carbon
filters.  Eye protection equipment  (preferably full face shields) must be worn
at all  times  while  working  1n  the  analytical  laboratory with PCDD/PCDF.
Various  types  of  gloves  can  be  used  by  personnel,  depending  upon the
analytical operation being accomplished.  Latex gloves are generally utilized,
and when handling samples thought  to be particularly hazardous, an additional
set of gloves are also  worn   beneath  the  latex  gloves (for example, Playtex
gloves supplied by American Scientific   Products,  Cat. No. 67216).  Bench-tops
and other work  surfaces  1n  the   laboratory   should  be covered with plastic-
backed absorbent paper during  all   analytical  processing.  When finely divided
samples  (dusts,  soils, dry  chemicals)   are  processed,  removal of these from
sample  contaners,  as   well   as   other   operations,   Including  weighing,
transferring, and mixing with   solvents,  should   all be accomplished within a
glove  box.   Glove boxes, hoods and the  effluents  from mechanical vacuum pumps
and gas chromatographs  on  the  mass  spectrometers  should  be vented  to the
atmosphere  preferably only  after passing through  HEPA particulate  filters and
vapor-sorblng charcoal.

     3.  All laboratory  ware,  safety   clothing,   and other  Items  potentially
contaminated with   PCDD/PCDF   1n   the  course   of  analyses   must be  carefully
secured  and subjected to proper disposal.     When feasible,  liquid wastes are
concentrated, and  the residues  are placed   1n approved steel  hazardous waste
drums  fitted with   heavy   gauge polyethylene   liners.   Glass  and  combustible
Items  are  compacted using  a dedicated   trash  compactor  used only  for  hazardous
waste  materials and then  placed 1n  the   same  type of disposal  drum.   Disposal
of  accumulated wastes   1s  periodically  accomplished  by  high   temperature
Incineration at EPA-aproved facilities.


                                 8280 - B -  1
                                                         Revision      0
                                                         Date September 1986

-------
     4.  Surfaces of laboratory benches,  apparatus and other appropriate areas
should be periodically subjected  to  surface  wipe tests using solvent-wetted
filter paper which 1s then  analyzed  to   check for PCDD/PCDF contamination 1n
the laboratory.  Typically, 1f the detectable  level of TCDD or TCDF from such
a test is greater than 50  ng/m2,  this indicates the need for decontamination
of the laboratory.  A typical  action  limit 1n terms of surface contamination
of the other PCDD/PCDF (summed) is 500 ng/m2.   In the event of a spill  within
the laboratory, absorbent paper is  used   to  wipe up the spilled material and
this is then placed into a hazardous  waste drum.  The contaminated surface is
subsequently  cleaned  thoroughly   by   washing   with  appropriate  solvents
(methylene chloride followed by methanol)  and laboratory detergents.  This 1s
repeated until wipe tests  Indicate  that  the levels of surface contamination
are below the limits cited.

     5.  In  the  unlikely  event  that  analytical  personnel experience skin
contact with PCDD/PCDF   or  samples  containing  these, the contaminated skin
area should Immediately  be  thoroughly  scurbbed  using  mild soap and water.
Personnel involved 1n any such  accident   should  subsequently be taken to the
nearest medical facility, preferably  a  facility whose staff is knowledgeable
in  the  toxicology  of   chlorinated   hydrocarbons.     Again,  disposal  of
contaminated clothing is accomplished by  placing 1t in hazardous waste drums.

     6.    It  1s  desirable  that  personnel  working  1n  laboratories where
PCDD/PCDF are  handled  be  given  periodic  physical  examinations  (at least
yearly).  Such examinations  should  Include  specialized tests, such as those
for urinary porphyrins  and  for  certain  blood  parameters which, based upon
published clinical  observations,  are  appropriate  for  persons  who  may be
exposed to PCDD/PCDF.  Periodic  facial  photographs  to document the onset of
dermatologlc problems are also advisable.
                                8280 - B - 2
                                                         Revision      0
                                                         Date  September 1986

-------
                                                                   Page  1 of 2
                   DIOXIN SAMPLE DATA SUMMARY  FORM  8280-1
LAB NAME
CONTRACT No.
CASE No.
                                          QUANTITY FOUND (ng/g)
SAMPLE NO.     FILE NAME       TCDD      PeCDD      HxCDD      HpCDD      OCDD
 DATA  RELEASE  AUTHORIZED  BY
                                 8280 - B -  3
                                                          Revision      0
                                                          Date   September  1986

-------
                                                                   Page 2 of 2



                   DIOXIN SAMPLE DATA SUMMARY FORM 8280-1



LAB NAME 	      CONTRACT No.	


CASE No. __^	

                                          QUANTITY FOUND (ng/g)


SAMPLE NO.     FILE NAME       TCDF      PeCDF'      HxCDF      HpCDF      OCDF
                                8280 -  B - 4
                                                         Revision
                                                         Date  September  1986

-------
                                                                   Page  1  of  2
                  DIOXIN SAMPLE DATA SUMMARY FORM 8280-1-W
LAB NAME
CONTRACT No.
CASE No.
                                          QUANTITY FOUND (ug/L)
SAMPLE NO.     FILE NAME       TCDD      PeCDD      HxCDD      HpCDD      OCDD
 DATA  RELEASE  AUTHORIZED  BY
                                 8280 - B -  5
                                                          Revision      0
                                                          Date  September  1986

-------
                                                                   Page  2  of 2



                  DIOXIN SAMPLE DATA SUMMARY FORM 8280-1-W



LAB NAME 	      CONTRACT No.  	


CASE No. 	

                                          QUANTITY FOUND (ug/L)


SAMPLE NO.     FILE NAME       TCDF      PeCDF      HxCDF      HpCDF      OCDF
                                 8280 -  B -  6
                                                         Revision
                                                         Date  September 1986

-------
                     DIOXIN RAW SAMPLE DATA FORM 8280-2
LAB NAME 	  ANALYST(s) 	  CASE No.
SAMPLE No. 	  TYPE OF SAMPLE 	CONTRACT No.


SAMPLE SIZE           % MOISTURE             FINAL EXTRACT VOLUME
EXTRACTION METHOD 	ALIQUOT USED FOR ANALYSIS


CLEAN UP OPTION
CONCENTRATION FACTOR                  DILUTION FACTOR
DATE EXTRACTED                        DATA ANALYZED
VOLUME 13Ci2-l,2,3,4-TCDD ADDED 	 TO SAMPLE VOLUME
VOLUME INJECTED	Wt 13c12-l,2,3,4-TCDD ADDED
Wt 13C12-2,3,7,8-TCDD ADDED 	 13C12-2,3,7,8-TCDD % RECOVERY


Wt 13C12-2,3,7,8-OCDD ADDED 	 13C12-OCDD % RECOVERY 	
 13Ci2-2,3,7,8-TCDD RRF 	  13C12-OCDD RRF 	

                              13Ci2-2,3,7,8-TCDD

 AREA  332 	AREA  334 	 RATIO 332/334 _


 13Ci2-OCDD  AREA  470 	 AREA 472 	  RATIO 470/472


 RT  2,3,7,8-TCDD  (Standard) 	  RT 2,3,7,8-TCDD  (Sample) 	


 13C12-2,3,7,8-TCDD -  13Ci2-l,2,3,4-TCDD Percent Valley 	
                                8280 - B - 7
                                                         Revision
                                                         Date  September 1986

-------
              DIOXIN INITIAL CALIBRATION STANDARD DATA SUMMARY

                                 FORM 8280-3

                                          CASE No.
Lab Name
Date of Initial Calibration
                        Contract No.

                        Analyst(s)	
Relative to 13Ci2-2,3,7,8-TCDD_
                            or 13Ci2-l,2,3,4-TCDD_
CALIBRATION
STANDARD
RRF
 1
RRF
 2
RRF   RRF
 3     4
RRF
 5
MEAN    %RSD
TCDD
PeCDD
HxCDD
HpCDD
OCDD
TCDF
 PeCDF
 HxCDF
 HpCDF
 OCDF
                                 8280 - B - 8
                                                          Revision      0
                                                          Date  September 1986

-------
                           FORM 8280-3 (Continued)
                           CONCENTRATIONS IN PG/UL
TCDD
PeCDD
HxCDD
HpCDD
OCDD
TCDF
PeCDF
HxCDF
HpCDF
OCDF
                                 8280 - B - 9
                                                          Revision      0
                                                          Date  September 1986

-------
                    DIOXIN CONTINUING CALIBRATION  SUMMARY

                                 FORM 8280-4


                                         CASE No.
Lab Name
Date of Initial Calibration
Relative to 13Ci2-2,3,7,8-TCDD_
                     Contract  No.

                     Analyst(s)	
                     or 13Ci2-l,2,3,4-TCDD
COMPOUND
RRF
RRF
%D
TCDD
PeCDD
HxCDD
HpCDD
OCDD
TCDF
PeCDF
HxCDF
HpCDF
OCDF
                                 8280 -  B -  10
                                                         Revision      0
                                                         Date  September  1986

-------
                    DIOXIN RAW SAMPLE DATA FORM 8280-5-A



LAB NAME 	  ANALYST(s) 	  CASE No.


CONTRACT No.                                SAMPLE No.
TCDD REQUIRED 320/322 RATIO WINDOW IS 0.65 - 0.89
QUANTITATED FROM 2,3,7,8-TCDD 	  1,2,3,4-TCDD 	  RRF
SCAN #  RRT   AREA       AREA       AREA       320/      CONFIRM
              322        320        257        322       AS TCDD
       	          •	Y/N      CONC.
                                             TOTAL  TCDD
 TCDF REQUIRED 304/306 RATIO WINDOW IS  0.65  -  0.89

 QUANTITATED FROM 2,3,7,8-TCDD 	 1,2,3,4-TCDD 	  RRF
 SCAN #  RRT   AREA       AREA       AREA       304/       CONFIRM
               306        304        243         306        AS  TCDD
 	:	Y/N       CONC.
                                             TOTAL TCDD
                                 8280 - B - 11
                                                          Revision
                                                          Date  September 1986

-------
                    DIOXIN RAW SAMPLE DATA FORM 8280-5-B
LAB NAME
ANALYST(s)
         CASE No.
CONTRACT No.
                 SAMPLE No.
PeCDD REQUIRED 320/322 RATIO WINDOW IS 0.55 - 0.75
QUANTITATED FROM 2,3,7,8-TCDD

SCAN #  RRT   AREA      AREA
              356       358
       AREA
       354
               1,2,3,4-TCDD
AREA
293
358/
356
                     RRF
CONFIRM
AS PeCDD
  Y/N
                                                                         CONC.
                                           TOTAL PeCDD
 PeCDF REQUIRED 342/340 RATIO WINDOW  IS 0.55 - 0.75

 QUANTITATED  FROM 2,3,7,8-TCDD	   1,2,3,4-TCDD
SCAN  #   RRT   AREA      AREA      AREA      AREA    342/
              340       342       338       277     340
                                        RRF
                                    CONFIRM
                                    AS  PeCDF
                                     Y/N
                                                                          CONC.
                                           TOTAL  PeCDF
                                8280 - B -  12
                                                         Revision      0
                                                         Date  September 1986

-------
                    DIOXIN RAW SAMPLE DATA FORM 8280-5-C
LAB NAME
ANALYST(s)
         CASE No.
CONTRACT No.
                  SAMPLE No.
HxCDD REQUIRED 392/390 RATIO WINDOW IS 0.69 - 0.93
QUANTITATED FROM 2,3,7,8-TCDD

SCAN #  RRT   AREA      AREA
              390       392
                1,2,3,4-TCDD
       AREA
       388
AREA
327
3927
390
                     RRF
CONFIRM
AS HxCDD
  Y/N
                                                                         CONC.
                                           TOTAL HxCDD

HxCDF REQUIRED 376/374
QUANTITATED FROM 2,3,7
SCAN # RRT AREA
376
RATIO WINDOW IS
,8-TCDD
AREA
374
AREA
372
0.69 - 0.93
1,2,3,4-TCDD
AREA
311
376/
374
RRF
CONFIRM
AS HxCDF
Y/N CONC.
                                           TOTAL  HxCDF
                                 8280 - B - 13
                                                          Revision       0
                                                          Date   September  1986

-------
                    DIOXIN RAW SAMPLE DATA FORM 8280-5-D
LAB NAME
ANALYST(s)
         CASE No.
CONTRACT No.
                  SAMPLE No.
HpCDD REQUIRED 426/444 RATIO WINDOW IS 0.83 - 1.12
QUANTITATED FROM 2,3,7,8-TCDD

SCAN #  RRT   AREA      AREA
              424       426
       AREA
       422
                1,2,3,4-TCDD
AREA
361
4267
424
                     RRF
CONFIRM
AS HpCDD
  Y/N
                                                                         CONC.
                                           TOTAL HpCDD

HpCDF REQUIRED 410/408
QUANTITATED FROM 2,3,7,
SCAN # RRT AREA
408
RATIO WINDOW IS
8-TCDD
AREA
410
AREA
406
0.83 - 1.
1,2,3
AREA
345
12
,4-TCDD
410/
408
RRF
CONFIRM
AS HpCDF
Y/N CONC.
                                           TOTAL HpCDF
                                 8280 - B - 14
                                                          Revision       0
                                                          Date  September 1986

-------
                    DIOXIN RAW SAMPLE DATA FORM 8280-5-E



LAB NAME 	  ANALYST(s) 	  CASE No..

CONTRACT No.                                  SAMPLE No. 	
OCDD REQUIRED 458/460 RATIO WINDOW IS 0.75 - 1.01
QUANTITATED FROM 2,3,7,8-TCDD 	    1,2,3,4-TCDD 	  RRF
SCAN #  RRT   AREA     *  AREA      AREA       458/      CONFIRM
              460         458       395        460       AS OCDD
                        	      	Y/N      CONC.
                                           TOTAL OCDD
OCDF REQUIRED 442/444 RATIO WINDOW IS 0.75 - 1.01

QUANTITATED FROM 2,3,7,8-TCDD 	  1,2,3,4-TCDD 	  RRF
SCAN #  RRT   AREA        AREA      AREA       442/      CONFIRM
              444         442       379        444       AS OCDF
                                         	         Y/N	CONC.
                                           TOTAL OCDF
                                 8280 - B - 15
                                                          Revision
                                                          Date   September  1986

-------
            DIOXIN SYSTEM PERFORMANCE CHECK ANALYSIS FORM 8280-6
LAB NAME
                    CASE No.
BEGINNING DATE

ENDING DATE
       TIME

       TIME
                   CONTRACT No._

                    ANALYST(s)
PC SOLUTION IDENTIFIER
PCDD's
                       ISOTOPIC RATIO CRITERIA MEASUREMENT
  IONS
RATIOED
RATIO AT
BEGINNING OF
12 HOUR PERIOD
RATIO AT
END OF 12   ACCEPTABLE
HOUR PERIOD   WINDOW
Tetra
320/322
                               0.65-0.89
Penta
358/356
                               0.55-0.75
Hexa
392/390
                               0.69-0.93
Hepta
426/424
                               0.83-1.12
Octa
458/460
                               0.75-1.01
 PCDF's

 Tetra
304/306
                               0.65-0.89
 Penta
342-340
                               0.55-0.75
 Hexa
376-374
                               0.69-0.93
 Hepta
410/408
                               0.83-1.12
 Octa
442/444
                               0.75-1.01
 Ratios  out  of criteria
 PCDD

 PCDF
      Beginning

      _ out of

       out of
                            End

                           out of

                           out of
 NOTE:   One form 1s required for each 12 hour period  samples  are  analyzed.
                                 8280 - B - 16
                                                          Revision      0
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4.3  DETERMINATION OF ORGANIC ANALYTES

     4.3.3  HIGH PERFORMANCE LIQUID CHROMATOGRAPHIC METHODS
                                   FOUR - 11
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                                 METHOD 8310

                      POLYNUCLEAR AROMATIC HYDROCARBONS
1.0  SCOPE AND APPLICATION

     1.1  Method 8310 1s used to  determine the concentration of certain poly-
nuclear aromatic hydrocarbons (PAH) 1n ground water and wastes.   Specifically,
Method 8310 is used to detect the following substances:
          Acenaphthene
          Acenaphthylene
          Anthracene
          Benzo(a)anthracene
          Benzo(a)pyrene
          Benzo(b)f 1uoranthene
          Benzo(ghi)perylene
          Benzo(k)f1uoranthene
Chrysene
Dibenzo(a,h)anthracene
Fluoranthene
Fluorene
Indeno(1,2,3-cd)pyrene
Naphthalene
Phenanthrene
Pyrene
     1.2  Use of Method 8310  presupposes  a  high  expectation of finding the
specific compounds of Interest.  If  the  user is attempting to screen samples
for any or all  of  the  compounds  listed  above, he must develop independent
protocols for the verification of Identity.

     1.3  The method detection limits for  each  compound 1n reagent water are
listed 1n Table 1.  Table  2  lists the practical quantisation limit (PQL) for
other matrices.  The sensitivity of  this  method usually depends on the level
of  Interferences  rather  than  instrumental  limitations.    The  limits  of
detection listed in Table  1  for the liquid chromatographic approach represent
sensitivities that can be  achieved  in  the  absence  of Interferences.  When
Interferences are present, the level of sensitivity will be lower.

     1.4  This method  1s  recommended  for  use  only  by experienced residue
analysts or  under the close supervision of such qualified persons.


2.0  SUMMARY OF METHOD

     2.1  Method 8310 provides high  performance liquid chromatographic  (HPLC)
conditions for the detection  of  ppb  levels  of certain polynuclear aromatic
hydrocarbons.  Prior  to   use  of  this  method, appropriate sample extraction
techniques must be used.   A  5-  to  25-uL  aliquot of the extract is injected
Into an HPLC, and compounds in  the  effluent are detected by ultraviolet  (UV)
and fluorescence detectors.

     2.2  If interferences  prevent  proper  detection  of  the  analytes  of
interest, the method may   also  be  performed  on extracts that have undergone
cleanup using silica gel column cleanup  (Method 3630).
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TABLE 1.  HIGH PERFORMANCE LIQUID CHROMATOGRAPHY OF PAHsa
Compound
Naphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthrene
Pyrene
Benzo (a) anthracene
Chrysene
Benzo (b) f 1 uoranthene
Benzo (k) f 1 uoranthene
Benzo(a)pyrene
D1 benzo (a , h) anthracene
Benzo (ghl)perylene
Indeno(l,2,3-cd)pyrene
Retention
time (m1n)
16.6
18.5
20.5
21.2
22.1
23.4
24.5
25.4
28.5
29.3
31.6
32.9
33.9
35.7
36.3
37.4
Col umn
capacity
factor (k1)
12.2
13.7
15.2
15.8
16.6
17.6
18.5
19.1
21.6
22.2
24.0
25.1
25.9
27.4
27.8
28.7
Method Detection
limit (ug/L)
UV Fluorescence
1.8
2.3
1.8
0.21
0.64
0.66
0.21
0.27
0.013
0.15
0.018 .
0.017
0.023
0.030
0.076
0.043
     a HPLC conditions:  Reverse  phase  HC-ODS S11-X, 5 micron particle size,
 1n a 250-mrn x 2.6-mm  I.D.  stainless steel column.  Isocratlc elutlon for 5 mln
 using aceton1tr1le/water   (4:6)(v/v),  then  linear  gradient  elutlon to 100%
 acetonltrlle over 25  m1n at  0.5  mL/m1n  flow  rate.  If columns having other
 Internal diameters  are used, the  flow  rate  should be adjusted to maintain a
 linear velocity  of  2  mm/sec.
 TABLE  2.   DETERMINATION  OF  PRACTICAL QUANTITATION  LIMITS  (PQL)  FOR  VARIOUS
           MATRICES3
    Matrix
  Factorb
 Ground water
 Low-level  soil  by  sonlcation  with  GPC  cleanup
 High-level  soil  and  sludges by  sonlcatlon
 Non-water  mlsclble waste
     10
    670
 10,000
100,000
      aSample  PQLs  are  highly   matrix-dependent.     The   PQLs  listed  herein are
      provided for  guidance  and may  not  always  be  achievable.
      bPQL  =  [Method  Detection  Limit  (Table  1)  X  [Factor  (Table  2)].
      aqueous  samples,  the  factor 1s  on  a wet-weight basis.
          For non-
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3.0  INTERFERENCES

     3.1  Solvents, reagents, glassware, and  other sample processing hardware
may yield discrete artifacts and/or elevated baselines, causing misinterpreta-
tion of the chromatograms.  All of  these materials must be demonstrated to be
free from Interferences,  under  the  conditions  of  the analysis, by running
method blanks.  Specific selection of reagents and purification of solvents by
distillation in all-glass systems may be required.

     3.2  Interferences coextracted from  the  samples  will vary considerably
from source to source.   Although  a  general cleanup technique 1s provided as
part  of  this  method,  individual  samples  may  require  additional cleanup
approaches to achieve the sensitivities stated 1n Table 1.

     3.3  The  chromatographlc  conditions   described   allow  for  a  unique
resolution of the specific PAH  compounds  covered  by this method.  Other PAH
compounds, in addition to matrix artifacts, may interfere.


4.0  APPARATUS AND MATERIALS

     4.1  Kuderna-Danish  (K-D) apparatus:

          4.1.1  Concentrator  tube:  10-mL, graduated  (Kontes K-570050-1025 or
     equivalent).  Ground-glass  stopper   1s  used  to  prevent evaporation of
     extracts.

          4.1.2  Evaporation   flask:      500-mL   (Kontes   K-570001-500  or
     equivalent).  Attach to concentrator  tube with springs.

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

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

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

     4.3  Water  bath;    Heated,  with concentric   ring  cover,   capable  of
temperature control  (+5'C).  The bath  should  be  used  1n  a hood.

     4.4  Syringe;   5-mL.

     4.5  High pressure syringes.

     4.6  HPLC apparatus;

          4.6.1  Gradient pumping  system:   Constant flow.

          4.6.2  Reverse  phase column:   HC-ODS   Sil-X,  5-micron  particle  size
     diameter, in  a  250-mm  x 2.6-mm   I.D.  stainless steel  column  (Perkin Elmer
     No.  089-0716  or equivalent).

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          4.6.3  Detectors:   Fluorescence and/or UV  detectors  may  be  used.

               4.6.3.1  Fluorescence detector:   .For  excitation at 280-nm  and
          emission greater than  389-nm  cutoff - (Corning 3-75.or  equivalent).
          Fluorometers should have  dispersive   optics  for excitation  and  can
          utilize either filter or.dispersive optics at the emission  detector.

               4.6.3.2  UV detector:   ,254-nm,  coupled  to  the  fluorescence
          detector.             .'••....         .     .,-...

          4.6.4  Strip-chart recorder: icompatlble  with  detectors.     A data
     system for measuring peak areas and retention times 1s recommended.

     4.7  Volumetric flasks;  1.0-, 50-, and 100-mL.


5.0  REAGENTS       ' , .   .             i ",-
                                          ','"'-.      '.'  '  •'
    ,5.1  Reagent water;   Reagent  water  1s  defined  as  water   1n which an
Interferent Is not observed at the  method detection.limit of the  compounds of
interest.          ,

     5.2  Aceton1tr11e;  HPLC quality, distilled In glass.   . .  •  •

     5.3  Stock standard solutions;

          5.3.1  Prepare stock standard solutions  at  a concentration of 1.00
     ug/uL by dissolving  0.0100  g  of  assayed  reference material  1n aceto-
     nitrile 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 1f
     they are certified by the manufacturer or by an Independent source.

          5.3.2  Transfer  the  stock  standard  solutions  Into Teflon-sealed
     screw-cap bottles.  Store at 4'C and protect from light.  Stock standards
     should be checked  frequently  for, signs  of degradation or evaporation,
     especially just prior to preparing calibration  standards from them.

    .1    5.3.3  Stock standard solutions must  be   replaced after one year, or
     sooner if comparison with check  standards  Indicates a  problem.

     5.4  Calibration  standards;  Calibration   standards  at a minimum  of  five
concentration  levels  should  be   prepared  through  dilution  of  the  stock
standards with acetonitrile.  One of   the  concentration levels should  be  at a
concentration  near, but   above,   the   method   detection  limit.  The remaining
concentration  levels  should  correspond to the  expected range of concentrations
found  in  real  samples  or  should;define  the  working  range  of the HPLC.  Cali-
bration  standards  must be replaced  .after  ;six  months, or sooner 1f comparison
with check standards  indicates a  problem.
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     5.5  Internal standards (1f Internal   standard  calibration 1s used);   To
use this approach, the analyst must select one or more Internal  standards that
are similar In analytical behavior to  the compounds of Interest.  The analyst
must further demonstrate that the measurement  of the Internal  standard 1s not
affected by method or matrix interferences.   Because of these  limitations, no
Internal standard can be suggested that 1s applicable to all samples.

          5.5.1  Prepare  calibration   standards   at   a   minimum  of  five
     concentration levels for each analyte as described 1n Paragraph 5.4.

          5.5.2  To each calibration standard, add  a known constant amount of
     one or more internal standards, and dilute to volume with  acetonltrlle.

          5.5.3  Analyze each calibration standard according to Section 7.0.

     5.6  Surrogate standards;  The analyst  should monitor the performance of
the  extraction,cleanup(Tf  necessary),  and  analytical  system  and  the
effectiveness of the method in dealing with each sample matrix by spiking each
sample, standard, and reagent water  blank  with  one or two surrogates (e.g.,
decafluorobiphenyl or other PAHs  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 for
HPLC analysis due to coelution problems.


6.0  SAMPLE COLLECTION,  PRESERVATION, AND HANDLING

     6.1  See the introductory  material  to  this  chapter, Organic Analytes,
Section 4.1.  Extracts must be stored under refrigeration and must be analyzed
within 40 days of extraction.


7.0  PROCEDURE

     7.1  Extraction;

          7.1.1   Refer to Chapter Two for guidance on choosing the appropriate
     extraction procedure.   In  general,  water  samples   are  extracted at  a
     neutral pH with methylene  chloride,  using  either  Method 3510 or 3520.
     Solid  samples are extracted using either Method 3540 or 3550.   To achieve
     maximum sensitivity with this method, the extract must be concentrated to
     1 mL.

          7.1.2   Prior   to  HPLC  analysis,  the  extraction  solvent  must be
     exchanged to acetonltrlle.    The  exchange  1s  performed  during the  K-D
     procedures  listed  in all  of  the  extraction  methods.   The exchange 1s
     performed as follows.

               7.1.2.1   Following  K-D of  the methylene chloride  extract  to
          1 mL using  the macro-Snyder column,  allow the  apparatus to  cool  and
          drain  for at  least  10 m1n.
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         7.1.2.2   Increase the temperature of the  hot water bath to 95-
     100*C.    Momentarily  remove  the   Snyder  column,  add  4  ml  of
     acetonltrile,  a  new boiling chip, and attach a two-ball mlcro-Snyder
     column.   Concentrate  the  extract  using  1  ml  of acetonltrile to
     prewet the  Snyder column.  Place the K-D apparatus on the water bath
     so  that  the  concentrator  tube  1s  partially  Immersed  1n the hot
     water.   Adjust the vertical position  of the apparatus and the water
     temperature,  as  required,  to  complete  concentration 1n 15-20 m1n.
     At  the proper rate  of   distillation  the  balls  of the column will
     actively chatter,  but   the  chambers  will  not  flood.    When the
     apparent volume  of liquid  reaches  0.5  ml, remove the K-D apparatus
     and allow 1t  to  drain and  cool for at least 10 m1n.

          7.1.2.3   When the  apparatus  1s  cool,  remove the mlcro-Snyder
     column and rinse Us  lower  joint   Into   the concentrator tube with
     about 0.2 ml  of   acetonltrile.    A  5-mL  syringe 1s recommended for
     this operation.   Adjust the  extract  volume  to  1.0 ml.  Stopper the
     concentrator   tube   and  store    refrigerated  at 4'C,  1f   further
     processing will  not  be  performed  Immediately.    If the extract will
     be stored longer than   two  days,   1t   should   be  transferred to  a
     Teflon-sealed screw-cap vial.   Proceed with HPLC analysis  1f  further
     cleanup  1s not required.

7.2  HPLC conditions  (Recommended);

     7.2.1  Using  the column  described   1n   Paragraph 4.6.2:   Isocratlc
elutlon  for   5 m1n   using   aceton1tr1le/water  (4:6)(v/v),  then linear
gradient elutlon to 100%   acetonltrile over   25  m1n at 0.5 mL/m1n flow
rate.  If columns  having  other Internal diameters are used, the  flow rate
should be adjusted to maintain a  linear velocity of 2 mm/sec.

7.3  Calibration;

     7.3.1  Refer  to  Method  8000  for  proper  calibration procedures.   The
procedure of Internal or external  standard  calibration may be  used.   Use
Table 1 and especially Table 2 for guidance on  selecting  the  lowest point
on the calibration curve.

     7.3.2  Assemble the necessary HPLC  apparatus  and establish  operating
parameters equivalent to those Indicated   1n  Section  7.2.1.   By Injecting
calibration standards, establish  the  sensitivity   limit  of the detectors
and the linear range of the analytical systems for each  compound.

     7.3.3  Before  using  any  cleanup  procedure,   the   analyst  should
process a  series  of  calibration  standards  through  the  procedure to
confirm elutlon  patterns  and  the  absence  of  Interferences  from the
reagents.

7.4  HPLC analysis;

     7.4.1  Table  1  summarizes  the  estimate  retention  times  of PAHs
determinable  by this method.   Figure  1  1s an example of the separation
achievable using  the conditions given 1n Paragraph 7.2.1.

                             8310 - 6
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                                                    Date  September 1986

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Column: HC-ODSSIL-X
Mobile Phase: 40% to 100% Acetonitrile in Water
Dectector:  Fluorescence
                   1  S
                 a
                 I
                                   IB
                  I
                  o>
                  CD
                        §
                        0>

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                        I
              N



              I
              i

              28
              — >
              o a
              N Jr
              C T3
             • 5 V
                                     I
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         7.4.2   If  Internal standard calibration 1s to be performed, add
     10  uL of  Internal standard to the sample prior to Injection.  Inject
     2-5 uL of the   sample  extract  with  a  high-pressure syringe or sample
     Injection loop.  Record the  volume  Injected  to the nearest 0.1 uL, and
     the resulting peak  size,  1n  area  units or peak heights.  Re-equilibrate
     the HPLC  column  at  the  Initial  gradient  conditions for at least 10 min
     between injections.

         7.4.3   Using either  the  internal  or external calibration procedure
     (Method 8000),  determine  the identity and quantity of each component peak
     in  the sample chromatogram  which  corresponds  to the compounds used for
     calibration  purposes.  See  Section  7.8  of  Method 8000 for calculation
     equations.

         7.4.4   If  the  peak   area   exceeds  the  linear  range of the system,
     dilute the extract  and  .^analyze.

         7.4.5   If  the  peak area measurement  is prevented by the presence of
     Interferences,  further  cleanup  is  required.

     7.5 Cleanup;

         7.5.1   Cleanup of  the  acetonltrile   extract  takes place  using Method
     3630 (Silica Gel  Cleanup).     Specific   Instructions  for  cleanup of the
     extract  for  PAHs is given 1n  Section 7.1  of  Method  3630.

          7.5.2   Following  cleanup,  analyze    the    samples   using  HPLC  as
     described 1n Section 7.4.


8.0  QUALITY CONTROL                  ',

     8.1  Refer  to  Chapter  One   for  specific  quality  control  procedures.
Quality control  to validate  sample extraction  is covered in Method 3500  and  1n
the extraction method used.   If  extract  cleanup was  performed,  follow  the QC
in Method 3600 and in the specific cleanup method.

     8.2  Mandatory quality  control  to  validate  the  HPLC  system operation  is
found 1n Method  8000, Section  8.6.

          8.2.1   The quality control  check  sample   concentrate (Method  8000,
     Section 8.6) should contain each  analyte at the  following  concentrations
     in acetonltrile:    naphthalene,  100  ug/mL;   acenaphthylene,  100  ug/mL;
     acenaphthene,  100 ug/mL;   fluorene,   100   ug/mL;  phenanthrene,  100  ug/mL;
     anthracene,  100 ug/mL;  benzo(k)fluoranthene,   5  ug/mL;  and any other  PAH
     at 10  ug/mL.

          8.2.2   Table 3 indicates the, calibration  and QC  acceptance criteria
     for this  method.    Table  4  gives  method  accuracy  and  precision  as
     functions of concentration for the analytes of  interest.   The contents of
     both Tables should be used to  evaluate a laboratory's ability to perform
     and generate acceptable data  by this method.


                                  8310-8
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     8.3  Calculate surrogate standard  recovery  on  all  samples,  blanks,  and
spikes.  Determine if  the  recovery  1s  within limits (limits established by
performing QC procedures outlined in Method 8000, Section  8.10).

          8.3.1  If recovery 1s  not  within  limits, the  following procedures
     are required.

               •  Check to  be  sure  there  are  no  errors  1n calculations,
                  surrogate solutions  and  Internal  standards.   Also, check
                  instrument performance.

               •  Recalculate the data and/or reanalyze  the extract 1f any of
                  the above checks reveal a problem.

               •  Reextract and reanalyze the sample  if none of the above are
                  a problem or flag the data as  "estimated concentration."


9.0  METHOD PERFORMANCE

     9.1  The method  was  tested  by  16  laboratories  using  reagent water,
drinking water,  surface water, and  three industrial wastewaters spiked at six
concentrations over the range  0.1  to  425  ug/L.   Single operator precision,
overall precision, and method accuracy  were  found  to be directly related to
the  concentration of  the   analyte  and  essentially  Independent of the sample
matrix.  Linear  equations  to  describe  these   relationships are  presented in
Table  4.

     9.2  This method has  been   tested  for  linearity  of spike recovery  from
reagent  water   and   has   been   demonstrated    to  be  applicable  over  the
concentration range from 8 x MDL to  800  x MDL with the following exception:
benzo(ghi)perylene  recovery  at 80  x  and  800   x  MDL  were  low  (35%  and  45%,
respectively).

     9.3  The accuracy and precision  obtained will  be determined by the sample
matrix,  sample-preparation technique, and  calibration procedures used.


 10.0  REFERENCES

 1.   "Development and  Application of  Test  Procedures for Specific Organic Toxic
Substances  1n Wastewaters, Category  9 -  PAHs,"   Report for  EPA Contract 68-03-
2624 (in preparation).

 2.   Sauter,  A.D.,  L.D.  Betowski, T.R. Smith, V.A. Strickler,  R.G.  Belmer,  B.N.
 Colby, and   J.E.  Wilkinson,   "Fused  Silica  Capillary   Column GC/MS for the
Analysis of Priority  Pollutants," Journal  of HRC&CC 4, 366-384, 1981.

 3.   "Determination  of  Polynuclear   Aromatic  Hydrocarbons   In  Industrial  and
Municipal   Wastewaters,"    EPA-600/4-82-025,    U.S.   Environmental Protection
Agency,  Environmental  Monitoring   and   Support  Laboratory,   Cincinnati,  Ohio
45268, September 1982.


                                  8310 - 9
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4.  Burke, J.A.  "Gas  Chromatography  for  Pesticide  Residue  Analysis; Some
Practical  Aspects,"  Journal  of   the  Association  of  Official  Analytical
Chemists, 48, 1037, 1965.

5.  "EPA  Method  Validation  Study   20,  Method  610  (Polynuclear  Aromatic
Hydrocarbons)," Report for EPA Contract 68-03-2624 (In preparation).

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

7.  Provost, L.P. and R.S.  Elder,  "Interpretation of Percent Recovery Data,"
American Laboratory, 15, pp. 58-63, 1983.
                                  8310 -  10
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TABLE 3.  QC ACCEPTANCE CRITERIA*
Parameter
Acenaphthene
Acenaphthylene
Anthracene
Benzo (a) anthracene
Benzo (a) pyrene
Benzo (b) f 1 uoranthene
Benzo (ghl ) peryl ene
Benzo (k) f 1 uoranthene
Chrysene
D1 benzo (a , h) anthracene
Fl uoranthene
Fluorene
Indeno (1 , 2 , 3-cd) pyrene
Naphthalene
Phenanthrene
Pyrene
Test
cone.
(ug/L)
100
100
100
10
10
10
10
5
10
10
10
100
10
100
100
10
Limit
for s
(ug/L)
40.3
45.1
28.7
4.0
4.0
3.1
2.3
2.5
4.2
2.0
3.0
43.0
3.0
40.7
37.7
3.4
Range
for 7
(ug/L)
D-105.7
22.1-112.1
11.2-112.3
3.1-11.6
0.2-11.0
1.8-13.8
D-10.7
D-7.0
D-17.5
0.3-10.0
2.7-11.1
D-119
1.2-10.0
21.5-100.0
8.4-133.7
1.4-12.1
Range
P. Ps
(%)
D-124
D-139
D-126
12-135
D-128
6-150
D-116
D-159
D-199
D-110
14-123
D-142
D-116
D-122
D-155
D-140
     s = Standard deviation of four recovery measurements, 1n ug/L.
     7 = Average recovery for four recovery measurements, 1n ug/L.
     p, ps = Percent recovery measured.
     D = Detected; result must be greater than zero.
     3Cr1ter1a from 40 CFR Part  136 for  Method 610.  These criteria are based
directly upon the method performance  data  In  Table 3.  Where necessary, the
limits for recovery have been broadened  to assure applicability of the limits
to concentrations below those used to develop Table 3.
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TABLE 4.  METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION3
Parameter
Acenaphthene
Acenaphthylene
Anthracene
Benzo (a) anthracene
Benzo(a)pyrene
Benzo (b) f 1 uoranthene
Benzo (gh1 )peryl ene
Benzo (k) f 1 uoranthene
Chrysene
D1 benzo (a , h) anthracene
Fl uoranthene
Fluorene
Indeno(l,2,3-cd)pyrene
Naphthalene
Phenanthrene
Pyrene i
Accuracy, as
recovery, x'
(ug/L)
0.52C+0.54
0.69C-1.89
0.63C-1.26
0.73C+0.05
0.56C+0.01
0.78C+0.01
0.44C+0.30
0.59C+0.00
0.77C-0.18
0.41C-0.11
0.68C+0.07
0.56C-0.52
0.54C+0.06
0.57C-0.70
0.72C-0.95
0.69C-0.12
Single analyst
precision, sr'
(ug/L)
0.397+0.76
0.367+0.29
0.237+1.16
0.287+0.04
0.387-0.01
0.217+0.01
0.257+0.04
0.447-0.00
0.327-0.18
0.247+0.02
0.227+0.06
0.447-1.12
0.297+0.02
0.397-0.18
0.297+0.05
0.257+0.14
Overall
precision,
S' (ug/L)
0.537+1.32
0.427+0.52
0.417+0.45
0.347+0.02
0.537-0.01
0.387-0. 00
0.587+0.10
0.697+0.10
0.667-0.22
0.457+0.03
0.327+0.03
0.637-0.65
0.427+0.01
0.417+0.74
0.477-0.25
0.427-0.00
     x1  = Expected  recovery  for  one  or  more  measurements  of  a  sample
           containing a concentration of C, 1n ug/L.

     sr' = Expected single analyst  standard  deviation  of measurements at an
           average concentration of 7, 1n ug/L.

     S1  = Expected Interlaboratory standard  deviation  of measurements at an
           average concentration found of 7, 1n ug/L.

     C   = True value for the concentration, 1n ug/L.

     7   = Average recovery found for measurements of samples containing a
           concentration of C, 1n ug/L.
                                   8310 -  12
                                                         Revision      0
                                                         Date  September 1986

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                                         METHOD 6310

                              POLYNUCLEAR AROMATIC HYDROCARBONS
 7.1.1
                                                        o
        Choose
     appropriate
     extraction
     procedure
 (see Chapter  2)
7.1.2
                                                    7.3.3
       Process
    a series  of
    calibration
     standards
       Exchange
       extract-
 ion solvent to
   •cetonltrlie
    during K-D
    procedures
 7.2
 7.4
       Perform
        HPLC
  analysis  (see
   Method 6000
for calculation
    aquations
    Set HPLC
   conditions
 7.3
       Refer to
    Method 6000
    for proper
    calibration
    techniques
                                                                             7.5.1
                          Cleanup using
                           Method 3630
7.3.2
     I  Assembla
HPLC apparatus:
     establish
     operating
    parameters
    0
                                     8310 - 13
                                                                Revision       0
                                                                Date   September 1986

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4.4  MISCELLANEOUS SCREENING METHODS
                                   FOUR -  12
                                                         Revision
                                                         Date  September 1986

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                                 METHOD 3810

                                  HEADSPACE
1.0  SCOPE AND APPLICATION

     1.1  Method 3810 was formerly Method  5020  In the second edition of this
manual.

     1.2  Method 3810 is a static  headspace technique for extracting volatile
organic compounds from samples.    It  is  a  simple  method that allows large
numbers of samples to be screened in a relatively short period of time.  It is
ideal  for  screening  samples  prior  to  using  the  purge-and-trap  method.
Detection limits for this method may  vary widely among samples because of the
large variability and complicated matrices of waste samples.  The method works
best for compounds with boiling points of less than 125°C.  The sensitivity of
this method will depend on the equilibria of the various compounds between the
vapor and dissolved phases.

     1.3  Due to the variability of this method, this procedure is recommended
for use only as a  screening  procedure for other, more accurate determinative
methods (Methods 8010, 8015, 8020, 8030, and 8240).


2.0  SUMMARY OF METHOD

     2.1  The sample is collected  in  sealed  glass containers and allowed to
equilibrate at 90'C.  A sample of  the  headspace gas is withdrawn with a gas-
tight syringe for screening analysis using  the conditions specified in one of
the GC or GC/MS determinative methods (8010, 8015, 8020, 8030, or 8240).


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 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 high-level and low-
 level  samples are  sequentially  analyzed.    To  reduce carryover, the sample
 syringe must be  rinsed out  between  samples  with reagent water.  Whenever an
 unusually concentrated sample  is  encountered,   it  should  be followed by an
 analysis of  reagent  water.  It may  be   necessary to wash out  the syringe with
detergent, rinse with  distilled  water,  and  dry  in  a  105*C oven between
 analyses.

      3.3  Before processing any  samples,  the  analyst  should demonstrate daily
 through  the  analysis of  an organic-free  water  or  solvent blank that the entire
 analytical  system  is interference-free.


                                   3810 - 1
                                                          Revision       0
                                                          Date  September  1986

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4.0  APPARATUS AND MATERIALS

     4.1  Refer to the specific determinative method for appropriate apparatus
and materials.

     4.2  Vials:    125-mL  Hypo-V1als   (Pierce   Chemical  Co.,  #12995,  or
equivalent), four each.

     4.3  Septa;  Tuf-Bond (Pierce #12720 or equivalent).

     4.4  Seals;  Aluminum (Pierce #132141 or equivalent).

     4.5  Crimper;  Hand  (Pierce #13212 or equivalent).

     4.6  Syringe;  5-mL,  gas-tight  with  shutoff  valve and chromatographic
needles.

     4.7  Microsyringe;   250- or 500-uL.

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


5.0  REAGENTS

     5.1  Refer to  the   specific  determinative  method  and  Method 8000 for
preparation of calibration standards.


6.0  SAMPLE COLLECTION,  PRESERVATION, AND HANDLING
                              \
     6.1  Refer  to   the Introductory   material   to   this  chapter,  Organic
Analytes, Section 4.1.


7.0  PROCEDURE

     7.1  Gas  chromatographic  conditions  and  Calibration;     Refer   to the
specific determinative method  for GCoperating conditions and to Method 8000,
Section 7.4,  for calibration procedures.

     7.2  Sample preparation;

          7.2.1  Place 10.0 g  of a  well-mixed  waste   sample into each  of two
     separate  125-mL  septum-seal vials.

          7.2.2  Dose one sample vial through the septum with 200 uL of  a
     50 ng/uL  calibration  standard  containing  the   compounds of interest.
     Label  this  "1-ppm spike."
                                   3810 - 2
                                                          Revision
                                                          Date  September 1986

-------
          7.2.3  Dose a  separate  (empty) 125-mL  septum  seal vial with 200 uL
    of the  same 50 ng/uL calibration standard.  Label this  "1-ppm standard."

          7.2.4  Place the  sample, 1-ppm-spike,  and l-;ppm-standard vials into
    a 90*C  water  bath for  1  hr.  Store the remaining sample vial at 4.0°C for
    possible  future analysis.

    7.3   Sample analysis:

          7.3.1  While maintaining the vials   at  90°C,  withdraw  2 ml of the
    headspace gas with  a   gas-tight  syringe  and  analyze by direct injection
    into  a  GC.  The GC  should  be operated using the same GC conditions listed
    in the  method being screened (8010, 8015, 8020, 8030, or 8240).

          7.3.2  Analyze the  1-ppm standard  and adjust  instrument sensitivity
    to give a minimum  response of   at   least  2 times the background.  Record
    retention times  (RT)  and peak areas of compounds of interest.

          7.3.3  Analyze the  1-ppm spiked  sample   in  the same  manner.  Record
    RTs  and peak  areas.

          7.3.4  Analyze the  undosed sample  as in  Paragraph  7.3.3.

          7.3.5   Use the results obtained  to   determine  if  the  sample  requires
     dilution or methanolic extraction  as  indicated in Method  5030.
8.0  QUALITY CONTROL

     8.1  Before  processing  any  samples,  the  analyst  should  demonstrate
through the analysis of a distilled  water method blank that all  glassware and
reagents are interference-free.  Each  time  a  set of samples is extracted or
there is a  change  in  reagents,  a  method  blank  should  be processed as a
safeguard against chronic laboratory contamination.   The blank samples should
be carried through all stages of the sample preparation and measurement.

     8.2  Standard  quality  assurance  practices  should  be  used  with this
method.  Fortified samples  should  be  carried  through  all stages of sample
preparation  and  measurement;  they  should   be  analyzed  to  validate  the
sensitivity and accuracy of the analysis.    If the fortified waste samples do
not indicate sufficient sensitivity to detect less  than or equal to 1 ug/g of
sample, then the sensitivity of the instrument should be increased.


9.0  METHOD PERFORMANCE

     9.1  No data provided.
                                  3810 - 3
                                                         Revision      0
                                                         Date  September 1986

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10.0  REFERENCES

1.  Hachenberg, H. and  A.  Schmidt,  Gas  Chromatographic Headspace Analysis,
Philadelphia:  Hayden &.Sons Inc., 1979.

2.  Frlant, S.L. and I.H.  Suffet,  "Interactive  Effects of Temperature, Salt
Concentration and  pH  on  Headspace  Analysis  for  Isolating  Volatile Trace
Organlcs 1n Aqueous Environmental Samples," Anal. Chem. 51, 2167-2172, 1979.
                                   3810 - 4
                                                          Revision       0
                                                          Date  September 1986

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     METHOD 3810

  HEAOSPACe METHOD
  C
    7. 1
        Set GC
      operating
      conoitIons
    7.2
   Prepare sample
    7.3
         Analyze
        Dy direct
        Injection
        into a  GC
7

3.5
01
II
C
Determine
if sample
required
lutlon or
let Mono 1 ic
xtractlon
  I     Stop      J
3810 - 5
                          Revision       0
                          Date  September  1986

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                                 METHOD 3820

          HEXADECANE EXTRACTION AND SCREENING OF PURGEABLE ORGANICS
1.0  SCOPE AND APPLICATION

     1.1  This method is a screening  procedure for use with purge-and-trap GC
or GC/MS.  The results of this  analysis are purely qualitative and should not
be used as an alternative to more detailed and accurate quantitation methods.


2.0  SUMMARY OF METHOD

     2.1  An aliquot of sample is  extracted with hexadecane and then analyzed
by GC/FID.  The  results  of  this  analysis  will indicate whether the sample
requires dilution or methanolic extraction prior to purge-and-trap GC or GC/MS
analysis.


3.0  INTERFERENCES

     3.1  Method interferences  may  be  caused  by  contaminants in solvents,
reagents, and glassware.  All  these  materials must be routinely demonstrated
to be free from  contaminants  by  running  laboratory reagent blanks.  Matrix
interferences may be  caused  by  contaminants  that  are coextracted from the
sample.  The extent of matrix interferences will vary considerably from sample
to sample depending upon the nature and diversity of the water being sampled.

     3.2  The flame   ionization  detector  varies  considerably in sensitivity
when comparing aromatics and  halogenated  methanes and ethanes.  Halomethanes
are  approximately  20x   less   sensitive   than  aromatics  and  haloethanes
approximately  lOx  less    sensitive.     Low-molecular-weight,  water-soluble
solvents  (e.g., alcohols and  ketones)  will  not  extract  from the water, and
therefore will not be detected by GC/FID.


4.0  APPARATUS AND MATERIALS

     4.1  Balance;  Analytical, capable of accurately weighing 0.0001 gm.

     4.2  Gas  Chromatograph;    An   analytical   system   complete  with  gas
chromatograph suitable for  on-column   injection  and all required accessories
including  syringes,  analytical  columns,  gases,  detector,  and strip-chart
recorder  (or equivalent).   A  data  system  is recommended for measuring peak
heights and/or peak areas.

          4.2.1  Detector:    Flame  ionization  (FID).

          4.2.2  GC   column:    3-m  x  2-mm   I.D.  glass   column  packed with
     10%  OV-101  on  100/120  mesh  Chromosorb  W-HP   (or   equivalent).   The
     column temperature  should be   programmed  from  80*C to 280'C at 16'C/min
     and  held at 280*C  for  10 min.
                                   3820 - 1
                                                          Revision       0
                                                          Date   September  1986

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     4.3  Centrifuge;   Capable of accommodating  50-mL glass  tubes.

     4.4  Vials and caps;   2-mL for GC autosampler.

     4.5  Volumetric flasks;     10-  and  50-mL   with  ground-glass  stopper  or
Tef1on-11ned screw-cap.

     4.6  Centrifuge tubes;  50-mL  with  ground-glass stopper or Teflon-Hned
screw-cap.

     4.7  Pasteur plpets;   Disposable.

     4.8  Bottles;  Teflon-sealed screw-cap.


5.0  REAGENTS

     5.1  Hexadecane and methanol;  Pesticide quality or equivalent.

     5.2  Reagent water;   Reagent  water  1s  defined  as  water  1n which an
Interference Is not observed at  the  method detection limit of each parameter
of  Interest.

     5.3  Stock standard solutions  (1.0.0 ug/uL):  Stock standard solutions can
be  purchased as certifiedsolutions  or  can  be  prepared from pure standard
materials.

          5.3.1   Prepare stock standard solutions by accurately weighing about
     0.0100 grams of pure material.    Dissolve  the material 1n methanol 1n a
     10-mL volumetric  flask and dilute  to  volume (larger volumes may be used
     at  the convenience of the analyst).    If compound purity 1s certified at
     96%  or greater, the weight   can  be  used without correction to calculate
     the  concentration of the  stock  standard.   Commercially available stock
     standards may be  used 1f they  are certified by the manufacturer.

          5.3.2   Transfer  the  stock  standard  solutions  Into Teflon-sealed
     screw-cap bottles.  Store at 4*C and protect from light.  These standards
     should be checked frequently for signs of degradation or evaporation.

     5.4  Standard mixture #1:    Standard  mixture  #1 should contain benzene,
toluene,  ethyl benzene, and xylene.  Prepare a stock solution containing these
compounds as described in Paragraph 5.3  and  then prepare a working standard
(through  dilution) 1n which the concentration of each compound 1n the standard
1s  100  ng/uL 1n methanol.

     5.5  Standard mixture #2:    Standard  mixture  #2 should contain n-nonane
and n-dodecane.    Prepare  a  stock  solution  containing  these compounds as
described In Paragraph 5.3.  Dilute the  stock standard with methanol so that
the concentration of each compound  1s 100 ng/uL.
                                   3820 - 2
                                                         Revision      0
                                                         Date  September 1986

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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 preparation;

          7.1.1  Water;

               7.1.1.1  Allow the contents of the 40-mL sample vial to come to
          room temperature.  Quickly transfer  the  contents of the 40-mL vial
          to a 50-mL volumetric flask.   Immediately add 2.0 mL of hexadecane,
          cap the flask, and shake  the  contents  vigorously  for 1 min.  Let
          phases separate.  Open the flask and add sufficient reagent water to
          bring the hexadecane layer into the neck of the flask.

               7.1.1.2  Transfer approximately 1 mL of the hexadecane layer to
          a 2.0-mL GC vial.    If  an  emulsion  is  present after shaking the
          sample, break it by:

                    1.  pulling the emulsion  through  a  small  plug of Pyrex
                        glass wool packed in a pi pet, or

                    2.  transferring the  emulsion  to  a  centrifuge tube and
                        centrifuging for several min.

          7.1.2  Standards;

                7.1.2.1  Add  200 uL of  the  working standard mixtures #1  and #2
          to   separate  40-mL  portions   of   reagent   water.     Follow  the
          instructions  in  Sections  7.1.1.1  and  7.1.1.2  with the immediate
          addition of  2.0  mL of hexadecane.

          7.1.3  Sediment/Soil;

                7.1.3.1  Add  approximately 10 g of sample  (wet weight) to 40 mL
          of  reagent   water  in  a  50-mL  centrifuge  tube.    Cap  and shake
          vigorously for  1  min.    Centrifuge   the  sample  briefly.  Quickly
          transfer the  supernatant water to a 50-mL volumetric  flask.

                7.1.3.2  Follow the instructions  given  in Sections 7.1.1.1 and
          7.1.1.2, starting  with the addition of 2.0 mL of  hexadecane.

      7.2 Analysis;

          7.2.1  Calibration:

                7.2.1.1  External standard  calibration:     The  GC/FID must be
          calibrated each  12-hour shiftforhalf of full-scale response when
          injecting  1-5  uL  of  each  extracted standard  mixture  #1  and #2
           (Paragraphs  5.4  and 5.5).
                                   3820 - 3
                                                          Revision       0
                                                          Date   September  1986

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     7.2.2  6C/FID  analysis:    Inject  the  same  volume  of hexadecane
extract for the sample  under  Investigation  as  was used to perform the
external standard calibration.  The  GC conditions used for the standards
analysis must also be the same as those used to analyze the samples.

     7.2.3  Interpretation of the  GC/FID  chromatograms:    There are two
options for interpretation of the GC/FID results.

          7.2.3.1  Option  A;    The  standard  mixture  #1  is  used  to
     calculate an  approximate  concentration  of  the  aromatics  in the
     sample.  Use this information  to  determine the proper dilution for
     purge-and-trap if the  sample  is  a  water.     If  the  sample  is a
     sediment/soil, use this information  to determine which GC/MS purge-
     and-trap method (low- or high-level) should  be used.   If aromatics
     are absent from the sample  or  obscured by higher concentrations of
     other purgeables, use Option B.

          7.2.3.2  Option B;  The response of standard mixture #2 is  used
     to  determine  which  purge-and-trap   method  should  be  used   for
     analyzing a sample.  All purgeables of interest have retention times
     less  than  the  n-dodecane  retention  time.    A  dilution  factor
     (Paragraph 7.2.4.1.3) may be calculated  for water samples, and  an X
     factor  (Paragraph 7.2.4.2.3) for soil/sediment samples, to determine
     whether the low-  or  high-level  purge-and-trap procedure should be
     used.

     7.2.4  Analytical decision point;

          7.2.4.1  Water samples;  Compare  the hexadecane sample extract
     chromatograms against an extracted  standard chromatogram.

               7.2.4.1.1   If no peaks  are  noted,  analyze  a  5-mL water
          sample by  the purge-and-trap method.

               7.2.4.1.2   If peaks are   present  prior  to the  n-dodecane
          peak and   aromatics  are   distinguishable,  follow  Option  A
           (Paragraph 7.2.3.1).

               7.2.4.1.3   If peaks are   present  prior  to the  n-dodecane
          but  the  aromatics   are   absent or   indistinguishable,  Option B
          should be  used as  follows:    If all  peaks  (prior to n-dodecane)
          are  <3%  of the n-nonane,   analyze  5 ml of water  sample by  the
          purge-and-trap method.   If  any   peak   is  >3%  of  the n-nonane,
          measure  the area of the major peak and calculate  the necessary
          dilution factor  as follows:

            dilution  factor = 50  x area of major peak  in sample
                                       peak  area of n-nonane

          The  water sample should be  diluted using  the calculated factor
          just prior to purge-and-trap GC or  GC/MS analysis.
                              3820 -  4
                                                     Revision      0
                                                     Date  September  1986

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               7.2.4.2   Soil/sediment  samples:   Compare the hexadecane sample
          extract  chromatograms  against  an  extracted  standard chromatogram.

                    7.2.4.2.1   If no peaks  are  noted,  analyze a  5-g  sample by
               the low-level purge-and-trap procedure.

                    7.2.4.2.2   If peaks  are  present  prior  to the n-dodecane
               and aromatics are  distinguishable,  follow  Option A  using the
               concentration information given  in Table 1 to determine whether
               to  analyze the  sample   by a  low- or  high-level purge-and-trap
               technique.

                    7.2.4.2.3   If peaks  are  present  prior  to n-dodecane but
               aromatics  are   absent  or  indistinguishable,  use  Option  B.
               Calculate an X  factor  for  the  sample  using   the  following
               equation:

                      X factor = area  of major  peak in sample
                                      area  of n-nonane

               Use the information provided  in  Table  1 to determine how the
               sample should be handled  for GC/MS analysis.

                    7.2.4.2.4   If  a   high-level    method   is  indicated,  the
               information provided in Table 2  can  be  used  to  determine the
               volume of methanol extract to add  to  5 ml of reagent  water for
               analysis  (see Methods  5030  and  8240  for methanol1c extraction
               procedure).


8.0  QUALITY CONTROL

     8.1  It is recommended that a reagent blank  be analyzed by  this  screening
procedure to ensure that no  laboratory  contamination  exists.   A blank  should
be performed for each set of samples undergoing extraction  and screening.


9.0  METHOD PERFORMANCE

     9.1  No data available.
10.0  REFERENCES

1.  U.S. EPA  Contract  Laboratory  Program,  Statement  of  Work  for Organic
Analysis, July 1985, Revision.
                                  3820 - 5

                                                         Revision      0
                                                         Date  September 1986

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TABLE 1.  DETERMINATION OF GC/MS PURGE-AND-TRAP METHOD

                             Approximate
   X Factor              Concentration.Range a                Analyze by

    0-1.0                  0-1,000 ug/kg                   Low-level method
    >1.0                   >1,000 ug/kg                    High-level method


      a This concentration range 1s based upon the response of aromatlcs to
GC/FID.  The concentration for halomethanes 1s 20x higher, and haloethanes
lOx higher, when comparing GC/FID responses.
TABLE 2.  QUANTITY OF METHANOL EXTRACT REQUIRED FOR ANALYSIS OF HIGH-LEVEL
      SOIL/SEDIMENTS

                             Approximate                      Volume of
   X Factor              Concentration Range a            Methanol Extract &

   0.25-5.0                  500-10,000 ug/kg                  100 ul
   0.5-10.0                1,000-20,000 ug/kg                   50 ul
   2.5-50.0                5,000-100,000 ug/kg                  10 ul
   12.5-250              25,000-500,000 ug/kg                 100 uL of
                                                            1/50 dilution  c


      a  Actual  concentration ranges  could  be   10   to  20  times higher than this
 1f the compounds  are  halogenated and the estimates are from GC/FID.

      D  The  volume of methanol added to  5 mL of water  being purged should  be
 100  uL.   Therefore 1f the  amount of  methanol extract  required 1s  less  than  100
 uL,  additional  methanol   should  be  added to   maintain  the constant  100-uL
 volume.

      c  Dilute  an aliquot  of  the methanol extract   and then take  100  uL  for
 analysis.
                                   3820 - 6
                                                          Revision      0
                                                          Date  September 1986

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                     METHOD 3B20

HEXAOECANE EXTRACTION ANO SCREENING OF PURGEABLE ORGANICS

7. 1



Prepare sample

7.3.1



Calibrate
GC/FIO each
12-hour shift

7.2.2



Perform
GC/FIO analysis
                      o
              3820 -  7
                                      Revision       0
                                      Date   September 1986

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                                       METHOD  3820

                HEXADECANE  EXTRACTION  AND  SCREENING OF PURGEABLE ORGANICS
                                       (Cont Inued)
7 .2.4
Compare chromatograms
of hexadecane sample
extract and extracted
      standard
                                                    7.2.4
                          Compare chromatograms
                          of hexadecane sample
                          extract ana extracted
                             1   standard
     Are  aromatic
   distinguishable?
                             7.2.4.2
                              Use low-level
                              purge-and-trap
                                procedure
                          7.2.4
    Use standard
mixture *1:  determine
purge-and-trap method
     to be used
    ard  mixture  #2
     to  determine
    purge—and-trap
     method  to use
                                                                                7.2.4.1
                                                              Use
                                                        purge-and-trap
                                                            method
   Use standard
   mixture #1 to
     determine
  purge-and-trap
method to be used
                              ard  mixture  »2
                               to  determine
                             ipurge-and-trap
                               method  to use
                                    3820 -  8
                                                               Revision        0
                                                               Date  September 1986

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                                  APPENDIX

                             COMPANY REFERENCES


The  following  listing  of frequently-used  addresses  Is  provided  for  the
convenience of users of this manual.   No endorsement  is intended or implied.


Ace Glass Company
1342 N.W. Boulevard
P.O. Box 688
Vlneland, NJ  08360
(609) 692-3333

Aldrich Chemical Company
Department T
P.O. Box 355
Milwaukee, WI  53201

Alpha Products
5570 - T W. 70th Place
Chicago, IL  60638
(312) 586-9810

Barneby and Cheney Company
E. 8th Avenue and N. Cassldy Street
P.O. Box 2526
Columbus, OH  43219
(614) 258-9501

Bio  - Rad Laboratories
2200 Wright Avenue
Richmond, CA  94804
(415) 234-4130

Burdick & Jackson Lab Inc.
1953 S. Harvey  Street
Muskegon, MO  49442

Calgon Corporation
P.O. Box  717
Pittsburgh, PA   15230
(412) 777-8000

Conostan  Division
Conoco Speciality Products,  Inc.
P.O. Box  1267
Ponca City, OK   74601
(405) 767-3456
                                 COMPANIES - 1
                                                          Revision
                                                          Date   September  1986

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Corning Glass Works
Houghton Park
Corning, NY  14830
(315) 974-9000

Dohrmann, Division of Xertex Corporation
3240 - T Scott Boulevard
Santa Clara, CA  95050
(408) 727-6000
(800) 538-7708

E. M. Laboratories, Inc.
500 Executive Boulevard
Elmsford, NY  10523

Fisher Scientific Co.
203 Fisher Building
Pittsburgh, PA  15219
(412) 562-8300

General  Electric Corporation
3135 Easton Turnpike
Fairfield, CT  06431
(203) 373-2211

Graham Manufactory Co., Inc.
20 Florence Avenue
Batavia, NY  14020
(716) 343-2216

Hamilton Industries
1316 18th Street
Two Rivers, WI  54241
(414) 793-1121

ICN Life Sciences Group
3300 Hyland Avenue
Costa Mesa, CA  92626

Johns -  Manvllle Corporation
P.O. Box 5108
Denver,  CO  80217

Kontes Glass Company
8000 Spruce Street
Vineland, NJ  08360

MilUpore Corporation
80 Ashby Road
Bedford, MA  01730
(617) 275-9200
(800) 225-1380
                                COMPANIES - 2
                                                         Revision
                                                         Date  September 1986

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National Bureau of Standards
U.S. Department of Commerce
Washington, DC  20234
(202) 921-1000

Pierce Chemical Company
Box 117
Rockford,  IL  61105
(815) 968-0747

Scientific Glass and Instrument,  Inc.
7246 - T Wynnwood
P.O. Box 6
Houston, TX  77001
(713) 868-1481

Scientific Products Company
1430 Waukegon Road
McGaw Park, IL  60085
(312) 689-8410

Spex Industries
3880 - T and Park Avenue
Edison, NJ  08820

Waters Associates
34  - T Maple Street
Mil ford, MA  01757
(617) 478-2000
(800) 252-4752

Whatman  Laboratory  Products,  Inc.
Clifton, NJ  07015
(201) 773-5800
                                 COMPANIES - 3
                                                          Revision
                                                          Date  September 1986

                                       .S. GOVERNMENT PRINTING OFFICE :  1987 O - 169-932

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