United States
             Environmental Protection
             Agency
Office of Solid Waste
and Emergency Response
Washington, DC 20460
November 1986
SW-846
Third Edition
             Solid Waste
&EPA      Test Methods
             for Evaluating Solid Waste
             Volume 1C: Laboratory Manual
             Physical/Chemical Methods
                                                  *

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

      The methods in this table are listed  sequentially by
      number.
      This table should not be used as a Table of Contents for
      SW-846. Refer to the Table of Contents found in Final
      Update II (dated September 1994) for the order in which
      the methods appear in SW-846.

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                           TABLE  OF. CONTENTS
                                     VOLUME ONE

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

CHAPTER ONE -- QUALITY CONTROL

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

CHAPTER TWO --CHOOSING THE CORRECT PROCEDURE

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

CHAPTER THREE -- METALLIC ANALYTES

      3.1   Sampling Considerations
      3.2   Sample Preparation Methods

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

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      Method 3020A:
      Method 3040:
      Method 3050A:
      Method 3051:
           Acid Digestion of Aqueous Samples and Extracts for Total
           Metals   for   Analyses  by,  Graphite-Furnace   Atomic
           Absorption (GFAA) Spectroscopy    '    .' ,,'.%''
           Dissolution Procedure for Oils, Greases, 'ojr|Waxes
           Acid Digestion .of Sediments, SI udges,-,ancl ffpils
           Microwave Assisted'Acid Digestion of-.Se.d\menjts,. Sludges,
           Soils, and Oils ,                      ••' f:^*ซv.-
3.3   Methods for Determination of Meta'ls
      Method
      Method
      Method
      Method
      Method
      Method
      Method
      Method
      Method
      Method
      Method
      Method
      Method
      Method
      Method
      Method
      Method
      Method
      •Method
      'Method
      Method
      Method
      Method
      Method
      Method
      Method
      Method
      Method
      Method
      Method
      Method
      Method
      Method
      Method
      Method
6010A:
6020:
7000A:
7020:
7040:
7041:
7060A:
7061A:
7062:
7080A:
7081:
7090:
7091:
7130:
7131A:
7140:
7190:
7191:
7195:
7196A:
7197:
7198:
7200:
7201:
7210:
7211:
7380:
7381:
7420:
7421:
7430:
7450:
7460:
7461:
7470A:
7471A:
      Method 7480:
      Method 7481:
      Method 7520:
      Method 7550:
      Method 7610:
      Method 7740:
                                                                       'iff.
Inductively Coupled Plasma-Atomic Emission Spectroscopy
Inductively Coupled Plasma - Mass Speetfometry
Atomic Absorption Methods         . >'''t;    '-..
Aluminum (AA, Direct Aspiration)
Antimony (AA, Direct Aspiration)    •,   r-  c*.    .,_  -^  ,
Antimony (AA, Furnace Technique)
Arsenic (AA, Furnace Technique)
Arsenic (AA, Gaseous Hydride)
Antimony and Arsenic (AA, Borohydride Reduction)
Barium (AA, Direct Aspiration)
Barium (AA, Furnace Technique)
Beryllium (AA, Direct Aspiration)
Beryllium (AA, Furnace Technique)     •--       	
Cadmium (AA, Direct Aspiration)    .
Cadmium (AA, Furnace Technique)    !.
Calcium (AA, Direct Aspiration,) ..',,.. ^
Chromium (AA, Direct Aspiration)  4^
Chromium (AA, Furnace Technique)       .      .-..• :,   ,
Chromium, Hexavalent (Coprecipitation)     v-,V*   i
Chromium, Hexavalent (Colorimetric)    .   ..-;'',
Chromium, Hexavalent (Delation/Extraction)  ..V,
Chromium, Hexavalent (Differential Pulse Polar9,gf.aphy)
Cobalt (AA, Direct Aspiration)
Cobalt (AA, Furnace Technique)^-           • •   -•  -•  '
Copper (AA, Direct Aspiration)
Copper (AA, Furnace Technique)
Iron (AA, Direct Aspiration)
Iron (AA, Furnace Technique)
Lead (AA, Direct Aspiration)
Lead (AA, Furnace Technique)
Lithium (AA, Direct Aspiration)
Magnesium (AA, Direct Aspiration)
Manganese (AA, Direct Aspiration)
Manganese (AA, Furnace Technique)
Mercury in Liquid Waste  (Manual  Cold-Vapor Technique)
Mercury in Solid or Semisolid Waste (Manual Cold-Vapor
Technique)
Molybdenum (AA, Direct Aspiration)
Molybdenum (AA, Furnace Technique)
Nickel (AA, Direct Aspiration)
Osmium (AA, Direct Aspiration)
Potassium (AA, Direct Aspiration)
Selenium (AA, Furnace Technique)
                              CONTENTS  -  2
                                                        Revision  2
                                                   September  1994

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            Hethod 7741A:     Selenium  (AA, Gasebus Hydride)
            Method 7742:      Seleniuitt  (AA, Borohydride Reduction)
            Method 7760A:     $:ilvef"(AA, Direct Aspiration)
            Hethod 7761:      Silver  (AA, Furnace Technique)
            Method 7770^     Sodium  (AA,rDirect Aspiration)
            Method 7780:      Strontium  (AA,, Direct Aspiration)
            Method 7840:      Thallium  (AA, Direct Aspiration)
            Method 7841:      Thallium  (AA, Furnace Technique)
            Method 7870:      Tin (AA, Direct Aspiration)
            Method 7910:      Vanadium  (AA, Direct Aspiration)
            Method 7911:      Vanadium  (AA, Furnace Technique)
            Method!7950:      Zinc (AA, Direct Aspiration)
            Method 7951:  ,    Zinc (AA, Furnace Technique)
APPENDIX -- COMPANY REFERENCES
        NOTE:  A  suffix  of "A" in the method  number indicates revisipn^onje
        (the method  has  been  revised once).  A suffix  of  "B"  in the method
        number indicates revision two (the method  has been revised tw1ceL;vIn
        order to  properly document the method  used for analysis, the effltlte
        method number Including the suffix letter designation  (e.g., A/pj
        must be Identified by  the analyst.   A  method reference found wVj
        the  RCRA  regulations   and the text  of  SW-846 methods  and  chapter
        refers, to the latest promulgated revision of the method, even thoii
       :;i'the method number does not include the appropriate letter suffix..*
                                    CONTENTS - 3                          Revision 2
                                                                      September 1994

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                                     VOLUME ONE

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

CHAPTER ONE. REPRINTED  --  QUALITY  CONTROL
                                                                         .. '•*
      !..(ฃ' Introduction                                           .;.  ฐ     Vl
      2.0  " QA Project  Plan                                        it       .
      3.0...., Field Operations                       '     ,
      4.0% Laboratory  Operations                                 *?r  v    v
      5.0   Definitions                           /r                  r     ''.'t
      6".0  .'References
          -"*'•' -.                                           ••'.
CHAPTER FOUR..- ORGANIC ANALYTES                     :    :

      4.1   Sampling  Considerations                                r"
      4.2   Sample  Preparation Methods
                                                                          t
           .,.,4.2.1       Extractions  and Preparations                     '-
        •'.•  •.-" 'r-                     •                                      '3M
            Method  3500A:      Organic Extraction and Sample Preparation
   ?-      .-Method  3510B:      Separatory Funnel  Liquid-Liquid Extraction
            'Method  3520B:      Continuous Liquid-Liquid Extraction
        	Method  3540B:      Soxhlet Extraction
        "    Mejthod  3541:       Automated Soxtilet  Extraction                5
            Method  3550A:      Ultrasonic Extraction
            Method  3580A:      Waste  Dilution                              ;]
            Method  5030A:      Purge-and-Trap                     •'.;•  '';   's
            Method  5040A:      Analysis of  Sorbent  Cartridges from1--Volatile  Organic
           }   .                Sampling  Train   (VOST):     Gas -Chromatogfaphy/Mass
                               Spectrometry Technique
            Method  5041:       Protocol  for  Analysis  of  Sorbent  Cartridges  from
        _r   	^                Volatile  Organic  Sampling  Train
        !r   ' '                 Capillary Column Technique
            Method  5100:       Determination of the Volatile Organic Concentration of
                               Waste  Samples                      .     ''   ,
            .Method  5110:       Determination of Organic Phase Vapor Pressure in Waste
            "'                   Samples

            4.2.2       Cleanup

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

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      Method 3611A:
      Method
      Method
      Method
      Method
      Method
      Method
       3620A:
       3630B:
       3640A:
       3650A:
       3660A:
       3665:
Alumina    Column
Petroleum Wastes "
Florisil Column Cleanup
Silica Gel Cleanup
Gel-Permeation Cleanup
Acid-Base Partition Cleanup
Sulfur Cleanup
Sulfuric Acid/Permanganate Cleanup
                                       Cleanup    and    Separation    of
4.3   Determination of Organic Analytes
      4.3.1
            Gas Chromatographic Methods
      Method 8000A:
      Method 8010B:
      Method 8011:

      Method 8015A:
      Method 8020A:
      Method 8021A:
Method
Method
Method
Method
Method
Method
             8030A:
             8031:
             8032:
             8040A:
             8060:
             8061:
      Method 8070:
      Method 8080A:

      Method 8081:

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

     •Method 8140:
      Method 8141A:
    „• • r
      Method 8150B:
      Method. 8151 :
                                                                      by
Gas Chromatography                         •  '  - --••
Halogenated Volatile Organics by Gas Chromatography
1,2-Dibromoethane  and  l,2-Dibromo-3-chloropropaTie
Microextraction and Gas Chromatography     .1
Nonhalogenated Volatile Organics by Gas Chr.bitiatography
Aromatic Volatile Organics by Gas ChromatogHphyr
Halogenated  Volatiles  by  Gas  Chromatography  Using
Photoionization and Electrolytic Conductivity Detectors
in Series: Capillary Column Technique
Acrolein and Acrylonitrile by Gas Chromatography
Acrylonitrile by Gas Chromatography
Acrylamide by Gas Chromatography                  '
Phenols by Gas Chromatography
Phthalate Esters
Phthalate Esters by  Capillary  Gas ChromatogVaphy with
Electron Capture Detection (GC/ECD)
Nitrosamines by Gas Chromatography         ;;
Organochlorine Pesticides and PolychlorinateU Biphenyls
by Gas Chromatography                      .
Organochlorine Pesticides and  PCBs  as  Aropl'ors by Gas
Chromatography:  Capillary Column Techniqu"e\!
Nitroaromatics and Cyclic Ketones         ;:1,
Polynuclear Aromatic Hydrocarbons       . ',','*
Haloethers by Gas Chromatography         !  ^
Chlorinated Hydrocarbons by Gas Chromatography
Chlorinated   Hydrocarbons  by  Gas   Chromatography:
Capillary Column Technique               . =..<
Organophosphorus Pesticides
Organophosphorus  Compounds  by   Gas   Chromatography:
Capillary Column Technique
Chlorinated Herbicides by Gas  Chromatography
Chlorinated  Herbicides  by  GC  Using  Methylation  or
Pentafluorobenzylation Derivatization:  Capillary Column
Technique
                              CONTENTS -  5
                                                              Revision 2
                                                          September 1994

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4.3.2       Gas Chromatographic/Mass, Spectroscopic Methods    .,.

Method 824QB:     Volatile Organic Compounds by  Gas  Chromatography/Mass
                  Spectrometry (GC/MS)
Method 8250A:     SemlvolatHe     Organic    Compounds    by    Gas
                  Chromatography/Mass Spectrometry (GC/MS)^    <
Method 8260A:     Volatile Organic Compounds by  Gas  Chromatography/Mass
                  Spectrometry.(GC/MS): Capillary Column Technique
Method 8270B:     Semivolatile     Organic    Compounds    by    Gas
                  Chromatography/Mass  Spectrometry  (G,C/MS):   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
                        PCDDs/PCOFs
Method 8290:      Polychlorinated    Dibenzodioxins    (PCDDs)     and
                  Polychlorinated Dibenzofurans (PCDFs) by High'-Resolution
  5f  .,             Gas  Chromatography/High-Resolutipn Mass  Spectrometry
,!;               (HRGC/HRMS)               ;      ''.,,"       '"^''   i
     ..Appendix A:       Procedures   for   the   Collection,   Handling,
   V, .                  Analysis, and  Reporting ,of Wipe Tests  Performed
   -.ฃ,'                  within the Laboratory                   '" ^   i
   ••'•>-                                                 .            , r.   *
4.3.3       High Performance Liquid Chromatographic Methods      . "!'   |

Method 8310:      Polynuclear Aromatic Hydrocarbons               •* •  \
Method 8315:      Determination of Carbonyl  Compounds by High Performance
 	            Liquid Chromatography (HPLC)
      Appendix A:       Recrystallization of  2,4-Dinitrophenylhydrazine
                        (DNPH)
Method 8316:      Acrylamide,  Acrylonitrile   and   Acrolein   by   High
                  Performance Liquid Chromatography  (HPLC)
Method 8318:      N-Methylcarbamates   by   High   Performance   Liquid
                  Chromatography (HPLC)
Method 8321:      Solvent  Extractable  Non-Volatile   Compounds  by  High
                  Performance   Liquid   Chromatography/Thermospray/Mass
                  Spectrometry (HPLC/TSP/MS) or Ultraviolet  (UV) Detection
Method 8330:      Nitroaromatics and Nitramines by High Performance Liquid
                  Chromatography (HPLC)
Method 8331:      Tetrazene  by  Reverse  Phase  High   Performance  Liquid
                  Chromatography (HPLC)


4.3.4       Fourier Transform Infrared Methods

Method 8410:      Gas Chromatography/Fourier Transform Infrared (GC/FT-IR)
                  Spectrometry  for  Semivolatile  Organics:    Capillary
                  Column
                        CONTENTS - 6                          Revision 2
                                                          September 1994

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      4.4   Miscellaneous Screening Methods                              • •

            Method 3810:      Headspace   "                             -•
            Method 3820:      Hexadecane  Extraction   and  Screening  of   Purgeable
                    v          Organics       "
            Method 4010:   •"'  Screening for  Pentachlorophenol by  Immunoassay
            Method 8275:      Thermal  Chromatography/Mass Spectrometry  (TC/MS)  for
                "•"•            Screening'Semivolatile Organic Compounds
                   J ..              •-.                                     "*<>!•
APPENDIX -- COMPANY REFERENCES
                A suffix'of "A*Mn the method  number indicates revision one
        (the method  has been revised once).  A  suffix  of "B"  in the method
       'number  indicates revision two (the method has been revised twice). In
       "'order to properly  document the method  used for analysis, the entire
        method  number Including the suffix letter designation  (e.g., A or B)
        must be Identified by the analyst.   A  method reference found within
        the  RCRA regulations  and the text  of SW-846  methods  and  chapters
        refers  to the latest  promulgated revision of the method, even though
        the method number  does not include the appropriate letter suffix?
                                                                       ••'
    Dr.,;).
                                    CONTENTS - 7                          Revision 2
                                                                      September 1994

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                                     VOLUME ONE

                                      SECTION  C
DISCLAIMER
ABSTRACT
TABLE OF CONTENTS
METHOD INDEX AND CONVERSION TABLE
PREFACE ,-.

CHAPTER ONE. REPRINTED -- QUALITY CONTROL

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

CHAPTER FIVE -- MISCELLANEOUS TEST METHODS
            Method
            Method
            Method
            Method
            Method
            Method
            Method
5050:
9010A:
9012:
9013:
9020B:
9021:
9022:
            Method 9030A:
            Method 9031:
            Method 9035:
            Method 9036:

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

            Method 9066:

            Method 9067:
            Method 9070:

            Method 9071A:

            Method 9075:

            Method 9076:
Bomb Preparation Method for Solid Waste
Total and Amenable Cyanide (Colorimetric, Manual)
Total and Amenable Cyanide  (Colorimetric, Automated UV)
Cyanide Extraction Procedure for Solids and Oils
Total Organic Hal ides (TOX)
Purgeable Organic Hal ides  (POX)
Total  Organic  Hal ides   (TOX)   by  Neutron  Activation
Analysis
Acid-Soluble and Acid-Insoluble Sulfides
Extractable Sulfides
Sulfate (Colorimetric, Automated, Chloranilate)
Sulfate (Colorimetric, Automated, Methylthymol  Blue, AA
ID
Sulfate (Turbidimetric)
Determination of Inorganic  Anions by Ion Chromatography
Total Organic Carbon                       .    -  r;.
Phenolics   (Spectrophotometric,  Manual   4--AAP'-':with
Distillation)                               ,  T
Phenolics    (Colorimetric,   Automated   4-^AP   with
Distillation)                              rr
Phenolics (Spectrophotometric,  MBTH with Distillation)
Total Recoverable Oil & Grease  (Gravimetric, Separatory
Funnel Extraction)
Oil and Grease Extraction Method for Sludge  and  Sediment
Samples                                     .  ^
Test Method for Total Chlorine in New and Used Petroleum
Products  by X-Ray Fluorescence  Spectrometry (XRF)
Test Method for Total Chlorine in New and Used Petroleum
Products  by Oxidative Combustion and Microcoulometry
                                     CONTENTS  -  8
                                                       Revision 2
                                                   September 1994

-------
            Method 9077:

                  Method A:
                  Method B:

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

CHAPTER SIX -- PROPERTIES

            Method 1312:
            Method 1320:
            Method 1330A:
            Method 9040A:
            Method 9041A:
            Method 9045B:
      .  ...  Method 9050:
     . " ''  Method 9080:
        ,'    Method 9081:
            Method 9090A:
            Method 9095:
            Method 9096:
                  Appendix A:
            Method 9100:

            Method 9310:
   ... P7    Method 9315:
                               Test  Methods  for  Total  Chlorine  in  New  and  Used
                               Petroleum  Products  (Field  Test  Kit  Methods)
                                    Fixed  End  Point  Test Kit  Method
                                    Reverse Titration Quantitative End Point Test Kit
                                    Method
                               Direct Titration Quantitative End Point Test Kit Method
                               Total Coliform:  Multiple  Tube  Fermentation technique
                               Total Coliform:  Membrane  Filter  Technique
                               Nitrate
                               Chloride (Colorimetric, Automated Ferricyanide AAI)
                               Chloride (Colorimetric, Automated Ferricyanide AAII)
                               Chloride (Titrimetric, Mercuric Nitrate)
                               Chloride (Titrimetric, Silver Nitrate)     -'*...•
                               Radium-228
                               Synthetic  Precipitation  Leaching  Procedure
                               Multiple Extraction  Procedure
                               Extraction Procedure for Oily Wastes
                               pH Electrometric Measurement
                               pH Paper Method
                               Soil  and Waste pH
                               Specific Conductance
                               Cation-Exchange Capacity of Soils (Ammonium Acetate)
                               Cation-Exchange Capacity of Soils (Sodium Acetate)
                               Compatibility Test for Wastes and Membrane Liners
                               Paint Filter Liquids Test
                               Liquid Release Test  (LRT)  Procedure
                                     LRT  Pre-Test
                               Saturated  Hydraulic  Conductivity,  Saturated  Leachate
                               Conductivity, and Intrinsic Permeability
                               Gross Alpha and Gross Beta
                               Alpha-Emitting Radium Isotopes
                              PART II   CHARACTERISTICS

CHAPTER SEVEN -- INTRODUCTION AND REGULATORY DEFINITIONS

      7.1   Ignilability
      712 " Corrosivity
   .   ,7 ..3   Reactivity
     . • * ^ ,„•

    •'•"""-"-    Test Method to Determine Hydrogen Cyanide  Released  from Wastes
     •,  ...   Test Method to Determine Hydrogen Sulfide  Released  from Wastes

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

-------
CHAPTER EIGHT -- METHODS FOR DETERMINING CHARACTERISTICS

      8.1   Ignitability

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

      8.2   Corrosivity

            Method 1110:      Corrosivity Toward Steel

      8.3   Reactivity
      8.4   Toxicity

            Method 1310A:     Extraction  Procedure  (EP)  .Toxicity  Test  Method  and
                              Structural Integrity Test                    ,;'),
            Method 1311:      Toxicity Characteristic Leaching Procedure   ;; r'

APPENDIX -- COMPANY REFERENCES                                             ]'b
        NOTE;   A suffix of "A"  in  the  method  number indicates revision one ..
        (the method  has been revised once).  A suffix  of "B"  in the method
        number  indicates revision two (the method  has been revised twice). In ?,
        order to properly  document the  method  used for analysis, the entire
        method  number  Including  the suffix letter designation  (e.g., A or B)
        must be Identified by the analyst.   A  method reference found within
        the.RCRA regulations  and the  text  of SW-846  methods  and  chapters
        refers  to the  latest  promulgated  revision of  the  method, even though
        the method number  does not  include the appropriate letter suffix.
                                    CONTENTS -  10                          Revision 2
                                                                       September  1994

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

      1.0   Introduction
     ,2.Q>  QA Project Plan
      3Vt)J   Field Operations
      4.0   Laboratory Operations
      5.0   Definitions
      6.0   References
                                 PART III    SAMPLING

CHAPTER NINE -- SAMPLING PLAN

      i9.1   Design and Development
      9.2   Implementation

CHAPTER TEN -- SAMPLING METHODS

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

CHAPTER ELEVEN -- GROUND WATER MONITORING

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


CHAPTER TWELVE -- LAND TREATMENT MONITORING

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

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

-------
SH-846 METHOD STATUS TABLE
      September 1994
METH NO.
THIRD ED
DATED
9/86
0010
0020
0030
1010
1020
J
i :;
i 1110
. i
!
\
1310
"
'
METH NO.
FINAL
UPDATE I
DATED
7/92
** ~
*" ~
*~ —
— —
1020A
~ ~
1310A
1311
"
METH NO.
FINAL
UPDT. II
DATED
9/94
~ **
~ *
~ *
~ **
~ "
~ "

"'
1312
METHOD TITLE
Modified Method 5
Sampling Train
Source Assessment
Sampling System
(SASS)
Volatile Organic
Sampling Train
Pensky-Martens
Closed-Cup Method
for Determining
Ignitability
Setaflash Closed-Cup
Method for
Determining
Ignitability
Corrosivity Toward
Steel
Extraction Procedure
(EP) Toxicity Test
Method and
Structural Integrity
Test
Toxicity
Characteristic
Leaching Procedure
Synthetic
Precipitation
Leaching Procedure
SH-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol.11
Chap 10
Vol II
Chap 10
Vol II
Chap 10
Vol 1C
Chap 8
Sec 8.1
Vol 1C
Chap 8
Sec 8.1
Vol 1C
Chap 8
Sec 8.2
Vol 1C
Chap 8
Sec 8.4
Vol 1C
Chap 8
Sec 8.4
Vol 1C
Chap 6
CURRENT
PROMUL-
GATED
METHOD
0010
Rev 0
9/86
0020
Rev 0
9/86
0030
Rev 0
9/86
1010
Rev 0
9/86
1020A
Rev 1
7/92
1110
Rev 0
9/86
1310A
Rev 1
7/92
1311
Rev 0
7/92
1312
Rev 0
9/94

-------
SU-846 METHOD STATUS TABLE (9/94),  CONTINUED
METH NO.
THIRD ED
DATED
9/86
1320
1330
3005
3010
~ ~*
3020
3040
3050
METH NO.
FINAL
UPDATE I
DATED
7/92
~ *"
1330A
3005A
3010A
_ .1
3020A
~ —
3050A
METH NO.
FINAL
UPDT. II
DATED
9/94
"
"


3015

V V
"
METHOD TITLE
Multiple Extraction
Procedure
Extraction Procedure
for Oily Wastes
Acid Digestion of
Waters for Total
Recoverable or
Dissolved Metals for
Analysis by FLAA or
ICP Spectroscopy
Acid Digestion of
Aqueous Samples and
Extracts for Total
Metals for Analysis
by FLAA or ICP
Spectroscopy
Microwave Assisted
Acid Digestion of
Aqueous Samples and
Extracts
Acid Digestion of
Aqueous Samples and
Extracts for Total
Metals for Analysis
by GFAA Spectroscopy
Dissolution
Procedure for Oils,
Greases, or Waxes
Acid Digestion of
Sediments, Sludges,
and Soils
SH-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol 1C
Chap 6
Vol 1C
Chap 6
Vol IA
Chap 3
Sec 3.2
Vol IA
Chap 3
Sec 3.2
Vol IA
Chap 3
Sec 3.2
Vol IA
Chap 3
Sec 3.2
Vol IA
Chap 3
Sec 3.2
Vol IA
Chap 3
Sec 3.2
CURRENT
PROMUL-
GATED
METHOD
1320
Rev 0
9/86
133QA
Rev 1
7/92
3005A
Rev 1
7/92
3010A
Rev 1
7/92
3015 	
Rev 0
9/94
3020A 	
. :';.}..
Rev 1
7/92
3040..,
Rev 0
9/86
3050A'
Rev 1
7/92

-------
SW-846 HETHOD STATUS TABLE (9/94),  CONTINUED
METH NO.
THIRD ED
DATED
9/86
v'
3500
'. S
,1 r
3510
i
3520
3540
S
3550
3580
3600
HETH NO.
FINAL
UPDATE I
DATED
7/92
~ ~
3500A
3510A
3520A
3540A
~ ~
~ ~
3580A
3600A
NETH NO.
FINAL
UPDT. II
DATED
9/94
3051
~ ~
3510B
3520B
3540B
3541
3550A
~ ~
3600B
NETHOD TITLE
Microwave Assisted
Acid Digestion of
Sediments, Sludges,
Soils, and Oils
Organic Extraction
and Sample
Preparation
Separatory Funnel
Liquid-Liquid
Extraction
Continuous Liquid-
Liquid Extraction
Soxhlet Extraction
Automated Soxhlet
Extraction
Ultrasonic Extrac-
tion
Waste Dilution
Cleanup
SH-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IA
Chap 3
Sec 3.2
Vol IB
Chap 4
Sec
4.2.1
Vol IB
Chap 4
Sec
4.2.1
Vol IB
Chap 4
Sec
4.2.1
Vol IB
Chap 4
Sec
4.2.1
Vol IB
Chap 4
Sec
4.2.1
Vol IB
Chap 4
Sec
4.2.1
Vol IB
Chap 4
Sec
4.2.1
Vol IB
Chap 4
Sec
4.2.2
CURRENT
PROMUL-
GATED
NETHOD
3051
Rev 0
9/94
3500A
Rev 1
7/92
3510B
Rev 2
9/94
3520B
Rev 2
9/94
3540B
Rev 2
9/94
3541
Rev 0
9/94
3550A
Rev 1
9/94
3580A
Rev 1
7/92
3600B
Rev 2
9/94

-------
SU-846 METHOD STATUS TABLE (9/94),  CONTINUED
METH NO.
THIRD ED
DATED
9/86
3610
3611
3620
3630
3640
3650
3660
~ ~
3810
HETH NO.
FINAL
UPDATE I
DATED
7/92
3610A
3611A
3620A
3630A
~ •"
3650A
3660A
~ ~
"
METH NO.
FINAL
UPDT. II
DATED
9/94
"
™ *
"
3630B
3640A
~ ~
— *"
3665
"
METHOD TITLE
Alumina Column
Cleanup
Alumina Column
Cleanup and
Separation of
Petroleum Wastes
Florisil Column
Cleanup
Silica Gel Cleanup
Gel -Permeation
Cleanup
Acid-Base Partition
Cleanup
Sulfur Cleanup
Sulfuric
Acid/Permanganate
Cleanup
Headspace
SW-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IB
Chap 4
Sec
4.2.2
Vol IB
Chap 4
Sec
4.2.2
Vol IB
Chap 4
Sec
4.2.2
Vol IB
Chap 4
Sec
4.2.2
Vol IB
Chap 4
Sec
4.2.2
Vol IB
Chap 4
Sec
4.2.2
Vol IB
Chap 4
Sec
4.2.2
Vol IB
Chap 4
Sec
4.2.2
Vol IB
Chap 4
Sec 4.4
CURRENT
PROMUL-
GATED
METHOD
3610A
Rev 1
7/92
3611A
Rev 1
7/92
3620A ...
Rev 1 ^
7/92
3630B
Rev 2
9/94
3640A
Rev 1
9/94
3650A -
Rev 1
7/92
3660A
Rev 1
7/92
3665
Rev 0
9/94
3810 ,
Rev 0
9/86

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

5030
5040
. i
~ ™
6010
HETH NO.
FINAL
UPDATE I
DATED
7/92
~ *"

5030A


~ ™
6010A
HETH NO.
FINAL
UPDT. II
DATED
9/94
•" ™
4010
(Update
IIA,
dated
8/93)
*~ ~
5040A
5041
5050
"
HETHOD TITLE
Hexadecane
Extraction and
Screening of
Purgeable Organics
Screening for
Pentachlorophenol
by Immunoassay
Purge-and-Trap
Analysis of Sorbent
Cartridges from
Volatile Organic
Sampling Train
(VOST): Gas
Chromatography/Mass
Spectrometry
Technique
Protocol for
Analysis of Sorbent
Cartridges from
Volatile Organic
Sampling Train
(VOST): Wide-bore
Capillary Column
Technique
Bomb Preparation
Method for Solid
Waste
Inductively Coupled
Plasma-Atomic
Emission
Spectroscopy
SW-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IB
Chap 4
Sec 4.4
Vol IB
Chap 4
Sec 4.4
Vol IB
Chap 4
Sec
4.2.1
Vol IB
Chap 4
Sec
4.2.1
Vol IB
Chap 4
Sec
4.2.1
Vol 1C
Chap 5
Vol IA
Chap 3
Sec 3.3
CURRENT
PROMUL-
GATED
HETHOD
3820
Rev 0
9/86
4010
Rev 0
8/93
5030A
Rev 1
7/92
5040A
Rev 1
9/94
5041
Rev 0
9/94
5050
Rev 0
9/94
6010A
Rev 1
7/92

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

-------
SH-846 METHOD STATUS TABLE (9/94), CONTINUED
HETH NO.
THIRD ED
DATED
9/86
j
7090
7091
7130
7131
7140
7190
f
7191
7195
HETH NO.
FINAL
UPDATE I
DATED
7/92
7081
•• ~
~ ~
~ ~
_ *•
•" ~
•~ —
~ ~
™ ~
HETH NO.
FINAL
UPDT. II
DATED
9/94
~ "
. .
™ ~
•• ™
7131A
~ ~
•• ~
~ *
"
METHOD TITLE
Barium (Atomic
Absorption, Furnace
Technique)
Beryllium (Atomic
Absorption, Direct
Aspiration)
Beryllium (Atomic
Absorption, Furnace
Technique)
Cadmium (Atomic
Absorption, Direct
Aspiration)
Cadmium (Atomic
Absorption, Furnace
Technique)
Calcium (Atomic
Absorption, Direct
Aspiration)
Chromium (Atomic
Absorption, Direct
Aspiration)
Chromium (Atomic
Absorption, Furnace
Technique)
Chromium, Hexavalent
(Coprecipitation)
SW-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
CURRENT
PROMUL-
GATED
METHOD
7081
Rev 0
7/92
7090
Rev 0
9/86
7091
Rev 0
9/86
7130
Rev 0
9/86
7131A
Rev 1
9/94
7140
Rev 0
9/86
7190
Rev 0
9/86
7191
Rev 0
9/86
7195
Rev 0
9/86

-------
SW-846 METHOD STATUS TABLE (9/94),  CONTINUED
METH NO.
THIRD ED
DATED
9/86
7196
7197
7198
7200
7201
7210
~ ™
7380
*• ™
METH NO.
FINAL
UPDATE I
DATED
7/92
7196A
V ซ•
™ ""
™ ~
* *
"
7211
~ •"
7381
METH NO.
FINAL
UPDT. II
DATED
9/94
* -
™ ™
* ~
™ **
V —
~ ~
• •*
•" ~
** —
METHOD TITLE
Chromium, Hexavalent
(Colorimetric)
Chromium, Hexavalent
(Chelation/Extrac-
tion)
Chromium, Hexavalent
(Differential Pulse
Polarography)
Cobalt (Atomic
Absorption, Direct
Aspiration)
Cobalt (Atomic
Absorption, Furnace
Technique)
Copper (Atomic
Absorption, Direct
Aspiration)
Copper (Atomic
Absorption, Furnace
Technique)
Iron (Atomic
Absorption, Direct
Aspiration)
Iron (Atomic
Absorption, Furnace
Technique)
SH-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
CURRENT
PROMUL-
GATED
METHOD
7196A
Rev 1
7/92
7197
Rev 0
9/86
7198
Rev 0
9/86
7200
Rev 0
9/86
7201
Rev 0
9/86
7210
Rev 0
9/86
7211
Rev 0
7/92
7380 "
\
Rev 0
9/86
7381
Rev 0
7/92

-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
METH NO.
THIRD ED
DATED
9/86
7420
7421
. "
7450
7460
"
7470
7471
7480
HETH NO.
FINAL
UPDATE I
DATED
7/92
~ ~
~ ••
7430
— —
~ ~
7461
™ ~
• ~
"
METH NO.
FINAL
UPDT. II
DATED
9/94
** ~
*m ~
" .
~ * .
* ~
~ —
7470A
7471A
"
METHOD TITLE
Lead (Atomic
Absorption, Direct
Aspiration)
Lead (Atomic
Absorption, Furnace
Technique)
Lithium (Atomic
Absorption, Direct
Aspiration)
Magnesium (Atomic
Absorption, Direct
Aspiration)
Manganese (Atomic
Absorption, Direct
Aspiration)
Manganese (Atomic
Absorption, Furnace
Technique)
Mercury in Liquid
Waste (Manual Cold-
Vapor Technique)
Mercury in Solid or
Semi sol id Waste
(Manual Cold-Vapor
Technique)
Molybdenum (Atomic
Absorption, Direct
Aspiration)
SW-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
CURRENT
PROMUL-
GATED
METHOD
7420
Rev 0
9/86
7421
Rev 0
9/86
7430
Rev 0
7/92
7450
Rev 0
9/86
7460
Rev 0
9/86
7461
Rev 0
7/92
7470A
Rev 1
9/94
7471A
Rev 1
9/94
7480
Rev 0
9/86

-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
HETH NO.
THIRD ED
DATED
9/86
7481
7520
7550
7610
7740
7741
™ ~
7760
"..
NETH NO.
FINAL
UPDATE I
DATED
7/92
"* ™*
* ~
™ ~
"
• ~
™ ™
"
7760A
7761
HETH NO.
FINAL
UPDT. II
DATED
9/94
~ ~
~ ~
~ ~
"
~ —
7741A
7742
™ •
"
METHOD TITLE
Molybdenum (Atomic
Absorption, Furnace
Technique)
Nickel (Atomic
Absorption, Direct
Aspiration)
Osmium (Atomic
Absorption, Direct
Aspiration)
Potassium (Atomic
Absorption, Direct
Aspiration)
Selenium (Atomic
Absorption, Furnace
Technique)
Selenium (Atomic
Absorption, Gaseous
Hydride)
Selenium (Atomic
Absorption,
Borohydride
Reduction)
Silver (Atomic
Absorption, Direct
Aspiration)
Silver (Atomic
Absorption, Furnace
Technique)
SW-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
CURRENT
PROMUL-
GATED
METHOD
7481
Rev 0
9/86
7520
Rev 0
9/86
7550
Rev 0
9/86
7610
Rev 0
9/86
7740
Rev 0
9/86
7741A
Rev 1
9/94
7742
Rev 0
9/94
7760A
Rev 1
7/92
7761
Rev 0
7/92
                                      10

-------
SH-846 METHOD STATUS TABLE (9/94), CONTINUED
METH NO.
THIRD ED
DATED
9/86
7770
~ —
7840
7841
7870
7910
7911
7950

METH NO.
FINAL
UPDATE I
DATED
7/92
— w
7780
""
~ •
• •.
~ ~
~ ~
• ™ ™
7951
METH NO.
FINAL
UPDT. II
DATED
9/94
*" ••
_ _
™ ~
~ •
™" •
* ~
~ ~
~ ~
"
METHOD TITLE
Sodium (Atomic
Absorption, Direct
Aspiration)
Strontium (Atomic
Absorption, Direct
Aspiration)
Thallium (Atomic
Absorption, Direct
Aspiration)
Thallium (Atomic
Absorption, Furnace
Technique)
Tin (Atomic
Absorption, Direct
Aspiration)
Vanadium (Atomic
Absorption, Direct
Aspiration)
Vanadium (Atomic
Absorption, Furnace
Technique)
Zinc (Atomic
Absorption, Direct
Aspiration)
Zinc (Atomic
Absorption, Furnace
Technique)
SH-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
CURRENT
PROMUL-
GATED
METHOD
7770
Rev 0
9/86
7780
Rev 0
7/92
7840
Rev 0
9/86
7841
Rev 0
9/86
7870
Rev 0
9/86
7910
i
Rev 0
9/86
7911
Rev 0
9/86
7950
Rev 0
9/86
7951
Rev 0
7/92
                                      11

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

8015
8020

8030
~ ~
METH NO.
FINAL
UPDATE I
DATED
7/92
8000A
8010A
8011
8015A
_ *.
8021
8030A
"
METH NO.
FINAL
UPDT. II
DATED
9/94
"
8010B

~ ™
8020A
8021A
~ ~
8031
METHOD TITLE
Gas Chromatography
Halogenated Volatile
Organics by Gas
Chromatography
1,2-Dibromoethane
and l,2-Dibromo-3-
chloropropane by
Microextraction and
Gas Chromatography
Nonhalogenated
Volatile Organics by
Gas Chromatography
Aromatic Volatile
Organics by Gas
Chromatography
Halogenated
Volatiles by Gas
Chromatography Using
Photoionization and
Electrolytic
Conductivity
Detectors in Series:
Capillary Column
Technique
Acrolein and
Acrylonitrile by Gas
Chromatography
Acrylonitrile by Gas
Chromatography
SH-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
CURRENT
PROMUL-
GATED
METHOD
8000A
Rev 1
7/92
8010B
Rev 2
9/94
8011
Rev 0
7/92
801 5A
Rev 1
7/92
8020A
Rev 1
9/94
8021A
Rev 1
9/94
8030A
Rev 1
7/92
8031
Rev 0
9/94
                                      12

-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
METH NO.
THIRD ED
DATED
9/86
— <•>
8040
8060

~ ••
8080

8090
METH NO.
FINAL
UPDATE I
DATED
7/92
"
8040A
"

8070

•
~ ™
METH NO.
FINAL
UPDT. II
DATED
9/94
8032
- — .
™ ~
8061
~ ~ •
8080A
8081
"
METHOD TITLE
Acryl amide by Gas
Chromatography
Phenols by Gas
Chromatography
Phthalate Esters
Phthalate Esters by
Capillary Gas
Chromatography with
Electron Capture
Detection (GC/ECD)
Nitrosamines by Gas
Chromatography
Organochlorine Pes-
ticides and
Polychlorinated
Biphenyls by Gas
Chromatography
Organochlorine
Pesticides and PCBs
as Aroclors by Gas
Chromatography:
Capillary Column
Technique
Nitroaromatics and
Cyclic Ketones
SH-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
CURRENT
PROMUL-
GATED
METHOD
8032
Rev 0
9/94
8040A
Rev 1
7/92
8060
Rev 0
9/86
8061
Rev 0
9/94
8070
Rev 0
7/92
8080A
Rev 1
9/94
8081
Rev 0
9/94
8090
Rev 0
9/86
                                      13

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

8140

8150

METH NO.
FINAL
UPDATE I
DATED
7/92
V •
8110
™ ™

"• -
8141
8150A

METH NO.
FINAL
UPDT. II
DATED
9/94
"
"
8120A
8121
~ •"
8141A
8150B
8151
METHOD TITLE
Polynuclear Aromatic
Hydrocarbons
Haloethers by Gas
Chromatography
Chlorinated
Hydrocarbons by Gas
Chromatography
Chlorinated
Hydrocarbons by Gas
Chromatography:
Capillary Column
Technique
Organophosphorus
Pesticides
Organophosphorus
Compounds by Gas
Chromatography:
Capillary Column
Technique
Chlorinated
Herbicides by Gas
Chromatography
Chlorinated
Herbicides by GC
Using Methyl ati on or
Pentafluorobenzyl-
ation Derivati-
zation: Capillary
Column Technique
SH-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec.
4.3.1
Vol IB
Chap 4
Sec
4.3.1
CURRENT
PROMUL-
GATED
METHOD
8100
Rev 0
9/86
8110
Rev 0
7/92
8120A
Rev 1
9/94
8121
Rev 0
9/94
8140
Rev 0
9/86
8141A
Rev 1
9/94
8150B
Rev 2
9/94
8151
Rev 0
9/94
                                      14

-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
METH NO.
THIRD ED
DATED
9/86
8240
8250

8270

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

8260
8270A


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

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

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

8310


™ ~
METH NO.
FINAL
UPDATE I
DATED
7/92

~ ~


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

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




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




9010A
— ™
METH NO.
FINAL
UPDT. II
DATED
9/94
.8321
8330
8331
8410
"
"
METHOD TITLE
Solvent Extractable
Non-Volatile
Compounds by High
Performance Liquid
Chromatography/Ther-
mospray/Mass
Spectrometry
(HPLC/TSP/MS) or
Ultraviolet (UV)
Detection
Nitroaromatics and
Nitramines by High
Performance Liquid
Chromatography
(HPLC)
Tetrazene by Reverse
Phase High
Performance Liquid
Chromatography
(HPLC)
Gas Chroma-
tography/Fourier
Transform Infrared
(GC/FT-IR) Spec-
trometry for
Semivolatile
Organics: Capillary
Column
Total and Amenable
Cyanide
(Colorimetric,
Manual)
Total and Amenable
Cyanide
(Colorimetric,
Automated UV)
SW-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IB
Chap 4
Sec
4.3.3
Vol IB
Chap 4
Sec
4.3.3
Vol IB
Chap 4
Sec
4.3.3
Vol IB
Chap 4
Sec
4.3.4
Vol 1C
Chap 5
Vol 1C
Chap 5
CURRENT
PROMUL-
GATED
METHOD
8321
Rev 0
9/94
8330
Rev 0
9/94
8331
Rev 0
9/94
8410
Rev 0
9/94
9010A
Rev 1
7/92
9012
Rev 0
9/86
                                      17

-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
METH NO.
THIRD ED
DATED
9/86
~ ~
9020
•"
9022
9030
— —
9035
9036
9038
METH NO.
FINAL
UPDATE I
DATED
7/92
9013
9020A
9021
~ ~
9030A
9031
™ "•

"* ~
METH NO.
FINAL
UPDT. II
DATED
9/94
~ ~
90206
"
, ~ ™
™ ~
~ ~
~ ~

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

-------
SW-846 METHOD STATUS TABLE (9/94),  CONTINUED
HETH NO.
THIRD ED
DATED
9/86
9040
9041
9045
9050
"
9060
9065
9066
9067
HETH NO.
FINAL
UPDATE I
DATED
7/92
~ ~
9041A
9045A
*• ~
* ~
~ ~
*" ™
ซ. —
."
METH NO.
FINAL
UPDT. II
DATED
9/94
9040A
™ ~
9045B
* —
9056
~ ~
™ ™
™ ™
"
METHOD TITLE
pH Electrometric
Measurement
pH Paper Method
Soil and Waste pH
Specific Conductance
Determination of
Inorganic Anions by
Ion Chromatography
Total Organic Carbon
Phenol ics
(Spectrophotometri c ,
Manual 4-AAP with
Distillation)
Phenol ics
(Colorimetric,
Automated 4-AAP with
Distillation)
Phenol ics
(Spectrophotometri c ,
MBTH with
Distillation)
SW-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol 1C
Chap 6
VolIC
Chap 6
Vol 1C
Chap 6
Vol 1C
Chap 6
Vol 1C
Chap 5
Vol 1C
Chap 5
Vol 1C
Chap 5
Vol 1C
Chap 5
Vol 1C
Chap 5
CURRENT
PROMUL-
GATED
METHOD
9040A
Rev 1
9/94
9041A
Rev 1
7/92
9045B
Rev 2
9/94
9050
Rev 0
9/86
9056
Rev 0
9/94
9060
Rev 0
9/86
9065
Rev 0
9/86
9066
Rev 0
9/86
9067
Rev 0
9/86
                                      19

-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
METH NO.
THIRD ED
DATED
9/86
9070
9071



9080
9081
METH NO.
FINAL
UPDATE I
DATED
7/92





~ ~
_ —
METH NO.
FINAL
UPDT. II
DATED
9/94

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

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

~ ~
•" ~*
* ~
™ ~
"
HETH NO.
FINAL
UPDT. II
DATED
9/94
."
~ ~
9096

~ ~
ซ. _
"" ~
~ ~

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

-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
METH NO.
THIRD ED
DATED
9/86
9252
"
9310
9315
9320
HCN Test
Method
H2S Test
Method
METH NO.
FINAL
UPDATE I
DATED
7/92
_ _
"
-"
~ ~
** •
HCN Test
Method
H2S Test
Method
METH NO.
FINAL
UPDT. II
DATED
9/94
9252A
9253
* ~
™ ~
~ ~
HCN Test
Method
H2S Test
Method
METHOD TITLE
Chloride
(Titrimetric,
Mercuric Nitrate)
Chloride
(Titrimetric, Silver
Nitrate)
Gross Alpha and
Gross Beta
Alpha-Emitting
Radium Isotopes
Radium- 228
Test Method to
Determine Hydrogen
Cyanide Released
from Wastes
Test Method to
Determine Hydrogen
Sulfide Released
from Wastes
SW-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol 1C
Chap 5
Vol 1C
Chap 5
Vol 1C
Chap 6
Vol 1C
Chap 6
Vol 1C
Chap 5
Vol 1C
Chap 7
Sec 7.3
Vol 1C
Chap 7
Sec 7.3
CURRENT
PROMUL-
GATED
METHOD
9252A
Rev 1
9/94
9253
Rev 0
9/94
9310
Rev 0
9/86
9315
Rev 0
9/86
9320
Rev 0
9/86
Guidance
Method
Only
Guidance
Method
Only
                                      22

-------
                                  DISCLAIMER


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

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

      Since  many  types and sizes of  glassware and supplies are  commercially
available, and  since  it is  possible to prepare reagents  and  standards in many
different ways, those specified in these methods may be replaced by any similar
types as long  as this  substitution does not affect  the overall  quality of the
analyses.
                                DISCLAIMER - 1                      Revision 0
                                                                     July 1992

-------
                                   ABSTRACT

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

      Several of the hazardous waste regulations  under Subtitle C of RCRA require
that  specific testing methods  described in SW-846  be employed  for  certain
applications.  Refer to 40  Code of Federal Regulations (CFR), Parts 260 through
270, for those specific requirements. Any reliable analytical method may be used
to meet other requirements under Subtitle C of RCRA.
                                  U.S. Environmental Protection Agency
                                        5 Library (PL-12J)
                                 ABSTRACT - 1                       Revision  2
                                                                September  1994

-------
                      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.
Method Number,
Current Revision
Third Edition
Ten
Ten
Ten
Eight
Eight
Eight
Eight
Six
Six
Three
Three
Three
Three
Three



(8.1)
(8.1)
8.2)
8.4)







Four (4.2.1)
Four (4.2.1
Four (4.2.1
Four
Four
4.2.1
4.2.1
Four (4.2.1
Four
Four
Four
Four
Four
Four
Four
Four
Four
Four
Four
Four
Three
Three
Three
4.2.2
4.2.2)
4.2.2]
4.2.2;
4.2.2)
[4.2.2]
4.2.2;
4.2.2'
4.4)
4.4)
(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

-------
                      METHOD INDEX AND CONVERSION TABLE
                                 (Continued)


Method Number,      Chapter Number,      Method Number,      Current Revision
Third Edition       Third Edition        Second Edition          Number
    7040               Three               7040                   0
    7041               Three               7041                   0
    7060               Three               7060                   0
    7061               Three               7061                   0
    7080               Three               7080                   0

    7090               Three               7090                   0
    7091               Three               7091                   0
    7130               Three               7130                   0
    7131               Three               7131                   0
    7140               Three               7140                   0

    7190               Tnree               7190                   0
    7191               Three               7191                   0
    7195               Three               7195                   0
    7196               Three               7196                   0
    7197               Three               7197                   0

    7198               Three               7198                   0
    7200               Three               7200                   0
    7201               Three               7201                   0
    7210               Three               7210                   0
    7380               Three               7380                   0

    7420               Three               7420                   0
    7421               Three               7421                   0
    7450               Three               7450                   0
    7460               Three               7460                   0
    7470               Three               7470                   0

    7471               Three               7471                   0
    7480               Three               7480                   0
    7481               Three               7481                   0
    7520               Three               7520                   0
    7550               Three               7550                   0

    7610               Three               7610                   0
    7740               Three               7740                   0
    7741               Three               7741                   0
    7760               Three               7760                   0
    7770               Three               7770                   0
                               METHOD  INDEX - 2
                                                          Revision
                                                          Date  September  1986

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

    7950
    8000
    8010
    8015
    8020

    8030
    8040
    8060
    8080
    8090

    8100
    8120
    8140
    8150
    8240

    8250
    8270
    8280
    8310
    9010

    9020
    9022
    9030
    9035
    9036

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






Four (4.3.1)
Four (
Four 1
4.3.1)
4.3.1)
Four (4.3.1)
Four (4.3.1)
Four (4.3.1)
Four |
Four i
,4.3.1)
,4.3.1)
Four (4.3.1)
Four (4.3.1)
Four <
Four
Four
Four
Four
Four
Four
[4.3.1)
[4.3.1)
[4.3.1)
14.3.2)
4.3.2)
4.3.2)
4.3.2)
Four (4.3.3)
Five
Five
Five
Five
Five
Five
Five
Six
Six
Six
Six











Method Number,
Second Edition
Current Revision
    Number
                       7840                   0
                       7841                   0
                       7870                   0
                       7910                   0
                       7911                   0

                       7950                   0
                       None (new method)      0
                       8010                   0
                       8015                   0
                       8020                   0

                       8030                   0
                       8040                   0
                       8060                   0
                       8080                   0
                       8090                   0

                       8100                   0
                       8120                   0
                       8140                   0
                       8150                   0
                       8240                   0

                       8250                   0
                       -8270                   0
                       None (new method)      0
                       8310                   0
                       9010                   0

                       9020                   0
                       9022                   0
                       9030                   0
                       9035                   0
                       9036                   0

                       9038                   0
                       9040                   0
                       9041                   0
                       9045                   0
                       9050                   0
                               METHOD  INDEX - 3
                                                          Revision      0
                                                          Date  September  1986

-------
                      METHOD INDEX AND CONVERSION TABLE
                                 (Continued)
Method Number,
Third Edition
Chapter Number,
Third Edition
Method Number.
Second Edition
Current Revision
    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
    H2S Test  Method    Seven
                       9060
                       9065
                       9066
                       9067
                       9070

                       9071
                       9080
                       9081
                       9090
                       9095

                       9100
                       9131
                       9132
                       9200
                       9250

                       9251
                       9252
                       9310
                       9315
                       9320

                       HCN Test Method
                       H2S Test Method
                         0
                         0
                         0
                         0
                         0

                         0
                         0
                         0
                         0
                         0

                         0
                         0
                         0
                         0
                         0

                         0
                         0
                         0
                         0
                         0

                         0
                         0
                               METHOD  INDEX - 4
                                                          Revision       0
                                                          Date  September  1986

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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
which may  cover  the  matrix/analyte/concentration  combination of Interests.
The  section  discusses  the   objective   of   the  testing  program  and  Its
relationship to the choice of  an analytical method.  Flow charts are presented
along with  tables  to  guide  in  the  selection  of  the  correct analytical
procedures  to  form the appropriate method.

     The  analytical methods are  separated  into distinct procedures describing
specific,   independent  analytical  operations.    These   include  extraction,
digestion,  cleanup, and  determination.     This   format  allows Unking of the
various  steps  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  1t
exhibits a particular characteristic.

      Volume II gives background   Information on  statistical  and nonstatistlcal
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 1s to orient the user to  the objective  of  the analysis,  and to assist
 in developing  data quality objectives, sampling  plans, and laboratory SOP's.

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


                                  PREFACE - 2
                                                          Revision      0
                                                          Date  September 1986

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   CHAPTER ONE
TABLE OF CONTENTS
Section
1.0
2.0















3.0






















INTRODUCTION 	
QA PROJECT PLAN 	 	
2.1 DATA QUALITY OBJECTIVES 	
2.2 PROJECT OBJECTIVES 	 	
2.3 SAMPLE COLLECTION 	 	
2.4 ANALYSIS AND TESTING 	
2.5 QUALITY CONTROL 	
2.6 PROJECT DOCUMENTATION 	
2.7 ORGANIZATION PERFORMING FIELD OR LABORATORY
OPERATIONS .... 	
2.7.1 Performance Evaluation 	
2.7.2 Internal Assessment by QA Function 	
2.7.3 External Assessment 	
2.7.4 On-Site Evaluation 	
2.7.4.1 Field Activities 	
2.7.4.2 Laboratory Activities 	
2.7.5 QA Reports 	 	 	
FIELD OPERATIONS 	
3.1 FIELD LOGISTICS 	
3.2 EQUIPMENT/INSTRUMENTATION 	
3.3 OPERATING PROCEDURES 	
3.3.1 Sample Management 	
3.3.2 Reagent/Standard Preparation 	
3.3.3 Decontamination 	
3.3.4 Sample Collection 	
3.3.5 Field Measurements 	
3.3.6 Equipment Calibration And Maintenance . . . .
3.3.7 Corrective Action 	 	
3.3.8 Data Reduction and Validation 	
3.3.9 Reporting 	
3.3.10 Records Management 	
3.3.11 Waste Disposal 	 	
3.4 FIELD QA AND QC REQUIREMENTS . 	
3.4.1 Control Samples 	
3.4.2 Acceptance Criteria 	 	 . . . .
3.4.3 Deviations 	
3.4.4 Corrective Action 	
3.4.5 Data Handling 	
3.5 QUALITY ASSURANCE REVIEW 	
3.6 FIELD RECORDS . . 	
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     ONE -  i                          Revision 1
                                      July 1992

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                               TABLE  OF  CONTENTS
                                  (continued)


Section                                                                   Page

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

5.0  DEFINITIONS	   23

6.0  REFERENCES	   29

INDEX	   30
                                   ONE  -  ii                          Revision 1
                                                                     July  1992

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

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

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

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

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

      2.    implementation  of the project plan; and

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

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

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


2.0  QA PROJECT PLAN

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

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

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

      The role and importance of DQOs  and project documentation are discussed
below in Sections 2.1  through 2.6.   Management and organization play a critical
role in determining the effectiveness of  a QA/QC program and ensuring that all
required  procedures are followed.   Section 2.7  discusses the   elements of an
organization's QA program that have been  found to ensure an effective program.
Field operations and laboratory operations (along  with applicable QC procedures)
are discussed  in Sections 3 and 4, respectively.


2.1  DATA QUALITY OBJECTIVES

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


2.2  PROJECT OBJECTIVES

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


                                    ONE - 2                          Revision 1
                                                                     July 1992

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


2.3  SAMPLE COLLECTION

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


2.4  ANALYSIS AND TESTING

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


2.5  QUALITY CONTROL

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

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

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

      Documentation   should   be  secured   in   a   facility   that   adequately
addresses/minimizes its deterioration for  the  length  of time  that  it is to b^e
retained.  A system allowing for the expedient retrieval of information should
exist.
                                    ONE  -  3                          Revision 1
                                                                     July 1992

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

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

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

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

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

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

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                                                      J.^tj./-r^*l-'''^'l'--';t"-"f.r.'*>'r!-*••'ซ'-..,.,-vr- .-.-*•*-V->
      2.7.1  Performance Evaluation

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

      2.7.2  Internal Assessment by QA Function

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

      2.7.3  External Assessment

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

      2.7.4  On-Site Evaluation

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

            2.7.4.1  Field Activities

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

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

                                    ONE - 5                         Revision 1
                                                                     July  1992

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

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

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

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

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

            2.7.4.2   Laboratory Activities

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

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

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

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

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

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

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

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

      2.7.5  QA Reports

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

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

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

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

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


3.1  FIELD LOGISTICS

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

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

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

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

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

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

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

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

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


3.2  EQUIPMENT/INSTRUMENTATION

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


3.3  OPERATING  PROCEDURES

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

      3.3.1  Sample Management

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

      3.3.2  Reagent/Standard Preparation

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

      3.3.3  Decontamination

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

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

   •  Applicability of the procedure,

   •  Equipment required,

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

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

   •  Precautions to be taken.

      3.3.5  Field Measurements

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

      3.3.6  Equipment Calibration  And Maintenance

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

      3.3.7  Corrective Action

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

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

      3.3.9  Reporting

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

      3.3.10 Records Management

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

      Pro.iect-specific  records  relate to field work performed  for a project.
      These records may include correspondence, chain-of-custody records, field
      notes, all reports  issued as a result of the work, and procedures used.

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

      3.3.11 Waste Disposal

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


3.4  FIELD QA AND QC REQUIREMENTS

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

      3.4.1  Control Samples

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

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

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

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

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

      3.4.2  Acceptance Criteria

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

      3.4.3  Deviations

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

      3.4.4  Corrective Action

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

      3.4.5  Data Handling

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

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


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3.5  QUALITY ASSURANCE REVIEW

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


3.6  FIELD RECORDS

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

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

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

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

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

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

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

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

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

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

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

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

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


4.1  FACILITIES

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


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

      Laboratories should be  designed so  that there is adequate  separation of
functions to  ensure  that no laboratory activity has  an  adverse effect on the
analyses. The 1 aboratory may require specialized facilities such as a perchloric
acid hood or glovebox.

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

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

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

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

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


4.2  EQUIPMENT/INSTRUMENTATION

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


4.3  OPERATING PROCEDURES

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

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

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

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

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

      4.3.2  Reagent/Standard Preparation

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

      4/3.3  General Laboratory Technigues

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

      4.3.4  Test Methods

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

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

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

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

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

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

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

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

      4.3.5  Equipment Calibration and Maintenance

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

      4.3.6  QC

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

      4.3.7  Corrective Action

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

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

      4.3.9  Reporting

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

      4.3.10 Records Management

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

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

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

      4.3.11 Waste Disposal

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


4.4  LABORATORY QA AND QC PROCEDURES

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

      4.4.1  Method  Proficiency

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

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

      4.4.2  Control Limits

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

      4.4.3  Laboratory  Control Procedures

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

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

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

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

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

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

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

      4.4.4  Deviations

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

      4.4.5  Corrective  Action

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

      4.4.6  Data Handling

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

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

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   •  Laboratory name and address.

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

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

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

   •  Method reference.

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

   •  Data qualifiers with appropriate references and narrative on the quality
      of the results.
4.5  QUALITY ASSURANCE REVIEW

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


4.6  LABORATORY RECORDS

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

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

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

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

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

      Laboratory records should include, at least, the following:

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

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

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

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

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

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

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

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

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

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

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

      The following terms are defined for use in this document:

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

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

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

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

CONTROL SAMPLE:
DATA QUALITY
OBJECTIVES (DQOs)
DATA VALIDATION:
DUPLICATE:


EQUIPMENT BLANK:

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

Using the following equation yields the percent recovery
(XR).

              %R  =  100  (x, - xu)/  K

see Equipment Rinsate, Method Blank, Trip Blank.

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

A  statement  of  the overall level  of  uncertainty that  a
decision-maker is  willing to  accept  in results  derived
from environmental data  (see  reference  2, EPA/QAMS, July
16, 1986).   This  is qualitatively distinct  from  quality
measurements such as precision, bias, and detection limit.

The process of evaluating  the  available data against  the
project DQOs to  make  sure  that  the objectives are met.
Data  validation  may   be  very  rigorous,   or  cursory,
depending on project  DQOs.  The available data reviewed
will include analytical  results,  field QC  data and lab QC
data, and may also include field records.

see  Matrix  Duplicate,   Field  Duplicate,  Matrix  Spike
Duplicate.

see Equipment Rinsate.

A  sample  of analyte-free  media  which  has been used to
rinse  the sampling equipment.   It  is  collected  after
completion of decontamination  and prior to sampling.  This
blank is useful in documenting adequate decontamination of
sampling equipment.

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


MATRIX DUPLICATE:


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

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

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

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

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

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

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

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

(l)The method detection limit, or

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

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

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

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

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

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

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

Determine the variance (S2) for each analyte as follows:
                           i-l
where xs = the ith measurement of  the  variable x
and x = the average value of x;
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ORGANIC-FREE
REAGENT WATER:
PRECISION:
                      Determine the standard deviation (s) for each analyte  as
                      fol1ows:
                                          2\1/2
               s = (S2)

Determine the MDL for each analyte as follows:
                                    MDL = t
                                           (n-1, a = .99)
                                (S)
where t(n.,     wx is the one-sided t-statistic appropriate
for the number"of samples used to determine (s), at the 99
percent level.

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

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

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

              RSD  = CV = 100 S/x,
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PROJECT:
QUALITY ASSURANCE
PROJECT PLAN
(QAPJP):
RCRA:

REAGENT BLANK:

REAGENT GRADE:
REAGENT WATER:
REFERENCE MATERIAL:
SPLIT SAMPLES:
STANDARD ADDITION:
STANDARD CURVE:
                      where:
                       x  ป the arithmetic mean of the xf measurements,  and S -
                      variance;  and the relative percent difference (RPD) when
                      only two samples are available.
               RPD = 100
                                                   - x2)/{(Xl
Single or  multiple data collection  activities that are
related through the same planning sequence.

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

The Resource Conservation and Recovery Act.

See Method Blank.

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

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

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

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

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

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

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

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


6.0  REFERENCES

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

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

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

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

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

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

7.   Generation  of Environmental   Data  Related to Waste Management Activities
     (Draft).   February 1989.   ASTM.
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                                     INDEX

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

The following methods are found in Chapter Five:
Method 5050:
Method 9010A:
Method 9012:

Method 9013:
Method 9020B:
Method 9021:
Method 9022:

Method 9030A:
Method 9031:
Method 9035:
Method 9036:

Method 9038:
Method 9056:

Method 9060:
Method 9065:

Method 9066:

Method 9067:

Method 9070:

Method 9071A:

Method 9075:


Method 9076:


Method 9077:

Method 9131:
      Method
      Method
      Method
      Method
      Method
      Method
      Method
9132:
9200:
9250:
9251:
9252A:
9253:
9320:
                        Bomb Preparation Method for Solid Waste
                        Total and Amenable Cyanide (Colorimetric, Manual)
                        Total   and   Amenable  Cyanide   (Colorimetric,
                        Automated UV)
                        Cyanide Extraction Procedure for Solids and Oils
                        Total Organic Hal ides (TOX)
                        Purgeable Organic Hal ides  (POX)
                        Total Organic Hal ides (TOX) by Neutron Activation
                        Analysis
                        Acid-Soluble and Acid-Insoluble Sulfides
                        Extractable Sulfides
                        Sulfate (Colorimetric, Automated, Chloranilate)
                        Sulfate  (Colorimetric,  Automated,  Methyl thymol
                        Blue, AA II)
                        Sulfate (Turbidimetric)
                        Determination   of   Inorganic
                        Chromatography Method
                        Total Organic Carbon
                        Phenolics (Spectrophotometric,
                        Distillation)
                        Phenolics  (Colorimetric,   Automated
                        Distillation)
                        Phenolics    (Spectrophotometric,    MBTH    with
                        Distillation)
                        Total  Recoverable  Oil  & Grease   (Gravimetric,
                        Separatory Funnel Extraction)
                        Oil and Grease  Extraction Method  for Sludge and
                        Sediment Samples
                                               Chlorine in  New  and Used
                                               by   X-Ray
                                           Anions   by   Ion
                                          Manual 4-AAP with
                                                 4-AAP with
                                               Fluorescence
                                               Chlorine  in  New and Used
                                               Oxidative  Combustion and
Test Method  for  Total
Petroleum   Products
Spectrometry (XRF)
Test Method  for  Total
Petroleum  Products  by
Microcoulometry
Test Methods for  Total  Chlorine in New and Used
Petroleum Products (Field Test Kit Methods)
Total  Coliform:     Multiple  Tube  Fermentation
Technique
Total Coliform:  Membrane Filter Technique
Nitrate
Chloride (Colorimetric,  Automated Ferricyanide AAI)
Chloride (Colorimetric,  Automated FerricyanideAAII)
                       Mercuric Nitrate)
                       Silver Nitrate)
                  Chloride (Titrimetric,
                  Chloride (Titrimetric,
                  Radium-228
                             FIVE - 1
                                               Revision 1
                                               September 1994

-------
                                  METHOD 5050

                    BOMB PREPARATION METHOD FOR SOLID WASTE
1.0   SCOPE AND APPLICATION

      1.1    This  method describes the sample  preparation  steps necessary to
determine total  chlorine in solid waste  and  virgin and used  oils,  fuels and
related materials,  including:  crankcase, hydraulic, diesel, lubricating and fuel
oils,  and kerosene  by bomb  oxidation and titration  or  ion  chromatography.
Depending on the analytical  finish chosen,  other halogens  (bromine and fluorine)
and other elements (sulfur and nitrogen) may also be determined.

      1.2    The  applicable  range of  this method  varies  depending  on the
analytical finish chosen.  In general, levels as low as  500 /ug/g chlorine in the
original  oil  sample  can be determined.   The  upper  range can be  extended to
percentage levels by dilution of the combustate.

      1.3    This  standard may  involve  hazardous materials,  operations, and
equipment.  This standard does not purport to address all  of the safety problems
associated with its use.  It is  the responsibility of the user  of this standard
to  establish  appropriate  safety and health  practices  and  determine  the
applicability of regulatory limitations prior to  use.  Specific safety statements
are given in Section 3.0.

2.0   SUMMARY OF METHOD

      2.1    The sample  is  oxidized  by combustion in  a bomb containing oxygen
under  pressure.    The  liberated halogen  compounds  are  absorbed in  a sodium
carbonate/sodium bicarbonate  solution.   Approximately 30  to  40 minutes are
required to prepare a sample by  this  method.  Samples with a high water content
(> 25%) may not combust efficiently and may require the addition  of a mineral oil
to facilitate combustion.  Complete combustion  is  still not guaranteed for such
samples.

      2.2    The bomb combustate solution can then be analyzed for the following
elements as their anion species by one or more of the following methods:
      Method          Title
      9252            Chloride  (Titrimetric,  Mercuric  Nitrate)
      9253            Chloride  (Titrimetric,  Silver  Nitrate)
      9056            Inorganic Anions by Ion Chromatography (Chloride, Sulfate,
                      Nitrate,  Phosphate,  Fluoride,  Bromide)
                                   5050 - 1                       Revision 0
                                                                  September 1994

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      NOTE: Strict  adherence  to all  of the  provisions  prescribed hereinafter
      ensures against explosive rupture of the bomb, or a blowout, provided the
      bomb  is  of  proper  design  and  construction  and   in  good  mechanical
      condition.   It is desirable,  however,  that  the  bomb, be enclosed  in a
      shield  of  steel  plate  at least  1/2  in.  (12.7 mm) thick,  or equivalent
      protection be provided against unforeseeable contingencies.

3.0   INTERFERENCES

      3.1     Samples  with  very  high water  content (> 25%)  may  not  combust
efficiently  and may  require  the  addition  of  a  mineral   oil  to  facilitate
combustion.

      3.2     To  determine  total  nitrogen  in samples, the  bombs  must  first be
purged of ambient air.  Otherwise,  nitrogen results will be biased high.

4.0   APPARATUS AND MATERIALS

      4.1     Bomb,  having  a  capacity of not less than  300 ml,  so constructed
that it will  not leak during the test, and  that quantitative  recovery of the
liquids from the bomb may be readily achieved.  The inner surface of the  bomb may
be made of stainless steel or any other material that will not be affected by the
combustion process or products.  Materials  used in the bomb assembly,  such as the
head gasket and  lead-wire  insulation,  shall  be  resistant to heat and chemical
action and shall not undergo  any reaction  that will  affect  the chlorine content
of the sample in the bomb.

      4.2     Sample cup, platinum or stainless  steel,  24 mm in outside diameter
at the bottom, 27 mm in outside diameter at the top,  12 mm in height outside, and
weighing 10 to 11 g.

      4.3     Firing wire,  platinum or stainless  steel,  approximately  No.  26 B
& S gage.

      4.4     Ignition circuit, capable of supplying sufficient current to ignite
the nylon thread or cotton  wicking without melting the wire.

      NOTE: The switch in the  ignition circuit shall  be of the type that remains
      open, except when held in closed position by the operator.

      4.5     Nylon sewing thread, or Cotton Wicking, white.

      4.6     Funnel, to fit a  100-mL volumetric flask.

      4.7     Class A volumetric flasks, 100-mL, one per sample.

      4.8     Syringe, 5- or 10-mL disposable plastic or glass.

      4.9     Apparatus for specific analysis methods are given  in the methods.

      4.10    Analytical balance:  capable of weighing to 0.0001 g.
                                   5050 - 2                       Revision 0
                                                                  September 1994

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5.0   REAGENTS

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

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

      5.3     Oxygen.   Free  of  combustible  material  and halogen  compounds,
available at  a pressure of 40 atm.

      WARNING: Oxygen vigorously accelerates combustion (see Appendix Al.l)

      5.4     Sodium bicarbonate/sodium  carbonate  solution.   Dissolve 2.5200 g
NaHC03 and 2.5440 g Na2C03 in  reagent water and dilute to  1 L.

      5.5     White oil.  Refined.

      5.6     Reagents and materials for specific analysis methods are given in
the methods.

6.0   SAMPLE  COLLECTION,  PRESERVATION, AND HANDLING

      6.1     All  samples must be collected  using a sampling plan that addresses
the considerations discussed in Chapter Nine.

      6.2     Ensure that the portion of the sample used for the test is repre-
sentative of  the sample.

      6.3     To minimize  losses of volatile halogenated  solvents  that may be
present in the sample, keep the field and laboratory samples as free of headspace
as possible.

      6.4     Because used oils may contain  toxic and/or carcinogenic substances
appropriate field and laboratory safety procedures should be followed.

7.0   PROCEDURE

      7.1     Sample Preparation

              7:1.1  Preparation of bomb and sample.  Cut a piece of firing wire
      approximately 100 mm in length and attach the free ends to the terminals.
      Arrange the wire  so that it will be just above and not touching the sample
      cup.  Loop  a cotton thread  around  the wire  so  that  the ends  will extend
      into the sampling cup.   Pipet  10 mL of the NaHC03/Na2C03 solution into the
      bomb, wetting the sides.   Take  an  aliquot of the  oil  sample  of approxi-
      mately 0.5 g using  a  5-  or 10-mL disposable plastic  syringe, and place in
      the sample cup.   The  actual  sample weight is determined by the difference


                                   5050 - 3                       Revision 0
                                                                  September 1994

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      between the weight of the empty and filled  syringe.  Do not use more than
      1 g of sample.

               NOTE:  After repeated use of the bomb for chlorine determination,
               a  film may be noticed on the inner  surface.  This dullness should
               be removed by periodic  polishing  of the bomb.   A satisfactory
               method  for doing this  is to rotate the bomb in a lathe at about
               300  rpm  and  polish the inside surface  with Grit  No.  2/0  or
               equivalent paper1 coated  with  a  light  machine  oil  to prevent
               cutting,  and  then with  a  paste  of grit-free  chromic oxide2 and
               water.  This procedure will remove  all  but very deep pits and put
               a  high  polish  on the surface.   Before  using the  bomb, it should
               be washed with soap and water to remove oil  or  paste left from the
               polishing  operation.  Bombs with porous or pitted surfaces should
               never  be  used because  of the  tendency to  retain  chlorine from
               sample  to  sample.

               NOTE:     If   the  sample  is  not   readily  combustible,  other
               nonvolatile, chlorine-free combustible diluents such as white oil
               may  be employed.   However, the combined  weight of  sample and
               nonvolatile diluent  shall  not  exceed  1 g.   Some  solid additives
               are  relatively insoluble but may  be satisfactorily  burned when
               covered with a layer of  white oil.

               NOTE:   The practice  of alternately running  samples high and low
               in chlorine content  should be  avoided  whenever possible.   It is
               difficult  to rinse the last  traces of chlorine from the walls of
               the  bomb,  and  the tendency  for  residual chlorine  to  carry over
               from sample  to  sample  has  been  observed  in  a  number  of
               laboratories.  When a sample high in chlorine has  preceded one low
               in chlorine content, the test  on the  low-chlorine sample should
               be repeated,  and one  or both  of  the  low  values  thus  obtained
               should  be considered  suspect  if they do  not agree  within the
               limits  of  repeatability  of  this  method.

               NOTE:  Do  not use more than  1 g total of sample and white oil  or
               other chlorine-free  combustible material.  Use of excess amounts
               of these  materials  could cause a  buildup  of dangerously  high
               pressure and possible  rupture of the bomb.

               7.1.2     Addition of oxygen.   Place the sample  cup  in position
      and arrange the  thread  so  that the end dips  into the  sample.  Assemble the
      bomb  and tighten   the  cover  securely.   Admit oxygen  slowly  (to  avoid
      blowing the oil  from the  cup) until  a pressure  is reached as indicated in
      Table 1.

               NOTE:  Do not  add oxygen  or  ignite the sample if the bomb has been
               jarred, dropped,  or  tiled.
     Ornery Polishing  Paper grit No. 2/0 may be purchased from the Behr-Manning
Co., Troy, NY.

     2Chromic oxide may be purchased  from  J.T.  Baker & Co.,  Phillipsburg,  NJ.

                                   5050 -  4                       Revision 0
                                                                  September 1994

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               7.1.3     Combustion.   Immerse the  bomb  in a  cold  water bath.
      Connect the terminals to the open electrical circuit.  Close the circuit
      to ignite the sample.  Remove the bomb from the bath after immersion for
      at least 10 minutes.  Release  the  pressure at  a slow,  uniform rate such
      that the operation requires at  least 1 min.  Open the bomb  and examine the
      contents.  If traces of  unburned oil or sooty deposits are found, discard
      the determination, and thoroughly clean the bomb before using it again.

               7.1.4     Collection of halogen solution.  Using reagent water and
      a funnel, thoroughly rinse the  interior of the bomb, the sample cup, the
      terminals,  and  the  inner  surface of the  bomb  cover  into  a  100-mL
      volumetric flask.  Dilute to the mark with reagent water.

               7.1.5     Cleaning procedure for  bomb and  sample cup.  Remove any
      residual fuse wire from the terminals and the cup.   Using hot water, rinse
      the interior of  the  bomb,  the  sample cup, the  terminals,  and  the inner
      surface of the bomb cover.   (If any  residue remains,  first scrub the bomb
      with Alconox solution).   Copiously rinse  the bomb,  cover,  and  cup with
      reagent water.

      7.2      Sample Analysis.   Analyze the combustate  for  chlorine  or other
halogens using the methods listed in Step 2.2.  It may be necessary to dilute the
samples so that the concentration will fall  within the range of standards.

      7.3      Calculations.    Calculate  the  concentrations  of each  element
detected in the sample according to the following equation:
                         Vcom x DF
                                                               (1)
      where:
Vcom
DF
W
                     concentration of element in the sample,
                     concentration of element in the combustate, jug/mL
                     total volume of combustate, ml
                     dilution factor
                     weight of sample combusted, g.
      Report  the concentration  of each  element  detected in  the  sample  in
micrograms per gram.
                         5050 - 5
                                                                  Revision 0
                                                                  September 1994

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      Example:  A 0.5-g oil sample was combusted,  yielding  10 ml of combustate.
The combustate  was  diluted to 100 ml  total  volume  and analyzed for chloride,
which was measured to be  5 /ug/mL.  The concentration of chlorine in the original
sample is then calculated as shown below:

                                5 UQ   x   (10 ml)  x  (10)
                    C0  -  '      ml                              (2)
                                         0.5 g
                    C0  =       1,000 M                         (3)
8.0   QUALITY CONTROL

      8.1   Refer to Chapter One for specific quality control procedures.

      8.2   One sample in ten should be bombed twice.  The results should agree
to within 10%, expressed as the relative percent difference of the resuHs.

      8.3   Analyze matrix spike and matrix spike duplicates - spike samples with
the  elements  of  interest  at  a   level  commensurate  with  the   levels  being
determined.   The  spiked  compounds  should be similar to .those expected in the
sample.  Any  sample  suspected  of containing  > 25% water should also be spiked
with organic chlorine.

      8.4   For   higher   levels   (e.g..  percent  levels),   spiking   may  be
inappropriate.    For these  cases,  samples  of  known  composition  should  be
combusted.  The results should agree to within 10% of the expected result.

      8.5   Quality  control  for  the analytical  method(s) of  choice  should be
f ol 1 owed .


9.0   PERFORMANCE

      See analytical methods referenced in Step  2.2.


10.0 REFERENCES

1.    ASTM Method D  808-81, Standard Test  Method  for Chlorine in New and Used
Petroleum Products (Bomb Method).   1988 Annual  Book of ASTM Standards.  Volume
05.01 Petroleum Products and Lubricants.

2.    Gaskill, A.; Estes, E. D.;  Hardison, D. L.;  and Myers, L. E.  Validation
of Methods for Determining  Chlorine  in  Used  Oils  and Oil  Fuels.   Prepared for
U.S. Environmental Protection Agency, Office of  Solid Waste.  EPA Contract No.
68-01-7075, WA 80.  July 1988.
                                   5050 - 6                       Revision 0
                                                                  September 1994

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      300 to 350
      350 to 400
      400 to 450
      450 to 500
                                   TABLE 1.
                                GAGE PRESSURES

Capacity of bomb, ml
Minimum
gage
pressure8, atm
Maximum
gage
pressure8,

atm
38
35
30
27
40
37
32
29
aThe minimum pressures are specified to provide sufficient oxygen for complete
combustion, and the maximum pressures represent a  safety requirement.  Refer to
manufacturers' specifications for appropriate gage pressure,  which may be lower
than those listed here.
                                   5050 - 7
                             Revision 0
                             September 1994

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                                   APPENDIX
                         Al.   PRECAUTIONARY  STATEMENTS
Al.1  Oxygen
      Warning--Oxygen vigorously accelerates combustion.
      Keep oil and grease away.   Do not  use  oil or grease on regulators, gages,
or control equipment.
      Use only with equipment conditioned for oxygen service by careful cleaning
to remove oil, grease, and other combustibles.
      Keep combustibles away from oxygen and eliminate ignition sources.
      Keep surfaces clean to prevent ignition  or  explosion,  or both, on contact
with oxygen.
      Always use a pressure regulator.  Release regulator tension before opening
cylinder valve.
      All equipment  and  containers used must be suitable  and  recommended for
oxygen service.
      Never attempt to transfer  oxygen from  cylinder in which it is received to
any other cylinder.  Do not mix gases in cylinders.
      Do not drop cylinder.  Make sure cylinder is secured at all  times.
      Keep cylinder valve closed when not in use.
      Stand away from outlet when opening cylinder valve.
      For technical use only.  Do not use for inhalation purposes.
      Keep cylinder out of sun and away from heat.
      Keep cylinders from corrosive environment.
      Do not use cylinder without label.
      Do not use dented or damaged cylinders.
      See Compressed Gas Association booklets G-4 and G4.1 for details of safe
practice in the use of oxygen.
                                   5050 - 8                       Revision 0
                                                                  September 1994

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              METHOD 5050
BOMB PREPARATION  METHOD FOR SOLID WASTE
        START

7.1.1 Prepare bomb
and sample

1
7.1.2 Slowly add
o ity gen to sample
cup

7.1.3 Immerse bomb
in cold wa ter ;
igni te sample ;
remove bomb from
water ; release
pressure; open bomb
I
7,1.4 Rinse bomb,
sample cup,
terminals . and bomb
. cover with water








•.
•*






7 . 1 . 5 Rinse bomb ,
sample cup,
terminals , and bomb
cover with hot
water
1
7 . 2 Analyze
combus ta te

1

7.3 Calculate
concentration of
each element
detected


/•" ^\
| STOP |

V J

                 5050  -  9
Revision 0
September 1994

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                                 METHOD 9010A

                          TOTAL AND AMENABLE CYANIDE
1.0   SCOPE AND APPLICATION

      1.1    Method 9010  is  used to determine the  concentration  of inorganic
cyanide (CAS Registry  Number  57-12-5) in wastes or leachate.  The method detects
inorganic cyanides that are present as either soluble salts or complexes.  It is
used  to determine  values for  both  total  cyanide  and cyanide  amenable  to
chlorination.  The "reactive" cyanide content of a waste,  that is, the cyanide
content that could generate toxic fumes when exposed to mild acidic conditions,
is not distilled by Method 9010  (refer to Chapter Seven).  However, Method 9010
is used to quantify the concentration of cyanide from the  reactivity test.

      1.2    The titration procedure using silver nitrate with p-dimethylamino-
benzal-rhodanine  indicator  is  used  for measuring  concentrations  of  cyanide
exceeding 0.1 mg/L (0.025 mg/250 mL of absorbing liquid).

      1.3    The colorimetric procedure is used for  concentrations below 1 mg/L
of cyanide and is sensitive to about 0.02 mg/L.

      1.4    This method was  designed to address the problem of "trace" analyses
(<1000 ppm). The method may also be used for "minor" (1000 ppm  - 10,000 ppm) and
"major" (>10,000 ppm)  analyses by adapting the  sample preparation techniques or
cell path length.   However, the  amount of sodium hydroxide in the standards and
the sample analyzed must be the same.

2.0   SUMMARY OF METHOD

      2.1    The cyanide, as  hydrocyanic acid  (HCN),  is released  from samples
containing  cyanide  by means   of  a reflux-distillation  operation  under acidic
conditions and absorbed in a scrubber containing sodium hydroxide solution.  The
cyanide  in  the  absorbing solution is  then  determined  colorimetrically  or
titrametrically.

      2.2    In  the  colorimetric measurement,  the cyanide  is   converted  to
cyanogen chloride (CNC1) by reaction of cyanide with chloramine-T at a pH less
than  8.  After the reaction  is  complete,  color  is  formed  on the  addition of
pyridine-barbituric acid  reagent.  The absorbance  is read at 578  nm  for  the
complex formed with pyridine-barbituric acid reagent and CNC1.  To obtain colors
of comparable intensity, it is essential  to  have the same  salt content in both
the sample and the standards.

      2.3    The  titration   measurement  uses  a standard  solution of  silver
nitrate to titrate cyanide in the presence of a silver sensitive indicator.

3.0   INTERFERENCES

      3.1    Interferences are eliminated or reduced by using the distillation
procedure.  Chlorine and sulfide  are interferences in Method 9010.
                                   9010A  -  1                      Revision 1
                                                                 July 1992

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      3.2    Oxidizing  agents  such  as  chlorine  decompose  most  cyanides.
Chlorine interferences can be removed  by adding an excess of sodium arsenite to
the waste prior to preservation and storage of the sample to reduce the chlorine
to chloride which does not interfere.

      3.3    Sulfide interference can  be removed  by  adding an excess of bismuth
nitrate to the waste (to precipitate the sulfide) before distillation.  Samples
that  contain  hydrogen  sulfide,  metal  sulfides,  or other compounds  that  may
produce  hydrogen  sulfide  during  the  distillation  should be  treated  by  the
addition of bismuth nitrate.

      3.4    High  results may be  obtained for  samples  that  contain nitrate
and/or nitrite.  During the distillation,  nitrate and nitrite will form nitrous
acid, which  will  react with some organic  compounds to  form  oximes.   These
compounds once formed will  decompose under test conditions  to generate  HCN.  The
possibility of interference of nitrate and nitrite is eliminated by pretreatment
with  sulfamic  acid  just  before  distillation.    Nitrate  and  nitrite  are
interferences when present at levels higher than 10 mg/L and in conjunction with
certain organic compounds.

      3.5    Thiocyanate is reported to be an  interference when present at very
high levels.  Levels of 10 mg/L were not found to interfere.

      3.6    Fatty acids,  detergents,  surfactants, and other compounds  may cause
foaming during the distillation when they are present in large concentrations and
will  make the  endpoint of  the  titration difficult  to  detect.  They  may  be
extracted at pH 6-7.

4.0   APPARATUS AND MATERIALS

      4.1    Reflux distillation apparatus such  as  shown in Figure 1 or Figure
2.  The boiling flask should be of  one liter size with inlet tube and provision
for  condenser.   The  gas   scrubber  may  be  a  270-mL  Fisher-Milligan  scrubber
(Fisher, Part No.  07-513)  or equivalent.  The  reflux apparatus may be  a Wheaton
377160 distillation unit or equivalent.

      4.2    Spectrophotometer -  Suitable for measurements  at 578 nm  with  a
1.0 cm cell or larger.

      4.3    Hot plate  stirrer/heating  mantle.

      4.4    pH meter.

      4.5    Amber light.

      4.6    Vacuum source.

      4.7    Refrigerator.

      4.8    5 mL microburette

      4.9    7 Class A  volumetric flasks  - 100 and  250 mL

      4.10   Erlenmeyer flask - 500 mL

                                   9010A - 2                      Revision 1
                                                                 July 1992

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5.0   REAGENTS
      5.1    Reagent  grade  chemicals  shall  be used  in  all  tests.   Unless
otherwise  indicated,  it is  intended that  all  reagents shall  conform to the
specifications of the Committee on Analytical  Reagents  of the American  Chemical
Society, where  such  specifications are available.  Other  grades may  be used,
provided it is  first  ascertained that the reagent is of  sufficiently high purity
to permit its use without lessening the accuracy of the determination.
      5.2    Reagent  water.   All  references to water  in this method  refer to
reagent water,  as defined in Chapter One.
      5.3    Reagents for sample  collection, preservation,  and  handling
             5.3.1    Sodium arsenite (0.1N),  NaAs02.   Dissolve  3.2 g NaAs02 in
      250 ml water.
             5.3.2    Ascorbic acid,  C6H806.
             5.3.3    Sodium  hydroxide  solution  (50%),  NaOH.     Commercially
      available.
             5.3.4    Acetic  acid  (1.6M)  CH3COOH.     Dilute   one  part  of
      concentrated acetic acid with 9 parts of water.
             5.3.5    2,2,4-Trimethylpentane,  C8H18.
             5.3.6    Hexane,  C6H14.
             5.3.7    Chloroform,  CHC13.
      5.4    Reagents for cyanides amenable to chlorination
             5.4.1    Calcium hypochlorite solution (0.35M), Ca(OCl)2.  Combine
      5 g of calcium hypochlorite and 100 ml of water.   Shake before using.
             5.4.2    Sodium hydroxide solution (1.25N), NaOH.  Dissolve 50 g of
      NaOH in 1 liter of water.
             5.4.3    Sodium arsenite (0.1N).   See  Step 5.3.1.
             5.4.4    Potassium iodide  starch  paper.
      5.5    Reagents for distillation
             5.5.1    Sodium hydroxide  (1.25N).  See Step 5.4.2.
             5.5.2    Bismuth  nitrate (0.062M),  Bi(NO)3 • 5H,0.   Dissolve  30 g
      Bi(NO)3 •  5H20 in 100 ml of water.  While stirring, adcf 250 ml of glacial
      acetic acid, CH3COOH.    Stir until  dissolved  and dilute to  1 liter  with
      water.
             5.5.3    Sulfamic  acid (0.4N), H2NS03H.   Dissolve 40  g  H2NS03H in
      1 liter of water.
                                   9010A -  3                      Revision  1
                                                                 July 1992

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             5.5.4    Sulfuric  acid  (18N),  H2S04.  Slowly and carefully add 500
      ml of concentrated H2S04  to  500 ml  of water.

             5.5.5    Magnesium chloride  solution (2.5M), MgCl2ซ 6H20.  Dissolve
      510 g of MgCl2 • 6H20  in  1 liter  of water.

             5.5.6    Lead  acetate paper.

      5.6    Reagents for spectrophotometric determination

             5.6.1    Sodium hydroxide solution (0.25N), NaOH.   Dissolve 10 g
      NaOH in 1 liter of water.

             5.6.2    Sodium phosphate monobasic (1M), NaH2P04 • H20.  Dissolve
      138 g of NaH2P04 •  H20  in 1  liter of  water.  Refrigerate this  solution.

             5.6.3    Chloramine-T  solution  (0.44%),  C^ClNNa02S.    Dissolve
      1.0 g  of white,  water  soluble  chloramine-T  in  100 ml  of water and
      refrigerate until ready to  use.

             5.6.4    Pyridine-Barbituric acid  reagent,  C5H5N • C4H4N203.   Place
      15 g of barbituric acid in  a 250-mL  volumetric flask and add just enough
      water to wash the sides of the flask  and  wet the barbituric  acid.  Add 75
      ml of  pyridine and mix.   Add 15  ml of  concentrated  hydrochloric acid
      (HC1), mix, and cool  to  room  temperature.   Dilute to 250 ml with water.
      This reagent is stable for  approximately six months if stored in a  cool,
      dark place.

             5.6.5    Stock potassium cyanide solution (1 ml = 1000 M9 CN"), KCN.
      Dissolve 2.51 g of KCN and  2 g KOH in 900 ml of water.  Standardize with
      0.0192N  silver  nitrate,  AgN03.   Dilute  to  appropriate concentration to
      achieve 1 ml =  1000 p,g of CN".

NOTE:        Detailed  procedure  for  AgN03  standardization  is   described  in
             "Standard Methods  for  the  Examination  of  Water and Wastewater",
             16th Edition,  (1985), Methods 412C and  407A.

             5.6.6    Intermediate standard potassium cyanide solution,  (1 ml =
      100 /itg CN"),  KCN.   Dilute 100 ml of stock potassium cyanide  solution  (1 ml
      = 1000 /ig CN") to 1000 ml with water.

             5.6.7    Working standard  potassium cyanide solution  (1 mL =  10 M9
      CN"),  KCN.  Prepare fresh daily by diluting 100 ml of intermediate standard
      potassium cyanide solution  and 10 mL of  IN NaOH to 1 liter with water.

      5.7    Reagents for titration procedure

             5.7.1    Rhodanine indicator - Dissolve 20 mg of p-dimethylamino-
      benzal-rhodanine, C12H12N2OS2,  in  100  mL of acetone.

             5.7.2    Standard  silver nitrate solution (0.0192N), AgN03.  Prepare
      by crushing approximately 5  g AgN03 and drying  to constant weight at  40ฐC.
      Weigh out 3.2647 g of dried AgN03.   Dissolve in 1  liter of water.


                                  9010A  -  4                      Revision 1
                                                                 July 1992

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NOTE:         Detailed  procedure  for  AgN03  standardization  is described  in
              "Standard  Methods  for the Examination of  Water and Wastewater",
              16th  Edition,  (1985), Methods 412C and 407A.

6.0   SAMPLE COLLECTION, PRESERVATION AND HANDLING

      6.1     All samples must be collected using a  sampling  plan that addresses
the considerations discussed in Chapter Nine.

      6.2     Samples should be  collected  in  plastic  or  glass containers.  All
containers must be thoroughly cleaned and rinsed.

      6.3     Oxidizing  agents  such as  chlorine decompose most cyanides.   To
determine whether oxidizing agents are present, test a drop of the sample with
potassium  iodide-starch test  paper.    A blue  color indicates  the need  for
treatment.  Add 0.1N sodium arsenite solution a few mL at a time  until a drop of
sample produces  no color on the  indicator paper.   Add an  additional  5  mL of
sodium arsenite solution for each  liter of sample.   Ascorbic  acid can be used as
an alternative although it is not  as  effective  as arsenite.  Add a few crystals
of ascorbic  acid at a  time until a drop of  sample  produces no color  on  the
indicator paper.  Then add  an additional 0.6 g of ascorbic acid for each liter
of sample volume.

      6.4    Aqueous samples must be  preserved by  adding 50% sodium hydroxide
until the pH is greater than or equal to 12 at the time of collection.

      6.5     Samples should be chilled to 4ฐC.

      6.6    When  properly  preserved,  cyanide  samples can be stored for up to
14 days prior to sample preparation steps.

      6.7    Solid and oily wastes may be  extracted prior  to analysis by method
9013.  It uses a dilute NaOH solution  (pH  = 12) as  the extractant.  This yields
extractable cyanide.

      6.8     If fatty acids, detergents, and surfactants are  a problem, they may
be extracted using  the  following procedure. Acidify the  sample with acetic acid
(1.6M) to pH 6.0 to 7.0.

CAUTION:      This procedure can produce lethal HCN gas.

Extract with isooctane, hexane,  or chloroform (preference in order named) with
solvent volume equal to  20% of  the sample volume.  One  extraction  is  usually
adequate to reduce the compounds below the interference  level.  Avoid multiple
extractions or a long contact time at low pH in order  to  keep the loss of HCN at
a minimum.  When the extraction is completed,  immediately raise the pH of the
sample to above 12 with 50% NaOH solution.
                                  9010A  - 5                      Revision  1
                                                                 July 1992

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7.0   PROCEDURE

      7.1    Pretreatment for cyanides amenable to chlorination

             7.1.1    This  test must be  performed under amber  light.   K3[Fe-
      (CN)J  may decompose  under UV light  and hence  will  test  positive  for
      cyamde amenable to  chlorination  if exposed to  fluorescent  lighting  or
      sunlight. Two identical sample aliquots are required to determine cyanides
      amenable to chlorination.

             7.1.2    To one 500 mL sample or to a  sample diluted to 500 ml,  add
      calcium hypochlorite  solution dropwise while  agitating and maintaining the
      pH between  11  and 12  with 1.25N  sodium hydroxide until  an excess  of
      chlorine is  present  as  indicated  by Kl-starch paper turning blue.   The
      sample will be subjected to alkaline chlorination by this step.

CAUTION:     The initial  reaction product of alkaline chlorination is the very
             toxic gas cyanogen chloride; therefore, it is necessary  that this
             reaction be performed in a hood.

             7.1.3    Test  for excess chlorine with Kl-starch paper and maintain
      this excess for one hour with continuous agitation.  A distinct blue color
      on the test  paper indicates a  sufficient  chlorine  level.   If necessary,
      add additional calcium hypochlorite solution.

             7.1.4    After one hour, add 1 ml portions  of 0.1N sodium  arsenite
      until Kl-starch paper  shows  no residual  chlorine.   Add 5 ml  of excess
      sodium arsenite to ensure the presence of excess  reducing agent.

             7.1.5    Test  for total cyanide as  described  below in  both  the
      chlorinated  and the  unchlorinated samples.   The  difference   of  total
      cyanide  in the chlorinated  and  unchlorinated  samples  is the  cyanide
      amenable to chlorination.

      7.2    Distillation Procedure

             7.2.1    Place 500 ml of sample, or sample  diluted to 500 ml in the
      one liter boiling flask.  Pipet 50 ml of 1.25N sodium hydroxide into the
      gas scrubber.   If the apparatus in Figure 1  is used,  add water  until  the
      spiral is covered.  Connect the boiling flask,  condenser, gas scrubber and
      vacuum trap.

             7.2.2    Start a  slow  stream of air entering  the  boiling flask by
      adjusting the vacuum  source.  Adjust the vacuum so that approximately two
      bubbles of air  per second enter the boiling flask through the  air inlet
      tube.

             7.2.3    If samples  are  known or suspected to contain sulfide,  add
      50 ml of 0.062M bismuth  nitrate solution through  the air inlet tube.  Mix
      for three  minutes.   Use lead  acetate paper  to check the  sample for  the
      presence of sulfide.  A positive test is indicated by a black color on the
      paper.
                                   9010A  - 6                      Revision 1
                                                                 July 1992

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             7.2.4    If samples are known or suspected to  contain  nitrate or
      nitrite, or if bismuth nitrate was  added to the sample, add 50 ml of 0.4N
      sulfamic acid solution through  the air inlet tube.  Mix for three minutes.

Note:        Excessive use of sulfamic acid could create method bias.

             7.2.5    Slowly add 50 ml of  18N sulfuric acid  through the air inlet
      tube.  Rinse the tube  with water and allow  the airflow  to mix the flask
      contents for three minutes.   Add 20 ml of 2.5M magnesium chloride through
      the air inlet and wash the inlet tube with a stream  of water.

             7.2.6    Heat  the solution to boiling.  Reflux for one hour.  Turn
      off heat and continue the  airflow for at least 15 minutes.  After cooling
      the  boiling  flask, and closing  the vacuum  source,  disconnect  the  gas
      scrubber.

             7.2.7    Transfer  the  solution  from the  scrubber into a 250-mL
      volumetric flask.  Rinse the scrubber into the volumetric flask.   Dilute
      to volume with water.

             7.2.8    If the manual  spectrophotometric determination  will  be
      performed, proceed to Step  7.3.1.    If  the titration procedure  will  be-
      performed, proceed to Step 7.7.

      7.3    Manual spectrophotometric determination

             7.3.1    Pipet  50  ml  of the  scrubber  solution into  a  100-mL
      volumetric flask.  If  the sample is later  found  to  be beyond  the linear
      range of the colorimetric determination and  redistillation  of a  smaller
      sample is  not  feasible,  a smaller aliquot may  be taken.  If  less  than
      50 ml is taken, dilute to 50 ml with 0.25N sodium hydroxide  solution.

NOTE:        Temperature  of  reagents  and  spiking  solution   can  affect  the
             response  factor of the  colorimetric  determination.   The reagents
             stored in the  refrigerator should be warmed to ambient temperature
             before  use. Samples  should  not be  left  in a warm instrument to
             develop  color,  but instead  they should be  aliquoted  to a  cuvette
             immediately prior to reading the absorbance.

             7.3.2    Add 15 ml  of  1M sodium phosphate solution and mix.  Add 2
      ml of chloramine-T and mix.   Some  distillates may contain compounds  that
      have chlorine demand.   One minute after the addition of chloramine-T,  test
      for excess chlorine with Kl-starch paper.   If the test  is negative,  add
      0.5  ml  chloramine-T.   After one  minute  recheck with Kl-starch paper.
      Continue to  add chloramine-T  in 0.5  ml increments  until  an  excess  is
      maintained. After  1  to 2  minutes,  add  5 ml  of pyridine-barbituric  acid
      solution and mix.

             7.3.3    Dilute to 100 ml with water and mix again.  Allow 8 minutes
      for color development  and then read  the  absorbance  at 578 nm  in a  1-cm
      cell within  15  minutes.   The sodium  hydroxide  concentration  will  be
      0.125N.
                                  9010A - 7                      Revision  1
                                                                 July  1992

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      7.4    Standard curve for samples without sulfide

             7.4.1    Prepare a series of standards by pipetting suitable volumes
      of working  standard potassium  cyanide  solution into  250-mL  volumetric
      flasks.  To each flask, add  50  ml of 1.25N sodium hydroxide and dilute to
      250 ml with water.   Prepare  using the  following table.   The  sodium
      hydroxide concentration will be 0.25N.

     ml of Working Standard Solution        Concentration
     _ (1 mL = 10 uo. CN')                   (uq CNVL)
                  0                            Blank
                1.0                             40
                2.0                             80
                5.0        v                   200
               10.0                            400
               15.0                            600
               20.0                            800

             7.4.2    After the standard solutions have been prepared according
      to the table above, pipet 50 ml of  each  standard  solution into a 100-mL
      volumetric flask and proceed to Steps 7.3.2 and 7.3.3 to obtain absorbance
      values for the  standard curve.   The final concentrations for the standard
      curve  will   be  one  half  of   the  amounts  in  the above  table  (final
      concentrations  ranging from 20 to 400 M9/L)-

             7.4.3    It  is recommended that at least two standards (a high and
      a low) be distilled and compared to  similar values on the curve to ensure
      that the  distillation  technique is  reliable.  If distilled standards do
      not agree within ฑ  10% of the  undistilled  standards,  the  analyst should
      find the cause  of the apparent error before proceeding.
             7.4.4    Prepare  a standard curve ranging from 20 to  400  jugA by
      plotting absorbance of standard versus the cyanide concentration

      7.5    Standard curve for samples with sulfide

             7.5.1    It  is imperative that all standards be  distilled in the
      same  manner as  the  samples  using  the  method  of standard  additions.
      Standards distilled  by  this  method will give  a  linear  curve,  at  low
      concentrations,  but  as  the   concentration   increases,   the  recovery
      decreases.  It is recommended that at least  five standards be distilled.

             7.5.2    Prepare  a series of  standards similar in concentration to
      those mentioned  in  Step 7.4.1  and  analyze  as  in  Step  7.3.    Prepare  a
      standard  curve  by plotting  absorbance  of  standard  versus  the  cyanide
      concentration.

      7.6    Calculation  -    If  the  spectrophotometric procedure is  used,
calculate the cyanide, in p.g/1, in the original sample as follows.
                       CN"  (Mg/L)  = A x B x C
                                     D x E
                                  9010A  - 8                      Revision  1
                                                                 July 1992

-------
      where:

             A =      M9/L CN"  read  from  standard curve.
             B =      ml of sample after  preparation  of colorimetric  analysis
                        (100 mL recommended).
             C =      ml of sample after  distillation (250 mL  recommended).
             D =      ml of original  sample  for distillation (500 mL
                        recommended) .
             E =      mL used for colorimetric analysis (50 mL recommended).

      7.7    Titration  Procedure

             7.7.1    Transfer  the gas  scrubber  solution  or  a  suitable aliquot
      from the 250-mL volumetric flask  to a  500-mL Erlenmeyer flask.  Add 10-12
      drops of the rhodanine indicator.

             7.7.2    Titrate with standard  0.0192N silver nitrate to the first
      change in  color  from  yellow  to  brownish-pink.  The  titration must  be
      performed slowly with constant stirring.  Titrate a water blank using the
      same  amount  of sodium hydroxide and  indicator as in the sample.   The
      analyst should  be familiar  with the  endpoint  of  the titration and  the
      amount of indicator to be used before actually titrating the  samples.   A
      5-mL buret may be conveniently used to obtain  a precise  titration.

NOTE:        The titration  is based on the following reaction:

                      Ag+ +  2CN -ป [Ag(CN)2r


             When all of the cyanide has complexed  and more silver nitrate  is
added, the  excess  silver  combines  with  the rhodanine  indicator  to  turn  the
solution yellow and then brownish-pink.


             7.7.3    Calculation  -  If  the titrimetric  procedure  is   used,
      calculate concentration of CN" in p.q/1 in the original  sample  as follows:
            -  (A ~B)  xDx*x  2 mole CN~  x  26. 02  gOT x 1 x 10'nflr
                 C           F    1 eg. AgN03    i mole CAT        1 9
      where:
             A =     mL of AgN03 for titration of sample.
             B =     mL of AgNO, for titration of blank.
             C =     mL of sample titrated  (250 recommended).
             D =     actual normality of AgNO, (0.0192N recommended).
             E =     mL of sample after distillation (250 recommended).
             F =     mL of original sample  before distillation (500
                       recommended).
                                  9010A - 9                     Revision 1
                                                                July  1992

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8.0   QUALITY CONTROL

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

      8.2    Employ a minimum of one reagent blank per analytical batch or one
in every  20  samples to determine  if  contamination or any memory  effects are
occurring.

      8.3    Analyze check standards  with every analytical  batch  of samples.
If the standards are not within 15% of the expected  value,  then the samples must
be reanalyzed.

      8.4    Run  one replicate sample for every 20  samples.  A replicate sample
is a sample brought through the entire sample preparation and analytical process.
The CV of the replicates should be 20% or less.  If this criterion is not met,
the samples should be reanalyzed.

      8.5    Run  one  matrix spiked  sample  every 20  samples  to  check the
efficiency of sample distillation by adding cyanide from the working standard or
intermediate  standard   to  500  mL  of  sample  to  ensure  a  concentration  of
approximately 40  jug/L.  The matrix spiked sample is brought through the entire
sample preparation and analytical process.

      8.6    The  method of  standard additions shall be used for the analysis of
all samples that suffer from matrix interferences such as  samples which contain
sulfides.
9.0   METHOD PERFORMANCE

      9.1    The titration procedure using silver nitrate is  used for measuring
concentrations of cyanide exceeding 0.1 mg/L.  The colorimetric procedure is used
for concentrations below 1  mg/L of cyanide and  is  sensitive to about 0.02 mg/L.

      9.2    EPA Method 335.2 (sample distillation with titration) reports that
in a  single laboratory using  mixed  industrial and domestic  waste  samples at
concentrations of 0.06 to 0.62 mg/L CN', the standard deviations for precision
were  +  0.005 to +  0.094,  respectively.   In  a single laboratory  using mixed
industrial  and domestic waste  samples  at  concentrations  of 0.28 and 0.62 mg/L
CN",  recoveries (accuracy)  were 85% and 102%,  respectively.

      9.3    In two  additional  studies using  surface water,  ground water, and
landfill leachate samples, the titration procedure was further evaluated.  The
concentration  range  used  in these  studies was 0.5  to  10 mg/L cyanide.   The
detection  limit was  found  to be 0.2 mg/L  for  both total  and amenable cyanide
determinations.    The  precision  (CV)  was  6.9  and  2.6 for  total  cyanide
determinations and 18.6 and 9.1  for amenable cyanide determinations.  The mean
recoveries were 94% and 98.9% for total  cyanide, and 86.7% and  97.4% for amenable
cyanide.
                                  9010A - 10                     Revision 1
                                                                 July 1992

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10.0  REFERENCES

1.    1985 Annual  Book of ASTM Standards, Vol. 11.01; "Standard Specification for
Reagent Water"; ATSM:  Philadelphia, PA, 1985,; D1193-77.

2.    1982  Annual  Book ASTM  Standards.  Part  19;  "Standard  Test  Methods for
Cyanide in Water"; ASTM:  Philadelphia, PA, 1982; 2036-82.

3.    Bark, L.S.; Higson, H.G. Talanta 1964, 2, 471-479.

4.    Britton,  P.; Winter,  J.;  Kroner, R.C. "EPA Method  Study 12, Cyanide  in
Water"; final  report to the  U.S.  Environmental Protection  Agency.   National
Technical  Information Service:  Springfield, VA, 1984; PB80-196674.

5.    Casey,  J.P.;   Bright,  J.W.;  Helms,   B.D.  "Nitrosation  Interference   in
Distillation Tests for Cyanide";  Gulf Coast Waste Disposal Authority:  Houston,
Texas.

6.    Egekeze, J.O.; Oehne, F.W. J. Anal. Toxicology 1979, 3,  119.

7.    Elly, C.T. iL Water Pollution Control Federation 1968,  40, 848-856.

8.    Fuller, W. Cyanide in the  Environment;  Van  Zyl,  D., Ed.; Proceedings  of
Symposium; December, 1984.

9.    Gottfried, G.J. "Precision, Accuracy, and MDL Statements for EPA Methods
9010, 9030, 9060, 7520, 7521,7550,  7551,  7910,  and  7911"; final  report to the
U.S.  Environmental  Protection Agency.   Environmental  Monitoring  and Support
Laboratory. Biospheric:  Cincinnati, OH, 1984.

10.   Methods for  Chemical  Analysis of  Water and Wastes;  U.S.  Environmental
Protection Agency.  Office of Research and Development.   Environmental Monitoring
and Support  Laboratory.   ORD Publication Offices of  Center for Environmental
Research Information:  Cincinnati, OH, 1983; EPA-600/4-79-020.

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

12.   Standard Methods for the Examination  of Water  and Wastewater, 16th ed.;
Greenberg,  A.E.;  Trussell,  R.R.; Clesceri,  L.S.,  Eds.;  American  Water Works
Association,  Water  Pollution  Control  Federation,   American  Public  Health
Association:  Washington,  DC,  1985.

13.   Umafia, M.; Beach, J.; Sheldon, L. "Revisions to Method  9010";  final report
to the U.S. Environmental  Protection Agency.  Office of Solid Waste.  Research
Triangle Institute:  Research Triangle Park, NC, 1986.

14.   Umafia, M.; Sheldon, L. "Interim Report: Literature Review"; interim report
to the U.S. Environmental  Protection Agency.  Office of Solid Waste.  Research
Triangle Institute:  Research Triangle Park, NC, 1986.
                                  9010A - 11                     Revision 1
                                                                 July 1992

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               FIGURE 1.
   APPARATUS FOR CYANIDE  DISTILLATION
 Cooling Water
Inlet Tube *
Screw Clamp
     I
                                      To Low Vacuum Source
                                      Gas Scrubber
                              Distilling Flask
      Heater ••
                   O
               9010A - 12
        Revision 1
        July 1992

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                     FIGURE  2.
       APPARATUS  FOR CYANIDE  DISTILLATION
                               Connecting Tubing
      Allihn Condenser
    Air Inlet Tube
One-Liter
Boiling Flask
                                                   Suction
                     9010A -  13
Revision 1
July  1992

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                                        METHOD 9010A

                               TOTAL  AND AMENABLE  CYANIDE
                                START
                         7.1  Pretreat sample
                            to  determine
                          cyanides amenable
                           to chlorination
                         7.2.1  Place sample
                           in  round bottom
                           flask; transfer *
                         NaOH  solution into
                         scrubber; construct
                            distillation
                              assembly
                          7.2.2 Turn vaccum
                            on and adjust
                             bubble rate
 7.2.3  Add  bismuth
nitrate solution to
   boil ing  flask
                     Yes
7.2.4  Add sulfamic
 acid  solution to
   boiling  flask
72.5 Add sulfuric
 acid;  rinse  inlet
 tube with water;
   add magnesium
  chloride; rinse
  inlet tube  with
       wa ter
    7 2.6  Boil
 solution;  reflux;
cool; close vacuum
      source
    7.2.7  Drain
 scrubber  solution
  into Erlenmeyer
       flask
    73  Perform
   colorimetric
analysis of sample
                                         9010A -  14
                                 Revision  1
                                 July 1992

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                                         METHOD  9010A
                                          (Continued)
  7.41 Prepare  a
 series of cyanide
 standards through
     dilution
   7.4 Does
sample contain
   sulfides?
  7.5.1  Distill
standards  in same
manner as  samples
   742 Perform
   co1 orimetric
    analysis of
     standards
7.7  Transfer sample
   to  flask; add
rhodanine  indicator
                          75.2  Prepare
                        standard curve of
                           absorbances
 7.4.3 Distill  at
least two  standards
     to check
   distillation
     recovery
   7.4  4  Prepare
 standard curve of
    abs orbances
    7.45  Check
   efficiency of
sample  distillation
  7.6  Compute
concentrations
                         7  7.2  Titrate
                       sample and water
                       blank with silver
                           nitrate
                                                7.7.3 Calculate
                                               concentration of
                                               cyanide in sample
                                                    STOP
                               STOP
                                          9010A  -  15
                                                        Revision  1
                                                        July 1992

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                                   METHOD  9012

             TOTAL AND AMENABLE CYANIDE (COLORIMETRIC.  AUTOMATED  UV)
1.0  SCOPE AND APPLICATION

     1.1  Method 9012 1s  used  to  determine  the  concentration  of  Inorganic
cyanide 1n  an  aqueous  waste  or  leachate.    The  method  detects  Inorganic
cyanides that are present as either  simple soluble salts  or  complex  radicals.
It is used to determine values for  both total  cyanide and cyanide amenable  to
chlorlnation.   Method  9012  1s  not  intended  to  determine  if a waste  is
hazardous by the characteristic of reactivity.


2.0  SUMMARY OF METHOD

     2.1  The cyanide, as hydrocyanic add (HCN), is released by refluxlng the
sample with strong acid and distillation  of the HCN Into an  absorber-scrubber
containing sodium  hydroxide  solution.    The  cyanide  1on   1n the  absorbing
solution Is then determined by automated UV colorimetry.

     2.2  In  the  color1metric  measurement,  the  cyanide  1s  converted  to
cyanogen chloride  (CNC1) by reaction  with  Chloramine-T  at   a pH less than 8
without hydrolyzing to the cyanate.   After the reaction Is complete, color 1s
formed on the addition of pyrldine-barblturic add reagent.  The concentration
of NaOH must be the  same  in  the  standards, the scrubber solutions, and any
dilution of the  original  scrubber  solution  to  obtain colors of comparable
Intensity.


3.0   INTERFERENCES

      3.1  Interferences are eliminated or  reduced  by procedures described In
Paragraphs 7.2.3,  7.2.4, and 7.2.5.

      3.2  Sulfides adversely affect the colorlmetric procedures.  Samples that
contain hydrogen sulfide, metal sulfides,  or other compounds that may produce
hydrogen sulfide during  the  distillation   should  be  treated by addition of
bismuth nitrate prior to distillation as described in Paragraph 7.2.3.

      3.3  High results may be obtained for samples that contain nitrate and/or
nitrite.  During the distillation, nitrate and nitrite will form nitrous add,
which will react with some organic  compounds to  form oxlmes.  These compounds
will  decompose  under  test  conditions   to  generate  HCN.    The  possible
Interference  of   nitrate  and  nitrite  1s  eliminated  by  pretreatment with
sulfamic add.
                                     9012 -  1
                                                         Revision      0
                                                         Date  September 1986

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4.0  APPARATUS AND MATERIALS

     4.1  Reflux distillation apparatus;  Such as shown in Figure 1  or 2.   The
boiling flask should be  of1-litersize  with  inlet tube and provision  for
condenser.  The gas absorber 1s a Fisher-Milligan scrubber (Fisher Catalog
#07-513) or equivalent.

     4.2  Potassium iodide-starch test paper.

     4.3  Automated continuous-flow analytical instrument with;

          4.3.1  Sampler.
          4.3.2  Manifold with UV digester.
          4.3.3  Proportioning pump.
          4.3.4  Heating bath with distillation coll.
          4.3.5  Distillation head.
          4.3.6  Colorimeter equipped with a 15-mm flowcell and 570 nm filter.
  v       4.3.7  Recorder.
 5.0   REAGENTS

      5.1   ASTM  Type  II water   (ASTM  D1193);    Water  should be monitored for
 Impurities.

      5.2   Sodium hydroxide  solution, 1.25 N;  Dissolve 50 g of NaOH in Type II
 water and dilute to  1  liter with  Type  II water.

      5.3   Bismuth nitrate solution:  Dissolve 30.0  g of B1(N03)3  in 100 ml of
 Type II water.While  stirring, add  250 ml  of glacial acetic acid.  Stir until
 dissolved.  Dilute to  1  liter with Type II  water.

      5.4   Sulfuric acid.  1:1:  Slowly  add   500 ml  of  concentrated ^$04  to
 500  ml of Type  II water.
           CAUTION:  this Is an exothermic reaction.

      5.5   Sodium dihydrogenphosphate,  1 M:   Dissolve  138 g  of NaH2P04ปH20  in
 1 liter of Type II water.

      5.6   Stock  cyanide solution:   Dissolve 2.51 g  of KCN  and  2 g  KOH in
 900  ml of  Type  II  water.    Standardize   with  0.0192  N  AgNOs.  Dilute to
 appropriate concentration so  that 1  ml =  1  mg CN.

      5.7   Intermediate  standard  cyanide  solution;  Dilute  100.0  ml  of stock
 (1 mL =  1 mg CN) to  1,000 ml  with Type II water  (1 ml = 100 ug CN).

      5.8   Working standard  cyanide solution;  Prepare fresh daily by diluting
 100.0 ml   of intermediatecyanide solution to   1,000 ml  with   Type II  water
 (1 ml =  10.0 ug CN).  Store in a  glass-stoppered  bottle.
                                     9012 - 2
                                                          Revision
                                                          Date  September 1986

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                                 Connecting Tubing
      Allihn Condenser
    Air Inlet Tube
One-Liter
Boiling Flask
                                                      Suction
        Figure 1. Apparatus for cyanide distillation.
                    9012 -  3
                                              Revision        0
                                              Date   September 1986

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COOLING WATER
INLET  TUBE*
SCREW  CLAMP
       HEATER~
                                        TO  LOW  VACUUM
                                           SOURCE
                                   - ABSORBER
                           ~ DISTILLING FLASK
                    O
     Figure 2. Cyanide distillation apparatus.
                  9012 - 4
                                       Revision      0
                                       Date  September 1986

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     5.9  Magnesium chloride solution;     Weigh  510   g   of   MgCl2'6H20  Into a
1,000-mL flask, dissolve, and dilute to 1 liter with  Type II  water.

     5.10  Sulfamlc add solution:  Dissolve 40  g of sulfamlc  add  1n Type II
water.  Dilute to 1 liter.

     5.11  Calcium hypochlorlte  solution;    Dissolve  5 g  of  calcium hypo-
chlorite [Ca(OCl)2] In 100 mL of Type II water.

     5.12  Reagents for automated colorlmetrlc determination;

          5.12.1  Pyr1d1ne-barb1tur1c acid reagent:   Place  15  g  of  barbituric
     add 1n a 250-mL volumetric flask, add  just enough Type II  water to wash
     the sides of the  flask,  and  wet  the  barbituric  acid.    Add 75 ml of
     pyrldlne and mix.  Add 15 mL  of  concentrated HC1, mix, and cool to room
     temperature.  Dilute to 250 ml with  Type II water  and mix.   This reagent
     1s stable for approximately six months 1f stored 1n a cool,  dark place.

          5.12.2  Chloramlne-T solution:    Dissolve   2.0 g  of   white,  water
     soluble chloram1ne-T 1n 500  ml  of  Type  II water and  refrigerate until
     ready to use.

          5.12.3  Sodium hydroxide, 1 N:   Dissolve  40   g of  NaOH  In Type II
     water, and dilute to 1 liter.

          5.12.4  All working  standards  should  contain 2  ml   of 1  N NaOH
     (Paragraph 5.12.3) per 100 ml.

          5.12.5  Dilution water and  receptacle  wash  water  (NaOH, 0.25 N):
     Dissolve 10.0 g NaOH 1n 500 ml of Type II water. Dilute to  1 liter.

     5.13  Ascorbic add;  Crystals.

     5.14  Phosphate buffer. pH 5.2:   Dissolve 13.6  g of potassium  dlhydrogen
phosphate and 0.28 g of  disodium  phosphate  1n  900 ml of  Type II water and
dilute to 1 liter.


6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

     6.1  All samples must  have  been  collected  using  a  sampling plan that
addresses the considerations discussed 1n Chapter Nine of this  manual.

     6.2  Samples should be collected 1n  plastic  or glass  bottles  of  1-Hter
size or larger.  All bottles  must be thoroughly cleaned and  thoroughly  rinsed
to remove soluble materials from containers.

     6.3  Oxidizing agents  such  as  chlorine  decompose most  cyanides.  To
determine whether oxidizing agents are present, test  a drop  of  the sample with
acidified potassium Iodide  (Kl)-starch test  paper  at  the  time  the sample 1s
collected; a blue color Indicates the need for treatment. Add  ascorbic  add a
                                    9012 - 5
                                                         Revision
                                                         Date  September 1986

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few crystals at a  time  until   a  drop  of  sample  produces   no  color on the
Indicator.  Then add an additional   0.6  g  of ascorbic add for each  liter of
water.

     6.4  Samples must be preserved by addition of 10 N sodium hydroxide  until
sample pH 1s greater than or equal  to 12 at the time of collection.

     6.5  Samples should be refrigerated  at  4*C, when possible,  and  analyzed
as soon as possible.


7.0  PROCEDURE

     7.1  Pretreatment for cyanides amenable to chlorlnation;

          7.1.1  Two  sample  allquots  are  required  to  determine  cyanides
     amenable to chlorlnation.  To one  500-mL aliquot, or to a volume diluted
     to 500 ml, add  calcium  hypochlorlte  solution  (Paragraph 5.11)  dropwlse
     while agitating and maintaining  the  pH  between  11  and 12 with sodium
     hydroxide  (Paragraph 5.2).
          CAUTION;  The Initial  reaction  product of alkaline chlorlnatlon 1s
                th~e  very  toxic  gas  cyanogen  chloride;    therefore,  It Is
                recommended that this  reaction  be  performed  1n  a hood.  For
                convenience, the sample may be  agitated 1n a 1-Hter beaker by
                means of a magnetic stirring device.

          7.1.2 Test  for residual  chlorine  with   Kl-starch paper (Paragraph
     4.4) and maintain this excess for 1  hr, continuing agitation.  A distinct
     blue color on  the test paper  Indicates  a sufficient chlorine level.  If
     necessary, add additional hypochlorlte solution.

          7.1.3 After 1 hr, add  0.5 g  portions   of ascorbic add until KI-
      starch paper  shows no  residual  chlorine.    Add  an additional  0.5 g of
     ascorbic  add  to  ensure the presence of excess  reducing agent.

          7.1.4 Test  for  total   cyanide   .1n   both  the  chlorinated  and
      unchlorlnated  allquots.    (The difference  of total  cyanide  1n  the
      chlorinated   and  unchlorlnated   allquots  1s   the  cyanide  amenable  to
      chlorlnatlon.)  .

      7.2  Distillation Procedure;

          7.2.1  Place 500  ml  of sample,  or  an   aliquot diluted  to 500 ml, In
      the  1-Hter boiling  flask.    P1pet   50  ml of sodium  hydroxide (Paragraph
      5.2) Into the absorbing tube.   If  the apparatus 1n Figure 1 1s  used, add
      Type II  water until  the   spiral   1s  covered.   Connect the boiling  flask,
      condenser, absorber,  and  trap 1n the train  (Figure  1  or  2).

           7.2.2  By adjusting  the  vacuum  source,   start   a slow  stream  of air
      entering the boiling flask so  that  approximately  two bubbles of air per
      second enter the flask through the air Inlet tube.
                                     9012 - 6
                                                          Revision      0
                                                          Date  September 1986

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     7.2.3  Use lead acetate paper to  check  the sample for the presence
of sulfide.  A positive test 1s  indicated by a black color on the paper.
If positive, treat the sample by adding 50 ml of bismuth nitrate solution
(Paragraph 5.3) through the air  inlet  tube  after  the air rate is set.
Mix for 3 min prior to addition of H2S04.

     7.2.4  If samples are suspected to contain N03 and/or N02, add 50 ml
of sulfamic acid solution  (Paragraph  5.10)  after  the  air rate is set
through the air inlet tube.  Mix for 3 min prior to addition of ^$04.

     7.2.5  Slowly add 50 ml  1:1  ^$04  (Paragraph 5.4) through the air
inlet tube.  Rinse the tube with  Type  II water and allow the airflow to
mix the flask contents  for  3  min.    Pour  20 ml of magnesium chloride
(Paragraph 5.9) into the air inlet and wash down with a stream of water.

     7.2.6  Heat the solution to boiling.    Reflux  for  1 hr.  Turn off
heat and continue the airflow  for  at  least  15 min.  After cooling the
boiling flask, disconnect absorber and close off the vacuum source.

     7.2.7  Drain the solution from the absorber into a 250-mL volumetric
flask.  Wash the absorber with Type   II water and add the washings to the
flask.  Dilute to the mark with Type  II water.

7.3  Automated colorimetric determination;

     7.3.1  Set up the manifold in  a hood  or a well-ventilated area as
shown in  Figure 3.

     7.3.2  Allow colorimeter and recorder to warm  up  for 30 min.  Run  a
 )ase!1ne with  all  reagents,  feeding Type  II  water  through the sample
 line.

     7.3.3  Place  appropriate  standards   in  the  sampler   in  order of
decreasing  concentration.   Complete   loading  of  the  sampler tray with
unknown samples.

     7.3.4  When the baseline becomes steady, begin the analysis.

7.4  Standard  curve for samples without  sulfide;

     7.4.1  Prepare a series of   standards   by pipetting suitable volumes
of standard solution  (Paragraph 5.8)   Into   250-mL volumetric flasks.  To
each standard  add 50 ml of  1.25   N   sodium  hydroxide and dilute to 250 ml
with Type II water.  Prepare as follows:
                                9012 - 7
                                                     Revision       0
                                                     Date  September  1986

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                                                 ft! SAMPLE
      10
      o
      ป-*
      ro

      I

      oo
O 70
01 n
rt- <
n -*
 o
rv a
o
VAST!

1^ 15
\8 tO
COIORIMETIB
57U MM
IS mm I/C •
199 BO23 0

70751 157
TURNS
/r/c
PUMP IUBE
1 0 MM ID
6
•
WASTE
8089
20 TURNS
TO SAMPLER WASH
^ RECEPTACLE
j ff? TO TOP OF PROBE
••••• A 10
1


i/o oin.1 r~ '
5 TURNS \





PUR ORN
BLK BLK
RED RIO
RED RtO
WHT WMT
BLK BLK
GRY GRV
ORN ORN
ORN ORN
CRY GRY
CRY CRY

M1/MIM
340 SAMPLE WASH
0.3? AIR
O 70 SAMPLE
0 70 DILUTION WATER
O 6O R| SAMPIE WASTE
O.3? AIR 1
I.OO RE SAMPLE C 3
0.4? BUMtR
0.10 r.HLOROMINE T
1.00 PVRIOIN* BARBITURIC
i.oo FROM r/c

                                                                                       PROPORTIONING

                                                                                           PUMP
o>
                                                          Figure 3. Cyanide manifold AA11.

-------
          ml of Working Standard Solution      Concentration.
                (1 ml  = 10 ug CN)	      (ug CN/250 ml)
                      0                              BUNK
                      1.0                             10
                      2.0                             20
                      5.0                             50
                    10.0                            100
                    15.0                            150
                    20.0                            200

          7.4.2   It  1s not Imperative that  all  standards be distilled 1n the
     same  manner  as  the  samples.     It   1s  recommended  that  at least two
     standards  (a high and  a   low)  be  distilled  and compared with similar
     values  on   the  curve  to  ensure that  the  distillation  technique 1s
     reliable.   If   distilled  standards  do   not  agree  within  + 10% of the
     undlstilled  standards,  the  analyst should find the cause of the apparent
     error before proceeding.

          7.4.3   Prepare a standard  curve by plotting absorbances of standards
     vs. cyanide  concentrations.

          7.4.4   To  check the  efficiency  of   the  sample distillation, add an
     Increment  of cyanide  from  either the   Intermediate standard  (Paragraph
     5.7)  or the working  standard   (Paragraph 5.8)  to  500  ml of sample to
     ensure  a level  of 20  ug/L.    Proceed with  the analysis as 1n Paragraph
     7.2.1.

     7.5  Standard  curve  for samples with  sulflde;

          7.5.1  All standards must be  distilled   1n   the   same manner as the
     samples.   A minimum of  3 standards shall  be distilled.

          7.5.2  Prepare a standard curve  by plotting  absorbances of standards
     vs. cyanide concentration.

     7.6  Calculation;  Prepare  a standard  curve   by  plotting peak heights of
standards against  th~e1r  concentration  values.     Compute   concentrations of
samples by comparing sample  peak heights with  the  standard  curve.


8.0  QUALITY CONTROL

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

     8.2  Employ a minimum  of  one  blank  per  sample  batch  to determine  If
contamination or any memory  effects are occurring.

     8.3  Verify calibration  with  an  Independently   prepared  check  standard
every 15 samples.
                                    9012 - 9
                                                         Revision
                                                         Date  September 1986

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     8.4  Run one spike duplicate sample  for  every  10 samples.  A duplicate
sample 1s a sample brought through the whole sample preparation process.

     8.5  The method of standard additions  shall  be used for the analysis of
all samples that suffer from matrix Interferences.


9.0  METHOD PERFORMANCE

     9.1  Precision and accuracy data are not available at this time.


10.0 REFERENCES

1.   Annual Book  of  ASTM  Standards,  Part  31,  "Water," Standard D2036-75,
Method B, p. 505 (1976).

2.   Goulden, P.O., B.K. Afghan, and  P. Brooksbank, Determination of Nanogram
Quantities of Simple and Complex  Cyanides  1n Water, Anal. Chem., 44(11), pp.
1845-49  (1972).

3.   Standard Methods for the Examination  of  Water and Wastewater, 14th ed.,
pp. 376  and 370, Method 413F and D  (1975).

4.   Technlcon AutoAnalyzer II Methodology,  Industrial Method No. 315-74 WCUV
Digestion and Distillation, Technlcon Industrial Systems, Tarrytown, New York,
10591  (1974).
                                     9012 - 10
                                                          Revision
                                                          Date   September  1986

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                                         METHOD 9018

                   TOTAL AND AMENABLE CYANIDE (COLORIMETRIC.  AUTOMATED UV)
 7.1
     I Pretreat
   to determine
      cyanides
    amenable to
   chlorination
7.2.1   Place
        sample
      in flack:
   pipet sodium
 hydroxide into
 absorbing tube
                            Are samples
                           suspected to
                            contain NO
                              and/or
                               NO 7
   I   Add
    sul?amlc
acid  solution
 through  air
  inlet  tube
                         rinse tube with
                          Type II water;
                          add magnesuim
                             chloride
7.2.2
 Introduce air
  stream into
 boiling flask
                          7.2.3
                         7.2.6
                              I   Boll
                              solution:
                           reflux:  cool:
                             close off
                           vacuum source
                                  Treat
    sample by
adding bismuth
     nitrate
    solution
                                                    7.2.7
                                                     Drain  solution
                                                     from absorber
                                                      into  flask
                                                     7.3
                                                          Perform
                                                          baseline
                                                       colorimetric
                                                          analysis
                                                       o
                                    9012  - 11
                                                            Revision       0
                                                            Date  September 1986

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                            METHOD 9012

      TOTAL AND AMENABLE CYANIDE (COLOPIMETfllC.  AUTOMATED UV)
                            (Continued)
7.5.1
       Distill
   standards In
    same manner
     as sample
7.5.Z
    Prepare
standard curve
of absorbances
7.4.2  Distill
       at least
  two standards
      to check
   distillation
    techniques
                                                    7.4.3
                                                       Prepare
                                                   standard curve
                                                   of absorbances
                           7.6
                              Compute
                          concentrations
                                                    7.4.41
       Check
    efficiency
     of sample
   distillation
                        (      Stop       J
                          9012 - 12
                                                  Revision       0
                                                  Date  September  1986

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                                  METHOD 9013
                           (APPENDIX TO METHOD 9010)

               CYANIDE EXTRACTION PROCEDURE FOR SOLIDS AND OILS
1.0   SCOPE AND APPLICATION

      1.1    The extraction procedure described in this method is designed for
the extraction of  soluble cyanides from solid and oil wastes.   The method is
applicable to oil,  solid, and multiphasic samples.  This method is  not applicable
to samples containing insoluble cyanide compounds.

2.0   SUMMARY OF METHOD

      2.1    If the  waste sample contains so much solid,  or solids  of such a
size as to interfere with agitation and  homogenization of the sample mixture in
the distillation  flask, or  so much oil  or grease  as  to interfere  with the
formation of a homogeneous emulsion, the sample may be extracted with water at
pH 10 or greater, and the extract distilled and analyzed by Method  9010.  Samples
that contain free water  are filtered and separated into an aqueous component and
a  combined  oil  and  solid component.   The nonaqueous  component may  then  be
extracted, and an aliquot of the extract  combined with an aliquot of the filtrate
in proportion to the composition of the sample.  Alternatively,  the components
may be  analyzed  separately,  and  cyanide  levels  reported  for each  component.
However, if the  sample solids are known  to contain sufficient levels of cyanide
(about 50 Mg/g) as to be well above the  limit of detection, the extraction step
may be  deleted and the  solids analyzed directly by Method 9010.  This can be
accomplished by diluting a small aliquot of the waste solid (1-10 g) in 500 mL
water in the distillation flask and  suspending the  slurry during distillation
with a magnetic stir-bar.

3.0   INTERFERENCES

      3.1    Potential interferences that may be encountered during analysis are
discussed in Method 9010.

4.0   APPARATUS AND MATERIALS

      4.1    Extractor - Any  suitable device that sufficiently agitates a sealed
container of one liter  volume or greater.   For the  purpose  of  this analysis,
agitation is sufficient when:

             1.        All  sample surfaces are continuously brought into contact
                      with extraction fluid, and

             2.        The  agitation prevents stratification  of the  sample and
                      fluid.

      4.2    Buchner funnel  apparatus

             4.2.1    Buchner funnel  -  500-mL capacity,  with 1-liter  vacuum
      filtration  flask.
                                   9013 - 1                       Revision 0
                                                                  July 1992

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             4.2.2    Glass wool - Suitable for filtering, 0:8  m diameter such
      as Corning Pyrex 3950.

             4.2.3    Vacuum  source  - Preferably a water driven  aspirator.   A
      valve or stopcock to release vacuum is required.

      4.3    Top-loading balance - capable of weighing 0.1 g.

      4.4    Separatory funnels - 500 ml.

5.0   REAGENTS

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

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

      5.3    Sodium hydroxide  (50% w/v), NaOH.  Commercially available.

      5.4    n-Hexane, C6HU.

6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1    All  samples  must  be  collected using a  plan  that  addresses  the
considerations discussed in Chapter 4 of this manual.  See Section 6.0 of Method
9010 for additional guidance.

7.0   PROCEDURE

      7.1    If  the waste  does not contain  any  free  aqueous phase,  go to Step
7.5.  If the sample is a homogeneous fluid or slurry that does not separate or
settle in the distillation flask when  using a Teflon coated magnetic stirring bar
but mixes  so  that the solids  are  entirely  suspended,  then the  sample  may be
analyzed by Method 9010 without an extraction step.

      7.2    Assemble  Buchner  funnel  apparatus.   Unroll  glass filtering fiber
and fold the fiber over itself  several times to make a pad about  1 cm thick when
lightly compressed.  Cut the  pad to fit the Buchner funnel.  Weigh the pad, then
place it  in  the funnel.  Turn the aspirator  on and wet the  pad  with  a known
amount of water.

      7.3    Transfer the sample  to the  Buchner  funnel in small aliquots, first
decanting the fluid.   Rinse the sample container with  known amounts of water and
add the rinses to the  Buchner funnel.  When no free water  remains in the funnel,
slowly open the stopcock to allow air to enter the vacuum  flask.  A small amount
of sediment may have passed through the glass fiber pad.  This will not interfere
with the analysis.
                                   9013 - 2                       Revision 0
                                                                  July 1992

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      7.4    Transfer  the  solid and the glass  fiber pad to  a  tared weighing
dish.  Since most greases and oils  will  not pass through the fiber pad, solids,
oils, and greases will be extracted together.  If the filtrate includes an oil
phase, transfer the filtrate  to  a  separatory funnel.   Collect and measure the
volume of the aqueous phase.  Transfer the oil phase to the weighing dish with
the solid.

      7.5    Weigh  the dish containing solid,  oil  (if any), and  filter pad.
Subtract the weight of the  dry  filter  pad.   Calculate  the net volume of water
present in the original  sample  by  subtracting the  total  volume  of rinses used
from the measured volume of the filtrate.

      7.6    Place the following in a  1-liter wide-mouthed bottle:

             500 ml water
             5 ml 50% w/v NaOH
             50 ml n-Hexane  (if a  heavy grease is present)

             If the weight of the solids (Step 7.5)  is greater than 25 g, weigh
      out a representative aliquot of 25 g and add it to the bottle; otherwise
      add all of the solids.  Cap the bottle.

      7.7    The pH of the  extract must be  maintained  above 10 throughout the
extraction step and  subsequent filtration.  Since some samples  may release acid,
the pH must be  monitored  as  follows.  Shake the extraction bottle and after one
minute, check the pH.  If the pH is  below  12, add  50%  NaOH in 5 ml increments
until it is at least 12.   Recap the bottle,  and  repeat  the procedure until the
pH does not drop.

      7.8    Place the bottle or bottles in  the tumbler, making sure
there is enough foam insulation  to  cushion the bottle.  Turn the tumbler on and
allow the extraction to run for about 16 hours.

      7.9  Prepare a Buchner funnel apparatus as in  Step 7.2 with a glass fiber
pad filter.

      7.10    Decant the extract to  the Buchner funnel.   Full recovery of the
extract is not necessary.

      7.11    If the extract contains an oil phase, separate the aqueous phase
using  a  separatory funnel.   Neither  the  separation  nor the  filtration are
critical, but are necessary to be able to measure the volume of the aliquot of
the  aqueous  extract  analyzed.    Small amounts  of  suspended solids  and oil
emulsions will  not interfere.

      7.12  At  this  point, an aliquot of the filtrate of the original sample may
be combined with an  aliquot  of the extract  in a proportion representative of the
sample.   Alternatively,   they may  be  distilled and analyzed  separately and
concentrations  given  for  each  phase.   This  is  described  by the  following
equation:

Liquid Sample AliauotfmU _ Solid Extracted(g)a  x  Total Sample Fi1trate(mL)c
   Extract Aliquot(mL)        Total Solid(g)D       Total  Extraction Fluid(mL)0


                                   9013 -  3                       Revision 0
                                                                  July 1992

-------
      "From Step 7.6.   Weight of solid sample used  for extraction.
      bFrom Step 7.5.  Weight  of solids  and oil phase with  the  dry weight of
      filter and tared dish subtracted.
      Includes volume of all  rinses added to the filtrate (Steps 7.2 and 7.3).
      d500 ml water plus total volume of NaOH solution.  Does not include hexane,
      which is subsequently removed (Step 7.11).
Alternatively,  the   aliquots   may  be  distilled   and  analyzed  separately,
concentrations for each phase reported separately, and the amounts of each phase
present in the sample reported separately.
8.0   QUALITY CONTROL
      8.1    Refer to Method 9010.
9.0   METHOD PERFORMANCE
      9.1    In a single laboratory study,  recoveries of  60 to 90% are reported
for solids and 88 to 92% for oils.  The reported CVs are less than 13.
10.0  REFERENCES
      10.1   Refer to Method 9010.
                                   9013 - 4                       Revision 0
                                                                  July 1992

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                                  METHOD  9013
                          (APPENDIX  TO METHOD 9010)

            CYANIDE  EXTRACTION  PROCEDURE  FOR  SOLIDS AND OILS
  7 .1  Analyze by
                             7.1 Does
                              sample
                            contain any
                            free fluid?
       7.1 Is sample
       a homogeneous
          slurry?
                        7 . 2 Assemble filter
                         apparatus; weigh
                         filter pad; place
                        in  funnel; wet pad
                         with  known amount
                            of water
                        7.3 Filter sample;
                           rinse sample
                          container wi th
                          known amount of
                              water
7.4  Separate phases
   in separatory
 funnel; transfer
   oil  phase to
   weighing dish
Yes
 7.5 Heigh solid &
oil  phases in tared
  weighing dish;
calculate amount of
  water in sample
                                   9013 -  5
                                                     Revision 0
                                                     July 1992

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                        METHOD 9013
                  (APPENDIX  TO METHOD  9010)

CYANIDE EXTRACTION PROCEDURE FOR SOLIDS AND OILS (CONTINUED)
                          9013 - 6
Revision 0
July 1992

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                                 METHOD 9020B

                          TOTAL ORGANIC HALIDES  (TOX)
1.0   SCOPE AND APPLICATION

      1.1    Method 9020 determines Total Organic Hal ides (TOX) as chloride in
drinking water  and ground waters.  The  method uses carbon  adsorption  with a
microcoulometric-titration detector.

      1.2    Method  9020  detects all  organic  halides containing  chlorine,
bromine, and  iodine  that  are adsorbed by granular  activated carbon  under the
conditions of the method.  Fluorine-containing species are not determined  by this
method.

      1.3    Method 9020 is applicable to samples whose  inorganic-halide concen-
tration does  not  exceed the organic-halide  concentration by more than  20,000
times.

      1.4    Method  9020  does  not  measure  TOX   of   compounds  adsorbed  to
undissolved solids.

      1.5    Method 9020 is restricted to use by, or under the supervision of,
analysts experienced in the operation  of  a pyrolysis/microcoulometer and in the
interpretation of the results.

      1.6    This method is provided as a recommended procedure.  It may  be used
as a  reference  for comparing the  suitability of other methods  thought to be
appropriate for measurement of TOX (i .e., by comparison of sensitivity, accuracy,
and precision of data).

2.0   SUMMARY OF METHOD

      2.1    A  sample  of  water  that  has been  protected  against the loss of
volatiles by the elimination of headspace in the sampling container, and that is
free  of  undissolved  solids,  is  passed  through  a  column  containing 40  mg of
activated carbon.   The  column  is  washed to remove any trapped inorganic halides
and is  then  combusted  to  convert  the  adsorbed organohalides  to  HX,  which is
trapped and titrated electrolytically using a microcoulometric detector.

3.0   INTERFERENCES

      3.1    Method  interferences may  be caused  by  contaminants,  reagents,
glassware,  and other sample-processing hardware.   All  these materials must be
routinely demonstrated  to be free from interferences under the conditions of the
analysis by running method blanks.

             3.1.1   Glassware   must  be  scrupulously  cleaned.    Clean  all
      glassware as soon as  possible after use by treating with chromate cleaning
      solution.   This  should  be  followed by detergent washing  in hot  water.
      Rinse with tap water  and distilled water and drain dry;  glassware which is
      not volumetric  should, in addition, be heated  in a muffle  furnace at 400ฐC
      for 15  to 30 min.   (Volumetric  ware  should  not be  heated in  a  muffle

                                   9020B  - 1                       Revision 2
                                                                  September 1994

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      furnace.)  Glassware should  be  sealed  and  stored in a clean environment
      after drying  and  cooling to prevent  any accumulation of  dust  or other
      contaminants.

             3.1.2    The use of high-purity reagents and gases helps to minimize
      interference problems.

      3.2    Purity of the activated carbon must be verified before use.  Only
carbon samples that register less  than  1,000 ng  CV/40 mg should be used.  The
stock of  activated carbon should  be  stored in  its  granular form in  a glass
container with a Teflon seal.  Exposure to the air must  be minimized, especially
during and after milling  and  sieving the activated  carbon.  No more than a 2-wk
supply should  be prepared  in advance.   Protect  carbon at all  times  from all
sources of halogenated organic vapors.  Store prepared  carbon  and packed columns
in glass containers with Teflon seals.

      3.3    Particulate matter will prevent the passage of the sample through
the adsorption  column.   Particulates  must, therefore, be  eliminated  from the
sample.  This  must  be  done as gently as possible,  with the least possible sample
manipulation,   in order to  minimize the loss of  volatiles.   It  should  also be
noted that the  measured TOX will be  biased by the exclusion of  TOX from compounds
adsorbed onto  the particulates.  The following  techniques may be used to remove
particulates;  however, data users  must  be  informed of the techniques  used and
their possible  effects on  the  data.   These techniques are listed  in  order of
preference:

             3.3.1    Allow the particulates  to settle in the sample  container
      and decant the supernatant liquid into the adsorption system.

             3.3.2    Centrifuge sample and decant  the supernatant liquid into
      the adsorption system.

             3.3.3    Measure Purgeable Organic Hal ides (POX)  of sample (see SW-
      846 Method 9021) and  Non-Purgeable Organic  Hal ides  (NPOX, that is, TOX of
      sample that  has been  purged of  volatiles)  separately,  where the  NPOX
      sample is centrifuged or filtered.

4.0   APPARATUS AND MATERIALS

      4.1    Adsorption system (a  schematic diagram of  the adsorption system is
shown in Figure 1):

             4.1.1    Adsorption module:  Pressurized  sample and nitrate-wash
      reservoirs.

             4.1.2    Adsorption columns:   Pyrex, 5-cm-long x 6-mm-O.D.  x
      2-mm-I.D.

             4.1.3    Granular  activated  carbon (GAC):  Filtrasorb-400,  Calgon-
      APC or equivalent,  ground or milled, and screened  to a 100/200 mesh range.
      Upon combustion  of  40 mg  of GAC, the apparent halide background  should be
      1,000 ng Cl" equivalent or less.
                                  9020B  - 2                       Revision 2
                                                                  September 1994

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              4.1.4    Cerafelt  (available  from Johns-Manville) or  equivalent:
      Form this material  into plugs to fit the  adsorption module  and  to  hold
      40 mg of GAC  in the adsorption columns.

              CAUTION: Do not touch this material with your fingers. Oily residue
              will contaminate carbon.

              4.1.5    Column holders.

              4.1.6    Class A volumetric flasks:  100-mL and 50-mL.

      4.2     Analytical  system:

              4.2.1    Microcoulometric-titration   system:      Containing   the
      following components  (a  flowchart of the  analytical  system is  shown in
      Figure  2):

                      4.2.1.1    Boat sampler:  Muffled at 800ฐC for at least 2-
              4 min  and cleaned  of any residue  by vacuuming  after  each run.

                      4.2.1.2    Pyrolysis  furnace.

                      4.2.1.3    Microcoulometer with integrator.

                      4.2.1.4    Titration  cell.

              4.2.2    Recording  device.

5.0   REAGENTS

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

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

      5.3     Sodium sulfite  (0.1  M), Na2S03:  Dissolve  12.6  g ACS  reagent grade
Na2S03 in  reagent  water  and  dilute to  1  L.

      5.4     Concentrated nitric acid (HN03).

      5.5     Nitrate-wash solution  (5,000 mg N03"/L), KN03:  Prepare a nitrate-
wash  solution by  transferring approximately  8.2 g of potassium nitrate  (KN03)
into  a  1-liter  Class A  volumetric  flask and diluting  to  volume  with reagent
water.

      5.6     Carbon dioxide  (C02):  Gas, 99.9% purity.

      5.7     Oxygen (02):  99.9%  purity.


                                   9020B  -  3                       Revision  2
                                                                  September 1994

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      5.8    Nitrogen  (N2):  Prepurified.

      5.9    Acetic  acid  in water (70%), C2H402:   Dilute 7 volumes of glacial
acetic acid with 3 volumes  of reagent water.

      5.10   Trichlorophenol solution, stock (1 /xL = 10 fj,g CV):  Prepare a stock
solution by accurately  weighing accurately 1.856 g  of trichlorophenol into a 100-
mL Class A volumetric  flask.  Dilute to volume with methanol.

      5.11   Trichlorophenol solution, calibration (1  juL = 500 ng Cl"), C6H3C130:
Dilute 5 ml of the trichlorophenol stock solution  to  100 ml with methanol.

      5.12   Trichlorophenol standard, instrument calibration:   First, nitrate-
wash a single column packed with  40  mg  of activated carbon, as instructed for
sample analysis,  and  then  inject the  column  with 10  /zL  of  the calibration
solution.

      5.13   Trichlorophenol standard, adsorption  efficiency (100 M9 Cl'/liter):
Prepare an adsorption-efficiency standard by injecting 10 juL of stock solution
into 1 liter of reagent water.

      5.14   Blank  standard:   The methanol used to  prepare  the calibration
standard should be used as  the blank standard.

6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1    All samples must be collected using  a sampling  plan that addresses
the considerations discussed in Chapter Nine.

      6.2    All samples should be collected  in bottles with Teflon  septa (e.g..
Pierce #12722  or equivalent)  and be protected  from  light.   If  this  is  not
possible, use amber glass 250-mL bottles  fitted with Teflon-lined caps.  Foil may
be substituted  for  Teflon  if  the sample is not  corrosive.   Samples  must  be
preserved  by acidification to  pH  <2 with  sulfuric acid,  stored  at 4ฐC,  and
protected against loss of volatiles by eliminating headspace in the container.
Samples should be analyzed  within 28 days.  The  container  must be washed and
muffled at 400"C before use, to minimize contamination.

      6.3    All glassware  must be dried  prior  to use according to the method
discussed in Sec. 3.1.1.

7.0   PROCEDURE

      7.1    Sample preparation:

             7.1.1   Special  care should  be taken in handling  the  sample  in
      order to minimize the loss  of volatile  organohalides.   The adsorption
      procedure should be performed simultaneously on  duplicates.

             7.1.2   Reduce residual chlorine by  adding sulfite  (5  mg sodium
      sulfite crystals  per  liter  of  sample).  Sulfite  should  be  added at the
      time  of   sampling  if  the   analysis   is  meant to  determine  the  TOX
      concentration at the time of sampling.  It should be recognized that TOX


                                   9020B -  4                       Revision 2
                                                                  September 1994

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may  increase  on  storage  of the sample.   Samples should be stored at 4ฐC
without headspace.

7.2    Calibration:

       7.2.1    Check the  adsorption  efficiency of  each  newly prepared
batch of carbon by analyzing 100 ml of the adsorption  efficiency standard,
in  duplicate, along  with  duplicates of the  blank  standard.   The net
recovery should  be within  10%  of the standard  value.

       7.2.2    Nitrate-wash  blanks  (method  blanks):     Establish  the
repeatability of the method background each day by first  analyzing several
nitrate-wash  blanks.   Monitor this background  by  spacing nitrate-wash
blanks between each group  of ten pyrolysis determinations.  The nitrate-
wash  blank values  are  obtained on  single columns  packed with40mgof
activated  carbon.   Wash  with the  nitrate  solution, as  instructed for
sample analysis, and then  pyrolyze the carbon.

       7.2.3    Pyrolyze duplicate instrument-calibration standards and the
blank  standard  each  day  before  beginning  sample   analysis.   The net
response  to  the  calibration   standard  should  be  within  10%  of  the
calibration-standard value.  Repeat analysis of the instrument-calibration
standard  after each  group of  ten  pyrolysis  determinations  and  before
resuming  sample  analysis,  and  after  cleaning  or  reconditioning  the
titration cell or pyrolysis system.

7.3    Adsorption procedure:

       7.3.1    Connect  two columns in series, each  containing  40 mg of
100/200-mesh activated carbon.

       7.3.2    Fill  the sample reservoir  and pass  a metered amount of
sample through the activated-carbon columns at a rate of approximately
3 mL/min.

       NOTE:  100 ml of sample  is the preferred volume for concentrations
       of TOX between 5 and 500 jug/L, 50 ml for 501 to 1000 /ug/L, and 25
       ml for 1001 to 2000 M9/L-  If the anticipated TOX is greater than
       2000 M9/U  dilute  the sample so  that 100 ml will contain between
       1 and  50  p.g TOX.

       7.3.3    Wash  the columns-in-series  with  2 mL of  the 5,000-mg/L
nitrate solution at a  rate  of approximately 2 mL/min to displace inorganic
chloride ions.

7.4    Pyrolysis procedure:

       7.4.1    The  contents  of each column  are pyrolyzed  separately.
After being  rinsed with  the  nitrate  solution,   the columns should be
protected from  the  atmosphere  and other sources  of  contamination until
ready for further analysis.
                             9020B  -  5                       Revision 2
                                                            September 1994

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             7.4.2    Pyrolysis of the sample is accomplished in two stages.  The
      volatile  components  are pyrolyzed  in  a  C02-rich  atmosphere  at  a  low
      temperature to ensure the  conversion  of brominated trihalomethanes to a
      titratable species.  The less  volatile components  are then pyrolyzed at a
      high temperature in an 02-rich atmosphere.

             7.4.3    Transfer the contents of each column to the quartz boat for
      individual analysis.

             7.4.4    Adjust gas  flow according to manufacturer's  directions.

             7.4.5    Position the sample for 2  min in the 200ฐC  zone  of the
      pyrolysis tube.

             7.4.6    After 2  min, advance the boat  into  the 800ฐC zone (center)
      of the pyrolysis furnace.  This  second and final  stage  of pyrolysis may
      require from 6 to 10 min to complete.

      7.5    Detection:  The effluent gases  are directly analyzed in the micro-
coulometric-titration cell. Carefully follow manual  instructions for optimizing
cell performance.

      7.6  '  Breakthrough:   The  unpredictable nature  of the  background bias
makes  it especially  difficult  to  recognize the  extent  of   breakthrough  of
organohalides from one column  to  another.  All second-column measurements for a
properly  operating  system should  not exceed  10%  of  the  two-column  total
measurement.   If the 10% figure is  exceeded,  one  of three events could have
happened:   (1)  the  first  column was overloaded and  a  legitimate measure  of
breakthrough was obtained,  in  which  case  taking  a  smaller  sample  may  be
necessary;  (2)  channeling  or  some  other  failure  occurred,  in which case  the
sample may need to be rerun; or (3)  a high random bias occurred, and the result
should be rejected  and the sample  rerun.   Because  it may not  be  possible  to
determine which event occurred, a  sample analysis should be repeated  often enough
to gain confidence in results. As a  general  rule, any analysis that is rejected
should be repeated whenever a sample is available.   In the event that repeated
analyses show that the  second column consistently  exceeds the 10% figure and the
total is too low  for the first column  to  be saturated  and the  inorganic Cl  is
less than 20,000  times the organic  chlorine value, then  the result  should  be
reported, but the data user should be informed of the problem.   If the  second-
column measurement is  equal to or less than the  nitrate-wash  blank value,  the
second-column value should be disregarded.
                                   9020B  -  6                       Revision 2
                                                                  September 1994

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      7.7     Calculations:  TOX as CV is calculated using the following formula:

           (C, - C3) + (C2 -  C3)
          	 =  M9A Total Organic  Halide
                   V

      where:

              C, = jx9 CT on the first column in series;

              C2 = jug Cl" on the second column  in series;

              C3 = predetermined,  daily, average, method-blank value
                    (nitrate-wash  blank for  a 40-mg carbon  column);  and

               V = the  sample  volume  in liters.

8.0   QUALITY CONTROL

      8.1     Refer to Chapter  One  for specific  quality  control guidelines.

      8.2     This method requires  that all  samples be run  in duplicate.

      8.3     Employ  a minimum  of  two blanks to establish the repeatability of
the  method background,   and  monitor  the  background  by  spacing  method  blanks
between each group of eight analytical determinations.

      8.4     After calibration, verify it with  an independently prepared check
standard.

      8.5     Run matrix  spike between every 10  samples and  bring it  through the
entire sample preparation and analytical process.

9.0   METHOD PERFORMANCE

      9.1     Under conditions of duplicate analysis, the method detection limit
is 10 M9/L.

      9.2     Analyses  of distilled  water,  uncontaminated ground  water,  and
ground  water  from  RCRA waste  management  facilities   spiked  with  volatile
chlorinated  organics  generally  gave  recoveries  between 75-100% over  the
concentration range  10-500 ng/L.   Relative standard  deviations  were generally
20% at concentrations greater  than 25 M9/L-  These data are shown in Tables 1
and 2.

10.0  REFERENCES

1.    Gaskill, A.,  Compilation and Evaluation of RCRA Method Performance Data,
Work Assignment No. 2,  EPA Contract No. 68-01-7075,  September 1986.
                                   9020B  -  7                       Revision 2
                                                                  September 1994

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2.    Stevens, A.A.,  R.C. Dressman, R.K. Sorrell,  and H.J. Brass, Organic Halogen
Measurements: Current Uses and Future  Prospects, Journal of  the  American  Water
Works Association, pp. 146-154, April  1985.

3.    Tate, C., B.  Chow, et al., EPA Method Study 32, Method 450.1, Total Organic
Hal ides (TOX), EPA/600/S4-85/080, NTIS: PB 86  136538/AS.
                                   9020B - 8                       Revision  2
                                                                   September 1994

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                       TABLE  1.  METHOD PERFORMANCE DATA8
Spiked
Compound
Bromobenzene
Bromodi chl oromethane
Bromoform
Bromoform
Bromoform
Bromoform
Bromoform
Chloroform
Chloroform
Chloroform
Chloroform
Chloroform
D1 bromodi chl oromethane
D1 bromodi chl oromethane
Tetrachl oroethyl ene
Tetrachl oroethyl ene
Tetrachl oroethyl ene
trans -Di chl oroethyl ene
trans-Di chl oroethyl ene
trans-Dichl oroethyl ene
Matrixb
D.W.
D.W
D.W.
D.W.
G.W.
G.W.
G.W.
D.W.
D.W.
G.W.
G.W.
G.W.
D.W.
D.W.
G.W.
G.W.
G.W.
G.W.
G.W.
G.W.
TOX
Concentration
(M9/L)
443
160
160
238
10
31
100
98
112
10
30
100
155
374
10
30
101
10
30
98
Percent
Recovery
95
98
110
100
140
93
120
89
94
79
76
81
86
73
79
75
78
84
63
60
"Results from Reference 2.

bG.W.  = Ground Water.
 D.W.  = Distilled Water.
                                   9020B - 9
Revision 2
September 1994

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                       TABLE 2. METHOD PERFORMANCE DATA3
Sample
Matrix

Unspiked
TOX Levels
(M9/L)
Spike
Level

Percent
Recoveries

Ground Water              68, 69                  100                  98, 99
Ground Water               5, 12                  100                 110, 110
Ground Water               5, 10                  100                  95, 105
Ground Water              54, 37                  100                 111, 106
Ground Water              17, 15                  100                  98, 89
Ground Water              11, 21                  100                  97, 89
aResults from Reference 3.
                                  9020B  -  10                       Revision 2
                                                                   September 1994

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Fig. 1. Schematic Diagram of Adsorption  System
  Sample
  Reservoir
  (1  of 4)

Nitrate Wash
Reservoir
GAC Column 1
GAC Column 2
                  9020B - 11
Revision 2
September 1994

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Fig. 2. Flowchart of Analytical System
                Sparging
                Device


Titration
Cell


Pyrolysis
Furnace
                                Boat
                                Inlet


Hlcrocoulometer
with Integrator


Strip Chart
Recorder
                                                     Adsorption
                                                     Module
                  9020B - 12
Revision 2
September 1994

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r
        START
          METHOD  9020B

TOTAL  ORGANIC HALIDES  (TOX)
1
7.1.1 Take special
care in handl ing
•ample to minimize
volati le loss
1
7.1.2 Add sulfite
to reduce residual
chlorine; store at
4 C without
headspace
1
7.2.1 Check
absorption
efficiency for each
batch of carbon
1
7.2.2 Analyze
nitrate- wash blanks
to es tabl ish
background
1
7.2.3 Pyrolyze
dupl ica te
ins t rument
calibration and
blank standards
each day

7.3.1 Connect in
series two columns
containing
activated carbon

•+

7.3.2 Till sample
sample through
activated carbon
co lumns
1
7.3.3 Hash columns
with ni t ra te
solution

7.4.1 Protect
columns from
contamina tion
,,
7.4.2 Pyrolyze
volatile components
in C02-rich
atmosphere at low
tempera ture
1
7.4.2 Pyrolyze less
at high temperature
in 02-rich
atmosphere

7.4.3 Transfer
contents of each
co lumn to quar tz
boat for analysis
                                                   7.4.4 Adjust  gas
                                                        flow
                                                    7.4.5 Position
                                                    sample for  2
                                                   minutes in 200 C
                                                   zone of pyrolysis
                                                        tube
                                                  7.4.6 Advance  boat
                                                    into 800 C zone
                                                     7 . 5 Analyze
                                                   effluent gases in
                                                   microcoulometric-
                                                    titration cell
                                                                               76 Is
                                                                             2nd column
                                                                            measurement = \. No
                                                                           or < nitrate wash
                                                                               blank?
            7.6 Is 2nd
              column
         measurement >10%
            of 2 column
              total?
7,7  Calculate TOX
     as Cl-
                                                                             7.6 Disregard
                                                                              d-column valu
          7.6  Reject and
              repeat
                                                 9020B  -  13
                                                  Revision 2
                                                  September 1994

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                                  METHOD  9021

                        PURGEABLE  ORGANIC HALIDES  (POX)
1.0  SCOPE AND APPLICATION

      1.1    Method  9021  determines  organically  bound  halides  (chloride,
bromide, and iodide) purged  from a sample of drinking water  or ground water.
They are  reported as chloride.   This method  is a quick  screening procedure
requiring about  10  minutes.   The  method  uses  a sparging  device,  a pyrolysis
furnace, and a microcoulometric-titration detector.

      1.2    Method 9021 detects purgeable organically bound chlorine, bromine,
and  iodine.   Fluorine  containing  species  are  not determined  by  this  method.
Method 9021 measures POX concentrations ranging from 5 to 1,000 M9/L.

      1.3    Method 9021 is restricted to use by, or under the supervision of,
analysts experienced in the operation  of a pyrolysis/microcoulometer and in the
interpretation of the results.

2.0  SUMMARY OF METHOD

      2.1    A sample of water, protected against the loss of volatiles by the
elimination of headspace in the sampling container, is transferred to a purging
vessel.  The volatile organic halides  are  purged  into a pyrolysis furnace using
a stream of C02 and the hydrogen  halide  (HX) pyrolysis  product is trapped and
titrated electrolytically using a microcoulometric detector.

3.0  INTERFERENCES

      3.1    Contaminants,  reagents,  glassware,  and  other  sample  processing
hardware may  cause  interferences.    Method  blanks must  be routinely  run to
demonstrate freedom from interferences under the conditions of the analysis.

             3.1.1   Glassware must be scrupulously clean.   Clean all glassware
      as soon as  possible after  use by treating with chromate cleaning solution.
      This should be followed by detergent washing in hot water.  Rinse with tap
      water  and  reagent  water and  dry  at  105ฐC for  1  hour  or  until  dry.
      Glassware which  is  not volumetric  should,  in  addition, be heated  in a
      muffle furnace at  300ฐC  for 15 to  30 minutes (Class A volumetric  ware
      should not be heated  in  a  muffle furnace).   Glassware  should be sealed and
      stored in  a clean environment  after  drying and cooling  to  prevent any
      accumulation of dust or other contaminants.

             3.1.2   Use high purity reagents and gases to minimize interference
      problems.

             3.1.3   Avoid using  non-PTFE  (polytetrafluoroethylene)  plastic
      tubing,  non-TFE  thread  sealants,   or  flow  controllers  with  rubber
      components in the purge gas stream.
                                   9021 - 1                       Revision 0
                                                                  July 1992

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      3.2    Samples  can be  contaminated  by  diffusion  of  volatile  organics
(methylene chloride) through  the septum seal into the  sample during shipment and
especially during storage.  A trip blank prepared from water and carried through
the sampling and handling protocol serves as a check on such contamination.  A
trip blank should be run with each analytical batch.

      3.3    Contamination by carry-over occurs  whenever  high level  and  low
level samples are sequentially analyzed.  To reduce carryover,  the purging device
and sample syringe must be  rinsed  with water  between  sample analyses.  Whenever
an unusually concentrated  sample  is encountered, it should  be  followed  by an
analysis of water to check for cross contamination.  For  samples containing large
amounts of water-soluble materials,  suspended solids, high boiling compounds or
high organohalide levels, wash out the purging device  with a detergent solution,
rinse it with water, and then dry it in a 105ฐC oven between analyses.

      3.4    All operations should be carried out in an area where halogenated
solvents, such as methylene chloride, are not being used.

      3.5    Residual  free chlorine interferes in the method.   Free chlorine
must be destroyed by adding sodium sulfite when the sample is collected.

4.0  APPARATUS AND MATERIALS

      4.1    Sampling  equipment (for discrete sampling)

             4.1.1    Vial  - 25-mL capacity or larger, equipped with a screw-cap
      with hole in center (Pierce #13075 or equivalent).

             4.1.2    Septum   -   Teflon  lined   silicone   (Pierce   #12722   or
      equivalent).  Detergent wash,  rinse with tap and reagent water, and dry at
      105ฐC for 1 hour before use.

      4.2    Analytical  system

             4.2.1    Microcoulometric-titration system containing the following
      components (a schematic diagram of the microcoulometric-titration system
      is shown in Figure 1).

                      4.2.1.1    Purging device.

                      4.2.1.2   Pyrolysis  furnace.

                      4.2.1.3   Titration  cell.

             4.2.2    Strip  chart  recorder  (optional)   -  The  recorder  is
      recommended to make  sure  the  peak is  down  to  baselines  before stopping
      integration.

             4.2.3    Microsyringes  - 10-juL and  25-^L with 0.006 in i.d. needle
      (Hamilton 702N or equivalent).

             4.2.4    Syringe valve  - 2  way,  with Luer  ends.
                                   9021 - 2                       Revision 0
                                                                  July 1992

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5.0  REAGENTS

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

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

      5.3    Sodium  sulfide, Na2S.  Granular, anhydrous.

      5.4    Acetic  acid  in  water  (70%), CH3COOH.  Dilute 7 volumes of glacial
acetic acid with 3 volumes of water.

      5.5    Sodium  chloride calibration  standard (1  /itg  Cl'/ML).   Dissolve
1.648 g NaCl in water and dilute to 1 liter.

      5.6    Carbon dioxide.

      5.7    Methanol,  CH3OH.  Store away from other solvents.

      5.8    Chloroform,  CHC13.

      5.9    Chloroform (stock) solution (1 /xL =  11.2 Mg of CHC1,  or  10 M9 Cl").
Prepare a stock solution by delivering accurately 760 ML  (1120  mg) of chloroform
into  a  100-mL  Class A volumetric  flask  containing  approximately  90 mL of
methanol .  Dilute to volume with methanol (10,000 mg of chlorine/L).

      5.10   Chloroform (calibration) solution (1 pi = 0.1 jug Cl").  Dilute  1 ml
of the chloroform stock  solution to 100 ml with methanol  (100 mg of chlorine/L).
      5.11   Chloroform  Quality  Control  (QC)  reference  sample  (100
Prepare an aqueous standard  by  injecting  100  nl of the chloroform calibration
standard (100 mg of C1"/L)  into  a  Class A  volumetric flask containing 100 ml of
water.  Mix and store  in a bottle with zero headspace.   Analyze within two hours
after preparation.

6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

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

      6.2    All  samples  should  be  collected  in bottles  with  Teflon  lined
silicone septa (e.g..  Pierce #12722 or equivalent)  and  be protected from light.
If this is  not  possible, use amber glass 250-mL bottles  fitted with Teflon lined
caps.

      6.3    All glassware must be cleaned prior to use  according to the process
described in Step 3.1.1.
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                                                                  July 1992

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      6.4    Special care  should  be taken in handling the  sample  in  order to
minimize the  loss of  volatile  organohalides.   This is  accomplished  through
elimination of headspace and by minimizing the number of transfers.

      6.5    Reduce  residual  chlorine,  if  present,  by adding  sodium  sulfite
(5 mg of sodium sulfite crystals per liter of sample). Sodium sulfite should be
added to empty sample bottles at the time of sampling.  Shake vigorously for 1
minute after bottle  has been  filled with  sample  and  properly  sealed.   Samples
should be stored at 4ฐC without headspace.  POX may increase during storage of
the sample.

      6.6    All samples must be analyzed within 14 days of collection.

7.0 PROCEDURE

      7.1    Calibration.

             7.1.1   Assembl e the spargi rig/pyrolysi s/mi crocoul ometri c-ti trati on
      apparatus  shown   in   Figure  1  in  accordance   with  the  manufacturer's
      specifications.   Typically  a  C02  flow  of  150  mi/min  and a  sparger
      temperature of 45 ฑ 5ฐC  are employed.  The pyrolysis  furnace should be set
      at 800 + 10ฐC.  Attach the titration cell to the pyrolysis tube outlet and
      fill   with electrolyte  (70% acetic  acid).   Flow  rate  and  temperature
      changes will affect the compounds that are purged and change the percent
      recovery of marginal  compounds.  Therefore, these parameters should not be
      varied.  Adjust gas flow rate according to manufacturer's directions.

             7.1.2   Turn   on the  instrument  and  allow  the  gas  flow  and
      temperatures to stabilize.  When the background current of the titration
      cell  has stabilized the instrument is ready for use.

             7.1.3   Calibrate  the microcoulometric-titration  system  for CT
      equivalents  by injecting various  amounts (1  to  80  pi)  of  the sodium
      chloride  calibration  standard  directly  into  the   titration  cell  and
      integrating the response using the POX integration mode.  If desired, the
      analog output  of the titration cell  can  be  displayed on a  strip chart
      recorder.  The range  of sodium chloride  amounts  should cover the range of
      expected  sample  concentrations  and  should always be less than 80  /ug of
      CT.   The  integrated response should read within 2% or 0.05 jug of the
      quantity  injected (whichever  is larger)  over the  range  1-80  ng CT.   If
      this calibration requirement is not met, then the instrument sensitivity
      parameters   should   be   adjusted  according   to   the   manufacturer's
      specifications to achieve an accurate response.

             7.1.4   Check the performance of the analytical  system daily by
      analyzing three  5-mL aliquots of  a  freshly prepared  100  jug/L chloroform
      check standard.  The mean of these three analyses should be between 0.4-
      0.55 /xg of CT  and the percent relative standard deviation  should  be 5% or
      less.   If these  criteria are not  met,  the system should be checked as
      described in the instrument maintenance manual in order  to  isolate the
      problem.
                                   9021 - 4                       Revision 0
                                                                  July 1992

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NOTE:   Low  chloroform  recovery  can  often  be traced to a vitrified inlet
        tube.  The tube should be checked regularly  and the analyst should
        be able to determine,  based on chloroform recoveries,  when the tube
        should be  replaced.

        7.1.5    Determine an  instrument blank daily by running an analysis
with the purge vessel empty.  The instrument blank should be 0.00 ฑ 0.05
Mg  of Cl".  Analyze a  calibration  blank sample daily.   The calibration
blank should be within 0.02 jug  of Cl" of the reagent blank.

7.2  Sample analysis

        7.2.1    Select  a  chloroform  spike concentration representative of
the expected levels in  the samples.   Using the chloroform stock solution,
prepare  a  spiking  solution   in  methanol   which  is  500  times  more
concentrated than  the  selected  spike concentration.   Add  10 /nL  of the
spiking solution to 5-mL  aliquots of the samples chosen for spiking (refer
to Section 8.0,  Quality Control, for guidance in selecting the appropriate
number of samples to be  spiked).

        7.2.2    Allow  sample  to come  to  ambient  temperature prior  to
drawing it  into the syringe.   Remove  the  plunger from a 5-mL  or 10-mL
syringe and  attach a closed  syringe valve.  If maximum  sensitivity  is
desired and the sample does not foam excessively, a 10-mL sample aliquot
may be analyzed.  Otherwise 5-mL aliquots should be used.  Open the sample
bottle (or standard) 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 mL.   Since this process  of  taking  an
aliquot destroys  the  validity  of  the  sample  for future analysis,  the
analyst should  fill a second syringe at this  time to  protect  against
possible loss of data (e.g., accidental spill),  or for duplicate analysis.

        7.2.3    Attach  the syringe valve assembly to the syringe valve on
the purging device.  Place the pyrolysis/microcoulometer system in the POX
integration mode to activate the integration system.  Immediately open the
syringe valves and  inject the sample into the purging chamber.

        7.2.4    Close both valves and purge  the  sample for 10 minutes.

        7.2.5    After integration is complete, open the syringe valves and
withdraw the purged sample.   Flush the syringe  and  purging device  with
water prior to analyzing other  samples.

        7.2.6    If the integrated response exceeds the working range of the
instrument, prepare a  dilution of  the sample  from  the aliquot  in  the
second syringe with water and reanalyze.  The water  must meet the criteria
of Step 7.1.5.   It may be necessary to heat and purge dilution waters.

7.3  Pyrolysis procedure

        7.3.1    Pyrolysis of the purged organic component of  the sample is
accomplished by pyrolyzing in a C02-rich atmosphere at a low temperature


                             9021 - 5                       Revision 0
                                                            July 1992

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      to ensure the  conversion  of brominated trihalomethanes to  a titratable
      species.

      7.4    Directly  analyze  the  effluent  gases  in  the  microcoulometric-
titration cell.  Carefully follow  instrument manual instructions for optimizing
cell performance.

      7.5    Calculations - POX  as Cl"  is calculated using the following formula:
         JL_  x 1000 = ng/l Purgeable Organic Halide
          V
      where:

             Qs = Quantity of POX as ^9 of Cl" in the sample aliquot.
             V  = Volume of sample aliquot in mL.

8.0  QUALITY CONTROL

      8.1    All quality  control  data should be maintained  and  available for
easy reference or inspection for 3 years.   This method is restricted to use by
or under supervision of experienced  analysts.  Refer to the appropriate section
of Chapter One for additional quality control guidelines.

      8.2    Analyze  a minimum of one  reagent  blank every 20 samples  or per
analytical batch, whichever is more frequent, to determine if contamination or
any memory effects are occurring.

      8.3    In  addition  to  the  performance check  mentioned  in  Step  7.1.4,
verify calibration with an independently prepared chloroform QC reference sample
every 15 samples.

      8.4    Analyze  matrix spiked  samples for  every 10  samples  or analytical
batch, whichever is  more  frequent.   The spiked  sample is  carried  through the
whole sample preparation process and analytical  process.

      8.5    Analyze  all samples in replicate.

9.0  METHOD PERFORMANCE

      9.1    Under  conditions of duplicate  analysis, the reliable  limit  of
detection is 5 jug/L.

      9.2    Analyses  of distilled  water,   uncontaminated ground water,  and
ground  water  from   RCRA  waste  management   facilities   spiked  with  volatile
chlorinated organics generally give recoveries of 44-128%  over the concentration
range of 29-4500 p.g/1.  Relative standard deviations are generally less than 20%
at concentrations greater than 25 ng/l.  These  data  are  shown  in  Tables 1 and
2.
                                   9021 - 6                       Revision 0
                                                                  July 1992

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10.0  REFERENCES

1.    Takahashi,  Y.;  Moore, R.T.;  Joyce,  R.J.  "Measurement  of  Total Organic
      Hal ides  (TOX) and  Purgeable  Organic  Hal ides (POX)  in Water Using Carbon
      Adsorption and Microcoulometric Determination";  Proceedings from Division
      of Environmental Chemistry, American Chemical Society Meeting,  March 23-
      28, 1980.

2.    Methods  for Chemical  Analysis  of  Water and Wastes;  U.S.  Environmental
      Protection  Agency.   Office of  Research and Development.   Environmental
      Monitoring and Support Laboratory.  ORD Publication Offices of Center for
      Environmental Research Information:  Cincinnati, OH, 1983; EPA-600/4-79-
      020.

3.    Fed. Regist. 1979, 45, 69468-69473; December 3.

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

5.    "Development  and  Evaluation  of Methods  for Total  Organic  Halide  and
      Purgeable Organic  Halide  in  Wastewater"; U.S.  Environmental  Protection
      Agency.  Environmental Monitoring and Support Laboratory. Cincinnati, OH,
      1984; EPA-600/4-84-008; NTIS-PB-84-134-337.

6.    1985 Annual  Book of ASTM  Standards,  Vol.  11.01; "Standard Specification
      for Reagent Water"; ATSM:   Philadelphia, PA, 1985;  D1193-77.

7.    Dohrmann.  Rosemount Analytical Division.   Santa Clara, CA 95052-8007.

8.    Cosa Instruments.  Norwood, NJ 21942.
                                   9021 - 7                       Revision 0
                                                                  July 1992

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                                         TABLE 1.
            PRECISION AND ACCURACY DATA FOR SELECTED PURGEABLE ORGANIC HALIDES
                                       (Reference 5)
Compound
Chloroform
Trichloroethene
Tetrachloroethene
Chlorobenzene
Dose1
(M9/L
as CT)
11
10
10
8
Average
Recovery
(M9/L
as CT)
11
6
5
3
Average
Percent
Recovery
100
60
50
38
Standard
Deviation
1.4
0.7
0.8
0.6
MDL2
(M9A)
4.5
2.2
3.2
2.03
Number of
Replicates
7
7
7
7
1Ten milliliter aliquot of spiked reagent water analyzed.

2The 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.

Practical MDL probably greater (approximately 5 to  6 jug/L) due to low recovery.
                                         9021 - 8
Revision 0
July 1992

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                                         TABLE 2.
                   PRECISION AND ACCURACY DATA FOR VARIOUS WATER SAMPLES
                                       (Reference 5)
Sample1
Tap Water
POTW Sewage
Chlorinated
Hydrocarbon
Plant
Wastewater
Chlorinated
Hydrocarbon
Plant
Wastewater
Chlorinated
Hydrocarbon
Plant
Wastewater
Solid Waste2
Leachate
Industrial
Wastewater
Aniline3
Wastewater
Aniline3
Wastewater
Background
Spike
Component
—
Chloroform
Chloroform
Chloroform
Chloroform
1,1-Dichloro-
ethane
Methyl ene
chloride
Chloroform
Chloroform
Level
(M9/L
as CT)
—
68
114
32
32
171
510
15,700
15,700
Spike Level
(M9/L
as CV)
0
29
460
1,500
4,500
800
800
15,000
45,000
Average
Percent
Recovery
—
128
77
50
87
41
65
150
91
Standard
Deviation
2
5
36
32
470
17
120
58
400
Number
of
Replicates
3
3
3
3
3
3
3
3
3
1Five milliliter sample aliquots analyzed.

2Diluted 200:1 prior to analysis.   Values for this sample are in mg/L for original
 sample.

3Diluted 10:1 prior to analysis.  Values are for undiluted sample.
                                         9021 - 9
Revision 0
July 1992

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              FIGURE 1.  '
MICROCOULOMETRIC  -  TITRATION SYSTEM
         j-
         0)
         o>
         *-
         
O ซO
U t-
O O)
L. 01
O 4->
•^- C
                                   O
                                   o
                                   O
                                   in
                                   CM
                                   t
                                   o
                                   O
                                   o
                                   GO
i
                                        1
                                O)
                               XI
                                3
                                C
                                O
                                I/)
                                3
                               .O
                          C
                          O

                     o t. 'ฃ
                    •i- 4>  ซ- r
                    •^- ^- +J r
                     O T- -r-  O>
              9021 - 10
                                Revision 0
                                July  1992

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                                        METHOD 9021
                           PURGEABLE  ORGANIC HALIDES (POX)
                             START
7.1.3  Adjust
 ins t rument
  sens i vi ty
 parameters;
 reca1ibra te
                        7.1.1  Assemble
                        appara tus;  set
                      carbon dioxide  flow
                       rate;  set  sparger
                         and pyrolysis
                      furnace  temperature
                         7.1.2  Turn on
                       instrument; allow
                         gas flow  and
                        temperatures to
                       stabilize;  allow
                      background cur rent
                       of titration cell
                         to stabilize
                      7.1.2 Calibrate the
                       microcoulometric -
                       titration system
                      for Cl-  equivalents
                        7.1.4  Analyze 3
                          aliquots of
                       chloroform check
                           standard
     7.1.4  Is
    XRSD <=* 5%
    nd the  mean
    0 4-0.55 ug
       C1-?
71.4  Check system;
  reanalyze check
     s tandard
   7.1.5  Analyze
calibration  blank;
     determine
 instrument  blank
   7.2.1  Select
      spiking
concentration; add
spiking solution to
appropriate  samples
  7.2.2  Transfer
sample to  syringe;
fill  second syringe
                                         9021  -  11
                                    Revision  0
                                    July  1992

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                               METHOD  9021
                               (Continued)
                        7.2.3  Attach syringe
                          valve  assembly to
                        purging  device; place
                            pyrolysis/
                           microcoulometer
                            system in POX
                          integration mode;
                         inject  sample into
                           purging chamber
                         7  2  4  Purge for 10
                               minutes
                                I
                           7  2 5 Withdraw
                           purged sample;
                          flush syringe and
                         purging nevice with
                               ma t a r
                               water
7.2.6  Dilute sample
from second syringe
    with water
                          731 Pyrolyze
                         sample in a, carbon
                           dioxide rich
                         atmosphere at a  low
                            tempera ture
  7 4 Analyze the
effluent gasses in
        the
 microcoulomet r ic-
  titration eel 1
 7.5  Calculate POX
      as Cl-
       STOP
                               9021  - 12
                      Revision 0
                      July  1992

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                                   METHOD 9022

           TOTAL ORGANIC HALIDES (TOX) BY NEUTRON ACTIVATION ANALYSIS
1.0  SCOPE AND APPLICATION

     1.1  Method  9022  determines  Total  Organic  Halldes  (TOX)  1n aqueous
samples.  The method uses a  carbon  adsorption procedure Identical to that of
Method  9020  (TOX  analysis  using  a  m1crocoulometr1c-t1tration  detector),
Irradiation by  neutron  bombardment,  and  then  detection  using a gamma-ray
detector.

     1.2  Method  9022  detects  all   organic  halldes  containing  chlorine,
bromine, and Iodine that are  adsorbed  by granular activated carbon under the
conditions of the method.  Each halogen can be quantltated Independently.

     1.3  Method 9022 1s restricted to  use  by,  or under the supervision of,
analysts experienced  1n  the  operation  of  neutron  activation analysis and
familiar with spectral Interferences.

     1.4  This method, which may  be  used  In  place  of Method 9020, has the
advantage  of  determining  the  Individual  concentrations  of  the  halogens
chlorine, bromine, and Iodine 1n addition to TOX.


2.0  SUMMARY OF METHOD

     2.1  A sample of  water  that  has  been  protected  against  the loss of
volatlles by the elimination of headspace  1n the sampling container, and that
1s free of undlssolved sol Ids, 1s passed  through a column containing 40 mg of
granular activated carbon (GAC).  The  column  Is washed to remove any trapped
Inorganic halldes.  The GAC sample  1s exposed to thermal neutron bombardment,
creating a radioactive Isotope.   Gamma-ray  emission, which 1s unique to each
halogen,  1s  counted.    The  areas  of  the  resulting  peaks   are  directly
proportional to the concentrations  of the halogens.


3.0  INTERFERENCES

     3.1  Method  Interferences  may  be  caused  by   contaminants,   reagents,
glassware, and other  sample processing hardware.   All these materials must be
routinely demonstrated to be free   from   Interferences under the  conditions of
the  analysis by running method blanks.

          3.1.1  Glassware must be  scrupulously   cleaned.  Clean  all  glassware
     as  soon  as  possible  after   use   by  treating   with  chromatic cleaning
     solution.  This  should  be  followed by  detergent washing  1n hot  water.
     Rinse with tap water and  distilled  water and drain dry; glassware which
     1s  not volumetric should, In addition,  be   heated in a muffle furnace at
                                     9022 -  1
                                                         Revision      0
                                                         Date  September 1986

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     400*C for 15 to 30 m1n.   Volumetric ware  should  not  be  heated  1n  a muffle
     furnace.   Glassware should be  sealed  and  stored 1n a clean  environment
     after drying and cooling  to  prevent  any  accumulation of dust  or other
     contaminants.

          3.1.2  The use of h1gh-pur1ty  reagents  and gases helps  to  minimize
     Interference problems.

     3.2  Purity of the activated carbon  must  be  verified before use.  Only
carbon samples that register less than 2,000  ng Cl"/40 mg GAC should  be used.
The stock of activated carbon should be stored in Its granular form in a glass
container with  a  Teflon  seal.    Exposure  to  the  air  must be minimized,
especially during and after milling and sieving the activated carbon.   No more
than a 2-wk supply should be prepared 1n advance.  Protect carbon at all times
from all sources of  halogenated  organic  vapors.   Store prepared carbon and
packed columns in glass containers with Teflon seals.


4.0  APPARATUS AND MATERIALS

     4.1  Adsorption system  (a general  schematic  of the adsorption system is
shown 1n Figure  1):

          4.1.1  Adsorption module  with  pressurized  sample and nitrate-wash
     reservoirs.

          4.1.2  Adsorption columns:  Pyrex, 5-cm long x 6-mm O.D. x 2-mm I.D.

          4.1.3  Granular  activated carbon  (GAC):  Filtrasorb-400, Calgon-APC
     or equivalent, ground or milled,   and  screened  to a  100/200 mesh range.
     Upon combustion of 40 mg of  GAC, the apparent halide background should be
     1000 ng  Cl~ equivalent or  less.

          4.1.4   Cerafelt  (available  from Johns-Manville) or equivalent:  Form
     this material  Into plugs   using  a 2-mm-I.D.   stainless steel borer with
     ejection rod to  hold  40 mg of GAC  in the  adsorption  columns.
          CAUTION:   Do not  touch  this  material   with  your   fingers.  01ly
                residue will  contaminate carbon.

          4.1.5   Column holders.

          4.1.6   Volumetric  flasks:   100-mL,  50-mL.

     4.2   Containers suitable  for containment  of samples and standards during
 Irradiation (e.g.,  1/5-dram  polyethylene snap-cap vial).

     4.3   Sample  introduction  system  and  a  reactor  generating  a thermal
 neutron  flux  capableo?achieving  enough  halogen  activity  for counting
 purposes  (e.g.,  a reactor having a neutron  flux of 5 x 10*2 neutrons/cm^/sec).

     4.4   A gamma-ray detector and  data-handling  system capable  of  resolving
 the halogen peaks from potential interferences and background.


                                     9022 -  2
                                                          Revision       0
                                                          Date  September 1986

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                                    N2
      ซo
      o
      ro
      ro
                                                   Sample

                                                   Reservoir

                                                   (1of4)
Nitrato Wash

Reservoir
      u>
                                                GAC Column 1
050
Bf (V
c* <
(/) O
ro a
a
r*
A


CT
                                                GAG Column 2
OO
                                                    Figure 1. Schematic diagram of adsorption system.

-------
5.0  REAGENTS

     5.1  Prepur1f1ed nitrogen.

     5.2  ASTM Type II water  (ASTM  D1193):    Water  should be monitored for
Impurities.

     5.3  Nitrate-wash solution (5,000  mg  N03~/L):    Prepare a nitrate-wash
solution by transferring approximately 8.2  g of potassium nitrate (KN03) Into
a 1-1 Her volumetric flask and diluting to volume with Type II water.

     5.4  Acetone and nanograde hexane (50% v/v mixture).

     5.5  Sodium sulflte. 0.1 M (ACS reagent grade, 12.6 g/L).

     5.6  Concentrated nitric acid  (HN03):  Reagent grade.

     5.7  Standards;  25-ug Cl, 2.5-ug Br, and 2.5-ug I.

     5.8  Radioactive standards to  be used for calibrating gamma-ray detection
systems.

     5.9  Trlchlorophenol solution, stock  (1 uL =  10 ug Cl'):   Prepare a  stock
solution by  accurately weighing accurately  1.856  g of trlchlorophenol Into a
100-mL volumetric flask.  Dilute  to volume with methanol.

     5.10  Trlchlorophenol standard, adsorption efficiency  (100 ug Cl~/11ter):
Prepare an adsorption-efficiency  standard by Injecting 10 uL of stock solution
Into 1 liter of Type  II water.


6.0 SAMPLE  COLLECTION, PRESERVATION, AND HANDLING

     6.1  All  samples must  have  been  collected  using  a sampling plan that
addresses the considerations discussed 1n Chapter  Nine of this  manual.

     6.2  All  samples should be collected   1n bottles with  Teflon septa  (e.g.,
Pierce #12722 or equivalent) and  be  protected  from  light.    If this Is not
possible, use amber glass, 250-mL,  fitted with Teflon-Hned caps.  Foil may be
substituted  for Teflon  If  the   sample  1s  not   corrosive.    Samples must be
protected against  loss of volatlles by eliminating headspace 1n the  container.
Containers must be  washed  and  muffled   at  400*C  before  use, to minimize
contamination.

     6.3  All  glassware must be   dried  prior  to  use according to  the method
discussed  In Paragraph 3.1.1.
                                     9022 - 4
                                                          Revision
                                                          Date  September 1986

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7.0  PROCEDURE

     7.1  Sample preparation:

          7.1.1  Special care should be taken  1n handling the sample 1n order
     to minimize the loss of volatile organohalldes.  The adsorption procedure
     should be performed simultaneously on the front and back columns.

          7.1.2  Reduce residual chlorine by  adding  sulfHe  (1  ml of 0.1 M
     sulflte per liter of sample).    Sulflte  should  be added at the time of
     sampling 1f the analysis 1s  meant  to determine the TOX concentration at
     the time of sampling.  It  should  be recognized that TOX may Increase on
     storage  of  the  sample.    Samples  should  be  stored  at  4*C without
     headspace.

          7.1.3  Samples containing undlssolved  solids  should be centrlfuged
     and decanted.

          7.1.4  Adjust  the  pH  of  the   sample  to  approximately  2  with
     concentrated HN03 just prior to adding the sample to the reservoir.

     7.2  Calibration;

          7.2.1  Check  the adsorption efficiency  of each newly prepared batch
     of carbon by analyzing  100 ml  of the adsorption efficiency standard, 1n
     duplicate,  along with duplicates of  the  blank  standard.  The net recovery
     should be within 5% of  the standard  value.

          7.2.2  Nitrate-wash  blanks    (method   blanks):       Establish   the
     repeatability  of   the   method  background  each  day  by  first  analyzing
     several  nitrate-wash blanks.  Monitor this background by spacing nitrate-
     wash blanks between each  group  of   eight   analysis determinations.   The
     nitrate-wash blank values  are obtained   on   single  columns  packed with 40
     mg of  activated carbon.    Wash  with the nitrate solution, as  Instructed
     for  sample  analysis, and then analyze the carbon.

          7.2.3  Prior  to each  day's operation, calibrate the Instrument using
     radioactive standards   (e.g.,  cobalt-60 and   rad1um-226   sources).   The
     Instrument  1s  calibrated such  that   gamma   rays  from  the  standards  fall
     within one  channel of   their true   energies.    A   100-sec blank  1s  then
     counted to  verify  that   no  stray   radioactive sources  are  within  sensing
     distance of the detector.  As  data  are  obtained throughout the  day,  peak
     locations 1n the  standards are monitored to  ensure  there 1s no  electronic
     drift  of the Instrument.  If drift   1s  noted,  the  system must  be  recali-
     brated.

     7.3  Adsorption procedure;

          7.3.1  Connect  1n   series  two   columns,   each containing 40 mg of
      100/200-mesh activated  carbon.
                                     9022 - 5
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                                                          Date  September 1986

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     7.3.2  Fill the sample reservoir and pass a metered amount of sample
through the activated-carbon columns at a rate of approximately 3 mL/m1n.
     NOTE:  100 ml of sample  1s  the preferred volume for concentrations
            of TOX between 5 and 500  ug/L,   50  ml for 501 to 1000 ug/L,
            and 25 ml for 1,001 to 2,000 ug/L.

     7.3.3  Wash the columns-1n-series with at  least  2 ml of the 5,000-
mg/L nitrate solution at  a  rate  of  approximately 2 mL/mln to displace
Inorganic chloride ions.

7.4  Activation;

     7.4.1  After the quartz collection tube with the GAC 1s removed from
the extraction unit, the GAC  and  cerafelt  pads are extruded, using the
packing  rod,  into  a   prewashed   plastic  container  (e.g.,  1/5-dram
polyethylene snap-cap vial).    The  vial  has  been  prewashed to remove
inorganic and organic chlorine by a  soak 1n distilled water, followed by
storage 1n a glass  jar  containing  50%  v/v  acetone and hexane.  After
extrusion, the  vial  is  removed  by  forceps  and  a1r-dr1ed  to remove
residual water,  acetone,  and  hexane.    After  extrusion,  the vial 1s
snapped shut, the hinge removed with a scalpel blade, the cap heat-sealed
to the vial with an electric soldering gun reserved for that purpose, and
a single-digit number placed on the vial with a marker pen.

     7.4.2  Samples plus a similar vial  containing  25 ug Cl, 2.5 ug Br,
and 2.5 ug  I standards are then Introduced into the reactor, generally by
placing them together 1n  a  5-dram  polyethylene vial and Inserting them
into   a   pneumatic-tube   transfer    "rabbit"  for  neutron  Irradiation.
Irradiation 1s  typically  for  a  15-min  period  at  a  thermal neutron
irradiation flux of 5 x 1012  neutrons/cm2/sec.  After returning  from the
reactor,  the rabbit is allowed to  "cool" for 20 min to allow  short-lived
radioisotopes  (primarily Al) present  1n  the GAC to decay.

7.5  Detection;

     7.5.1  Analysis  is  performed   using  a  lithium-drifted   germanium
 [Ge(L1)]  gamma-ray detector with  an   amplifier and a 4096-channel memory
unit for  data  storage.   The  analyses  can be performed either  manually,
with the  operator changing  samples   and  transferring  the data  to magnetic
tape,  or  automatically,  with  both   functions  performed by an  automatic
sample changer.

     7.5.2  Analysis begins by counting  the   standard  and  samples  for  a
suitable  time  period  (e.g.,  200-sec   "live"   time  for the  standards and
samples).   The operator   records  the time Intervals between  samples and
the  "dead"  time of  each sample  1n  a  logbook  for  later use  in  calculating
halogen concentrations  in each sample.

     7.5.3  Breakthrough;   The   unpredictable  nature  of  the background
bias   makes   1t especially   difficult   to    recognize   the  extent  of
breakthrough of organohalides  from   one  column   to another.   All  second-
                                9022 - 6
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                                                     Date  September  1986

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column measurements for a properly operating system should not exceed 10%
of the two-column total measurement.   If the 10% figure is exceeded, one
of three events could have happened:  (1) the first column was overloaded
and a legitimate  measure  of  breakthrough  was  obtained, 1n which case
taking a smaller sample may  be  necessary;  (2) channeling or some other
failure occurred, 1n which case the sample may need to be rerun; or (3) a
high random bias occurred,  and  the  result  should  be rejected and the
sample rerun.  Because 1t  may  not  be possible to determine which event
occurred, a sample  analysis  should  be  repeated  often  enough to gain
confidence 1n results. As a  general  rule, any analysis that 1s rejected
should be repeated whenever a  sample  1s  available.   In the event that
repeated analyses show that  the  second  column consistently exceeds the
10% figure and the total 1s too  low for the first column to be saturated
and the Inorganic  Cl  1s  less  than  20,000  times the organic chlorine
value, then the result should  be  reported,  but the data user should be
Informed of the problem.  If the second-column measurement 1s equal to or
less than the nitrate-wash blank value, the second-column value should be
disregarded.


7.6  Calculations;

     7.6.1  Chlorine, bromine, and Iodine  can  be analyzed within a 200-
sec counting period taking place 20 to 40 m1n after Irradiation.

     7.6.2  Chlorine  1s analyzed using the 1642-KeV gamma ray produced by
37.l-m1n 38C1.  Bromine   1s  analyzed  using  the  616-KeV gamma ray from
!7.7-m1n 80Br,  and   Iodine  1s  analyzed  using  the  442-KeV  gamma ray
produced by 25-m1n W&l.
      7.6.3   The  calculation used for quantltatlon 1s:

                           counting time  std.   „  uq 1n std.
 ppm halogen

 where:
cts unk.
cts std.
counting time unk.     sample vol.
                                   x  e
                                       Xt
      cts unk.  = the Integrated area of   the  appropriate gamma-ray peak  1n
                 the unknown  with  background   subtracted   and   the total
                 multiplied by 1 +  [(%   dead  time   unknown - %  dead  time
                 std.)/200].  The latter  correction   1s usually  less  than
                 4% and corrects for pile-up  errors.

      cts std.  = the Integrated area of   the  appropriate gamma-ray peak  1n
                 the standard with background subtracted.
      counting time std.  = the  "live1
                           standard.
                         counting  time  1n seconds of  the
      counting time unk.  = the  "live"   counting  time  1n  seconds  of  the
                            unknown.
                                9022 - 7
                                                     Revision       0
                                                     Date  September 1986

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          ug 1n  std.  =  the   number of  mlcrograms   of  the   stable   element   1n
                       question in the  standard  (25 for Cl,  2.5  for Br and  I).

          sample vol.  = the volume of sample passed through the  GAC column,  In
                        ml.

          eXt  =  the  decay  correction  to  bring all   statistics  back   to
                  t = 0;  X =  0.693/ti/2,   where   tj/2  =  the   half-life   1n
                  minutes.

          t = the time Interval 1n minutes  from  the  end of  the count of  the
              standard until the end of the count  of the sample.

          7.6.4  No further calculations are  necessary  as  long as the final
     sample Is counted within 40 min after the end of  irradiation.


8.0  QUALITY CONTROL

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

     8.2  Before performing any  analyses,  the  analyst  must demonstrate  the
ability to generate acceptable accuracy  and  precision with this procedure by
analyzing appropriate quality-control check samples.

     8.3  The laboratory  must  develop  and  maintain  a  statement of method
accuracy for their  laboratory.    The  laboratory  should update the accuracy
statement regularly as  new  recovery measurements are made.

     8.4  Employ a minimum  of  one  blank  per  sample  batch to determine If
contamination 1s occurring.

     8.5  Verify calibration  with  an  Independently  prepared check standard
every 15 samples.

     8.6  Run one  spike duplicate  sample  for  every   10  samples.  A duplicate
sample  is a  sample brought  through the  whole sample preparation and analytical
process.

     8.7   It is recommended   that   the  laboratory   adopt  additional quality-
assurance practices  for use  with  this method.   The specific practices that
would be most productive will  depend upon   the needs  of the laboratory  and  the
precision of the sampling  technique.   Whenever possible,  the laboratory should
perform analysis of  standard   reference  materials and participate in  relevant
performance-evaluation studies.

     8.8   Quality  control  for the analysis  phase  is very  straightforward in as
much as the instrument is  a noncontact  analyzer.  That  1s,  only  the  radiation
emitted from the sample — not the sample  Itself  — should  touch  the  analyzer.
                                     9022 - 8
                                                          Revision
                                                          Date   September  1986

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Because contamination of the system 1s  not usually a problem (unless a sample
spills on 1t),  the  most  serious  quality-control  Issues  deal with uniform
neutron flux, counting geometry, and  spectral  Interpretation.  The amount of
radioactivity Induced 1n a sample 1s directly proportional to the neutron flux
1t 1s exposed to.  Because this  flux  can vary depending on how the sample 1s
positioned 1n relation to the reactor core during Irradiation, 1t 1s essential
that a known standard be Irradiated with  every  sample batch to act as a flux
monitor.  Care must also be taken  to ensure that the standard and all samples
associated with  the  standard  are  counted  at  the  same  distance from the
detector.
9.0  METHOD PERFORMANCE

     9.1  The following statistics are based on seven replicate analyses:
                                                      Combined   Pooled
                        Chlorine   Bromlne   Iodine   average    	
River water   7
Well water    *  (ppb)
WWTP effluent
38.2
0.16
50.7
0.30
242
0.56
17
0.076
4.7
0.038
35.2
0.033

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                            METHOD 9022

                  TOTAL ORGANIC HALIOES  (TOX)  BY

                    NEUTRON ACTIVATION ANALYSIS
7.1.1
        Take
       special
  care handling
     cample to
  minimize loss
   of volat1les
7.1.2
                       7.2,2
Analyze nitrate—wash
 blanks to establish
   repeatability of
  method background
      each day
Add culfite to
reduce residual
   chlorine
7.1.3
                          7.2.3
   Remove GAC
     quartz
collection tube
         Calibrate
       instrument
    each day using
      radioactive
       standards
 Centrifuge and
 decant camples
   with undls-
 solved solids
                          7.3.1
                                                    7.4. 1
       Extrude
       GAC and
      cerafelt
    pads into a
     preMashed
   plastic vial
                                 Connect
                                in aeries
       two  columns
        containing
        activated
         carbon
                             7.4.2  Introduce
                                    samples
  and standards
   into reactor
   for neutron
   irradiation
7.


1.3
— — ' Adjust
pH of sample
prior to adding
•ample to

reservoir


                          7.3.21
                                  Fill
                                 •ample
                          reservlor:  pass
                           •ample through
                             activated
                           carbon columns
                                                    7.5.1
                             Anaylze using
                             Ge (Li) gamma
                             ray detector
7.2.1
•c
ef f Ic
each
c
Check
Isorpt ion
lency for
batch of
•rbon
i

                          7.3.3
                                 Displace
                                Inorganic
                            chloride  ions
                               by washing
                             columns  with
                           nitrate aolut.
                                                    7.5.2
                                    To
                                   analyze.
                             count standard
                               and aamples
                             for a suitable
                              tine period
                                                      o
                       9022 - 10
                                               Revision       0
                                               Date  September 1986

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                       METHOD 9OZZ

TOTAL ORGANIC  HALIDES  (TOX) BY NEUTRON ACTIVATION ANALYSIS
                        (Continued)
           Is 2nd column
         naacurement > 1OX
            of S column
              total?
                                       OKregard
                                     second-column
                                         value
                    9022 -  11
                                             Revision       0
                                             Date  September 1986

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                                 METHOD 9030A

                   ACID-SOLUBLE AND ACID-INSOLUBLE SULFIDES
1.0   SCOPE AND APPLICATION

      1.1    The distillation procedure described in this method is designed for
the determination of sulfides in aqueous, solid waste materials, or effluents.

      1.2    This  method provides only  a semi-quantitative  determination  of
sulfide  compounds  considered "acid-insoluble"  (e.g.,  CuS and  SnS2)  in  solid
samples.  Recovery  has been shown to be 20 to 40% for CuS, one  of the most stable
and insoluble compounds, and 40 to 60% for SnS2 which is slightly more soluble.

      1.3    This  method is not  applicable to  oil or  multiphasic  samples  or
samples  not  amenable  to the distillation procedure which can  be  analyzed  by
Method 9031.

      1.4    Method 9030 is suitable for measuring  sulfide  concentrations  in
samples which contain between 0.2 and 50 mg/kg of sulfide.

      1.5    This  method is not  applicable  for distilling  reactive sulfide,
however, Method 9030 is used to quantify the concentration of sulfide from the
reactivity test.  Refer to Chapter Seven,  Step 7.3.4.1 for the determination of
reactive sulfide.

      1.6    This method measures total sulfide  which is usually defined as the
acid-soluble fraction  of a waste.  If,  however, one has previous knowledge of the
waste  and  is concerned  about both  soluble  sulfides  such  as  H.S,  and  metal
sulfides, such as CuS  and SnS_, then total sulfide  is defined  as  the combination
of both acid-soluble and acicf-insoluble fractions.   For  wastes where only metal
sulfides are suspected to be present,  only the acid-insoluble fraction needs to
be performed.

2.0  SUMMARY OF METHOD

      2.1    For acid-soluble  sulfide samples,  separation of sulfide from the
sample matrix is accomplished  by  the  addition of  sulfuric acid to the sample.
The sample is heated to 70ฐC and the  hydrogen sulfide (H2S) which is formed is
distilled under  acidic  conditions and carried by  a  nitrogen stream into zinc
acetate gas scrubbing bottles where it is precipitated  as zinc  sulfide.

      2.2    For acid-insoluble sulfide samples,  separation of sulfide from the
sample  matrix  is   accomplished  by   suspending  the  sample   in  concentrated
hydrochloric acid by vigorous agitation.  Tin(II) chloride is  present to prevent
oxidation of  sulfide  to  sulfur  by the metal  ion  (as  in copper(II)),  by the
matrix, or by dissolved oxygen in the reagents.  The prepared sample is distilled
under acidic conditions at 100ฐC under a stream of nitrogen.   Hydrogen sulfide
gas is released from the sample and collected in gas scrubbing  bottles containing
zinc(II) and a strong acetate buffer.  Zinc sulfide precipitates.
                                   9030A -  1                      Revision 1
                                                                 July 1992

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      2.3    The sulfide in the zinc sulfide precipitate is oxidized to sulfur
with a known excess amount of iodine.  Then the excess iodine is determined by
titration  with  a  standard  solution of  phenyl  arsine  oxide (PAO)  or  sodium
thiosulfate until  the  blue iodine starch  complex  disappears.   As  the  use of
standard sulfide  solutions  is not possible because  of  oxidative degradation,
quantitation is based on the PAO or sodium thiosulfate.

3.0   INTERFERENCES

      3.1    Aqueous samples must be taken with a minimum of aeration to avoid
volatilization of  sulfide  or reaction with oxygen,  which  oxidizes sulfide to
sulfur compounds that are not detected.

      3.2    Reduced  sulfur  compounds,   such  as  sulfite   and  hydrosulfite,
decompose in acid, and  may  form sulfur dioxide.  This  gas may  be carried over to
the zinc acetate  gas scrubbing bottles and subsequently react  with the iodine
solution yielding false high values.  The addition of  formaldehyde into the zinc
acetate gas scrubbing  bottles removes this interference.  Any sulfur dioxide
entering the scrubber will  form an addition compound with the  formaldehyde which
is unreactive towards the iodine in the acidified mixture.  This method shows no
sensitivity to sulfite or hydrosulfite at concentrations up  to 10 mg/kg of the
interferant.

      3.3    Interferences  for acid-insoluble  sulfides have  not  been  fully
investigated.   However, sodium  sulfite  and  sodium  thiosulfate  are  known to
interfere in the procedure  for soluble sulfides.  Sulfur  also  interferes because
it may be reduced  to sulfide by tin(II) chloride in  this procedure.

      3.4    The iodometric method suffers interference from reducing^substances
that  react with  iodine,  including  thiosulfate, sulfite,  and  various organic
compounds.

      3.5    The  insoluble  method should  not  be used for the determination of
soluble  sulfides  because  it can reduce  sulfur to  sulfide, thus  creating  a
positive interference.

4.0   APPARATUS AND MATERIALS

      4.1    Gas  evolution  apparatus  as shown  in Figure 1

             4.1.1    Three neck flask -  500-mL, 24/40  standard  taper joints.

             4.1.2    Dropping funnel -  100-mL, 24/40 outlet joint.

             4.1.3    Purge gas  inlet tube - 24/40 joint,  with coarse frit.

             4.1.4    Purge gas outlet - 24/40 joint reduced to 1/4 in. tube.

             4.1.5    Gas scrubbing bottles - 125-mL, with  1/4  in. o.d. inlet
      and outlet tubes.  Impinger tube must be fritted.

             4.1.6    Tubing -  1/4 in. o.d. Teflon  or polypropylene.  Do not use
      rubber.

                                   9030A  - 2                     Revision 1
                                                                 July 1992

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NOTE:        When  analyzing  for  acid-insoluble  sulfides,  the  distillation
             apparatus is identical to that used in the distillation procedure
             for  acid-soluble  sulfides  except  that  the  tubing  and  unions
             downstream  of   the   distillation  flask   must  be  all   Teflon,
             polypropylene or other  material resistant to   gaseous  HC1.   The
             ground glass joints should be fitted with Teflon sleeves to prevent
             seizing and to prevent gas leaks.  Pinch clamps  should also be used
             on the joints to prevent leaks.

      4.2    Hot plate stirrer.

      4.3    pH meter.

      4.4    Nitrogen regulator.

      4.5    Flowmeter.

      4.6    Top-loading balance - capable of weighing  0.1  g.

5.0   REAGENTS

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

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

      5.3    Zinc acetate  solution for sample preservation  (2N),  Zn(CH,COO)2 •
2H20.  Dissolve 220 g of zinc acetate dihydrate  in 500  mL of reagent  water.

      5.4    Sodium  hydroxide (IN),  NaOH.   Dissolve 40 g  of NaOH  in reagent
water and  dilute to 1 liter.

      5.5    Formaldehyde  (37%  solution), CH20.   This solution  is commercially
available.

      5.6    Zinc acetate  for the  scrubber

             5.6.1     For  acid-soluble  sulfides:     Zinc  acetate  solution
      (approximately  0.5M).   Dissolve about  110  g  zinc  acetate  dihydrate in
      200  ml of reagent water.  Add 1 mL  hydrochloric acid (concentrated), HC1,
      to prevent precipitation  of  zinc hydroxide.   Dilute to  1  liter.

             5.6.2     For acid-insoluble sulfides:  Zinc acetate/sodium acetate
      buffer.   Dissolve  100 g sodium acetate, NaC2H302,  and 11 g  zinc acetate
      dihydrate in 800 mL of reagent  water.   Add 1 mL concentrated hydrochloric
      acid and dilute to 1 liter.  The resulting pH  should  be 6.8.

      5.7    Acid to  acidify  the sample

                                   9030A  -  3                     Revision 1
                                                                 July 1992

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      H2S04.
             5.7.1     For acid-soluble sulfides:  Sulfuric acid (concentrated),
             5.7.2     For acid-insoluble sulfides:  Hydrochloric acid (9.8N),
      HC1.    Place  200 ml  of  reagent water  in  a  1-liter beaker.   Slowly add
      concentrated HC1 to bring the total volume to 1 liter.

      5.8    Starch solution - Use either an aqueous  solution or soluble starch
powder mixtures.  Prepare an aqueous solution as follows.  Dissolve 2 g soluble
starch and 2 g salicylic acid, C?H603, as a  preservative, in 100 ml hot reagent
water.

      5.9    Nitrogen.

      5.10   Iodine solution  (approximately 0.025N)

             5.10.1    Dissolve 25 g potassium iodide, KI, in 700 ml of reagent
      water  in  a  1-liter volumetric flask.   Add  3.2 g  iodine,  I2.   Allow to
      dissolve.   Add the  type and  amount  of  acid  specified in  Step 7.3.2.
      Dilute to 1 liter and standardize as  follows.

             5.10.2    Dissolve approximately 2  g KI in 150 ml of reagent water.
      Add exactly 20 ml of the iodine solution (Step  5.10.1) to be titrated and
      dilute to 300 ml with reagent water.

             5.10.3    Titrate with  0.025N  standardized  phenylarsine oxide or
      0.025N sodium  thiosulfate until the  amber  color  fades to yellow.   Add
      starch indicator solution.  Continue titration drop by  drop until  the blue
      color disappears.

             5.10.4    Run in replicate.

             5.10.5    Calculate the normality as  follows.

      Normality (I2)  = ml of titrant x normality of titrant
                              sample size in ml

      5.11   Sodium  sulfide nonanhydrate, Na2S  • 9H20.  For the preparation of
standard solutions to be used for calibration curves.  Standards must be prepared
at pH >  9 and  <  11.   Protect  standard from exposure to  oxygen by preparing it
without  headspace.  These standards are unstable and should be prepared daily.

      5.12   Tin(II)  chloride,  SnCl2, granular.

      5.13   Titrant.

             5.13.1    Standard  phenylarsine oxide  solution  (PAO)  (0.025N),
      C6H5AsO.   This  solution  is commercially available.

CAUTION:        PAO is toxic.
                                   9030A - 4                     Revision 1
                                                                 July 1992

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             5.13.2    Standard sodium thiosulfate solution (0.025N), Na2S20, •
      5H,0.   Dissolve 6.205 ฑ 0.005 g Na2S,0, • 5H20 in 500 ml reagent water.  Add
      9 ml IN NaOH and dilute to 1 liter.

      5.14   Sodium hydroxide  (6N),  NaOH.   Dissolve 240 g of sodium hydroxide
in 1 liter of reagent water.

      5.15   Hydrochloric acid (6N), HC1.   Place 51 mL of reagent water  in a 100
mL Class A volumetric  flask.   Slowly add  concentrated  HC1  to bring  the total
volume to 100 ml.

6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

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

      6.2    All  aqueous  samples  and effluents must  be preserved  with  zinc
acetate and sodium hydroxide.  Use four drops  of 2N zinc acetate solution per 100
mL of sample. Adjust the pH to  greater than 9 with 6N sodium hydroxide solution.
Fill the sample bottle completely and stopper with a minimum of aeration.  The
treated sample is  relatively stable  and can  be  held for up to seven  days.   If
high concentrations of sulfide  are expected to be in  the  sample, continue.adding
zinc acetate  until  all the sulfide has precipitated.  For solid samples,  fill the
surface of the  solid  with 2N  zinc  acetate until  moistened.   Samples  must be
cooled to 4ฐC and stored headspace free.

      6.3    Sample Preparation

             6.3.1     For  an   efficient   distillation,   the  mixture  in  the
      distillation flask must  be of  such  a consistency  that the motion of the
      stirring bar is  sufficient to keep the  solids  from settling.  The mixture
      must be  free of solid  objects that  could  disrupt  the  stirring  bar.
      Prepare the  sample using  one  of  the procedures  in this  section  then
      proceed with the distillation step (Section 7.0).

             6.3.2     If the sample is aqueous, shake the sample container to
      suspend any  solids,  then quickly decant  the  appropriate  volume (up to
      250 mL) of the  sample  to  a  graduated  cylinder,  weigh  the  cylinder,
      transfer to the distillation flask and reweigh  the  cylinder  to the nearest
      milligram.    Be  sure that a  representative  aliquot is  used, or  use  the
      entire sample.

             6.3.3     If the  sample  is aqueous  but  contains soft  clumps of
      solid,  it may be possible to break the clumps and homogenize the sample by
      placing the sample container on a jar mill and tumble or roll the sample
      for a few hours.   The slurry may then be aliquotted and weighed as above
      to the nearest milligram then  diluted with reagent water  up to  a total
      volume  of 250 mL  to  produce  a mixture that is completely suspended by the
      stirring bar.

             6.3.4     If the sample  is primarily aqueous, but contains a large
      proportion of solid,  the  sample may  be  roughly separated by phase and the
      amount  of each phase measured  and weighed to  the  nearest milligram into

                                   9030A -  5                      Revision  1
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      the distillation flask  in  proportion to their abundance  in  the sample.
      Reagent water  may  be  added  up  to  a total  volume of  250  ml_.   As  a
      guideline,  no  more  than  25  g dry  weight  or  50  g  of  sludge can  be
      adequately suspended in the apparatus.

             6.3.5     If the sample contains solids  which  absorb  water  and
      swell, limit the sample size  to 25 g dry weight.   Otherwise, the solids
      will restrict the fluid motion and lower the recovery.

             6.3.6     If the  sample contains  solid objects  that  cannot  be
      reduced in size by  tumbling,  the  solids must be  broken  manually.  Clay-
      like solids  should  be  cut  with a spatula or scalpel in  a crystallizing
      dish.  If the solids can be reduced to a size that they can be suspended
      by the stirring bar, the solid and liquid can be proportionately weighed.

             6.3.7     Non-porous harder objects,  for example stones or pieces
      of metal,  may be weighed and discarded.  The  percent weight of non-porous
      objects should  be  reported  and  should be   used  in the  calculation  of
      sulfide concentration  if  it  has  a  significant  effect  on the reported
      result.

7.0   PROCEDURE

      For acid-soluble sulfide samples,  go to 7.1
      For acid-insoluble sulfide samples,  go to  7.2

      7.1    Acid-Soluble Sulfide

             7.1.1     In a preliminary experiment,  determine  the  approximate
amount of sulfuric acid required to  adjust a measured amount of the  sample to pH
less than or equal to 1.   The sample size should be chosen so that  it contains
between 0.2  and 50 mg of sulfide.   Place  a known amount of  sample  or sample
slurry in a beaker.  Add reagent water until the total  volume is 200 ml.   Stir
the mixture and  determine the  pH.  Slowly add sulfuric acid until  the  pH is less
than or equal to 1.  Discard this preliminary sample.

CAUTION:     Toxic hydrogen sulfide may  be  generated from  the acidified sample.
             This  operation must be performed in  the hood and the  sample left
             in the hood until the sample has been  made alkaline  or the sulfide
             has been destroyed.  From the amount of sulfuric acid  required to
             acidify the sample  and the  mass or volume of  the sample acidified,
             calculate the amount of acid required to acidify the sample to be
             placed in the distillation flask.

             7.1.2     Prepare the gas evolution apparatus as shown in Figure 1
      in a fume hood.

                       7.1.2.1    Prepare a hot water bath at 70ฐC by filling a
             crystallizing dish  or other suitable container with  water and place
             it on a  hot plate  stirrer.   Place a  thermometer in the bath  and
             monitor the temperature to maintain the bath at 70ฐC.
                                   9030A  -  6                      Revision 1
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                 7.1.2.2    Assemble the three neck 500-mL flask, fritted
       gas inlet tube, and exhaust tube.  Use Teflon sleeves to seal the
       ground glass joints.  Place a Teflon coated stirring bar into the
       flask.
                       i
                 7.1.2.3    Place  into  each gas scrubbing bottle 10 ฑ 0.5
       mi  of the  0.5M  zinc  acetate  solution,   5.0 ฑ  0.1  ml of  37%
       formaldehyde and 100 +  5.0 ml reagent water.

                 7.1.2.4    Connect   the  gas  evolution  flask  and  gas
       scrubbing bottles  as  shown in Figure  1.   Secure all  fittings and
       joints.

       7.1.3     Carefully  place  an  accurately  weighed  sample  which
contains 0.2 to 50 mg  of sulfide into the flask.   If necessary, dilute to
approximately 200 ml with reagent water.

       7.1.4     Place the dropping  funnel onto the flask making sure its
stopcock is closed.  Add  the volume  of sulfuric  acid calculated in Step
7.1.1  plus  an additional  50 ml  into  the dropping  funnel.    The  bottom
stopcock must be closed.

       7.1.5     Attach the  nitrogen inlet  to the  top of  the  dropping
funnel gas shut-off valve.  Turn on  the nitrogen purge gas and adjust the
flow  through  the sample  flask to  25 mL/min.  The  nitrogen  in the gas
scrubbing  bottles  should bubble  at  about   five bubbles  per  second.
Nitrogen pressure  should  be  limited to approximately  10 psi  to prevent
excess stress on the glass system  and fittings.  Verify that there are no
leaks  in the  system.   Open  the nitrogen  shut-off valve leading  to the
dropping funnel.  Observe  that the  gas flow  into  the sample vessel will
stop  for  a   short  period  while  the   pressure   throughout  the  system
equalizes.    If  the gas  flow through  the sample  flask does  not  return
within a minute, check for leaks  around the  dropping funnel.   Once flow
has stabilized,  turn  on  magnetic  stirrer.   Purge system for  15 minutes
with nitrogen to remove oxygen.

       7.1.6     Heat  sample to 70ฐC.   Open dropping funnel  to a position
that  will  allow  a flow  of sulfuric  acid  of  approximately 5  mL/min.
Monitor the system  until  most  of the  sulfuric acid  within  the  dropping
funnel has entered the sample flask.  Solids which absorb water and swell
will  restrict  fluid  motion   and,  therefore,  lower  recovery  will  be
obtained.  Such samples should  be limited  to  25 g dry weight.

       7.1.7     Purge,  stir,  and maintain a temperature of  70ฐC  for a
total of 90 minutes  from start  to finish. Shut off nitrogen supply.  Turn
off heat.

       7.1.8     Proceed to Step 7.3  for the analysis of the zinc sulfide
by titration.
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7.2    Acid-Insoluble Sulfide

       7.2.1     As the concentration of HC1  during distillation must be
within a narrow range for successful distillation of H2S, the water content
must be controlled.  It is  imperative  that the fina-1 concentration of HC1
in the  distillation  flask  be about 6.5N  and that the sample  is  mostly
suspended  in  the  fluid  by the  action of the  stirring  bar.   This  is
achieved by adding 50 ml of reagent water, including water in the sample,
100 ml  of  9.8N  HC1,  and the  sample  to the distillation  flask.   Solids
which absorb water and  swell  will restrict fluid  motion  and,  therefore,
lower recovery will be obtained.  Such samples should be limited to 25 g
dry weight.  Other samples  can range from 25  to 50 g.

       7.2.2     If the  matrix  is  a dry  solid, weigh a  portion  of the
sample such that  it contains 0.2 to 50 mg of sulfide.   The  solid should be
crushed to reduce  particle size  to  1  mm or less.   Add 50 ml  of reagent
water.

       7.2.3     If the matrix is aqueous,  then a  maximum of 50 g of the
sample may be used.   No additional  water may be  added.   As none  of the
target compounds  are volatile,  drying  the sample may be preferable to
enhance the sensitivity by  concentrating the sample.  If less than  50 g of
the sample is required  to  achieve the  0.2 to 50 mg of sulfide range for
the test, then add reagent  water to a total  volume of 50 ml.

       7.2.4     If the matrix is a moist solid, the water content of the
sample must  be  determined   (Karl Fischer  titration,  loss on  drying,  or
other suitable means)  and  the water  in the sample included in the total
50 ml of water needed for the  correct  HC1 concentration.   For example, if
a 20 g  sample weight is needed  to achieve the desired sulfide level  of
0.2 to 50 mg and the sample is 50% water then 40 ml rather than 50 ml of
reagent water is  added along with the sample and 100 ml of  9.8N HC1 to the
distillation flask.

       7.2.5     Weigh the  sample  and  5  g  SnCU   into the  distillation
flask.  Use up to  50  ml  of reagent water,  as calculated  above, to rinse
any glassware.

       7.2.6     Assemble the distillation apparatus as in Figure 1. Place
100 ฑ 2.0 ml of zinc  acetate/sodium acetate buffer solution and 5.0 ฑ 0.1
ml of 37%  formaldehyde  in  each  gas scrubbing bottle.   Tighten the pinch
clamps on the distillation  flask joints.

       7.2.7     Make sure  the stopcock is closed  and then add 100 ฑ1.0
ml of 9.8N HC1 to the dropping funnel.  Connect the nitrogen line to the
top of  the funnel  and turn the  nitrogen  on  to pressurize  the dropping
funnel headspace.

       7.2.8     Set  the nitrogen flow at 25  mL/min.  The  nitrogen in the
gas scrubbing bottles should bubble  at about five  bubbles per second.
Purge the oxygen from the system for about 15 minutes.
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       7.2.9     Turn on the magnetic stirrer.   Set  the stirring bar to
spin as fast as possible.   The  fluid  should  form a vortex.   If not, the
distillation will  exhibit  poor recovery.  Add  all of  the  HCL  from the
dropping funnel to the flask.

       7.2.10    Heat the water bath to  the  boiling  point (100ฐC).   The
sample may or may  not be  boiling.   Allow  the purged  distillation to
proceed for  90 minutes at  100ฐC.   Shut  off  nitrogen supply.   Turn off
heat.

       7.2.11    Proceed to Step 7.3 for  the  analysis of the zinc sulfide
by titration.

7.3    Titration of Distillate

       7.3.1     Pipet  a   known  amount  of  standardized 0.025N  iodine
solution (See Step 5.10.5)  in a 500-mL flask, adding an amount in excess
of that needed to oxidize the sulfide.  Add enough  reagent water to bring
the volume to 100 ml.  The volume of standardized  iodine solution should
be about 65 mL for samples with 50 mg of sulfide.

       7.3.2     If the distillation  for acid-soluble  sulfide  is  being
used, add 2 ml  of 6N HC1.  If the distillation for acid-insoluble sulfides
is performed, 10 ml of 6N HC1 should be added to the iodine.

       7.3.3     Pipet both of the gas scrubbing bottle solutions to the
flask, keeping  the end  of the pipet  below  the  surface of  the iodine
solution.  If  at any  point in  transferring the  zinc  acetate solution or
rinsing the bottles,  the amber color of the iodine  disappears or fades to
yellow, more 0.025N iodine  must be  added.  This  additional amount must be
added to the amount from Step  7.3.1 for  calculations.   Record the total
volume of standardized 0.025N iodine solution used.

       7.3.4     Prepare a  rinse solution  of a known amount of standardized
0.025N iodine  solution, 1  ml of 6N HC1,  and reagent water  to rinse the
remaining white precipitate (zinc sulfide)  from  the gas  scrubbing bottles
into the flask.  There  should  be no visible  traces of precipitate after
rinsing.

       7.3.5     Rinse  any  remaining  traces  of  iodine from  the  gas
scrubbing  bottles  with reagent water, and transfer  the  rinsate  to the
flask.

       7.3.6     Titrate the solution in the flask with standard 0.025N
phenylarsine oxide or 0.025N sodium thiosulfate  solution until the amber
color fades to yellow.  Add  enough  starch  indicator  for the solution to
turn dark blue and titrate until the blue disappears.  Record the volume
of titrant used.
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             7.3.7     Calculate the concentration of sulfide using the following
      equation:
(ml I2  x  N I2)  -  (ml  titrant  x  N  titrant) x 1 2 eq.
                                               32.06 g
                                                             sulfide(mg/kg)or
        sample weight (kg) or sample volume (L)                      (rog/L)


8.0   QUALITY CONTROL

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

      8.2    A  reagent blank  should be  run  once in  twenty  analyses  or per
analytical  batch, whichever is more frequent.

      8.3    Check  standards are  prepared  from water  and a known  amount of
sodium sulfide.  A  check  standard  should  be  run with each analytical batch of
samples, or once in twenty samples.   Acceptable recovery will depend on the level
and matrix.

      8.4    A matrix spiked sample should be run for each analytical batch or
twenty samples,  whichever is more  frequent,  to determine  matrix effects.  If
recovery is low, acid-insoluble sulfides are  indicated.  A matrix spiked sample
is a sample brought  through the whole sample preparation  and analytical process.

9.0   METHOD PERFORMANCE

      9.1    Accuracy  -  Accuracy   for  this  method  was  determined by three
independent laboratories by measuring percent  recoveries  of spikes for both clean
matrices (water) and actual waste samples.  The results are summarized below.

For Acid-Soluble Sulfide

      Accuracy of titration step only
        Lab A 84-100% recovery
        Lab B 110-122% recovery
      Accuracy for entire method for clean matrices (H20)
        Lab C 94-106% recovery
      Accuracy of entire method for actual waste samples
        Lab C 77-92% recovery

      Spiking levels ranged from 0.4 to 8 mg/L

For Acid-Insoluble Sulfide

      The  percent  recovery was  not as  thoroughly studied  for  acid-insoluble
      sulfide as it was for acid-soluble sulfide.
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      Accuracy of entire method for synthetic waste samples
        Lab C 21-81% recovery

      Spiking levels ranged from 2.2 to 22 mg/kg


      9.2    Precision

For Acid-Soluble Sulfide

      Precision of titration step only
        Lab A    CV%    2.0 to 37
        Lab B    CV%    1.1 to 3.8
      Precision of entire method for clean matrices (H20)
        Lab C    CV%    3.0 to 12
      Precision of entire method for actual waste samples
        Lab C    CV%    0.86 to 45

For Acid-Insoluble Sulfide

      Precision of entire method with synthetic wastes
        Lab C    CV     1.2 to 42

      9.3    Detection Limit - The detection limit was determined by analyzing
seven replicates at 0.45 and 4.5 mg/L.  The detection limit was calculated as the
standard deviation times the student's  t-value  for  a  one-tailed test with n-1
degrees of freedom at  99% confidence level.  The detection  limit  for a clean
matrix (H20)  was found  to  be between 0.2 and 0.4 mg/L.   <

10.0  REFERENCES

1.    Test Methods for Evaluating  Solid Waste,  Physical/Chemical  Methods, 2nd
ed.; U.S.  Environmental  Protection Agency.   Office of Solid Waste and Emergency
Response.   U.S.  Government  Printing Office:  Washington,  DC, 1982, revised 1984;
SW-846.

2.    Methods for  Chemical Analysis of Water  and Wastes; U.S.  Environmental
Protection Agency.  Office of Research and Development.  Environmental Monitoring
and Support  Laboratory.   ORD Publication Offices of  Center  for Environmental
Research Information:  Cincinnati, OH,   1979; EPA-600/4-79-020.

3.    CRC Handbook of Chemistry and Physics. 66th ed.;  Weast,  R., Ed.; CRC: Boca
Raton, FL, 1985.

4.    Standard Methods for  the Examination  of  Water  and Wastewater,  16th ed.;
Greenberg, A.E.;  Trussell, R.R.;  Clesceri,  L.S.,  Eds.;  American  Water Works
Association,   Water  Pollution  Control   Federation,   American  Public  Health
Association:   Washington,  DC, 1985; Methods 427, 427A, 427B,  and 427D.

5. .   Andreae, M.O.;  Banard, W.R. Anal.  Chem. 1983,  55,  608-612.

6.    Barclay, H. Adv.  Instrum.  1980, 35(2). 59-61.


                                  9030A - 11                     Revision 1
                                                                 July 1992

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7.    Bateson, S.W.; Moody, G.J.; Thomas, J.P.R. Analyst 1986, 111. 3-9.
8.    Berthage, P.O. Anal. Chim. Acta 1954, 10 310-311.
9.    Craig, P.O.; Moreton, P.A. Environ. Techno!. Lett. 1982, 3, 511-520.
10.   Franklin, G.O.; Fitchett, A.M. Pulp & Paper Canada 1982, 83(10), 40-44.
11.   Fuller, W.  In Cyanide in the Environment; Van Zyl, D.,  Ed.;  Proceedings of
Symposium; December, 1984.
12.   Gottfried, G.J. "Precision, Accuracy, and MDL Statements for EPA Methods
9010, 9030, 9060, 7520, 7521, 7550, 7551, 7910, and 7911"; final report to the
U.S. Environmental Protection Agency (EMSL-CI); Biopheric.
13.   Kilroy, W.P. Talanta 1983, 30(6). 419-422.
14.   Kurtenacher, V.A.; Wallak, R.  L, Anorq.  \L Allg.  Chem. 1927, 161 202-209.
15.   Landers, D.H.; David, M.B.; Mitchell,  M.J.  Int. J.  Anal.  Chem 1983,   14,
245-256.
16.   Opekar, F.; Brukenstein, S. Anal. Chem. 1984, 56ป  1206-1209.
17.   Ricklin, R.D.; Johnson, E.L. Anal. Chem. 1983, 55, 4.
18.   Rohrbough,  W.G.;  et  al.  Reagent  Chemicals.  American  Chemical  Society
Specifications. 7th ed.; American Chemical Society:  Washington, DC,  1986.
19.   Snedecor, G.W.; Ghran,  W.G.  Statistical  Methods; Iowa State University:
Ames, IA, 1980.
20.   Umana, M.;  Beach,  J.; Sheldon, L. "Revisions to Method 9010"; final report
to the U.S.  Environmental  Protection Agency on Contract  No. 68-01-7266; Research
Triangle Institute:  Research Triangle Park, NC, 1986;  Work Assignment No. 1.
21.   Umana, M.;  Sheldon,  L. "Interim Report:  Literature Review";  interim report
to the U.S.  Environmental  Protection Agency in Contract  No. 68-01-7266; Research
Triangle Institute:  Research Triangle Park, NC, 1986;  Work Assignment No. 3.
22.   Wang, W.; Barcelona, M.J. Environ. Inter. 1983, 9, 129-133.
23.   Wronski, M. Talanta 1981, 28, 173-176.
24.   Application Note 156; Princeton Applied Research  Corp.:   Princeton, NJ.
25.   Guidelines  for  Assessing and Reporting  Data Quality for Environmental
Measurements; U.S.  Environmental  Protection Agency.   Office  of Research and
Development. U.S. Government Printing Office:    Washington, DC, 1983.
26.   Fed. Regist. 1980, 45(98). 33122.
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27.   The Analytical Chemistry of  Sulfur  and  Its  Compounds.  Part I; Karchmer,
J.H., Ed.; Wiley-Interscience:  New York,  1970.

28.   Methods for the Examination of Water and  Associated Materials;  Department
of the Environment:  England, 1983.

29.   "Development and  Evaluation of a Test Procedure for Reactivity Criteria for
Hazardous Waste"; final report to  the  U.S.  Environmental  Protection Agency on
Contract 68-03-2961; EAL:   Richmond, CA.

30.   Test Method  to Determine Hydrogen  Sulfide  Released from  Wastes;   U.S.
Environmental Protection Agency.  Office of Solid Waste.  Preliminary unpublished
protocol, 1985.

31.   1985 Annual  Book of ASTM Standards. Vol. 11.01;  "Standard Specification for
Reagent Water"; ASTM:  Philadelphia, PA, 1985; D1193-77.
                                  9030A -  13                     Revision  1
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                         FIGURE  1.
                  GAS  EVOLUTION  APPARATUS
                          H2SO4 (HCI for Acid Insoluble Sulfides)
Hot Water Bath
with Magnetic Stirrer
                                                                      N2 Out
Zinc Acetate
and
Formaldehyde
Scrubbing
Bottles
                        Stirring Bar
                        9030A  -  14
              Revision 1
              July 1992

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                                     METHOD 9030A
                   ACID-SOLUBLE  AND  ACID-INSOLUBLE  SULFIDES
                                            START
7.1.1 Choose  sample
size; place sample
  in beaker:  add
water;  measure pK;
add cone,  sulfuric
   acid to pH 1;
  discard  sample
Acid-Soluble
                                    Acid - Ins oluble
  7.1.1  Calculate
 amt.  of sulfuric
  acid needed  to
   acidify  fresh
 sample  for purge;
fresh  sample is to
 be used for Step
      7.1.4
 7.1.2  Prepare gas
evolution apparatus
71.3  Place weighed
 sample  in flask;
 dilute  with water
   if  necessary
    7.1.4 Place
  dropping  funnel
  onto  flask; add
sulfuric acid (from
  Step  7 1.1) to
  dropping  funnel
   7.1.5  Adjust
  nitrogen flow;
 check  for leaks;
 turn on  3tirrer;
  purge system of
oxygen  for 15 mins.
               7.1.6 Heat  to 70 C;
                add sulfuric acid
                 to flask; close
                 dropping  funnel
                 when acid nears
                    depletion
               7.1.7 Purge, stir,
                 and heat  for 90
                 mins.;  shut off
               nitrogen; turn off
                      heat
                7.1.8 Analyze by
                    titration
                                       9030A  -  15
                                                        Revision 1
                                                        July  1992

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                                          METHOD  9030A
                                           (Continued)
                                     7.2.1 Hater content
                                       of distillation
                                     must be controlled;
                                     cone, of HC1 should
                                          be 6.5N
            7.2.1 Limit  sample
             size to 25  g dry
                  •eight
                        7.2.1 Sample size
                        may be 25 -  SO  g
7.2.2  Weigh sample;
crush  if necessary;
  add  SO mL Hater
  7.2.2-7.2.4
Type of matrix?
                                        7.2.3 Is  <
                                        50g sample
                                          needed?
  7.2.4 Determine
 •ater content of
  sample; include
total oater needed
  for correct HC1
      cone .
                      7.2.3 Add .ater  to
                      sample for a  total
                        volume of SO mL
                                          9030A  -  16
                                            Revision  1
                                            July  1992

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                                          METHOD  9030A
                                           (Continued)
 7.2.5 Place sample
   in flask;  add
  stannous chloride
  7.2.6 Assembl e
   dis ti 1 la t ion
 apparatus; place
zinc aceta te/ sodium
acetate buffer and
  f o rmaldehyde  in
 scrubbing bottles
 7.2.7 Add 100  ml
    9.8N HC1  to
  dropping funnel
7.2.8 Set nitrogen
flow; purge  ays tern
 of oxygen for  15
       mins .
   7.2.9  Turn on
stirrer ;  add HC1 to
distillation flask
                          7 2.10  Heat water
                            bath  to boil;
                           distill for 90
                           mins.  at 100 C;
                         shut  off nitrogen;
                            turn  off heat
                          7.2.11 Analyze by
                              titration
                          7.3.1 Pipet known
                          amount of 0.025N
                         iodine solution in
                           flask; bring to
                          volume with water
7.3.2  Add 10 ml 6N
        HC1
7.3.2  Add 2 ml 6N
       HC1
                                           9030A  -  17
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                                                           July  1992

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                             METHOD  9030A
                              (Continued)
                             7.3.3 Pipet
                          scrubbing bottle
                            solution into
                          Erlenmeyer flask
7.3.4  Prepare rinse
solution  of 0.02SN
iodine solution, 6N
  HC1.  and water
   733
 Does the
amber color
 of iodine
disappear?
No
7.3.3  Add more
iodine;  record
total  volume of
  iodine used
                         7.3.5 Rinse traces
                           of iodine from
                         scrubbing bottles;
                         transfer rinses to
                               flask
                           7.3.6 Titrate
                           solution until
                         amber color fades;
                            add starch
                         indicator; titrate
                         until blue color
                         disappears; record
                         volume of titrant
                               used
                         7.3.7 Calculate the
                         cone, of sulfide in
                             the sample
                               STOP
                              9030A  -  18
                                           Revision  1
                                           July  1992

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                                 METHOD 9031

                             EXTRACTABLE SULFIDES
1.0   SCOPE AND APPLICATION

      1.1    The extraction procedure described in this method is designed for
the extraction of sulfides from matrices that are not directly amenable to the
distillation procedure Method 9030.  Specifically, this method is designed for
the extraction of soluble sulfides.  This method  is  applicable to oil, solid,
multiphasic, and all  other  matrices not amenable to  analysis  by Method 9030.
This method is not  applicable  for  reactive sulfide.  Refer to Chapter Seven for
the determination of reactive sulfide.

      1.2    Method 9031 is suitable for measuring sulfide in solid samples at
concentrations above 1 mg/kg.

2.0   SUMMARY OF METHOD

      2.1    If the  sample  contains  solids  that  will  interfere with agitation
and  homogenization  of  the  sample mixture,  or so much  oil  or grease  as  to
interfere  with  the formation  of  a  homogeneous  emulsion in  the distillation
procedure, the sample may be filtered and the solids extracted with water at pH
> 9 and  <  11.  The extract is then  combined with the filtrate  and  analyzed by the
distillation  procedure.    Separation of  sulfide  from the  sample matrix  is
accomplished by the  addition  of  sulfuric acid to the sample.   The  sample is
heated to 70ฐC and the hydrogen sulfide (H2S) which is  formed is distilled under
acidic  conditions  and  carried by  a nitrogen  stream into  zinc  acetate  gas
scrubbing bottles where it is precipitated as zinc sulfide.

      2.2    The sulfide in the zinc sulfide precipitate is oxidized to sulfur
with a known amount of excess iodine.  Then the excess iodine is determined by
titration  with  a  standard solution of  phenylarsine oxide  (PAO) or  sodium
thiosulfate until the blue iodine starch  complex disappears.  The use of standard
sulfide solutions  is  not possible  because  of  their  instability  to oxidative
degradation.  Therefore quantitation is  based on the PAO or sodium thiosulfate.

3.0   INTERFERENCES

      3.1    Samples  with  aqueous  layers  must  be  taken  with  a minimum  of
aeration  to avoid volatilization of sulfide  or  reaction  with  oxygen  which
oxidizes sulfide to sulfur compounds that are not detected.

      3.2    Sulfur compounds such as sulfite and hydrosulfite  decompose in acid
and may form sulfur dioxide.  This gas  may be carried over to the zinc acetate
gas scrubbing bottles and subsequently  react with the iodine solution yielding
false high  values.   The  addition of formaldehyde  into  the zinc  acetate  gas
scrubbing bottles removes this interference.   Any sulfur dioxide entering the
scrubber will  form an addition  compound with the formaldehyde  which is unreactive
towards the iodine in the acidified mixture.  This method shows no sensitivity
to sulfite or hydrosulfite at  concentrations up to  10 mg/kg of the interferant.
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      3.3    The iodometric method suffers interference from reducing substances
that  react  with  iodine  including  thiosulfate,  sulfite,  and  various  organic
compounds.

      3.4    Interferences have been observed when analyzing samples with high
metal content such as electroplating waste and chromium containing tannery waste.

4.0   APPARATUS AND MATERIALS

      4.1    Extractor - Any suitable device that sufficiently agitates a sealed
container of one  liter  volume or greater.   For  the  purpose  of this analysis,
agitation is sufficient when:

             1.       All  sample  surfaces are continuously brought into contact
                      with extraction  fluid,  and

             2.       The agitation prevents stratification  of the  sample and
                      fluid.

Examples  of  suitable extractors are  shown  in Figures  2  and 3.  The  tumble-
extractors turn the extraction bottles end-over-end at a rate of about 30 rpm.
The  apparatus  in Figure  2 may  be  easily  fabricated  from plywood.  The jar
compartments must be padded with polyurethane foam to absorb shock.   The drive
apparatus is a Norton jar mill.

      4.2    Buchner funnel  apparatus

             4.2.1    Buchner funnel  -  500-mL  capacity,  with  1-liter  vacuum
      filtration flask.

             4.2.2    Glass wool  - Suitable for filtering, 0.8  m diameter such
      as Corning Pyrex 3950.

             4.2.3    Vacuum source -  Preferably a water  driven  aspirator.   A
      valve or stopcock to release vacuum is required.

      4.3    Gas  Evolution apparatus as shown in Figure 1

             4.3.1    Three neck  flask - 500-mL,  24/40 standard tapered joints.

             4.3.2    Dropping funnel  -  100-mL,  24/40 outlet  joint.

             4.3.3    Purge gas  inlet  tube  -  24/40  joint with course frit.

             4.3.4    Purge gas  outlet  -  24/40  joint  reduced  to 1/4  inch  tube.

             4.3.5    Gas scrubbing bottles - 125-mL, with 1/4 in.  o.d. inlet and
      outlet tubes.  Impinger tube must not be fritted.

             4.3.6    Tubing - 1/4 in.  o.d.  Teflon or  polypropylene.  Do not use
      rubber.
      4.4    Hot plate stirrer.
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      4.5    pH meter.

      4.6    Nitrogen regulator.

      4.7    Flowmeter.

      4.8    Separatory funnels - 500-mL.

      4.9    Tumbler - See Figures 2 and 3.

      4.10   Top-loading balance - capable of weighing 0.1 g.

5.0   REAGENTS

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

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

      5.3    Zinc  acetate  (for sample preservation)  (2N), Zn(CH3COO)2 •  2H20.
Dissolve 220 g of zinc acetate dihydrate in 500 mL of water.

      5.4    Sodium hydroxide (50% w/v  in water),  NaOH.  Commercially available.

      5.5    Tin  (II) chloride, SnCl2 • 2H20,  granular.

      5.6    n-Hexane, C6H,..

      5.7    Nitrogen, N2.

      5.8    Sulfuric acid (concentrated), H2S04.

      5.9    Zinc acetate for the scrubber (approximately 0.5M).   Dissolve 110
g zinc acetate  dihydrate  in 200 mL of water. Add  1  mL concentrated hydrochloric
acid, HC1, to prevent precipitation of zinc hydroxide.   Dilute to 1 liter.

      5.10   Formaldehyde (37% solution), CH20.  Commercially available.

      5.11   Starch solution.   Use either an aqueous solution  or soluble starch
powder mixtures.   Prepare an aqueous  solution  as  follows.  Dissolve 2 g soluble
starch and 2 g salicylic acid, C7H603,  as a preservative, in 100 mL hot water.

      5.12   Iodine solution (approximately 0.025N).  Dissolve 25 g of potassium
iodide, KI,  in 700 mL of water in a  1-liter  volumetric flask.   Add  3.2  g of
iodine, I2.  Allow to dissolve.  Dilute to 1  liter and standardize as follows.
Dissolve approximately 2 g KI  in 150 mL  of water.  Pipet exactly  20 mL of the
iodine solution to be titrated and dilute  to  300 mL with water.   Titrate with
0.025N standard phenylarsine oxide, or  0.025N  sodium thiosulfate,  Na2S203, until
the amber color fades.  Add starch indicator solution  until  the solution turns

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deep blue.  Continue titration  drop  by drop until  the blue color disappears.
Run in replicate.   Calculate the normality as follows:

          Normality (I2) = ml of titrant x normality of titrant
                                 Volume of sample (ml)

      5.13   Sodium  sulfide  nonanhydrate Na2S • 9H20, for  the preparation of
standard solutions to be used for calibration curves.  Standards must be prepared
at pH > 9 and < 11.

      5,14   Titrant.

             5.14.1   Standard  phenylarsine  oxide   (PAO)   solution  (0.025N),
      C^HjAsO. This solution  is  commercially available.

CAUTION:     PAO  is toxic.

             5.14.2  Standard sodium thiosulfate solution  (0.025N),   Na2S20, •
      5H20.   Dissolve 6.205 ฑ 0.005  g  Na2S,03  • 5H,0 in  500 ml of water.  Add
      9 ml IN NaOH and  dilute to 1 liter.

6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

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

      6.2    All   samples  must  be  preserved  with  zinc  acetate  and  sodium
hydroxide.  Use four drops of 2N zinc acetate  solution per  100  mL  of aqueous or
multiphasic sample.  Adjust the pH to greater  than 9.0 with  50% NaOH.  Fill the
sample bottle completely  and stopper  with  a  minimum of aeration.   For solid
samples, fill  the surface of solid with 2N zinc acetate until moistened.  Samples
must be cooled to  4ฐC during storage.

7.0   PROCEDURE

      7.1    Assemble the  Buchner  funnel apparatus.   Unroll the glass wool and
fold the  fiber  over  itself several times to make a  pad  about  1  cm thick when
lightly compressed.  Cut the pad to fit the Buchner funnel.  Dry  and weigh the
pad, then place it in the  funnel.  Turn on  the aspirator  and wet the pad with a
known amount of water.

      7.2    Transfer a sample  that contains  between  1 and  50  mg  of sulfide to
the Buchner funnel.  Rinse the sample container with known  amounts of water and
add the rinses to the Buchner funnel.  When no free water  remains in the funnel,
slowly open the stopcock to allow air to enter the vacuum flask. A small amount
of sediment may  have passed through the glass fiber pad.  This will  not interfere
with the analysis.

      7.3    Transfer  the solid  and  the  glass fiber  pad to a  dried tared
weighing dish.  Since most  greases  and oils will not  pass  through the fiber pad,
solids, oils,  and greases  will be extracted  together.  If the filtrate includes
an oil  phase,  transfer the  filtrate to a separatory funnel.   Collect and measure
the volume of the  aqueous  phase.   Transfer  the oil  phase to the weighing dish
with the solid and glass fiber pad.

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      7.4    Weigh the dish containing  solid, oil (if any),  and glass fiber pad.
Subtract the weight of the dry glass fiber pad.  Calculate the volume of water
present in the original sample by subtracting the total volume of rinses from the
measured volume of the filtrate.

      7.5    Place the following in a  1-liter wide-mouth bottle:

              500 ml water
              5 ml 50% w/v NaOH
              1 g SnCl, . 2H20
              50 ml n-hexane (if an oil or grease is present).

Cap the bottle with a Teflon or polyethylene lined cap and shake vigorously to
saturate the solution with stannous chloride.   Direct a stream of nitrogen gas
at about 10 mL/min into the bottle  for  about 1 minute to purge the headspace of
oxygen.  If the weight of the solids  (Step  7.4)  is greater than 25 g, weigh out
a representative aliquot of  25  g and add  it to the  bottle while still  purging
with nitrogen.  Otherwise,  add  all  of the solids.  Cap the  bottle;  avoid the
influx of air.

      7.6    The pH of the extract  must be  maintained at > 9 or < 11 throughout
the extraction step and subsequent filtration.  Since some samples may release
acid, the pH must  be monitored as follows.   Shake the extraction bottle and wait
1 minute.  Open the bottle under a  stream of nitrogen and check the pH.  If the
pH is below 9, add 50% NaOH in 5  ml  increments until  it is at least 9.  Recap the
bottle, and repeat the procedure until  the pH does not drop.  The  bottle must be
thoroughly purged of oxygen before  each recapping.   Oxygen will oxidize sulfide
to  elemental  sulfur  or  other  sulfur  containing compounds  that will   not  be
detected.

      7.7    Place the bottle in the tumbler,  making sure there  is enough foam
insulation to cushion the bottle.   Turn the tumbler  on and allow  the extraction
to run for about 18 hours.

      7.8    Prepare  a Buchner  funnel  apparatus  as in  Step 7.1 with  a glass
fiber pad filter.

      7.9    Decant the extract to the Buchner funnel.

      7.10   If the extract  contains an oil phase,  separate the aqueous phase
using  a  separatory funnel.   Neither  the  separation nor the  filtration are
critical, but are  necessary to be able to measure  the volume of  the  aqueous
extract analyzed.  Small  amounts of suspended  solids and oil emulsions will not
interfere with the extraction.

      7.11   At this  point,  an  aliquot of  the filtrate  of the  original  sample
may be combined  with an aliquot of the extract  in a proportion representative cf
the sample.  Calculate the proportions as follows:

Aliquot of the Filtrate(mL)   Solid Extracted(q)a x  Total Sample  Filtrate(mL)0
Aliquot of the Extract(mL)  "  Total  Solid(g)6      Total Extraction Fluid(mL)d
                                   9031 - 5                       Revision 0
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aFrom Step 7.5.   Weight of solid sample used for extraction.

bFrom Step 7.4.  Weight of solids and oil phase with the dry weight of filter and
tared dish subtracted.

Includes volume of all rinses added  to the filtrate (Steps 7.1  and 7.2).

d500 mL water plus total volume of NaOH  solution.  Does not  include hexane, which
is subsequently removed (Step 7.10).

Alternatively,  the   samples   may  be  distilled   and   analyzed   separately,
concentrations for each phase  reported  separately, and the  amounts of each phase
present in the sample  reported separately.

      7.12   Distillation of  Sulfide

             7.12.1   In a  preliminary experiment,  determine the  approximate
      amount of sulfuric acid  required  to adjust a measured amount of the sample
      to pH less than  or equal to 1.   The sample size should be chosen so that
      it contains  between  1.0 and  50  mg of sulfide.   Place  a  known  amount of
      sample or sample slurry in a  beaker.   Add  water  until the total volume is
      200 ml.  Stir the mixture and determine  the  pH.  Slowly add sulfuric acid
      until the pH is  less than or equal to 1.

CAUTION;     Toxic hydrogen sulfide may be generated from  the acidified sample.
             This  operation must be performed in  the hood and  the sample left
             in the hood until the sample  has  been made alkaline or the sulfide
             has been  destroyed.

      From the amount  of  sulfuric  acid required to  acidify the  sample and the
      mass or  volume  of  the  sample  acidified,  calculate the amount  of acid
      required to acidify the sample to be placed in the distillation flask.

             7.12.2   Prepare  the gas  evolution apparatus  as shown in Figure 1
      in a fume hood.

                      7.12.2.1   Prepare a  hot water bath  at 70'C  by filling a
             crystallizing dish or other suitable container with water and place
             it on a  hotplate stirrer.   Place a thermometer in  the  bath and
             monitor the temperature to maintain  the  bath  at 70ฐC.

                      7.12.2.2  Assemble  the  three  neck  500-mL  flask, fritted
             gas inlet tube,  and exhaust tube.  Use Teflon sleeves to seal the
             ground glass joints.  Place a Teflon coated stirring bar into the
             flask.

                      7.12.2.3   Place  into each gas scrubbing  bottle 10 ฑ 0.5
             mL  of  the 0.5M  zinc acetate solution,  5.0 ฑ  0.1 ml of  37%
             formaldehyde and 100 + 5.0 ml water.

                      7.12.2.4   Connect  the   gas  evolution  flask   and  gas
             scrubbing bottles  as  shown in Figure 1.   Secure all  fittings and
             joints.


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        7.12.3   Carefully place an accurately weighed sample which contains
1.0  to  50  mg  of sulfide  into  the  flask.   If  necessary,  dilute  to
approximately 200 mL with water.

        7.12.4   Place the dropping funnel  onto the flask making sure its
stopcock is closed.  Add the  volume of sulfuric  acid calculated in Step
7.1.1  plus  an additional 50  ml  into  the  dropping funnel.   The bottom
stopcock must be closed.

        7.12.5   Attach  the nitrogen inlet to the top of the dropping funnel
gas shut-off valve.  Turn on  the nitrogen  purge  gas and adjust the flow
through the sample flask to  25 mL/min.   The nitrogen in the gas scrubbing
bottles  should  bubble at  a  rate  of  about  five  bubbles  per  second.
Nitrogen pressure  should be limited to approximately  10 psi to prevent
excess stress on the glass system and  fittings.   Verify that  there are no
leaks  in the  system.  Open the nitrogen  shut-off valve leading  to the
dropping funnel.  Observe that  the  gas flow into the sample vessel will
stop  for  a  short   period  while  the  pressure   throughout  the  system
equalizes.    If the  gas  flow  through  the  sample flask  does not return
within a minute, check for  leaks around the dropping  funnel.  Once flow
has stabilized,  turn on  the magnetic stirrer.   Purge  the  system for 15
minutes with nitrogen  to  remove oxygen.

        7.12.6   Heat sample  to 70ฐC. Open  dropping  funnel  to a position
that will allow a flow  of  sulfuric acid of approximately 5 mL/min. Monitor
the system until most  of  the sulfuric acid contained within  the dropping
funnel has entered the sample flask.   Close the  dropping funnel  while a
small amount of acid  remains.  Immediately close the gas shut-off valve to
the dropping funnel.

        7.12.7   Purge,  stir, and maintain a  temperature of 70ฐC for a total
of 90 minutes from start  to finish.   Shut off nitrogen supply.  Turn off
heat.

7.13   Titration of  Distillate

       7.13.1   Pipet a known amount  of standardized 0.025N iodine solution
(see Step  5.12). in a  500-ml  flask,  adding an amount in excess  of that
needed to oxidize the  sulfide.   Add enough water to bring the volume to
100 ml.  The volume of  standardized  iodine  solution should  be about 65 ml
for samples with 50 mg of sulfide.

       7.13.2   Add 2 ml  of  6N HC1 to  the iodine.

       7.13.3   Pipet both of  the gas scrubbing bottle solutions into the
flask,  keeping  the  end  of  the  pipet  below the surface of the  iodine
solution.  If at any point  in transferring the zinc acetate solution or
rinsing the bottles,  the  amber color of the iodine disappears or fades to
yellow, more 0.025N iodine must  be added.   This additional amount must be
added to the amount from Step 7.13.1 for calculations.  Record the total
volume of standardized 0.025N iodine solution used.

       7.13.4   Prepare a rinse solution of  a known amount of  standardized
0.025N iodine solution, 1 ml of 6N HC1, and water to rinse the remaining

                             9031 -  7                        Revision 0
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      white precipitate (zinc sulfide) from the gas scrubbing bottles into the
      flask.  There should be no visible traces of precipitate after rinsing.

             7.13.5   Rinse any remaining traces of iodine from the gas scrubbing
      bottles with water, and transfer the rinses to the flask.

             7.13.6   Titrate the solution  in  the flask with  standard 0.025N
      phenylarsine oxide or 0.025N sodium thiosulfate solution until the amber
      color fades to yellow.  Add enough starch  indicator  for the solution to
      turn dark blue and titrate until the blue disappears.  Record the volume
      of titrant used.

             7.13.7   Calculate  the  concentration of sulfide  in  the sample as
      follows:
 [(ml of I2 x N of I2)  -  (ml  of titrant  x  N  of  titrant)](16.03)
	 =  sulfide(mg/kg)
                    sample weight (kg)


8.0  QUALITY CONTROL

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

      8.2    A  reagent  blank  should  be  run  every  twenty  analyses  or per
analytical  batch, whichever  is more frequent.

      8.3    Check  standards are prepared  from water  and  a known  amount of
sodium sulfide.  A  check standard should  be run  with each analytical batch of
samples or once  every  twenty samples.   Acceptable  recovery will  depend on the
level and matrix.

      8.4    A matrix  spiked sample should  be run for each analytical batch or
twenty samples,  whichever is more frequent, to  determine matrix effects.  If
recovery is low, acid-insoluble sulfides are indicated.  A matrix spiked sample
is a sample brought  through the whole sample preparation  and analytical process.

      8.5    Verify the calibration with an  independently prepared QC reference
sample every  twenty samples  or  once  per analytical batch, whichever is more
frequent.

9.0  METHOD PERFORMANCE

      9.1    Accuracy   -  Accuracy for  this method  was  determined   by   three
independent laboratories  by  measuring percent  recoveries   of spikes for  waste
samples.  The results are summarized below.

      Accuracy for  the entire method  for  four  synthetic waste samples 70-104%
      recovery


                                   9031 - 8                       Revision 0
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      9.2  Precision
      Precision of entire method for four synthetic waste samples
      Percent coefficient of variation     1.0-34
10.0  REFERENCES
1.  Test Methods for Evaluating Solid Waste,  Physical/Chemical Methods, 3rd ed.;
U.S.  Environmental  Protection Agency.   Office  of  Solid Waste  and Emergency
Response. U.S. Government Printing Office: Washington,  DC,1987; SW-846; 955-001-
00000-1.
2.    Methods  for  Chemical  Analysis of  Water and Wastes;  U.S.  Environmental
Protection Agency.  Office of Research and Development.  Environmental Monitoring
and Support  Laboratory.   ORD  Publications  Office.    Center  for Environmental
Research Information:  Cincinnati, OH,  1979; EPA-600/4-79-020,  Method 376.1.
3.    CRC Handbook of Chemistry and Physics. 66th ed.;  Weast,  R.,  Ed.; CRC: Boca
Raton, FL, 1985.
4.    Standard Methods for  the Examination  of Water  and Wastewater. 16th ed.;
Greenberg, A.E.;  Trussell,  R.R.; Clesceri,  L.S.,  Eds.; American  Water Works
Association,  Water  Pollution  Control  Federation,   American  Public  Health
Association:  Washington, DC, 1985; Methods 427, 427A, 427B, and 427D.
5.    Andreae, M.O.; Bernard, W.R. Anal.  Chem. 1983,  55, 608-612.
6.    Barclay, H.  Adv. Instrum. 1980, 35(2K 59-61.
7.    Bateson, S.W.; Moody, G.J.; Thomas, J.P.R. Analyst 1986,  111. 3-9.
8.    Berthage, P.O. Anal. Chim.  Acta 1954,  10, 310-311.
9.    Craig, P.O.; Moreton, P.A.  Environ. Techno!.  Lett. 1982,  3, 511-520.
10.   Franklin, G.O.; Fitchett, A.W. Pulp & Paper Canada 1982,  83(10K 40-44.
11.   Fuller, W. Cyanide  in  the  Environment;  Van Zyl,  D.,  Ed.;  Proceedings of
Symposium; December 1984.
12.   Gottfried, G.J. "Precision, Accuracy,  and MDL Statements for EPA Methods
9010,  9030, 9060,  7520, 7521, 7550, 7551, 7910, and 7911";  final report to the
U.S. Environmental Protection Agency (EMSL-CI); Biopheric.
13.   Kilroy, W.P. Talanta 1983,  30(6). 419-422.
14.   Kurtenacher, V.A.; Wallak,  R. Z.  Anorq. U. Chem. 1927, 161. 202-209.
15.   Landers, D.H.; David, M.B.; Mitchell,  M.J. Int.  J. Anal.  Chem. 1983, 14,
245-256.
16.   Opekar, F.;  Brukenstein, S. Anal. Chem. 1984,  56,  1206-1209.
17.   Ricklin, R.D.; Johnson, E.L. Anal.  Chem. 1983,  55, 4.
                                   9031 - 9                       Revision 0
                                                                  July 1992

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

19.   Snedecor, G.W.; Ghran,  W.G.  Statistical Methods;  Iowa  State University
Press:  Ames, IA,  1980.

20.   Umana, M.; Beach,  J.;  Sheldon, L. "Revisions to Method  9010";  final report
to the  Environmental  Protection Agency  on Contract No.  68-01-7266;  Research
Triangle Institute:  Research Triangle Park, NC, 1986; Work Assignment No. 1.

21.   Umana, M.; Sheldon, L. "Interim Report:  Literature Review"; interim report
to the U.S.  Environmental Protection Agency in Contract  No. 68-01-7266; Research
Triangle Institute:  Research Triangle Park, NC, 1986; Work Assignment No. 3.

22.   Wang, W.; Barcelona, M.J. Environ. Inter. 1983, 9, 129-133.

23.   Wronksi, M.  Talanta 1981, 28, 173-176.

24.   Application Note  156; Princeton Applied Research Corp.:   Princeton, NJ.

25.   Guidelines  for  Assessing and Reporting Data  Quality for Environmental
Measurements:  U.S.  Environmental  Protection  Agency Office  of Research and
Development:  Washington, DC, 1983.

26.   Fed. Regist. 1980, 45(98), 33122.

27.   The Analytical Chemistry  of  Sulfur and Its Compounds. Part  I; Karchmer,
J.H., Ed.; Wiley-Interscience:  New York,  1970.

28.   Methods for the Examination of Water and Associated Materials; Department
of the Environment:  England, 1983.

29.   "Development and Evaluation of a  Test  Procedure for Reactivity  Criteria for
Hazardous Waste"; final  report  to  the U.S. Environmental  Protection Agency on
Contract 68-03-2961; EAL:  Richmond, CA.

30.   1985 Annual  Book of ASTM Standards.  Vol. 11.01; "Standard Specification for
Reagent Water"; ATSM:   Philadelphia, PA, 1985; D1193-77.
                                   9031  -  10                      Revision 0
                                                                  July 1992

-------
                         FIGURE  1.
                  GAS  EVOLUTION  APPARATUS
                          H2S04 (HCI for Acid Insoluble Sulfides)
Hot Water Bath
with Magnetic Stirrer
Zinc Acetate
and
Formaldehyde
Scrubbing
Bottles
                        Stirring Bar

                                                                       N20ut
                         9031 - 11
                Revision 0
                July 1992

-------
                            FIGURE  2.
                        TUMBLER-EXTRACTOR
                                                        Foam-Inner Liner
1-L Bottle
with Cap
         Jar Mill Drive
                                             Box Wheels Plywood Construction
                           9031  -  12
Revision 0
July 1992

-------
                                            FIGURE 3.
                                            EXTRACTOR
        l-Gallon PlasUc
        or Glass Bottle
                                                                           Foam Bonded lo Cover
                                                                                       Box Assembly
                                                                                       Plywood Construction
Totally Enclosed
Fan Cooled Motor
30 rpm, 1/8 HP
                                            9031  -  13
Revision  0
July 1992

-------
        METHOD  9031
          SULFIDES
START

7 . 1 Assemble
Buchner funnel
apparatus
1
7.2 Transfer s mple
to funnel ; rise
sample contain r w/
known amt . f
wa ter ; add r i ses
to funnel; filter
until no free water
remains in funnel

7 . 3 Transfer solid
and fiber pad to
dried tared
weighing dish

73 Transfer S \v
filtrate to / N.
separator/ funnel; ^r 7.3 Does x_^
collect aqueous Yes S fil trate x^
phase and measure ' C include an oil )
volume ; transfer x^ phase? /
oil phase to ^v /
weighing dish X. >^



t)o
•
7.4 Heigh dish and
contents; subtract
glass fiber pad (if
total volume of
rinses from volume
of filtrate
7 5 Place nater ,
NaOH, stannous
chloride, and
•* n-hexane (if oil or
grease is present)
in 1 L bottle
1
7.5 Cap bottle with
Teflon lined cap
and shake; direct
ni trogen into
bottle for 1 minute
to purge oxygen
1

//.B Is weight \No 7.5 Add all solids;
f of the solids > J— — f cap bottle
V 25 9? S
Yes
7.5 Welgh out 25 g;
add to bottle nhile
purging


o


         9031 - 14
Revision 0
July 1992

-------
                                        METHOD  9031
                                         (Continued)
                            7.6 PH  of
                       extraction must be
                       > 9 and < 11; shake
                       bottle 1 min.; open
                         under nitrogen;
                            check pH
 7.6 Add  5  mL
aliquot of  NaOH
                                 No
                       7.7 Place  bottle in
                        tumbler;  turn on
                       and extract  for 18
                              hours
                       7.8 Prepare Buchner
                       funnel  apparatus as
                           in  Step 7.1
                       7.9 Decant extract
                           into  funnel
                         7.10 Place  extract
                            in separatory
                         funnel;  collect and
                          measure volume of
                            aqueous  phase
   7 .11 Combine
aqueous en tract and
  original  sample
    filtrate  in
     aliquots
propertional  to the
 sample;  calculate
    proportions
                                                   7.12.1 Choose
        ize;  place
         amt.  of
        in beaker;
sample
   knoii
 sample
add -at
        dd  cone.
sulfuri  acid  to
      pH =  1
 7 12.2  Calculate
amount of  sulfuric
  acid needed  to
  acidify  sample
                                          9031  -  15
                                    Revision 0
                                    July 1992

-------
METHOD 9031
(Continued)

7.12.2 Prepare gas
evolution apparatus

7.12.3 Place
weighed sample in
flask; dilute with
water if necessary

7.12.4 Place
dropping funnel
onto flask; add
sulfuric acid from
Step 7.12.1 to
dropping funnel

7.12.5 Adjust
ni t r ogen flow;
check for leaks;
turn on stirrer;
purge system of
OMygen for 15
minutes
1
7.12.6 Heat to 70C;
add sulfuric acid
to flaak ; close —
funnel when acid
near a depletion

7 . 12. 7 Purge, stir .
and heat for 90
•* min . ; shut off
nitrogen; turn off
heat

7.13 Analyze by
ti tra tion
I
7.13.1 Pipet known,
amount of 0.025N
an Erlenmeyer
flask; dilute with
water
i
7.13.2 Add 2 mL 6N
HC1 to flask
1
7.13.3 Pipet
scrubber solution —
into flask

1

/ 7.13.3 >v 7.13.3 Add more
S Does amber >,Yes iodine solution;
( iodine color J > record total volume
>v disappear? / of iodine solution
N. / used
No
7.13.4 Prepare
iodine solution, 6N
HC1 , and water



1
7.135 Rinse traces
of iodine from
scrubbing bottle;
transfer rinses to
flask with pipet
1
7.13 6 Titrate
flask solution
until amber color
fades; add starch
indicator; titrate
until blue color
disappears; record
volume of titrant
used
1
7.13.7 Calculate
the concentration
of sulfide in the
sample

          STOP
9031 - 16
Revision 0
July 1992

-------
                                 METHOD  9035
               SULFATE (COLORIMETRIC.  AUTOMATED, CHLORANILATE)

1.0  SCOPE AND APPLICATION
     1.1  This automated method 1s  applicable   to   ground water, drinking and
surface waters, and domestic  and  Industrial   wastes   containing 10  to 400 mg
$04-2/11ter.

2.0  SUMMARY OF METHOD
     2.1  When solid barium  chloranllate  1s   added  to a solution containing
sulfate, barium sulfate  1s  precipitated,  releasing   the highly colored add
chloranllate 1on.   The  color  Intensity  1n   the   resulting chloranlUc add
solution 1s proportional to the amount of sulfate present.
3.0  INTERFERENCES
     3.1  Cations such as calcium,  aluminum,   and   Iron Interfere by precipi-
tating the chloranllate.  These  Ions  are  removed by passage through an Ion-
exchange column.
     3.2  Samples should be centrlfuged or filtered before analysis.

4.0  APPARATUS AND MATERIALS
     4.1  Automated continuous-flow analytical  Instrument, with;
          4.1.1  Sampler I.
          4.1.2  Continuous filter.
          4.1.3  Manifold.
          4.1.4  Proportioning pump.
          4.1.5  Colorimeter:  Equipped with 15 mm tubular flowcell  and 520  nm
                 filters.
          4.1.6  Recorder.
          4.1.7  Heating bath, 45*C.
     4.2  Magnetic stlrrer.
                                  9035 - 1
                                                         Revision
                                                         Date  September 1986

-------
5.0  REAGENTS

     5.1  ASTM Type II water  (ASTM  D1193):     Water  should  be  monitored  for
Impurities.
     5.2  Barium chloranllate;  Add 9  g of barium chloranllate  (BaC^C^O^  to
333 ml of spectrophotometrlc grade  ethyl  alcohol  and dilute to 1  liter with
Type II water.

     5.3  Acetate buffer, pH 4.63:  Dissolve  13.6 g of sodium acetate 1n Type
II water.  Add 6.4 ml of acetic add and dilute to 1 liter with  Type II water.
Make fresh weekly.

     5.4  NaOH-EDTA solution;  Dissolve 65 g of  NaOH  and 6 g EDTA 1n Type II
water and dilute to 1 liter.    This  solution  1s  also used to clean out the
manifold system at end of sampling run.

     5.5  Ion exchange resin;  Dowex-50  W-X8,  1on1c  form-H+.   The column 1s
prepared by sucking a slurry of the  resin Into 12 1n. of 3/l6-1n O.D. tubing.
This may be conveniently done by using  a plpet and a loose-fitting glass wool
plug 1n the tube.  The  column,  upon  exhaustion, turns red.  Ensure that air
does not enter the column.

     5.6  Stock solution;  Dissolve  1.4790  g  of oven-dried  (105*C) Na2S04 1n
Type II water and dilute to  1 liter  1n a volumetric flask (1.0 ml = 1.0 mg).

     5.7  Standards ;   Prepare  a  series  of  standards  by diluting suitable
volumes of stock solution  to  100.0 ml  with  Type  II water.   The following
dilutions are suggested.

          Stock Solution (ml)               Concentration (mg/L)

                 1.0                                  10
                 2.0                                  20
                 4.0                                  40
                 6.0                                  60
                 8.0                                  80
                10.0                                100
                15.0                                150
                20.0                                200
                30.0                                300
                40.0                                400
 6.0   SAMPLE COLLECTION,  PRESERVATION, AND HANDLING

      6.1   All  samples  must   have   been  collected  using  a sampling plan that
 addresses  the  considerations discussed  1n Chapter Nine of this manual.

      6.2   Refrigerate  at 4'C.
                                   9035 - 2
                                                          Revision
                                                         Date  September 1986

-------
7.0  PROCEDURE

     7.1  Set up manifold as shown 1n  Figure  1.   (Note that any precipitated
BaS04 and the unused barium  chloranllate  are  removed by filtration.   If any
BaS04 should  come  through  the  filter,  1t  1s   complexed  by the NaOH-EDTA
reagent.)

     7.2  Allow both colorimeter and recorder to  warm  up  for 30 min.   Run a
baseline with all reagents,  feeding  Type  II  water through the sample line.
Adjust dark current and  operative  opening  on colorimeter to obtain suitable
baseline.

     7.3  Place Type II water wash tubes  1n alternate openings in sampler and
set sample timing at 2.0 min.

     7.4  Place working standards in  sampler  1n  order of decreasing concen-
tration.  Complete filling of sampler tray with unknown samples.

     7.5  Switch sample line from Type II water to sampler and begin analysis.

     7.6  Calculation;

          7.6.1  Prepare   a  standard  curve   by  plotting  peak  heights  of
     processed standards against known   concentrations.  Compute concentration
     of  samples  by comparing sample peak heights with  standard curve.


8.0  QUALITY  CONTROL

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

     8.2 Calibration  curves must be  composed  of   a  minimum  of a blank  and
three  standards.  A linear calibration curve  should be made for every  hour of
continuous  sample analysis.

     8.3 Dilute samples   1f  they  are  more concentrated  than  the  highest
standard or 1f  they fall on the plateau  of  a  calibration curve.

     8.4 Employ a minimum of  cne blank  per   sample  batch  to determine 1f
contamination has occurred.

     8.5 Verify calibration  with  an   independently  prepared check standard
every  15 samples.

     8.6 Run one spike  duplicate  sample  for   every 10   samples.    A  spike
duplicate sample is a  sample brought  through the whole sample  preparation  and
analytical  process.
                                   9035 - 3
                                                          Revision
                                                          Date   September  1986

-------













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-------
9.0  METHOD PERFORMANCE

     9.1  Precision and accuracy data are available 1n Method 375.1 of Methods
for Chemical Analysis of Water and Wastes.


10.0 REFERENCES

1.   Bertolacinl, R.J., and  J.E.  Barney,  II,  Colorlmetric Determination of
Sulfate with Barium Chloranilate, Anal. Chem., 29(2), pp. 281-283 (1957).

2.   Gales, M.E., Jr.,  W.H.  Kaylor,  and  J.E.  Longbottom, Determination of
Sulphate by Automatic Colorlmetric Analysis, Analyst, 93, 97 (1968).
                                   9035 - 5
                                                          Revision
                                                          Date   September  1986

-------
                            METHOD 9035

          SULFATE (COLORIMETRIC.  AUTOMATED.  CHLORANILATE)
                                                        0
 7.1


Set up manifold
 7.3
  7 •'
 	1  Place
        work ing
    standards in
   sampler:  fill
    sampler tray
       Warm up
   colorimeter.
    recorder;
obtain suitable
    baseline
                                                     7.5
  Switch sample
 line to sampler
   and analyze
 7.3
  Place water
 wash tubes in
    •ampler
                                                    7.6.1
      Compute
   concentration
    of samples
    o
[     Stop      J
                     9035 - 6
                                                Revision       0
                                                Date  September  1986

-------
                                 METHOD 9036

         SULFATE (COLORIMETRIC.  AUTOMATED,  METHYLTHYMOL BLUE.  AA II)


1.0  SCOPE AND APPLICATION

     1.1  This automated method 1s  applicable  to  ground water,  drinking and
surface waters, and domestic and Industrial wastes.

     1.2  Samples 1n the range of 0.5 to 300 mg S04~2/I1ter can be analyzed.


2.0  SUMMARY OF METHOD

     2.1  The sample 1s  first  passed  through  a sodium-form cation-exchange
column to remove multlvalent  metal  Ions.     The sample containing sulfate 1s
then reacted with an alcohol solution of barium chloride and methyl thymol  blue
(MTB) at a pH of 2.5-3.0  to  form  barium  sulfate.  The combined solution 1s
raised to a pH  of  12.5-13.0  so  that  excess  barium  reacts with MTB.   The
uncomplexed MTB color 1s gray; 1f 1t 1s all chelated with barium,  the color 1s
blue.  Initially, the barium  and  MTB  are  equlmolar and equivalent to 30 mg
S04~2/I1ter; thus the  amount  of  uncomplexed  MTB  1s  equal  to the sulfate
present.


3.0  INTERFERENCES

     3.1  The Ion-exchange  column  eliminates  Interferences from multlvalent
cations.  A  mid-scale  sulfate  standard  containing  Ca++ should be analyzed
periodically to ensure that the column 1s  functioning properly.

     3.2  Samples with pH  below  2  should  be  neutralized because high add
concentrations elute cations  from the Ion-exchange resin.

     3.3  Turbid samples should be filtered or centrlfuged.


4.0  APPARATUS AND  MATERIALS

     4.1  Automated continuous-flow analytical Instrument:

          4.1.1  Sampler.

          4.1.2  Manifold:  High-  or low-level  (Figure  1).

          4.1.3  Proportioning pump.

          4.1.4  Heating bath:  Operable at the temperature specified.

          4.1.5  Colorimeter:  Equipped  with  15   mm   flowcell   and  460  nm
                 Interference filters.
                                   9036 -  1
                                                         Revision
                                                         Date  September 1986

-------
                                                    TO WASTE  O>
n- <
ION EXC
COLUMN
WASTES
.w
fir"
:HANGE
116 GOO6 01
o no ST/
SLEEVING
157-B095
J20
TURNS
TO SAMPLER
WASH RECEPTACLE
170 0103 01
A 7
5 UinNS |
tNDARD
•
157 0370
[••••••• . J
7? I 116-04B9
7UMNS

1
116 O4R9 01

•
01

COLORIMETER *
TO F/C PUMP wAซ:Tr
TUBE
460 NM
5 mm F/C "2.0 mm 10


GRN. GRN.
BLK. BLK.
GRN. GRN.
ORN. GRN.
GRY, GRY.
BLK. BLK.
RED RED
ORN. ORN.
GRN. GRN.
PROPORTIONl
PIIMD
MVMIN
2.0
0.32 AIR
2.OO DILUTION WATER
O.1O SAMPLE
7.OO WASTE
O.32 AIR
0.70 METHYLTHYMOL BLUE
O.42*"SOniUM HYDROXIDE
2.00 FROM F/C
MG
RANGE 0 30 mci/l CHANGE THE WATER

AND  SAMPLE  TUBES TO GRY/GRY (1.00)
                                         SAMPLING RATE 30/hr. 8.1
                                        •0.034  POLYETHYLENE
                                       ••SILICONF RURRER
(/> o
n> 3
o
FIGURE 1 SULFATE  MANIFOLD  AA11
n
-j
vo
00
O)

-------
          4.1.6  Filters:  Of specified transmittance.

          4.1.7  Recorder.
5.0  REAGENTS

     5.1  ASTM Type II water  (ASTM  D1193):    Water  should be monitored for
Impurities.

     5.2  Barium chloride;   Dissolve  1.526  g  of  barium chloride dlhydrate
(BaCl2'2H20) in 500 mL of Type II water and dilute to 1 liter.

     5.3  Methyl thymol  blue;    Dissolve   0.1182  g  of   methylthymol   blue
(3'3"-bi s-N,N-b1s       carboxymethyl-ami no      methyl thymolsulfone-phthale1n
pentasodium salt) 1n 25 ml of  barium chloride solution  (Paragraph 5.2).  Add
4 ml of 1.0 N  hydrochloric  add,  which  changes the color to bright orange.
Add 71 ml of water and dilute to 500 mL with ethanol.  The pH of this solution
1s 2.6.  This reagent should be prepared  the day before and stored 1n a brown
plastic bottle 1n the freezer.

     5.4  Buffer,  pH 10.5 + 0.5:  Dissolve  6.75 g  of  ammonium chloride  1n
500 mL of Type II water.    Add  57  mL of concentrated ammonium hydroxide and
dilute to 1 liter with Type II water.

     5.5  Buffered EDTA;  Dissolve 40 g  of tetrasodlum EDTA 1n pH 10.5 buffer
(Paragraph 5.4) and dilute to 1 liter with buffer.

     5.6  Sodium hydroxide solution  (50%):  Dissolve  500  g NaOH In 600 mL of
Type II water, cool, and dilute to 1 liter.

     5.7  Sodium hydroxide.  0.18  N:    Dilute  14.4  mL  of sodium hydroxide
solution (Paragraph 5.6) to 1 liter.

     5.8  Ion-exchange resin:  Bio-Rex  70,  20-50  mesh, sodium form, Bio-Rad
Laboratories, Richmond, California.  Free  from fines by stirring with several
portions of  Type  II  water  and  decant  the  supernate  before  settling 1s
complete.

     5.9  Dilution water:  Add  0.75  mL  of sulfate stock solution  (Paragraph
5.10) and 3 drops of  Brij-35  (available from Technicon) to 2  liters of Type II
water.

     5.10  Sulfate stock  solution, 1 mL  =  1  mg  S04~2:  Dissolve 1.479  g of
dried Na2S04  (105*C)  In Type  II water and dilute to  1  liter.

     5.11  Dilute sulfate  solution,  1 mL  =  0.1  mg   S04~2:  Dilute  100 mL of
sulfate  stock  solution  (Paragraph  5.10) to  1 liter.
                                   9036 - 3
                                                          Revision
                                                          Date   September  1986

-------
     5.12  High-level working  standards,  10-300  mg/L:     Prepare high-level
working  standards  by  diluting  the  following  volumes  of  stock  standard
(Paragraph 5.10) to 100 ml:

               Stock Solution (ml)        Concentration (mg/L)

                        1                         10
                        5                         50
                       10                        100
                       15                        150
                       25                        250
                       30                        300

     5.13  Low-level  working  standards.  0.5-30  mg/L:    Prepare  low-level
working  standards by diluting the following volumes of dilute sulfate solution
(Paragraph 5.11) to  100 mL:

                Stock Solution (mL)        Concentration  (mg/L)

                        0.5                       0.5
                        1                         1.0
                        5                         5.0
                       10                        10.0
                       15                        15.0
                       25                        25.0
                       30                        30.0


6.0  SAMPLE  COLLECTION, PRESERVATION, AND HANDLING

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

     6.2 Refrigerate at 4*C.


7.0  PROCEDURE

     7.1 Set  up manifold  for high-   (10-300  mg/L SO^2) or  low-  (0.5-30 mg/L
S04"2)  level samples as described in  Figure 1.

     7.2 The  ion-exchange column is  prepared by pulling a slurry  of the resin
into a  piece of glass tubing 7.5-1n.  long, 2.0-mrn I.D., and  3.6-mm O.D.  This
is conveniently done by using a  pi pet   and a loose-fitting glass  wool plug in
the tubing.  Care  should be  taken  to avoid allowing air bubbles  to enter the
column.   If  air bubbles become  trapped,  the column should be prepared again.
The column can exchange the  equivalent   of  35  mg  of calcium.  For the high-
level manifold, this corresponds  to  about  900  samples with  200 mg/L Ca.  The
column  should  be prepared  as often   as   necessary  to ensure  that  no more than
50% of  its capacity  1s used.
                                   9036 - 4
                                                          Revision
                                                          Date   September  1986

-------
     7.3  Allow the colorimeter, recorder,  and printer  to warm up for 30 min.
Pump all reagents until a stable baseline 1s achieved.

     7.4  Analyze all working standards 1n duplicate at the beginning of a run
to develop a standard curve.  The  A  and B control standards must be analyzed
every hour to ensure that the system remains properly calibrated.  Because the
chemistry 1s nonlinear, the 180-mg/L  standard  1s  set at 50% on the recorder
using the standard calibration control on the colorimeter.

     7.5  At the end  of  each  day,  the  system  should  be  washed with the
buffered  EDTA  solution  (Paragraph  5.5).    This  1s  done  by  placing the
methyl thymol blue line  and  the  sodium  hydroxide  line  1n  water for a few
minutes and then 1n the buffered  EDTA  solution  for 10 m1n.  Wash the system
with water for 15 m1n before shutting down.

     7.6  Prepare a standard curve by  plotting peak heights of five processed
standards against known concentrations.    Compute concentration of samples by
comparing sample peak  heights with the standard  curve.  Note that this is not
a  linear curve but a third order curve.
8.0  QUALITY  CONTROL

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

     8.2   Calibration  curves must be   composed  of  a  minimum  of a blank and
three  standards.    A   calibration   curve  should  be  made  for  every hour of
continuous sample  analysis.

     8.3   Dilute samples   if  they  are  more   concentrated  than  the highest
standard or 1f they fall  on the  plateau of  a calibration curve.

     8.4   Employ a minimum, of   one  blank  per  sample  batch to determine if
contamination has  occurred.

     8.5   Verify calibration  with  an Independently  prepared check standard
every  15 samples.

     8.6   Run one  spike duplicate sample  for   every  10 samples.  A duplicate
sample is  a sample brought through  the whole sample preparation and analytical
process.


9.0  METHOD PERFORMANCE

     9.1   Precision and accuracy data are available in Method 375.2 of Methods
for  Chemical  Analysis  of  Water  and  Wastes.
                                   9036 - 5
                                                          Revision       0
                                                          Date  September  1986

-------
10.0 REFERENCES

1.   Coloros, E., M.R. Panesar,  and  P.P. Parry, "Linearizing the Calibration
Curve in Determination  of  Sulfate  by  the  Methyl thymol Blue Method," Anal.
Chem. 48, 1693 (1976).

2.   Lazrus, A.L.,  K.C.  Hill,  and  J.P.  Lodge,  "Automation  in Analytical
Chemistry," Technicon Symposia, 1965.
                                   9036 - 6
                                                          Revision
                                                          Date  September 1986

-------
                            METHOD 9036

    SUUFATE  (COLORXMETRIC.  AUTOMATED.  METMYLTHVMOL BLUE.  A*  II)
                                                       O
Set up manifold
                                                    7.4
        Oevelop
      • standard
    curve:  check
    calibration
    every hour
 7.2
  Prepare Ion
••change column
                                                    7.5
    Mash syntem
  down at end of
       day
 7.3
     I  Kara up
   colorimeter.
   recorder end
   printer. Get
•table  baseline
                                                    7.6
     Compute
  concentration
   Of samples
    Q
f     Stop      J
                     9036 - 7
                                                Revision       0
                                                Date   September 1986

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                                 METHOD 9038

                           SULFATE (TURBIDIMETRIC)
1.0  SCOPE AND APPLICATION

     1.1  This method 1s  applicable  to  ground  water,   drinking and surface
waters, and domestic and Industrial wastes.

     1.2  This method 1s  suitable  for  all  concentration  ranges of sulfate
(S04~2); however, 1n order to  obtain  reliable readings, use a sample aliquot
containing not more than 40 mg/L of S04~2.

     1.3  The minimum detectable limit 1s approximately 1 mg/L of S04~2.


2.0  SUMMARY OF METHOD

     2.1  Sulfate 1on  1s  converted  to  a  barium  sulfate  suspension under
controlled conditions.  The  resulting  turbidity  Is determined by a nephelo-
meter,  filter  photometer,  or  spectrophotometer  and  compared  with a curve
prepared from standard sulfate solution.


3.0  INTERFERENCES

     3.1  Color and turbidity  due  to  the  sample  matrix can cause positive
Interferences which must be accounted for by use of blanks.

     3.2  Silica 1n concentrations over 500 mg/L will Interfere.


4.0  APPARATUS AND MATERIALS

     4.1  Magnetic stlrrer;  Variable speed  so  that  1t can be held constant
just below splashing.Use  Identical  shapes  and sizes of magnetic stirring
bars.

     4.2  Photometer  (one of the following, given 1n order of preference):

          4.2.1  Nephelometer.

          4.2.2  Spectrophotometer:  For use  at  420 nm  with  light path  of
                 4 to 5 cm.

          4.2.3  Filter photometer:   With  a  violet  filter having a maximum
                 near 420 nm and a light path of 4 to 5 cm.

     4.3  Stopwatch;  If the magnetic stlrrer Is not equipped with an accurate
timer.
                                   9038 - 1
                                                         Revision
                                                         Date  September 1986

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     4.4  Measuring spoon;   Capacity 0.2 to 0.3 ml.


5.0  REAGENTS

     5.1  ASTM Type II water  (ASTM  D1193):    Water  should be monitored  for
Impurities.

     5.2  Conditioning reagent;  Slowly add  30  ml concentrated HC1  to 300 ml
Type II water, 100 ml 95% ethanol or Isopropanol, and 75 g NaCl  In solution in
a container.  Add 50 ml glycerol and mlx.b

     5.3  Barium chloride (BaCl2):  Crystals, 20 to 30 mesh.

     5.4  Sodium carbonate solution; (approximately  0.05  N):    Dry 3 to 5 g
primary standard N32C03 at 250*Cfor 4 hr  and cool  in a desiccator.   Weigh
2.5 + 0.2 g  (to the nearest  mg),  transfer to a 1-1 Her volumetric flask,  and
fill to the mark with Type II water.

     5.5   Proprietary reagents;  Such  as  Hach  Sulfaver  or  equivalent,  are
acceptable.

     5.6   Standard sulfate solution  (1.00  ml  =  100  ug  S04"2):  Prepare by
Paragraph  5.6.1 or 5.6.2.

           5.6.1  Standard sulfate solution from

               5.6.1.1  Standard sulfuric  add,   0.1   N:    Dilute  3.0  ml
           concentrated ^04 to  1   liter  with  Type  II  water.  Standardize
           against 40.0 ml of 0.05 N  Na2C03  solution (Paragraph 5.4) with about
           60 ml Type  II water  by titrating potentlometrically to  a pH of about
           5.   Lift electrodes  and rinse  Into   beaker.   Boll gently for 3 to 5
           m1n under a watch glass  cover.    Cool   to room temperature.  Rinse
           cover glass Into beaker.    Continue  tltratlon to the  pH Inflection
           point.  Calculate the normality of ^04  using:

                         N  =     A   x   B
                                53.00   x   C


           where:

                A  =  g  Na2C03  weighed into  1  liter flask  (Paragraph 5.4);

                B  =  ml N32C03 solution  used  in the  standardization;

                C  =  ml acid  used in tltratlon;

                5.6.1.2  Standard acid, 0.02 N:     Dilute appropriate amount of
           standard  add,  0.1 N (Paragraph  5.6.1.1)  to 1  liter  (use 200.00 ml
           standard  acid 1f  normality  1s   0.1000  N).  Check by standardization
           against 15  ml of  0.05 N Na2C03  solution  (Paragraph  5.4).


                                  9038 -  2
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                                                          Date   September  1986

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               5.6.1.3  Place 10 ml standard  sulfurlc add,  0.02 N (Paragraph
          5.6.1.2) in a 100-mL volumetric flask and dilute to the mark.
          5.6.2  Standard sulfate solution  from  NapSO^     Dissolve 147.9  mg
     anhydrous Na2S04 in  Type  II  water  in  a  1-liter  volumetric flask and
     dilute to the mark with Type II water.

6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING
     6.1  All samples must  have  been  collected  using  a sampling plan that
addresses the considerations discussed in Chapter Nine of  this manual.
     6.2  Preserve by refrigerating at 4*C.

7.0  PROCEDURE
     7.1  Formation of barium sulfate turbidity;
          7.1.1   Place a  100-mL  sample,  or  a suitable  portion  diluted  to
     100 mL, into a 250-mL Erlenmeyer flask.
          7.1.2   Add exactly 5.0 mL conditioning reagent  (Paragraph 5.2).
          7.1.3   Mix in the stirring apparatus.
          7.1.4   While the solution  is being  stirred, add a measured spoonful
     of BaCl2 crystals  (Paragraph 5.3) and begin timing immediately.
          7.1.5   Stir  exactly 1.0 min at constant  speed.
     7.2  Measurement  of  barium sulfate turbidity;
          7.2.1   Immediately  after the   stirring   period  has   ended,  pour
     solution  into  absorbance cell.
          7.2.2   Measure  turbidity  at 30-sec  intervals for 4 min.
          7.2.3   Record the maximum reading obtained  in the 4-min  period.
     7.3  Preparation  of  calibration curve;
          7.3.1   Prepare  calibration curve   using standard   sulfate solution
      (Paragraph  5.6).
          7.3.2   Space standards at 5-mg/L increments in  the 0-40  mg/L sulfate
     range.
          7.3.3   Above 50 mg/L  the  accuracy decreases and the  suspensions lose
     stability.
                                  9038 - 3
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                                                         Date  September 1986

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          7.3.4  Check reliability of calibration  curve by running a standard
     with every three or four samples.

     7.4  Correction for sample color and turbidity;

          7.4.1  Run a sample  blank  using  steps  7.1  and  7.2,  without the
     addition of barium chloride (Paragraph 7.1.4).

     7.5  Calculation;

          7.5.1  Read mg $04-2 from linear calibration curve:

                                      _o
                        2       mg SO.    x  1,000

                 m9 S0~ /L  '
                      4              ml sample
8.0  QUALITY CONTROL
     8.1  All quality control data should be maintained and available for easy
reference or Inspection.

     8.2  Calibration curves must be  composed  of  a  minimum  of a blank and
three standards.   A  calibration  curve  should  be  made  for  every hour of
continuous sample analysis.

     8.3  Dilute samples  if  they  are  more  concentrated  than  the highest
standard or 1f they fall on the plateau of a calibration curve.

     8.4  Employ a minimum  of  one  blank  per  sample  batch to determine if
contamination has occurred.

     8.5  Verify calibration  with  an  Independently  prepared check standard
every 15 samples.

     8.6  Run one spike  duplicate  sample  for  every  10  samples.   A spike
duplicate sample 1s a sample brought  through the whole sample preparation and
analytical process.


9.0  METHOD  PERFORMANCE

     9.1  Thirty-four analysts  1n 16 laboratories analyzed six synthetic water
samples containing exact Increments  of   Inorganic   sulfate with the following
results:
                                   9038 - 4
                                                         Revision
                                                         Date  September 1986

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Increment as
Sulfate
(mg/L)
8.6
9.2
110
122
188
199
Precision as
Standard Deviation
(mg/L)
2.30
1.78
7.86
7.50
9.58
11.8
Accuracy
Bias
(X)
-3.72
-8.26
-3.01
-3.37
+0.04
-1.70
as
Bias
(mg/L)
-0.3
-0.8
-3.3
-4.1
+0.1
-3.4
(Data from: FWPCA Method Study 1, Mineral and Physical Analyses.)


     9.2  A synthetic unknown sample containing 259 mg/L sulfate, 108 mg/L Ca,
82 mg/L Mg, 3.1 mg/L K, 19.9 mg/L Na, 241 mg/L chloride, 0.250 mg/L nitrite N,
1.1 mg/L nitrate N, and  42.5  mg/L  total alkalinity (contributed by NaHC03),
was analyzed 1n 19 laboratories  by  the turb1d1metr1c method, with a relative
standard deviation of 9.IX and a relative error of 1.2%.


10.0 REFERENCES

1.   Annual  Book  of  ASTM  Standards,  Part 31,  "Water,"  Standard D516-68,
Method B, p. 430 (1976).

2.   Standard Methods  for the Examination of Water and Wastewater,  14th ed.,
p. 496, Method 427C, (1975).
                                  9038 - 5
                                                         Revision
                                                         Date  September 1986

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                             METHOD 9036

                       SULFATE (TUR0IDZMETAIC)
C
 7.1.1
        Place
        •ample
    In flask for
    formation of
  barium aulfate
     turbidity
 7.1.8
       Add
  conditioning
 reagent and mix
 7.1.4
    Add BaClt
 crystals:  stir
  for 1 minute
 7.3.1
  Pour solution
 into absorbance
      cell
     o
     o
        Measure
      turbidity;
     record mm*.
       reading
                                                      7.3
      Prepare
    calibration
       curve
                                                      7.4
   Correct for
   •ample color
  and turbidity
                                                      7.5
                                                                  -2
                                                      Calculate  SO,
f     Stop      J
                     9038 - 6
                                                Revision       0
                                                Date   September  1986

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                                  METHOD 9056

            DETERMINATION OF INORGANIC ANIONS BY ION CHROMATOGRAPHY
1.0   SCOPE AND APPLICATION

      1.1   This method  addresses  the sequential determination  of the anions
chloride, fluoride,  bromide,  nitrate, nitrite, phosphate,  and  sulfate in the
collection solutions from the  bomb combustion of solid waste samples,  as well as
all water samples.

      1.2   The method detection  limit (MDL), the minimum concentration  of a
substance that can be measured and reported with 99% confidence that the value
is  above zero,  varies  for  anions   as  a  function  of  sample  size  and  the
conductivity scale used.  Generally, minimum detectable concentrations are in the
range of 0.05 mg/L for P  and 0.1 mg/L  for Br", CT,  N03",  N02", P043',  and S042' with
a  100-jiL sample  loop  and  a  10-/Ltmho  full-scale  setting  on  the conductivity
detector.  Similar values may  be achieved by using a higher scale  setting and an
electronic integrator.  Idealized detection limits of an order of magnitude lower
have been determined in  reagent water by  using a l-jumho/cm full-scale setting
(Table  1).    The  upper   limit  of  the method  is  dependent on  total  anion
concentration and may be determined experimentally.  These limits  may be  extended
by appropriate dilution.

2.0   SUMMARY OF METHOD

      2.1   A small  volume of combustate  collection solution or other  water
sample, typically 2 to 3  ml, is  injected into  an  ion chromatograph to flush and
fill a constant volume sample loop.  The sample is then injected  into  a stream
of carbonate-bicarbonate  eluent  of the same strength as the collection  solution
or water sample.

      2.2   The sample is pumped through three different ion exchange columns and
into a conductivity detector.  The first two columns, a precolumn  or guard column
and  a  separator column,  are  packed  with  low-capacity,  strongly basic  anion
exchanger.  Ions are separated into discrete bands based on their affinity for
the exchange  sites of the  resin.   The last column is a suppressor column that
reduces the background conductivity of the eluent to a low or negligible level
and  converts  the  anions  in  the  sample  to their  corresponding acids.    The
separated anions in their acid  form are measured using an electrical-conductivity
cell.  Anions are  identified  based on their retention  times compared to known
standards.  Quantitation  is accomplished by measuring the peak height or  area and
comparing it to a calibration curve generated from known standards.

3.0   INTERFERENCES

      3.1   Any species with a retention time similar to that of the desired ion
will interfere.   Large quantities of  ions eluting close to the ion of  interest
will also result in an interference.  Separation can be improved by adjusting the
eluent concentration and/or flow rate. Sample  dilution  and/or the use of the
method of standard additions  can also be  used.   For example,  high  levels of
organic acids may be present in  industrial  wastes,  which  may  interfere  with


                                   9056 -  1                       Revision 0
                                                                  September 1994

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inorganic anion analysis.  Two common species, formate and acetate, elute between
fluoride and chloride.

      3.2   Because  bromide  and nitrate  elute  very close  together,  they  are
potential  interferences  for  each other.   It is advisable not to have Br"/N03"
ratios higher than 1:10 or 10:1  if  both anions are to be quantified.  If nitrate
is observed to  be an interference with bromide,  use of an alternate  detector
(e.g.. electrochemical detector) is recommended.

      3.3   Method interferences may  be  caused  by contaminants  in the  reagent
water, reagents, glassware,  and other sample processing apparatus  that  lead  to
discrete artifacts or elevated baseline in ion chromatograms.

      3.4   Samples  that  contain  particles  larger  than  0.45 /xm and  reagent
solutions  that  contain particles  larger than 0.20  jum require  filtration  to
prevent damage to instrument columns and  flow systems.

      3.5   If a packed bed suppressor column is used, it will be slowly  consumed
during analysis and, therefore, will need to be regenerated.   Use  of either  an
anion fiber suppressor or  an  anion micromembrane suppressor eliminates the time-
consuming regeneration step through the use  of a continuous  flow  of regenerant.

4.0   APPARATUS AND MATERIALS

      4.1   Ion chromatograph,  capable  of delivering 2 to  5  ml  of eluent per
minute at a pressure  of 200 to 700 psi  (1.3 to 4.8 MPa).   The  chromatograph shall
be equipped with an injection valve, a 100-/uL sample loop,  and set up with the
following components, as  schematically illustrated in Figure  1.

            4.1.1    Precolumn, a guard column placed before the separator column
      to protect  the separator  column from being  fouled  by particulates  or
      certain organic constituents (4 x 50 mm,  Dionex P/N 030825  [normal run],
      or P/N 030830 [fast run], or equivalent).

            4.1.2    Separator   column,   a  column  packed  with   low-capacity
      pellicular anion exchange resin that is styrene divinylbenzene-based has
      been found to be suitable for resolving F",  Cl", N02",  P04"3,  Br',  N03", and
      S04"2 (see Figure 2)  (4 x 250 mm, Dionex P/N 03827  [normal run], or P/N
      030831 [fast run], or equivalent).

            4.1.3    Suppressor  column,  a  column  that is capable of converting
      the eluent  and  separated anions to their respective  acid  forms  (fiber,
      Dionex P/N 35350, micromembrane, Dionex P/N 38019 or equivalent).

            4.1.4    Detector,    a    low-volume,    flowthrough,    temperature-
      compensated, electrical  conductivity   cell  (approximately  6 juL   volume,
      Dionex,  or equivalent)  equipped  with a  meter capable of  reading from 0  to
      1,000 /Ltseconds/cm on a linear scale.

            4.1.5    Pump, capable of delivering a constant flow of approximately
      2 to 5 mL/min throughout the test and tolerating a pressure  of 200 to
      700 psi  (1.3 to 4.8 MPa).
                                   9056 - 2                       Revision 0
                                                                  September 1994

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      4.2   Recorder,  compatible  with the  detector output with  a full-scale
response time in 2 seconds or less.

      4.3   Syringe, minimum capacity of 2 ml and equipped with  a male pressure
fitting.

      4.4   Eluent and regenerant  reservoirs,  suitable containers for storing
eluents and regenerant.  For example, 4 L collapsible bags can be used.

      4.5   Integrator, to integrate the area under the chromatogram.  Different
integrators can perform this task  when  compatible with the electronics of the
detector  meter  or  recorder.    If  an integrator  is  used,  the  maximum  area
measurement must be within the linear range of the integrator.

      4.6   Analytical balance, capable of weighing to the nearest 0.0001 g.

      4.7   Pipets, Class A volumetric flasks, beakers:  assorted sizes.

5.0   REAGENTS

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

      5.2   Reagent water.   All  references  to water in this method  refer to
reagent water, as defined in Chapter One.   Column life may be extended by passing
reagent water through a 0.22-jum filter prior to use.

      5.3   Eluent, 0.003M NaHC03/0.0024M Na2C03.   Dissolve  1.0080 g of sodium
bicarbonate (0.003M NaHC03) and 1.0176 g of sodium carbonate (0.0024M Na2C03) in
reagent water and dilute to 4 L with reagent water.

      5.4   Suppressor regenerant  solution.  Add  100  ml of IN H2S04  to 3  L of
reagent water in a collapsible bag and dilute to 4 L with reagent water.

      5.5   Stock solutions (1,000 mg/L).

            5.5.1    Bromide  stock  solution (1.00  ml  =  1.00  mg Br').    Dry
      approximately 2 g of sodium bromide  (NaBr)  for 6 hours at 150ฐC, and cool
      in a desiccator.  Dissolve 1.2877 g of the dried salt  in  reagent water,
      and dilute to 1 L with  reagent water.

            5.5.2   Chloride stock solution (1.00 ml = 1.00 mg Cl").  Dry sodium
      chloride (NaCl) for 1 hour at 600ฐC, and cool in a desiccator.  Dissolve
      1.6484 g of the dry salt  in reagent  water,  and dilute to 1 L with reagent
      water.

            5.5.3   Fluoride stock solution (1.00 ml = 1.00 mg F").   Dissolve
      2.2100 g of sodium fluoride (NaF) in reagent water,  and dilute to 1 L with
      reagent water.  Store in chemical-resistant glass or polyethylene.

                                   9056 - 3                       Revision 0
                                                                  September 1994

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            5.5.4    Nitrate stock  solution  (l.OQ  ml  =  1.00  mg  N03').   Dry
      approximately  2 g  of sodium  nitrate  (NaN03)  at  105ฐC for  24  hours.
      Dissolve exactly 1.3707 g of the dried  salt in  reagent water,  and  dilute
      to 1 L with reagent water.

            5.5.5    Nitrite stock solution  (1.00 ml = 1.00 mg N02").    Place
      approximately 2 g of sodium nitrate (NaN02)  in a 125 mL beaker  and  dry to
      constant weight (about 24 hours) in a desiccator  containing concentrated
      H2S04.   Dissolve 1.4998 g of the dried salt in  reagent water,  and  dilute
      to  1  L with  reagent  water.    Store  in  a  sterilized glass  bottle.
      Refrigerate and prepare monthly.

            NOTE: Nitrite  is easily  oxidized,  especially  in  the  presence of
            moisture, and only fresh reagents are to  be used.

            NOTE:  Prepare   sterile  bottles  for  storing  nitrite  solutions by
            heating for 1 hour at 170ฐC  in  an air oven.

            5.5.6    Phosphate stock solution (1.00 ml =  1.00 mg P043"). Dissolve
      1.4330 g of potassium dihydrogen phosphate (KH2P04)  in  reagent  water, and
      dilute to 1 L with reagent water.  Dry sodium  sulfate  (Na2S04)  for  1  hour
      at 105ฐC and cool in  a desiccator.

            5.5.7    Sulfate stock solution  (1.00 mL = 1.00 mg  S042").  Dissolve
      1.4790  g  of the dried  salt in  reagent water, and dilute  to  1  L  with
      reagent water.

      5.6   Anion working   solutions.    Prepare  a  blank and  at  least   three
different working solutions  containing the following  combinations of anions. The
combination anion solutions must be  prepared in Class A  volumetric flasks.  See
Table 2.

            5.6.1    Prepare a  high-range standard  solution  by  diluting the
      volumes of each anion  specified  in Table  2  together to 1 L with reagent
      water.

            5.6.2    Prepare the intermediate-range standard solution by diluting
      10.0 ml of the high-range standard solution (see Table 2) to 100 ml  with
      reagent water.

            5.6.3    Prepare the low-range standard solution  by  diluting 20.0 ml
      of the intermediate-range standard solution (see Table 2) to 100 ml  with
      reagent water.

      5.7   Stability of standards.   Stock standards  are  stable for  at least 1
month when stored at 4ฐC.  Dilute working standards  should be prepared weekly,
except those that contain nitrite  and  phosphate, which should be prepared  fresh
daily.

6.0   SAMPLE COLLECTION,  PRESERVATION, AND HANDLING

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

                                   9056  - 4                       Revision 0
                                                                  September 1994

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      6.2   Analyze the samples as  soon as possible after collection.  Preserve
by refrigeration at 4ฐC.

7.0   PROCEDURE

      7.1   Calibration

            7.1.1   Establish   ion   chromatographic   operating   parameters
      equivalent to those indicated in Table 1.

            7.1.2   For each analyte of interest, prepare calibration standards
      at  a minimum  of  three  concentration  levels  and  a  blank  by  adding
      accurately measured volumes of one or more stock  standards  to a Class A
      volumetric flask  and diluting  to  volume with  reagent water.    If  the
      working range exceeds the linear range of the system, a sufficient number
      of standards  must be  analyzed to allow an accurate  calibration  curve to be
      established.   One of the standards  should  be  representative of a concen-
      tration near,  but  above, the  method  detection limit  if  the  system is
      operated on an applicable attenuator range.  The  other standards should
      correspond to the range of concentrations expected  in  the sample or should
      define the working range of  the detector.   Unless the attenuator range
      settings  are proven  to  be  linear,  each setting  must  be  calibrated
      individually.

            7.1.3   Using  injections of 0.1 to 1.0  ml (determined by injection
      loop volume)  of each  calibration standard, tabulate  peak  height or area
      responses against the concentration.  The results  are  used  to prepare a
      calibration curve  for each  analyte.   During this procedure,  retention
      times must be recorded.

            7.1.4   The  working calibration  curve  must be  verified  on  each
      working day,  or whenever the anion  eluent  strength  is  changed,  and  for
      every batch of samples.   If the response  or retention  time for any analyte
      varies from  the  expected values by more  than ฑ  10%,  the test  must be
      repeated,  using fresh calibration standards.   If the  results  are still
      more than + 10%, an entirely new calibration curve must be  prepared  for
      that analyte.

            7.1.5   Nonlinear  response  can result when the  separator column
      capacity is exceeded (overloading).   Maximum  column loading (all anions)
      should not exceed about  400  ppm.

      7.2   Analyses

            7.2.1   Sample preparation. When  aqueous samples are injected,  the
      water passes  rapidly through the columns,  and a negative  "water dip" is
      observed  that may  interfere  with  the early-eluting  fluoride  and/or
      chloride ions.  The  water dip  should  not  be  observed  in  the  combustate
      samples;  the  collecting  solution is a concentrated eluent  solution that
      will "match"  the eluent strength when diluted to 100-mL with reagent water
      according to the bomb combustion procedure.   Any dilutions required in
      analyzing other water samples  should  be made with the  eluent solution.
      The water  dip, if present, may be removed by adding concentrated eluent to


                                   9056 -  5                        Revision  0
                                                                  September  1994

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all samples and standards.   When  a manual  system  is used, it is necessary
to micropipet  concentrated buffer  into  each  sample.    The  recommended
procedures follow:

(1)   Prepare a 100-mL stock of eluent 100 times normal concentration by
      dissolving  2.5202  g  NaHC03 and 2.5438 g  Na2C03  in  100-mL reagent
      water.  Protect the volumetric flask from air.

(2)   Pipet 5 ml  of each sample into a  clean  polystyrene micro-beaker.
      Micropipet 50 /xL of the concentrated buffer into the beaker and stir
      well.

Dilute the samples with eluent, if necessary,  to concentrations within the
linear range of the calibration.

      7.2.2   Sample  analysis.

              7.2.2.1    Start   the   flow of   regenerant  through  the
      suppressor column.

              7.2.2.2    Set up the recorder range for maximum sensitivity
      and any additional  ranges needed.

              7.2.2.3    Begin to  pump  the eluent through  the columns.
      After a stable baseline is obtained, inject a midrange standard.  If
      the peak height  deviates  by more than 10% from  that of the previous
      run, prepare fresh standards.

              7.2.2.4    Begin  to  inject standards  starting  with  the
      highest concentration standard and decreasing in concentration.  The
      first sample should be a quality control  reference sample to check
      the calibration.

              7.2.2.5    Using the  procedures  described in  Step  7.2.1,
      calculate the regression  parameters for the initial standard curve.
      Compare these values with those  obtained  in  the  past.    If they
      exceed the  control  limits,  stop   the  analysis  and  look for  the
      problem.

              7.2.2.6    Inject  a  quality control  reference sample.   A
      spiked sample or a sample  of known content must  be  analyzed with
      each  batch   of  samples.    Calculate  the  concentration  from  the
      calibration  curve  and compare  the known  value.   If  the  control
      limits are exceeded,  stop the analysis  until  the problem is  found.
      Recalibration is necessary.

              7.2.2.7    When an acceptable value has  been  obtained for
      the quality control sample, begin  to inject the samples.

              7.2.2.8    Load  and  inject a  fixed  amount of  well-mixed
      sample.    Flush  injection  loop  thoroughly,  using each  new sample.
      Use the  same size loop  for standards  and samples.   Record  the
                             9056 - 6                       Revision 0
                                                            September 1994

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      resulting  peak size in  area  or peak height  units.   An automated
      constant volume  injection system may also be  used.

               7.2.2.9    The  width  of the retention time window used to
      make  identifications should  be based  on measurements  of actual
      retention  time variations  of standards over  the  course of a day.
      Three times the  standard deviation of a retention time can be used
      to calculate a suggested window size for a compound.  However, the
      experience of the analyst should weigh heavily in the interpretation
      of chromatograms.

               7.2.2.10   If the response for the peak exceeds  the working
      range of the system, dilute the sample with an appropriate amount of
      reagent water  and reanalyze.

               7.2.2.11   If the  resulting  chromatogram  fails to produce
      adequate resolution,  or if  identification  of specific  anions  is
      questionable,  spike  the sample  with  an  appropriate  amount  of
      standard and reanalyze.

      NOTE: Nitrate  and sulfate  exhibit the greatest amount  of change,
      although all  anions are affected to some degree.   In some cases,
      this   peak    migration   can   produce    poor    resolution    or
      misidentification.

7.3   Calculation

      7.3.1    Prepare   separate  calibration  curves for  each anion  of
interest by plotting peak size in  area, or peak height units of standards
against concentration values.   Compute sample concentration by comparing
sample peak response with the standard curve.

      7.3.2    Enter  the  calibration  standard  concentrations and  peak
heights from  the integrator  or  recorder  into  a  calculator with linear
least squares capabilities.

      7.3.3    Calculate the following parameters:   slope (s), intercept
(I), and correlation coefficient  (r).  The  slope  and intercept  define a
relationship between  the concentration and  instrument  response  of the
form:
                                       (1)


where:
       yi = predicted instrument response
       $i = response slope
       Xj = concentration of standard i
       I = intercept
                             9056 - 7                       Revision 0
                                                            September 1994

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      Rearrangement of the above equation yields the concentration corresponding
      to an instrumental measurement:
                             x,  =  (y, -  I)/s,   (2)

      where:

             Xj = calculated concentration  for a  sample
             yj = actual  instrument  response for  a sample
             Sj and I are calculated slope and  intercept  from calibration above.

            7.3.4    Enter  the  sample  peak  height   into  the  calculator,  and
      calculate the sample concentration in milligrams per liter.

8.0   QUALITY CONTROL

      8.1   All quality control  data should be maintained and  available  for easy
reference and inspection.  Refer to Chapter One for additional quality control
guidelines.

      8.2   After every 10  injections,  analyze a midrange calibration standard.
If the instrument response has changed by more than 5%, recalibrate.

      8.3   Analyze one in every ten samples in duplicate.  Take the duplicate
sample through the entire sample preparation and analytical process.

      8.4   A matrix spiked sample  should  be  run for each analytical batch or
twenty samples, whatever is more frequent, to determine matrix effects.

9.0   METHOD PERFORMANCE

      9.1   Single-operator accuracy and precision  for  reagent,  drinking and
surface water, and  mixed domestic  and industrial  wastewater are listed  in Table
3.

      9.2   Combustate samples.  These data are based on 41 data points obtained
by six laboratories who each analyzed four used crankcase oils and  three  fuel oil
blends with crankcase in duplicate.  The oil samples  were combusted using Method
5050.  A data  point  represents  one duplicate analysis  of  a  sample.   One data
point was judged to be an outlier and was not included in the results.

            9.2.1    Precision.  The precision of the method as determined by the
      statistical examination of interlaboratory test results is as follows:

            Repeatability - The difference between successive results obtained
      by the sample  operator with  the  same apparatus under constant operating
      conditions on  identical test  material would exceed,  in  the long  run,  in
      the normal  and  correct  operation  of the test method, the following values
      only in 1 case in 20 (see Table 4):


      *where x is the average of two results in /ng/g.


                                   9056 - 8                       Revision 0
                                                                  September 1994

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                         Repeatability =20.9

            Reproduclbilitv - The difference between two single and independent
      results obtained by different  operators working in different laboratories
      on identical test  material  would exceed,  in  the  long  run,  the following
      values only in 1 case in 20:
                        Reproducibility =42.1


      *where x is the average value of two results  in M9/9-

            9.2.2    Bias.   The  bias  of this  method varies with concentration,
      as shown in Table 5:

                     Bias  =  Amount  found  - Amount expected

10.0  REFERENCES

1.    Environmental  Protection  Agency.   Test Method for  the  Determination  of
Inorganic Anions in Water  by Ion Chromatography.  EPA Method 300.0.   EPA-600/4-
84-017.  1984.

2.    Annual Book  of ASTM Standards,  Volume  11.01  Water  D4327,  Standard  Test
Method for Anions in Water by Ion  Chromatography, pp.  696-703.  1988.

3.    Standard Methods for the Examination of Water and Wastewater,  Method  429,
"Determination of Anions by Ion  Chromatography with Conductivity Measurement,"
16th Edition of Standard Methods.

4.    Dionex, 1C 16  Operation and  Maintenance Manual,  PN  30579,  Dionex  Corp.,
Sunnyvale, CA  94086.

5.    Method  detection  limit   (MDL)   as  described  in  "Trace  Analyses   for
Wastewater," J.  Glaser, D. Foerst,  G.  McKee,  S.  Quave,  W.  Budde,  Environmental
Science and Technology, Vol. 15, Number 12, p.  1426,  December  1981.

6.    Gaskill, A.;  Estes,  E. D.; Hardison,  D.  L.; and Myers, L.  E.   Validation
of Methods for Determining Chlorine in Used Oils and Oil  Fuels.  Prepared for
U.S. Environmental  Protection Agency Office of Solid Waste.   EPA Contract No. 68-
01-7075, WA 80.   July 1988.
                                   9056 -  9                        Revision  0
                                                                  September 1994

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                                   TABLE 1.
                CHROMATOGRAPHIC CONDITIONS  AND METHOD DETECTION
                            LIMITS IN REAGENT WATER
Analyte
Fluoride
Chlorine
Nitrite-N
o-Phosphate-P
Nitrate-N
Sul fate
Retention8
time
min
1.2
3.4
4.5
9.0
11.3
21.4
Relative
retention
time
1.0
2.8
3.8
7.5
9.4
17.8
Method"
detection limit,
mg/L
0.005
0.015
0.004
0.061
0.013
0.206
Standard conditions:

Columns - As specified in 4.1.1-4.1.3
Detector - As specified in 4.1.4
Eluent - As specified in 5.3

Concentrations of mixed standard (mg/L)
            Fluoride 3.0
            Chloride 4.0
            Nitrite-N 10.0
Sample loop - 100 juL
Pump volume - 2.30 mL/min
o-Phosphate-P 9.0
Nitrate-N 30.0
Sulfate 50.0
aThe retention time given for each anion  is based on the equipment  and analytical
conditions described in the method.  Use  of other analytical columns or different
elutant concentrations will effect retention times accordingly.

bMDL calculated from data obtained using  an attentuator setting of  l-/umho/cm full
scale.  Other settings would produce an MDL proportional to their  value.
                                   9056  -  10
            Revision 0
          ,  September 1994

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                                   TABLE  2.
         PREPARATION OF STANDARD SOLUTIONS  FOR  INSTRUMENT CALIBRATION
High
Range
Standard1
Fluoride (F")
Chloride (CV)
Nitrite (N02")
Phosphate (P043')
Bromide (Br)
Nitrate (N(V)
Sulfate (S042-)
10
10
20
50
10
30
100
An ion
concentration
mg/L
10
10
20
50
10
30
100
Intermediate-
range standard,
mg/L
(see 5.6.2)
1.0
1.0
2.0
5.0
1.0
3.0
10.0
Low-range
standard,
mg/L (see
5.6.3)
0.2
0.2
0.4
1.0
0.2
0.6
2.0
1Milliliters of each stock solution  (1.00 mL = 1.00 mg) diluted to 1 L (see sec.
 5.6.1).
                                   9056 -  11                        Revision  0
                                                                   September 1994

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                                    TABLE 3.
                     SINGLE-OPERATOR ACCURACY AND PRECISION
Samp] e
Analyte type
Chloride



Fluoride



Nitrate-N



Nitrite-N



o-Phosphate-P



Sulfate



RW
DW
SW
WW
RW
DW
SW
WW
RW
DW
SW
WW
RW
DW
SW
WW
RW
DE
SW
WW
RW
DW
SW
WW
Spike
mg/L
0.050
10.0
1.0
7.5
0.24
9.3
0.50
1.0
0.10
31.0
0.50
4.0
0.10
19.6
0.51
0.52
0.50
45.7
0.51
4.0
1.02
98.5
10.0
12.5
Number
of
replicates
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
Mean
recovery,
%
97.7
98.2
105.0
82.7
103.1
87.7
74.0
92.0
100.9
100.7
100.0
94.3
97.7
103.3
88.2
100.0
100.4
102.5
94.1
97.3
102.1
104.3
111.6
134.9
Standard
deviation,
mg/L
0.0047
0.289
0.139
0.445
0.0009
0.075
0.0038
0.011
0.0041
0.356
0.0058
0.058
0.0014
0.150
0.0053
0.018
0.019
0.386
0.020
0.04
0.066
1.475
0.709
0.466
RW = Reagent water.
DW = Drinking water.
SW = Surface water.
WW = Wastewater.
                                   9056 - 12
                                         Revision  0
                                         September 1994

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                                   TABLE 4.
               REPEATABILITY AND REPRODUCIBILITY FOR CHLORINE IN
              USED OILS BY BOMB OXIDATION AND ION CHROMATOGRAPHY
Average value,   '         Repeatability,          Reproducibility,
     M9/9                      M9/9                        M9/9
500
1,000
1,500
2,000
2,500
3,000
467
661
809
935
1,045
1,145
941
1,331
1,631
1,883
2,105
2,306
                                   TABLE 5.
              RECOVERY  AND BIAS  DATA FOR CHLORINE IN USED OILS BY
                     BOMB OXIDATION AND ION CHROMATOGRAPHY
Amount
Expected
M9/9
320
480
920
1,498
1,527
3,029
3,045
Amount
found
M9/9
567
773
1,050
1,694
1,772
3,026
2,745

Bias,
M9/9
247
293
130
196
245
-3
-300

Percent,
bias
+77
+61
+14
+13
+16
0
-10
                                   9056  -  13                       Revision 0
                                                                  September 1994

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           FIGURE 1
SCHEMATIC OF ION CHROMATOGRAPH

                                                      WASTE
 (1)  Eluent  reservoir
 (2)  Pump
 (3)  Precolumn
 (4)  Separator  column
 (5)  Suppressor column
 (6)  Detector
 (7)  Recorder or Integrator,  or both
          9056  -  14
Revision 0
September 1994

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       FIGURE 2
TYPICAL ANION  PROFILE
                  so;1
         MINUTES
      9056 - 15
Revision 0
September 1994

-------
(   Start    J
                                    METHOD 9056
             DETERMINATION OF INORGANIC ANIONS  BY  ION CHROMATOGRAPHY
1
7.1.1 Establish ion
chromatographic
operating
parameters.
1
7.1 .2 Prepare
calibration
standards at a
minimum of three
concentration
levels and a blank.
\r
7.1 .3 Prepare
calibration curve.
V
7.1.4 Verify the
calibration curves
each working day or
whenever the anion
eluent is changed,
and for every batch
of samples.


/ ^\^ 7.2.1 If a dilution
/ 7.2.1 Are\ Aqueous is necessary the
/samples aqueousSj 	 w, dilution should
\ <" extracts?/ w bซ madซ witn
N. • / eluent solution.
[Extracts
7.2.2 Analyze
standards beginning
with the highest
concentration and
decreasing in
concentration.
1
7.2.1 Add
concentrated
4 	 ซli|ซnt tn qll
samples and
standards to
remove water dip.


w
W

7.2.2.5 Compare
results to
calibration curve;
if results exceed
control limits,
identify problem
before proceeding.
\1
7.2.2.6 Inject a
spiked sample of
known cone.;
calculate the cone.
from the calibration
curve; if result
exceeds control
limits, find problem
before proceeding.
> f
7.2.2.7 Begin
sample analysis.
\r
7.2.2.8 Analyze all
samples in same
manner.
^r
./7.2.2.10\
./Does responseV
f for peak exceed
>^ working /
\^ range? /
TNO
Y
7.3.1 Prepare
sample calibration
curves for each
anion of interest
and compute sample
concentration.

^

7.2.2.10 Dilute
! ^ sample with
reagent water.

7.3.3 Calculate
w concentrations
f from instrumental
response.
4
( Stop J
                                     9056  -  16
Revision 0
September 1994

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                                 METHOD 9060

                            TOTAL ORGANIC CARBON
1.0  SCOPE AND APPLICATION

     1.1  Method 9060 1s used to determine the concentration of organic carbon
1n ground  water,  surface  and  saline  waters,  and  domestic and Industrial
wastes.  Some restrictions are noted 1n Sections 2.0 and 3.0.

     1.2  Method 9060 1s  most  applicable  to  measurement  of organic carbon
above 1 mg/L.


2.0  SUMMARY OF METHOD

     2.1  Organic carbon 1s  measured  using  a  carbonaceous  analyzer.  This
Instrument converts the organic carbon 1n  a sample to carbon dioxide (C02) by
either catalytic combustion or wet chemical oxidation.  The C02 formed 1s then
either measured directly by an Infrared detector or converted to methane (CH4)
and measured by a flame 1on1zat1on detector.    The  amount of C02 or CH4 In a
sample 1s directly proportional to  the concentration of carbonaceous material
1n the sample.

     2.2  Carbonaceous analyzers are capable of  measuring all forms of carbon
1n a sample.    However,  because  of  various properties of carbon-containing
compounds 1n liquid samples,  the  manner  of  preliminary sample treatment as
well as the  Instrument  settings  will  determine  which  forms of carbon are
actually measured.  The forms of  carbon   that  can be measured by Method 9060
are:

       1.  Soluble, nonvolatile organic carbon:  e.g., natural  sugars.

       2.  Soluble, volatile organic  carbon:    e.g., mercaptans,  alkanes, low
          molecular weight alcohols.

       3.   Insoluble,  partially volatile   carbon:     e.g.,  low molecular weight
          oils.

       4.   Insoluble,   particulate   carbonaceous  materials:     e.g.,  cellulose
           fibers.

       5.   Soluble or Insoluble   carbonaceous   materials   adsorbed  or entrapped
           on Insoluble Inorganic suspended matter:   e.g.,  oily matter adsorbed
           on silt particles.

      2.3   Carbonate  and bicarbonate are  Inorganic  forms of carbon and must  be
 separated from the total  organic  carbon  value.    Depending on the Instrument
 manufacturer's Instructions,  this  separation   can  be accomplished by either a
 simple mathematical  subtraction,  or by  removing  the carbonate and bicarbonate
 by converting them to C02 with  degassing prior to analysis.


                                   9060 - 1
                                                          Revision       0
                                                          Date  September  1986

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3.0  INTERFERENCES

     3.1  Carbonate and bicarbonate carbon represent an Interference under the
terms of this test and must be  removed or accounted for 1n the final  calcula-
tion.

     3.2  This procedure 1s applicable  only  to homogeneous samples which can
be Injected Into  the  apparatus  reprodudbly  by  means of a m1crol1ter-type
syringe or plpet.  The openings of the syringe or plpet limit the maximum size
of particle which may be Included 1n the sample.

     3.3  Removal of carbonate  and  bicarbonate  by acidification and purging
with nitrogen, or other Inert gas, can  result 1n the loss of volatile organic
substances.
4.0  APPARATUS AND MATERIALS

     4.1  Apparatus  for  blending  or  homogenizing  samples;    Generally,  a
War1 ng-type blender Is satisfactory.

     4.2  Apparatus for total and dissolved organic carbon;

          4.2.1  Several  companies   manufacture   analyzers   for  measuring
     carbonaceous material In  liquid  samples.    The most appropriate system
     should be selected based on consideration  of  the types of samples to be
     analyzed, the expected concentration range, and the forms of carbon to be
     measured.

          4.2.2  No specific analyzer  1s  recommended  as  superior.   If the
     technique of chemical oxidation 1s  used,  the laboratory must be certain
     that the Instrument  Is  capable  of  achieving  good carbon recoveries In
     samples containing parti culates.


5.0  REAGENTS

     5.1  ASTM Type II water   (ASTM  D1193);    Water  should be monitored for
Impurities, and  should be boiled and cooled to  remove
      5.2   Potassium hydrogen   phthalate,   stock  solution,  1,000 mg/L carbon:
 Dissolve  0.2128 g  of potassium  hydrogen phthalate  (primary standard grade) 1n
 Type  II water and  dilute  to  100.0  ml.
      NOTE;   Sodium  oxalate   and  acetic   add  are not  recommended as stock
           solutions.

      5.3   Potassium hydrogen  phthalate, standard  solutions;   Prepare standard
 solutions from the stock  solution  by dilution with  Type II water.
                                   9060 - 2
                                                         Revision
                                                         Date  September 1986

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     5.4  Carbonate-bicarbonate, stock  solution,  1,000  mg/L  carbon:  Weigh
0.3500 g of sodium bicarbonate and0.4418g of sodium carbonate and transfer
both to the same 100-mL volumetric flask.  Dissolve with Type II water.

     5.5  Carbonate-bicarbonate,  standard  solution;    Prepare  a  series of
standards similar to Step 5.3.
     NOTE;  This standard 1s not required by some Instruments.

     5.6  Blank solution;  Use the same  Type  II water as was used to prepare
the standard solutions.
6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

     6.1  All samples must be collected  using  a sampling plan that addresses
the considerations discussed 1n Chapter Nine of this manual.

     6.2  Sampling and storage  of  samples  1n  glass  bottles 1s preferable.
Sampling and storage 1n plastic  bottles such as conventional polyethylene and
cubital ners 1s permissible 1f  1t  1s  established  that the containers do not
contribute contaminating organlcs to the samples.
     NOTE;  A brief study performed  1n the EPA Laboratory Indicated that Type
          II water stored 1n new,  1-qt  cubital ners did not show any Increase
          1n organic carbon after 2 weeks' exposure.

     6.3  Because of the possibility  of  oxidation or bacterial decomposition
of some components of aqueous samples,  the time between sample collection and
the start of analysis should be minimized.   Also, samples should be kept cool
(4*C) and protected from sunlight and atmospheric oxygen.

     6.4  In Instances where analysis  cannot  be  performed  within 2 hr from
time of sampling, the sample 1s acidified  (pH ฃ 2) with HC1 or


7.0  PROCEDURE

     7.1  Homogenize the sample 1n a blender.
     NOTE;   To  avoid  erroneously  high  results,   Inorganic  carbon must be
          accounted for.  The preferred method  1s to measure total carbon and
          Inorganic carbon and to  obtain  the  organic carbon  by subtraction.
          If this 1s not possible, follow  Steps 7.2 and 7.3 prior to analysis;
          however, volatile organic  carbon may be lost.

     7.2  Lower  the pH of the sample to 2.

     7.3  Purge  the sample with nitrogen for  10 m1n.

     7.4  Follow Instrument  manufacturer's   Instructions  for  calibration,
procedure,  and calculations.

     7.5  For calibration of the Instrument,  a  series of  standards should be
used that encompasses the expected concentration range of the samples.


                                  9060 - 3
                                                         Revision      0
                                                         Date  September 1986

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     7.6  Quadruplicate analysis 1s required.  Report both the average and the
range.


8.0  QUALITY CONTROL

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

     8.2  Employ a minimum  of  one  blank  per  sample  batch to determine 1f
contamination or any memory effects are occurring.

     8.3  Verify calibration  with  an  Independently  prepared check standard
every 15 samples.

     8.4  Run one spike duplicate sample  for  every  10 samples.  A duplicate
sample  Is a sample brought through the whole sample preparation and analytical
process.


9.0  METHOD PERFORMANCE

     9.1  Precision and accuracy data are available 1n Method 415.1 of Methods
for Chemical Analysis of Water  and Wastes.


10.0 REFERENCES

1.   Annual Book  of ASTM  Standards,  Part  31,   "Water,"  Standard D 2574-79,
p. 469  (L976).

2.   Standard Methods  for the  Examination of Water and Wastewater,  14th ed.,
p. 532, Method 505  (1975).
                                   9060 - 4
                                                          Revision
                                                          Date  September 1986

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                           METHOD 9060

                      TOTAL ORGANIC CARBON
(
    5"rt
o
7.1
  Homogenize
the •ample in
  e blender
7.2
                                                 Follow manufacturer's
                                                   Instructions  for
                                                     cal Ibretlon.
                                                    procedure,  ana
                                                  calculatlonc using
                                                 carbonaceous analyzer
  Lower the
  •ample PH
7.3
                                                   7.5
                                                     Use series  of
                                                     standards  for
                                                      calibration
  Purge the
 •ample with
  nitrogen
                                                   7.6
                                                     Ouadruplicate
                                                       analysis
   O
                                                   f      Stop       j
                    9060 - 5
                                               Revision       0
                                               Date   September 1986

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                                 METHOD 9065

       PHENOLICS (SPECTROPHOTOMETRIC.  MANUAL 4-AAP WITH DISTILLATION)


1.0  SCOPE AND APPLICATION

     1.1  This method 1s applicable to the analysis of ground water,  drinking,
surface, and saline waters, and domestic and Industrial wastes.

     1.2  The method 1s capable of measuring  phenolic materials at the 5 ug/L
level when the colored end product  1s extracted and concentrated 1n a solvent
phase using phenol as a standard.

     1.3  The method 1s capable  of  measuring phenolic materials that contain
more than 50 ug/L  1n  the  aqueous  phase  (without solvent extraction) using
phenol as a standard.

     1.4  It 1s not  possible  to  use  this  method  to differentiate between
different kinds of phenols.


2.0  SUMMARY OF METHOD

     2.1  Phenolic materials react with  4-am1noant1pyr1ne  1n the presence of
potassium ferrlcyanide at a pH of 10 to form a stable reddish-brown antlpyrlne
dye.  The amount  of  color  produced  1s  a  function of the concentration of
phenolic material.


3.0  INTERFERENCES

     3.1  For most samples a  preliminary  distillation  1s required to remove
Interfering materials.

     3.2  Color response of phenolic  materials  with 4-am1noant1pyr1ne Is not
the  same for all compounds.    Because  phenolic-type wastes usually contain a
variety of phenols, 1t 1s not possible to duplicate a mixture of phenols to be
used as a standard.  For  this   reason  phenol has been selected as a standard
and  any color produced by the reaction of other phenolic compounds 1s reported
as phenol.  This value  will  represent  the minimum concentration of phenolic
compounds present 1n the sample.

     3.3  Interferences from sulfur compounds are  eliminated by acidifying the
sample  to a pH of <4 with H2S04  and aerating briefly by stirring.

     3.4  Oxidizing agents such   as   chlorine,  detected  by the liberation of
Iodine  upon acidification  1n  the presence  of  potassium  Iodide, are  removed
Immediately after sampling by the addition  of  an excess  of ferrous ammonium
sulfate.  If  chlorine  1s not  removed,  the phenolic compounds may  be partially
oxidized and  the  results may be  low.
                                   9065 - 1
                                                          Revision
                                                         Date  September  1986

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4.0  APPARATUS AND MATERIALS
     4.1  Distillation apparatus;   All   glass,   consisting  of a  1-liter Pyrex
distilling apparatus with Graham condenser.
     4.2  pH meter.
     4.3  Spectrophotometer;  For use at 460 or 510 nm.
     4.4  Funnels.
     4.5  Filter paper.
     4.6  Membrane filters.
     4.7  Separatory funnels;  500- or 1,000-mL.
     4.8  Nessler tubes;  Short or long form.
5.0  REAGENTS
     5.1  ASTM Type II water  (ASTM  D1193):    Water  should be monitored for
Impurities.
     5.2  Sulfurlc add solution. ^504;  Concentrated.
     5.3  Buffer solution;  Dissolve 16.9 g NfyCl 1n 143 ml concentrated  NfyOH
and dilute to 250 ml  with Type II  water.   Two ml  of buffer  should adjust
100 ml  of distillate to pH 10.
     5.4  Am1noant1pyr1ne solution;  Dissolve 2 g of 4-am1noant1pyr1ne (4-AAP)
In Type II water and dilute to 100 ml.
     5.5  Potassium ferrlcyanlde solution;  Dissolve  8 g of K3Fe(CN)s 1n Type
II water and dilute to 100 ml.
     5.6  Stock phenol .solution;  Dissolve 1.0  g phenol 1n freshly boiled and
cooled  Type II water and dilute to 1 liter (1 ml • 1 ng phenol).
     NOTE;  This solution Is hydroscoplc and toxic.
     5.7  Working  solution A;  Dilute 10  ml  stock phenol  solution to 1  liter
with Type II water (1 ml = 10 ug phenol).
     5.8  Working  solution B;  Dilute 100 ml of working solution A to 1,000 ml
with Type II water (1 ml = 1 ug phenol).
     5.9  Chloroform.
                                  9065 - 2
                                                         Revision
                                                         Date  September 1986

-------
     5.10  Ferrous ammonium sulfate;  Dissolve 1.1  g  1n 500 ml Type II water
containing 1 mL concentrated H2S04 and  dilute  to 1 liter with freshly boiled
and cooled Type II water.


6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

     6.1  All samples must  have  been  collected  using  a sampling plan that
addresses the considerations discussed 1n Chapter Nine of this manual.

     6.2  Biological  degradation  1s  Inhibited  by the addition  of 1^04 to
pH <4.  Store at 4*C.  The sample should be stable for 28 days.


7.0  PROCEDURE

     7.1  Distillation;

          7.1.1  Measure  500 ml of   sample  Into  a  beaker.    Lower  the pH to
     approximately  4 with concentrated  ^$04   (1  mL/L),  and  transfer to the
     distillation apparatus.

          7.1.2  Distill  450 mL   of  sample,   stop   the  distillation,  and when
     boiling ceases, add  50 mL of warm  Type   II  water to  the  flask  and resume
     distillation until  500 mL have been collected.

          7.1.3   If the   distillate  1s  turbid,  filter  through  a prewashed
     membrane filter.

     7.2 Direct photometric method;

          7.2.1   Using  working   solution   A    (5.6),  prepare  the   following
     standards 1n 100-mL volumetric flasks:

               Working Solution  A (mL)      Concentration (ug/L)

                         0.0                         0.0
                         0.5                        50.0
                         1.0                       100.0
                         2.0                       200.0
                         5.0                       500.0
                         8.0                       800.0
                        10.0                      1000.0

           7.2.2   To 100  mL of  distillate   or   to  an aliquot diluted to 100 mL
      and/or standards, add 2 mL  of buffer   solution  (5.2) and mix.   The  pH of
      the sample  and standards  should be 10 +  0.2.

           7.2.3   Add 2.0 mL am1noant1pyr1ne solution (5.3) and mix.

           7.2.4  Add 2.0 mL potassium ferr1 cyanide solution (5.4)  and mix.

           7.2.5  After 15 m1n  read absorbance at 510 nm.

                                   9065 - 3
                                                          Revision      0
                                                          Date  September 1986

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7.3  Chloroform extraction method:
          CAUTION:This method should be performed 1n a hood; chloroform
               1s toxic.

     7.3.1  Using  working  solution  B   (5.7),  prepare  the  following
standards.  Standards may be  prepared  by pipetting the required volumes
Into the separatory funnels and diluting to 500 ml with Type II water:

          Working Solution B (ml)      Concentration (uq/L)

                  0.0                          0.0
                  3.0                          6.0
                  5.0                         10.0
                  10.0                        20.0
                  20.0                        40.0
                  25.0                        50.0

     7.3.2  Place 500 ml of distillate or an aliquot diluted to 500 ml In
a separatory funnel.  The  sample  should  not  contain more than 50 ug/L
phenol.

     7.3.3  To sample and standards  add  10  ml of buffer solution (5.2)
and mix.  The pH should be 10 +  0.2.

     7.3.4  Add 3.0 ml am1noant1pyr1ne solution (5.3) and mix.

     7.3.5  Add 3.0 ml potassium ferr1cyanide solution  (5.4)  and mix.

     7.3.6  After 3 mln,  extract with  25  ml of chloroform  (5.9).  Shake
the separatory funnel at  least 10 times, let CHC13 settle, shake again 10
times,  and  let chloroform settle again.

     7.3.7  Filter chloroform extract through   filter  paper.   Do not add
more chloroform.

     7.3.8  Read  the absorbance  of  the   samples and standards against the
blank  at  460 nm.

7.4  Calculation;

     7.4.1  Prepare a standard curve by  plotting the  absorbance values of
standards versus  the corresponding  phenol concentrations.

     7.4.2  Obtain concentration value   of  sample directly  from standard
curve.
                              9065 - 4
                                                     Revision
                                                     Date  September 1986

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8.0  QUALITY CONTROL

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

     8.2  Calibration curves must be  composed  of  a  minimum  of a blank and
three standards.   A  calibration  curve  should  be  made  for  every hour of
continuous sample analysis.

     8.3  Dilute samples  1f  they  are  more  concentrated  than  the highest
standard or 1f they fall on the plateau of a calibration curve.

     8.4  Employ a minimum  of  one  blank  per  sample  batch to determine 1f
contamination has occurred.

     8.5  Verify calibration  with  an  Independently  prepared check standard
every 15 samples.

     8.6  Run one spike duplicate sample  for  every  10 samples.  A duplicate
sample 1s a sample brought through the whole sample preparation and analytical
process.


9.0  METHOD PERFORMANCE

     9.1  In a single  laboratory  using  sewage  samples at concentrations of
3.8, 15, 43, and and 89  ug/L,  the standard deviations were +0.5, +0.6, +0.6,
and +1.0 ug/L, respectively.  At concentrations of 73, 146, 299, anH 447 ug/L,
the standard deviations were +1.0, +1.8, +4.2, and +5.3 ug/L,  respectively.

     9.2  In a single  laboratory using sewage samples at concentrations of 5.3
and 82 ug/L, the recoveries were  78% and 98%,respectively.  At concentrations
of 168 and 489 ug/L, the recoveries were 97% and 98%, respectively.


10.0 REFERENCES

1.  Annual  Book  of   ASTM  Standards,   Part 31,   "Water,"  Standard D1783-70,
p. 553  (1976).

2.  Standard Methods  for  the  Examination   of  Water and Wastewater,  14th  ed.,
pp.  574-581, Method 510  through 510C  (1975).
                                   9065 - 5
                                                          Revision
                                                          Date  September 1986

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                                          METHOD 9065

                PHENOLICS (SPECTROPHOTOMETRIC.  MANUAL  4-AAP KITH DISTILLATION)
C
    o
 7.1.1
        Measure
      '  sample
    Into beaker;
   lower pH wltn
    concentrated
 7.1.2|


  Olซtlll  cample
  !•  distillate
     turbid?
   Add buffer
 solution;  Din
7.3.3
                                                                                     Add
                                                                               amlnoantpyrlna
                                                                                  solution
                                                                              7.2.4
                                                                               Add potassium
                                                                                ferrlcyanlda
                                                                               solution:
                                                                              7.a.g[


                                                                              Read  abaorbanca
                                                                              7.3.1
                                                                                     Prepare
                                                                                    standards
                                                                                using working
                                                                                  solution 8
                                                                                 0
                                     9065 - 6
                                                                Revision       0
                                                                Date   September 1986

-------
                            METHOD 906S

  PHENOLICS (SPECTROPHOTOMETRIC.  MANUAL 4-AAP  WITH DISTILLATION)
                            (Continued)
    o
7.3.8
     1   Place
  distillate or
dilutea aliquot
  In separatory
       funnel
7.3.3)

        Add
buffer solution
 to cample and
 standards:  mix
7.3.4
      Add
aminoantipyrlne
 solution;  mix
7.3.5
 Add potassium
 ferricyanide
 solution:  mix
    0
     O
                                                    7.3.6
   Extract with
    chloroform
 7.3.7
      Filter
    chloroform
     •xtracts
 7.3.8|


 Read absorbance
                                                     7.4
    Calculate
  concentration
 value of sample
f     Stop      J
                     9065 - 7
                                                Revision       0
                                                Date   September 1986

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                                 METHOD 9066
         PHENOLICS (COLORIMETRIC. AUTOMATED 4-AAP WITH DISTILLATION)
                 f.
1.0  SCOPE AND ALLIGATION
     1.1  This method 1s applicable  to  the  analysis  of ground water and of
drinking, surface, and saline waters.
     1.2  The method  1s capable of  measuring  phenolic  materials from  2 to
500 ug/L 1n the aqueous phase using phenol as a standard.

2.0  SUMMARY OF METHOD
     2.1  This automated method 1s  based  on  the  distillation of phenol and
subsequent reaction of the  distillate  with alkaline ferrlcyanide (K3Fe(CN)6)
and 4-am1no-ant1pyr1ne (4-AAP) to form a  red complex which 1s measured at 505
or 520 nm.

3.0  INTERFERENCES
     3.1  Interferences from sulfur compounds are eliminated by acidifying the
sample to a pH of <4.0 with H2S04 and aerating briefly by stirring.
     3.2  Oxidizing agents such  as  chlorine,  detected  by the liberation of
Iodine upon acidification 1n  the  presence  of  potassium Iodide, are removed
Immediately after sampling by the  addition  of  an excess of ferrous ammonium
sulfate  (5.5).   If  chlorine  1s  not  removed,  the phenolic compounds may be
partially oxidized and the results may be low.
     3.3  Background contamination from  plastic  tubing and sample containers
1s eliminated by  filling the  wash  receptacle  by siphon  (using Kel-F tubing)
and using glass  tubes for the samples and standards.

4.0  APPARATUS AND MATERIALS
     4.1  Automated continuous-flow analytical Instrument;
          4.1.1   Sampler: Equipped with continuous mixer.
          4.1.2   Manifold.
          4.1.3   Proportioning pump  II or III.
          4.1.4   Heating bath with distillation coll.
          4.1.5   Distillation head.
                                   9066 - 1
                                                          Revision
                                                          Date   September  1986

-------
          4.1.6  Colorimeter:   Equipped  with  a   50  mm  flowcell   and   505 or
                 520 nm filter.

          4.1.7  Recorder.
5.0  REAGENTS

     5.1  ASTM Type II water  (ASTM  D1193):     Water  should be monitored  for
Impurities.

     5.2  Distillation reagent;  Add  100  ml  of concentrated phosphoric add
(85% H3P04) to 800 ml of Type II water, cool  and dilute to 1 liter.

     5.3  Buffered  potassium  ferrlcyanlde;       Dissolve   2.0  g  potassium
ferrlcyanide, 3.1 g boric add,  and  3.75  g  potassium chloride 1n 800 ml of
Type II water.  Adjust  to  pH  of  10.3  with  IN sodium hydroxide (5.3)  and
dilute  to  1 liter.   Add  0.5 ml  of  Brlj-35  (available  from  Technlcon).
(Br1j-35 1s a wetting agent and  1s a proprietary Technlcon product.)  Prepare
fresh weekly.

     5.4  Sodium hydroxide  (1 N):  Dissolve  40  g  NaOH  1n 500 ml of Type II
water, cool and dilute to 1 liter.

     5.5  4-Am1noant1pyr1ne;  Dissolve 0.65  g  of 4-am1noant1pyr1ne 1n 800 mL
of Type II water and dilute to 1 liter.  Prepare fresh each day.

     5.6  Ferrous ammonium  sulfate;   Dissolve  1.1 g ferrous ammonium sulfate
In 500 ml Type  IIwatercontaining  1  ml  ^$04  and dilute to  1 liter with
freshly boiled  and cooled Type II water.

     5.7  Stock phenol;  Dissolve 1.00 g phenol 1n 500 mL of Type  II water and
dilute to 1,000 ml.  Add 0.5  mL  concentrated ^$04 as preservative (1.0 mL =
1.0  mg phenol).
          CAUTION:  This solution Is toxic.

     5.8  Standard phenol solution A;  Dilute 10.0 mL of stock phenol solution
(5.6) to 1,000  mL  (1.0 mL - 0.01 mg phenol).

     5.9  Standard phenol solution  B;    Dilute  100.0  mL of standard phenol
solution A  (5.8) to 1,000 mL with Type II water  (1.0 mL = 0.001 mg phenol).

     5.10  Standard phenol  solution C;    Dilute  100.0  mL of standard phenol
solution B  (5.9) to 1,000 mL with Type II water  (1.0 mL = 0.0001 mg phenol).

     5.11  Using standard solution A, B, or C, prepare the following standards
1n 100-mL volumetric  flasks.   Each  standard  should be preserved by adding 2
drops of concentrated HgSCty to 100.0 mL:
                                   9066 -  2
                                                          Revision
                                                         Date  September 1986

-------
         Standard Solution (ml)          Concentration  (ug/L)

             Solution C

                1.0                             1.0
                2.0                             2.0
                3.0                             3.0
                5.0                             5.0

             Solution B

                1.0                            10.0
                2.0                            20.0
                5.0                            50.0
               10.0                           100.0

             Solution A

                2.0                           200.0
                3.0                           300.0
                5.0                           500.0


6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

     6.1  All samples must  have  been  collected  using  a sampling plan that
addresses the considerations discussed 1n Chapter Nine of this manual.

     6.2  Biological degradation 1s Inhibited by  the acidification to a pH <4
with H2$04.  The sample should be  kept  at 4*C and analyzed within 28 days of
collection.


7.0  PROCEDURE

     7.1  Set up the manifold as shown In Figure 1.

     7.2  Fill  the wash receptacle by  siphon.    Use Kel-F tubing with a fast
flow (1  I1ter/hr).

     7.3  Allow colorimeter and  recorder  to  warm  up  for  30  m1n.   Run a
baseline with all  reagents,  feeding  Type  II  water through the sample line.
Use polyethylene tubing for sample line.   When new tubing Is used, about 2 hr
may be required to obtain a  stable  baseline.    This 2-hr time period may be
necessary to remove  the residual phenol from the tubing.

     7.4  Place appropriate phenol standards 1n sampler 1n order of decreasing
concentration.   Complete  loading of  sampler  tray with unknown samples, using
glass tubes.  If samples  have  not  been preserved as Instructed 1n  Paragraph
6.2, add concentrated  ^04 to 100 ml of sample.  Run with sensitivity setting
at full  scale or 500.
                                  9066 - 3
                                                         Revision
                                                         Date  September 1986

-------
                              To Waste
* N ป
      I
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ft)
00
                                                                                        Ml/min
                                                                                                              SAMPLER
x^
RESAMPLE

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BATH WITH
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nnnn
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50 mm Tubular f/c


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BLACK ^ RACK
G ^ G
0 ^ O
O _ O
GRAY ^ GRAY
BLACK ^ BLACK
Y < r
0 ^ W
0 _ W
GRAY ^ GRAY
0.32 AIR
2.00 SAMPLE
0.42 DISTILLING SOL.
O.42 WASTE FROM
STILL
1.0 RESAMPLE WASTE
O.32 AIR
1.2 RESAMPLE
O.23 4 AAP

r
A-2
O 23 BUFFERED POTASSIUM
FERRI CYANIDE
J.O WASTE FROM F/C
PROPORTIONING
PUMP
SAMPLE RATE 2O/hr. 1:2
* Kซi-r
• ซ 100 ACIOFLEX
• •ป POLYETHYLENE
                                             COLORIMETER   RECORDER
                                                           Figure 1. Phenol Autoanalyzer II

-------
     7.5  Switch sample from Type II water to sampler and begin analysis.

     7.6  Calculation;

          7.6.1  Prepare a linear standard  curve  by plotting peak heights of
     standards against concentration values.  Compute concentration of samples
     by comparing sample peak heights with standards.


8.0  QUALITY CONTROL

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

     8.2  Calibration curves must be  composed  of  a  minimum  of a blank and
three standards.   A  calibration  curve  should  be  made  for  every hour of
continuous sample analysis.

     8.3  Dilute samples  1f  they  are  more  concentrated  than  the highest
standard or 1f they fall on the plateau of a calibration curve.

     8.4  Employ a minimum  of  one  blank  per  sample  batch to determine If
contamination has occurred.

     8.5  Verify calibration  with  an  Independently  prepared check standard
every 15 samples.

     8.6  Run one spike duplicate sample  for  every  10 samples.  A duplicate
sample  1s a sample brought through the whole sample preparation and analytical
process.


9.0  METHOD PERFORMANCE

     9.1  In a single  laboratory  using  sewage  samples at concentrations of
3.8, 15, 43, and 89 ug/L,  the  standard deviations were +0.5, +0.6, +0.6, and
+1.0 ug/L, respectively.   At  concentrations  of  73, 146, 2997 and 447 ug/L,
the standard deviations were +1.0, +1.8, +4.2, and +5.3 ug/L,  respectively.

     9.2  In a single  laboratory using sewage  samples at concentrations of 5.3
and 82  ug/L, the recoveries were 78% and 98%,  respectively.  At concentrations
of 168  and 489 ug/L,  the  recoveries were 97% and 98%, respectively.
                                   9066 - 5
                                                          Revision
                                                         Date  September  1986

-------
10.0 REFERENCES

1.   Gales, M.E. and R.L.  Booth,  "Automated  4AAP Phenolic Method," AWWA 68,
540 (1976).

2.   Standard Methods for the Examination of  Water and Wastewater,  14th ed.,
p. 574, Method 510, (1975).

3.   Technlcon  AutoAnalyzer II  Methodology,  Industrial  Method  No.l27-71W,
AA II.
                                   9066 - 6
                                                          Revision
                                                          Date  September 1986

-------
                                          METHOD 9066

                  PHENOLICS (COLORIMETRXC.  AUTOMATED 4-AAP WITH DISTILLATION)
C
  7.1 I


 Set up manifold
  7.2
    Fill wash
    receptacla
  7.3
     warm up
 colorimeter end
    recorder
  7.3 J


  Run e beeellne
     Q
     O
  7.4
   Lead phenol
  •tenderdc end
 unknown aamp1e•
                                                     7.5
  Switch eenple
   to •ampler:
    analyze
  7.6
     Compute
  eoncentratIon
    of sample*
f     stop      j
                                                                               7.4
                                                                                  Add  cone.
                                      9066 -  7
                                                                 Revision       0
                                                                 Date   September  1986

-------
                                 METHOD 9067

           PHENOLICS (SPECTROPHOTOMETRIC.  MBTH WITH  DISTILLATION)
1.0  SCOPE AND APPLICATION

     1.1  This method 1s applicable to the analysis of ground water,  drinking,
surface, and saline waters, and .domestic and Industrial  wastes.

     1.2  The method 1s capable of measuring  phenolic materials at the 2 ug/L
level when the colored end product  1s extracted and concentrated 1n a solvent
phase using phenol as a standard.

     1.3  The method 1s capable  of  measuring phenolic materials that contain
from 50 to 1,000 ug/L 1n  the aqueous phase (without solvent extraction) using
different kinds of phenols.

     1.4  It Is not  possible  to  use  this  method  to differentiate between
different kinds of phenols.
2.0  SUMMARY OF METHOD

     2.1  This method 1s based on the coupling  of phenol  with MBTH 1n an add
medium using eerie ammonium sulfate as  an  oxldant.  The coupling takes place
1n the p-pos1t1on; 1f this position  1s  occupied, the MBTH reagent will react
at a free opposition.  The colors obtained have maximum absorbance from 460 to
595 nm.   For phenol  and most  phenolic mixtures,  the absorbance  1s 520 and
490 nm.
3.0  INTERFERENCES

     3.1  For most samples a  preliminary  distillation  1s required to remove
Interfering materials.

     3.2  Color response of phenolic materials  with  MBTH 1s not the same for
all compounds.   Because  phenol1c-type  wastes  usually  contain a variety of
phenols, 1t 1s not possible to duplicate a  mixture of phenols to be used as a
standard.  For this reason,  phenol  has  been  selected as a standard and any
color produced by the  reaction  of  other  phenolic  compounds 1s reported as
phenol.  This  value  will  represent  the  minimum  concentration of phenolic
compounds present 1n the sample.

     3.3  Interferences from sulfur compounds are eliminated by acidifying the
sample to a pH of less than 4.0 with H2S04 and aerating briefly by stirring.

     3.4  Oxidizing agents such  as  chlorine,  detected  by the liberation of
Iodine upon acidification  1n  the  presence  of  potassium Iodide, are removed
Immediately after sampling by the  addition  of  an excess of ferrous ammonium
                                  9067 -  1
                                                         Revision      0
                                                         Date  September 1986

-------
sulfate (see Paragraph  5.11).     If   chlorine  1s  not  removed, the phenolic
compounds may be partially oxidized and  the  results may be low.

     3.5  Phosphate causes a precipitate  to form; therefore, phosphoric add
should not be used for preservation.   All  glassware should be phosphate free.

     3.5  High concentrations of aldehydes may  cause  Interferences.


4.0  APPARATUS AND MATERIALS

     4.1  Distillation apparatus;  All  glass,   consisting   of a 1-Hter  Pyrex
distilling apparatus with Graham condenser.

     4.2  pH Meter.

     4.3  Spectrophotometer.

     4.4  Funnels.

     4.5  Filter paper.

     4.6  Membrane filters.

     4.7  Separatory  funnels.
 5.0   REAGENTS

      5.1  ASTM  Type  II water   (ASTM  D1193):    Water  should be monitored for
 Impurities.

      5.2  Sulfurlc add.  IN:  Add  28  ml  of concentrated H2S(>4 to 900 mL of
 Type  II water,  mix,  and dilute to 1 liter.

      5.3  MBTH   solution.  0.05%:     Dissolve   0.1  g  of  3-methyl-2-benzo-
 thlazoHnone hydrazone hydrochlorlde 1n 200 ml of Type II water.

      5.4  Cerlc ammonium  sulfate solution;   Add 2.0 g of
      and  2.0 ml of concentrated ^$04 to  150  ml of Type
 solid has dissolved,  dilute to 200 ml with Type II water.
2H?0 and 2.0 ml of concentrated ^$04 to   150  ml of Type II water.  After the
      5.5   Buffer solution;  Dissolve, 1n the  following  order:  8 g of sodium
 hydroxide,  2 g  EDTA (dlsodium  salt), and 8  g  boric add 1n 200 ml of Type II
 water.  Dilute  to 250 ml with  Type  II water.

      5.6   Working buffer solution;    Make  a  working  solution  by mixing an
 appropriate volume of buffer solution (5.5) with an equal volume of ethanol.

      5.7   Chloroform.
                                   9067 -  2
                                                         Revision
                                                         Date  September 1986

-------
     5.8  Stock phenol;  Dissolve 1.00 g phenol 1n 500 ml of Type II water and
dilute to  1,000  ml.    Add  1  g  CuS04  and  0.5  ml  concentrated H2S04 as
preservative (1.0 ml = 1.0 mg phenol).

     5.9  Standard phenol solution A;  Dilute 10.0 ml of stock phenol solution
(5.8) to 1,000 ml (1.0 ml = 0.01 mg phenol).

     5.10  Standard phenol solution B:    Dilute  100.0  ml of standard phenol
solution A (5.9) to 1,000 ml with Type II water (1.0 ml ซ= 0.001 mg phenol).

     5.11  Ferrous ammonium sulfate;  Dissolve  1.1 g ferrous ammonium sulfate
1n 500 ml Type II watercontaining  1  ml  concentrated H2S04 and dilute to 1
liter with freshly sorted and cooled Type II water.


6.0  SAMPLE COLLECTION,  PRESERVATION, AND HANDLING

     6.1  All samples must  have  been  collected  using  a sampling plan that
addresses the considerations discussed 1n Chapter Nine of this manual.

     6.2  Biological degradation  1s  Inhibited by  acidification  to a pH of <4
with H2$04.  The sample  should be kept  at 4*C and analyzed within 28 days of
collection.
7.0   PROCEDURE

      7.1  Distillation;

          7.1.1   To  500 ml of sample,  adjust the pH  to approximately 4  with
      1  N  sulfurlc add solution  (5.2).

          7.1.2   Distill over 450 mL  of  sample,  add  50  mL of warm Type II
      water  to flask,  and resume  distillation until 500 mL has been collected.

          7.1.3   If  the  distillate  1s  turbid,  f11ter  through  a prewashed
      membrane filter.

      7.2  Concentration above 50 ug/Li

          7.2.1   To  100 mL of distillate or  an aliquot diluted to 100 mL, add
      4  mL of MBTH solution  (5.3).

          7.2.2   After 5 m1n, add  2.5  mL  of eerie ammonium sulfate solution
      (5.4).

          7.2.3   Walt another 5  m1n and  add  7  mL of working buffer solution
      (5.6).

          7.2.4   After 15 m1n, read the absorbance at 520 nm against a reagent
      blank.  The  color 1s stable for 4 hr.
                                   9067 -  3
                                                         Revision
                                                         Date  September 1986

-------
    7.3  Concentration below 50 ug/L;

         7.3.1  To 500 ml of distillate 1n  a  separatory funnel, add 4 ml of
    MBTH solution  (5.3).

         7.3.2  After 5 m1n, add  2.5  ml  of eerie ammonium sulfate solution
     (5.4).

         7.3.3  After an  additional  5  m1n,  add  7  ml  of  working buffer
    solution  (5.6).

         7.3.4  After 15 m1n,  add 25 ml  of chloroform.  Shake the separatory
    funnel  at least  20  times.    Allow  the  layer  to  separate and pass the
    chloroform  layer through filter paper.

         7.3.5  Read the absorbance at 490 nm against  a  reagent blank.

     7.4  Calculation;

         7.4.1   Prepare  a   standard  curve  by   plotting  absorbances  against
     concentration values.

         7.4.2   Obtain  concentration  value  of   sample directly  from prepared
     standard curve.
8.0  QUALITY CONTROL

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

     8.2  Calibration curves must be  composed  of  a  minimum  of a blank and
three standards.   A  calibration  curve  should  be  made  for  every hour of
continuous sample analysis.

     8.3  Dilute samples  1f  they  are  more  concentrated  than  the highest
standard or 1f they fall on the plateau of a calibration curve.

     8.4  Employ a minimum  of  one  blank  per  sample  batch to determine 1f
contamination has occurred.

     8.5  Verify calibration  with  an  Independently  prepared check standard
every 15 samples.

     8.6  Run one spike duplicate sample  for  every  10 samples.  A duplicate
sample 1s a sample brought through the whole sample preparation and analytical
process.
                                  9067 - 4
                                                         Revision
                                                         Date  September 1986

-------
9.0  METHOD PERFORMANCE

     9.1  Precision and accuracy data are not available at this time.


10.0 REFERENCES

1.   FHestad, H.O., E.E. Ott, and F.A. Gunther, "Automated Colorometrlc Micro
Determination of Phenol by  0x1dative Coupling with 3-Methyl-benzoth1azol1none
Hydrazone," Technlcon International Congress, 1969.             i

2.   Gales, M.E., "An  Evaluation  of the 3-Methyl-benzoth1azol1none Hydrazone
Method for the Determination  of  Phenols  1n  Water and Wastewater," Analyst,
100, No. 1197, 841  (1975).
                                   9067 - 5
                                                         Revision
                                                         Date  September 1986

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                    METHOD 9067

PHENOLICS  (SPECTHOPHOTOMETRIC.  MBTM WITH DISTILLATION]
7.1.1
	 1 Add
copper sulfate
solution
to sample to
adjust pH

7. 1.2


Distill sample
                   Ic distillate
                      turbid?
              9067 -  6
                                       Revision      0
                                       Date   September  1986

-------
                            METHOD 9067

      PHENOLICS  (SPECTflOPHOTOMETRIC.  MBTH WITH DISTILLATION)

                             (Continued)
7.2. 1
       Add MBTH
      solution
  to distillate
    or Olluted
      allauot
                  Above
  Amount of    >>^Be low
concentration
                                                    7.3.1
     Add MBTH
     SOlution
to distil late
in separatory
     funne 1
7 .2.2
        Add
 eerie ammonium
      culfate
     solution
7.2.3
                                                    7.3.2
                            Add cerlc
                         ammonia sulfate
                            solution
  Add working
buffer solution
                                                    7.3.3
                           Add working
                         buffer solution
7.2.4
Read absorbance
                                                    7.3.4
                                                            Add
                             enJoroform;
                           shake:  f 1 Iter
                             chloroform
                                layer
                           7.4
                             Calculate
                           concentration
                          value of cample
                                                    7.3.5
                                                    Read cbsorbanca
                         (      Stop       J
                      9067 - 7
                                                 Revision       0
                                                 Date   September  1986

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                                 METHOD 9070

TOTAL RECOVERABLE OIL AND GREASE (GRAVIMETRIC.  SEPARATORY FUNNEL EXTRACTION)


1.0  SCOPE AND APPLICATION

     1.1  This method measures  the  fluorocarbon-113  extractable matter from
surface and saline waters and Industrial, domestic, and aqueous wastes.  It 1s
applicable  to  the  determination  of  relatively  nonvolatile  hydrocarbons,
vegetable oils, animal fats, waxes, soaps, greases, and related matter.

     1.2  The method 1s not  applicable  to  measurement of light hydrocarbons
that volatilize at temperatures  below  70*C.   Petroleum fuels, from gasoline
through No. 2 fuel  oils,  are  completely  or  partially  lost 1n the solvent
removal operation.

     1.3  Some crude oils and heavy fuel oils contain a significant percentage
of  residue-type  materials   that   are   not  soluble  1n  fluorocarbon-113.
Accordingly, recoveries of these materials will be low.

     1.4  The method covers the  range  from  5  to  1,000 mg/L of extractable
material.

     1.5  When determining the  level  of  oil   and  grease In sludge samples,
Method 9071 1s to be employed.


2.0  SUMMARY OF METHOD

     2.1  The 1-liter  sample  1s  acidified  to  a  low  pH  (2) and serially
extracted with  fluorocarbon-113   1n  a  separatory  funnel.    The solvent 1s
evaporated from the extract and the residue 1s weighed.


3.0  INTERFERENCES

     3.1  Matrix  Interferences will  likely  be  coextracted  from the sample.
The extent of these Interferences  will   vary from waste to waste, depending on
the nature and diversity of the waste being analyzed.


4.0  APPARATUS AND MATERIALS

     4.1  Separatory  funnel;  2,000-mL,  with Teflon  stopcock.

     4.2  Vacuum  pump, or other source  of  vacuum.

     4.3  Flask;  Boiling,  125-mL  (Corning No. 4100  or equivalent).

     4.4  Distilling  head;  Clalsen or  equivalent.
                                  9070 - 1
                                                         Revision
                                                         Date  September 1986

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     4.5  Filter paper;   Whatman No.  40,  11  cm.


5.0  REAGENTS

     5.1  Hydrochloric add, 1:1:  Mix  equal   volumes of concentrated HC1  and
Type II water.

     5.2  Fluorocarbon-113  (l,l,2-trichloro-l,2,2-trifluoroethane):    Boiling
point, 48ฐC.

     5.3  Sodium sulfate;  Anhydrous crystal.

     5.4  ASTM Type II water  (ASTM  D1193):    Water  should be monitored for
impurities.


6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

     6.1  A representative  sample  should  be  collected  1n  a 1-Hter glass
bottle.  If analysis 1s to be delayed for more than a few hours, the sample 1s
preserved by the addition of  5  mL  HC1  (5.1)  at the time of collection and
refrigerated at 4*C.

     6.2  Collect a representative sample  1n  a  wide-mouth glass bottle that
has been rinsed with the solvent  to  remove any detergent film and acidify 1n
the sample bottle.

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

     6.4  Because losses  of  grease  will  occur  on  sampling equipment, the
collection  of  a  composite  sample  is  impractical.    Individual  portions
collected at prescribed time Intervals  must  be analyzed separately to obtain
the average concentration over  an extended period.


7.0   PROCEDURE

      7.1  Mark  the sample bottle at  the water meniscus for later determination
of sample volume.  If  the sample was not acidified at time of  collection, add
5 mL  HC1  (5.1)  to the  sample bottle.  After mixing the sample,  check the pH by
touching pH-sensitive  paper to  the cap  to  ensure  that the pH 1s 2 or lower.
Add more add  if necessary.

      7.2   Pour  the sample Into  a separatory funnel.

      7.3   Tare  a boiling flask  (pre-dried 1n   an  oven at 103ฐ  and stored  in a
desiccator).   Use gloves when handling  flask to avoid adding fingerprints.
                                   9070 - 2
                                                          Revision
                                                          Date   September  1986

-------
     7.4  Add 30 ml fluorocarbon-113 (5.2) to the sample bottle and rotate the
bottle to rinse the sides.   Transfer  the solvent Into the separatory funnel.
Extract by shaking vigorously for  2  min.    Allow the layers to separate and
filter the solvent layer through  a funnel containing solvent-moistened filter
paper.
     NOTE:  An emulsion that fails to dissipate can be broken by pouring about
          1 g sodium  sulfate  (5.3)  into  the  filter  paper cone and slowly
          draining the emulsion through the salt.  Additional 1-g portions can
          be added to the cone as required.

     7.5  Repeat Step  7.4  twice  more,  with  additional  portions  of fresh
solvent, combining all solvent in the boiling flask.

     7.6  Rinse the tip of the  separatory  funnel, the filter paper, and then
the funnel with a total of  10-20  ml  solvent and collect the rinsings in the
flask.

     7.7  Connect the boiling flask to  the  distilling head and evaporate the
solvent by Immersing the  lower half  of   the  flask 1n water at 70*C.  Collect
the solvent  for reuse.  A solvent blank should accompany each set of  samples.

     7.8  When the temperature  1n  the   distilling  head  reaches 50*C or the
flask  appears dry, remove the distilling  head.  To remove solvent vapor, sweep
out the flask for 15 sec  with air  by inserting a glass tube that Is  connected
to a vacuum  source.  Immediately  remove  the  flask from heat source and wipe
the outside  to remove excess moisture and fingerprints.

     7.9  Cool the boiling flask 1n a desiccator for 30 min and weigh.

     7.10  Calculation;

                      mg/L total oil and  grease  =

          where:

               R =   residue, gross weight of  extraction  flask minus the tare
                     weight;

               B =   blank determination,  residue  of equivalent   volume   of
                     extraction  solvent, mg;  and

               V =   volume of  sample  in liters,  determined by  refilling  sample
                     bottle   to   calibration  line   and   correcting   for acid
                     addition,  if necessary.


 8.0   QUALITY CONTROL

      8.1   All  quality  control  data  should be maintained and  available for easy
 reference or inspection.
                                   9070 - 3
                                                          Revision
                                                          Date  September 1986

-------
     8.2  Employ a minimum  of  one  blank  per  sample  batch to determine  1f
contamination has occurred.

     8.3  Verify calibration  with  an  Independently  prepared check standard
every 15 samples.

     8.4  Run one spike duplicate sample for  every 10 samples 1f possible.   A
duplicate sample 1s a sample brought  through the whole sample preparation and
analytical process.


9.0  METHOD PERFORMANCE

     9.1  The two oil  and  grease  methods  (Methods  9070  and 9071) 1n this
manual were tested on sewage by  a  single laboratory.  This method determined
the oil and grease level 1n the sewage to be 12.6 mg/L.  When 1-Hter portions
of the sewage were dosed with  14.0  mg  of  a  mixture  of No. 2 fuel oil and
Wesson oil, the  recovery was 93%, with a standard deviation of +0.9 mg/L.


10.0 REFERENCES

1.   Blum,  K.A.,  and  M.J.  Taras,  "Determination  of  Emulsifying  011  1n
Industrial Wastewater," JWPCF Research Suppl., 40, R404  (1968).

2.   Standard Methods for  the Examination  of Water and Wastewater,  14th ed.,
p. 515.
                                   9070 - 4
                                                         Revision
                                                         Date  September 1986

-------
                                        METHOD 9070

                              TOTAL RECOVERABLE OIL AND GREASE

                          (Gravimetric.  Separatory Funnel Extraction)
       Has
cample acidified?
   Pour  cample
 Into  ceparatory
     funnel
    O
                                                       0
7.3

Tare boiling
flask

7.4
1
flourc
113: E
filter
la>


Vdd
jcarbon-
ixtract:
solvent
rer

7.5
Repeat twice
adding fresh
solvent

7.5


Combine solvent
In boiling
flask





                         o
7.7 1
Evaporate
solvent:
collect for
reuse


7.8

Remove solvent
vapor


7.9
Cool

flask ana
weigh


O             C
9.0

Calculate total
amount of
grease and oil


                                    9070 - 5
                                                             Revision       o
                                                             Date  September  1986

-------
                                 METHOD 9071A

       OIL AND GREASE EXTRACTION METHOD FOR SLUDGE AND SEDIMENT SAMPLES


1.0  SCOPE AND APPLICATION

      1.1    Method  9071 is  used  to quantify  low concentrations of  oil  and
grease (10 mg/L)  by chemically drying a wet sludge sample and then extracting via
the Soxhlet  apparatus.   It is  also  used  to recover oil  and  grease  levels in
sediment and soil samples.

      1.2    Method  9071  is  used  when  relatively  polar,  heavy  petroleum
fractions are present, or when the levels of nonvolatile greases challenge the
solubility limit of the solvent.

      1.3    Specifically,  Method  9071  is  suitable  for  biological  lipids,
mineral hydrocarbons, and some industrial  wastewaters.

      1.4    Method  9071 is  not  recommended  for  measurement of low-boiling
fractions that volatilize at temperatures below 70ฐC.

2.0  SUMMARY OF METHOD

      2.1    A 20-g  sample  of wet  sludge with a  known  dry-sol ids  content is
acidified to pH 2.0 with 0.3 mL concentrated HC1.

      2.2    Magnesium  sulfate  monohydrate  will combine with 75% of  its  own
weight in water in forming MgS04 • 7H20 and is used to dry the acidified sludge
sample.

      2.3    Anhydrous  sodium  sulfate  is  used to  dry  samples  of soil  and
sediment.

      2.4    After   drying,   the    oil   and   grease   are  extracted   with
trichlorotrifluoroethane (Fluorocarbon-113)1 using  the Soxhlet apparatus.

3.0  INTERFERENCES

      3.1    The  method  is  entirely  empirical,  and duplicate results  can be
obtained only by strict adherence to all  details of the processes.

      3.2    The  rate and time  of extraction  in the Soxhlet apparatus  must be
exactly as directed because of varying solubilities of the different greases.

      3.3    The  length  of  time  required  for drying  and cooling  extracted
material must be constant.

      3.4    A gradual increase in weight may  result  due to the  absorption of
oxygen; a gradual loss of weight may result  due to volatilization.
     Replacement solvent will  be specified in a forthcoming regulation.

                                   9071A  -  1                       Revision 1
                                                                  September 1994

-------
4.0  APPARATUS AND MATERIALS
      4.1     Soxhlet  extraction  apparatus.
      4.2     Analytical balance.
      4.3     Vacuum pump  or  some other vacuum  source.
      4.4     Extraction thimble: Filter  paper.
      4.5     Glass wool or small glass beads to fill thimble.
      4.6     Grease-free  cotton:   Extract nonabsorbent cotton with  solvent.
      4.7     Beaker:  150-mL.
      4.8     pH  Indicator to determine acidity.
      4.9     Porcelain mortar.
      4.10    Extraction flask: 150-mL.
      4.11    Distilling apparatus:  Waterbath  at 70ฐC.
      4.12    Desiccator.
5.0  REAGENTS
      5.1     Reagent  grade  chemicals  shall be  used  in  all  tests.   Unless
otherwise  indicated,  it  is  intended  that  all  reagents  shall conform  to the
specifications of the Committee on  Analytical Reagents of the American Chemical
Society, where such  specifications are available.   Other  grades  may be used,
provided it is first ascertained  that the reagent is of sufficiently  high purity
to permit its use without lessening the accuracy of the determination.
      5.2     Reagent  water.   All references to water in this  method refer to
reagent water, as defined in Chapter One.
      5.3     Concentrated hydrochloric acid (HC1).
      5.4     Magnesium sulfate monohydrate:  Prepare MgS04  • H20 by  spreading a
thin layer in a dish and drying  in an oven at 150ฐC overnight.
      5.5     Sodium sulfate,  granular,  anhydrous (Na2S04):  Purify  by heating at
400ฐC for 4 hours in a shallow tray, or by precleaning the sodium sulfate with
methylene chloride.  If the sodium sulfate is precleaned with methylene chloride,
a method blank must be analyzed, demonstrating that there is  no interference from
the sodium sulfate.
                                   9071A  -  2                       Revision 1
                                                                  September 1994

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      5.6    Trichlorotrif1uoroethane (1,1,2-trichloro-1,2,2-trif1uoroethane):
Boiling  point,  47ฐC.    The  solvent  should  leave no  measurable residue  on
evaporation;  distill if necessary.2

6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1    Transfers  of  the  solvent   trichlorotrifluoroethane  should  not
involve any plastic tubing in the assembly.

      6.2    Sample  transfer implements:  Implements  are  required to transfer
portions  of solid,  semisolid,  and  liquid  wastes  from sample  containers  to
laboratory  glassware.   Liquids  may be transferred  using a  glass  hypodermic
syringe.  Solids may be transferred using a  spatula, spoon,  or coring device.

      6.3    Any turbidity or  suspended  solids  in the extraction flask should
be removed by filtering through grease-free  cotton or glass  wool.

7.0  PROCEDURE

      7.1    Determination of Sample Dry Weight Fraction

      Weigh 5-10 g  of the sample into a tared crucible.  Determine the dry weight
fraction of the sample by drying overnight at 105ฐC.

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

      Allow to cool in a desiccator before weighing:

                      dry weight fraction  =    q  of dry sample
                                                g  of  sample

      7.2    Sample Handling

             7.2.1    Sludge  Samples

                      7.2.1.1     Weigh out 20 + 0.5 g of wet sludge with a known
             dry-weight fraction (Section 7.1).   Place  in a  150-mL beaker.

                      7.2.1.2     Acidify to a pH of 2 with approximately 0.3 mL
             concentrated HC1.

                      7.2.1.3     Add 25  g prepared Mg2S04 •   H20  and  stir  to a
             smooth paste.

                      7.2.1.4     Spread paste  on  sides of  beaker to  facilitate
             evaporation.   Let  stand  about  15-30 min  or until  substance  is
             solidified.
     Replacement solvent will  be specified in  a forthcoming  regulation.

                                  9071A  -  3                       Revision 1
                                                                  September 1994

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                 7.2.1.5    Remove solids and  grind to  fine  powder in a
         mortar.

                 7.2.1.6    Add the powder to the paper extraction thimble.

                 7.2.1.7    Wipe beaker and mortar  with  pieces of  filter
         paper  moistened with  solvent  and  add to  thimble.

                 7.2.1.8    Fill thimble with glass  wool  (or glass beads).

         7.2.2    Sediment/Soil Samples

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

                 7.2.2.2    Blend 10 g  of the  solid  sample of known dry
         weight fraction with  10 g of  anhydrous sodium sulfate, and place
         in an extraction thimble. The extraction thimble must  drain  freely
         for  the  duration of the extraction period.

 7.3     Extraction

         7.3.1    Extract in Soxhlet apparatus using trichlorotrifluorocarbon
 at a rate of  20 cycles/hr for  4  hr.

         7.3.2    Using grease-free cotton, filter the extract into  a pre-
 weighed 250-mL boiling flask.  Use  gloves to avoid  adding fingerprints to
 the flask.

         7.3.3    Rinse flask and cotton with  solvent.

         7.3.4    Connect  the  boiling   flask  to  the distilling head  and
 evaporate the solvent by immersing the  lower half of the flask in water at
 70ฐC.   Collect  the  solvent  for reuse.   A solvent blank should accompany
 each analytical  batch  of samples.

         7.3.5    When the temperature  in the  distilling head reaches 50ฐC
 or the flask  appears dry, remove the distilling head.  To remove solvent
 vapor, sweep  out the flask for  15 sec with air by  inserting a glass tube
 that is connected to a vacuum  source.  Immediately remove the flask from
 the  heat  source  and  wipe  the  outside  to  remove excess moisture  and
 fingerprints.

         7.3.6    Cool the boiling flask in a  desiccator for 30  min  and
 weigh.

         7.3.7    Calculate oil  and grease  as a  percentage of the total dry
 solids.  Generally:

% of oil and grease  =      gain  in weight of flask (q)  x  100
                        wt.  of wet solids (g)  x dry weight fraction
                              9071A  -  4                       Revision 1
                                                             September 1994

-------
8.0  QUALITY CONTROL
      8.1    All  quality control data should  be  maintained and available for
easy reference  and inspection.   Refer to Chapter One  for additional quality
control guidelines.
      8.2    Employ  a minimum  of one  blank  per  analytical  batch  or twenty
samples, whichever is more  frequent, to determine if contamination has  occurred.
      8.3    Run  one matrix  duplicate and  matrix  spike  sample every twenty
samples or analytical batch, whichever is  more  frequent.  Matrix  duplicates and
spikes are brought through  the whole sample preparation and  analytical  process.
      8.4    The  use of corn oil is recommended as a reference sample  solution.
9.0  METHOD PERFORMANCE
      9.1    Two  oil and grease  methods (Methods  9070 and  9071)  were  tested on
sewage by a single laboratory.   When 1-liter portions of the sewage were dosed
with 14.0 mg of  a  mixture of No.  2 fuel  oil and Wesson oil, the recovery was 93%,
with a standard deviation of + 0.9 mg/L.
10.0 REFERENCES
1.    Blum, K.A. and  M.J. Taras,  "Determination of Emulsifying Oil in Industrial
Wastewater," JWPCF Research Suppl., 40, R404 (1968).
2.    Standard Methods for the Examination  of  Water and Wastewater,   14th ed.,
p. 515, Method 502A (1975).
                                   9071A  -  5                       Revision 1
                                                                  September 1994

-------
                                METHOD  9071A
 OIL  AND  GREASE EXTRACTION METHOD  FOR  SLUDGE AND  SEDIMENT  SAMPLES
                                  (     Start     J
                                    7.1 Determine
                                  dry weight fraction
                                     of sample.
 7.2.1.1 Weigh
   a sample of
   wet sludge
   and place in
    beaker.
  Sludge
  7.2 Is
 sample
sludge or
sediment/
  soil?
Soil/Sediment
7.2.2.1 Decant
  water; mix
sample; discard
foreign objects.
     7.2.1.2
   Acidify to
     pH 2.
                                                 7.2.2.2 Blend
                                                 with sodium
                                                 sulfate; add
                                                 to extraction
                                                   thimble.
   7.2.1.3 Add
     and stir
magnesium sulfate
  monohydrate.
      1
     7.2.1.5
   Remove and
   grind solids
     to a fine
     powder.
•o
                                 9071A  -  6
                                                Revision 1
                                                Septenter 1994

-------
                                METHOD 9071A
OIL AND GREASE  EXTRACTION METHOD FOR SLUDGE  AND SEDIMENT SAMPLES
                                 (Continued)
      7.2.1.6 Add
       powder to
         paper
       extraction
        thimble.
      7.2.1.7 Wipe
       beaker and
       mortar; add
       to thimble.
       7.2.1.8 Fill
      thimble with
       glass wool.
7.3.1 Extract
 in Soxhlet
apparatus for
  4 hours.
 7.3.2 Filter
 extract into
boiling flask.
 7.3.3 Rinse
  flask with
   solvent.
                                      7.3.4
                                  Evaporate and
                                      collect
                                 solvent for reuse.
                                   7.3.5 Remove
                                   solvent vapor.
 7.3.6 Cool
 and weigh
boiling flask.
    7.3.7
 Calculate %
   oil and
   grease.
                                                                (     StฐP     )
                                   9071A -  7
                                        Revision  1
                                        September 1994

-------
                                  METHOD 9075

                TEST METHOD FOR TOTAL CHLORINE IN NEW AND USED
          PETROLEUM PRODUCTS BY X-RAY FLUORESCENCE  SPECTROMETRY  (XRF)
1.0   SCOPE AND APPLICATION

      1.1   This test method covers the determination of total chlorine in new
and  used  oils,  fuels,  and related materials,  including crankcase, hydraulic,
diesel,  lubricating and  fuel  oils,  and  kerosene.    The chlorine  content of
petroleum products  is often required prior to their use as a fuel.

      1.2   The applicable  range of this method  is  from 200 /ug/g to percent
levels.

      1.3   Method  9075 is restricted to  use  by,  or  under the supervision of,
analysts experienced in the operation of an X-ray fluorescence spectrometer and
in the interpretation of the results.

2.0   SUMMARY OF METHOD

      2.1   A well-mixed sample, contained in a disposable plastic sample cup,
is loaded into an X-ray fluorescence (XRF) spectrometer.   The  intensities of the
chlorine  Ka  and  sulfur  Ka  lines  are  measured,  as are  the  intensities  of
appropriate background lines.   After background correction, the net intensities
are  used with  a  calibration  equation  to determine the  chlorine  content.   The
sulfur intensity is used to correct for absorption by sulfur.

3.0   INTERFERENCES

      3.1   Possible interferences include metals, water,  and  sediment in the
oil.  Results  of spike recovery measurements and measurements  on diluted samples
can be used to check for interferences.

      Each sample,  or one  sample  from a group of closely  related samples, should
be  spiked  to  confirm that matrix  effects are not  significant.   Dilution of
samples that may contain  water or sediment can produce incorrect results, so
dilution should  be undertaken w'ith caution and  checked by spiking.   Sulfur
interferes with the chlorine determination, but a correction is made.

      Spike recovery measurements  of  used crankcase oil  showed  that diluting
samples five to one allowed accurate measurements on approximately 80% of the
samples.  The other 20% of the samples were not accurately analyzed by XRF.

      3.2   Water  in samples  absorbs  X-rays  emmitted  by chlorine.   For  this
inter-ference, use  of as short an X-ray counting time  as  possible is beneficial.
This  appears  to be related  to  stratification  of   samples  into  aqueous  and
nonaqueous layers while in the analyzer.

      Although a  correction  for water  may  be  possible,  none  is  currently
available.   In general,  the presence of  any free water as a separate phase or a



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water content greater than  25% will reduce the chlorine  signal by 50 to 90%.  See
Sec. 6.4.
4.0   APPARATUS AND MATERIALS

      4.1   XRF spectrometer, either energy dispersive or wavelength dispersive.
The instrument must be able  to accurately resolve and measure the intensity of
the chlorine and sulfur lines with  acceptable precision.

      4.2   Disposable sample cups with suitable plastic film such as Mylar9.

5.0   REAGENTS

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

      5.2   Mineral oil, mineral  spirits or paraffin oil  (sulfur- and chlorine-
free), for  preparing standards and dilutions.

      5.3   1-Chlorodecane  (Aldrich Chemical Co.),  20.1% chlorine,  or  similar
chlorine compound.

      5.4   .Di-n-butyl sulfide (Aldrich Chemical Co.), 21.9% sulfur by weight.

      5.5   Quality control  standards such as the standard reference materials
NBS 1620, 1621, 1622, 1623,  and 1624 for sulfur in oil standards; and NBS 1818
for chlorine in oil standards.

6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   All samples must be collected using a sampling plan that addresses
the considerations discussed in Chapter Nine.

      6.2   The collected sample  should be kept headspace free prior to prepara-
tion and analysis to minimize volatilization losses of organic halogens.  Because
waste oils may contain toxic and/or carcinogenic substances, appropriate field
and laboratory safety procedures should be followed.

      6.3   Laboratory sampling of the sample  should  be performed on a well-mixed
sample of oil.   The mixing should be kept to  a minimum and carried out as nearly
headspace free  as possible to minimize volatilization losses of organic halogens.

      6.4   Free water, as  a separate phase, should be  removed  and  cannot be
analyzed by this method.
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7.0   PROCEDURE
      7.1   Calibration and standardization.

            7.1.1     Prepare  primary  calibration  standards  by diluting  the
      chlorodecane and n-butyl sulfide with mineral  spirits or similar material.

            7.1.2     Prepare working calibration standards that contain sulfur,
      chlorine, or both according to the following  table:
      Cl:
       S:

      1.
      2.
      3.
      4.
500, 1,000, 2,000, 4,000, and 6,000 /ig/g
0.5, 1.0, and 1.5% sulfur
0.5% S, 1,000 jig/g Cl
0.5% S, 4,000 Mg/g Cl
1.0% S,   500 Mg/g Cl
1.0% s, 2,000 Mg/g ci
5.
6.
7.
s.
                              1.0% S, 6,000 Mg/g Cl
                              1.5% s, 1,000 Mg/g ci
                              1.5% s, 4,000 Mg/g ci
                              1.5% s, 6,000 Mg/g ci
      Once the  correction  factor  for  sulfur  interference  with chlorine  is
      determined,  fewer standards may be required.

            7.1.3     Measure  the intensity  of  the chlorine  Ka line  and  the
      sulfur Ka line as well as the intensity of a suitably chosen background.
      Based on counting statistics, the relative  standard deviation of each peak
      measurement  should be 1% or less.

            7.1.4     Determine  the  net chlorine  and sulfur  intensities  by
      correcting each peak for background.   Do  this for all of the calibration
      standards  as well  as for a paraffin blank.

            7.1.5     Obtain a linear calibration curve for  sulfur by performing
      a least squares fit of the net sulfur  intensity to the standard concentra-
      tions,  including the  blank.   The  chlorine content of  a standard should
      have little  effect on the net sulfur  intensity.

            7.1.6     The  calibration equation   for  chlorine  must  include  a
      correction  term  for  the  sulfur  concentration.   A suitable  equation
      follows:
      where:
            I
            m,
            S
   b, k*
                           Cl =  (ml + b)  (1 + k*S)
= net chlorine intensity
= adjustable parameters
= sulfer concentration
                                                      (1)
      Using  a  least  squares  procedure,  the  above  equation or  a  suitable
      substitute should  be  fitted  to the  data.   Many  XRF instruments  are
      equipped  with suitable  computer programs to perform  this  fit.   In  any
      case, the  resulting equation should be shown to be accurate by analysis of
      suitable  standard materials.
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      7.2   Analysis.

            7.2.1     Prepare a calibration curve  as described  in Sec. 7.1.  By
      periodically measuring  a very stable sample containing  both sulfur and
      chlorine,  it may be possible to use  the  calibration  equations for more
      than  1  day.   During each day, the  suitability  of the calibration curve
      should  be checked by analyzing standards.

            7.2.2     Determine the net chlorine  and  sulfur intensities for a
      sample  in the same manner as done for the standards.

            7.2.3     Determine the chlorine and  sulfur concentrations  of the
      samples from the calibration equations.  If the sample concentration for
      either  element is beyond the range  of the  standards, the  sample should be
      diluted with mineral oil and reanalyzed.

8.0   QUALITY CONTROL

      8.1   Refer to Chapter One for specific quality control procedures.

      8.2   One sample in ten should be analyzed in triplicate  and  the relative
standard deviation reported.  For each triplicate,  a separate preparation should
be made, starting from the original sample.

      8.3   Each sample, or one sample in ten from a group of similar samples,
should  be  spiked with the  elements of interest  by  adding  a  known  amount of
chlorine or sulfur to the sample.  The spiked amount should be between 50% and
200% of the sample concentration,  but  the minimum addition  should  be at least
five times the limit  of detection.   The percent recovery should be  reported and
should be between 80% and 120%.  Any sample suspected of containing >25% water
should also be spiked with organic chlorine.

      8.4   Quality control  standard check samples should be analyzed every day
and should agree within 10% of the expected value of the standard.

9.0   METHOD  PERFORMANCE

      9.1   These data are based on 47 data points obtained by seven  laboratories
who each  analyzed four  used crankcase oils  and  three fuel  oil  blends  with
crankcase in  duplicate.   A  data point represents one duplicate  analysis  of a
sample.   Two data points  were determined to  be outliers  and are not included in
these results.

      9.2   Precision.   The  precision of  the method  as  determined   by  the
statistical  examination of interlaboratory test results  is as follows:

            Repeatability -  The difference between successive results obtained
      by the  same  operator  with  the  same apparatus under  constant  operating
      conditions on identical test material would exceed, in  the  long  run, in
      the normal and  correct  operation  of  the test method, the following values
      only in 1 case in 20 (see Table 1):
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                         Repeatability =5.72

      *where x is the average of two  results  in  /xg/g.

            Reproducibility -  The difference between two  single and independent
      results obtained by different operators working in  different laboratories
      on identical test material would exceed,  in the long run,  the following
      values only in 1 case in 20:


                        Reproducibility = 9.83
      *where x is the average  value  of two results in

      9.3   Bias.  The bias of this test method varies with concentration,  as
shown in Table 2:

                    Bias  =  Amount  found  - Amount expected.

10.0  REFERENCE

1.     Gaskill, A.;  Estes, E.D.; Hardison, D.L.; and Myers, I.E.  Validation of
      Methods for Determining Chlorine in Used Oils and Oil  Fuels.  Prepared for
      U.S.  Environmental Protection Agency, Office of Solid Waste.  EPA Contract
      No. 68-01-7075,  WA  80.   July 1988.
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                  TABLE  1.   REPEATABILITY AND REPRODUCIBILITY
                         FOR CHLORINE IN USED OILS BY
                        X-RAY  FLUORESCENCE  SPECTROMETRY
Average value,              Repeatability,            Reproducibility,
    M9/9                         M9/9                      M9/9
500
1,000
1,500
2,000
2,500
3,000
128
181
222
256
286
313
220
311
381
440
492
538
               TABLE 2.  RECOVERY AND BIAS DATA FOR CHLORINE IN
                 USED OILS BY X-RAY FLUORESCENCE SPECTROMETRY
Amount
expected,
M9/9
320
480
920
1,498
1,527
3,029
3,045
Amount
found,
M9/9
278
461
879
1,414
1,299
2,806
2,811

Bias,
M9/9
-42
-19
-41
-84
-228
-223
-234

Percent
bias
-13
-4
-4
-6
-15
-7
-8
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                              METHOD 9075
        TEST METHOD FOR TOTAL CHLORINE  IN NEW AND USED
PETROLEUM  PRODUCTS  BY X-RAY  FLUORESCENCE SPECTROMETRY
                                    (XRF)
              START
           7  1.1 • 7 1.2
        Prepare calibration
             s tandards
           713 Measure
           intensity of
           standard! and
            background
        7 14 Determine net
           intensity for
          standards and a
          paraffin blank
           7.1 5 - 7 1.6
            Construct
        calibration curves
          for sulfur and
            chlorine
            72.1 Check
        calibration curves
           periodically
        throughout the day
722 Determine net
chlorine and sulfur
  intensities for
     sample
  7.23 Determine
chlorine and sulfur
concentrations from
calibration curves
      72.3
     Is sample
   concentration
  beyond range of
    standards?
723 Dilute  sanpli
 • ith mineral  oil
                               9075 -  7
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                                  METHOD 9076

           TEST METHOD FOR TOTAL CHLORINE IN NEW AND USED PETROLEUM
             PRODUCTS BY OXIDATIVE COMBUSTION AND MICROCOULOMETRY
1.0   SCOPE AND APPLICATION

      1.1   This test method covers the determination of total chlorine in new
and  used  oils, fuels  and  related materials,  including  crankcase, hydraulic,
.diesel, lubricating  and fuel oils,  and kerosene by  oxidative  combustion and
microcoulometry.  The chlorine content of petroleum products is often required
prior to their use as a fuel.

      1.2   The  applicable range  of  this method  is  from  10  to  10,000  /zg/g
chlorine.

2.0   SUMMARY OF METHOD

      2.1   The  sample  is placed  in  a quartz  boat at  the inlet of  a high-
temperature quartz combustion tube.  An inert carrier gas such as argon, carbon
dioxide, or nitrogen sweeps across the inlet  while oxygen flows into the center
of the combustion tube.  The  boat and sample are advanced into a vaporization
zone of approximately  3008C to volatilize the  light  ends.  Then  the  boat is
advanced to the center of the combustion tube,  which is at  1,000'C.  The oxygen
is diverted to pass directly over the sample to oxidize any  remaining refractory
material.  All during this  complete combustion  cycle, the chlorine  is converted
to chloride and oxychlorides, which then  flow into  an attached titration cell
where they quantitatively react with silver ions.  The  silver ions thus consumed
are coulometrically replaced.  The total current required to  replace the silver
ions is a measure of the chlorine present in the injected samples.

      2.2   The reaction occurring in  the  titration  cell as chloride enters is:

                           CV +  Ag+ -	> AgCl                  (1)

      The silver ion  consumed  in the above  reaction is generated coulometrically
thus:

                             Agฐ	>  Ag+ + e                  (2)

      2.3   These microequivalents of silver are equal to the number of micro-
equivalents of titratable sample ion entering the titration cell.

3.0   INTERFERENCES

      3.1   Other titratable halides will  also  give  a positive response.  These
titratable halides include HBr and  HI  (HOBr  +  HOI do  not precipitate silver).
Because these oxyhalides do not react in the titration cell, approximately 50%
microequivalent response is detected from bromine and iodine.

      3.2   Fluorine as fluoride does  not  precipitate silver,  so it  is not an
interferant nor is it detected.


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      3.3   This  test method  is  applicable in  the  presence of  total  sulfur
concentrations of up  to 10,000 times the chlorine level.

4.0   APPARATUS AND MATERIALS1

      4.1   Combustion furnace.   The  sample should  be oxidized in an electric
furnace capable of maintaining a  temperature of  1,000ฐC to oxidize the organic
matrix.

      4.2   Combustion tube,  fabricated  from quartz  and constructed so that a
sample, which  is  vaporized  completely  in the inlet  section,  is swept into the
oxidation zone by an  inert  gas where  it  mixes with  oxygen and is burned.  The
inlet end of the tube connects to a boat insertion device where the sample can
be  placed  on  a  quartz   boat by  syringe,   micropipet,  or  by being  weighed
externally.  Two gas ports are provided,  one for an inert gas  to flow across the
boat and one for oxygen to enter  the combustion tube.

      4.3   Microcoulometer,  Stroehlein  Coulomat  702 CL or equivalent,  having
variable gain  and bias control,  and  capable of measuring the potential  of the
sensing-reference electrode  pair, and  comparing this  potential  with  a bias
potential,  and applying  the  amplified  difference  to  the  working-auxiliary
electrode pair so as  to generate  a titrant.  The microcoulometer output signal
shall be proportional to the  generating current.  The microcoulometer may have
a digital meter and circuitry to  convert this output signal directly to a mass
of chlorine (e.g., nanograms)  or to a concentration of chlorine (e.g., micrograms
of chlorine or micrograms per gram).

      4.4   Titration cell.    Two  different configurations have been applied to
coulometrically titrate chlorine  for this method.

            4.4.1     Type I uses a sensor-reference pair of electrodes to detect
      changes in silver ion  concentration and a generator anode-cathode pair of
      electrodes to maintain constant silver ion  concentration and an inlet for
      a gaseous  sample  from  the  pyrolysis  tube.   The  sensor,  reference,  and
      anode  electrodes  are  silver  electrodes.   The  cathode  electrode  is  a
      platinum wire.   The  reference  electrode  resides in a  saturated  silver
      acetate half-cell.   The electrolyte contains 70% acetic acid in water.

            4.4.2     Type  II  uses  a sensor-reference  pair  of  electrodes  to
      detect changes  in silver ion concentration and a generator anode-cathode
      pair of electrodes to maintain constant silver  ion concentration, an inlet
      for a gaseous sample that passes through a 95% sulfuric acid dehydrating
      tube from the pyrolysis tube,  and a sealed two-piece titration cell with
      an exhaust tube to  vent fumes to an external exhaust.  All electrodes can
      be removed  and replaced independently without reconstructing the cell
      assembly.   The  anode  electrode is  constructed of silver.   The  cathode
      electrode is  constructed of platinum.   The anode  is separated  from the
     1Any apparatus that meets the performance criteria of this section may be
used to conduct analyses by this methodology.  Three commercial analyzers that
fulfill the requirements for apparatus Steps 4.1 through 4.4 are: Dohrmann
Models DX-20B and MCTS-20 and Mitsubishi Model TSX-10 available from Cosa
Instrument.

                                   9076 - 2                       Revision 0
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      cathode by a 10% KN03 agar bridge, and continuity is maintained  through an
      aqueous  10% KN03 salt bridge.   The sensor electrode  is constructed of
      silver.  The reference electrode is a silver/silver chloride ground glass
      sleeve, double-junction electrode with aqueous 1M KN03 in the outer chamber
      and aqueous 1M KC1 in the inner  chamber.

      4.5   Sampling syringe, a microliter syringe of 10  /zL capacity  capable of
accurately delivering  2 to 5 p.1 of  a  viscous  sample  into the  sample  boat.

      4.6   Micropipet, a positive displacement micropipet capable of  accurately
delivering 2 to 5 /uL of a viscous sample  into the sample boat.

      4.7   Analytical balance.  When  used to weigh a sample of 2 to 5 mg onto
the boat, the balance shall be accurate to + 0.01 mg.  When used to determine the
density of the sample,  typically 8 g per 10 mL, the balance shall be accurate to
ฑ 0.1 g.

      4.8   Class A volumetric flasks:  100 mL.

5.0   REAGENTS

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

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

      5.3   Acetic acid, CH3C02H.  Glacial.

      5.4   Isooctane, (CH3)2CHCH2C(CH3)3 (2,2,4-Trimethylpentane).

      5.5   Chlorobenzene, C6H5C1.

      5.6   Chlorine,  standard  stock  solution  -   10,000  ng  Cl//iL,  weigh
accurately 3.174 g of chlorobenzene into 100-mL Class A volumetric flask.  Dilute
to the mark with  isooctane.

      5.7   Chlorine,  standard  solution.   1,000  ng  Cl//iL,  pipet 10.0  mL of
chlorine stock solution (Sec.  5.6) into a 100-mL volumetric flask and dilute to
volume with isooctane.

      5.8   Argon, helium, nitrogen, or carbon dioxide,  high-purity grade (HP)
used as the carrier gas.  High-purity grade gas has a  minimum purity of 99.995%.

      5.9   Oxygen,  high-purity grade  (HP), used as the  reactant gas.

      5.10  Gas regulators.  Two-stage regulator must  be used on the reactant and
carrier gas.

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      5.11  Cell Type 1.
            5.11.1    Cell  electrolyte solution.  70% acetic acid: combine  300
      ml reagent water with 700 ml acetic acid  (Sec. 5.3) and mix well.
            5.11.2    Silver acetate, CH3C02Ag.   Powder purified for  saturated
      reference electrode.
      5.12  Cell Type 2.
            5.12.1    Sodium acetate, CH3C02Na.
            5.12.2    Potassium nitrate,  KN03.
            5.12.3    Potassium chloride, KC1.
            5.12.4    Sulfuric acid (concentrated),  H2S04.
            5.12.5    Agar,  (jelly strength  450 to 600 g/cm2).
            5.12.6    Cell  electrolyte solution -  85% acetic  acid:  combine  150
      ml reagent water with  1.35  g sodium acetate (Sec. 5.12.1) and  mix well;
      add 850 ml acetic acid  (Sec. 5.3)  and mix well.
            5.12.7    Dehydrating  solution - Combine 95 ml sulfuric acid (Sec.
      5.12.4) with 5 ml reagent water and mix well.
            CAUTION: This is an exothermic reaction and may proceed with bumping
            unless  controlled by  the addition  of sulfuric  acid.   Slowly  add
            sulfuric acid to reagent water.   Do not  add  water to  sulfuric acid.
            5.12.8    Potassium nitrate (10%), KN03.  Add 10 g potassium nitrate
      (Sec. 5.12.2) to 100 ml  reagent water and mix well.
            5.12.9    Potassium nitrate  (1M),   KN03.    Add   10.11  g   potassium
      nitrate (Sec. 5.12.2) to 100 mL reagent water and mix  well.
            5.12.10   Potassium chloride (1M),  KC1.    Add  7.46 g   potassium
      chloride (Sec. 5.12.3) to 100 ml reagent water and mix well.
            5.12.11   Agar  bridge  solution - Mix 0.7 g agar (Sec. 5.12.5), 2.5g
      potassium nitrate  (Sec. 5.12.2),  and 25 ml  reagent  water and heat to
      boiling.
6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING
      6.1   All  samples must be collected using a sampling plan that  addresses
the considerations discussed  in Chapter Nine.
      6.2   Because the collected  sample  will be analyzed for  total halogens, it
should be kept headspace free and refrigerated prior to preparation and analysis
to minimize volatilization losses of organic halogens.  Because waste oils  may
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contain toxic and/or carcinogenic substances, appropriate field and laboratory
safety procedures should be followed.

      6.3   Laboratory subsampling of the sample should be performed on a well-
mixed sample of oil.

7.0   PROCEDURES

      7.1   Preparation of apparatus.

            7.1.1     Set  up the analyzer as  per the equipment manufacturer's
      instructions.

            7.1.2     Typical  operating conditions:   Type 1.

                      Furnace  temperature	   1,000'C
                      Carrier  gas  flow	      43 cm3/min
                      Oxygen gas flow	     160 cm3/min
                      Coulometer
                        Bias	   250 mV
                        Gain	      25%

            7.1.3     Typical  operating conditions:   Type 2.

                      Furnace  temperature	   H-1 850ฐC
                                                          H-2 1,000'C
                      Carrier  gas  flow	   250 cm3/min
                      Oxygen gas flow	   250 cm3/min
                      Coulometer
                        End  point  potential  (bias)	   300 mV
                      Gain G-l	     1.5 coulombs/A mV
                          G-2	     3.0 coulombs/A mV
                          G-3	     3.0 coulombs/A mV
                      ES-1  (range  1)	   25 mV
                      ES-2  (range  2)	   30 mV

            NOTE:  Other  conditions   may   be   appropriate.     Refer   to  the
            instrumentation manual.

      7.2   Sample introduction.

            7.2.1     Carefully fill  a 10-juL syringe with 2  to 5  /uL  of sample
      depending on the  expected concentration of total  chlorine.   Inject the
      sample through the septum onto the cool boat,  being certain to touch the
      boat with the needle tip to  displace the last  droplet.

            7.2.2     For viscous samples that cannot be drawn  into the syringe
      barrel,  a positive displacement micropipet may  be used.  Here, the 2-5 /iL
      of sample is placed on  the  boat from the  micropipet  through the opened
      hatch port.  The same technique  as with the syringe is used to  displace
      the last droplet into  the boat.  A tuft of  quartz  wool  in  the boat can aid
      in completely transferring the sample from the micropipet into the boat.
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      NOTE: Dilution of samples to reduce viscosity is not  recommended due
      to  uncertainty  about  the  solubility  of  the  sample  and  its
      chlorinated constituents.   If a  positive displacement micropipet is
      not  available,  dilution may  be attempted to  enable  injection of
      viscous samples.

      7.2.3     Alternatively, the  sample  boat  may  be  removed  from the
instrument and  tared on an analytical  balance.   A  sample of 2-5 mg is
accurately weighed directly into the boat and the boat and  sample returned
to the inlet of the  instrument.

                          2-5  juL  = 2-5 mg

      NOTE: Sample dilution may be required to ensure that the titration
      system  is  not overloaded  with  chlorine.    This  will  be somewhat
      system  dependent  and  should   be  determined  before   analysis  is
      attempted.   For  example,  the MCTS-20 can  titrate up  to 10,000 ng
      chlorine in a  single  injection  or weighed  sample, while the DX-20B
      has  an  upper limit of  50,000 ng  chlorine.  For  2  to  5 juL sample
      sizes, these correspond to nominal concentrations in the sample of
      800 to 2,000 /xg/g  and 4,000 to  10,000 jug/g,  respectively.  If the
      system is overloaded, especially with inorganic chloride, residual
      chloride may persist in  the  system and affect results of subsequent
      samples.  In general, the  analyst should  ensure that the baseline
      returns to normal before running the next sample.  To speed baseline
      recovery, the electrolyte  can be drained from the  cell  and replaced
      with fresh electrolyte.

      NOTE: To determine total chlorine, do not extract  the sample either
      with reagent water or with an  organic solvent such as toluene or
      isooctane.  This  may lower the inorganic chlorine content as well as
      result in losses of volatile solvents.

      7.2.4     Follow  the manufacturer's recommended procedure for moving
the sample and boat  into the  combustion tube.

7.3   Calibration and  standardization.

      7.3.1     System  recovery  -  The  fraction  of chlorine in a standard
that  is  titrated  should  be  verified  every  4   hours  by  analyzing  the
standard solution (Sec. 5.7).  System recovery is typically 85% or better.
The pyrolysis tube should be replaced whenever system  recovery drops below
75%.

      NOTE: The  1,000  ;ug/g system  recovery sample  is  suitable  for all
      systems except the MCTS-20  for  which a 100 /ig/g  sample should be
      used.

      7.3.2     Repeat  the  measurement  of  this   standard  at  least three
times.
                             9076 - 6                       Revision 0
                                                            September 1994

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            7.3.3     System blank  -  The blank  should be  checked  daily with
      isooctane.  It is typically less than 1 /zg/g chlorine.  The system blank
      should be subtracted from both samples and standards.

      7.4   Calculations.

            7.4.1     For systems  that  read  directly  in mass units of chloride,
      the following equations apply:
                Chlorine,  M9/9 (wt/wt) = (V )  (Ds)  (RF)   " B                (3)

or


                Chlorine,  M9/9 (wt/wt) =    (M)P(Rh)      - B                (4)

where:

Display     =   Integrated value in nanograms  (when  the  integrated values are
                displayed  in micrograms,  they must be multiplied by 103)
                DisplayB = blank measurement    Displays = sample measurement

      V     =   Volume of  sample  injected in  microliters
                VB  =  blank volume               Vs  =  sample volume

      D     =   Density of sample,  grams  per  cubic centimeters
                DB  =  blank density              Ds  =  sample density

     RF     =   Recovery factor =  ratio of chlorine       =    Found -  Blank
                determined in standard minus  the  system           Known
                blank, divided by  known standard  content

      B     =   System blank, /zg/g chlorine               =       Disp1ayB


      M     =   Mass  of sample,  mg

            7.4.2     Other systems internally compensate for recovery factor,
      volume, density, or  mass and  blank,  and thus read  out directly in parts
      per million chlorine units.   Refer to instrumentation manual.

8.0   QUALITY CONTROL

      8.1   Refer to Chapter One for specific quality control procedures.

      8.2   Each sample should be analyzed twice.  If the results do not agree
to within  10%,  expressed   as  the  relative percent difference  of the  results,
repeat the analysis.

      8.3   Analyze matrix spike and matrix spike duplicates - spike  samples with
a chlorinated organic at a level of total  chlorine  commensurate with the levels
being determined.  The spike recovery should be reported and should be between
                                   9076 - 7                       Revision 0
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80 and 120% of the expected value.  Any sample suspected of containing >25% water
should also be spiked with organic chlorine.

9.0   METHOD  PERFORMANCE

      9.1   These data are based on 66 data points obtained by 10 laboratories
who  each  analyzed  four  used crankcase  oils  and three  fuel  oil  blends  with
crankcase  in  duplicate.   A data point represents one  duplicate  analysis  of a
sample.  One  laboratory  and  four  additional data points  were  determined to be
outliers and  are not included in these results.

      9.2   Precision.   The  precision  of  the  method as  determined  by  the
statistical examination of interlaboratory test results is as  follows:

      Repeatability - The difference  between successive results obtained by the
same operator with  the same apparatus under constant  operating  conditions on
identical test material would exceed, in the long run,  in  the normal and correct
operation of the  test method the following values  only in 1 case in 20 (see Table
1):

                         Repeatability = 0.137 x*
      *where x is the average of two results in

            Reproducibility - The difference between two single and independent
      results obtained by different  operators working in different laboratories
      on identical test material would exceed,  in  the  long  run,  the following
      values only in 1 case in 20:


                        Reproducibility = 0.455 x*


      *where x is the average value of two results in  ng/g.

      9.3   Bias.  The bias of this test  method  varies  with concentration,  as
shown in Table 2:

                     Bias  = Amount found - Amount expected

10.0  REFERENCE

1.    Gaskill, A.; Estes,  E.D.; Hardison,  D.L.; and Myers, I.E.  "Validation  of
      Methods for Determining Chlorine in Used Oils and Oil  Fuels."   Prepared
      for U.S.  Environmental  Protection  Agency, Office of  Solid Waste.  EPA
      Contract No. 68-01-7075, WA80.  July 1988.

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

3.    Standard Instrumentation, 3322 Pennsylvania Avenue, Charleston, WV 25302.
                                   9076 -  8                       Revision  0
                                                                  September 1994

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                                   TABLE 1.
               REPEATABILITY AND REPRODUCIBILITY FOR CHLORINE IN
                    USED OILS BY MICROCOULOMETRIC TITRATION
Average value               Repeatability,                 Reproducibility,
    M9/9                         M9/9                           M9/9
500
1,000
1,500
2,000
2,500
3,000
69
137
206
274
343
411
228
455
683
910
1,138
1,365
                                   TABLE 2.
               RECOVERY AND BIAS DATA FOR CHLORINE IN USED OILS
                         BY  MICROCOULOMETRIC TITRATION
Amount
expected,
M9/9
320
480
920
1,498
1,527
3,029
3,045
Amount
found
M9/9
312
443
841
1,483
1,446
3,016
2,916
j
Bias,
M9/9
-8
-37
-79
-15
-81
-13
-129

Percent
bias
-3
-8
-9
-1
-5
0
-4
                                   9076 - 9                       Revision 0
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                           METHOD 9076
TEST METHOD FOR TOTAL CHLORINE  IN NEW AND USED PETROLEUM
  PRODUCTS BY  OXIDATIVE  COMBUSTION  AND MICROCOULOMETRY
7.2.2 Inject
 sample into
  cool boat
   ซith
 micropipet
                      724 Hove
                      sample and
                       boat into
                      combus tion
                         tube
                     7.3.1  Verify
                        sys tern
                       recovery
                     every  4 hours
7 2.1 Inject
 sample into
  cool boat
Kith syringe
                                                         732 R.p.at
                                                          •tandard
                                                          raซaiurซraซnt
                                                          at Uaซt
                                                          thrซซ tiซซป
                                                          733 Cheek
                                                         >yit*n blank
                                                          daily ปith
                                                           iaooetan*
                                                         7.4 Calculate
                                                           chlorine
                                                         concentration
                                                     {      STOP       )
                           9076 -  10
                                                                 Revision 0
                                                                 September 1994

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                                  METHOD 9077

           TEST METHODS FOR TOTAL CHLORINE IN  NEW AND USED PETROLEUM
                       PRODUCTS (FIELD TEST KIT METHODS)
1.0   SCOPE AND APPLICATION

      1.1    The  method  may be used  to  determine if a new  or used petroleum
product meets or  exceeds  requirements for total  halogen measured as chloride.
An analysis of the chlorine content of petroleum products is often  required prior
to their  use as  a  fuel.   The method is specifically designed  for used oils
permitting onsite testing at remote locations by nontechnical  personnel to avoid
the delays for laboratory testing.

      1.2    In  these field  test  methods,  the  entire  analytical  sequence,
including  sampling,  sample pretreatment, chemical reactions,  extraction,  and
quantification, are combined in a single kit using predispensed  and encapsulated
reagents.  The overall objective is to provide a  simple, easy to  use procedure,
permitting nontechnical  personnel  to perform a  test  with analytical  accuracy
outside of a laboratory  environment in under 10 minutes.  One of the kits is
preset at  1,000  ng/g total chlorine  to  meet regulatory requirements  for used
oils.  The other kits provide quantitative results  over  a range of  750  to
7,000 /Ltg/g and 300  to 4,000 ng/g.

2.0   SUMMARY OF METHOD

      2.1    The  oil  sample (around 0.4  g by volume)  is dispersed in a solvent
and reacted  with  a mixture of metallic  sodium  catalyzed  with  naphthalene and
diglyme at ambient temperature.  This process converts all organic halogens to
their respective sodium halides.   All  halides in  the treated mixture, including
those present prior to the reaction, are  then extracted  into an aqueous buffer,
which is  then  titrated  with mercuric nitrate using diphenyl carbazone  as the
indicator.  The end point of the titration is the formation of the blue-violet
mercury diphenylcarbazone complex.   Bromide and iodide are  titrated and reported
as chloride.

      2.2    Reagent  quantities are preset  in  the fixed end point kit (Method
A) so that the color of the  solution at  the  end of the titration indicates
whether the  sample  is above 1,000 /jg/g  chlorine  (yellow)  or below  1,000 M9/g
chlorine  (blue).

      2.3    The  first quantitative kit (Method  B)  involves a reverse titration
of a fixed volume  of mercuric nitrate with the extracted sample such that the end
point is denoted  by  a change from blue to  yellow in the titration vessel over the
range of  the kit  (750 to 7,000 /ng/g).   The final  calculation  is based  on the
assumption that the oil has a specific gravity of 0.9 g/cm .

      2.4    The  second quantitative kit (Method C)  involves  a  titration of the
extracted sample with mercuric nitrate by means of a 1-mL microburette such that
the end point  is  denoted by a change from pale  yellow  to red-violet  over the
range of  the kit (300 to  4,000 ng/g).   The concentration of  chlorine  in the
original oil is then read from a scale on the microburette.


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                                                                  September 1994

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             NOTE: Warning—All reagents are encapsulated or  contained  within
             ampoules.  Strict adherence to the operational  procedures included
             with the kits  as well as accepted safety procedures (safety glasses
             and gloves) should be observed.

             NOTE; Warning—When crushing the glass ampoules,  press  firmly  in
             the center of the ampoule once.  Never attempt to recrush  broken
             glass  because the glass  may come  through the  plastic and cut
             fingers.

             NOTE;  Warning—In  case  of  accidental  breakage  onto  skin  or
             clothing, wash with large amounts  of water. All  the ampoules are
             poisonous and should not be taken  internally.

             NOTE; Warning—The gray  ampoules contain metallic  sodium.  Metallic
             sodium is a flammable water-reactive solid.

             NOTE; Warning—Do not ship kits on passenger aircraft.  Dispose  of
             used kits properly.

             NOTE; Caution—When the sodium ampoule in  either kit  is crushed,
             oils that contain more than 25% water will cause the sample to turn
             clear to light gray.  Under these circumstances,  the  results may
             be biased excessively low and should be disregarded.

3.0   INTERFERENCES

      3.1    Free water, as a  second phase, should be removed.   However,  this
second phase can be analyzed  separately for  chloride content if desired.
                                   9077  -  2                       Revision 0
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                                   METHOD A

                        FIXED END POINT TEST KIT METHOD
4.0A  APPARATUS AND MATERIALS

      4.1A   The  CLOR-D-TECT  10001  is  a complete  self-contained  kit.    It
includes:   a sampling  tube to withdraw a fixed  sample  volume for analysis; a
polyethylene test tube #1  into which the sample is introduced for dilution and
reaction with metallic sodium; and a  polyethylene tube #2 containing a buffered
aqueous  extractant,   the  mercuric  nitrate  titrant,  and  diphenyl  carbazone
indicator.  Included are instructions to conduct the test and a color chart to
aid in determining the end point.

5.0A  REAGENTS

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

      5.2A   All  necessary reagents are contained within the  kit.

      5.3A   The  kit  should be examined  upon  opening  to see that  all  of the
components  are present  and  that all the  ampoules  (4)   are  in place  and not
leaking.  The  liquid  in  Tube #2  (yellow cap)  should be approximately 1/2 in.
above the 5-mL line and  the  tube  should  not  be leaking.  The ampoules are not
supposed to be completely  full.

6.0A  SAMPLE COLLECTION,  PRESERVATION, AND HANDLING

      6.1A   All  samples must be collected using  a sampling plan that addresses
the considerations discussed in Chapter Nine.

      6.2A   Because the collected sample will be analyzed for total halogens,
it should be kept headspace free and refrigerated  prior   to preparation and
analysis to minimize  volatilization losses of organic halogens.  Because waste
oils may  contain  toxic and/or carcinogenic substances,  appropriate field and
laboratory  safety procedures should be followed.

7.0A  PROCEDURE

      7.1A   Preparation.  Open analysis carton,  remove  contents, mount plastic
test tubes in the provided holder. Remove syringe and glass sampling capillary
from foil pouch.
     Available from Dexsil Corporation, One Hamden Park Drive, Hamden, CT 06517.

                                   9077 - 3                       Revision 0
                                                                  September 1994

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              NOTE:  Perform the test in a warm,  dry  area with adequate light.
              In cold weather, a truck cab is sufficient.   If a warm area is not
              available,  Step  7.3A should be performed while warming Tube #1 in
              palm of hand.

      7.2A    Sample  introduction.   Remove white cap from  Tube  #1.   Using the
plastic syringe, slowly draw the oil up the  capillary tube  until  it reaches the
flexible adapter tube.   Wipe excess  oil  from the  tube with  the provided tissue,
keeping capillary vertical.   Position  capillary  tube into Tube #1,  and detach
adapter tubing, allowing capillary  to drop to the bottom of the tube.  Replace
white cap on tube.  Crush the capillary  by squeezing the test tube  several times,
being careful not to break the glass reagent ampoules.

      7.3A    Reaction.  Break the lower  (colorless) capsule containing the clear
diluent solvent  by  squeezing the sides of  the test tube.   Mix  thoroughly by
shaking the tube vigorously  for 30 seconds.    Crush  the upper  grey  ampoule
containing metallic sodium, again by squeezing the sides of the test tube.  Shake
vigorously  for 20 seconds.   Allow reaction  to proceed  for 60 seconds,  shaking
intermittently several  times while  timing with a watch.

              NOTE: Caution—Always  crush the clear ampoule in each tube first.
              Otherwise, stop the test and start over using another complete kit.
              False  (low) results may occur  and allow a contaminated sample to
              pass without  detection if  clear ampoule is not crushed first.

      7.4A    Extraction.  Remove caps from both tubes.  Pour the clear buffered
extraction solution  from Tube  #2 into Tube  #1.  Replace the white cap on Tube #1,
and shake  vigorously  for  10  seconds.   Vent tube by partially  unscrewing  the
dispenser cap. Close cap securely,  and  shake for an additional  10  seconds.  Vent
again, tighten cap, and  stand  tube  upside down on  white  cap.   Allow phases to
separate for  2 minutes.

      7.5A    Analysis.   Put  filtration  funnel  into  Tube  #2.   Position  Tube #1
over funnel and open nozzle on dispenser cap.   Squeeze the sides of Tube #1 to
dispense the  clear aqueous lower phase  through the  filter into  Tube  #2 to the
5 ml line  on Tube #2.  Remove the filter funnel.   Replace  the yellow cap on Tube
#2 and close the nozzle on  the dispenser cap.   Break the colorless lower capsule
containing  mercuric nitrate  solution by squeezing the sides  of  the  tube,  and
shake for  10 seconds.    Then  break the upper colored ampoule containing  the
diphenylcarbazone  indicator,  and  shake   for  10  seconds.    Observe  color
immediately.

      7.6A    Interpretation of results

              7.6.1A Because all reagent levels are  preset,  calculations are not
      required.  A blue solution  in  Tube #2  indicates a chlorine content in the
      original oil  of less than 1,000 ng/g, and  a  yellow color indicates  that
      the chlorine concentration is  greater than 1,000 ng/g.  Refer to the color
      chart enclosed with the kit in interpreting the titration end  point.

              7.6.2A Report the results  as  <  or >  1,000 jug/g chlorine in the oil
      sample.
                                   9077 - 4                       Revision 0
                                                                  September 1994

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8.0A  QUALITY CONTROL

      8.1A   Refer to Chapter One for specific quality control procedures.

      8.2A   Each  sample  should be tested  two  times.   If the  results  do not
agree, then a third test must be performed.   Report the results of the two that
agree.

9.0A  METHOD PERFORMANCE

      9.1A   No formal  statement is made about either the precision or bias of
the overall test  kit  method for determining chlorine in  used  oil  because the
result merely states whether there  is conformance  to the  criteria for success
specified in the procedure,  (i.e., a blue or yellow color in the final solution).
In a collaborative study,  eight laboratories analyzed four used crankcase oils
and three fuel oil blends with crankcase  in duplicate  using the test kit.  Of the
resulting 56 data points, 3 resulted  in incorrect  classification of the oil's
chlorine content (Table 1).   A data point represents one duplicate analysis of
a sample.   There  were  no disagreements within  a laboratory on  any duplicate
determinations.
                                   9077 - 5                       Revision 0
                                                                  September 1994

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                                   TABLE  1.
                 PRECISION AND BIAS  INFORMATION  FOR  METHOD A-
                        FIXED END POINT TEST KIT METHOD
  Expected
concentration,
    M9/9
                              Percent aareementb
Expected results,   Percent
                    correct3  Within     Between
320
480
920
1,498
1,527
3,029
3,045
< 1,000
< 1,000
< 1,000
> 1,000
> 1,000
> 1,000
> 1,000
100
100
100
87
75
100
100
100
100
100
100
100
100
100
100
100
100
87
75
100
100
aPercent correct--percent correctly identified as above or below
   1,000 /ug/g.

bPercent agreement--percent agreement within or between laboratories.
                                   9077  - 6
                                                Revision 0
                                                September 1994

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       START
                             METHOD 9077,  METHOD A
                      FIXED END POINT TEST  KIT METHOD
7.1A Open  test kit
7.2A Draw oil into
  capillary tube:
remove  excess oil;
drop capillary tube
 into Tube t\ and
cap Tube ฃ1; crush
  capillary tube
    7.3A  Break
colorless capsule;
  mix;  crush grey
capsule;  nix; allow
reaction  to proceed
    for 60 sec.
 7.4A Pour Tube t2
solution into Tube
  fl: mix; vent;
  allow phases to
     separate
7.5A Filter aqueous
lower phase in Tube
 tl into Tube t2.
   remove filter
   funnel; break
colorless capsule;
 mix; break upper
 colored capsule;
•ix; observe color
                          7.6.1 Chlorine
                         content is > 1000
                               "9/9
 7.6A What
 color is
solution in
 Tube
 7.6.1  Chlorine
content is < 1000
     "9/9
                                                         7.6.2 Report
                                                            results
                                                            STOP
                                    9077 -  7
                                                                            Revision  0
                                                                            Septenter 1994

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                                   METHOD B

           REVERSE TITRATION QUANTITATIVE END POINT TEST KIT METHOD

4.OB APPARATUS AND MATERIALS

      4.IB     QuantiClor2  kit components (see Figure  1).

               4.1.IB  Plastic reaction bottle:  1 oz, with flip-top dropper cap
      and a crushable glass ampoule containing sodium.

               4.1.2B  Plastic buffer bottle:  contains 9.5 ml of aqueous buffer
      solution.

               4.1.3B  Titration vial:  contains  buffer bottle and indicator-
      impregnated paper.

               4.1.4B  Glass vial:  contains 2.0 ml of solvents.

               4.1.5B  Micropipet and plunger,  0.25 ml.

               4.1.6B  Activated carbon filtering column.

               4.1.7B  Titret and valve assembly.

      4.2B     The  reagents  needed  for the  test  are packaged  in disposable
containers.

      4.3B     The  procedure  utilizes  a  Titret.    Titrets    are  hand-held,
disposable cells  for titrimetric analysis.   A Titret is an  evacuated  glass
ampoule (13 mm diameter) that contains an exact amount of a standardized liquid
titranta   A  flexible valve  assembly is attached  to  the tip  of the ampoule.
Titrets  employ the  principle of reverse  titration;  that is,  small  doses  of
sample are added to the titrant to the appearance of the end point color.  The
color change indicates that the equivalency point has been reached.  The flow of
the sample into  the  Titret may  be  controlled  by using  an  accessory  called a
Titrettor* .

5.OB  REAGENTS

      5.IB     The crushable glass ampoule,  which  is inside the  reaction bottle,
contains 85 mg of metallic sodium in a light oil  dispersion.

      5.2B     The buffer bottle contains 0.44 g of NaH?PO, •  2H?0 and 0.32 ml of
HN03 in  distilled  water.

      5.3B     The  glass vial  contains 770 mg Stoddard Solvent (CAS  No.  8052-
41-3), 260 mg toluene, 260 mg butyl  ether,  260  mg diglyme, 130 mg naphthalene,
and 70 mg demulsifier.
     2Quanti-Chlor Kit, Titrets , and Titrettor*  are manufactured by Chemetrics,
Inc., Calverton, VA  22016.  U.S. Patent No. 4,332,769.

                                   9077 - 8                       Revision 0
                                                                  September 1994

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      5.4B     The Titret contains  1.12 mg mercuric nitrate in distilled water.

      5.SB     The indicator-impregnated paper contains approximately 0.3 mg of
diphenylcarbazone and 0.2 mg of brilliant yellow.

6.OB  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      See Section 6.0A of Method A.

7.OB PROCEDURE

      7.IB     Shake  the glass  vial  and pour  its  contents into  the reaction
bottle.

      7.2B     Fill the micropipet  with a well-shaken oil sample by pulling the
plunger until  its top edge is even with the top edge of the micropipet.  Wipe off
the excess oil  and transfer the sample into the reaction bottle  (see Figure 2.1).

      7.3B     Gently  squeeze most of the air out of  the reaction bottle (see
Figure 2.2).  Cap the bottle securely, and shake vigorously for 30 seconds.

      7.4B     Crush the sodium  ampoule by pressing against the outside wall of
the reaction bottle (see Figure 2.3).

               CAUTION:  Samples  containing  a  high  percentage  of water  will
               generate  heat  and  gas, causing  the reaction  bottle walls  to
               expand.  To release  the gas, briefly loosen the cap.

      7.5B     Shake the reaction  bottle vigorously for 30 seconds.

      7.6B     Wait 1 minute.  Shake the reaction bottle occasionally during this
time.

      7.7B     Remove the buffer bottle from the  titration vial, and slowly pour
its contents into the reaction bottle (see Figure 2.4).

      7.8B     Cap the reaction  bottle and  shake gently  for  a  few seconds.   As
soon as the foam subsides,  release the gas by  loosening  the cap.   Tighten the
cap, and shake vigorously for 30 seconds.   As before,  release  any gas that has
formed, then turn the reaction bottle upside down (see Figure  2.5).

      7.9B     Wait 1 minute.

      7.10B    While holding the filtering  column in a vertical  position, remove
the plug.  Gently tap the column to settle the carbon  particles.

      7.11B    Keeping the reaction bottle  upside down, insert the  flip top into
the end of the filtering column  and position the  column over the titration vial
(see Figure 2.6).  Slowly squeeze  the lower  aqueous layer  out of the reaction
bottle and into the filtering column.   Keep squeezing until the  first drop of oil
is squeezed out.
                                   9077 - 9                       Revision 0
                                                                  September 1994

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              NOTE; Caution—The aqueous layer should flow through the filtering
              column into the titration vial  in  about 1 minute.  In rare cases,
              it may be  necessary  to  gently  tap the column to begin the flow.
              The  indicator  paper  should remain  in  the titration vial.

      7.12B   Cap  the  titration  vial  and shake  it vigorously  for 10 seconds.

      7.13B   Slide the flexible end of the valve assembly over the tapered tip
of the Titret so that it fits snugly (see Figure 3.1).

      7.14B   Lift (see  Figure 3.2) the control bar  and  insert  the assembled
Titret into the Titrettor" .

      7.15B   Hold the Titrettor*  with the sample pipe in  the  sample, and press
the control bar to snap the pre-scored tip of the Titret (see Figure 3.3).

              NOTE:  Caution—Because  the  Titret  is sealed under  vacuum,  the
              fluid inside may be  agitated when  the  tip snaps.

      7.16B   With the tip of the  sample pipe in the sample, briefly press the
control  bar to pull in  a  SMALL  amount  of  sample  (see Figure 3.3).   The contents
of the Titret will  turn purple.

              CAUTION;  During  the  titration, there will   be  some  undissolved
              powder  inside the  Titret.   This does  not interfere with  the
              accuracy of the test.

      7.17B   Wait 30  seconds.

      7.18B   Gently press the control bar again to allow another SMALL amount
of the sample to be drawn into the Titret.

              CAUTION: Do not  press the  control  bar unless the sample  pipe is
              immersed in the sample.  This prevents air from being drawn into
              the  Titret.

      7.19B   After each addition, rock the entire assembly to mix the contents
of the Titret.  Watch for a color change from purple to very pale yellow.

      7.20B   Repeat Steps 7.18B and  7.19B until the color change occurs.

              CAUTION; The end point color change (from purple to pale  yellow)
              actually goes  through an intermediate gray  color.   During this
              intermediate  stage,  extra caution should  be taken to bring in
              SMALL amounts  of sample and  to mix the Titret contents well.

      7.21B   When the color of the liquid in the Titret changes to PALEv YELLOW,
remove the Titret from  the Titrettor*1  .  Hold the Titret in a vertical  position
and carefully read the  test result on the scale  opposite the liquid level.

      7.22B   Calculation

              7.22.IB  To obtain  results in micrograms per gram total chlorine,
      multiply scale units on the Titret by 1.3  and  then subtract 200.

                                   9077  - 10                       Revision 0
                                                                  September 1994

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8.OB  QUALITY CONTROL

      8.IB     Refer  to Chapter One for specific quality control procedures.

      8.2B     Each  sample  should  be  tested two times.  If the results do  not
agree to within 10%, expressed as the relative percent difference of the results,
a third test must be performed.   Report the results  of the two that  agree.

9.OB  METHOD PERFORMANCE

      9.IB     These  data  are based  on  49  data   points  obtained  by  seven
laboratories who  each analyzed four used crankcase oils and  three fuel  oil blends
with crankcase in duplicate.   A data point represents one duplicate analysis of
a sample.   There were no outlier  data points or laboratories.

      9.2B     Precision.   The precision  of the method as  determined by  the
statistical examination of inter!aboratory test results is as  follows:

               Repeatability - The difference between  successive results obtained
               by the same  operator  with  the same  apparatus under  constant
               operating conditions on identical test material  would  exceed,  in
               the  long  run,  in the normal  and correct operation of the test
               method, the following values only in  1 case  in 20 (see Table  2):

                          Repeatability = 0.31 x*
      *where x is the average of two results in M9/g-

              Reproducibility   -   The   difference  between  two  single   and
              independent  results  obtained  by different operators working  in
              different  laboratories on  identical test  material would  exceed,
              in the long  run, the following values only in 1 case in 20:

                         Reproducibility  =  0.60 x*


      *where x is the average value of  two results in  M9/9-

      9.3B    Bias.  The bias of this test method varies with concentration,  as
shown in Table 3:

                     Bias = Amount  found  - Amount expected
                                  9077 - 11                       Revision 0
                                                                  September 1994

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                                   TABLE 2.
            REPEATABILITY AND REPRODUCIBILITY FOR CHLORINE IN USED
              OILS BY THE QUANTITATIVE END POINT TEST KIT METHOD
Average value,                Repeatability,        Reproducibility,
    Mg/g                          Mg/g                    Mg/g
1,000
1,500
2,000
2,500
3,000
310
465
620
775
930
600
900
1,200
1,500
1,800
                                   TABLE 3.
            RECOVERY AND BIAS DATA FOR CHLORINE IN USED OILS BY THE
                    QUANTITATIVE END POINT TEST KIT METHOD
Amount
expected,
Mg/g
320 (< 750)a
480 (< 750 )a
920
1,498
1,527
3,029
3,045
Amount
found,
Mg/g
776
782
1,020
1,129
1,434
1,853
2,380

Bias,
Mg/g
+16
+32
+100
-369
-93
-1,176
-665

Percent
bias
+3
+4
+11
-25
-6
-39
-22
a The lower limit of the kit is 750
                                   9077  -  12                       Revision 0
                                                                  September 1994

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                                                      Reaction bottle
Titration via
        ——x
     f Buffer
       bottle
                                              Filtering
                                              Column
Valve assembly
                            Micro pipet
  Figure 1.  Components of CHEMetrics Total Chlorine in Waste Oil Test Kit
           (Cat. No. K2610).
                               9077 - 13
                             Revision 0
                             September 1994

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Push plunger
down to
transfer
sample
            Figure 2.1
                                                             Figure 2.2
                      * Crush
          Figure 23
                                          Buffer Bottle
                 Figure 2.4
              Reaction bottle
              upsidedown in
              component tray
         Figure 2.5
Aqueous
Layer
                                                        Filtering Column
                                                                        Figure 2.6
                                                         Titration Vial
         Figure  2.   Reaction-Extraction Procedure.
                            9077 -  14
                           Revision  0
                           September 1994

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Attaching
                   Valve
                   Assembly
 Assembly
  Figure 3.1
        / \
                    Titret
                      Lift control bar
 Snapping

 the Tip
    Figure 3.2
 Performing the

 Analysis

    Figure 33

  Watch for
  color change
  here

Press control bar

  Sample pipe
Readihg

the Result
  Figure 3.4
 Read
 scale units
 when color
 changes
 permanently
        Figure 3.  Titration  Procedure
                 9077 -  15
                Revision 0
                September 1994

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                  METHOD 9077, METHOD B
REVERSE TITRATION QUANTITATIVE  END  POINT  TEST  KIT METHOD
        STURT
7. IB Shake glass
vial ; pour into
reaction bottle

7.2B Fill
micropipet with
oil; remove excess
oil; t ransf er oil
to reaction bottle
1

from reaction
bottle; cap ; mix
1
7 . 4B Crush sodium
ampoule
1
7. SB - 7 .68 Shake
reaction bottle for
30 ปecondป ; wait
one minute

7 . 7B Pour buffer
into reaction
bottle

•ป

7. SB - 7.9B Shake
gently; release
gaซ; shake; release
gas ; turn bottle
upside down; wait
one minute
1
7 .108 Prepare
filtering column
1
7.11B Filter lower
aqueous layer
through f il ter ing
column into
ti tration vial
1
7.12B Shake vial
I
7 .13B Assemble
valve assembly over
Titret

7.14B Insert Titret
into Titrettor

-ป
7 15B Snap tip of
Titret
1
7.16B - 7.20B Pull
•mal 1 amount of
•ample into Titret;
win ; wait 30
seconds ; repeat
changes from purple
to pale yel 1 ow
I
7.21B When color
changes to pale
yel 1 ow , remove
Titret; record test
result from Titret
1
7.22B Calculate
concentration of
chlorine in ug/g

STOP J

                       9077 -  16
Revision 0
Septenter 1994

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                                   METHOD C

             DIRECT TITRATION QUANTITAVE END POINT TEST KIT METHOD

4.0C  APPARATUS AND MATERIALS

      4.1C   The  CHLOR-D-TECT Q40003  is  a complete  self-contained kit.   It
includes:  a sampling syringe to  withdraw a  fixed  sample volume for analysis; a
polyethylene test tube #1 into which the sample is introduced for dilution and
reaction with  metallic sodium;  a  polyethylene tube #2 containing  a buffered
aqueous extractant and the diphenylcarbazone  indicator; a microburette containing
the mercuric nitrate titrant; and a plastic filtration funnel.  Also included are
instructions to conduct the test.

5.0C  REAGENTS

      5.1C   All  necessary reagents are contained within the kit.  The diluent
solvent containing the catalyst,  the metallic  sodium, and the diphenylcarbazone
are separately glass-encapsulated in the precise quantity required for analysis.
A predispensed volume  of  buffer  is contained  in the second polyethylene tube.
Mercuric.nitrate titrant  is also supplied in a sealed titration burette.

      5.2C   The  kit  should be  examined  upon  opening  to   see that  all  of the
components are present and that  all ampoules (3) are in place and not leaking.
The liquid in Tube #2  (clear cap) should be approximately 1/2 in.  above the 5-mL
line and the tube  should  not  be  leaking.   The ampoules are not supposed to be
completely full.

6.0C  SAMPLE COLLECTION,  PRESERVATION, AND HANDLING

      6.1C   See  Section  6.0A of Method A.

7.0C  PROCEDURE

      7.1C   Preparation.  Open analysis carton, remove contents, mount plastic
test tubes in the provided holder.

             NOTE:  Perform  the  test  in a warm, dry  area  with adequate light.
             In cold weather, a truck cab is sufficient.   If a warm area is not
             available, Step 7.3C  should be performed while warming Tube #1 in
             palm  of hand.

      7.2C   Sample introduction.  Unscrew the white dispenser cap from Tube #1.
Slide the plunger in the empty syringe a few  times to make certain  that it slides
easily.  Place the top of the syringe in the oil sample to be tested, and pull
back on  the  plunger until it reaches  the stop and cannot be  pulled further.
Remove the syringe from the sample container, and wipe any excess oil from the
outside of the syringe with the  enclosed tissue.  Place the tip of the syringe
in Tube #1, and dispense the oil  sample by depressing the plunger. Replace the
white cap on the tube.
     Available from Dexsil Corporation, One Hamden Park Drive,  Hamden, CT 06517.

                                   9077 -  17                       Revision 0
                                                                  September 1994

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      7.3C   Reaction.  Break the lower (colorless) capsule containing the clear
diluent solvent  by  squeezing the sides  of  the test tube.   Mix thoroughly by
shaking the  tube vigorously  for 30  seconds.   Crush  the upper  grey  ampoule
containing metallic sodium,  again by squeezing the  sides of the test tube.  Shake
vigorously for 20 seconds.   Allow reaction  to proceed  for 60 seconds,  shaking
intermittently several times while timing with a watch.

             CAUTION:  Always  crush  the  clear ampoule  in  each  tube  first.
             Otherwise, stop the test and start over using another  complete kit.
             False  (low)  results may  occur  and allow a contaminated sample to
             pass without detection if clear ampoule is  not  crushed first.

      7.4C   Extraction.  Remove caps from both tubes.  Pour  the clear buffered
extraction solution from Tube  #2 into Tube #1.   Replace the white cap on Tube #1,
and shake  vigorously for  10  seconds.   Vent tube by partially  unscrewing the
dispenser cap.  Close cap securely,  and shake for an additional 10 seconds.  Vent
again, tighten cap,  and stand tube upside down on white  cap.  Allow phases to
separate for 2 minutes.

             NOTE: Tip Tube #2 to an angle of only about 45ฐ.  This will prevent
             the holder from  sliding out.

      7.5C   Analysis.  Put filtration  funnel  into  Tube  #2.   Position Tube #1
over funnel and open nozzle on dispenser cap.  Squeeze the sides  of Tube #1 to
dispense the clear aqueous lower phase through the filter  into Tube #2 to the 5-
mL line on Tube #2.   Remove the filter funnel,  and close  the  nozzle  on the
dispenser cap.  Place the plunger rod in the titration burette and press until
it clicks  into  place.   Break  off (do  not  pull off) the  tip on the titration
burette.   Insert the burette  into  Tube #2, and  tighten the cap.   Break the
colored ampoule,  and shake gently for  10  seconds.  Dispense titrant dropwise by
pushing down on burette rod in small  increments.  Shake the tube  gently to mix
titrant with solution in Tube #2 after  each  increment.  Continue adding titrant
until  solution turns from  yellow to red-violet.  An  intermediate pink color may
develop in the solution, but should be  disregarded.  Continue titrating until a
true red-violet color is realized.   The chlorine concentration of the original
oil sample is read  directly off the titrating  burette  at the tip of the black
plunger.  Record this result immediatley as  the red-violet color will fade with
time.

8.0C QUALITY CONTROL

      8.1C   Refer  to Chapter One for specific quality control procedures.

      8.2C   Each  sample  should be tested  two times.    If the  results  do not
agree to within 10%, expressed as the relative percent difference of the results,
a third test must be performed.  Report the results of the two that agree.

9.0C METHOD PERFORMANCE

      9.1C   These data are based on  96 data points  obtained  by 12 laboratories
who each analyzed six used crankcase oils and two fuel oil  blends with crankcase
in duplicate.  A data point represents one duplicate analysis of  a sample.
                                   9077  -  18                       Revision 0
                                                                  September 1994

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      9.2C   Precision.   The precision  of the  method  as determined  by the
statistical examination of interlaboratory test  results  is  as  follows:

             Repeatability - The difference between successive results obtained
             by  the same  operator with  the same  apparatus  under constant
             operating conditions on identical test material would  exceed, in
             the  long  run,  in the  normal  and correct  operation  of the test
             method, the following values only in 1  case in 20 (see  Table 4):


                         Repeatability = 0.175 x*
      *where x is the average of two results  in

             Reproducibility - The difference between two single and independent
             results  obtained  by  different  operators  working  in different
             laboratories on identical  test material would  exceed,  in the long
             run, the following values  only in 1  case  in  20:


                        Reproducibility =  0.331 x*


      *where x is the average value of  two results in  /xg/g.

      9.3C   Bias.  The bias of this test method  varies with concentration, as
shown in Table 5:

                     Bias = Amount  found  - Amount expected

10.0 REFERENCE

1.    Gaskill, A.; Estes,  E.D.;  Hardison, D.L.; and Myers,  I.E.   Validation of
      Methods for Determining  Chlorine in Used Oils and Oil Fuels.  Prepared for
      U.S. Environmental Protection Agency, Office of Solid Waste.  EPA Contract
      No. 68-01-7075, wA 80.   July  1988.
                                  9077 - 19                      Revision 0
                                                                 September 1994

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                                   TABLE 4.
            REPEATABILITY AND REPRODUCIBILITY  FOR CHLORINE  IN  USED
              OILS BY THE QUANTITATIVE END POINT TEST KIT METHOD
Average value,                Repeatability,         Reproducibility,
500
1,000
1,500
2,000
2,500
3,000
4,000
88
175
263
350
438
525
700
166
331
497
662
828
993
1,324
                                   TABLE 5.
            RECOVERY AND BIAS DATA FOR CHLORINE IN USED OILS BY THE
                    QUANTITATIVE END  POINT TEST KIT METHOD
Amount
expected,
Aig/9
664
964
1,230
1,445
2,014
2,913
3,812
4,190
Amount
found,
Mg/g
695
906
1,116
1,255
1,618
2,119
2,776
3,211

Bias,
Mg/g
31
-58
-114
-190
-396
-794
-1,036
-979

Percent
bias
+5
-6
-9
-13
-20
-27
-27
-23
                                   9077 -  20                      Revision 0
                                                                  September 1994

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                     METHOD 9077,  METHOD  C
DIRECT TITRATION QUANTITAVE END  POINT TEST  KIT METHOD
                        START
                  7.1C Open test  kit
                  7  2C Draw oil  into
                    •yringe;  remove
                     excess  oil;
                  dispense oil  into
                       Tube  #1
                     7 3C Break
                  colorless capsule;
                   mix; crush grey
                  capsule; mix; allow
                  reaction to proceed
                   for 60 seconds
                   7.4C Pour Tube  #2
                  solution into Tube
                   tl; mix; vent;
                   allow phases to
                      separate
                  7.SC Filter aqueous
                  lower phase in  Tube
                  t\ into Tube 12;
                    remove filter
                       funnel
7.SC Place plunger
    in  titraton
  burette; press;
 break  off.burette
tip;- insert burette
 in Tube f2\ break
 colored ampoule;
       shake
   7.SC Dispense
  titrant; shake;
  repeat process
  until solution
 turns from yellow
   to red-violet
 7.SC  Record level
  from titrating
      burette
      STOP
                           9077  -  21
                          Revision  0
                          September 1994

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                                 METHOD 9131

            TOTAL COLIFORM;  MULTIPLE TUBE FERMENTATION TECHNIQUE


1.0  SCOPE AND APPLICATION

     1.1  This method is used to  determine  the  presence  of a member of the
coliform group in ground water and surface water.

     1.2  The coliform group, as analyzed for in this procedure, is defined as
all aerobic and facultative  anaerobic, gram-negative, non-spore-forming,  rod-
shaped bacteria that ferment lactose with gas formation within 48 hr at 35*C.


2.0  SUMMARY OF METHOD

     2.1  The multiple-tube fermentation technique  is a three-stage procedure
1n which the results are statistically expressed 1n terms of the Most Probable
Number (MPN).  These  stages  —  the  presumptive stage, confirmed stage, and
completed test — are  briefly  summarized  below.    (For  the analysis to be
accurate, a five-tube test is required.)

          2.1.1  Presumptive Stage:  A series of lauryl tryptose broth primary
     fermentation tubes are Inoculated with graduated quantities of the sample
     to be tested.   The  Inoculated tubes  are  Incubated at  35 + 0.5*C  for
     24 + 2 hr, at which time  the  tubes are examined for gas formation.  For
     the~tubes in which no gas  is formed, continue Incubation and examine for
     gas formation at the end of 48  +  3  hr.  Formation of gas in any amount
     within 48 + 3 hr is a positive presumptive test.

          2.1.2  Confirmed Stage:  The confirmed  stage is used on all primary
     fermentation tubes  showing  gas  formation  during  the  24-hr and 48-hr
     periods.   Fermentation  tubes  containing  brilliant  green lactose bile
     broth are Inoculated with medium  from the tubes  showing a positive result
     1n the presumptive test.    Inoculation  should  be  performed as soon as
     possible after gas formation occurs.   The  inoculated tubes are Incubated
     for 48 + 3 hr at 35 +   0.5*C.     Formation  of gas at any time 1n the tube
     Indicates a positive  confirmed test.

          2.1.3  Completed Test:    The   completed  test  1s  performed on all
     samples showing a positive  result in the  confirmed test.   It can also be
     used as a quality control measure on 20% of all  samples analyzed.  One or
     more plates of  eosin   methylene   blue  are streaked  with   sample  to be
     analyzed.  The streaked plates are  incubated for 24 + 2 hr at 35 + 0.5*C.
     After  Incubation, transfer  one or  more typical  colonies  (nucleated, with
     or without metallic  sheen)  to  a   lauryl tryptose broth fermentation tube
     and a  nutrient agar  slant.    The  fermentation  tubes and  agar  slants are
     Incubated at 35 + 0.5*C for 24+2 hr,  or for 48 + 3 hr 1f  gas  is not
     produced.   From the  agar  slants   corresponding  to  the fermentation  tubes
     1n  which  gas  formation   occurs,  gram-stained   samples are examined
                                   9131 -  1
                                                         Revision
                                                         Date  September 1986

-------
     microscopically.   The formation of  gas   1n  the  fermentation  tube  and the
     presence of gram-negative,  non-spore-forming,  rod-shaped  bacteria 1n the
     agar  culture  may  be   considered   a   satisfactorily  completed  test,
     demonstrating the positive  presence of  coHform bacteria  1n  the analyzed
     sample.

     2.2  More detailed treatment  of  this  method  1s  presented 1n Standard
Methods for the Examination  of  Water  and  Wastewater and 1n  Microbiological
Methods for Monitoring the Environment (see References, Section 10.0).


3.0  INTERFERENCES

     3.1  The  distribution  of  bacteria  1n  water  1s  Irregular.   Thus,  a
five-tube test 1s required 1n this method for adequate statistical accuracy.

     3.2  The presence of residual chlorine  or other halogens  can prevent the
continuation  of  bacterial  action.    To  prevent  this  occurrence,   sodium
thlosulfate should be added to the sterile sample container.

     3.3  Water samples high 1n  copper,  zinc,  or  other heavy metals can be
toxic to bacteria.   Chelatlng  agents such as ethylenedlaminetetraacetlc add
(EDTA) should be added only when heavy metals are suspected of being present.

     3.4  It 1s Important to  keep  1n  mind  that  MPN tables  are probability
calculations and Inherently have poor precision.   They Include a 23% positive
bias that generally results in high  value.    The precision of the MPN can be
Improved by increasing the number  of  sample portions examined and the number
of samples analyzed from the same sampling point.


4.0  APPARATUS AND MATERIALS

     4.1  Incubators:

          4.1.1   Incubators must maintain  a  uniform  and constant temperature
     at  all times in all areas, that   1s,  they must not vary more than +0.5'C
     1n  the areas used.   Obtain  such  accuracy  by using a water-jacketed or
     anhydric-type  Incubator with   thermostatically controlled low-temperature
     electric  heating  units properly  insulated  and  located 1n or adjacent to
     the walls or floor of the chamber and preferably  equipped with mechanical
     means  of  circulating air.   If  a  hot-air type incubator is used,  humidity
     must be maintained at 75-80%.

          4.1.2   Alternatively,  use  special  Incubating   rooms well Insulated
     and equipped with properly  distributed   heating units and with forced air
     circulation, provided that  they  conform to desired temperature limits and
     relative   humidity.    When   such   rooms  are  used,  record  the  dally
     temperature  range in  areas  where plates or tubes are Incubated.   Provide
     Incubators with  open  metal  wire  or  sheet  shelves so spaced as to  assure
     temperature  uniformity throughout  the   chamber.    Leave  a 2.5-cm space
     between  walls  and stacks of dishes or baskets of  tubes.
                                   9131 - 2
                                                          Revision      0
                                                          Date   September  1986

-------
          4.1.3   Maintain  an  accurate   thermometer  with  the bulb  Immersed  1n
     liquid (glycerine,  water,  or mineral  oil)  on each  shelf 1n  use within the
     Incubator and record  dally  temperature   readings  (preferably  morning and
     afternoon).   It 1s  desirable,  1n  addition,  to  maintain a  maximum and
     minimum registering thermometer within the  incubator  on the middle  shelf
     to record the gross temperature range over a 24-hr period.   At intervals,
     determine temperature  variations  within  the  Incubator   when  filled  to
     maximum capacity.   Install a recording thermometer,  whenever possible,  to
     maintain a   continuous  and  permanent   record  of  temperature.   Mercury
     thermometers should  be  graduated  in   0.5'C   increments   and calibrated
     annually against an NBS certified  thermometer.  Dial  thermometers should
     be calibrated quarterly.

          4.1.4   Keep water depth  1n   the water  bath  sufficient to Immerse
     tubes to upper level  of media.

     4.2  Hot-a1r  sterilizing  ovens:    Use  hot-air   sterilizing  ovens   of
sufficient size  to prevent Internalcrowding, constructed  to give  uniform and
adequate sterilizing temperatures of  170  +   10*C   and equipped with suitable
thermometers.  As an alternative, use  a temperature-recording  Instrument.

     4.3  Autoclaves:

          4.3.1   Use  autoclaves  of  sufficient   size  to prevent   internal
     crowding, constructed to provide  uniform temperatures  within the chambers
     (up to and Including   the  sterilization  temperature  of  121*C);  equipped
     with an accurate thermometer, the  bulb   of which 1s  located  properly  on
     the exhaust  line  so  as  to  register  minimum  temperature  within the
     sterilizing  chambers   (temperature-recording   Instrument   1s  optional);
     equipped  with  pressure  gauge   and  properly  adjusted   safety  valves
     connected directly with  saturated-steam  power  lines or  directly to a
     suitable special steam generator  (do not  use  steam from  a boiler treated
     with amines for corrosion control);  and  capable  of reaching  the desired
     temperature within 30 m1n.

          4.3.2  Use  of  a  vertical   autoclave or  pressure   cooker  1s not
     recommended  because   of   difficulty   1n   adjusting  and  maintaining
     sterilization temperature and the potential hazard.   If a  pressure cooker
     1s used 1n emergency or special circumstances, equip 1t with an  efficient
     pressure gauge and a thermometer, the  bulb  of which is  2.5 cm  above  the
     water level.

     4.4  Colony counters;  Use  Quebec-type  colony counter,  dark-field model
preferred, or  one  providing  equivalent  magnification  (1.5  diameters)  and
satisfactory visibility.

     4.5  pH Equipment;  Use electrometrlc pH meters, accurate to at.  least 0.1
pH units,  for determining pH values of  media.  See Method 9040 for standardi-
zation of  a pH meter.
                                  9131 - 3
                                                         Revision
                                                         Date  September 1986

-------
     4.6  Balances;  Use balances providing a sensitivity of at  least  0.1 g  at
a load of 150 g, with appropriate weights.   Use an  analytical  balance  having a
sensitivity of 1 mg under a load  of  10 g  for weighing small  quantities  (less
than 2 g) of materials.  Single-pan rapid-weigh balances are most convenient.

     4.7  Media  preparation  utensils;    Use  boroslHcate  glass or  other
suitable noncorroslve equipment such as  stainless   steel.  Use  glassware that
1s clean and free of residues, dried agar,  or other foreign materials  that may
contaminate media.

     4.8  Pipets and graduated cylinders;

          4.8.1  Use plpets of any convenient size, provided that they deliver
     the required volume accurately and quickly.  The error of calibration for
     a given manufacturer's   lot  must  not  exceed  2.5%.   Use plpets having
     graduations distinctly marked and  with  unbroken tips.  Bacteriological-
     transfer plpets or plpets conforming  to  the APHA standards given 1n the
     latest edition of Standard Methods  for the Examination of Dairy Products
     may be used.  Optimally, protect  themouth end of all plpets by a cotton
     plug to eliminate hazards to  the worker or possible sample contamination
     by  saliva.

          4.8.2 Use graduated cylinders meeting  ASTM  Standards  (D-86 and D-
     216) and with  accuracy  limits   established  by  the  National Bureau of
     Standards, where  appropriate.

     4.9 P1pet containers;   Use  boxes  of  aluminum  or stainless steel, end
measurement 5 to 7.5 cm, cylindrical   or   rectangular, and  length  about 40 cm.
When these are  not available,  paper   wrappings  may be substituted.  To avoid
excessive charring during  sterilization, use best-quality sulfate  pulp (Kraft)
paper.   Do not  use copper  or  copper alloy  cans or boxes as  plpet containers.

     4.10  Dilution bottles or tubes;

          4.10.1   Use  bottles  or   tubes  of  resistant  glass,  preferably
     boroslHcate  glass, closed  with  glass   stoppers  or  screw caps equipped
     with  liners that  do  not  produce  toxic  or bacteriostatlc  compounds on
     sterilization.

          4.10.2   Do not use  cotton plugs  as  closures.   Mark gradation levels
     Indelibly  on  side  of   dilution  bottle  or  tube.    Plastic bottles of
     nontoxlc material  and   acceptable  size  may  be  substituted for glass,
     provided that they can be sterilized  properly.

     4.11   Petri dishes;   Use glass or plastic Petri dishes about  100 x 15 mm.
Use dishes  the  bottoms of  which  are   free from bubbles and scratches and flat
so that the medium will be of uniform  thickness throughout  the plate.  For  the
membrane-filter technique, use  loose-Hd glass or  plastic  dishes, 60 x  15  mm,
or tight-lid dishes, 50 x  12  mm.    Sterilize Petri dishes and  store 1n metal
cans  (aluminum  or  stainless  steel,   but  not  copper),  or  wrap 1n paper —
preferably  best-quality sulfate  pulp  (Kraft)  — before  sterilizing.
                                   9131 - 4
                                                          Revision
                                                          Date   September  1986

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     4.12  Fermentation tubes and vials;   Use only 10-iran x 75-mm fermentation
tubes.  When tubes areusedforatest  of gas production,  enclose a shell
vial, Inverted.  Use a vial  of  such  size  that 1t will be filled completely
with medium and at least partly submerged 1n the tube.

     4.13  Inoculating equipment;   Use  wire  loops  made  of 22- or 24-gauge
nickel alloy (chromel, n1chrome, or  equivalent) or plat1num-1r1d1um for flame
sterilization.  Single-service transfer  loops  of aluminum or stainless steel
are satisfactory.  Use loops at least 3 mm 1n diameter.  Sterilize by dry heat
or steam.  Single-service hardwood applicators  also  may be used.  Make these
0.2 to 0.3 cm 1n diameter  and  at  least  2.5 cm longer than the fermentation
tube; sterilize by dry heat and store 1n glass or other nontoxlc containers.


5.0  REAGENTS

     5.1  ASTM Type II water  (ASTM  D1193):    Water  should be monitored for
Impurities.

     5.2  Buffered water;

          5.2.1  To prepare stock phosphate  buffer   solution, dissolve 34.0 g
     potassium d1hydrogen phosphate  (KHgPC^) 1n  500  ml Type II water, adjust
     to pH 7.2 + 0.5 with 1  N  sodium  hydroxide (NaOH), and dilute to 1 liter
     with Type II water.

          5.2.2  Add  1.25  ml   stock  phosphate  buffer  solution  and  5.0 ml
     magnesium chloride  solution  (38 g  MgCl2/Hter Type  II water or
     81.1 g  MgCl2-6H20/l1ter   Type  II water)  to   1   liter  Type   II water.
     Dispense  1n amounts that will provide   99  +  2.0  ml or 9 + 0.2 ml after
     autoclavlng for  15  m1n.

          5.2.3  Peptone water:   Prepare a  10%  solution of peptone in Type II
     water.  Dilute a  measured  volume to provide a final 0.1% solution.  Final
     pH  should be 6.8.

          5.2.4  Dispense  1n amounts to provide  99   +   2.0  ml  or 9 + 0.2 ml
     after autoclavlng for 15 m1n.

          5.2.5  Do not  suspend bacteria 1n  any  dilution water for  more than
     30  m1n  at room   temperature  because   death  or  multiplication may occur,
     depending on the  species.
                                   9131 - 5
                                                          Revision
                                                          Date   September  1986

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5.3  Lauryl tryptose broth;

     5.3.1  Components of the broth are:

              Tryptose                    20.0  g
              Lactose                      5.0  g
              01phosphate hydrogen
                 phosphate, K2HP04         2.75 g
              Potassium d1hydrogen
                 phosphate, KH2P04         2.75 g
              Sodium chloride, NaCl        5.0  g
              Sodium lauryl sulfate        0.1  g
              Type II water                1    liter

Lauryl tryptose broth 1s also available 1n a prepackaged dry powder form.

     5.3.2  Make  lauryl  tryptose  broth  of  such strength that  adding
100-mL or  10-mL portions of  sample  to medium will not reduce Ingredient
concentrations below those of the standard medium.  Prepare 1n accordance
with Table 1.

           TABLE 1.  PREPARATION OF LAURYL TRYPTOSE BROTH


Inoculum
(ปL)
1
10
10
100
100
100

Amount of
Medium 1n Tube
(mL)
10 or more
10
20
50
35
20
Volume of
Medium +
Inocul urn
(mL)
11 or more
20
30
150
135
120
Dehydrated Lauryl
Tryptose Broth
Required
(g/Hter)
35.6
71.2
53.4
106.8
137.1
213.6
      5.3.3  Dispense the  broth   Into   fermentation   tubes  which contain
 Inverted vials.   Add an amount  sufficient  to  cover  the  Inverted vial, at
 least partially,  after sterilization has  taken place.  Sterilize at  121*C
 for 12 to 15 m1n.  The pH should be 6.8 + 0.2  after  sterilization.

 5.4  Brilliant green lactose bile broth;

      5.4.1  Components of the broth are:

               Peptone                 10.0     g
               Lactose                 10.0     g
               Oxgall                  20.0     g
               Brilliant green          0.0133  g
               Type II water            1       liter
                              9131  - 6
                                                     Revision
                                                     Date   September  1986

-------
     This broth 1s also available 1n a prepackaged dry powder form.

          5.4.2  Dispense the  broth  Into  fermentation  tubes  which contain
     Inverted vials.  Add an amount  sufficient to cover the Inverted vial,  at
     least partially, after sterilization has taken place.  Sterilize at 121'C
     for 12 to 15 m1n.  The pH should be 7.2 + 0.2 after sterilization.

     5.5  Ammonium oxalate-crystal violet  (Mucker's);    Dissolve 2 g crystal
violet  (90%  3ye  content)  Tn  20  nil  95%  ethyl  alcohol,  dissolve  0.8 g
(NH4)2C204'H20  1n 80 ml  Type II water,  mix  the two solutions,  and age for
24 hr before use; filter through paper Into a staining bottle.

     5.6  Lugol's solution, Gram's modification:    Grind  1 g Iodine crystals
and 2 g KI in a mortar.Add"TypeII water, a few m1111liters at a time, and
grind thoroughly  after  each  addition  until  solution  1s  complete.  Rinse
solution Into an amber glass bottle with the remaining water (using a total  of
300 ml).

     5.7  Counterstain:  Dissolve  2.5  g  safranln  dye  1n  100 ml 95% ethyl
alcohol.  Add 10 ml to 100 ml Type II water.

     5.8  Acetone alcohol;   Mix  equal  volumes  of  ethyl alcohol, 95%, with
acetone.

     5.9  Gram staining kits;  Commercially  available kits may be substituted
for 5.5, 5.6, 5.7, and 5.8.


6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

     6.1  All samples must  have  been  collected  using  a sampling plan that
addresses the considerations discussed in U.S. EPA, 1978.

     6.2  Clean all glassware  thoroughly  with  a  suitable detergent and hot
water, rinse with hot water to remove all traces of residual washing compound,
and finally rinse with Type  II  water.    If mechanical glassware washers are
used, equip them with Influent  plumbing  of stainless steel or other nontoxic
material.  Do  not  use  copper  piping  to  distribute  Type  II  water.  Use
stainless steel or other nontoxic material for the rinse-water system.

          6.2.1  Sterilize glassware, except when  1n metal containers, for not
     less than 60 min  at  a  temperature  of  170*C,  unless 1t  is known from
     recording thermometers that  oven  temperatures  are uniform, under which
     exceptional condition use 160*C.   Heat  glassware  in metal  containers to
     170*C for not  less than 2 hr.

          6.2.2  Sterilize sample bottles not made  of plastic as  above, or 1n
     an autoclave at  121*C  for   15  m1n.     Perform  a  sterility  check  on one
     bottle per batch.
                                  9131 - 7
                                                         Revision
                                                         Date  September 1986

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          6.2.3   If water containing residual  chlorine  and other halogens 1s
     to be collected,  add   sufficient  ^$203  to  clean sample bottle before
     sterilization to  give  a  concentration  of  about  100 mg/L 1n the sample.
     To a   120-mL bottle   add   0.1  ml   10%  solution  of  ^28203  (this will
     neutralize  a sample containing about 15 mg/L residual chlorine).  Stopper
     bottle,  cap, and   sterilize  by   either  dry  or  moist heat, as directed
     previously.

          6.2.4   Collect water  samples high  1n  copper or zinc and  wastewater
     samples  high 1n  heavy  metals 1n  sample  bottles containing a chelatlng
     agent that  will  reduce metal   toxlclty.  This 1s particularly significant
     when  such samples are  1n transit  for 4  hr  or more.  Use 372 mg/L of the
     tetrasodlum salt  of ethylenedlaminetetraacetlc  add  (EDTA).  Adjust EDTA
     solution to pH  6.5 before  use.     Add  EDTA separately to  sample bottle
     before bottle  sterilization (0.3  mL 15%  solution 1n a 120-mL  bottle) or
     combine It  with  the ^28203 solution before addition.

     6.3   When the  sample  1s  collected,   leave  ample  air space  1n  the bottle
(at least  2.5 cm) to facilitate mixing by shaking, preparatory to examination.
Be careful to take   samples  that  will   be  representative of the water being
tested and avoid  sample   contamination   at  time  of  collection or In period
before examination.

     6.4  Keep sampling bottle  closed   until  the  moment  1t  1s  to  be filled.
Remove stopper and hood  or  cap  as   a   unit,  taking  care to avoid soiling.
During sampling, do not handle  stopper  or   cap and  neck of bottle and protect
them from contamination.    Hold  bottle   near  base,   fill 1t without rinsing,
replace stopper or cap Immediately, and  secure hood  around neck of bottle.


7.0  PROCEDURE

     7.1  Presumptive stage;

          7.1.1  Inoculate  a   series   of   fermentation   tubes   ("primary"
     fermentation tubes) with appropriate  graduated quantities  (multiples and
     submultlples of  1 mL)  of  sample.     Be  sure  that the concentration of
     nutritive  Ingredients 1n the mixture  of medium and added sample conforms
     to the  requirements given  1n  Paragraph  5.3.     Use a sterile plpet for
     Initial  and subsequent  transfers   from  each  sample  container.   If the
     plpet becomes contaminated before transfers are completed,  replace with a
     sterile plpet.   Use   a  separate sterile  plpet  for transfers from each
     different  dilution.   Do not  prepare  dilutions  1n direct sunlight.  Use
     caution when  removing   sterile plpets  from  the  container;  to avoid
     contamination, do not drag   plpet   tip  across  exposed ends of plpets or
     across  Ups and  necks of  dilution   bottles.  When removing sample, do not
     Insert  plpets more than 2.5  cm   below  the surface of sample or dilution.
     When discharging sample portions, hold  plpet  at  an angle of about 45*,
     with tip touching the Inside neck   of  the  tube.  The portions of sample
     used for Inoculating  lauryl-tryptose-broth  fermentation tubes will vary
     1n size and number with the  character of the water under examination, but
                                   9131 - B
                                                         Revision      0
                                                         Date  September 1986

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1n general use decimal multiples and submultiples  of 1 ml.   Use Figure 1
as a guide to preparing  dilutions.   After adding sample,  mix thoroughly
by shaking the test tube rack.  Do not invert the tubes.

     7.1.2  Incubate inoculated fermentation tubes at  35 + 0.5*C.   After
24 + 2 hr shake each tube gently and examine it and, if no gas has  formed
and been trapped in the  inverted  vial,  reincubate and reexamine  at the
end of  48  +  3  hr.    Record  presence  or  absence  of gas formation,
regardless of amount, at each examination of the tubes.

     7.1.3  Formation of gas  in  any  amount  in  the inner fermentation
tubes or vials within 48 +  3 hr constitutes a positive presumptive test.
Do not confuse the  appearance  of  an  air  bubble  in a clear tube with
actual gas production.  If gas is formed as a result of fermentation, the
broth medium will become cloudy.  Active fermentation may be shown by the
continued appearance  of  small  bubbles  of  gas  throughout  the medium
outside the inner vial when the fermentation tube is shaken gently.

     7.1.4  The absence of gas  formation  at  the  end  of  48+3 hr of
incubation constitutes a negative test.   An arbitrary limit of 48 hr for
observation doubtless excludes  from  consideration occasional members of
the coliform group that form gas very slowly and generally are of limited
sanitary  significance.

7.2  Confirmed stage;

     7.2.1  Submit all primary fermentation  tubes  showing any amount of
gas within  24  hr  of  incubation  to  the  Confirmed  Test.   If active
fermentation appears  in the primary fermentation tube earlier than 24 hr,
transfer  to the confirmatory  medium  without  waiting for the full 24-hr
period to elapse.     If  additional  primary  fermentation tubes show gas
production at the end of 48-hr  incubation, submit these to the Confirmed
Test.

     7.2.2  Gently shake or rotate  primary fermentation tube showing gas
and do one  of  two   things:   (a)  with  a  sterile  metal  loop, 3 mm 1n
diameter,  transfer   one  loopful  of  culture  to  a  fermentation  tube
containing brilliant  green lactose  bile  broth,  or (b) Insert a sterile
wooden applicator at  least  2.5  cm  long  Into  the  culture, remove it
promptly, and plunge  it  to  the  bottom  of fermentation tube containing
brilliant green lactose bile broth.  Remove and discard applicator.

     7.2.3  Incubate  the inoculated  brilliant  green  lactose bile broth
tube for  48 + 3 hr at 35 +  0.5*C.  Formation of gas in any amount 1n the
inverted  viaT of the  brilliant green lactose bile broth fermentation tube
at any time within 48 + 3 hr constitutes a positive Confirmed Test.

7.3  Completed test;

     7.3.1  Use  the  Completed  Test  on  positive  confirmed  tubes  to
establish definitely the  presence  of  col 1 form  bacteria  and provide
quality control data  for 20% of all samples analyzed.
                              9131 - 9
                                                    Revision      0
                                                    Date   September  1986

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                       Water
                       sample
                — 1 ml
Delivery
volume
Culture dishes
Actual volume
of sample in
dish
                             \
 1 ml
0.1 ml
1 ml
   0.1 ml
                                10'2 ml
                                     10'3 ml
            Figure  1.  Preparation of  dilutions.
                          9131 - 10
                                                    Revision  	p_
                                                    Date   September
                                                    1986

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     7.3.2  Streak one or more eosin methylene blue plates from each tube
of brilliant green lactose  bile  broth  showing  gas as soon as possible
after the appearance of gas.    Streak  plates to ensure presence of some
discrete colonies separated by at  least  0.5  cm.  Observe the following
precautions  when  streaking  plates  to  obtain  a  high  proportion  of
successful Isolations  if  coll form  organisms  are  present:  (a) use an
Inoculating needle slightly curved at  the  tip;  (b) tap and Incline the
fermentation tube to avoid picking up any membrane or scum on the needle;
(c) Insert end of  needle  into  the  liquid  in  the  tube to a depth of
approximately 5.0 mm; and  (d)  streak  plate  with curved section of the
needle 1n contact with the agar to avoid a scratched or torn surface.

     7.3.3  Incubate plates (Inverted) at 35 + 0.5*C for 24+2 hr.

     7.3.4  The colonies  developing  on  eosin  methylene  blue agar are
called: typical (nucleated,  with  or  without  metallic sheen); atypical
(opaque, unnucleated, mucoid, pink  after  24-hr Incubation); or negative
(all others).  From each of these  plates, pick one or more typical well-
Isolated coliform colonies or, 1f  no  typical colonies are present, pick
two or more colonies considered  most  likely  to consist of organisms of
the coliform group and  transfer  growth  from  each isolate to a lauryl-
tryptose-broth fermentation tube and to a nutrient agar slant.
     NOTE:  If possible, when transferring colonies, choose well-Isolated
          colonies and barely  touch  the  surface  of  the colony with a
          flame-sterilized, air-cooled  transfer  needle  to minimize the
          danger of transferring a mixed culture.

     7.3.5  Incubate secondary broth tubes at 35  +  0.5*C for 24+2 hr;
1f gas 1s not produced within 24+2 hr, reincubate and examine again at
48+3  hr.    Microscopically  examine  gram-stained  preparations  (see
Paragraph 7.4) from those 24-hr  agar slant cultures corresponding to the
secondary tubes that show gas.

     7.3.6  Formation of gas   in  the  secondary  tube of lauryl tryptose
broth within 48 +  3  hr  and  demonstration of gram-negative, non-spore-
forming,  rod-shaped  bacteria   1n   the   agar   culture   constitute  a
satisfactory Completed Test, demonstrating  the  presence  of a member of
the coliform group.

7.4  Gram-stain procedure;

     7.4.1  Prepare a light emulsion of the bacterial growth from an  agar
slant in a drop of Type II  water  on  a  glass slide.  A1r-dry or fix by
passing the slide through a flame  and  stain for 1 m1n with the ammonium
oxalate-crystal violet solution.   Rinse  the   slide  1n tap water; apply
Lugol's solution for 1 m1n.   (See Paragraphs 5.5-5.8 for reagent.)

     7.4.2  Rinse  the  stained  slide  in  tap  water.    Decolorize for
approximately  15 to 30 sec with  acetone alcohol by holding  slide between
the fingers and letting  acetone  alcohol  flow  across the  stained smear
until no more  stain  is  removed.    Do not over-decolorize.  Counterstaln
with safranln  (Paragraph 5.7)  for 15 sec, then  rinse with tap water,  blot
dry with bibulous paper, and examine microscopically.

                             9131 - 11
                                                    Revision      0
                                                    Date  September 1986

-------
         7.4.3  Cells that decolorize and accept  the safranln stain are pink
    and defined as gram-negative 1n  reaction.   Cells that do not decolorize
    but retain the crystal  violet  stain  are  deep  blue and are defined as
    gram-positive.

    7.5  Computing and recording of MPN;

         7.5.1  The calculated density of  col 1 form  bacteria 1n a sample can
    be obtained from the MPN table, based  on the number of positive tubes In
    each dilution of the  confirmed  or  completed  test.   Table 2 shows MPN
    Indices and 95% confidence limits for  potable water testing, and Table 3
    describes the MPN Indices and 95% confidence limits for general use.
 TABLE 2.  MPN  INDEX AND 95% CONFIDENCE LIMITS FOR VARIOUS COMBINATIONS OF
      POSITIVE  AND NEGATIVE RESULTS WHEN FIVE 10-mL PORTIONS ARE USED
Number of Tubes
Giving Positive
Reaction out of
5 of 10 mL each
0
1
2
3
4
5
MPN
Index per
100 mL
<2.2
2.2
5.1
9.2
16
>16
95% Confidence Limits
Lower Upper
0 6.0
0.1 12.6
0.5 19.2
1.6 29.4
3.3 52.9
8.0 Infinite
          7.5.2  Three dilutions are  necessary   for  the  determination of the
     MPN Index.  For example (see  Table  3),  1f five 10-mL,  five  1.0-mL, and
     five 0.1-mL portions of the samples  are  used  as Inocula and  four of the
     10-mL,  two of the 1-mL, and  none  of the 0.1-mL portions of Inocula give
     positive results, the coded result 1s  4-2-0 and the MPN Index  1s 22 per
     100 mL.

          7.5.3  In cases when the serial   decimal   dilution 1s other than 10,
     1,  and 0.1 mL, or when  more  than  three  sample volumes are  used 1n the
     series, refer to the sources  cited  1n Section 10.0, References, for the
     necessary density determination procedures.

          7.5.4  All MPN values for  water  samples   should be reported on the
     basis of a 100-mL sample.


8.0  QUALITY CONTROL

     8.1  Extensive quality control procedures are provided In Part IV of U.S.
EPA, 1978 (see Section 10.0, References).    These procedures should be adhered
to at all times.
                                  9131 - 12
                                                         Revision      0
                                                         Date  September 1986

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            TABLE 3.  MPN  INDEX FOR SERIAL DILUTIONS OF SAMPLE
Number of Tubes
Giving Positive
Reaction out of

5 of
10 mL
each
0
0
0
0
1
1
1
1
1
2
2
2
2
2
2
3
3
3
3
3
3
3
4
4
4
4
4

5 Of
1 mL
each
0
0
1
2
0
0
1
1
2
0
0
1
1
2
3
0
0
1
1
2
2
3
0
0
1
1
1

5 of
0.1 mL
each
0
1
0
0
0
1
0
1
0
0
1
0
1
0
0
0
1
0
1
0
1
0
0
1
0
1
2
MPN
Index
per
100 mL
<2
2
2
4
2
4
4
6
6
5
7
7
9
9
12
8
11
11
14
14
17
17
13
17
17
21
26
95%
Confidence



Lower

<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
1
1
2
2
3
1
2
2
4
4
5
5
3
5
5
7
9
Limits


Upper

7
7
11
7
11
11
15
15
13
17
17
21
21
28
19
25
25
34
34
46
46
31
46
46
63
78
Source:  U.S. EPA, 1978.
                          (Continued on next page)
                                  9131 - 13
                                                         Revision      0
                                                         Date  September 1986

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            TABLE 3.  MPN INDEX FOR SERIAL DILUTIONS OF SAMPLE
                                (Continued)
Number of Tubes
Giving Positive
Reaction out of
5 of
10 mL
each
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5 of
1 mL
each
2
2
3
3
4
0
0
0
1
1
1
2
2
2
3
3
3
3
4
4
4
4
4
5
5
5
5
5
5
5 of
0.1 mL
each
0
1
0
1
0
0
1
2
0
1
2
0
1
2
0
1
2
3
0
1
2
3
4
0
1
2
3
4
5
MPN
Index
per
100 mL
22
26
27
33
34
23
31
43
33
46
63
49
70
94
79
110
140
180
130
170
220
280
350
240
350
540
920
1600
^2400
95%
Confidence
Limits
Lower
7
9
9
11
12
7
11
15
11
16
21
17
23
28
25
31
37
. 44
35
43
57
90
120
68
120
180
300
640

Upper
67
78
80
93
93
70
89
110
93
120
150
130
170
220
190
250
340
500
300
490
700
850
1000
750
1000
1400
3200
5800

Source:  U.S. EPA, 1978,
                                  9131 - 14
                                                         Revision      0
                                                         Date  September 1986

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     8.2  Samples must  be  maintained  as  closely  as  possible  to original
condition  by  careful  handling  and  storage.    Sample  sites  and sampling
frequency  should   provide   data   representative   of  characteristics  and
variability of the water quality  at  that  site.   Samples should be analyzed
immediately.  They  should  be  refrigerated  at  a  temperature  of 1-4*C and
analyzed within 6 hr.

     8.3  Quality control of  culture  media  1s  critical  to the validity of
microbiological analysis.  Some  important  factors to consider are summarized
below:

          8.3.1  Order media to last for  only  1  yr; always use oldest stock
     first.  Maintain an inventory  of  all  media ordered, including a visual
     inspection record.

          8.3.2  Hold unopened media for no  longer  than  2 yr.  Opened media
     containers should be discarded after 6 mo.

          8.3.3  When preparing  media  keep  containers  open  as  briefly as
     possible.  Prepare media  in  delonized  or  distilled (Type II) water of
     proven  quality.    Check  the  pH   of  the  media  after  solution  and
     sterilization;  it  should  be  within  0.2  units  of  the  stated value.
     Discard and remake if  it is not.

          8.3.4  Autoclave  media  for  the  minimal  time  specified  by  the
     manufacturer because the  potential  for  damage increases with Increased
     exposure  to heat.  Remove  sterile  media  from  the autoclave as soon as
     pressure  Is zero.  Effectiveness  of  the sterilization should be checked
     weekly, using  strips or ampuls of Bacillus stearothemophelus.

          8.3.5  Agar plates should be  kept   slightly  open  for 15 min after
     pouring or  removal from refrigeration to  evaporate free moisture.   Plates
     must be free of lumps, uneven surfaces, pock marks, or bubbles, which can
     prevent good contact between the agar and medium.

          8.3.6  Avoid  shaking  fermentation tubes, which can entrap air  1n the
     Inner  vial  and produce a false positive result.

          8.3.7  Store  fermentation tube media in  the dark at room temperature
     or 4*C.    If   refrigerated,  Incubate  overnight  at  room  temperature to
     detect false positive  gas  bubbles.

          8.3.8  Quality  control  checks of  prepared  media should  include the
      incubation  of  5% of  each batch   of   medium   for  2 days at  35'C  to  inspect
      for growth  and positive/negative checks with  pure culture.

      8.4 Analytical quality  control  procedures  should  include;

           8.4.1   Duplicate  analytical   runs  on   at   least  10%  of  all  known
     * positive  samples analyzed.
                                   9131 - 15
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          8.4.2  At least one positive  control  sample  should  be  run  each month
     for each parameter tested.

          8.4.3  At least one negative   (sterile)   control  should be run  with
     each series of samples using buffered  water  and  the medium batch used  at
     the beginning of the test series  and following every  tenth sample.   When
     sterile controls indicate contamination,   new  samples should be obtained
     and analyzed.

          8.4.4  The Type II  water  used  should   be  periodically checked for
     contamination.

          8.4.5  For routine MPN tests, at  least  5% of the positive confirmed
     samples should be tested by the complete test.


9.0  METHOD PERFORMANCE

     9.1  No data provided.


10.0 REFERENCES

1.   Standard Methods for the  Examination  of  Water and Wastewater, 15th ed.
(1980).

2.   U.S.  Environmental  Protection   Agency,   Microbiological  Methods  for
Monitoring the  Environment,  EPA 600/8-78-017, December 1978.
                                  9131 - 16
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                                                         Date  September 1986

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                                            METHOD 9i3>

                       TOT*L COLIFOซM:  MULTIPLE TUBE FERMENTATION TECHNIOJE
     Presumpt1ve
        Stage
7.1.1
Inoculate • series of
 fermentation tubes
   with graouateo
quantities of cample
   7.1.8
         Incubate
        Inoculates
      fermentation
         tubes
.X 7.1.2 ^s.
Has
f ormea
. hour
gas >v
ifter Z* > ป
-c? jr
Xres
7.1.2

Relncubate ane
reexamine at
eno of 46 hours



   Confirmeo
     Stage
                                                       7.2.1
   Submit  tubes
  for  whIch  gas
'has  formea.  to
 Conflrmeo Test
                                                       7.S.2
                                                              Shake
                                                              tube:
  place  culture
  In  tube  with
  green  lactose
   bile  brotn
                                                       7.2.3
                                                        Incubate  bile
                                                       broth  tube  for
                                                          48  hours
        7.1.3
                                        9131 ~ 17
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                                                                  Date  September 1986

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                        TOTAL COLIFORM:
               MetnoB 913.1

          MULTIPLE TUBE FERMENTATION' TECHNIQUE
                (Contlnueo)
      Comoleteo
        Test
   7.3.1
                                of bacterial
                                growth from
                              agar slant for
                                 gram-staIn
          Submit
        tuoes for
     which gas has
        formed to
    Completed Test
7.3.2
                             7.4. i
Air-dry or fix
     Streak aosin
netnylene blue elates
  from each tube of
     bile broth
    snowing gas
                             7.4.2
                                                                                 7.3.5
                                                      Reincubate:
                                                     examine  again
                                                      at  6 hours
 stained prep-
 arations froT.
slant cultures
     (see 7.4)
    Decolor lie.
   counterstein
 with safrenln;
     examine
   7.3.3[


       Incubate
   inverted plates
                             7.4.3
       Gram
 negative  cells
 are  pink:  gram
 positive  cells
 are  deeo  blue
7.3.4
      Pick typical
  colonies:  transfer
       growth to
   fermentation tube
    •no agar slant
                             7.3.5
7.5
    'Calculate
   density of
    collform
 bacteria from
   MPN table
      Incubate
     secondary
    broth  tubes
   for 24  hours
                        (      Stop       1
                                         9131 -  18
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                                                                   Date  September 1986

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                                 METHOD 9132

                  TOTAL COLIFORM; MEMBRANE-FILTER TECHNIQUE
1.0  SCOPE AND APPLICATION

     1.1  This method 1s used  to  determine  the  presence  of  a member of a
collform group 1n wastewater and ground water.

     1.2  The conform group analyzed  1n  this  procedure Includes all  of the
organisms  that produce  a colony  with a golden-green  metallic sheen  within
24 hr of Inoculation.
2.0  SUMMARY OF METHOD

     2.1  A predetermined amount  of  sample  1s  filtered  through a membrane
filter which retains the bacteria found 1n the sample.

     2.2  In  the  two-step  enrichment   procedure,  the  filters  containing
bacteria are placed on an  absorbent  pad saturated with lauryl tryptose broth
and Incubated at 35'C + 0.5*C for  2  hr.  The filters are then transferred to
an absorbent pad saturated with  M-Endo  media  or to a dish containing M-Endo
agar and incubated for another 21+1  hr at 35ฐC + 0.5ฐC.  Sheen colonies are
then counted under magnification and reported per 100 ml of original sample.

     2.3  A more detailed treatment  of  this  method 1s presented in Standard
Methods for the Examination  of  Water  and  Wastewater and 1n Microbiological
Methods for Monitoring the Environment (see References, Section 10.0).


3.0  INTERFERENCES

     3.1  The presence of residual chlorine  or  other halogen can prevent the
continuation  of  bacterial  action.    To  prevent  this  occurrence,  sodium
thiosulfate should be added.

     3.2  Water samples high 1n  copper,  zinc,  or  other heavy metals can be
toxic to bacteria.   Chelating  agents such as ethylenediaminetetraacetic acid
(EDTA) should only be added when heavy metals are suspected of being present.

     3.3  Turbidity caused  by  the  presence  of  algae  or other interfering
material may  not  permit  testing  of  a  sample  volume  sufficient to yield
significant results.  Low coliform estimates  may be caused by the presence of
high numbers of noncoliforms or of toxic substances.

     3.4  Samples containing large amounts  of suspended solids will interfere
with colony growth and with the  subsequent counting of colonies on the filter
membrane.  When this is the case, use Method 9131.
                                  9132 - 1
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4.0  APPARATUS AND MATERIALS

     4.1  Dilution bottles or tubes;

          4.1.1  Use bottles or tubes of resistant glass, preferably borosill-
     cate glass, closed with glass stoppers or screw caps equipped with liners
     that do not produce toxic or bacterlostatlc compounds on sterilization.

          4.1.2  Do not use cotton plugs  as closures.  Mark graduation levels
     Indelibly on  side  of  dilution  bottle  or  tube.    Plastic bottles of
     nontoxlc material  and  acceptable  size  may  be  substituted for glass,
     provided that they can be sterilized properly.

     4.2  Plpets and graduated cylinders;

          4.2.1  Use pipets of any convenient size, provided that they deliver
     the  required volume accurately  and quickly.  The error of calibration for
     a  given manufacturer's  lot  must  not  exceed  2.5%.   Use pipets having
     graduations distinctly marked and  with  unbroken tips.  Bacteriological-
     transfer pipets or pipets conforming  to  the APHA  standards given 1n the
     latest edition of Standard Methods  for the  Examination of Dairy Products
     may  be used.  Optimally, protect themouth  end of  all pipets  by a cotton
     plug to  eliminate hazards to   the worker or  possible  sample contamination
     by saliva.

          4.2.2  Use graduated  cylinders  meeting  ASTM  Standards  (D-86 and
     D216)  and  with  accuracy  limits  established  by   the National  Bureau of
     Standards  where appropriate.

     4.3  Containers for  culture medium;

          4.3.1  Use clean borosilicate  glass  flasks  presterillzed  to reduce
     bacterial  contamination.  Any  size  or  shape  of   flask may be  used, but
     Erlenmeyer flasks with metal   caps,  metal   foil   covers,  or screw  caps
     provide  for adequate mixing of the medium  and  are  convenient for storage.

     4.4  Culture dishes;

          4.4.1  Use  Petri-type dishes, 60  by  15  mm,   50  x  12 mm,  or other
     appropriate size.   The bottoms  of  the dishes  should be flat  and large
     enough so  that  the  absorbent pads for the  culture  nutrient will  lie flat.
     Wrap clean culture  dishes  before  sterilization,  singly or  1n convenient
     numbers,  in metal  foil  if  sterilized  by  dry heat,  or in suitable paper
     substitute  when  autoclaved.     If   glass   Petri   dishes  are  used,  use
     borosilicate or  equivalent glass.     Because  covers  for  such dishes  are
      loose  fitting,  take  precautions  to   prevent  possible  loss of  medium by
     evaporation,  with   resultant   change  in  medium   concentration,  and to
     maintain a humid  environment for optimal colony  development.

          4.4.2  Disposable plastic dishes that are tight  fitting and meet  the
      specifications  noted above also  may  be   used.  Suitable  sterile plastic
     dishes are available commercially.


                                  9132 - 2
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                                                          Date  September 1986

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4.5  Filtration units;

     4.5.1  The  filter-holding  assembly  (constructed  of  glass,  auto-
clavable plastic, porcelain, or  any noncorroslve bacteriologically  Inert
metal) consists of a seamless funnel fastened by a locking device or held
1n place by magnetic force or  gravity.    The design should be such that
the membrane filter will  be  held  securely  on  the porous plate of the
receptacle without mechanical damage and  all fluid will  pass through the
membrane during filtration.

     4.5.2  Separately wrap  the  two  parts  of  the  assembly  1n  heavy
wrapping paper for sterilization  by  autoclavlng  and storage until use.
Alternatively, treat  unwrapped  parts  by  ultraviolet  radiation before
using them.  Field units may  be  sanitized by Igniting methyl alcohol or
Immersing 1n boiling water for 5 m1n.  Do not Ignite plastic parts.

     4.5.3  For filtration, mount  receptacle  of filter-holding assembly
1n a 1-Hter filtering flask  with  a  side tube or other suitable device
such that a pressure differential can  be exerted on the filter membrane.
Connect flask to an  electric  vacuum  pump,  a  filter pump operating on
water pressure, a hand  aspirator,  or  other  means of securing pressure
differential.  Connect an  additional  flask  between filtering flask and
vacuum source to trap carry-over water.

4.6  Filter membranes;

     4.6.1  Use membrane filters  with  a  rated  pore diameter such that
there 1s complete retention of conform  bacteria   (0.45 + 0.02 urn).  Use
only those  filter  membranes  that  have  been  found,  through adequate
quality control testing and certification by the manufacturer, to exhibit
full retention of  the  organisms   to  be  cultivated,  stability 1n use,
freedom from chemical extractables  Inimical to the  growth and development
of bacteria, a satisfactory speed of filtration, no significant Influence
on medium  pH,  and  no  Increase   1n  number  of   confluent  colonies or
spreaders.  Preferably, use membranes  grid-marked   1n such a manner that
bacterial growth  1s  neither  Inhibited  nor  stimulated  along the grid
lines.  Store membrane  filters  held   1n  stock 1n  an environment without
extremes of temperature  and  humidity.    Obtain   no  more than a year's
supply at any one time.

     4.6.2  If presterlllzed membrane  filters  are   to be used, use those
for which the manufacturer  has certified that the sterilization technique
has  neither  Induced   toxldty  nor   altered  the   chemical  or physical
properties of the  membrane.    If  the  membranes   are sterilized  In the
laboratory, remove the  paper  separators  —  but not the absorbent paper
pads — from the packaged filters.     Divide filters Into groups of 10 to
12, or other convenient units, and  place 1n  10-cm Petrl dishes or wrap 1n
heavy wrapping paper.   Autoclave for 10 mln  at 121*C.  At the end of the
sterilization  period,  let   the   steam   escape   rapidly  to  minimize
accumulation of water condensation  on  filters.
                             9132 - 3
                                                    Revision
                                                    Date  September 1986

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    4.7  Absorbent pads;

         4.7.1  Absorbent pads consist  of  disks  of  filter  paper or other
    material known to  be  of  high  quality  and  free  of sulfites or other
    substances that could Inhibit  bacterial  growth.  Use pads approximately
    48 mm 1n diameter and of sufficient  thickness to absorb 1.8 to 2.2 ml of
    medium.  PresterlUzed absorbent pads  or pads subsequently sterilized 1n
    the laboratory should release less than 1 mg total acidity (calculated as
    CaCOs) when  titrated  to the  phenolphthaleln end point,  pH 8.3,   using
    0.02 N NaOH.  Where there  1s evidence of absorbent pad toxlclty, presoak
    pads 1n Type II water at 121*C  (In  an autoclave) for 15 mln, decant the
    water, and repackage pads  1n  a  large  Petrl dish for sterilization and
    subsequent use.    Sterilize  pads  simultaneously  with membrane filters
    available In resealable Kraft  envelopes  or separately In other suitable
    containers.  Dry pads so  they  are  free of visible moisture before use.
    See sterilization procedure described above for membrane filters.

         4.7.2  As a substrate  substitution for nutrient-saturated absorbent
    pads,  1.5% agar may be added to the total col 1 form M-Endo broth medium.

    4.8  Forceps;

         4.8.1  Forceps should be  round-tipped,  without corrugations on the
    Inner  sides of the  tips.  Sterilize before use by dipping in  95% ethyl or
    absolute  methyl alcohol and flaming.

    4.9   Incubators

          4.9.1  Use  Incubators to  provide  a temperature   of  35 +  0.5*C and to
    maintain  a  high  level  of  humidity (approximately 90%  relative humidity).

    4.10  Microscope  and  light source;

          4.10.1   Count  membrane-filter colonies  with a magnification of  10 to
     15 diameters  and  a  light   source   adjusted  to give maximum sheen discern-
    ment.    Optimally,   use  a  binocular  wide-field dissecting microscope.
    However,  a small   fluorescent   lamp  with  magnifier  is acceptable.   Use
    cool-white fluorescent lamps.   Do  not  use a microscope illuminator with
    optical system for light concentration  from an  incandescent light source
     for coliform colony identification on Endo-type  media.


5.0  REAGENTS

     5.1  ASTM Type II water  (ASTM  D1193):    Water  should be monitored for
     impurities.
                                  9132 - 4
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                                                         Date  September 1986

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     5.2  M-Endo medium:

         5.2.1  Components  of  the medium  are:

                Tryptose or polypeptone         10.0  g
                Thlopeptone or thiotone          5.0  g
                Casltone or trypticase           5.0  g
                Yeast extract                    1.5  g
                Lactose                         12.5  g
                Sodium chloride, NaCl            5.0  g
                D1potassium hydrogen
                   phosphate,  K?HP04             4.375  g
                Potassium d1hydrogen
                   phosphate,  KH2P04             1.375  g
                Sodium lauryl  sulfate            0.050  g
                Sodium desoxycholate             0.10 g
                Sodium sulflte, Na2S03           2.10 g
                Basic fuchsln                    1.05 g
                Distilled (Type II) water       1  liter

          5.2.2 Rehydrate 1n 1  liter   Type  II water  containing  20 ml 95%
     ethanol.   Heat  to  boiling  1n a  water  bath  to   avoid degradation of
     carbohydrates,  promptly remove  from heat,  and  cool to below 45*C.   Do not
     sterilize by  autoclavlng.   Final pH should be  between 7.1  and 7.3.

          5.2.3 Store finished medium  1n  the  dark  at  2 to 10ฐC and  discard
     any unused medium after 96 hr.  Medium 1s light  sensitive.
          NOTE: This medium may  be solidified by  adding 1.2% to 1.5% agar
               before boiling.

     5.3  Lauryl  tryptose broth;  See Method 9131,  Paragraph 5.3.


6.0  SAMPLE COLLECTION, PRESERVATION,  AND  HANDLING

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

     6.2  Clean all glassware  thoroughly  with  a   suitable detergent and hot
water, rinse with  hot water to remove all  traces of residual washing compound,
and finally, rinse with distilled   (Type  II)  water.  If mechanical glassware
washers are used,  equip  them  with  Influent  plumbing  of stainless steel or
other nontoxlc material.    Do  not  use  copper  piping  to distribute Type II
water.  Use stainless  steel  or  other  nontoxlc material for the rinse-water
system.

          6.2.1  Sterilize glassware,  except when 1n metal containers,  for not
     less than 60 m1n  at  a  temperature  of  170*C,  unless  1t 1s known from
     recording thermometers that  oven  temperatures   are uniform, under which
     exceptional condition use  160*C.    Heat  glassware 1n metal containers to
     170'C for not less than 2  hr.
                                  9132 - 5
                                                         Revision
                                                         Date  September 1986

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         6.2.2  Sterilize  sample bottles not made of plastic, as above, or 1n
     an  autoclave  at  121*C  for  15 m1n.

         6.2.3  For  plastic bottles  that  distort  on  autoclavlng, use low-
     temperature   ethylene  oxide  gas   sterilization.    If  water containing
     residual  chlorine and  other halogens   1s  to be collected, add sufficient
     Na2$203   to   clean   sample  bottle   before   sterilization  to  give  a
     concentration of about 100 mg/L  1n  the  sample.   To a  120-mL bottle add
     0.1 ml 10% solution of Na?S203   (this  will  neutralize a  sample containing
     about  15  mg/L residual chlorine).   Stopper bottle, cap, and sterilize by
     either dry or moist heat,  as directed  previously.

          6.2.4  Collect water  samples high  1n  copper or zinc and wastewater
     samples high  1n  heavy  metals   1n   sample   bottles containing a chelatlng
     agent  that will  reduce metal  toxldty.  This  1s particularly significant
     when such samples are  1n transit for 4  hr  or more.  Use 372 mg/L of the
     tetrasodlum  salt of ethylenediaminetetraacetic add  (EDTA).  Adjust EDTA
     solution  to pH 6.5   before  use.   Add  EDTA  separately to sample bottle
     before bottle sterilization (0.3 mL 15% solution 1n a  120-mL bottle) or
     combine 1t with  the N32S203 solution before addition.

     6.3  When the sample 1s  collected,  leave   ample  air space 1n the bottle
(at least 2.5 cm)  to facilitate mixing by shaking,  preparatory to examination.
Be careful  to take  samples  that  will  be  representative of the water being
tested and avoid   sample  contamination  at  time   of  collection or 1n period
before examination.

     6.4  Keep sampling  bottle  closed until  the   moment  It 1s to be  filled.
Remove stopper and hood   or  cap  as a  unit,   taking  care  to avoid soiling.
During sampling,  do not  handle  stopper or   cap and  neck of bottle, and  protect
them from contamination.   Hold  bottle  near base,  fill 1t without rinsing,
replace stopper  or cap  Immediately,  and  secure hood around neck of bottle.

     6.5  Start  bacteriological examination of   a   water  sample promptly after
collection to avoid unpredictable  changes.    If   samples cannot be processed
within 1 hr of collection,  use  an  Iced  cooler for  storage during transport to
the laboratory.

     6.6  Hold temperature of all  stream pollution  samples below  10*C during  a
maximum transport time of 6 hr.  Refrigerate these  samples upon  receipt 1n  the
laboratory and process within 2 hr.    When  local conditions  necessitate delays
1n delivery of samples longer than  6  hr,  make  field  examinations  using  field
laboratory facilities  located  at  the   site  of  collection  or use delayed-
1ncubat1on procedures.
                                  9132 - 6
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                                                         Date  September 1986

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7.0  PROCEDURES

     7.1  Selection of sample size;

          7.1.1  Size  of  sample  will  be  governed  by  expected  bacterial
     density, which In  finished-water  samples  will  be  limited only by the
     degree of turbidity.

          7.1.2  An Ideal sample volume will yield growth of about 50 col 1 form
     colonies and not more then 200  colonies  of all types.  Examine finished
     waters by filtering duplicate portions of the same volume, such as 100 to
     500 ml or more,  or  by  filtering  two  diluted  volumes.  Examine other
     waters by filtering three  different  volumes,  depending on the expected
     bacterial density.  When less than 20 ml of sample (diluted or undiluted)
     is filtered, add a small amount  of  sterile dilution water to the funnel
     before filtration.    This  increase  in  water  volume  aids  in uniform
     dispersion  of  the  bacterial   suspension  over  the  entire  effective
     filtering surface.

     7.2  Filtration of sample;

          7.2.1  Using sterile forceps,  place  a  sterile  filter over porous
     plate of receptacle, grid side  up.   Carefully place matched funnel unit
     over receptacle and  lock  1t  in  place.    Filter  sample under partial
     vacuum.   With filter   still  in place,  rinse funnel  by  filtering three
     20- to 30-mL  portions  of  sterile  dilution  water.   Unlock and remove
     funnel, immediately remove filter with  sterile  forceps, and place 1t on
     sterile pad or agar with a rolling motion to avoid entrapment of air.

          7.2.2  Use  sterile  filtration  units  at  the  beginning  of  each
     filtration  series  as   a    minimum   precaution   to  avoid  accidental
     contamination.  A filtration  series   1s considered to be interrupted when
     an Interval of  30  min or   longer  elapses  between sample filtratlons.
     After such Interruption, treat  any   further  sample  filtration as a new
     filtration series and sterilize all membrane-filter holders 1n use.

          7.2.3  Decontaminate this  equipment  between successive filtratlons
     by use of flowing steam, boiling  water, or, 1f available, an ultraviolet
     sterilizer.  When using the   UV sterilization procedure, a 2-m1n exposure
     to UV radiation 1s  sufficient and should kill 99.9% of all bacteria.  Eye
     protection  is recommended  to  protect against  stray  radiation  from a
     non-light-tight  sterilization  cabinet.     This  UV  equipment  1s  not
     commercially  available and  is  not   required,  although  its  use  1s
     recommended.

     7.3  Two-step enrichment technique;

          7.3.1  Place a sterile absorbent  pad  in  the  upper half of a sterile
     culture  dish  and pipet   enough  enrichment  medium  (1.8  to  2.0 mL  lauryl
     tryptose  broth)  to  saturate   pad.     Carefully  remove  any  surplus liquid.
                                   9132 - 7
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                                                          Date  September 1986

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Aseptlcally place filter through which the sample has been passed on pad.
Incubate filter, without Inverting dish, for 1.5 to 2 hr at 35 + 0.5*C 1n
an atmosphere of at least 90% relative humidity.

     7.3.2  Remove enrichment culture  from  Incubator,  11ft filter from
enrichment pad, and roll  It  onto  the  agar  surface.  Incorrect filter
placement 1s  at  once  obvious,  because  patches  of unstained membrane
Indicate entrapment of air.   Where  such patches occur, carefully reseat
filter on agar  surface.    If  the  liquid  medium 1s used, prepare final
culture by removing enrichment culture  from Incubator and separating the
dish halves.  Place  a  fresh  sterile  pad  1n  bottom  half of dish and
saturate It with 1.8 to 2.0 ml  of final M-Endo medium.  Transfer filter,
with same precautions as above,  to  new  pad.    Discard used pad.  With
either the agar or the  liquid medium,   invert dish and Incubate for 20 to
22 hr at 35 + 0.5'C.

7.4  Counting;

     7.4.1  The typical coliform colony has a pink to  dark-red color with
a metallic surface sheen.  The  sheen   area  may  vary 1n  size  from a small
pinhead to complete coverage of the colony surface.  Count sheen colonies
with the aid  of a  low-power   (10  to 15 magnifications) binocular wide-
field dissecting microscope or  other   optical   device,  with  a cool-white
fluorescent  light  source directed  above  and   as  nearly perpendicular as
possible to  the plane  of the   filter.    The  total   count of colonies
 (coliform  and noncollform) on   Endo-type  medium  has   no relation to the
total number  of bacteria present  in the original sample  and,  so  far as 1s
known,  no  significance  can  be   inferred  or   correlation  made with the
quality of the water  sample.

7.5  Calculation of coliform density;

     7.5.1   Report coliform density as (total)  collforms/100  mL.  Compute
the  count, using membrane  filters with 20 to 80 coliform colonies and not
more than  200  colonies of  all  types per  membrane,   by the  following
equation:


                   (Total)                _ coliform colonies counted x 100
           coliform colonies/100 ml       ~        ml sample filtered


     7.5.2  Water  of  drinking-water quality:

             7.5.2.1   With  water of good  quality,   the number of coliform
     colonies will be less than  20   per  membrane.   In  this  event, count
     all  coliform  colonies  and  use   the   formula  given above  to  obtain
      coliform density.

             7.5.2.2   If confluent growth  occurs, that  1s, growth covering
      either  the entire  filtration   area of   the   membrane   or a portion
      thereof, and  colonies are  not discrete,  report results  as  "confluent
      growth  with or without  conforms."  If the total  number of bacterial


                              9132 -  8
                                                     Revision       0
                                                     Date  September 1986

-------
    colonies, conforms plus noncoliforms,  exceeds 200 per membrane, or
    1f the colonies  are  too  indistinct  for accurate counting,  report
    results as "too numerous to count"  (TNTC).  In either case, request
    a new sample and select more  appropriate volumes to be filtered per
    membrane, remembering that  the  standard  drinking-water portion is
    100 mL.   Thus,  instead  of  filtering  100  mL per membrane, 50-mL
    portions may  be  filtered  through  each  of  two  membranes, 25-mL
    portions may be filtered through each of four membranes, etc.   Total
    the coliform counts observed on  the  membranes and report as number
    per 100 mL.

    7.5.3  Water of other than drinking-water quality:

           7.5.3.1  As with potable water  samples,  if  no filter has a
    coliform count falling in the ideal range, total the conform counts
    on all filters and report  as  number  per  100 mL.  For example, if
    duplicate 50-mL portions  were  examined  and  the two membranes had
    five and three coliform colonies,  respectively, report the count as
    eight conform colonies per 100 mL, I.e.,

                     (5 + 3) x 100
                       (50 + 50)


         7.5.3.2   Similarly,  if   50-,   25-,  and   10-mL   portions  were
    examined and   the  counts  were   15,   6,   and   1   coliform  colonies,
    respectively,  report the count  as  25/100  mL,  I.e.,

                     15 + 6) x 100
                     50 + 25 + 10)


          7.5.3.3   On  the  other hand,  if   10-,  1.0-,  and 0.1-mL portions
    were  examined  with   counts   of   40,   9,   and   1   coliform colonies
     respectively,  select   only  the  10-mL  portion  for calculating the
     coliform density because this  filter  had a coliform count falling  in
     the  ideal  range.   The  result  is 400/100 mL,  i.e.,

                    (40 x  100)
                        10


     In this  last  example,  if the  membrane with 40  coliform colonies  also
     had  a  total   bacterial   colony count  greater  than 200, report the
     coliform count as 400/100 mL.

          7.5.3.4    Report  confluent  growth  or membranes with colonies
     too  numerous  to  count,  as described   in 7.5.2,  above.   Request  a new
     sample and select more appropriate volumes for filtration.

     7.5.4   Statistical reliability of membrane filter results:  Although
the statistical  reliability of   the membrane filter technique is  greater
than that of the MPN   procedure,   membrane counts really are not absolute
numbers.   Table 1  illustrates some 95% confidence limits.

                             913-2  - 9
                                                    Revision      0
                                                    Date September  1986

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         TABLE 1.   95% CONFIDENCE LIMITS FOR MEMBRANE-FILTER RESULTS
                             USING 100-mL SAMPLE
                                                 95% Confidence Limits
     Number of Coliform
      Colonies Counted                         Lower               Upper
1 0.05
2 0.35
3 0.81
4 1.4
5 2.0
3.0
4.7
6.3
7.7
9.2
8.0  QUALITY CONTROL

     8.1  Extensive quality control procedures are provided in Part IV of U.S.
EPA, 1978 (see Section 10.0, References).   These procedures should be adhered
to at all times.

     8.2  Samples must  be  maintained  as  closely  as  possible  to original
condition  by  careful  handling  and  storage.    Sample  sites  and sampling
frequency  should   provide   data   representative   of  characteristics  and
variability of the water quality  at  that  site.   Samples should be analyzed
immediately.  If this  is  not  practical,  they  should  be refrigerated at a
temperature of 1-4*C and analyzed within 6 hr.

     8.3  Quality control of  culture  media  is  critical  to the validity of
microbiological analysis.  Some  important  factors to consider are summarized
below:

          8.3.1  Order media to last for  only  1  yr; always use oldest stock
     first.  Maintain an inventory  of  all  media ordered, including a visual
     inspection record.

          8.3.2  Hold unopened media for no  longer  than  2 yr.  Opened media
     containers should be discarded after 6 mo.

          8.3.3  When preparing  media,  keep  containers  open  as briefly as
     possible.  Prepare media  in  deionized  or  distilled (Type II) water of
     proven  quality.    Check  the  pH   of  the  media  after  solution  and
     sterilization; it  should  be  within  0.2  units  of  the  stated value.
     Discard and remake if  it is not.

          8.3.4  Autoclave  media  for  the  minimal  time  specified  by  the
     manufacturer, because  the potential  for  damage increases with increased
     exposure to heat.  Remove  sterile  media  from  the autoclave as soon as
     pressure is zero.  Effectiveness  of  the sterilization should be checked
     weekly, using strips or ampuls of Bacillus stearothemophelus.
                                  9132 - 10  '
                                                         Revision      0
                                        '                Date  September 1986

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         8.3.5  Agar plates should be  kept  slightly  open  for 15 m1n after
    pouring or  removal from refrigeration to evaporate free moisture.  Plates
    must be free of lumps, uneven surfaces, pock marks, or bubbles, which can
    prevent good contact between the agar and medium.

         8.3.6  Quality control checks of  prepared  media should  Include the
    Incubation  of  5% of each batch  of  medium  for 2 days at 35*C to Inspect
    for growth  and positive/negative checks with pure culture.

    8.4  Analytical quality control procedures should Include;

         8.4.1  Duplicate analytical  runs  on  at  least  10%  of  all known
    positive  samples analyzed.

         8.4.2  At least one positive control sample should be run each month
    for each  parameter tested.

         8.4.3  At least one negative   (sterile)  control  should  be run with
    each series of samples using buffered  water and the medium batch used at
    the beginning  of the test series  and following every tenth sample.  When
    sterile controls Indicate contamination,  new  samples should  be obtained
    and analyzed.

         8.4.4  The Type II  water  used  should  be periodically  checked for
    contamination.

    8.5  Quality control specifications for membrane filters;

         8.5.1  Membrane filters can  be  purchased  sterile  or packaged for
    sterilization. They can be sterilized by autoclavlng, ethylene oxide, or
    Irradiation.   Membrane manufacturers  should certify  that their membranes
    meet stated specifications  on   sterility, retention,  recovery, pore size,
    flow rate,  pH, total acidity, phosphate, and other  extractables.

         8.5.2  Membrane   performance   should   be  tested to   ensure  proper
    results.   Each lot ordered  should  be   inspected  for proper  shape, grid
     lines,  diffusability,   and  correct   colony   development.    Membranes
    containing  sizable areas with no colony  development are  questionable.


9.0 METHOD PERFORMANCE

     9.1  No data  provided.


10.0 REFERENCES

1.   Standard Methods  for the Examination  of  Water  and  Wastewater,  15th  ed.

2.   Bordner,   R.H.,   et  al.,   Microbiological   Methods  for Monitoring   the
Environment,   Environmental   Monitoring   and   Support  Laboratory,   U.S.   EPA,
Cincinnati, OH,  EPA-600/8-78-017,  1978.

                                  9132 - 11
                                                         Revision       0
                                                         Date  September 1986

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               METHOD 9132

TOTAL COLIFORM: MEMBRANE FILTER TECHNIQUE
                 Start
              7. 1
                   Select
              sample size on
              basis expected
                 Bacterial
                  density
           7.2
           Filter sample with
           sterile aparatus;
           rinse funnel: remove
           filate and place on
           sterile pad or agar
         9132 -  12
                                    Revision       0	
                                    Date   September 1986

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                                         METHOD  9132

                          TOTAL  COLIFORM:  MEMBRANE FILTER TECHNIQUE
                                         (Continued)
7.4.1
       Roll
   filter onto
  •gar surface:
     Incubate
                                                     Which medium  >v based
7.3.2.
       Remove
from Incuoator
  roll  filter
   onto egar
    surface
                            culture  fllsn:
                            saturate  with
                            M-Endc medium
                          7.4.2
                                 Place
                           filter on pad:
                             Invert dish:
                               Incubate
7

.3.2 f
Inc
saturat
pad: tr
filter

7
.3.2
Remove
r om
:ubator;
.e fresh
•ansf er
to pea



Invert dish
and Incubate


7
.5.1


Count sheen
colonies


7.6


Calculate
coliform
density
                                                  f     Stop       J
                                     9132 - 13
                                                                Revision       Q
                                                                Date   September  1986

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                                 METHOD 9200

                                   NITRATE
1.0  SCOPE AND APPLICATION

     1.1  This method 1s applicable to the analysis of ground water,  drinking,
surface, and saline waters, and  domestic and Industrial  wastes.   Modification
can be made to remove or  correct for turbidity,  color, salinity,  or  dissolved
organic compounds in the sample.

     1.2  The applicable range of concentration 1s 0.1 to 2 mg N03-N  per liter
of sample.


2.0  SUMMARY OF METHOD

     2.1  This method 1s  based  upon  the  reaction  of  the nitrate 1on with
brudne sulfate 1n a 13 N H2S04 solution at a temperature of 100*C.   The color
of the resulting complex 1s measured  at  410  nm.  Temperature control  of the
color reaction 1s extremely critical.


3.0  INTERFERENCES

     3.1  Dissolved organic matter will cause an  off  color in 13 N  H?S04 and
must be compensated  for  by  additions  of  all  reagents except the Erucine-
sulfanilic acid reagent.   This  also  applies  to  natural  color,  not due to
dissolved organics, that is present.

     3.2  If the sample is  colored  or  if  the  conditions of the test cause
extraneous coloration, this  interference  should  be  corrected  by running a
concurrent sample under the same conditions but in the absence of the bruclne-
sulfanilic acid reagent.

     3.3  Strong  oxidizing  or  reducing  agents  cause  interference.    The
presence  of oxidizing agents may  be  determined  by a residual chlorine test;
reducing  agents may be detected with potassium permanganate.

          3.3.1  Oxidizing agents'  Interference 1s  eliminated by the addition
     of sodium arsenite.

          3.3.2  Reducing  agents may be oxidized  by addition of H202-

     3.4  Ferrous and   ferric   Iron and   quadrivalent  manganese  give  slight
positive  interferences, but   in  concentrations   less  than   1  mg/L these are
negligible.
                                   9200 -  1
                                                         Revision      0
                                                         Date  September 1986

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     3.5  Uneven heating of the samples and standards during the reaction time
will result  in  erratic  values.    The  necessity  for  absolute  control  of
temperature  during  the  critical  color  development  periodcannotb~e~too
strongly emphasized.


4.0  APPARATUS AND MATERIALS

     4.1  Spectrophotometer  or  filter   photometer  suitable  for  measuring
absorbance at 410 nm.

     4.2  Sufficient number of 40-  to  50-mL  glass  sample tubes for reagent
blanks, standards, and samples.

     4.3  Neoprene-coated wire racks to hold sample tubes.

     4.4  Water bath suitable for use  at  100*C.   This bath should contain a
stirring mechanism so that all tubes are at the same temperature and should be
of  sufficient capacity  to  accept  the  required  number  of  tubes without a
significant drop  in temperature when the tubes are immersed.

     4.5  Water bath suitable for use at 10-15ฐC.
 5.0   REAGENTS

      5.1  ASTM Type  II water   (ASTM  D1193):    Water  should be monitored for
 impurities.

      5.2  Sodium  chloride  solution  (30%):    Dissolve  300  g  NaCl in Type II
 water and dilute  to  1  liter.

      5.3  Sulfuric acid  solution;  Carefully  add 500 ml concentrated H2S04 to
 125  mL Type  II water.Cooland keep tightly stoppered to prevent absorption
 of atmospheric moisture.

      5.4  Brucine-sulfam'lic  acid reagent;   Dissolve  1  g brucine sulfate —
 (C23H26N2ฐ4)2>H2S04*7H2ฐ ~ and O-1 9   sulfanilic  acid  (NH2C6H4S03H-H20)  in
 70 ml hot Type  II water.   Add  3 ml concentrated HC1, cool, mix, and dilute to
 100  ml with  Type  II  water. Store   in  a dark bottle at 5*C.  This solution is
 stable for  several months; the pink color that develops slowly does not  affect
 its  usefulness.   Mark  bottle with  warning,   "CAUTION:   Brucine Sulfate is
 toxic; do not ingest."

      5.5   Potassium  nitrate stock  solution (1.0  ml   = 0.1 mg  N03-N):  Dissolve
 0.7218 g   anhydrous  potassium nitrate  (KNOs)   in Type II water   and  dilute to
 1 liter in  a volumetric flask.  Preserve with  2  ml  chloroform per  liter.  This
 solution  is stable  for at least 6  mon.

      5.6   Potassium  nitrate  standard   solution   (1.0  ml   =  0.001'mg  NO^-N):
 Dilute 10.0 ml of the stock solution(5.5)to  1  liter  in  a  volumetric flask.
 This standard solution should be  prepared fresh  weekly.


                                   9200 - 2
                                                          Revision       0
                                                          Date  September 1986

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     5.7  Acetic acid (1+3);   Dilute  1  volume glacial acetic acid (CHsCOOH)
with 3 volumes of Type II water.

     5.8  Sodium hydroxide (1 N):   Dissolve  40  g  of NaOH in Type II water.
Cool and dilute to 1 liter.
6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

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

     6.2  Analysis should be done as  soon  as  possible.   If analysis can be
done within 24 hr, the  sample  should  be  preserved by refrigeration at 4*C.
When samples must be stored for more than 24 hr, they should be preserved with
sulfuric acid (2 mL/L concentrated ^$04) and refrigerated.


7.0  PROCEDURE

     7.1  Adjust the pH of  the  samples  to  approximately 7 with acetic acid
(Paragraph 5.7) or sodium hydroxide  (Paragraph  5.8).  If necessary, filter to
remove  turbidity.  Sulfuric  acid  can  be  used  in  place of acetic acid, if
preferred.

     7.2  Set up the required number  of  sample  tubes  in the rack to handle
reagent blank, standards, and samples.  Space tubes evenly throughout the rack
to allow for even flow of bath water between the tubes.  This should assist in
achieving uniform heating of all tubes.

     7.3  If it is necessary to correct  for color or dissolved organic matter
which will cause color on heating, run a set of duplicate samples to which all
reagents, except the brucine-sulfanilic acid, have been added.

          7.3.1  Add 0.5 mL brucine-sulfanilic acid reagent (Paragraph 5.4) to
     each tube  (except the  interference  control  tubes) and carefully mix by
     swirling; then place  the  rack  of  tubes  in  the  100'C water bath for
     exactly 25 min.
          CAUTION:  Immersion  of  the  tube  rack  into  the  bath should not
               decrease the temperature of  the  bath  by  more than 1~2*C.  In
               order to keep this temperature decrease to an absolute minimum,
               flow of bath water between   the  tubes should not be restricted
               by crowding too many  tubes into the rack.  If color development
                in the  standards  reveals  discrepancies  in the procedure, the
               operator   should  repeat  the  procedure  after  reviewing  the
                temperature control steps.

     7.4   Pipet  10.0 mL of standards and  samples or an  aliquot of the samples
diluted to  10.0 mL  into the sample tubes.
                                   9200 - 3
                                                          Revision       0
                                                          Date  September  1986

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     7.5  If the samples are  saline,   add  2  mL  of  the 30% sodium chloride
solution (Paragraph 5.2) to the  reagent  blank,   standards, and samples.  For
freshwater samples, sodium chloride solution may   be omitted.  Mix contents of
tubes by swirling and place rack 1n cold-water bath  (0-10*C).

     7.6  Plpet 10.0 ml of  sulfurlc  add  solution  (Paragraph 5.3) Into each
tube and mix by swirling.  Allow  tubes  to come to  thermal  equilibrium  1n the
cold bath.  Be sure  that  temperatures  have  equilibrated 1n all tubes  before
continuing.

     7.7  Remove rack of tubes from  the   hot-water  bath,  Immerse 1n the cold-
water bath, and allow to reach thermal equilibrium (20-25*C).

     7.8  Read absorbance against the reagent  blank   at  410  nm  using a  1-cm or
longer cell.

     7.9  Calculation;

          7.9.1  Obtain  a  standard  curve  by  plotting  the   absorbance  of
     standards run by the   above  procedure  against  mg/L  N03-N.   (The color
     reaction does not  always  follow Beer's law.)

          7.9.2  Subtract  the  absorbance  of  the  sample without the  brudne-
     sulfanlUc  reagent  from the absorbance  of the sample containing  brudne-
     sulfanlUc  add and determine  mg/L  N03-N.    Multiply by an appropriate
     dilution factor 1f less than  10 ml of sample 1s taken.


8.0 QUALITY CONTROL

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

     8.2   Linear calibration curves must be  composed  of a minimum of a blank
and five  standards.  A  set of standards  must be Included with each  batch  of
samples.

     8.3  Dilute samples  1f   they  are  more  concentrated  than  the highest
standard  or 1f  they  fall on the plateau of a calibration curve.

     8.4  Verify calibration   with  an  Independently  prepared check  standard
every  15  samples.

     8.5   Run one  spike duplicate  sample  for  every  10 samples.  A duplicate
sample 1s a sample brought through  the whole  sample preparation and analytical
process.
                                   9200 - 4
                                                         Revision
                                                         Date  September 1986

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9.0  METHOD PERFORMANCE

     9.1  Twenty-seven analysts In fifteen laboratories analyzed natural-water
samples containing exact Increments  of  Inorganic nitrate,  with the following
results:
Increment as
Nitrogen, Nitrate
(mg/L N)
0.16
0.19
1.08
1.24
Precision as
Standard Deviation
(mg/L N)
0.092
0.083
0.245
0.214
Accuracy
Bias
(%)
-6.79
+8.30
+4.12
+2.82
as
Bias
(mg/L N)
-0.01
+0.02
+0.04
+0.04
10.0 REFERENCES

1.   Annual Book of ASTM Standards, Part 31, "Water," Standard D992-71, p. 363
(1976).

2.   Jenkins, D. and  L. Medsken,   "A  Bruclne  Method for the Determination of
Nitrate  1n Ocean,  Estuarlne, and  Fresh Water," Anal.Chem., 36, p. 610  (1964).

3.   Standard Methods for the  Examination  of  Water and Wastewater, 14th ed.,
p. 427,  Method 419D  (1975).
                                   9200 - 5
                                                          Revision
                                                          Date   September  1986

-------
                METHOD  9200

                  NITRATE
7.1


Adjust pH
of camples to
7; filter If
necessary

7.2


Set up cample
tubes In rack
   Correct  for
color,  dissolves
     organic
     matter?
                                   Hun
                                duplicate
     sulfanlllc
    acid  reagent
    to  each  tube
   •ample*  with
       bruclne
sulfanlllc  acid
        Bathe
   rack  of  tubes
 in 100  *C  water
     for 25 mln
         9200 -  6
                                   Revision       0
                                   Date   September 1986

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                            METHOD 9200

                              NITRATE
                            (Continued)
      Pipette
  standards and
   camples into
   •ample tubes
                         Read absorbance
                         against reagent
                          blank 410 nm
                Yes
 7.6
      Pipette
  sulfurlc acid
  solution Into
 each tube:  mix
                           7.5
                                                    7.9.1
                                Obtain  a
                              J  standard
                              absorbance
                               curve  and
                               calculate
                              mg NOj-N/1
Add 30X sodium
   chloride
 solution; mix
                        f      Stop       J
 7.7
     I  Immerse
  tubes In cold
water:  allow to
  reach thermal
   equilibrium
                        9200  - 7
                                                   Revision       0
                                                   Date   September 1986

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                                 METHOD 9250
             CHLORIDE (COLORIMETRIC.  AUTOMATED FERRICYANIDE AAI)
1.0  SCOPE AND APPLICATION
     1.1  This automated  method  1s  applicable  to  ground  water,  drinking,
surface,  and  saline  waters,  and  domestic  and  Industrial  wastes.     The
applicable range 1s 1 to 250 mg Cl per liter of sample.

2.0  SUMMARY OF METHOD
     2.1  Thlocyanate 1on (SCN) 1s liberated from mercuric thlocyanate through
sequestration of mercury by chloride 1on to form un-1on1zed mercuric chloride.
In the presence of ferric 1on,  the  liberated SCN forms highly colored ferric
thlocyanate  1n  a  concentration   proportional   to  the  original  chloride
concentration.
3.0  INTERFERENCES
     3.1  No significant Interferences.

4.0  APPARATUS AND MATERIALS
     4.1  Automated continuous-flow analytical Instrument;
          4.1.1  Sampler I.
          4.1.2  Continuous filter.
          4.1.3  Manifold.
          4.1.4  Proportioning pump.
          4.1.5  Colorimeter: equipped with 15-mm  tubular flowcell and 480-nm
                 filters.
          4.1.6  Recorder.
 5.0   REAGENTS
      5.1   ASTM  Type  II  water   (ASTM   D1193):    Water   should be monitored for
 Impurities.
      5.2   Ferric ammonium sulfate;     Dissolve  60  g   of  FeNH4(S04)2*12H20  in
 approximately 500 mL TypeIIwater.     Add  355  mL  of concentrated  HN03 and
 dilute to 1  liter with  Type II water.   Filter.

                                   9250 - 1
                                                         Revision       0
                                                          Date   September  1986

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     5.3  Saturated mercuric thiocyanate;  Dissolve 5 g of Hg(SCN)2 1n 1 liter
of Type II water.Decantancifiltera portion of the saturated supernatant
liquid to use as the reagent and refill the bottle with distilled water.

     5.4  Sodium chloride stock solution (0.0141  N  NaCl):  Dissolve 0.8241 g
of pre-dried (140*C) NaCl in Type II water.  Dilute to 1 liter in a volumetric
flask (1 ml = 0.5 mg Cl).

          5.4.1  Prepare a series of standards by diluting suitable volumes of
     stock solution to 100.0 ml with  Type  II water.  The following dilutions
     are suggested:

             Stock
          Solution  (ml)       Concentration (mg/L)

                1.0                       5.0
                2.0                      10.0
                4.0                      20.0
                8.0                      40.0
              15.0                      75.0
              20.0                     100.0
              30.0                     150.0
              40.0                     200.0
              50.0                     250.0

     Choose  three of the nine standard  concentrations   1n such  a way that  the
     chosen  standards will  bracket  the  expected   concentration range of  the
     sample.


6.0  SAMPLE  COLLECTION,  PRESERVATION,  AND  HANDLING

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

     6.2  No special requirements for  preservation.


7.0  PROCEDURE

     7.1  No advance sample  preparation  1s   required.    Set up manifold, as
shown  1n  Figure 1.  For  water samples  known to be consistently low  1n chloride
content,  1t  1s  advisable to use only one Type  II water Intake line.

     7.2  Allow both colorimeter and recorder  to  warm   up   for  30  min. Run  a
baseline with all  reagents,  feeding   Type II water through the sample line.
Adjust  dark  current and operative  opening   on  colorimeter to obtain stable
baseline.
                                   9250 - 2
                                                          Revision
                                                          Date   September 1986

-------
9250
3
O 73
o> n
r+ <
m -*
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\A/AQW Tl IRPQ- OWP
                                       FIGURE 1. CHLORIDE MANIFOLD   AA-I

-------
     7.3  Place Type II water wash tubes  1n alternate openings in sampler and
set sample timing at 2.0 min.

     7.4  Place  working  standards   in   sampler   in  order  of  decreasing
concentrations.  Complete filling of sampler tray with unknown samples.

     7.5  Switch sample line from Type II water to sampler and begin analysis.

     7.6  Calculation;

          7.6.1  Prepare standard curve by  plotting peak heights of processed
     standards against known concentrations.  Compute concentration of samples
     by comparing sample peak heights with standard curve.


8.0  QUALITY CONTROL

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

     8.2  Calibration curves must be  composed  of  a  minimum  of a blank and
three standards.  Employ a minimum of  one blank per sample batch to determine
if contamination has occurred.

     8.3  Dilute samples  if  they  are  more  concentrated  than  the highest
standard or  1f they fall on the plateau of a calibration curve.

     8.4  Verify calibration  with  an  independently  prepared check standard
every 15 samples.

     8.5  Run one spike duplicate sample  for  every  10 samples.  A duplicate
sample  is a  sample brought through the whole sample preparation and analytical
process.


9.0  METHOD  PERFORMANCE

     9.1  Precision and accuracy data are available 1n Method  325.1 of Methods
for  Chemical Analysis  of Water and Wastes.


10.0 REFERENCES

1.   O'Brien,  J.E., "Automatic Analysis of  Chlorides  in Sewage," Waste  Engr.,
33,  670-672  (Dec. 1962).

2.   Standard  Methods  for the Examination   of  Water and Wastewater,  14th ed.,
p. 613, Method 602  (1975).
                                   9250 - 4
                                                         Revision
                                                         Date  September 1986

-------
                             METHOD 9290

         CHLORIDE (COUORXNETRIC.  AUTOMATED FCRRXCYANIOE AAX)
C
  7.1
 Set up manifold
   •• enown In
    Figure 1
  7.2
       Pleco
      working
  •teneerdc and
unknown eemplee
in cempler trey
        Warm up
     colorimeter
   end recorder:
 obtein • eteble
      beeeline
                                                      7.5
 Switch sample
    line to
•empler; enolyze
  7.3
        Piece
     weter weซh
      tube* in
      •empler;
     •et timing
7.6.11
      I Prepere
      •tenderd
 curve:  compute
  concentration
    of eemplee
                                                    f      Stop      J
                       9250 - 5
                                                 Revision       o
                                                 Date  September 1986

-------
                                 METHOD 9251

            CHLORIDE (COLORIMETRIC.  AUTOMATED FERRICYANIDE AAII)
1.0  SCOPE AND APPLICATION

     1.1  This automated  method  1s  applicable  to  ground  water,  drinking,
surface,  and  saline  waters,  and  domestic  and  Industrial  wastes.     The
applicable range 1s 1-200 mg Cl~ per liter of sample.


2.0  SUMMARY OF METHOD

     2.1  Thlocyanate 1on (SCN) 1s liberated from mercuric thlocyanate through
sequestration of mercury by chloride 1on to form un-1on1zed mercuric chloride.
In the presence of ferric 1on,  the  liberated SCN forms highly colored ferric
thlocyanate  1n  a  concentration   proportional   to  the  original   chloride
concentration.
3.0  INTERFERENCES

     3.1  No significant Interferences.


4.0  APPARATUS AND MATERIALS

     4.1  Automated continuous-flow analytical Instrument;

          4.1.1  Sampler I.

          4.1.2  Analytical cartridge.

          4.1.3  Proportioning  pump.

          4.1.4  Colorimeter:   Equipped with  15-mm  tubular  flowcell  and 480-nm
                 filters.

          4.1.5  Recorder.

          4.1.6  Digital printer (optional).


 5.0   REAGENTS

      5.1  ASTM Type  II water   (ASTM   D1193):     Water  should  be monitored  for
 Impurities.

      5.2  Mercuric thlocyanate  solution;   Dissolve   4.17  g of HgfSCN)? In  500
 mL methanoTiDilute  to 1  literwith methanol,  mix,  and  filter through filter
 paper.


                                   9251 -  1
                                                          Revision      0
                                                          Date   September  1986

-------
     5.3  Ferric nitrate solution, 20.2%:  Dissolve 202 g of Fe(N03)3'9H20  1n
500 ml of Type IIwater.Add  31.5  ml  concentrated nitric acid,  mix, and
dilute to 1 liter with Type II water.

     5.4  Color  reagent;    Add  150  ml  of  mercuric  thiocyanate  solution
(Paragraph 5.2) to 150 ml of ferric nitrate solution (Paragraph 5.3),  mix, and
dilute to 1 liter with Type  II  water.    A combined color reagent is commer-
cially available.

     5.5  Sodium chloride stock solution (0.0141  N  NaCl):  Dissolve 0.8241 g
of pre-dried (140*C) NaCl in Type II water.  Dilute to 1 liter in a volumetric
flask (1 ml = 0.5 mg Cl').

          5.5.1  Prepare a series of standards by diluting suitable volumes of
     stock solution to 100.0 ml with  Type  II water.  The following dilutions
     are suggested:

              Stock
          Solution  (ml)       Concentration (mg/L)

               1.0                      5.0
               2.0                     10.0
               4.0                     20.0
               8.0                     40.0
              15.0                     75.0
              20.0                    100.0
              30.0                    150.0
              40.0                    200.0

     Choose three of the nine standard  concentrations  1n such a way that the
     chosen standards will  bracket  the  expected  concentration range of the
     sample.


6.0  SAMPLE COLLECTION,  PRESERVATION, AND HANDLING

     6.1  All  samples must  have  been  collected   using   a sampling plan that
addresses the  considerations discussed 1n Chapter Nine of  this manual.

     6.2  No special requirements for preservation.

7.0  PROCEDURE

     7.1  When particulate matter  is  present,  the   sample  must  be filtered
prior to  the   determination.    The  sample   may  be   centrlfuged   1n place  of
filtration.  Set up the manifold, as shown 1n Figure  1.
                                   9251 -  2
                                                          Revision
                                                         Date  September  1986

-------
      <ฃ>
      ro
      I

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WASTE
;K -6-
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\y- 	 ป i
4 WASTE
TO SAMPLER

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. „ WASTE TUBE
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PUR. ORG.
BLK. BLK.
PUR. PUR.
ORG. CRN.
BLK. BLK.
BLK. BLK.
GRY. GRY.
ORG. CRN.
GRY. GRY.
WHT. WHT.
GRY. GRY.
PROPOR
PU
M1/MIN
3.40 OIL. WATER
0.32 AIR
2.50 OIL. WATER
0.10 SAMPLE
0.32 AIR
0.32 AIR
1.00 RESAMPLE
0.10 OIL. WATER
1.00 COLOR REAGENT
0.60 SAMPLE WASTE
1.00 FROM F/C.
TIONING
MP
A4
to
oo
                                                         Figure 1. Chloride Manifold AATIO 200 mg C1/L.

-------
     7.2  Allow both colorimeter and recorder to  warm  up  for 30 min.  Run a
baseline with all reagents, feeding Type II water through the sample line.

     7.3  Place  working  standards   in   sampler   in  order  of  decreasing
concentrations.  Complete filling of sampler tray with unknown samples.

     7.4  When a stable baseline has been obtained, start the sampler.
              t
     7.5  Calculation:  Prepare  standard  curve  by  plotting peak heights of
processed standards against  known  concentrations.   Compute concentration of
samples by comparing sample peak  heights  with standard curve. Note that this
is not a linear curve, but a second order curve.   (See Paragraph 8.2.)


8.0  QUALITY CONTROL

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

     8.2  Calibration curves must be  composed  of  a  minimum  of a blank and
three standards.  Employ a minimum of  one blank per sample batch to determine
if contamination has occurred.

     8.3  Dilute samples   if  they  are  more  concentrated  than  the highest
standard or 1f they fall on the plateau of a calibration curve.

     8.4  Verify calibration  with  an  independently  prepared check  standard
every 15 samples.

     8.5  Run one spike duplicate sample  for  every  10 samples.  A duplicate
sample is a sample brought through the whole sample preparation and analytical
process.


9.0  METHOD PERFORMANCE

     9.1  Precision and accuracy data are not available at this time.


10.0 REFERENCES

1.   O'Brien, J.E., "Automatic Analysis of  Chlorides in Sewage," Waste  Engr.,
33, 670-672  (Dec. 1962).

2.   Technicon   AutoAnalyzer  II,   Industrial  Method  No.  99-70W,   Technicon
Industrial Systems, Tarrytown, New  York,  10591  (Sept. 1973).
                                   9251 - 4
                                                          Revision
                                                          Date   September 1986

-------
                     METHOD 925J

CHLORIDE (COLORIMETRIC.  AUTOMATED FERRICVANIOE AA II)
                       Yes
        7.8
              Warm up
            i color-
            imeter and
       recorder;  run •
         baseline with
          all reagents
                                  7.1
Filter
        7.3 I
            I  Place
             working
         standards and
       unknown samples
       in sampler tray
        7.4
         Obtain stable
       baseline:  start
           sampler
7. S.I
curs
cone
o<
Prepare
standard
e: compute
•ntration
samples
      f     stop      }
                9251 -  5
                                          Revision       0
                                          Date   September  1986

-------
                                 METHOD 9252A

                   CHLORIDE  (TITRIMETRIC, MERCURIC NITRATE)
1.0   SCOPE AND APPLICATION

      1.1    This method  is applicable to ground water, drinking, surface, and
saline waters, and domestic and industrial wastes.

      1.2    The method is suitable for all  concentration  ranges of chloride
content; however,  in  order to avoid large titration  volume,  a sample aliquot
containing not more than  10 to 20 mg Cl"  per  50  ml  is  used.

      1.3    Automated  titration may be  used.

2.0   SUMMARY OF METHOD

      2.1    An  acidified sample  is titrated  with  mercuric  nitrate  in the
presence of mixed diphenylcarbazone-bromophenol blue  indicator.  The end point
of the titration is the formation of the blue-violet mercury diphenylcarbazone
complex.

3.0   INTERFERENCES

      3.1    Anions  and cations at  concentrations normally found  in surface
waters do not interfere.   However,  at the  higher concentration often found in
certain wastes,  problems may occur.

      3.2    Sulfite  interference  can be eliminated by oxidizing the 50 ml of
sample solution with 0.5-1 ml of H202.

      3.3 Bromide and iodide are also titrated with mercuric  nitrate  in the same
manner as chloride.

      3.4 Ferric and chromate  ions  interfere  when present  in excess of 10 mg/L.


4.0   APPARATUS AND MATERIALS

      4.1    Standard laboratory titrimetric equipment, including 1 mL or 5 mL
microburet with 0.01 mL gradations.

      4.2    Class A volumetric flasks:   1 L and 100  mL.

      4.3    pH Indicator paper.

      4.4    Analytical balance:  capable of weighing to 0.0001 g.

5.0   REAGENTS

      5.1    Reagent-grade  chemicals shall  be  used  in  all   tests.    Unless
otherwise indicated,  it is intended  that  all  reagents  shall  conform  to the


                                  9252A  - 1                       Revision 1
                                                                  September 1994

-------
specifications of the Committee on Analytical  Reagents of the American Chemical
Society, where  such specifications are available.   Other grades may be used,
provided it is first ascertained that the reagent is of sufficiently high purity
to permit its use without lessening the accuracy of  the  determination.

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

      5.3     Standard sodium chloride  solution,  0.025 N:  Dissolve 1.4613 g
ฑ 0.0002 g of sodium  chloride  (dried at 600ฐC for  1  hr)  in chloride-free water
in a 1 liter Class A volumetric flask and dilute to the mark with  reagent water.

      5.4     Nitric acid  (HN03)  solution:  Add 3.0 mL concentrated  nitric acid
to 997 mL of reagent  water ("3  + 997" solution).

      5.5    , Sodium hydroxide  (NaOH) solution (lOg/L):   Dissolve approximately
10 g of NaOH  in reagent water  and dilute to 1 L with  reagent water.

      5.6     Hydrogen peroxide (H202):   30%.

      5.7     Hydroquinone  solution  (10  g/L):     Dissolve  1  g   of  purified
hydroquinone in reagent water in a  100 mL Class A volumetric flask and dilute to
the mark.

      5.8     Mercuric nitrate  titrant (0.141 N):  Dissolve 24.2 g Hg(N03)2 • H20
in 900 mL of reagent water acidified with 5.0 mL concentrated HN03  in a 1 liter
volumetric  flask and dilute   to the  mark with  reagent  water.    Filter,  if
necessary.   Standardize against standard  sodium chloride solution (Step 5.3)
using the procedures outlined in Sec. 7.0.  Adjust to exactly 0.141  N and check.
Store in a dark bottle. A 1.00 mL aliquot is equivalent to 5.00 mg  of chloride.

      5.9    Mercuric nitrate  titrant  (0.025  N):   Dissolve 4.2830  g Hg(N03)2 •
H20 in 50 mL  of  reagent   water  acidified  with   0.05 mL   of  concentrated
HN03 (sp. gr. 1.42)  in  a 1 liter volumetric  flask  and dilute  to the mark with
reagent  water.    Filter,  if  necessary.   Standardize against  standard  sodium
chloride solution (Sec. 5.3) using the  procedures outlined in Sec.  7.0.  Adjust
to exactly 0.025 N  and check.   Store in a dark bottle.

      5.10   Mercuric nitrate  titrant (0.0141 N):  Dissolve 2.4200 g Hg(N03)2 •
H20 in 25 mL of reagent water  acidified with 0.25 mL  of  concentrated HN03 (sp.
gr. 1.42)  in  a  1 liter Class  A volumetric flask and dilute to  the mark with
reagent  water.    Filter,  if  necessary.   Standardize against  standard  sodium
chloride solution (Sec. 5.3) using the  procedures outlined in Sec.  7.0.  Adjust
to exactly  0.0141 N  and check.   Store in a dark  bottle.  A 1  mL aliquot  is
equivalent to 500 p,g  of chloride.

      5.11   Mixed  indicator reagent:  Dissolve 0.5 g crystalline diphenylcar-
bazone and 0.05 g bromophenol blue powder in 75 mL 95% ethanol in  a  100 mL Class
A volumetric  flask  and dilute  to the  mark with 95% ethanol.  Store  in  brown
bottle and discard  after 6 months.
                                  9252A - 2                       Revision 1
                                                                  September 1994

-------
      5.12   Alphazurine  indicator  solution:   Dissolve 0.005 g of alphazurine
blue-green dye in 95% ethanol  or isopropanol  in  100 mL  Class A volumetric flask
and dilute to the mark with 95% ethanol or isopropanol.

6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

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

      6.2    There are no special requirements  for preservation.

7.0   PROCEDURE

      7.1    Place 50 mL of sample  in  a vessel for titration.   If the concentra-
tion is greater than 20 mg/L chloride,  use 0.141 N mercuric  nitrate titrant (Sec.
5.8) in Sec. 7.6, or dilute sample  with reagent  water.  If the concentration is
less than 2.5 mg/L of chloride, use  0.0141 N mercuric nitrate titrant (Sec. 5.10)
in Sec. 7.6.  Using a 1 mL or 5 mL microburet, determine an indicator blank on
50 mL chloride-free water using Sec. 7.6.  If the concentration is less than
0.1 mg/L of chloride, concentrate an appropriate volume to 50 mL.

      7.2    Add 5 to 10 drops of mixed indicator reagent  (Sec. 5.11); shake or
swirl solution.

      7.3    If a blue-violet or red color appears, add HN03 solution (Sec. 5.4)
dropwise until  the color changes to yellow.  Proceed to Sec.  7.5.

      7.4    If  a yellow  or orange  color  forms  immediately  on addition of the
mixed indicator,  add NaOH solution  (Sec.  5.5) dropwise until  the color changes
to  blue-violet;  then add  HN03  solution  (Sec.  5.4)  dropwise until  the  color
changes to yellow.

      7.5    Add 1 mL excess HN03 solution  (Sec. 5.4).

      7.6    Titrate with 0.025  N  mercuric  nitrate  titrant  (Sec.  5.9) until a
blue-violet color persists throughout the  solution.  If volume  of titrant exceeds
10  mL  or is less  than 1  mL,  use  the 0.141 N  or  0.0141 N  mercuric nitrate
solutions, respectively.  If necessary, take a small sample  aliquot.  Alphazurine
indicator solution (Sec. 5.12) may be added with  the indicator to sharpen the end
point.  This will change color shades.  Practice runs should be made.

             Note: The use of indicator modifications  and the presence of heavy
             metal  ions  can  change  solution  colors without  affecting  the
             accuracy of the determination.  For example,  solutions containing
             alphazurine may  be  bright blue  when neutral,  grayish purple when
             basic, blue-green when acidic,  and  blue-violet at the chloride end
             point.  Solutions containing about  100 mg/L nickel  ion and normal
             mixed  indicator  are purple  when neutral, green  when  acidic,  and
             gray  at  the chloride  end  point.  ' When  applying this  method  to
             samples  that  contain  colored  ions  or  that  require  modified
             indicator, it is  recommended that the operator become familiar with
             the specific color changes involved by experimenting with solutions
             prepared as standards  for comparison of color effects.


                                  9252A - 3                       Revision 1
                                                                  September 1994

-------
              7.6.1    If  chromate  is  present  at  <100  mg/L  and  iron  is not
      present, add 5-10 drops of alphazurine indicator solution  (Sec. 5.12) and
      acidify to a pH of 3 (indicating  paper).  End point will  then be an olive-
      purple color.

              7.6.2    If  chromate  is  present  at  >100  mg/L  and  iron  is not
      present, add 2 ml of fresh hydroquinone solution  (Sec. 5.7).

              7.6.3    If ferric ion is present use a volume containing no more
      than 2.5 mg of ferric ion or  ferric ion plus chromate ion.  Add 2 ml  fresh
      hydroquinone solution  (Sec.  5.7).

              7.6.4    If  sulfite ion  is  present,  add 0.5  mL  of H202 solution
      (Sec. 5.6) to a 50  ml  sample and mix for 1 min.

      7.7     Calculation:

                                (A  - B)N x 35,450
          mg chloride/liter  = 	
                                  ml of sample

             where:

                      A = ml titrant for sample;

                      B = ml titrant for blank;  and

                      N = normality of mercuric  nitrate titrant.

8.0   QUALITY CONTROL

      8.1    All  quality control  data should be maintained  and  available for
easy reference or inspection.  Refer to Chapter One  for  specific quality control
guidelines.

      8.2    Analyze  a  standard  reference  material  to  ensure  that  correct
procedures are being followed and  that  all  standard reagents have been prepared
properly.

      8.3    Employ  a minimum  of one  blank per  analytical  batch  or  twenty
samples, whichever is  more frequent, to determine if contamination has occurred.

      8.4    Run  one  matrix  spike  and  matrix duplicate every analytical  batch
or twenty samples, whichever  is more frequent. Matrix spikes and duplicates are
brought through the whole sample preparation and analytical process.

9.0   METHOD PERFORMANCE

      9.1  Water  samples—A  total  of 42 analysts  in 18 laboratories analyzed
synthetic water samples containing exact increments of chloride, with the results
shown in Table 1. In  a  single laboratory,  using surface  water samples  at  an
average  concentration of  34 mg  CV/L,  the  standard  deviation was +1.0.  A


                                  9252A - 4                       Revision 1
                                                                  September 1994

-------
synthetic unknown sample containing  241 mg/L chloride, 108 mg/L Ca, 82 mg/L Mg,
3.1 mg/L K,  19.9 mg/L Na, 1.1 mg/L nitrate N,  0.25 mg/L nitrate N,  259  mg/L
sulfate and 42.5 mg/L total alkalinity (contributed by NaHC03) in reagent water
was analyzed  in  10  laboratories  by  the  mercurimetric method, with  a  relative
standard deviation of 3.3% and a relative error of 2.9%.

      9.2  Oil combustates--These data  are based on 34  data  points obtained by
five laboratories who each analyzed  four used crankcase oils and three fuel  oil
blends with crankcase oil  in duplicate.  The samples were combusted using Method
5050.   A data point  represents  one  duplicate  analysis  of a  sample.   One  data
point was judged to be an outlier and was not  included  in these  results.

           9.2.1  Precision and  bias.

                  9.2.1.1  Precision.  The precision of the method as determined
           by the statistical  examination of inter!aboratory test results is as
           follows:

                  Repeatability   -  The  difference  between successive  results
           obtained by the same operator with the same apparatus  under constant
           operating conditions on identical test material would exceed, in the
           long run,  in  the normal and correct  operation of the test method,  the
           following values only  in  1 case in  20 (see Table  2):

                         Repeatability = 7.61
           *where x is the average of two  results  in

                  Reproducibility  -  The  difference   between  two  single  and
           independent  results  obtained  by different  operators  working  in
           different laboratories on identical  test material would exceed,  in
           the long run, the following values only in  1  case  in  20:


                        Reproducibility = 20.02 /x*


           *where x is the average value of two'results  in  p.g/g.

                  9.2.1.2    Bias.     The   bias  of  this  method  varies   with
           concentration,  as shown in Table 3:

                    Bias  =  Amount  found - Amount expected
                                  9252A -  5                       Revision  1
                                                                  September 1994

-------
10.0  REFERENCES

1.    Annual Book of ASTM Standards, Part 31,  "Water,"  Standard D512-67,  Method
A, p. 270 (1976).

2.    Standard Methods  for  the  Examination of Water and Wastewater,  15th  ed.,
(1980).

3.    U.S.  Environmental  Protection Agency, Methods  for Chemical Analysis  of
Water and Wastes, EPA 600/4-79-020  (1983), Method 325.3.
                                  9252A - 6                       Revision  1
                                                                  September 1994

-------
          TABLE  1.  ANALYSES OF  SYNTHETIC  WATER  SAMPLES
              FOR CHLORIDE  BY MERCURIC NITRATE METHOD
Increment as         Precision as          Accuracy as
  Chloride        Standard Deviation     Bias      Bias
   (mg/L)               (mg/L)           (%)      (mg/L)
17
18
91
97
382
398
1.54
1.32
2.92
3.16
11.70
11.80
+2.16
+3.50
+0.11
-0.51
-0.61
-1.19
+0.4
+0.6
+0.1
-0.5
-2.3
-4.7
           TABLE 2.  REPEATABILITY AND REPRODUCIBILITY
                FOR CHLORINE  IN USED OILS BY BOMB
             OXIDATION  AND MERCURIC NITRATE  TITRATION
    Average value,        Repeatability,     Reproducibility,
        M9/9                M9/9                 M9/9
500
1,000
1,500
2,000
2,500
3,000
170
241
295
340
381
417
448
633
775
895
1,001
1,097
                            9252A -  7                       Revision 1
                                                            September 1994

-------
    TABLE 3.  RECOVERY AND BIAS DATA FOR CHLORINE  IN
             USED OILS BY BOMB OXIDATION AND
               MERCURIC NITRATE TITRATION
 Amount          Amount
expected,        found,        Bias,        Percent
  M9/9           M9/9          Aig/9          bias
   320             460          140           +44
   480             578           98           +20
   920             968           48           +5
 1,498           1,664          166           +11
 1,527           1,515         - 12           - 1
 3,029           2,809         -220           - 7
 3,045           2,710         -325           -11
                       9252A - 8                       Revision 1
                                                       September 1994

-------
                      METHOD  9252A
   CHLORIDE  (TITRIMETRIC,  MERCURIC  NITRATE)
(      START       J
   7  1 Place SO mL
 sample in titration
  vessel; determine
  concentration of
  mercuric nitrate
  titrant to use in
 Step 7.6; determine
 an indicator blank
  7.2 Add indicator
  to iamplซ;  shale*
                                                  7 . 4  Add sodium
                                                  hydroซidซ until
                                                     sanpl* is
                                                 bluซ-violซt;  add
                                                 nitric acid until
                                                 sampl* is yซlloซ
 7.3  Add nitric acid
   until sampla is
7.5  Add 1 ml nitric
      acid
                          7.6 Titrat* ซith
                          mercuric nitrate
                          until blue-violet
                          color persists
                           7.7 Calculate
                          concentration of
                         chloride in  sample
                        (      STOP       J
                       9252A  -  9
                                         Revision  1
                                         September 1994

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                                  METHOD 9253

                    CHLORIDE  (TITRIMETRIC. SILVER NITRATE)
1.0   SCOPE AND APPLICATION

      1.1    This  method  is  intended primarily for oxygen bomb combustates or
other waters where  the chloride content is 5 mg/L or more and where interferences
such as  color  or  high concentrations  of heavy metal  ions render  Method 9252
impracticable.

2.0   SUMMARY OF METHOD

      2.1    Water adjusted to pH 8.3  is titrated with silver nitrate solution
in the presence of potassium chromate indicator.  The end  point is indicated by
persistence of the orange-silver chromate color.

3.0   INTERFERENCES

      3.1    Bromide, iodide, and sulfide are titrated  along with the chloride.
Orthophosphate and polyphosphate interfere if present in concentrations greater
than 250 and 25 mg/L, respectively.  Sulfite and objectionable color or turbidity
must be eliminated.  Compounds that precipitate at pH 8.3 (certain hydroxides)
may cause error by occlusion.

      3.2    Residual sodium carbonate from the bomb combustion may react with
silver nitrate to produce the precipitate, silver carbonate.   This competitive
reaction may interfere with the  visual detection of the end  point.   To remove
carbonate from the  test solution, add small quantities of sulfuric acid followed
by agitation.

4.0   APPARATUS AND MATERIALS

      4.1    Standard laboratory titrimetric equipment, including 1 mL or 5 mL
microburet with 0.01 mL gradations, and 25 mL buret.

      4.2    Analytical balance:  capable of weighing to  0.0001 g.

      4.3    Class A volumetric flask:   1 L.

5.0   REAGENTS

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

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

      5.3    Hydrogen peroxide (30%), H202.

                                   9253 - 1                       Revision 0
                                                                  September 1994

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      5.4     Phenolphthalein  indicator  solution  (10  g/L).

      5.5     Potassium chromate  indicator solution.  Dissolve 50 g of potassium
chromate (K2Cr04)  in 100 mL of reagent water  and add silver nitrate (AgN03) until
a slightly red precipitate is produced.   Allow the solution  to  stand, protected
from light, for at least 24 hours after the addition of AgN03.   Then  filter  the
solution to remove the  precipitate.and dilute to  1 L with reagent water.

      5.6     Silver nitrate  solution, standard (0.025N).  Crush  approximately
5 g  of silver  nitrate (AgNOJ  crystals and  dry  to constant  weight at 40ฐC.
Dissolve 4.2473 + 0.0002 g of the crushed,  dried  crystals in reagent water  and
dilute  to  1  L with  reagent water.   Standardize  against  the  standard NaCl
solution, using the procedure given  in Section 7.0.

      5.7     Sodium chloride  solution,  standard  (0.025N).   Dissolve 1.4613 g
ฑ 0.0002 g of sodium chloride (dried  at 600ฐC for 1 hr)  in chloride-free water
in a 1 liter Class A volumetric flask and dilute to the mark  with reagent water.

      5.8     Sodium hydroxide solution (0.25N).  Dissolve approximately 10 g of
NaOH in reagent water and dilute to  1 L with reagent water.

      5.9     Sulfuric acid (1:19),  H2S04. Carefully add 1 volume of concentrated
sulfuric acid to  19 volumes of reagent water, while mixing.

6.0   SAMPLE COLLECTION, PRESERVATION, AND  HANDLING

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

      6.2    There are  no special requirements for preservation.

7.0   PROCEDURE

      7.1     Pour 50 mL or less  of the  sample,  containing between 0.25 mg  and
20 mg of chloride  ion, into a white porcelain container.  Dilute  to approximately
50 mL with reagent water, if necessary. Adjust the pH to the  phenolphthalein  end
point (pH 8.3) using H2S04  (Sec.  5.9) or  NaOH  solution  (Sec.  5.8).

      7.2    Add approximately 1.0 mL of K_Cr04 indicator solution and mix.   Add
standard AgN03  solution dropwise from  a 25 mL  buret  until the orange color
persists throughout the sample when  illuminated  with a yellow light or viewed
with yellow goggles.   Be consistent with endpoint recognition.

      7.3    Repeat the procedure described in Sees. 7.1 and 7.2 using  exactly
one-half as much original  sample, diluted to 50 mL with  halide-free water.

      7.4     If  sulfite ion  is  present, add  0.5 mL  of H.02  to  the   samples
described in Sees. 7.2  and 7.3 and mix for 1  minute.  Adjust tne  pH, then  proceed
as described in Sees.  7.2 and 7.3.
                                   9253 - 2                       Revision 0
                                                                  September 1994

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      7.5     Calculation

              7.5.1    Calculate the chloride ion concentration in the original
      sample,  in milligrams per liter, as follows:
              Chloride  (mg/L)  =  [(Vj - V2) x N x 71,000] / S

              where:

              Vj =     Milliliters of standard AgNO,  solution  added  in titrating
                      the sample prepared in Sec.  7.1.

              V2 =     Milliliters of standard AgNO.  solution  added  in titrating
                      the sample prepared in Sec.  7.3.

              N =     Normality of standard AgN03  solution.

              S ป     Milliliters of original sample  in  the  50. ml test sample
                      prepared in Sec.  7.1.

         71,000 =     2 x 35,500 mg Cl'/equivalent,  since \ll  - 2V?.


8.0   QUALITY CONTROL

      8.1     All  quality control data should be  maintained  and available for
easy reference or inspection.  Refer to Chapter One for specific quality control
guidelines.

      8.2     Analyze  a  standard reference  material   to ensure  that  correct
procedures are being followed and that  all  standard  reagents  have been prepared
properly.

      8.3     Employ  a minimum  of one  blank per  analytical batch  or twenty
samples, whichever is more frequent, to determine if contamination has occurred.

      8.4     Run  one matrix spike and  matrix duplicate every analytical batch
or twenty samples, whichever is more frequent.  Matrix spikes  and duplicates are
brought through the whole sample preparation and analytical  process.


9.0   METHOD  PERFORMANCE

      9.1     These  data  are  based  on   32  data  points   obtained  by  five
laboratories who each analyzed four used crankcase  oils and three fuel oil blends
with crankcase in duplicate.  The samples were combusted using Method 5050.  A
data point represents one duplicate analysis of a sample.  Three data points were
judged to be outliers and were not included in these  results.

              9.1.1    Precision.   The precision  of the method as determined by
      the  statistical   examination  of  inter- laboratory  test  results is  as
      f ol 1 ows :
                                   9253 - 3                       Revision 0
                                                                  September 1994

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             Repeatability - The difference between successive results obtained
      by  the  same operator with  the  same apparatus under  constant  operating
      conditions on identical test material would exceed,  in  the  long run,  in
      the normal and correct operation of the test method, the following values
      only in 1 case in 20 (see Table 1):

                          Repeatability = 0.36 x*
      *where x is the average of two results in M9/9-

             Reproducibilitv - The difference between two single and independent
      results obtained by different  operators working in different laboratories
      on identical test material would exceed,  in the  long  run,  the following
      values only in 1 case in 20:
                         Reproducibility =  0.71 x*
       where x is the average of two  results  in M9/9-
             9.1.2    Bias.  The bias of this method varies with concentration,
      as shown in Table 2:
                     Bias = Amount found - Amount expected

10.0  REFERENCES

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

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

3.    Gaskill, A.;  Estes,  E.  0.;  Hardison, D. L.; and Myers, L.  E.   "Validation
of Methods for Determining Chlorine in Used  Oils and Oil  Fuels,"  Prepared  for
U.S. Environmental  Protection Agency,  Office of Solid Waste.  EPA  Contract  No.
68-01-7075, WA 80.   July 1988.
                                   9253 -  4                       Revision  0
                                                                  September 1994

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                                   TABLE  1.
            REPEATABILITY AND REPRODUCIBILITY  FOR CHLORINE  IN  USED
              OILS BY BOMB OXIDATION AND SILVER NITRATE TITRATION
Average value                Repeatability         Reproducibility
500
1,000
1,500
2,000
2,500
3,000
180
360
540
720
900
1,080
355
710
1,065
1,420
1,775
2,130
                                   TABLE 2.
              RECOVERY AND BIAS DATA FOR CHLORINE IN USED OILS BY
                  BOMB OXIDATION AND SILVER NITRATE TITRATION
Amount                Amount
expected              found              Bias,           Percent
                      (M9/g)              (Mg/g)           bias
320
480
920
1,498
1,527
3,029
3,045
645
665
855
1,515
1,369
2,570
2,683
325
185
-65
17
-158
-460
-362
+102
+39
-7
+1
-10
-15
-12
                                   9253 - 5                       Revision 0
                                                                  September 1994

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                             METHOD 9253
            CHLORIDE  (TITRIMETRIC,  SILVER NITRATE)
                              START
                         7.1 Place SO ml
                        sample in  porcelain
                            container
 74 Add hydrogen
peroxide; mn  far 1
     minute
                    Yes
  741.
sulfite ion
present in
  sample?
                                No
                        7.1 Adjust pH to
                               83
                       7.2 Add 10 ml
                     potassium chromate;
                      stir; add silver
                       nitrate until
                       orange color
                         persists
 7.3 Repeat steps
 7.1 and 72 ซith
1/2 as much sample
 diluted to SO ml
                       7.S Calculate
                      concentration of
                     chloride in  sampli
                                                      STOP
                             9253 -  6
                                         Revision 0
                                         Septenter 1994

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                                 METHOD 9320

                                 RADIUM-228
1.0  SCOPE AND APPLICATION

     1.1  This method covers  the  measurement  of  radium-228 1n ground water
and, 1f desired, the determination of  rad1um-226  on the same sample.   If the
level of rad1um-226 1s above  3  pC1/L,  the  sample must also be measured for
rad1um-228.

     1.2  This technique 1s devised so  that  the beta activity from actinium-
228, which 1s produced by decay  of  radium-228, can be determined and  related
to the rad1um-228 that 1s present 1n the sample.

     1.3  To  quantify  act1n1um-228   and   thus  determine  rad1um-228,  the
efficiency of  the  beta  counter  for  measuring  the  very  short half-lived
actin1um-228 (avg. beta energy of 0.404  keV)  is to be calibrated with a beta
source of comparable average beta energy.


2.0  SUMMARY OF METHOD

     2.1  The radium 1n the water  sample is collected by coprec1p1tat1on with
barium and lead sulfate  and  purified  by repredpitation from EDTA solution.
Both radium-226 and radium-228 are  collected  in  this manner.  After a 36-hr
ingrowth of  actin1um-228  from  radium-228,  the  actinium-228  is carried on
yttrium oxalate, purified and beta  counted.    If radium-226 1s also desired,
the activity in the supernatant can  be reserved for coprecipltation on barium
sulfate, dissolving  1n  EDTA  and  storing  for  Ingrowth  in  a sealed radon
bubbler.
3.0   INTERFERENCES

      3.1  As evidenced by the results of the performance studies, the presence
of strontium-90  in the water  sample  gives  a positive bias to the rad1um-228
activity measured.  However, strontium-90 1s  not likely to be found in ground
water,  except  possibly 1n monitoring wells around a radioactive burial site.

      3.2  Excess barium  in  the  water   sample  might  result in a falsely high
chemical yield.


4.0   APPARATUS

      4.1  Gas-flow proportional counting system  (low-background beta <3 cpm).

      4.2  Electric hot plate.
                                   9320 - 1
                                                          Revision       0
                                                          Date   September  1986

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     4.3   Centrifuge.
     4.4   Membrane  filters; Matrlcel 47-mrn.
     4.5   Drying lamp.
     4.6   Glassware.
     4.7   Stainless steel  counting  planchets.
     4.8   Analytical  balance.
5.0  REAGENTS
     5.1   ASTM Type II   water  (ASTM  D1193):    Water  must  be monitored for
Impurities.
     5.2   Acetic add.  17.4 N:    Glacial   CFhCOOH  (concentrated) sp. gr. 1.05,
99.8%.
     5.3   Ammonium hydroxide.  15 N:  NfyOH (concentrated) sp gr. 0.90, 56.6%.
     5.4  Ammonium oxalate.  5%:   Dissolve  5g   (NH/j) 20304 '^O  1n Type II water
and dilute to 100 ml.
     5.5  Ammonium sulfate,  200  mg/mL:     Dissolve  20  g  (NH4)2S04 1n Type II
water and dilute to 100 ml.
     5.6  Ammonium sulflde.  2%:   Dilute 10 ml (Nfy^S  (20-24%), to  100 ml with
Type II water.
     5.7  Barium carrier,  16 mg/mL,  standardized:   Dissolve 2.846 g BaCl2*2H20
1n Type II water, add 0.5 ml  16  N   HN03,  and  dilute  to 100 ml with Type II
water.
     5.8  Citric add. 1 M:  Dissolve  19.2  g C^HoOT-F^O  1n  Type  II water and
dilute to 100 ml.
     5.9  EDTA reagent, basic (0.25 M):  Dissolve  20  g  NaOH  1n  750 ml  Type  II
water, heat, and slowly  add  93 g disodlum ethylened1m'tr1loacetate dlhydrate
(Na2CioH1408N2ซ2H20) while stirring.   After  the  salt  is in solution,  filter
through coarse filter paper, and dilute to 1 liter.
     5.10  Lead carrier. 15  mg/mL:    Dissolve  2.397  g   Pb(N03)2 1n  TyPe  I I
water, add 0.5 mL 16 N HNOs, and dilute to 100 mL with Type II water.
     5.11  Lead carrier. 1.5 mg/mL:  Dilute  10  mL lead carrier (15  mg/mL) to
100 mL with Type II water.
                                  9320 - 2
                                                         Revision
                                                         Date  September 1986

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6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

     6.1  All samples must have been collected 1n a manner which addresses the
considerations discussed in Chapter Nine of this manual.

     6.2  It  is  recommended  that  samples  be  preserved  at  the  time  of
collection  by adding enough  1 N  HN03  to the sample  to  bring 1t  to  pH 2
(15 mL 1 N HN03 per liter of sample is usually sufficient).  If samples are to
be collected without preservation,  they  should  be brought to the laboratory
within 5 days,  then  preserved,  and  held  in  the  original container for a
minimum of 16 hr before analysis or transfer  of the sample.  See also Note to
Paragraph 7.2 below.

     6.3  The container  choice  should  be  plastic  (rather  than  glass) to
prevent loss due to breakage during transportation and handling.


7.0  PROCEDURE

     7.1  Calibrations;

          7.1.1  Counter efficiency:   The beta   counter may be calibrated with
     actinium-228 or stront1um-89  (tj/2  =51  d).  Strontium-89 has an average
     beta energy of 0.589  KeV, while   the average beta energy for actinium-228
     is 0.404 KeV.  A  standard   stront1um-89   tracer  solution can be used to
     determine beta efficiencies over  a range of precipitate weights on the
     stainless steel planchet.
      7.2  For each  liter of water,  add  5 mL  1 M CsttQQffyO, and a few drops of
 methyl  orange indicator.   The  solution  should be  red.
      NOTE:  At the  time  of sample  collection add  2 mL  16 N HN03 for each liter
           of water.

      7.3  Add   10   mL  lead  carrier  (15 mg/mL),   2 mL  strontium  carrier
 (10 mg/mL),   2.0 mL  barium carrier  (16 mg/mL),  and 1 mL  yttrium  carrier
 (18 mg/mL);  stir well.    Add   15   N NH/iOH  until  a  definite yellow color is
 obtained;  then add  a few drops excess.  Heat to incipient boiling and maintain
 at this temperature for  30 min.

      7.4  Precipitate lead and barium sul fates by adding 18 N H2$OA until the
 red color reappears; then add  0.25 mL  excess.  Add 5  mL (NH4)2S04  (200 mg/mL)
 for each liter of sample.  Stir frequently  and keep at a temperature of about
 90*C for 30  min.

      7.5  Cool slightly; then   filter  with  suction   through a 47-mm matricel
 membrane filter (GA6,0.45-m1cron pore size).  Make a  quantitative  transfer of
 precipitate  to the filter  by   rinsing  last particles  out  of beaker with a
 strong jet of water.

      7.6  Carefully place filter with  precipitate  1n the bottom  of a 250-mL
 beaker.  Add about 10 mL 16 N  HNOs and  heat  gently until the filter completely
                                   9320 - 3
                                                          Revision      0
                                                          Date  September 1986

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dissolves.  Transfer the precipitate Into a polypropylene centrifuge tube  with
additional 16 N HN03.  Centrifuge and discard supernatant.

     7.7  Wash the precipitate with 15  mL  16 N HMOs,  centrifuge,  and discard
supernatant.  Repeat this washing a second time.

     7.8  Add 25 ml basic EDTA  reagent,  heat  1n  a hot-water bath, and  stir
well.  Add a few drops 10 N NaOH 1f the precipitate does not readily dissolve.

     7.9  Add 1 ml strontium-yttrium mixed carrier and stir thoroughly.  Add a
few drops 10 N NaOH If any precipitate forms.

     7.10  Add 1 ml  (NH^SOi  (200  mg/mL)  and  stir  thoroughly.   Add 17.4 N
acetic add until barium sulfate precipitates;  then  add 2 ml excess.  Digest
in a  hot  water  bath  until  precipitate  settles.    Centrifuge and discard
supernatant.

     7.11  Add 20 ml basic EDTA  reagent,  heat  1n a hot-water bath, and stir
until precipitate dissolves.   Repeat steps  7.9  and 7.10.  (Note time of last
barium sulfate  precipitation;  this  1s  the  beginning  of  the act1nium-228
Ingrowth  time.)

     7.12  Dissolve  the precipitate  in  20  ml  basic  EDTA reagent  as before;
then add  1.0 ml yttrium carrier  (9   mg/mL)  and 1 ml lead carrier  (1.5 mg/mL).
If any precipitate forms, dissolve by adding  a  few drops 10 N NaOH.  Cap the
polypropylene  tube and age at  least  36  hr.

     7.13  Add 0.3 mL  (NH4)?S  and  stir  well.    Add  10 N NaOH dropwise with
vigorous  stirring until lead sulfide precipitates;  then add 10 drops excess.
Stir Intermittently  for about  10 mln.   Centrifuge  and decant supernatant Into
a clean tube.
      7.14  Add 1  mL lead carrier (1.5 mg/mL),  0.1 mL  (NHa^S, and a few drops
 10 N, NaOH.   Repeat precipitation  of  lead   sulfide as before.  Centrifuge and
 filter supernate  through Whatman #42  filter paper  into  a clean tube.  Wash
 filter with a few mL water.   Discard residue.

      7.15  Add 5  mL 18 N NaOH,  stir well, and digest in a  hot-water bath until
 yttrium hydroxide coagulates.  Centrifuge   and decant  supernate into a beaker.
 Save for barium  yield  determination   (step 7.20).    (Note  time of yttrium
 hydroxide precipitation; this is the end of the  act1nium-228 Ingrowth time and
 beginning of actin1um-228 decay time.)

      7.16  Dissolve the precipitate in  2 mL 6 N   HN03.  Heat and  stir in a hot
 water bath about  5 min.   Add  5  mL water  and reprecipltate yttrium hydroxide
 with 3 mL 10 N NaOH.    Heat  and  stir in a hot water bath until precipitate
 coagulates.  Centrifuge and  add  this   supernate to the supernate produced in
 step 7.15 1n order to determine barium  yield.

      7.17  Dissolve precipitate with 1  mL 1 N HN03 and heat in hot-water bath
 a few minutes. Dilute  to  5  mL  and  add 2   mL 5%  (NH/^CeO/i^O.  Heat to
 coagulate,  centrifuge, and discard supernatant.


                                   9320  - 4
                                                         Revision     0
                                                         Date  September 1986

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     7.18  Add 10 mL water, 6 drops  1  N  HN03 and 6 drops 5%
Heat and stir 1n  a  hot-water  bath  a  few  minutes.  Centrifuge and~discard
supernatant.

     7.19  To determine  yttrium  yield,  transfer  quantitatively  to a tared
stainless steel planchet  with  a  minimum  amount  of  water.    Dry under an
Infrared lamp to a constant weight and count in a low-background beta counter.

     7.20  To the supernatant from step  7.15,  add  4  mL  16 N HN03 and 2 mL
    J2S04 (200 mg/mL), stirring well after  each  addition.  Add 17.4 N acetic
acid until barium sulfate precipitates; then add 2 mL excess.  Digest on a hot
plate until precipitate settles.  Centrifuge and discard supernatant.

     7.21  Add 20 mL basic EDTA  reagent,  rest  1n a hot-water bath, and stir
until precipitate dissolves.  Add a  few  drops  10 N NaOH if precipitate does
not readily dissolve.

     7.22  Add 1 mL  (M^SOA (200  mg/mL)  and  stir  thoroughly.  Add 17.4 N
acetic acid until barium sulfate precipitates;  then  add 2 mL excess.  Digest
in a  hot-water  bath  until  precipitate  settles.    Centrifuge  and discard
supernatant.

     7.23  Wash  precipitate  with  10  mL  water.    Centrifuge  and  discard
supernatant.

     7.24  Transfer  precipitate to  a   tared   stainless  steel planchet with  a
minimum  amount of water.   Dry  under   an  infrared   lamp and weigh  for barium
yield determination.

     7.25  Calculation;

           7.25.1  Calculate  the rad1um-228 concentration, D,  in picocurles per
     liter as  follows:

                              \+    *
               r                 ?ll
                                        x   	=r—   x  —4—
          2.22 XEVR        (1.e-Xt2)
                 is a factor to  correct  the  average  count  rate  to the count
        -Xt,       rate at the beginning  of  counting  time.
           Z)
                                   9320 - 5
                                                          Revision
                                                          Date   September  1986

-------
         where:
                 C = Average net count rate, cpm;
                 E = Counter efficiency, for act1n1um-228, or comparable beta
                     energy nucllde;
                 V = Liters of  sample used;
                 R = Fractional chemical yield of yttrium carrier  (Step 7.19)
                     multiplied by  fractional  chemical  yield   of  barrier
                     carrier  (Step 7.24);
               2.22 = Conversion  factor    from   disintegrations/minute   to
                     plcocurles;
                 X =  The  decay  constant for actlnlum-228  (0.001884 mln'1);
                tj =  The  time  Interval   (In m1n)   between   the first yttrium
                     hydroxide  precipitation 1n  Step   7.15  and the start of
                     the  counting time;
                t2 =  The  time  Interval of  counting  In  mln; and
                13 =  The  Ingrowth time of   act1n1um-228  1n  m1n measured  from
                     the  last barium  sulfate   precipitation  In Step  7.11 to
                     the  first yttrium hydroxide precipitation  1n  Step 7.15.
8.0  QUALITY CONTROL
     8.1  All quality control  data should be maintained and available for easy
reference or Inspection.
     8.2  Employ a minimum  of  one  blank  per  sample  batch  to  determine If
contamination or any memory effects are occurring.
     8.3  Run one spike duplicate sample  for  every  10 samples.   A duplicate
sample 1s a sample brought through the whole sample preparation and analytical
process.
9.0  METHOD PERFORMANCE
     9.1  No data provided.
                                  9320 - 6
                                                         Revision
                                                         Date  September 1986

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10.0 REFERENCES

1.   Greenberg, A.E., J.J. Connors,  and  D.J. Jenkens, eds., Standard Methods
for the Examination of Water and  Wastewater, 15th ed., American Public Health
Assoc., Washington, D.C., Method 707, p. 600, 1980.

2.   Johnson,  J.O.,  Determination   of   Radium   228   in  Natural  Waters.
Radiochemical Analysis of Water.  U.S. Geol. Surv., Water Supply Paper 1696-G.
U.S. Govt. Printing Office, Washington, D.C., 1971.

3.   Krieger, H.L., Prescribed Procedures  for Measurement of Radioactivity in
Drinking Water, Environmental  Monitoring  and  Support  Laboratory, U.S. EPA,
Cincinnati, OH, EPA-600/4-75-008,  1976.
                                   9320 - 7
                                                          Revision
                                                          Date  September 1986

-------
                                          METHOD 9320

                                          RAOIUM-asa
C
    Start
 7.1.1
       Calibrate
    beta counter
     Mltti Ac-228
       or Sr-89
  7.2
                            7.5
                          Cool  slightly:
                              filter
      Add
-ซHsฐ*ฐ Htฐ and
 ffiethyl orange
 indicator to
    water
7.6 1

Put filter ana
precipitate in
beaker:
add HNOt:
heat: centrifuge:
discard

super-note

                                                      7.9
                                                     —	1  Add
                                                          strontium
                                                       yttrium nixed
                                                        carrier;  add
                                                            Ma OH
  7.3
        Add
 lead, strontium.
   barium,  and
     yttrium
  carriers;  ctlr
                            7.7
                                  Wash
                           precipitate:
                             centerfuge;
                              discard
                             super-note
  7.3
 Add NHซOH until
   yellow color
  obtained:  heat
                            7.7
                             Repeat once
                                                      7.10
                                                            Add
 (NH^)rSO<:  add
CH COOH; digest:
  centrifuge:
discard supern.
                                                      7.11
                                                    Add basic  EOTA
                                                    reagent: heat:
                                                       • tlr
  7.4
         Add
          to
 precipitate
 lead and barium
  •ulfates;  add
            stir
                            7.8
                         Add basic EOTA
                         reagent: heat:
                             • tlr
Repeat sections
 7.9 and 7.1O
                                      9320 - 8
                                                                 Revision       0
                                                                 Date  September  1986

-------
                                           METHOD  9320

                                           RAOHJM-228
                                           (Continued)
  7. 12
        Dissolve
     precipitate
    In EOTA;  ooa
    yttrium ana
   lead carriers
       Does
precipitate form?
  Cap tube and
  age at least
    36 hours
                                                       7.H
    Centrifuge and
        filter
                                                                                 7. 17
         Dilute:
  	1  add
   (NHซ) 2CiOซ-H,.0:
  heat:centrifuge
    and discard
     Gupernate
                                                       7.IS   Add
                                                             NaOH;
     stir;  digest:
       centrifuge
       and decant
       •upernate
                                                                              7. 16
  Add water.  HNO/.
  (NH^)Z CiOVHj.0:
heat:centrlfuge ana
 discard Bupernate
                                                    7.16
Dissolve precipitate:
  heat and stir;  add
      water and
    repreclpltate
  yttrium hydroxide
   7.191 Transfer
  ———J    to
        planchet;
        determine
    yttrium yield
    using counter
         Add
        
-------
                 METHOD 9320

                 RAOIUM-ase
                 (Continued)
        Old
    precipitate
      readily
     dissolve?
Add (NHซ)iSO<:  stir;
add CH3COOH;  digest:
centrifuge:  discard
     supernate
   7.23
         Wash
     precipitate:
     centri fuge;
       discard
      supernate
7.24
precl
plane
we
Dar]
Transfer
pltate to
net: dry:
Ign for
urn yield
7.25
r
cone
uslr
Calculate
•adlum-228
:entratlon
ig formula
in text
 (      Stop       J
         9320 - 10
                                    Revision       0
                                    Date   September 1986

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                            CHAPTER SIX

                            PROPERTIES


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

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

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                                  METHOD  1312

                  SYNTHETIC PRECIPITATION LEACHING PROCEDURE
1.0 SCOPE AND APPLICATION

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

2.0   SUMMARY OF METHOD

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

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

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

3.0   INTERFERENCES

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

4.0   APPARATUS AND MATERIALS

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

      4.2    Extraction Vessels

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


                                   1312 -  1                       Revision 0
                                                                  September 1994

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      vessel (see Step 4.3.1).  These vessels shall have an internal volume of
      500-600 ml and be equipped to accommodate a 90-110 mm filter.  The devices
      contain VITON*1 0-rings which should be replaced  frequently.  Suitable ZHE
      devices known to EPA are identified in Table 3.

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

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

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

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

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

      4.3    Filtration Devices:   It is recommended  that all  filtrations be
performed in a hood.

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

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

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

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

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

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

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

      4.6    ZHE Extract Collection Devices:  TEDLARฎ2 bags or glass,  stainless
steel or PTFE gas-tight syringes are used to collect the initial liquid  phase and
the  final  extract  when  using the  ZHE device.    These devices  listed  are
recommended for use under the following conditions:

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

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

             4.6.2    If  a waste  contains  a significant  amount  of nonaqueous
      liquid  in  the  Initial  liquid phase  (i.e..  >1 %  of total  waste),  the
      syringe or the TEDLAR0 bag may be used for both the initial solid/liquid
      separation and the  final extract filtration.  However,  analysts should use
      one or the other, not both.

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

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

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

      4.9    Beaker or Erlenmeyer flask, glass, 500  ml.

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

      4.11   Magnetic  stirrer.

5.0   REAGENTS

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

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

             5.2.1    Reagent water for  volatile extractions may be  generated
      by passing  tap  water through  a  carbon  filter bed  containing  about  500
      grams of activated carbon (Calgon Corp., Filtrasorb-300 or equivalent).
                                   1312 - 4                       Revision 0
                                                                  September 1994

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              5.2.2    A  water  purification   system  (Millipore  Super-Q  or
      equivalent)  may also  be used  to generate  reagent water  for volatile
      extractions.

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

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

      5.4     Extraction fluids.

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

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

              5.4.2    Extraction fluid  #2:   This fluid  is made  by adding the
      60/40 weight percent mixture of sulfuric and nitric acids   (or  a suitable
      dilution) to reagent water  (Step  5.2)  until  the  pH is  5.00 + 0.05.  The
      fluid is used  to determine  the Teachability of soil from a site that is
      west of the Mississippi River.

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

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

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

6.0   SAMPLE COLLECTION,  PRESERVATION,  AND HANDLING

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

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


                                   1312 - 5                       Revision 0
                                                                  September 1994

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

      6.3    Preservatives shall not be added to samples before extraction.

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

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

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

7.0   PROCEDURE

      7.1    Preliminary Evaluations

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

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

                      7.1.1.1     If  the sample  will obviously  yield  no free
             liquid when subjected  to pressure filtration (i.e., is 100% solid),
             weigh  out  a representative  subsample  (100  g minimum)  and proceed
             to Step 7.1.3.

                      7.1.1.2     If   the  sample   is liquid   or  multiphasic,
             liquid/solid  separation  to  make  a  preliminary determination  of
             percent solids is required.   This  involves  the  filtration device


                                   1312 - 6                       Revision 0
                                                                  September 1994

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discussed in Step 4.3.2, and is outlined in Steps 7.1.1.3 through
7.1.1.9.

         7.1.1.3  Pre-weigh the filter and the container that will
receive the filtrate.

         7.1.1.4    Assemble filter holder and filter following the
manufacturer's instructions.   Place  the  filter  on the  support
screen and secure.

         7.1.1.5   Weigh out  a subsample  of  the waste  (100  gram
minimum) and record the weight.

         7.1.1.6  Allow slurries to stand to permit the solid phase
to settle.  Samples that settle slowly may be centrifuged prior to
filtration.   Centrifugation  is  to  be  used  only as  an  aid  to
filtration.  If used, the liquid  should be decanted and filtered
followed by filtration  of the  solid  portion of the  waste through
the same filtration system.

         7.1.1.7  Quantitatively transfer the sample to the filter
holder (liquid and solid phases).  Spread  the  sample evenly over
the surface  of the filter.   If filtration of the  waste  at  4ฐC
reduces the amount  of expressed liquid over what would be expressed
at room  temperature,  then allow  the sample to  warm up  to  room
temperature in the device before filtering.

         Gradually  apply vacuum or gentle  pressure  of  1-10 psig,
until  air or pressurizing gas moves  through the  filter.   If this
point is not reached under 10 psig, and if no additional liquid has
passed through  the  filter in any 2-minute interval, slowly increase
the pressure in 10  psig  increments  to  a  maximum of 50 psig.  After
each incremental  increase of 10 psig, if the pressurizing gas has
not moved  through  the  filter,  and  if  no additional  liquid  has
passed through the  filter  in any 2-minute interval, proceed to the
next 10-psig increment.   When the pressurizing gas begins to move
through  the  filter,  or when  liquid  flow  has  ceased at  50  psig
(i.e., filtration does not result in any  additional filtrate within
any 2-minute period), stop the filtration.

NOTE;    If sample  material (>1 %  of  original  sample weight)  has
obviously adhered to the container used  to transfer  the sample to
the filtration apparatus,  determine the  weight of this residue and
subtract it from the sample weight determined  in  Step  7.1.1.5 to
determine the weight of the sample that  will be filtered.

NOTE:  Instantaneous application of high pressure  can degrade the
glass fiber filter and may cause premature plugging.

         7.1.1.8    The material in the filter holder  is defined as
the solid phase of the sample, and the filtrate is defined as the
liquid phase.
                      1312 -  7                       Revision 0
                                                     September 1994

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             NOTE:   Some samples, such as oily wastes  and some paint wastes,
             will obviously contain some material that appears to be a liquid,
             but even after applying vacuum or pressure filtration,  as outlined
             in  Step 7.1.1.7, this material  may  not filter.   If  this  is the
             case,  the  material  within the filtration device  is defined as a
             solid.   Do not  replace  the  original filter  with  a fresh filter
             under  any  circumstances.  Use only one  filter.

                      7.1.1.9     Determine  the weight of the liquid  phase by
             subtracting the weight of the filtrate container (see Step 7.1.1.3)
             from the total weight of the filtrate-filled container.  Determine
             the weight of the  solid  phase  of the  sample  by  subtracting the
             weight of  the liquid phase from the weight of  the total sample, as
             determined in Step  7.1.1.5 or 7.1.1.7.

                      Record   the  weight   of   the liquid   and   solid  phases.
             Calculate  the percent  solids as  follows:

                                Weight of  solid (Step 7.1.1.9)
      Percent solids =  	   x 100

                        Total  weight of waste  (Step  7.1.1.5 or  7.1.1.7)

             7.1.2    If the percent solids determined in Step 7.1.1.9 is equal
      to or greater than 0.5%,  then proceed either  to Step 7.1.3 to determine
      whether the solid material requires  particle  size reduction  or to Step
      7.1.2.1 if it  is noticed that a  small amount of the filtrate is entrained
      in wetting  of the  filter.   If the percent  solids   determined  in  Step
      7.1.1.9 is less than 0.5%, then proceed to  Step 7.2.9 if the nonvolatile
      1312 analysis is to be  performed, and to Step 7.3 with a fresh portion of
      the waste if  the  volatile  1312 analysis is  to  be performed.

                      7.1.2.1     Remove the solid phase and  filter  from the
             filtration apparatus.

                      7.1.2.2     Dry the  filter and  solid  phase  at  100  + 20ฐC
             until  two  successive weighings yield the same  value within + 1 %.
             Record the final weight.

             Caution:  The  drying  oven should  be vented  to  a   hood  or  other
             appropriate device  to eliminate  the  possibility of  fumes from the
             sample escaping  into  the  laboratory.    Care  should be  taken to
             ensure that the sample  will  not  flash or violently  react  upon
             heating.

                      7.1.2.3     Calculate the percent dry  solids as follows:


Percent        (Weight  of dry sample + filter) -  tared weight of filter
dry solids  =  	   x 100

                  Initial weight of sample (Step 7.1.1.5 or 7.1.1.7)
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                7.1.2.4    If  the percent dry solids  is  less than 0.5%,
       then proceed to Step 7.2.9 if the nonvolatile 1312 analysis is to
       be performed, and to Step 7.3 if the volatile 1312 analysis is to
       be performed.   If the percent dry solids is greater than or equal
       to 0.5%, and if the nonvolatile 1312 analysis is to be performed,
       return  to  the  beginning  of this  Step  (7.1)  and,  with  a fresh
       portion  of sample,  determine whether  particle  size  reduction is
       necessary  (Step 7.1.3).

       7.1.3    Determination of whether the sample requires particle-size
reduction (particle-size is reduced during  this step):   Using the solid
portion of the  sample, evaluate  the solid  for particle size.  Particle-
size reduction  is required, unless the solid has a surface area per gram
of material  equal  to or greater than 3.1 cm2,  or is smaller than 1 cm in
its narrowest  dimension  (i.e.,  is capable  of passing through  a  9.5 mm
(0.375 inch)  standard  sieve).   If the surface area is smaller  or the
particle size larger than  described above,  prepare  the solid portion of
the sample for extraction by crushing, cutting, or grinding the waste to
a surface area  or particle size  as described above.   If the solids are
prepared for  organic  volatiles  extraction, special  precautions  must be
taken (see Step 7.3.6).

       NOTE:   Surface area  criteria  are  meant for  filamentous  (e.g..
       paper, cloth, and similar) waste materials.  Actual measurement of
       surface  area is not  required, nor  is  it recommended. For materials
       that do  not  obviously  meet  the criteria, sample-specific methods
       would  need to  be developed  and  employed to  measure  the surface
       area. Such methodology is currently not  available.

       7.1.4    Determination  of  appropriate extraction  fluid:

                7.1.4.1    For soils, if the sample  is from a  site that is
       east of the Mississippi River,  extraction fluid #1 should be used.
       If the sample is from a site that is  west  of the Mississippi River,
       extraction fluid #2 should be used.

                7.1.4.2    For wastes and wastewater, extraction fluid #1
       should be  used.

                7.1.4.3    For  cyanide-containing  wastes and/or  soils,
       extraction fluid #3 (reagent water)  must be used because leaching
       of cyanide-containing samples  under  acidic  conditions may result
       in the formation of hydrogen cyanide gas.

       7.1.5    If the aliquot of the sample used  for  the  preliminary
evaluation (Steps 7.1.1 - 7.1.4)  was determined to be 100% solid at Step
7.1.1.1,  then  it  can  be used for  the Step 7.2 extraction  (assuming at
least 100 grams  remain), and the Step 7.3  extraction  (assuming at least 25
grams remain).   If the aliquot  was subjected to the  procedure  in  Step
7.1.1.7,  then another  aliquot shall be used for the volatile extraction
procedure in  Step  7.3.    The aliquot  of  the  waste  subjected  to  the
procedure in Step 7.1.1.7  might  be appropriate  for  use for  the Step 7.2
extraction if an adequate amount  of solid (as determined by Step 7.1.1.9)


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      was obtained.  The amount of solid necessary is dependent upon whether a
      sufficient amount of extract will be produced to support the  analyses.  If
      an  adequate  amount  of solid  remains,  proceed  to Step  7.2.10  of the
      nonvolatile 1312 extraction.

      7.2    Procedure When  Volatiles Are Not Involved

      A  minimum  sample  size  of  100  grams  (solid  and   liquid  phases)  is
recommended.  In some cases,  a larger  sample size may be appropriate, depending
on the  solids  content of  the waste  sample  (percent solids,  See  Step 7.1.1),
whether the initial liquid phase  of the waste will be miscible with the aqueous
extract of the  solid, and whether inorganics, semivolatile organics, pesticides,
and herbicides are all analytes of concern.   Enough solids should be generated
for extraction  such that the volume of  1312 extract will  be sufficient to support
all of the analyses  required.  If the amount  of extract generated by a single
1312 extraction will  not be sufficient to perform all  of the  analyses, more than
one extraction  may be performed and the extracts from each combined  and aliquoted
for analysis.

             7.2.1    If the  sample will obviously yield no liquid when subjected
      to pressure filtration (i.e.,  is 100 % solid,  see Step 7.1.1), weigh out
      a subsample of the sample (100 gram minimum) and proceed to Step 7.2.9.

             7.2.2    If the sample   is  liquid  or  multiphasic,  liquid/solid
      separation is required. This involves the filtration device described in
      Step 4.3.2 and is outlined in  Steps 7.2.3 to 7.2.8.

             7.2.3   Pre-weigh the container that will receive the filtrate.

             7.2.4    Assemble  the  filter  holder  and filter  following  the
      manufacturer's instructions.   Place the filter on the support screen and
      secure.  Acid wash the filter if evaluating the  mobility  of metals (see
      Step 4.4).

             NOTE;    Acid  washed  filters may  be  used for all  nonvolatile
             extractions even when metals are not of concern.

             7.2.5  Weigh  out a subsample of the sample (100 gram minimum) and
      record the weight.   If  the waste contains <0.5 % dry solids (Step 7.1.2),
      the liquid portion of the waste, after filtration, is defined as the 1312
      extract.  Therefore,   enough of the  sample  should  be filtered so that the
      amount of filtered liquid will  support all  of the  analyses required of the
      1312 extract.  For wastes  containing >0.5 % dry  solids (Steps  7.1.1  or
      7.1.2),  use  the percent solids information obtained  in  Step  7.1.1  to
      determine  the  optimum  sample  size (100  gram  minimum) for filtration.
      Enough solids should  be generated by filtration  to support the analyses to
      be performed on the   1312  extract.

             7.2.6  Allow  slurries to  stand to permit  the solid phase to settle.
      Samples that settle  slowly may  be  centrifuged  prior to filtration.   Use
      centrifugation  only  as  an  aid   to  filtration.     If  the  sample  is
      centrifuged,  the  liquid  should be decanted  and  filtered  followed  by
      filtration of the solid portion  of the  waste through  the same filtration
      system.

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        7.2.7  Quantitatively transfer the sample (liquid and solid phases)
to the  filter  holder (see Step 4.3.2).  Spread  the waste sample evenly
over the surface of the filter.  If filtration of the waste at 48C reduces
the  amount of  expressed  liquid  over what would  be expressed  at room
temperature, then allow the sample to warm up to room temperature in the
device  before filtering.

        Gradually apply  vacuum or  gentle pressure of  1-10  psig, until air
or pressurizing gas moves  through  the  filter.    If this  point  if not
reached under 10 psig,  and if no additional liquid  has passed through the
filter,in  any 2-minute  interval,  slowly increase the pressure in 10-psig
increments to maximum of 50 psig.  After each incremental  increase of 10
psig, if the pressurizing gas has not moved through the  filter, and if no
additional liquid has passed through the  filter in  any 2-minute interval,
proceed to the next  10-psig increment.  When the pressurizing gas begins
to move through the filter,  or when the liquid flow has  ceased at 50 psig
(i.e.,  filtration  does not result  in any additional filtrate  within a
2-minute period), stop the filtration.

        NOTE;  If waste material (>1 % of the original sample weight) has
        obviously adhered to the container used to  transfer the sample to
        the filtration apparatus, determine the weight of this residue and
        subtract  it  from the sample weight determined in  Step  7.2.5,  to
        determine the weight of  the waste sample that will  be filtered.

        NOTE:Instantaneous application of high pressure  can degrade the
        glass fiber  filter and may cause premature  plugging.

        7.2.8  The material  in  the filter holder  is defined as  the solid
phase of  the  sample, and the  filtrate is  defined  as the liquid phase.
Weigh the filtrate.   The liquid phase may now  be either analyzed (see Step
7.2.12) or stored at 4ฐC until time of analysis.

        NOTE:  Some wastes, such  as oily wastes and some paint wastes, will
        obviously contain some material which appears to be a liquid.  Even
        after applying vacuum or pressure filtration, as outlined in Step
        7.2.7, this  material  may  not  filter.   If  this  is the  case,  the
        material within  the  filtration  device  is  defined as a solid,  and
        is  carried through the extraction as a solid.  Do  not replace the
        original filter with a fresh filter under any circumstances.  Use
        only one filter.

        7.2.9    If the  sample contains <0.5% dry solids  (see Step 7.1.2),
proceed to Step  7.2.13.   If the  sample contains >0.5 % dry solids (see
Step 7.1.1 or  7.1.2),  and  if  particle-size  reduction   of the  solid was
needed in Step 7.1.3, proceed to Step 7.2.10.   If the sample as received
passes a 9.5 mm  sieve, quantitatively transfer the solid  material into the
extractor bottle along  with the filter used to separate the initial liquid
from the solid phase, and proceed to Step 7.2.11.

        7.2.10   Prepare the  solid  portion of the sample for extraction by
crushing, cutting,  or grinding  the waste to  a surface  area or  particle-
size as described in Step 7.1.3.  When the surface area or particle-size
has been appropriately altered, quantitatively transfer the solid material

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      into an extractor bottle.  Include the filter used to  separate the initial
      liquid from the solid phase.

             NOTE:  Sieving of the waste is not normally required.  Surface area
             requirements  are  meant for filamentous  (e.g.,  paper,  cloth) and
             similar waste materials.  Actual measurement of surface area  is not
             recommended.  If sieving is necessary, a Teflon-coated sieve  should
             be used to avoid contamination of the  sample.

             7.2.11   Determine the amount  of extraction fluid to add  to the
      extractor vessel as follows:

                        20 x % solids  (Step 7.1.1)  x weight of waste
                               filtered   (Step 7.2.5 or 7.2.7)
Weight of         =  	
extraction fluid
                                            100

             Slowly add this  amount of  appropriate extraction fluid  (see Step
      7.1.4) to the extractor vessel.  Close the extractor bottle tightly  (it is
      recommended that Teflon tape  be used to ensure  a tight seal),  secure in
      rotary extractor  device,  and rotate at 30  + 2  rpm  for 18 +  2   hours.
      Ambient temperature (i.e., temperature of room in which extraction takes
      place) shall be maintained at 23 ฑ 2ฐC during the extraction period.

             NOTE:  As  agitation  continues, pressure may  build  up within the
             extractor bottle for some types of sample  (e.g.. limed or calcium
             carbonate-containing  sample  may  evolve  gases  such  as   carbon
             dioxide).  To relieve excess  pressure,  the  extractor bottle  may be
             periodically  opened  (e.g.,  after  15  minutes, 30 minutes,  and  1
             hour) and vented into  a hood.

             7.2.12   Following  the 18 + 2 hour extraction, separate the material
      in the  extractor  vessel   into its component  liquid  and  solid  phases by
      filtering through a  new  glass fiber filter,  as  outlined  in  Step   7.2.7.
      For final filtration  of the  1312 extract,  the glass  fiber filter  may be
      changed,  if necessary,  to  facilitate filtration.   Filter(s)   shall  be
      acid-washed (see Step 4.4) if evaluating the mobility of metals.

             7.2.13   Prepare  the  1312 extract as  follows:
                               i
                      7.2.13.1   If the sample  contained no initial liquid  phase,
             the  filtered liquid material  obtained from Step 7.2.12 is defined
             as the 1312 extract.   Proceed to Step 7.2.14.

                      7.2.13.2   If compatible  (e.g.,  multiple  phases  will not
             result on combination), combine the  filtered liquid resulting from
             Step 7.2.12 with the  initial  liquid  phase of  the sample obtained
             in  Step  7.2.7.    This  combined   liquid  is defined  as   the 1312
             extract.  Proceed  to Step 7.2.14.

                      7.2.13.3   If  the  initial  liquid phase of the  waste,  as
             obtained from Step 7.2.7,  is  not  or may not be compatible with the
             filtered liquid resulting from Step  7.2.12, do not combine these

                                   1312 -  12                       Revision 0
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              liquids.   Analyze  these  liquids, collectively defined  as the  1312
              extract,  and combine the results mathematically, as described  in
              Step  7.2.14.

              7.2.14   Following collection of the  1312  extract,  the pH of the
      extract should be recorded.  Immediately aliquot and preserve  the extract
      for analysis.  Metals aliquots must be acidified with nitric acid to  pH <
      2.  If precipitation is observed upon addition  of nitric acid to a small
      aliquot of the extract,  then  the  remaining portion of the extract for
      metals analyses shall not be acidified and the  extract  shall  be analyzed
      as  soon   as  possible.    All  other  aliquots  must   be   stored  under
      refrigeration  (4ฐC)  until  analyzed.   The  1312 extract shall be prepared
      and analyzed according to appropriate analytical methods.   1312 extracts
      to be analyzed for metals  shall  be acid digested except  in those instances
      where digestion causes loss of  metallic analytes.  If an analysis of the
      undigested extract shows that the concentration of any regulated metallic
      analyte exceeds  the regulatory level,  then  the waste  is  hazardous and
      digestion  of the  extract  is  not necessary.   However,  data on undigested
      extracts  alone cannot  be used to demonstrate that  the  waste  is  not
      hazardous.   If  the individual  phases  are  to be  analyzed  separately,
      determine  the volume of  the  individual  phases (to + 0.5 %), conduct the
      appropriate analyses, and combine  the results mathematically  by using a
      simple volume-weighted average:

                                         (V,) (C,)  + (V2) (C2)
      Final Analyte Concentration  =  	
                                              V, +  V2
      where:

      V, = The volume of the first phase (L).
      CT = The concentration of the analyte of concern in the first phase (mg/L).
      V2 = The volume of the second phase (L).
      C2 = The concentration of the analyte  of concern in the second phase
           (mg/L).

              7.2.15   Compare the analyte concentrations in the 1312  extract with
      the  levels identified  in  the  appropriate  regulations.   Refer to Section
      8.0  for quality assurance requirements.

      7.3     Procedure When Volatiles Are Involved

      Use  the ZHE  device to  obtain 1312  extract for  analysis  of  volatile
compounds only.   Extract resulting from  the  use  of  the  ZHE  shall not be used to
evaluate the mobility of non-volatile analytes (e.g., metals, pesticides, etc.).

      The ZHE device has approximately a 500 ml  internal  capacity.  The ZHE can
thus accommodate a maximum of 25 grams of solid (defined as that fraction of a
sample from which no additional  liquid may be forced out  by an applied pressure
of 50 psig), due to the  need to add  an  amount  of  extraction fluid  equal  to 20
times the weight of the solid phase.
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      Charge the ZHE with sample only once and do not open the device until the
final extract (of the solid) has been collected.   Repeated filling  of the ZHE to
obtain 25 grams of solid is not permitted.

      Do not allow the  sample,  the  initial  liquid  phase, or the extract to be
exposed to the atmosphere for any more time than is absolutely necessary.  Any
manipulation of these materials should be  done when cold  (4ฐC) to minimize loss
of volatiles.

             7.3.1    Pre-weigh the  (evacuated)  filtrate collection  container
      (see Step 4.6) and set aside.   If using a  TEDLAR* bag, express all liquid
      from  the ZHE  device  into  the bag,  whether  for  the initial   or final
      liquid/solid separation,  and  take an  aliquot from  the liquid in the bag
      for analysis.  The containers listed in Step 4.6 are recommended for use
      under the conditions stated in Steps 4.6.1-4.6.3.

             7.3.2    Place  the ZHE  piston within the body of the ZHE (it may be
      helpful  first  to  moisten  the  piston  0-rings  slightly with extraction
      fluid).   Adjust the piston within  the ZHE body  to a height  that will
      minimize the distance  the piston will have to move once the ZHE is charged
      with sample (based upon  sample size requirements determined from Step 7.3,
      Step  7.1.1  and/or 7.1.2).  Secure  the gas inlet/outlet  flange (bottom
      flange)  onto  the  ZHE  body  in  accordance  with  the  manufacturer's
      instructions.  Secure the glass fiber filter between the support screens
      and set aside.  Set liquid inlet/outlet flange (top flange)  aside.

             7.3.3    If the sample  is 100%  solid (see Step 7.1.1),  weigh out
      a subsample (25 gram maximum)  of the waste, record  weight, and proceed to
      Step 7.3.5.

             7.3.4    If the sample  contains  <0.5% dry solids (Step 7.1.2), the
      liquid portion of waste,  after filtration,  is defined as the  1312 extract.
      Filter enough  of  the  sample so that the  amount  of filtered liquid will
      support  all  of the volatile analyses  required.  For samples containing
      >0.5%  dry solids  (Steps 7.1.1  and/or 7.1.2),  use the  percent solids
      information obtained in  Step 7.1.1 to determine  the  optimum sample size to
      charge into the ZHE.  The recommended sample size  is as follows:

                      7.3.4.1     For samples containing  <5% solids  (see Step
             7.1.1),  weigh  out a 500  gram  subsample of waste  and record the
             weight.

                      7.3.4.2     For wastes  containing   >5%  solids (see  Step
             7.1.1),  determine  the  amount of waste to charge into the ZHE as
             follows:

                                             25
Weight of waste to charge ZHE =  	   x 100
                                  percent solids (Step 7.1.1)

             Weigh out  a subsample of the  waste of the  appropriate  size and
      record the weight.
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        7.3.5    If particle-size reduction  of the solid  portion  of the
sample  was  required  in  Step  7.1.3,  proceed  to Step 7.3.6.  If particle-
size reduction was not  required in Step 7.1.3, proceed to Step 7.3.7.

        7.3.6    Prepare the sample for extraction by crushing, cutting, or
grinding the solid portion of the waste to a surface area or particle size
as described in Step 7.1.3.1.  Wastes and appropriate reduction equipment
should  be  refrigerated,   if  possible,  to  4"C  prior to particle-size
reduction.   The means  used  to effect particle-size  reduction  must not
generate heat  in  and  of itself.   If reduction of the solid phase of the
waste  is  necessary,  exposure  of the  waste  to the atmosphere  should be
avoided to the extent possible.

        NOTE;    Sieving  of the  waste  is  not  recommended  due  to  the
        possibility   that   volatiles  may  be   lost.     The  use  of  an
        appropriately  graduated ruler  is recommended  as  an  acceptable
        alternative.   Surface  area requirements are meant for filamentous
        (e.g..  paper,   cloth)  and  similar  waste  materials.    Actual
        measurement of surface area  is not recommended.

        When  the  surface  area or  particle-size  has  been appropriately
altered, proceed to Step 7.3.7.

        7.3.7    Waste slurries need  not  be allowed to stand to permit the
solid phase to settle.  Do not centrifuge samples prior to filtration.

        7.3.8    Quantitatively transfer the entire sample (liquid and solid
phases) quickly to the  ZHE.   Secure  the filter and support screens into
the top flange of the device  and  secure  the top flange to  the ZHE body in
accordance with the manufacturer's instructions.  Tighten all ZHE fittings
and place the device in the vertical position  (gas inlet/outlet flange on
the bottom).   Do  not  attach  the  extraction  collection device to the top
plate.

        Note:   If  sample  material  (>1% of  original  sample  weight)  has
        obviously adhered to the container used to transfer the sample to
        the ZHE, determine the weight of  this residue and subtract it from
        the sample weight determined in Step 7.3.4 to determine the'weight
        of the waste sample that will be filtered.

        Attach  a gas  line to   the gas inlet/outlet  valve  (bottom flange)
and, with the liquid  inlet/outlet valve  (top flange) open, begin applying
gentle pressure of 1-10  psig  (or more if  necessary) to force all headspace
slowly  out  of  the ZHE device  into  a  hood.   At  the  first appearance of
liquid  from the liquid inlet/outlet valve,  quickly close  the  valve and
discontinue pressure.   If filtration of  the waste  at  4ฐC  reduces  the
amount  of  expressed  liquid  over  what  would  be  expressed  at  room
temperature, then allow the sample to warm up to room temperature in the
device before filtering.   If  the waste  is 100 %  solid (see Step 7.1.1),
slowly increase the pressure  to a maximum of 50 psig to force most of the
headspace out of the device and proceed  to Step 7.3.12.
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             7.3.9    Attach  the  evacuated  pre-weighed  filtrate  collection
      container  to  the liquid inlet/outlet  valve  and open the  valve.   Begin
      applying gentle  pressure  of 1-10 psig to force  the  liquid phase of the
      sample into the  filtrate  collection  container.   If no additional liquid
      has passed through  the  filter  in any 2-minute interval, slowly increase
      the pressure  in  10-psig increments to  a  maximum of 50 psig.  After each
      incremental  increase of  10 psig,  if  no  additional  liquid  has  passed
      through the filter  in any  2-minute interval, proceed to the next 10-psig
      increment.   When liquid  flow  has ceased  such  that  continued pressure
      filtration at 50 psig does not  result in  any  additional  filtrate within a
      2-minute  period, stop  the filtration.   Close  the  liquid inlet/outlet
      valve, discontinue  pressure  to the piston,  and disconnect and weigh the
      filtrate collection container.

             NOTE:  Instantaneous  application of high  pressure can degrade the
             glass  fiber  filter  and may cause premature plugging.

             7.3.10   The  material  in the  ZHE is defined as the solid phase of
      the sample and the  filtrate  is defined as the liquid phase.

             NOTE;  Some  samples,  such as oily wastes and  some paint wastes,
             will obviously contain some material  which appears  to be a liquid.
             Even  after applying pressure filtration,  this material  will  not
             filter.   If  this is the case, the material within the filtration
             device  is defined   as a solid,  and  is carried  through  the 1312
             extraction as  a solid.

             If the original waste contained  <0.5 % dry solids  (see Step 7.1.2),
      this filtrate is defined  as the 1312  extract  and is  analyzed directly.
      Proceed to Step  7.3.15.

             7.3.11   The  liquid phase may now  be  either analyzed immediately
      (see Steps 7.3.13 through 7.3.15) or stored at 4ฐC under minimal headspace
      conditions until  time of  analysis.   Determine  the weight of extraction
      fluid #3 to add  to  the ZHE as follows:
                                 20 x % solids (Step 7.1.1) x weight
                               of waste filtered (Step 7.3.4 or 7.3.8)
Weight of extraction fluid =  	
                                                 100

             7.3.12   The  following  steps detail  how  to add  the appropriate
      amount of  extraction fluid  to the  solid material within the  ZHE  and
      agitation of the  ZHE vessel.   Extraction fluid #3  is  used in  all  cases
      (see Step 5.4.3).

                      7.3.12.1  With  the ZHE in the vertical  position, attach a
             line from the extraction fluid reservoir to the liquid inlet/outlet
             valve.   The line used  shall  contain fresh  extraction  fluid  and
             should be preflushed with fluid to eliminate any air  pockets in the
             line.   Release  gas pressure  on the  ZHE   piston  (from  the  gas
             inlet/outlet valve), open  the liquid  inlet/outlet valve, and begin
             transferring  extraction fluid  (by  pumping  or similar means)  into

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       the ZHE.  Continue pumping extraction fluid into the ZHE until the
       appropriate amount of fluid has been  introduced into the device.

                7.3.12.2  After  the  extraction  fluid  has been  added,
       immediately close the liquid inlet/outlet valve and disconnect the
       extraction fluid line.   Check the ZHE to ensure that all valves are
       in  their closed  positions.    Manually rotate the  device  in  an
       end-over-end  fashion  2 or  3  times.   Reposition  the ZHE  in the
       vertical  position with the liquid  inlet/outlet  valve on  top.
       Pressurize the ZHE to 5-10 psig (if  necessary) and slowly open the
       liquid inlet/outlet valve to bleed out any headspace (into a hood)
       that may  have been introduced  due  to  the addition  of extraction
       fluid.  This  bleeding  shall  be done quickly and  shall  be stopped
       at the first  appearance of liquid from the valve.   Re-pressurize
       the ZHE with  5-10  psig  and check  all  ZHE fittings  to ensure that
       they are closed.

                7.3.12.3  Place the ZHE in  the rotary extractor apparatus
       (if it is not  already  there) and  rotate at 30 +  2  rpm for 18+2
       hours.   Ambient temperature (i .e.,  temperature of  room in which
       extraction  occurs)  shall  be   maintained  at  23  +  2ฐC  during
       agitation.

       7.3.13   Following  the  18+2  hour agitation period,  check the
pressure behind  the  ZHE piston by  quickly opening and closing  the gas
inlet/outlet valve and noting  the escape  of gas.   If the pressure has not
been maintained  (i.e. . no gas release  observed),  the  ZHE  is  leaking.
Check the ZHE  for leaking as  specified  in Step  4.2.1,  and  perform the
extraction again with a new sample of waste.  If the pressure within the
device has been maintained,  the material  in the extractor vessel is once
again separated into its component liquid and solid phases.  If the waste
contained an initial  liquid  phase,  the liquid  may  be filtered directly
into the  same filtrate collection container  (i .e., TEDLAR0 bag) holding the
initial   liquid  phase  of the  waste.    A  separate  filtrate  collection
container must  be used if combining would  create multiple phases, or there
is  not  enough  volume left within the  filtrate  collection  container.
Filter through the glass fiber filter, using the ZHE device as discussed
in Step 7.3.9.  All extracts shall  be filtered and collected if the TEDLAR
bag is used,  if the extract is multiphasic, or if the waste contained an
initial  liquid phase  (see Steps 4.6 and 7.3.1).

       NOTE:   An in-line glass fiber filter may be used to  filter the
       material within  the ZHE if it  is suspected that the  glass fiber
       filter has been ruptured

       7.3.14   If  the original sample contained no initial  liquid phase,
the filtered liquid material  obtained  from  Step 7.3.13  is  defined as the
1312 extract.    If  the sample  contained an  initial  liquid phase,  the
filtered liquid material  obtained  from Step 7.3.13 and the initial  liquid
phase (Step 7.3.9) are collectively defined as the 1312  extract.

       7.3.15   Following  collection  of  the  1312 extract,  immediately
prepare the extract for analysis and store  with minimal  headspace at 4ฐC


                            1312  -  17                      Revision 0
                                                            September 1994
*

-------
      until analyzed.   Analyze the 1312 extract  according  to the appropriate
      analytical  methods.    If the  individual  phases  are  to   be  analyzed
      separately  (i.e.,  are  not   miscible),   determine  the volume  of  the
      individual phases (to 0.5%), conduct the appropriate  analyses, and combine
      the results mathematically by using a simple volume- weighted average:
                              (V,) (C,)  + (V2)  (C2)
      Final Analyte
      Concentration   ,               V, + V2

      where:

      V, = The volume of the first phases (L).
      C, = The concentration of the analyte of  concern in the first  phase (mg/L).
      V2 = The volume of the second phase (L).
      C2 = The concentration of the analyte of concern in the second phase
           (mg/L).

             7.3.16  Compare the analyte concentrations in the 1312 extract with
      the levels identified in the appropriate regulations.  Refer to Step 8.0
      for quality assurance requirements.

8.0   QUALITY CONTROL

      8.1    A minimum of one blank (using the same extraction fluid  as used for
the samples) for every 20 extractions that  have been conducted in  an extraction
vessel.  Refer to Chapter One for additional quality control protocols.

      8.2    A  matrix spike  shall   be  performed for  each waste type  (e.g..
wastewater treatment sludge, contaminated soil, etc.)  unless the result exceeds
the regulatory level and the data is being used solely to demonstrate that the
waste property exceeds the regulatory level.  A minimum of one matrix spike must
be analyzed for each analytical batch.   As a minimum, follow the matrix spike
addition guidance provided in each analytical  method.

             8.2.1  Matrix spikes are to be added after filtration of the 1312
      extract and before preservation.  Matrix spikes  should not be added prior
      to 1312 extraction of the sample.

             8.2.2   In most cases,  matrix  spike levels should be  added  at a
      concentration equivalent to the  corresponding regulatory  level.   If the
      analyte concentration  is  less than one half the  regulatory  level,  the
      spike  concentration  may  be  as  low  as  one  half  of  the  analyte
      concentration, but may not be  less than five times the method detection
      limit.  In order  to avoid differences  in  matrix effects, the matrix spikes
      must be added  to  the  same nominal volume of  1312  extract as that which was
      analyzed for the unspiked sample.

             8.2.3    The  purpose  of  the  matrix  spike  is  to  monitor  the
      performance of  the  analytical  methods  used, and to  determine  whether

                                   1312 - 18                       Revision 0
                                                                  September  1994

-------
      matrix interferences exist.   Use  of other internal  calibration methods,
      modification of  the  analytical  methods, or  use  of  alternate analytical
      methods may be needed to accurately measure the analyte concentration in
      the  1312  extract when  the recovery  of the matrix  spike is  below the
      expected analytical method performance.

             8.2.4    Matrix  spike recoveries are  calculated  by the following
      formula:

             %R  (% Recovery) = 100  (Xs - Xu)  / K
      where:
             X6 = measured  value for the spiked  sample
             Xu = measured  value for the unspiked sample,  and
             K  = known value  of the spike in the sample.

      8.3  All  quality control measures  described in the appropriate analytical
methods shall be followed.


      8.4    The  use  of internal  calibration  quantitation  methods  shall  be
employed for a metallic contaminant if:  (1) Recovery of the  contaminant from the
1312 extract  is not at  least  50% and  the  concentration  does  not  exceed the
appropriate  regulatory level,  and  (2)  The  concentration  of  the  contaminant
measured in the extract is  within 20% of the appropriate regulatory level.

             8.4.1.   The method  of  standard  additions shall be employed as the
      internal calibration  quantitation method for each metallic contaminant.
                                 i
             8.4.2    The   method of  standard   additions  requires  preparing
      calibration standards in the  sample matrix rather than  reagent water or
      blank  solution.    It requires  taking  four identical  aliquots of the
      solution and adding known  amounts  of standard to three of these aliquots.
      The forth aliquot is  the unknown.   Preferably,  the first addition should
      be prepared so that  the resulting concentration  is  approximately 50% of
      the expected concentration of  the  sample.   The second and third additions
      should be prepared so that the concentrations are approximately 100% and
      150% of the expected  concentration of the  sample.  All  four aliquots are
      maintained at  the  same  final  volume by adding reagent  water  or a  blank
      solution, and may need dilution  adjustment  to maintain the signals in the
      linear range of the instrument technique.  All four aliquots are analyzed.

             8.4.3    Prepare  a  plot,  or subject data  to linear regression,  of
      instrument signals or external-calibration-derived concentrations as the
      dependant  variable  (y-axis)  versus concentrations  of the additions  of
      standards as the independent variable (x-axis).   Solve for the intercept
      of the abscissa (the  independent variable,  x-axis)  which  is the concentra-
      tion in the unknown.

             8.4.4   Alternately, subtract the instrumental signal orexternal-
      calibration-derived concentration of the  unknown  (unspiked)  sample from
      the instrumental  signals or external-calibration-derived concentrations of
      the  standard  additions.    Plot  or subject  to  linear regression of the
      corrected  instrument signals  or external-calibration-derived  concentra-


                                  1312  -  19                       Revision 0
                                                                  September 1994

-------
      tions as the dependant variable versus the independent variable.  Derive
      concentrations for the unknowns using the internal calibration curve  as if
      it were an external calibration curve.
      8.5
periods:
Samples  must  undergo  1312  extraction within  the  following  time
                      SAMPLE MAXIMUM HOLDING TIMES (davs)








Volatiles
Semi-
volatiles
Mercury
Metals,
except
mercury
From: Field
Collec-
tion

To: 1312
extrac-
tion

14

14
28

180

From: 1312
extrac-
tion

To: Prepara-
tive
extrac-
tion
NA

7
NA

NA

From: Prepara-
tive
extrac-
tion

To: Determi-
native
analysis
14

40
28

180

Total
Elapsed
Time





28

61
56

360

NA = Not Applicable
If sample  holding  times are exceeded, the values  obtained  will  be considered
minimal  concentrations.   Exceeding  the  holding  time is  not  acceptable  in
establishing that a waste does not exceed the regulatory level.  Exceeding the
holding  time  will  not  invalidate characterization  if the waste  exceeds the
regulatory level.

9.0   METHOD PERFORMANCE

      9.1    Precision  results for semi-volatiles and metals:  An eastern soil
with high organic content and a western soil with low organic content were used
for the semi-volatile and metal  leaching experiments.  Both types of soil were
analyzed prior to contaminant spiking.  The results are shown in Table 6.  The
concentration of contaminants leached from the soils were reproducible, as shown
by the moderate  relative standard deviations (RSDs)  of the recoveries (averaging
29% for the compounds and elements analyzed).

      9.2    Precision  results for volatiles:   Four different soils were spiked
and tested for the  extraction of volatiles.  Soils One and Two were from western
and eastern Superfund sites.  Soils Three  and  Four were mixtures of a western
soil  with low organic content and  two  different municipal sludges.  The results
are shown  in  Table 7.   Extract  concentrations of volatile organics  from the
eastern soil were lower  than from the western soil.  Replicate Teachings of Soils
                                   1312  -  20
                                                      Revision 0
                                                      September 1994

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Three and  Four showed lower  precision  than the leachates  from the Superfund
soils.

10.0  REFERENCES

1.    Environmental  Monitoring Systems  Laboratory,  "Performance  Testing  of
      Method 1312; QA Support  for  RCRA  Testing:   Project Report".  EPA/600/4-
      89/022.   EPA Contract  68-03-3249  to Lockheed  Engineering  and Sciences
      Company, June 1989.

2.    Research Triangle Institute,  "Interlaboratory Comparison of Methods 1310,
      1311, and 1312 for Lead  in Soil".   U.S. EPA Contract 68-01-7075, November
      1988.
                                   1312  -  21                       Revision 0
                                                                  September 1994

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                         Table 1.  Volatile Analytes1
Compound                                                      CAS No.
Acetone                                                       67-64-1
Benzene                                                       71-43-2
n-Butyl alcohol                                               71-36-3
Carbon disulfide                                              75-15-0
Carbon tetrachloride                                          56-23-5
Chlorobenzene                                                108-90-7
Chloroform                                                    67-66-3
1,2-Dichloroethane                                           107-06-2
1,1-Dichloroethylene                                          75-35-4
Ethyl acetate                                                141-78-6
Ethyl benzene                                                100-41-4
Ethyl ether                                                   60-29-7
Isobutanol                                                    78-83-1
Methanol                                                      67-56-1
Methylene chloride                                            75-09-2
Methyl ethyl ketone                                           78-93-3
Methyl isobutyl ketone                                       108-10-1
Tetrachloroethylene                                          127-18-4
Toluene                                                      108-88-3
1,1,1,-Trichloroethane                                        71-55-6
Trichloroethylene                                             79-01-6
Trichlorofluoromethane                                        75-69-4
l,l,2-Trichloro-l,2,2-trifluoroethane                         76-13-1
Vinyl chloride                                                75-01-4
Xylene                                                      1330-20-7
1  When testing for any or all  of these analytes,  the zero-headspace extractor
  vessel shall  be  used  instead of the  bottle extractor.
                                   1312  - 22                       Revision 0
                                                                  September 1994

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                Table  2.   Suitable  Rotary Agitation  Apparatus1
Company
Location
 Model No.
Analytical Testing and
  Consulting Services,
  Inc.

Associated Design and
  Manufacturing Company
Environmental Machine and
  Design, Inc.

IRA Machine Shop and
  Laboratory

Lars Lande Manufacturing
Mi Hi pore Corp.
Warrington, PA
 (215) 343-4490
Alexandria, VA
(703) 549-5999
Lynchburg, VA
(804) 845-6424

Santurce, PR
(809) 752-4004
 4-vessel extractor (DC20S);
 8-vessel extractor (DC20);
12-vessel extractor (DC20B)
 2-vessel
 4-vessel
 6-vessel
 8-vessel
(3740-2);
(3740-4);
(3740-6);
(3740-8);
12-vessel (3740-12);
24-vessel (3740-24)

 8-vessel (08-00-00)
 4-vessel (04-00-00)

 8-vessel (011001)
Whitmore Lake, MI 10-vessel (10VRE)
(313) 449-4116     5-vessel (5VRE)
Bedford, MA
(800) 225-3384
 4-ZHE or
 4 1-liter
 bottle extractor
 (YT300RAHW)
1  Any device  that rotates the extraction vessel in an end-over-end fashion at 30
ฑ2 rpm is acceptable.
                                   1312  -  23
                                  Revision 0
                                  September 1994

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             Table 3.  Suitable Zero-Headspace Extractor Vessels1
Company
Location
Model No.
Analytical Testing &
  Consulting Services, Inc.

Associated Design and
  Manufacturing Company

Lars Lande Manufacturing2
Millipore Corporation
Environmental Machine
and Design, Inc.
Warrington, PA
(215) 343-4490

Alexandria, VA
(703) 549-5999

Whitmore Lake, MI
(313) 449-4116

Bedford, MA
(800) 225-3384

Lynchburg, VA
(804) 845-6424
C102, Mechanical
Pressure Device

3745-ZHE, Gas
Pressure Device

ZHE-11, Gas
Pressure Device

YT30090HW, Gas
Pressure Device

VOLA-TOX1, Gas
Pressure Device
1  Any device  that meets the specifications listed in Step 4.2.1  of the method  is
suitable.

2  This device uses  a 110 mm filter.
                                   1312  -  24
                                  Revision 0
                                  September 1994

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                      Table 4.  Suitable Filter Holders1
Company
Nucleopore Corporation
Micro Filtration
Systems
Millipore Corporation
Location
Pleasanton, CA
(800) 882-7711
Dublin, CA
(800) 334-7132
(415) 828-6010
Bedford, MA
(800) 225-3384
Model/
Catalogue #
425910
410400
302400
311400
YT30142HW
XX1004700
Size
142 mm
47 mm
142 mm
47 mm
142 mm
47 mm
1  Any device capable of separating  the  liquid  from the solid phase of the waste
is suitable, providing that it is chemically compatible with the waste and the
constituents to be analyzed.  Plastic devices (not listed above) may be used when
only  inorganic  analytes are  of  concern.   The 142  mm  size  filter  holder is
recommended.
                       Table 5.  Suitable Filter Media1
Company
Millipore Corporation
Nucleopore Corporation
Whatman Laboratory
Products, Inc.
Micro Filtration
Systems
Location Model
Bedford, MA AP40
(800) 225-3384
Pleasanton, CA 211625
(415) 463-2530
Clifton, NJ GFF
(201) 773-5800
Dublin, CA GF75
(800) 334-7132
(415) 828-6010
Pore
Size
(Mm)
0.7
0.7
0.7
0.7
1 Any filter that meets the specifications  in Step 4.4 of the Method is suitable.
                                   1312  -  25                       Revision 0
                                                                  September 1994

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       TABLE 6 - METHOD 1312 PRECISION RESULTS  FOR  SEMI-VOLATILES AND METALS
Eastern Soil (oH 4.2)



FORTIFIED ANALYTES
bis(2-chloroethyl)-
ether
2-Chlorophenol
1 ,4-Dichlorobenzene
1,2-Dichlorobenzene
2-Methylphenol
Nitrobenzene
2,4- Dime thy 1 phenol
Hexachlorobutadiene
Acenaphthene
2 ,4-Dinitrophenol
2 ,4-Dinitrotoluene
Hexachlorobenzene
famma BHC (Lindane)
eta BHC
METALS
Lead
Cadmium
Amount
Spiked
(Mg)

1040
1620
2000
8920
3940
1010
1460
6300
3640
1300
1900
1840
7440
640

5000
1000
Amount
Recovered*
(Mg)

834
1010
344
1010
1860
812
200
95
210
896**
1150
3.7
230
35

70
387

% RSD


12.5
6.8
12.3
8.0
7.7
10.0
18.4
12.9
8.1
6.1
5.4
12.0
16.3
13.3

4.3
2.3
Western Soil (oH 5.0)
Amount
Recovered*
(Mg)

616
525
272
1520
1130
457
18
280
310**
23**
585
10
1240
65.3

10
91

% RSD


14.2
54.9
34.6
28.4
32.6
21.3
87.6
22.8
7.7
15.7
54.4
173.2
55.2
51.7

51.7
71.3
 * - Triplicate analyses.
** - Duplicate analyses; one value was rejected as an outlier  at  the  90%
     confidence level using the Dixon Q test.
                                    1312 - 26
Revision 0
September 1994

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                    TABLE 7 - METHOD  1312  PRECISION RESULTS FOR VOLATILES

Soil
No. 1
Soil
No. 2
Soil No
. 3
(Western and
(Western)

Compound Name
Acetone
Acrylonltrile
Benzene
n- Butyl Alcohol
(1-Butanol)
Carbon disulfide
Carbon tetrachloride
Chlorobenzene
Chloroform
1 , 2-Dichloroethane
1 , 1-Dichloroe thane
Ethyl acetate
Ethylbenzene
Ethyl ether
Isobutanol (4 -Methyl
-1-propanol)
Methylene chloride
Methyl ethyl ketone ,
(2-Butanone)
Methyl isobutyl
ketone
1,1,1, 2 -Tetrachloro-
ethane
1,1,2, 2 -Tetrachloro -
ethane
Tetrachloroethene
Toluene
1,1,1-Trichloro-
e thane
1,1,2-Trichloro-
e thane
Trichloroethene
Trlchloro-
f luorome thane
1,1,2-Trichloro-
trlfluoroe thane
Vinyl chloride
Avg.
%Rec.*
44.0
52.5
47.8

55.5
21.4
40.6
64.4
61.3
73.4
31.4
76.4
56.2
48.0

0.0
47.5

56.7

81.1

69.0

85.3
45.1
59.2

47.2

76.2
54.5

20.7

18.1
10.2

%RSD
12.4
68.4
8.29

2.91
16.4
18.6
6.76
8.04
4.59
14.5
9.65
9.22
16.4

ND
30.3

5.94

10.3

6.73

7.04
12.7
8.06

16.0

5.72
11.1

24.5

26.7
20.3
(Eastern)
Avg.
%Rec.
43.8
50.5
34.8

49.2
12.9
22.3
41.5
54.8
68.7
22.9
75.4
23.2
55.1

0.0
42.2

61.9

88.9

41.1

58.9
15.2
49.3

33.8

67.3
39.4

12.6

6.95
7.17

* %RSD
2.25
70.0
16.3

14.6
49.5
29.1
13.1
16.4
11.3
39.3
4.02
11.5
9.72

ND
42.9

3.94

2.99

11.3

4.15
17.4
10.5

22.8

8.43
19.5

60.1

58.0
72.8
Sludge)
Avg.
%Rec.**
116.0
49.3
49.8

65.5
36.5
36.2
44.2
61.8
58.3 .
32.0
23.0
37.5
37.3

61.8
52.0

73.7

58.3

50.8

64.0
26.2
45.7

40.7

61.7
38.8

28.5

21.5
25.0


%RSD
11.5
44.9
36.7

37.2
51.5
41.4
32.0
29.1
33.3
54.4
119.8
36.1
31.2

37.7
37.4

31.3

32.6

31.5

25.7
44.0
35.2

40.6

28.0
40.9

34.0

67.8
61.0
Soil No. 4
(Western and
Sludge)
Avg.
%Rec.*** %RSD
21.3 71.4
51.8 4.6
33.4 41.1

73.0 13.9
21.3 31.5
24.0 34.0
33.0 24.9
45.8 38.6
41.2 37.8
16.8 26.4
11.0 115.5
27.2 28.6
42.0 17.6

76.0 12.2
37.3 16.6

40.6 39.0

39.8 40.3

36.8 23.8

53.6 15.8
18.6 24.2
31.4 37.2

26.2 38.8

46.4 25.4
25.6 34.1

19.8 33.9

15.3 24.8
11.8 25.4
  * Triplicate analyses
 ** Six replicate analyses
*** Five replicate analyses
                                         1312 - 27
Revision 0
September 1994

-------
  Motor
(30ฑ 2 rpm)
                    Extraction Vessel Holder
      Figure 1.  Rotary Agitation Apparatus
     Top Flange

  Support Screen
      Support Screen
        Vlton
 Bottom Flange—*{_
   Preuuriztd Gas -n
            VUv*
                       Liquid Into/Outlet Valve
                              Sample
                    x      "ซw     a
                               Gas
                               Pressure
                                QauQe
Figure 2.  Zero-Headspace Extractor  (ZHE)
                    1312 - 28
                                                  Revision 0
                                                  September 1994

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                          METHOD 1312

      SYNTHETIC PRECIPITATION  LEACHING  PROCEDURE
         Liquid
  Prepare filtrate
   according to
   appropriate
    methods.
 Analyze filtrate.
                         [     Start     )

                                   ~^
                               Select
                            representative
                               sample.
  Separate liquids
    from solids,
      filtrate
  becomes SPLP
      extract.
<0'5% ' Calculate \  >ฐ'5%
          % solids.
Separate liquids
  from solids.
           particle   N.  Ves
          reduction
          required?
f     Stop     J
                              Extract w/
                         appropriate fluid via:
                         1. Bottle extraction
                            for non-volatiles,
                         2. ZHE for volatiles.
                                        Reduce particle
                                       size to <9.5 mm.
                              o
                           1312  - 29
                                                Revision 0
                                                September  1994

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                          METHOD  1312

SYNTHETIC PRECIPITATION LEACHING PROCEDURE  (continued)
                           O

Discard
Solids
Solids

>
r
Separate liquids
from solids.
                                Extract
                              Is
                            extract
                          compatible
                          with initial
                            liquid
                            phase?
Prepare and analyze
    each liquid
    separately,
  mathematically
  combine results.
                        Combine extract
                        with liquid phase
                           of waste.
                                                       I
f      Stop    J
                        Prepare extract
                          according to
                          appropriate
                           methods.
                         Analyze extract.
                       f    Stop     J
                            1312  - 30
                  Revision  0
                  September 1994

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                                 METHOD 1320

                        MULTIPLE EXTRACTION PROCEDURE
1.0  SCOPE AND APPLICATION

     The Multiple  Extraction  Procedure  (MEP)   described  In  this method Is
designed to simulate the leaching  that  a  waste will  undergo from repetitive
precipitation of acid rain on  an  improperly designed sanitary landfill.  The
repetitive extractions reveal  the  highest  concentration of each constituent
that is likely to leach in  a  natural environment.  Method 1320 is applicable
to liquid, solid, and multiphase samples.


2.0  SUMMARY OF METHOD

     Waste  samples  are  extracted  according  to  the  Extraction  Procedure
Toxicity Test  (Method 1310, Chapter  8)  and  analyzed for the constituents of
concern listed in Chapter 7,  Table 7-1: Maximum Concentration of Contaminants
for Characteristic of EP  Toxicity,  using  the  7000 and 8000 series methods.
Then the solid portions of the samples that remain after application of Method
1310 are re-extracted nine times  using  synthetic acid rain extraction fluid.
If the concentration of any constituent  of  concern increases from the 7th or
8th extraction to the 9th  extraction,  the  procedure is repeated until these
concentrations decrease.
3.0  INTERFERENCES

     Potential interferences  that  may  be  encountered  during  analysis are
discussed in the appropriate analytical methods.


4.0  APPARATUS AND MATERIALS

     4.1  Refer to Method 1310.


5.0  REAGENTS

     5.1  Refer to Method 1310.

     5.2  Sulfuric acidtm'tric acid, 60/40 weight percent mixture:  Cautiously
mix 60 g of concentrated sulfuric acid with 40 g of concentrated nitric acid.


6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

     6.1  Refer to Method 1310.
                                   1320 -  1
                                                         Revision
                                                         Date  September 1986

-------
7.0  PROCEDURE

     7.1  Run the Extraction Procedure (EP) test 1n Method 1310.

     7.2  Analyze the extract for the constituents of interest.

     7.3  Prepare a synthetic acid rain  extraction  fluid by adding the 60/40
weight percent sulfuric  acid  and  nitric  acid  to distilled deionized water
until the pH is 3.0 + 0.2.

     7.4  Take the solid phase  of  the  sample remaining after the Separation
Procedure of the Extraction Procedure  and  weigh  it.   Measure an aliquot of
synthetic acid rain extraction fluid equal to 20 times the weight of the solid
sample.  Do not allow the solid sample to dry before weighing.

     7.5  Combine the solid  phase  sample  and  acid  rain  fluid in the same
extractor as used in the EP  and  begin  agitation.  Record the pH within 5-10
min  after agitation has been started.

     7.6  Agitate the mixture for  24  hr,  maintaining the temperature at 20-
40*C (68-104'F).  Record the pH at the end of the 24-hr extraction period.

     7.7  Repeat the Separation Procedure  as described in Method 1310.

     7.8  Analyze the extract for the constituents of concern.

     7.9  Repeat steps  7.4-7.8 eight additional times.

     7.10 If,  after  completing  the  ninth  synthetic   rain   extraction, the
concentration  of any of the  constituents  of   concern is increasing over that
found  in the  7th and 8th  extractions, then continue extracting with synthetic
acid rain until the concentration in the extract ceases to increase.

     7.11 Report  the   initial  and  final  pH  of  each  extraction  and  the
concentration  of each listed constituent of concern 1n each extract.


8.0  QUALITY  CONTROL

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

     8.2  Employ a minimum  of  one  blank per sample   batch  to determine  1f
contamination  or any memory effects  are occurring.

     8.3  All  quality control measures  suggested  1n the  referenced analytical
methods should be followed.
                                   1320 - 2
                                                          Revision
                                                          Date   September 1986

-------
9.0  METHOD PERFORMANCE
     9.1  No data provided.

10.0  REFERENCES
     10.1  None required.
                                   1320 - 3
                                                         Revision
                                                         Date  September 1986

-------
                                     METHOD 1330

                             MULTIPLE EXTRACTION PROCEDURE
CEO            O
  7.1
  Run extraction
  procedure test
  (Method 1310)
  7.2
                          o
                         7.5
       Combine
     G agitate
    BO lid phase
sample and acid
   rain fluid:
    record pH
  Analyze metale
   according to
      Table l
  7.3
                                               7.7
      Repeat
    separation
    procedure
  (Method 1310)
      Agitate
 mixture for 24
 hre; record pH
    at end.
       Prepare
    nthetic acid
    n extraction
      fluid
                                               7.8
      Analyze
    extract  for
   conatltuente
    of concern
   0
 7.9  |


 Repeat 8 times
 	1  weigh
     solid phase
     of sample;
    oeasure acid
 rain extraction
   o
    o
Is concentr. of
Sth extraction >
  the 7th and
     8th?
                        7.11
                              Report
                             initial
                           •nd final
                          extraction
                       pH and concetr.
                       of constituents

-------
                                 METHOD 1330A
                     EXTRACTION PROCEDURE FOR OILY WASTES

1.0  SCOPE AND APPLICATION
      1.1    Method  1330  is used to determine the  mobile  metal  concentration
(MMC) in oily wastes.
      1.2    Method  1330 is applicable to API  separator sludges, rag oils, slop
oil emulsions, and other oil wastes derived from petroleum refining.
2.0  SUMMARY OF METHOD
      2.1    The  sample  is separated  into  solid  and  liquid components  by
filtration.
      2.2    The  solid  phase is placed  in  a Soxhlet extractor,  charged with
tetrahydrofuran,  and extracted.   The  THF  is removed,  the extractor  is then
charged with toluene, and the sample is reextracted.
      2.3    The  EP  method  (Method 1310)  is run on the dry solid residue.
      2.4    The  original  liquid,  combined  extracts,  and  EP  leachate  are
analyzed for the  EP metals.
3.0  INTERFERENCES
      3.1    Matrix  interferences  will  be  coextracted  from the sample.   The
extent  of  these  interferences  will  vary considerably  from  waste to  waste,
depending on the  nature and diversity of the particular refinery  waste being
analyzed.
4.0  APPARATUS AND MATERIALS
      4.1    Soxhlet extraction apparatus.
      4.2    Vacuum  pump or other source  of vacuum.
      4.3    Buchner funnel 12.
      4.4    Electric heating mantle.
      4.5    Paper extraction thimble.
      4.6    Filter  paper.
      4.7    Muslin  cloth disks.
      4.8    Evaporative flask - 250-mL.
      4.9    Balance -  Analytical, capable of weighing to ฑ 0.5 mg.

                                   1330A  - 1                       Revision 1
                                                                  July 1992

-------
5.0  REAGENTS

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

      5.3    Tetrahydrofuran, C4H80.

      5.4    Toluene, C6H5CH3.

6.0  SAMPLE COLLECTION,  PRESERVATION,  AND HANDLING

      6.1    Samples must be collected  in glass containers having a total volume
of at least 150 mL.   No  solid material  should  interfere with sealing the sample
container.

      6.2    Sampling  devices  should  be  wiped clean  with paper  towels  or
absorbent cloth, rinsed  with  a small  amount of hexane followed by acetone rinse,
and dried between samples.   Alternatively,  samples can be taken with disposable
sampling devices in beakers.

7.0  PROCEDURE

      7.1    Separate the  sample (minimum 100 g)  into  its  solid  and  liquid
components. The liquid component is  defined as that  portion of the sample which
passes through a 0.45 ium filter media under a pressure differential  of 75 psi.

      7.2    Determine the quantity  of liquid (mL) and the concentration of the
toxicants of concern in the liquid phase (mg/L).

      7.3    Place  the  solid  phase   into  a  Soxhlet  extractor,  charge  the
concentration flask with 300 mL tetrahydrofuran, and extract for 3 hours.

      7.4    Remove the flask containing tetrahydrofuran and replace  it with one
containing 300 mL toluene.

      7.5    Extract the solid a second time, for 3 hours,  with the toluene.

      7.6    Combine the tetrahydrofuran and toluene extracts.

      7.7    Analyze the combined extracts for the toxicants of concern.

      7.8    Determine the quantity  of liquid (mL) and the concentration of the
toxicants of concern in the combined extracts (mg/L).

      7.9    Take the solid  material remaining  in the Soxhlet  thimble and  dry
it at 100ฐC for 30 minutes.
                                   1330A  - 2                       Revision 1
                                                                  July 1992

-------
      7.10   Run the EP  (Method 1310) on the dried solid.
      7.11   Calculate the mobile  metal  concentration  (MMC)  in mg/L using the
following formula:
               MMC = 1,000 x
                              (Li + L2 +  L3)
             where:
             Q, =     Mass of toxicant in initial liquid phase of sample (amount
                      of liquid  x concentration  of toxicant)  (mg).
             Q2 =     Mass of toxicant in combined  organic  extracts of sample
                      (amount  of liquid x concentration of toxicant) (mg).
             Q3 =     Mass of toxicant in EP extract of solid (amount of extract
                      x concentration  of  toxicant) (mg).
             L1 =     Volume of  initial liquid  (ml).
             L, =     Volume of  liquid in  THF  and toluene extract  (Step 7.8)
                      (ml).
             L3 =     Volume of  liquid in EP  (mL)  = 20  x [weight of  dried solid
                      from Step  7.9 (g)].
8.0  QUALITY CONTROL
      8.1    Any  reagent  blanks or replicates  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.
9.0  METHOD PERFORMANCE
      9.1    No data provided.
10.0  REFERENCES
1.    Rohrbough,  W.G.; et  al .  Reagent  Chemicals,  American Chemical  Society
Specifications. 7th ed.; American Chemical Society: Washington, DC,  1986.
2.    1985 Annual  Book  of ASTM Standards.  Vol. 11.01; "Standard Specification for
Reagent Water"; ASTM:  Philadelphia, PA,   1985; D1193-77.
                                   1330A  -  3                       Revision 1
                                                                  July 1992

-------
     Figure  1.   Extractor
                   4.0
                   1
                                       9.0
     Non-Clogging  Support  Bushing

1-Inch Blade at 30' to Horizontal
         1330A - 4
Revision 1
July 1992

-------
                                                                  2-Liter Plastic or Glass Bottles
                      1/15-Horsepower Electric Motor
  co
  co
   I

  en
                                                              Screws for Holding Bottles
                                                                                                                             -I


                                                                                                                             ro
                                                                                                                             ft)
-J
O>
r>
€•ป•
o
-5
*< •JB
   i/i
•—• -••
to o
ซO 3
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-------
                                        Figure 3.   EPRI  Extractor
        l-Gallon Plastic
        or Glass Bottle
Totally Enclosed
Fan Cooled Motor
30 rpm, 1/8 HP
                                                               	.     Fฐam Bonded to Cover
 Box Assembly
 Plywood Construction
                                                1330A - 6
Revision  1
July 1992

-------
Figure 4.   Compaction Tester
                                                 m   Combined Weight
                                                    0.33 kg (0.73 Ib)
                                              3.15 cm
                                              (1.25")
                                               Sample
                                                   Elastomeric
                                                   Sample Holder
                                  3.3 c
                                  (1.3"
                                                    t
                                                   7.1cm
                                                   (2.8")
                                                 J.
           1330A - 7
Revision  1
July  1992

-------
               METHOD  1330A
EXTRACTION  PROCEDURE  FOR  OILY WASTE
   (      START       J
    7.1 Separate  sample
      into liquid and
      •olid phases
   7.8 Determine
quantity of liquid
 and  concentration
  of  toxicant* in
 combined extracts
      7.2 Determine
    quantity of liquid
     and concentration
      of toxicants in
      liquid phase
 7.9  Remove solids
 from thimble and
       dry
      7.3 Place solid
    phase in extractor,
       add THF to
      concentration
    flask, extract for
         3 hours
7.10  Run EP (1310)
  on  dried solids  .
-7.4 Replace THF
flask Kith toluene
concentration flask
1
7.5-7.7 Extract for
3 hours; combine
extracts; analyze
combined extracts
7.11 Calculate
mobile metal
concentration

( STOP J

                 1330A -  8
                               Revision  1
                               July  1992

-------
                                 METHOD 9040A

                         pH ELECTROMETRIC MEASUREMENT
1.0  SCOPE AND APPLICATION

      1.1    Method 9040 is used to measure the pH of aqueous wastes and those
multiphase wastes where the aqueous phase  constitutes  at least 20% of the total
volume of the waste.

      1.2    The corrosivity of concentrated acids and bases,  or of concentrated
acids  and  bases  mixed with  inert substances, cannot  be measured.    The  pH
measurement requires some water content.

2.0   SUMMARY

      2.1    The pH of the sample  is determined electrometrically using either
a glass  electrode  in  combination with a  reference potential  or  a combination
electrode.    The measuring  device  is  calibrated  using  a series of  standard
solutions of known pH.

3.0   INTERFERENCES

      3.1    The  glass  electrode, in  general,   is  not  subject to  solution
interferences from color, turbidity, colloidal matter, oxidants, reductants, or
moderate (<0.1 molar solution) salinity.

      3.2    Sodium error at pH levels >10 can be reduced or eliminated by using
a low-sodium-error electrode.

      3.3    Coatings  of  oily  material   or  particulate  matter  can  impair
electrode response.  These coatings can usually be removed by gentle wiping or
detergent washing,  followed  by rinsing with  distilled  water.   An  additional
treatment with hydrochloric acid (1:10) may be necessary to remove any remaining
film.

      3.4    Temperature effects on the electrometric  determination of pH arise
from two sources.   The first  is  caused  by the change in electrode  output at
various temperatures.   This interference should be controlled with instruments
having temperature compensation or by calibrating the electrode-instrument system
at the temperature of  the samples.   The second source of temperature effects is
the change  of pH due to changes in  the sample as the temperature changes.  This
error is sample-dependent and  cannot be controlled.   It  should,  therefore,  be
noted by reporting both the pH and temperature at  the time of analysis.

4.0   APPARATUS AND MATERIALS

      4.1    pH meter:  Laboratory or field model.  Many instruments are commer-
cially available with  various specifications and optional  equipment.

      4.2    Glass electrode.
                                   9040A  -  1                       Revision 1
                                                                  September 1994

-------
      4.3    Reference electrode:  A silver-silver chloride or other reference
electrode of constant potential may be used.

             NOTE:  Combination  electrodes  incorporating  both  measuring  and
             referenced functions are convenient to use and are  available with
             solid, gel-type filling materials that require minimal maintenance.

      4.4    Magnetic stirrer  and Teflon-coated stirring  bar.

      4.5    Thermometer and/or temperature sensor for automatic compensation.

5.0   REAGENTS

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

      5.2    Primary  standard  buffer  salts are available  from  the National
Institute of Standards and Technology  (NIST)  and should  be  used in situations
where extreme accuracy is  necessary.   Preparation  of reference solutions from
these  salts requires  some  special  precautions and  handling,  such as  low-
conductivity dilution water, drying ovens,  and  carbon-dioxide-free purge gas.
These solutions should be replaced at least once each month.

      5.3    Secondary  standard  buffers  may  be  prepared  from  NIST  salts  or
purchased as solutions from  commercial  vendors.  These  commercially available
solutions  have been  validated  by  comparison  with  NIST  standards and  are
recommended for routine use.

6.0   SAMPLE COLLECTION,  PRESERVATION,  AND HANDLING

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

      6.2    Samples should be analyzed as soon as possible.     ^

7.0   PROCEDURE

      7.1    Calibration:

             7.1.1    Because of the wide  variety of pH meters and accessories,
      detailed operating procedures cannot  be incorporated into this  method.
      Each  analyst must  be acquainted with the  operation of each  system  and
      familiar with all  instrument functions.  Special attention  to care of the
      electrodes is recommended.

             7.1.2    Each  instrument/electrode system must  be calibrated at a
      minimum of two  points that bracket the expected pH of the samples and are
      approximately three pH  units or more apart.   (For corrosivity characteri-
      zation, the calibration of the pH meter should include  a  buffer  of pH 2
      for  acidic  wastes and  a pH  12  buffer  for  caustic  wastes.)    Various

                                  9040At- 2                       Revision  1
                                                                  September 1994

-------
      instrument  designs  may   involve   use   of   a  dial   (to  "balance"  or
      "standardize") or a  slope  adjustment,  as outlined in the manufacturer's
      instructions.  Repeat adjustments on successive portions of the two buffer
      solutions until readings are within 0.05 pH units of the buffer solution
      value.

      7.2    Place the sample or buffer solution in a clean glass beaker using
a sufficient volume to cover  the  sensing elements of the electrodes and to give
adequate clearance for  the magnetic stirring bar.   If  field measurements are
being made, the electrodes  may be immersed directly into  the sample stream to an
adequate depth and moved in a manner to ensure sufficient sample movement across
the electrode-sensing element as indicated by drift-free readings (<0.1 pH).

      7.3    If the sample temperature differs by more than 2ฐC from the buffer
solution, the measured pH  values must  be  corrected.  Instruments  are equipped
with automatic or  manual compensators that electronically adjust for temperature
differences.  Refer to manufacturer's instructions.

      7.4    Thoroughly rinse and gently wipe the electrodes  prior to measuring
pH of samples.  Immerse the electrodes into the sample beaker or sample stream
and gently  stir at a constant rate to provide homogeneity  and  suspension of
solids.   Note and record  sample pH and  temperature.  Repeat  measurement on
successive aliquots of sample until values differ by <0.1 pH units.  Two or three
volume changes are usually sufficient.

8.0   QUALITY CONTROL

      8.1    Refer to Chapter One for the appropriate QC protoc'ols.

      8.2    Electrodes must be thoroughly rinsed  between  samples.

9.0   METHOD PERFORMANCE

      9.1    Forty-four analysts in twenty laboratories analyzed six synthetic
water samples containing exact increments  of hydrogen-hydroxyl  ions,  with the
following results:
                                                      	Accuracy as	
                      Standard Deviation               Bias         .   Bias
pH Units                   pH Units                      %             pH Units
   3.5
   3.5
   7.1
   7.2
   8.0
   8.0
0.10
0.11
0.20
0.18
0.13
0.12
-0.29
-0.00
+1.01
-0.03
-0.12
+0.16
-0.01

+0.07
-0.002
-0.01
+0.01
10.0 REFERENCES

1.    National Bureau of Standards, Standard Reference Material Catalog 1986-87,
      Special Publication 260.
                                   9040A  -  3
                                     Revision 1
                                     September 1994

-------
          METHOD  9040A
pH  ELECTROMETRIC MEASUREMENT
           7.1 Calibrate pH
               meter.
           7.2 Place sample
           or buffer solution
           in glass beaker.
              7.3 Does
             temperature
            differ by more
            than 2C from
               buffer?
 7.3 Correct
measured pH
  values.
             7.4 Immeroe
             electrodes and
             measure pH of
               sample.
          7.4 Note and record
          pH and temperature;
          repeat 2 or 3 times
             with different
               aliquots.
            9040A -  4
           Revision  1
           September 1994

-------
                                 METHOD 9041A

                                oH  PAPER METHOD
1.0  SCOPE AND APPLICATION
      1.1    Method 9041 may be used to measure pH as an alternative to Method
9040 (except as noted in Step 1.3) or in cases where pH measurements by Method
9040 are not possible.

      1.2    Method 9041  is not applicable to wastes  that  contain components
that may mask or alter the pH paper color change.

      1.3    pH  paper  is  not  considered  to  be  as  accurate  a  form of  pH
measurement as pH meters.   For  this  reason,  pH measurements taken with Method
9041 cannot be used to  define a waste as corrosive  or noncorrosive (see RCRA
regulations 40 CFR ง261.22(a)(l).

2.0  SUMMARY OF METHOD

      2.1    The approximate pH  of the waste  is  determined  with wide-range pH
paper.  Then a more accurate  pH  determination  is made using "narrow-range" pH
paper whose accuracy has been determined (1) using a series of buffers or (2) by
comparison with a calibrated pH meter.

3.0  INTERFERENCES

      3.1    Certain wastes may inhibit or mask changes in the pH paper.  This
interference can  be determined by adding small amounts of acid or base to a small
aliquot of the waste and observing whether the pH paper undergoes the appropriate
changes.

CAUTION:     THE ADDITION  OF ACID  OR BASE  TO WASTES  MAY  RESULT  IN  VIOLENT
             REACTIONS  OR  THE  GENERATION  OF TOXIC  FUMES  (e.g..  hydrogen
             cyanide).   Thus,  a decision  to  take  this  step requires  some
             knowledge of the waste.  See Step 7.3.3 for additional precautions.

4.0  APPARATUS AND MATERIALS

      4.1    Wide-range pH paper.

      4.2    Narrow-range pH paper:   With  a  distinct  color change for every 0.5
pH unit  (e.g., Alkaacid  Full-Range  pH Kit, Fisher Scientific  or equivalent).
Each batch  of narrow-range pH  paper must  be  calibrated versus  certified  pH
buffers or by comparison with a pH meter which has been calibrated with certified
pH buffers.  If the incremental  reading of the narrow-range pH paper is within
0.5 pH units,  then the agreement between the buffer or the calibrated pH meter
with the paper must be within 0.5 pH units.

      4.3    pH Meter (optional).
                                   9041A  -  1                       Revision 1
                                                                  July 1992

-------
5.0  REAGENTS

      5.1    Certified pH buffers:  To be used for calibrating the pH paper or
for calibrating the pH meter that will  be used subsequently to calibrate the pH
paper.

      5.2    Dilute acid (e.g..  1:4 HC1).

      5.3    Dilute base (e.g..  0.1 N NaOH).

6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

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

7.0  PROCEDURE

      7.1    A  representative  aliquot  of the waste must be  tested with wide-
range pH paper to determine the approximate pH.

      7.2    The  appropriate  narrow-range  pH paper is chosen and  the  pH of a
second aliquot of the  waste  is determined.  This measurement should be performed
in duplicate.

      7.3    Identification of interference:

             7.3.1    Take  a third aliquot  of the waste,  approximately 2 mL in
      volume, and  add acid  dropwise until  a pH change is observed.   Note the
      color change.

             7.3.2    Add base dropwise to  a fourth aliquot  and  note the color
      change.   (Wastes  that have a buffering capacity may  require additional
      acid or base to result in a measurable pH change.)

             7.3.3    The observation of the appropriate color change is a strong
      indication that no interferences have occurred.

CAUTION      ADDITION OF ACID OR  BASE TO SAMPLES MAY RESULT IN VIOLENT REACTIONS
             OR THE GENERATION OF TOXIC FUMES.  PRECAUTIONS MUST BE TAKEN.  THE
             ANALYST  SHOULD PERFORM THESE TESTS IN A WELL-VENTILATED HOOD WHEN
             DEALING  WITH UNKNOWN SAMPLES.

8.0  QUALITY CONTROL

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

      8.2    All pH determinations must be performed in duplicate.

      8.3    Each  batch of pH  paper must  be  calibrated  versus  certified pH
buffers or a pH meter which has been calibrated with certified pH buffers.
                                   9041A  -  2                       Revision 1
                                                                  July 1992

-------
9.0  METHOD PERFORMANCE
      9.1    No data provided.
10.0  REFERENCES
      10.1   None required.
                                   9041A  - 3                       Revision 1
                                                                  July 1992

-------
   METHOD 9041A

 pH PAPER  METHOD



       START
   7.1  Determine
approximate pH with
•ide-range pH paper
    7.2  Select
    appropriate
  narrov range pH
paper; determine pH
in duplicate on 2nd
      aliquot
  7.3.1 Using 3rd
 aliquot, add acid
 to Haste until pH
changes; note color
      change
 7.3.2  Add base to
 4th aliquot; note
   color change
7.3.3  Determine if
interferences have
     occurred
      STOP
     9041A  - 4
Revision  1
July  1992

-------
                                 METHOD 9045B

                               SOIL AND WASTE pH
1.0   SCOPE AND APPLICATION
      1.1    Method 9045  is  an electrometric procedure for measuring pH  in
soils and waste samples.  Wastes may be solids, sludges, or non-aqueous
liquids.  If water is present, it must constitute less than 20% of the total
volume of the sample.

2.0   SUMMARY OF METHOD

      2.1    The sample is mixed with reagent water, and the pH of the
resulting aqueous solution is measured.

3.0   INTERFERENCES

      3.1    Samples with very low or very high pH may give incorrect
readings on the meter.  For  samples with a true pH of >10, the measured pH may
be incorrectly low.  This error can be minimized by using a low-sodium-error
electrode.  Strong acid solutions, with a true pH of <1, may give incorrectly
high pH measurements.

      3.2    Temperature fluctuations will cause measurement errors.

      3.3    Errors will occur when the electrodes become coated.  If an
electrode becomes coated with an oily material  that will not rinse free, the
electrode can (1) be cleaned with an ultrasonic bath, or (2) be washed with
detergent, rinsed several  times with water, placed in 1:10 HC1 so that the
lower third of the electrode is submerged, and then thoroughly rinsed with
water, or (3) be cleaned per the manufacturer's instructions.

4.0   APPARATUS AND MATERIALS

      4.1    pH Meter with means for temperature compensation.

      4.2    Glass Electrode.

      4.3    Reference electrode:  A silver-silver chloride or other
reference electrode of constant potential  may be used.

             NOTE:  Combination electrodes incorporating both measuring and
             referenced functions are convenient to use and are available
             with solid, gel-type filling materials that require minimal
             maintenance.

      4.4    Beaker:  50-mL.

      4.5    Thermometer and/or temperature sensor for automatic
compensation.

      4.6    Analytical balance:  capable of weighing 0.1 g.

                                  9045B -  1                     Revision 2
                                                                September 1994

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5.0   REAGENTS

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

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

      5.3    Primary standard buffer salts are available from the National
Institute of Standards and Technology (NIST)  and should be used in situations
where extreme accuracy is necessary.  Preparation of reference solutions from
these salts requires some special precautions and handling, such as low-
conductivity dilution water, drying ovens, and carbon-dioxide-free purge gas.
These solutions should be replaced at least once each month.

      5.4    Secondary standard buffers may be prepared from NIST salts or
purchased as solutions from commercial  vendors.   These commercially available
solutions, which have been validated by comparison with NIST standards, are
recommended for routine use.

6.0   SAMPLE PRESERVATION AND HANDLING

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

      6.2    Samples should be analyzed as soon as possible.

7.0   PROCEDURE

      7.1    Calibration:

             7.1.1   Because of  the wide  variety  of  pH meters  and
      accessories, detailed operating procedures cannot be incorporated into
      this method.  Each analyst must be acquainted with  the operation of each
      system and familiar with  all  instrument-functions.   Special  attention to
      care of the electrodes is recommended.

             7.1.2   Each  instrument/electrode  system must  be  calibrated  at  a
      minimum of two points that bracket the  expected pH  of the samples and
      are approximately three pH units  or more apart.  Repeat adjustments on
      successive portions of the two buffer solutions until  readings are
      within 0.05 pH units of the buffer solution value.

      7.2    Sample preparation and pH measurement of soils:

             7.2.1   To  20 g of  soil in a  50-mL beaker, add  20 mL of  reagent
      water, cover,  and continuously stir the suspension  for 5 minutes. .
                                       9045B  -  2                 Revision 2
                                                                September 1994

-------
Additional dilutions are allowed if working with hygroscopic soils and
salts or other problematic matrices.

       7.2.2    Let the soil  suspension  stand for about 1  hour  to allow
most of the suspended clay to settle out from the suspension or filter
or centrifuge off the aqueous phase for pH measurement.

       7.2.3    Adjust  the  electrodes  in the  clamps  of the electrode
holder so that, upon lowering the electrodes into the beaker, the glass
electrode will be immersed just deep enough into the clear supernatant
solution to establish a good electrical  contact through the ground-glass
joint or the fiber-capillary hole.  Insert the electrodes into the
sample solution in this manner.  For combination electrodes, immerse
just below the suspension.

       7.2.4    If the  sample temperature differs by more  than  2ฐC from
the buffer solution, the measured pH values must be corrected.

       7.2.5    Report  the  results  as  "soil pH measured in water  at 	
ฐC" where "	ฐC" is the temperature at which the test was conducted.

7.3    Sample preparation and pH measurement of waste materials:

       7.3.1    To 20 g of  waste  sample  in a  50-mL beaker,  add  20 ml  of
reagent water, cover,  and continuously stir the suspension for 5
minutes.  .  Additional  dilutions are allowed if working with hygroscopic
wastes and salts or other problematic matrices.

       7.3.2    Let the waste suspension stand for about 15 minutes to
allow most of the suspended waste to settle out from the suspension or
filter or centrifuge off aqueous phase for pH measurement.

       NOTE:  If the waste is hygroscopic and absorbs all the reagent
       water, begin the experiment again using 20 g of waste and 40 mL
       of reagent water.

       NOTE:  If the supernatant is multiphasic, decant the oily phase
       and measure the pH of the aqueous phase.  The electrode may need
       to be cleaned (Step 3.3) if it becomes coated with an oily
       material.

       7.3.3    Adjust  the  electrodes  in the  clamps  of the  electrode
holder so that,  upon lowering the electrodes  into the beaker, the glass
electrode will be immersed  just deep enough into the clear supernatant
to establish good electrical  contact through  the ground-glass joint or
the fiber-capillary hole.   Insert the electrode into the sample solution
in this manner.   For combination electrodes,  immerse just below the
suspension.

       7.3.4    If the  sample temperature  differs  by more  than  2ฐC  from
the buffer solution, the measured pH values must be  corrected.

       7.3.5    Report  the  results  as  "waste  pH measured  in  water  at  	
ฐC" where "	ฐC" is the temperature at which  the test was conducted.

                             9045B  - 3                 Revision  2
                                                      September 1994

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8.0   QUALITY CONTROL
      8.1    Refer to Chapter One for the appropriate QC protocols.
      8.2    Electrodes must be thoroughly rinsed between samples.
9.0   METHOD PERFORMANCE
      9.1    No data provided.
10.0  REFERENCES
1.    Black, Charles Allen;  Methods of Soil  Analysis;  American Society of
      Agronomy:  Madison, WI, 1973.
2.    National  Bureau of Standards,  Standard Reference Material Catalog, 1986-
      87, Special  Publication 260.
                                  9045B - 4                 Revision 2
                                                            September 1994

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                                             METHOD 9045B

                                          SOIL  AND  WASTE pH
                                  Start
                                    J
                               7.1 Calibrate
                             each instrument/
                                electrode
                                 system.
 7.2.1 Add 20 mL
water to 20 g soil;
 stir continuously
  for 5 minutes.
                            Is the
                          sample soil
                          or waste?
  7.3.1 Add 20 mL
water to 20 g waste;
  stir continuously
   for 5 minutes.
  7.2.2 Let soil
   suspension
   stand for 1
  hour or filter.
                                                      7.3.2 Let waste
                                                        suspension
                                                       stand for 15
                                                     minutes or filter.
                                       Insert
                                     electrodes
                                    into sample
                                     solution.
                                        Do
                                      sample
                                     and buffer
                                    sol'n temps
                                      vary by
                                        2C?
  Correct
measured pH
  values.
                                      Report
                                     results and
                                    temperature
                                                            Is
                                                        supernatant
                                                       multiphasic?
                                                                                     Repeat experiment
                                                                                      with 20 g waste
                                                                                      and 40 mL water.
                               Decant oily
                                 phase;
                              measure pH of
                             aqueous phase.
                                                                                              Aqueous
                                                                                               Phase
                                               9045B -  5
                                                                          Revision 2
                                                                          September 1994

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                                 METHOD 9050

                            SPECIFIC CONDUCTANCE
1.0  SCOPE AND APPLICATION

     1.1  Method 9050 1s used to measure the specific conductance of drinking,
ground, surface, and saline waters and domestic and Industrial  aqueous wastes.
Method 9050 1s not applicable to solid samples.


2.0  SUMMARY OF METHOD

     2.1  The specific conductance  of  a  sample  1s  measured  using a self-
contained conductivity meter (Wheatstone bridge-type or equivalent).

     2.2  Whenever possible, samples are  analyzed  at  25*C.   If samples are
analyzed at different temperatures,  temperature  corrections must be made and
results reported at 25*C.


3.0  INTERFERENCES

     3.1  Platinum electrodes can  degrade  and  cause  erratic results.  When
this happens, as evidenced by erratic  results  or flaking off of the platinum
black, the electrode should be replatlnlzed.

     3.2  The specific conductance cell can  become  coated with oil and other
materials.  It  1s  essential  that  the  cell  be  thoroughly  rinsed and, 1f
necessary, cleaned between samples.


4.0  APPARATUS AND MATERIALS

     4.1  Self-contained conductivity instruments;    an Instrument consisting
of a source of alternating current, a Wheatstone bridge, null Indicator, and a
conductivity cell  or  other  instrument  measuring  the  ratio of alternating
current through the cell to voltage  across  1t.  The latter has the advantage
of a   linear  reading  of  conductivity.    Choose  an  Instrument  capable of
measuring conductivity with an error not  exceeding IX or 1 umho/cm, whichever
is greater.


          Platinum-electrode  or   non-platinum-electrode  specific conductance


          Water bath.

     4.4  Thermometer;   capable   of  being  read  to  the  nearest  O.TC and
covering  the  range 23*   to  27*C.    An  electrical thermometer having  a small
thermistor sensing element  1s convenient because of Its rapid response.


                                   9050 - 1
                                                         Revision       0
                                                         Date  September 1986

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5.0  REAGENTS

     5.1  Conductivity  water;    Pass  distilled  water  through  a mixed-bed
deionizer and discard first1,000  ml.    Conductivity  should be less than 1
umho/cm.

     5.2  Standard potassium chloride  (0.0100 M):  Dissolve 0.7456 g anhydrous
KC1 in conductivity water and make up to 1,000 ml at 25*C.  This solution will
have a specific conductance of 1,413 umho/cm at 25*C.


6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

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

     6.2  All sample containers must be  prewashed and thoroughly rinsed. Both
plastic and glass containers are  suitable.

     6.3  Aqueous samples should  be stored at 4*C and analyzed within 24 hr.


7.0  PROCEDURE

     7.1  Determination of cell   constant;    Rinse  conductivity cell with at
least three portions of 0.01 NKClsolution.  Adjust temperature of a fourth
portion to  25.0  +  0.1'C.    Measure  resistance  of  this  portion and note
temperature.  Compute cell constant, C:


          c = (o.001413)(Rซci) i  + 0.0191  (t - 25)

          where:

                 RKCI = measured  resistance, ohms; and

                 t = observed temperature, *C.


     7.2  Conductivity measurement;  Rinse cell  with  one or more portions of
sample.   Adjust temperatureofa  final  portion  to  25.0 + 0.1'C.  Measure
sample  resistance or conductivity and  note temperature.

     7.3  Calculation;  The  temperature   coefficient  of most waters is only
approximately thesame   as  that of   standard  KCl   solution;   the  more  the
temperature of measurement deviates  from  25.0*C, the greater the uncertainty
in applying the temperature  correction.  Report  all conductivities at 25.0*C.
                                   9050 - 2
                                                          Revision
                                                          Date  September 1986

-------
          7.3.1   When  sample  resistance  is measured,  conductivity  at  25*C  is


                        (l.OOO.OOOHC)
               K =
               where:
                       1 + 0.0191  (t -  25)
                    K = conductivity,  umho/cm;
                    C = cell  constant,  cm-L;
                    Rm = measured resistance  of sample,  ohms;  and
                    t = temperature of measurement.

          7.3.2  When sample conductivity  is  measured,  conductivity at 25'C
     is:

                        1,000, ooo) (c)
               *   1 + 0.0191 (t - 25)


               where:

                     Km = measured conductivity, umho at  t*C, and other units
                          are defined as above.

     NOTE:  If conductivity readout is in umho/cm, delete the factor 1,000,000
            1n the numerator.
8.0  QUALITY CONTROL

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

     8.2  Analyze check standards after approximately every 15 samples.

     8.3  Run 1 duplicate sample for every 10 samples.


9.0  METHOD PERFORMANCE

     9.1  Three synthetic samples were tested with the following results:

Conduc-
tivity
umho s/ cm
147.0
303.0
228.0


No. of
Results
117
120
120
Relative
Standard
Deviation
%
8.6
7.8
8.4

Relative
Error
%
9.4
1.9
3.0
                                  9050 - 3
                                                         Revision
                                                         Date  September 1986

-------
10.0  REFERENCES

1.  Standard Methods for the  Examination of Water and Wastewater,  16th ed.
(1985),  Method 205.
                                  9050 - 4
                                                         Revision
                                                         Date  September 1986

-------
     METHOD 9OSO

SPECIFIC CONDUCTANCE
7. 1
r
and tt
solut
eel
Measure
•esistance
;mp of KC1
on: cole.
1 constant
7.2
res
cor
<
ten
Measure
cample
ictance or
iductivity
ind note
nperetufe
    7.3
       Calculate
        •ample
      conductivity
       at 25 "C
  f      Stop      J
9050 - 5
                          Revision       o
                          Date  September  1986

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                                 METHOD 9080

            CATION-EXCHANGE CAPACITY OF SOILS (AMMONIUM ACETATE)


1.0  SCOPE AND APPLICATION

     1.1  Method 9080 1s  used  to  determine  the cation-exchange capacity of
soils.  The method Is  not  applicable to soils containing appreciable amounts
of verm1cul1te clays,  kaolin,  halloyslte,  or  other l:l-type clay minerals.
They should be analyzed  by  the  sodium  acetate  method (Method 9081).  That
method (9081) 1s  also  generally  the  preferred  method  for very calcareous
soils.  For distinctly acid  soils,  the cation-exchange capacity by summation
method (Chapman, p. 900; see Paragraph 10.1) should be employed.


2.0  SUMMARY

     2.1  The soil 1s mixed with an  excess  of 1 N ammonium acetate solution.
This results in an exchange  of  the ammonium cations for exchangeable cations
present 1n the soil.    The  excess  ammonium  is  removed,  and the amount of
exchangeable ammonium 1s determined.


3.0  INTERFERENCES

     3.1  Soils containing appreciable  vermiculite clays, kaolin, halloyslte,
or other l:l-type clay  minerals  will  often  give  lower values for exchange
capacity.  See Paragraph 1.1 above.

     3.2  With calcareous soils,   the  release  of  calcium carbonate from the
soil Into the  ammonium acetate   solution   limits  the  saturation of exchange
sites  by the ammonium ion.     This  results  in artificially low  cation-exchange
capacities.


4.0  APPARATUS AND MATERIALS

     4.1  Erlenmeyer flask;   500-mL.

     4.2  Buchner funnel or equivalent:   55-mm.

     4.3  Sieve;   2-mm.

     4.4  Aeration apparatus  (assembled as  in Figure  1):

          4.4.1   Kjeldahl flask:   800-mL.

          4.4.2   Erlenmeyer flask:  800-mL.

          4.4.3   Glass  wool filter.
                                   9080 - 1
                                                          Revision
                                                          Date  September  1986

-------
                                                                   to Next Unit
         From Air Scrubbers
                                        Soil Sample
                                        Plus 150 ml.
                                        5% Na2C03
                                        and
                                        Few Drops
                                        Paraffin Oil
                                                                                Suction
                                                                    (Aeration Rate of
                                                                    450 to 500 Liters
                                                                    Per Hour)
                                                                   Orifice
                                                                   in Glass
                                                                   Tube
500-ml
Wide Mouth
Erlenmeyer
Flask

  N/10
  in 100 ml
  Water
     Figure 1.  Diagram of aeration unit for determination of absorbed ammonia. Six to twelve
such units is a convenient number for routine work; they can be mounted on a portable rack.
(Apparatus as modified by Dr. A. P. Vanselow, Dept. of Soils & Plant Nutrition,  Univerity of
California, Riverside, Calif.).
                                    9080  - 2
                                                                Revision       p
                                                                Date  September  1986

-------
          4.4.4  Glass  tubing.

          4.4.5  Flow meter.
5.0  REAGENTS

     5.1  Ammonium acetate  (N^OAc),  1  N:    Dilute  114 ml of glacial  acetic
acid (99.5%)  with water to  a  volume of approximately 1 liter.  Then add  138 mL
of concentrated ammonium hydroxide  (NffyOH) and add water to obtain a volume of
about 1,980 ml.  Check the  pH   of  the resulting solution, add more NfyOH, as
needed, to obtain a pH of 7,  and dilute  the solution to a volume of 2  liters
with water.

     5.2  Isopropyl alcohol;  99%.

     5.3  Ammonium chloride (NfyCl),  1 N:   Dissolve  53.49 g of NfyCl  in Type
II water, adjust the pH to  7.0  with NfyOH, and dilute to 1 L.

     5.4  Ammonium chloride (NfyCl),  0.25  N:    Dissolve  13.37 g of N^Cl in
Type II water,  adjust the pH  to 7.0 with NfyOH, and dilute to 1 L.
     5.5  Ammonium oxalate ((NfyJ^OV^O), 10%:  Add  90 mL of Type II water
to 10 g of ammonium oxalate ((Nf^) 2^2ฐ4 '^O) and mix well.
     5.6  Dilute ammonium hydroxide   (NH/jOH):    Add  1 volume of concentrated
NH40H to an equal volume of water.
     5.7  Silver nitrate (AgNOs),  0.10  N:   Dissolve  15.39 g of NgNOs in Type
II water, mix well, and dilute to  1  L.

     5.8  Reagents for aeration option:

          5.8.1  Sodium carbonate  solution  (^003) , 5%:  Add 95 ml of Type II
     water to 5 g of N32C03 and mix  well.

          5.8.2  Paraffin oil.

          5.8.3  Sulfurlc  acid  (H2S04),   0.1    N   standard:    Add  2.8  ml
     concentrated ^64 to Type  II   water  and   dilute  to  1 L.  Standardize
     against a base of known concentration.

          5.8.4  Sodium hydroxide  (NaOH) , 0.1 N  standard:  Dissolve 4.0 g NaOH
     1n Type II water and dilute to  1 L.  Standardize against an add of known
     concentration.

          5.8.5  Methyl red Indicator,  0.1%:  Dissolve 0.1 g in 99.9 ml of 95%
     ethanol and mix well .
                                  9080 - 3
                                                         Revision
                                                         Date  September 1986

-------
    5.9  Reagents for distillation option;

         5.9.1  Sodium chloride, NaCl  (acidified),  10%:    Dissolve 100 g of
    NaCl (ammonium-free)   in  900  ml  of  Type   II  water;  mix  well.   Add
    approximately   0.42  ml  of   concentrated    HC1  to  make  the  solution
    approximately 0.005 N.

         5.9.2  Sodium hydroxide (NaOH),  1 N:   Dissolve 40 g of NaOH  in Type
    II water and dilute to 1 L.

         5.9.3  Boric add (H3B03),  2% solution:    Dissolve 20  g H3B03 in 980
    ml Type II  water and mix well.

         5.9.4  Standard  sulfurlc  add (1^04), 0.1 N:  See Step 5.8.3.

         5.9.5   Bromocresol  green-methyl   red  mixed   indicator:    Triturate
    0.1  g  of bromocresol  green  with  2  ml  0.1  N NaOH  in  an  agate mortar and
    add  95% ethyl  alcohol  to  obtain  a   total  volume  of 100  ml.   Triturate
    0.1  g  of methyl red   with   a  few  mL  of  95% ethyl  alcohol  in an agate
    mortar.  Add  3  ml of  0.1  N  NaOH  and  dilute the solution  to  a  volume of
     100  ml with 95% ethyl alcohol.    Mix  75  ml of the bromocresol  green
     solution with  25 mL of the  methyl   red  solution and dilute  the mixture to
    200  ml with 95% ethyl  alcohol.


6.0 SAMPLE COLLECTION,  PRESERVATION, AND HANDLING

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


7.0  PROCEDURE

     7.1   Sieve a  sample  aliquot of the  soil  through a 2-mm  screen  and allow
the sieved  soil  to air dry (at   a  temperature  of  <60*C).   Place  10 g of the
air-dried soil in  a 500-mL Erlenmeyer  flask  and   add   250 mL of neutral, 1  N
NH40Ac.   (Use 25 g of soil  if  the exchange capacity is very low, e.g.,  3-5 meq
per 100 g.)  Shake the  flask thoroughly and  allow  it to  stand  overnight.

     7.2  Filter the soil  with light  suction  using a  55-mm Buchner  funnel or
equivalent.  Do not allow the soil  to become dry and cracked.

     7.3  Leach the soil  with  the  neutral   NH40Ac  reagent until  no test  for
calcium can be obtained in the effluent  solution.  (For the calcium test,  add
a few drops each of 1 N NH4C1   and 10% ammonium oxalate, dilute NH40H to 10 mL
of the leachate in a  test  tube,  and  heat  the  solution to near the  boiling
point.  The  presence  of  calcium   is  indicated   by  a  white precipitate  or
turbidity.)

     7.4  Then leach the soil  four times with  neutral  1 N NH4C1 and once with
0.25 N NH4C1.
                                  9080 - 4
                                                         Revision      0
                                                         Date  September 1986

-------
     7.5  Wash out  the  electrolyte  with  150  to  200  ml  of 99% Isopropyl
alcohol.  When the test for chloride  in the leachate (use 0.10 AgNOs)  becomes
negligible, allow the soil to drain thoroughly.

     7.6  Determine the adsorbed Nfy either  by the aeration method (Paragraph
7.7) or by the acid-NaCl method (Paragraph 7.8).

     7.7  Aeration method;

          7.7.1  Place an  excess  of  0.1  N  standard  ^$04  in  the 500-mL
     Erlenmeyer flask on the aeration  apparatus   (50  ml is an ample quantity
     for most soils) and  add  10  drops  of  methyl  red indicator and enough
     distilled water to make the total volume about 100 ml.

          7.7.2  Attach  the  flask  to  the  apparatus.    Then  transfer the
     ammonium-saturated sample of soil   (from Paragraph 7.5) quantitatively to
     the 800-mL Kjeldahl  flask  located  in  the  flow  line  Just before the
     Erlenmeyer flask with the standard  acid.     Use a rubber policeman and a
     stream of distilled water from a  wash bottle, as needed, to complete the
     transfer.

           7.7.3  Add 150 ml N32C03 solution  and   a  few drops of paraffin oil
     and attach the flask to the apparatus.

           7.7.4  Apply  suction to the outflow   end of the apparatus and adjust
     the rate of flow to  450  to  500   liters  of air  per hr.  Continue the
     aeration for  17 hr.

           7.7.5  Shut off the  suction   and  remove  the  flask.   Titrate the
     residual acid in the absorption  solutions with standard 0.1 N NaOH from
     the original  red color through orange  to  yellow at the end point.  From
     the   titration  values  obtained  with  the   soil  and  blank  solutions,
     calculate the content of adsorbed ammonium in milligram equivalents per
     100 g soil.

     7.8   Acid-NaCl method;

           7.8.1  Leach  the ammonium-saturated  soil from Paragraph 7.5 with 10%
     acidified NaCl until 225 mL  have   passed  through the sample.  Add small
     portions at a time,  allowing  each portion  to  pass through the sample
     before adding the  next portion.

           7.8.2  Transfer the leachate   quantitatively  to  an 800-mL Kjeldahl
     flask, add 25 mL of  1 N NaOH,  and distill  60  mL of the solution into
     50 mL of 2% H3B03.

           7.8.3  Add  10 drops of  bromocresol  green-methyl  red mixed indicator
     and  titrate the  boric acid solution with  standard 0.1  N HgSCty.  The color
     change is  from bluish  green   through  bluish purple  to pink at the end
     point.   Run blanks on the .reagents. Correct  the titration  figure for the
     blanks and calculate the milliequivalents of  ammonium  in  100 g of soil.
                                   9080 - 5
                                                          Revision      0
                                                          Date  September 1986

-------
          7.8.4  Results  should  be  reported  as  "determined  with ammonium
     acetate" at pH 7.

8.0  QUALITY CONTROL
     8.1  All quality control data should be maintained and available for easy
reference or inspection.
     8.2  Employ a minimum  of  one  blank  per  sample  batch to determine if
contamination or any memory effects are occurring.
     8.3  Material  of  known  cation-exchange   capacity  must  be  routinely
analyzed.

9.0  METHOD  PERFORMANCE
     9.1  No data provided.
10.0  REFERENCES
     1.   This  method  is  based  on  Chapman,  H.D.,  "Cation-exchange  Capacity,"
pp. 891-900, 1n C.A.  Black  (ed.),  Method   of Soil  Analysis,  Part 2:  Chemical
and Microbiological  Properties, Am. Soc. Agron., Madison, Wisconsin  (1965).
                                   9080 - 6
                                                          Revision
                                                          Date  September 1986

-------
                             METHOD 9O80

             CATION-EXCHANGE CAPACITY (AMMONIUM  ACETATE)
C
  7.1
       Sieve ป
  •ample of coll
   through 2—mm
    •creen;  dry
  7. 1
        Place
       •oil in
     flack;  mOO
    NH OAC:  let
 •tana overnight
  7.2
   Filter Boll
   with light
    •uctlon
                                                     7.3
Leach soil with
neutral NHOAc
                                                     7.3
    Tact for
    calcium
                                               Yes
                                                          7.3
                                                        Calcium
                                                       detected?
                                                     7.4
                                                       Leach soil
                                                       with NH^Cl
                      9080 -  7
                                                 Revision       0
                                                 Date  September  1986

-------
                               METHOD 9060

               CATION-EXCHANGE CAPACITY  (AMMONIUM ACETATE!
                                (Continued)
7.5
ot
elect
e
Mash
t the
rolyte:
•oil to
rain
           Aeration method
'which method ls\. Acid-Nad  method
	'  "".D determine  ^	
7.7.1
   Place  HtSO4 in
  aeration apparatus
   flack;  add methyl
  red indicator  and
   distilled Mater
                                                       7.8.1
                           Leach  soil  fron
                            Step  7.5 with
                           acidified Had
   7.7.Z
          Attach
   	1  flask  to
        apparatus:
     transfer soil
   • ample  (7.5)  to
    Kleldahl  flack
                           7.B.2
                                  Transfer
                                  leachate
                               to  KJeldahl
                               flack:  add
                             NaOH.  distill
                           into HBOj  to] .
      o
                         9080 - 8
                                                    Revision       0
                                                    Date   September  1986

-------
                            METHOD 9O80

            CATION-EXCHANGE CAPACITY (AMMONIUM ACETATE)
                             (Continued)
7.7.3   Add
	——I  Na.COj
   solution and
  paraffin oil:
  attach flask
  to apparatus
                                                    7.6.31
 Titrate H.BOt
 solution <h
     H,S04
7.7.41
 Asrate for 17
     hours
7.8.3
     I Run
 blanks; correct
   tltratlon
   figure for
    blanks:
7.7.5J

      Shut off
suction:  remove
 flask:  titrate
 residual acid
7.6.31
   Calculate
   •wnonium
    in soil
7.7.5
     Calculate
    content of
     absorbed
                     9080  - 9
                                                Revision       0
                                                Date   September  1986

-------
                                 METHOD 9081

             CATION-EXCHANGE CAPACITY OF SOILS (SODIUM ACETATE)
1.0  SCOPE AND APPLICATION

     1.1  Method 9081 Is applicable  to  most  soils,  Including calcareous  and
noncalcareous soils.   The  method  of  cation-exchange  capacity by summation
(Chapman, 1965, p. 900; see Paragraph  10.1)  should be employed for distinctly
add soils.
2.0  SUMMARY OF METHOD

     2.1  The soil sample is mixed with  an excess of sodium acetate solution,
resulting in an exchange of the  added  sodium cations for the matrix cations.
Subsequently, the  sample  is  washed  with  isopropyl  alcohol.    An ammonium
acetate solution  is  then  added,  which  replaces  the  adsorbed sodium with
ammonium.  The concentration of displaced  sodium is then determined by atomic
absorption, emission spectroscopy, or an equivalent means.


3.0  INTERFERENCES

     3.1  Interferences can occur during  analysis  of  the extract for sodium
content.  Thoroughly investigate  the  chosen  analytical method  for potential
interferences.
4.0  APPARATUS AND MATERIALS

     4.1  Centrifuge tube and stopper;  50-mL, round-bottom,  narrow neck.

     4.2  Mechanical shaker.

     4.3  Volumetric flask;  100-mL.


5.0  REAGENTS

     5.1  Sodium acetate  (NaOAc), 1.0 N;    Dissolve 136 g of NaC2H202'3H20 in
water and dilute 1t to 1,000 mL.   The  pH of this solution should be 8.2.  If
needed, add a few drops of acetic  acid or NaOH solution to bring the reaction
of the solution to pH 8.2.

     5.2  Ammonium acetate  (NH^Ac), 1  N:    Dilute  114 mL of glacial acetic
acid (99.5%) with water to a volume of approximately 1 liter.  Then add 138 mL
of concentrated ammonium  hydroxide  (NH40H) and add water to obtain a volume of
about 1,980 mL.  Check the  pH  of  the resulting solution, add more NH40H, as
needed, to obtain a pH of 7, and  dilute  the solution to a volume of 2 liters
with water.
                                  9081 - 1
                                                         Revision      0
                                                         Date  September 1986

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     5.3  Isopropyl  alcohol;  99%.


6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

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


7.0  PROCEDURE

     7.1  Weigh 4 g of medium- or fine-textured soil or 6 g of coarse-textured
soil and transfer the sample  to a 50-mL, round-bottom, narrow-neck centrifuge
tube.   (A fine soil has >50% of  the particles <0.074 mm, medium soil has >50%
>0.425 mm, while a coarse soil has more than 50% of Its particles >2 mm.

     7.2  Add 33 mL of 1.0  N NaOAc   solution,  stopper the tube, shake 1t In a
mechanical shaker for 5 m1n, and centrifuge 1t until the supernatant liquid Is
clear.

     7.3  Decant the liquid, and  repeat Paragraph 7.2 three more times.

     7.4  Add 33 mL of 99%  Isopropyl alcohol,  stopper the tube, shake It 1n a
mechanical shaker for 5 m1n, and  centrifuge 1t until the supernatant liquid Is
clear.

     7.5  Repeat the procedure described 1n Paragraph 7.4 two more times.

     7.6  Add 33 mL  of  NfyOAc   solution,  stopper  the  tube,  shake It In a
mechanical shaker for 5 min, and  centrifuge 1t until the supernatant liquid Is
clear.  Decant the washing  Into a 100-mL volumetric flask.

     7.7  Repeat the procedure described 1n Paragraph 7.6 two more times.

     7.8  Dilute the combined washing  to the 100-mL mark with ammonium acetate
solution and determine the  sodium concentration by atomic absorption, emission
spectroscopy, or-an equivalent method.


8.0 QUALITY CONTROL

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

     8.2   Employ  a  minimum  of  one  blank  per   sample  batch  to determine 1f
contamination or  any memory effects are occurring.

     8.3  Materials of   known  cation-exchange   capacity   must be  routinely
analyzed.
                                   9081 - 2
                                                          Revision
                                                          Date  September 1986

-------
9.0  METHOD PERFORMANCE

     9.1  No data provided.


10.0  REFERENCES

     10.1 This method 1s  based  on Chapman, H.D., "Cation-exchange Capacity,"
pp. 891-900, 1n C.A. Black (ed.),  Method  of Soil Analysis, Part 2:  Chemical
and Microbiological Properties, Am. Soc. Agron., Madison, Wisconsin (1965).
                                   9081 - 3
                                                          Revision
                                                          Date  September 1986

-------
                         NCTMOD 9Oai

                     CAPACITY or SOILS (SODIUM ACETATE)
 7.1 I

      weigh
    out aainoi*.
   transfar to
cantrifuga tuba
      Add
NaOAc aolutlon;
     ahaka:
    cantrifuga
 7.3
Da cant liquid:
rapaat 3 aiora
    tinas
 7.4
 Add laopropyl
alcohol:  ahaka:
  cantrifuga
 7.S
       8 wore
    tiawa
   CD
                                                 O
  7.6 I  Add
      '  NHdOAC
 •olution: ahaka:
    centrifuga:
  Decant Mashing
    into flask
                                              7.7
      Repeat
    procedure
                                                    Dilute
                                                   combined
                                              7.8
   with aMonlui
      ecetete
      aolutlon
                                              7.a
    Oateralna
     •odlun
  cencantratien
r-o
                   9081 - 4
                                          Revision       0
                                          Date  September 1986

-------
                                 METHOD 9090A

               COMPATIBILITY TEST FOR WASTES  AND  MEMBRANE  LINERS
1.0  SCOPE AND APPLICATION

      1.1    Method  9090 is  intended  for use  in  determining the  effects of
chemicals  in  a surface  impoundment, waste  pile,  or landfill  on  the physical
properties of flexible membrane liner (FML) materials intended  to contain them.
Data from these tests will  assist in deciding whether a given liner material is
acceptable for the intended application.

2.0  SUMMARY OF METHOD

      2.1    In order to estimate waste/liner compatibility, the liner material
is immersed in the chemical  environment for minimum  periods of  120 days at room
temperature (23 + 2ฐC) and at 50 + 2ฐC.   In cases where the FML will be used in
a chemical environment at elevated temperatures, the immersion  testing shall be
run at the elevated  temperatures  if they are expected  to be  higher than 50ฐC.
Whenever possible, the use of longer exposure times  is recommended.  Comparison
of measurements of the membrane's physical properties, taken periodically before
and after contact with the waste fluid, is used  to estimate the compatibility of
the liner with the waste over time.

3.0  INTERFERENCES (Not Applicable)

4.0   APPARATUS AND MATERIALS

NOTE:   In general, the following definitions will  be used in this method:

      1.  Sample  -   a  representative  piece of the liner material proposed for
                      use that  is of sufficient size to  allow for the removal of
                      all  necessary specimens.

      2. Specimen -   a  piece  of material,  cut  from  a  sample,  appropriately
                      shaped and prepared so that it is  ready to use for a test.

      4.1    Exposure tank  - Of a size sufficient to contain the samples, with
provisions for supporting the  samples  so  that  they  do  not  touch  the bottom or
sides of the tank or each other, and for stirring the liquid in the tank.  The
tank should be compatible with the waste fluid and impermeable to  any  of the
constituents they are intended  to contain.  The tank shall  be  equipped  with a
means for maintaining the solution at room temperature  (23 ฑ 2ฐC)  and 50 ฑ 2ฐC
and for preventing evaporation of the solution  (e.g., use a cover equipped with
a reflux condenser,  or  seal  the  tank with a Teflon  gasket  and  use an airtight
cover).   Both  sides of  the liner material  shall  be  exposed  to  the chemical
environment.  The pressure inside the tank must be the same as that outside the
tank.  If the liner has a side that (1)  is not exposed to the waste  in actual use
and (2) is not  designed  to withstand exposure to the chemical environment, then
such a liner may be treated with only the barrier surface exposed.
                                   9090A  -  1                       Revision 1
                                                                  July 1992

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      4.2    Stress-strain machine  suitable  for  measuring elongation,  tensile
strength, tear resistance, puncture resistance, modulus of elasticity,  and ply
adhesion.

      4.3    Jig for testing puncture resistance  for use with FTMS 101C, Method
2065.

      4.4    Liner  sample labels and  holders made  of materials known  to be
resistant to the specific wastes.

      4.5    Oven at 105 ฑ 2ฐC.

      4.6    Dial micrometer.

      4.7    Analytical balance.

      4.8    Apparatus for determining extractable content of liner materials.

NOTE:   A minimum quantity of representative  waste  fluid  necessary  to  conduct
        this  test has not  been specified  in this method because the amount will
        vary  depending upon the waste composition and the type of liner material.
        For  example, certain organic  waste  constituents,  if  present  in  the
        representative  waste  fluid,  can  be  absorbed  by  the liner  material,
        thereby changing the  concentration of  the chemicals in the waste.  This
        change  in waste composition  may require the waste  fluid  to be replaced
        at least monthly  in  order to maintain representative conditions in the
        waste  fluid.    The  amount  of  waste  fluid  necessary  to  maintain
        representative waste conditions will depend on factors such as the volume
        of constituents   absorbed  by  the  specific  liner  material  and  the
        concentration of the  chemical  constituents  in the  waste.

5.0  REAGENTS  (Not Applicable)

6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1    For information on what constitutes  a representative sample of the
waste fluid,  refer to the following guidance document:

      Permit Applicants'  Guidance  Manual for Hazardous Waste Land  Treatment,
      Storage,  and Disposal  Facilities; Final Draft; Chap. 5,  pp. 15-17;
      Chap. 6,  pp. 18-21;  and Chap. 8, pp. 13-16, May 1984.

7.0  PROCEDURE

      7.1    Obtain a  representative sample  of  the waste fluid.   If  a waste
sample is received in more than one container, blend thoroughly.  Note any signs
of stratification.  If stratification  exists,  liner samples must be placed in
each of the phases.   In cases where  the waste  fluid  is expected to stratify and
the  phases cannot  be  separated, the  number  of immersed  samples  per exposure
period can be increased  (e.g.. if the waste fluid  has two phases, then 2 samples
per exposure  period  are needed) so that test samples exposed at each level of the
waste can be  tested.  If the  waste to be  contained in the  land disposal  unit is
in solid form,  generate a synthetic leachate  (see Step 7.9.1).


                                  9090A  - 2                       Revision 1
                                                                  July 1992

-------
      7.2    Perform the following tests on unexposed samples of the polymeric
membrane  liner material at  23 ฑ  2ฐC  (see  Steps 7.9.2  and 7.9.3  below for
additional  tests  suggested  for  specific  circumstances).   Tests  for  tear
resistance and tensile  properties are to be performed according to the protocols
referenced  in  Table  1.  See Figure  1 for cutting  patterns  for nonreinforced
liners, Figure 2 for cutting patterns  for  reinforced liners, and Figure 3 for
cutting patterns for semi crystal line liners. (Table 2, at the end  of this method,
gives characteristics of various polymeric liner materials.)

      1.     Tear resistance, machine and transverse directions,  three specimens
             each direction for nonreinforced liner materials only.  See Table
             1 for appropriate test method, the  recommended test speed, and the
             values to  be reported.

      2.     Puncture  resistance, two  specimens,  FTMS  101C,  Method 2065.   See
             Figure 1,  2, or 3, as applicable,  for sample  cutting patterns.

      3.     Tensile  properties,   machine   and  transverse  directions,  three
             tensile specimens in each direction.  See Table 1 for appropriate
             test  method,  the recommended  test speed,  and  the values to be
             reported.   See  Figure 4  for tensile  dumbbell cutting  pattern
             dimensions for nonreinforced liner samples.

      4.     Hardness,  three  specimens,  Duro A  (Duro  D if  Duro A  reading is
             greater than 80),  ASTM D2240.   The  hardness  specimen thickness for
             Duro  A  is 1/4 in., and  for Duro  D  it  is 1/8  in.   The specimen
             dimensions are 1 in. by 1 in.

      5.     Elongation at break.  This test is to be performed only on membrane
             materials that do not have a fabric  or other nonelastomeric support
             as part of the liner.

      6.     Modulus  of elasticity,  machine and  transverse directions,  two
             specimens each direction  for semi crystalline liner materials only,
             ASTM D882 modified Method A (see Table 1).

      7.     Volatiles content, SW 870, Appendix  III-D.

      8.     Extractables content, SW 870, Appendix III-E.

      9.     Specific gravity, three specimens,  ASTM D792  Method A.

      10.     Ply adhesion,  machine and transverse directions,  two specimens each
             direction  for  fabric  reinforced liner materials only,  ASTM  D413
             Machine Method, Type A -- 180 degree peel.

      11.     Hydrostatic resistance test, ASTM  D751 Method A, Procedure 1.

      7.3    For each test condition,  cut five pieces of  the  lining material of
a size to fit the sample holder,  or at least 8 in. by 10 in.  The fifth sample
is an extra sample.  Inspect all samples for flaws and discard  unsatisfactory
ones.   Liner materials with  fabric reinforcement  require  close inspection to
ensure  that threads  of  the  samples  are  evenly  spaced  and straight  at  90*.
Samples containing a fiber scrim support may be  flood-coated along the exposed

                                  9090A  -  3                       Revision 1
                                                                  July 1992

-------
edges with a solution recommended by the liner manufacturer,  or another procedure
should be  used  to  prevent the scrim from being directly exposed.   The flood-
coating solution will typically contain 5-15% solids dissolved in a solvent.  The
solids content can be the liner formula or the base polymer.

      Measure the following:

      1.     Gauge thickness, in.  -- average of the four corners.

      2.     Mass, Ib. -- to one-hundredth of a Ib.

      3.     Length, in.  --  average  of the lengths of the  two  sides  plus the
             length measured through the liner center.

      4.     Width, in. -- average of the widths of the two ends plus the width
             measured through the  liner center.

NOTE:   Do not  cut these liner samples into  the test  specimen  shapes  shown in
        Figure  1, 2, or 3 at this time.  Test  specimens will be cut as specified
        in Step 7.7,  after exposure to  the waste fluid.

      7.4    Label  the liner  samples  (e.g..  notch  or use  metal  staples  to
identify the sample) and hang in the waste fluid by a wire hanger or a weight.
Different liner materials  should be immersed in separate tanks to avoid exchange
of plasticizers  and  soluble  constituents when  plasticized  membranes are being
tested.   Expose the liner  samples to the  stirred waste  fluid held  at  room
temperature and at 50 + 2"C.

      7.5    At  the  end  of 30, 60, 90,  and  120 days of exposure,  remove one
liner  sample  from each test condition to  determine the  membrane's  physical
properties (see Steps 7.6  and 7.7).  Allow the liner sample  to cool in the waste
fluid until the  waste  fluid  has  a stable room temperature.  Wipe off as  much
waste as possible and rinse briefly with  water.  Place wet sample in a labeled
polyethylene bag or aluminum foil  to prevent  the  sample from  drying out.   The
liner sample should be tested as soon as  possible after removal  from the waste
fluid at room temperature, but in  no case later than  24 hours  after removal.

      7.6    To test the immersed  sample, wipe off any remaining waste and rinse
with deionized water.   Blot sample  dry and measure  the following as in Step 7.3:

      1.     Gauge thickness, in.

      2.     Mass, Ib.

      3.     Length, in.

      4.     Width, in.

      7.7  Perform the following tests on the exposed samples  (see Steps 7.9.2
and  7.9.3  below for additional  tests  suggested  for  specific  circumstances).
Tests for tear resistance and tensile properties are  to be performed according
to the  protocols  referenced  in Table 1.    Die-cut  test   specimens following
suggested cutting patterns.   See Figure 1  for  cutting patterns for nonreinforced


                                   9090A  - 4                       Revision 1
                                                                  July 1992

-------
liners, Figure 2 for cutting patterns  for  reinforced  liners,  and Figure 3 for
semi crystal line liners.

      1.     Tear resistance, machine and transverse directions, three specimens
             each direction for materials  without  fabric  reinforcement.   See
             Table 1 for appropriate test method, the recommended test specimen
             and speed of test, and the values to be reported.

      2.     Puncture resistance, two  specimens, FTMS  101C,  Method 2065.   See
             Figure 1, 2, or 3, as applicable, for  sample cutting patterns.

      3.     Tensile  properties,  machine   and  transverse  directions,  three
             specimens each direction.  See Table 1  for  appropriate test method,
             the recommended test specimen  and speed of test, and the values to
             be reported.   See Figure 4 for  tensile dumbbell  cutting pattern
             dimensions for nonreinforced liner samples.

      4.     Hardness, three  specimens,  Duro A (Duro  D  if Duro A  reading is
             greater than 80), ASTM 2240.   The hardness specimen thickness for
             Duro A is  1/4  in.,  and  for  Duro  D  is  1/8  in.   The  specimen
             dimensions are 1  in. by 1 in.

      5.     Elongation at break.  This test is to be performed only on membrane
             materials that do  not have a fabric or other nonelastomeric support
             as part of the liner.

      6.     Modulus  of  elasticity,  machine and  transverse directions,  two
             specimens each direction  for semicrystalline liner materials only,
             ASTM D882 modified Method A (see Table 1).

      7.     Volatiles content, SW 870, Appendix III-D.

      8.     Extractables content, SW 870,  Appendix III-E.

      9.     Ply adhesion,  machine and transverse directions, two specimens each
             direction for  fabric  reinforced liner materials only, ASTM  D413
             Machine Method, Type A -- 180 degree peel.

      10.     Hydrostatic resistance test,  ASTM D751 Method A, Procedure 1.

      7.8  Results and reporting

             7.8.1    Plot the  curve for each property  over  the time period 0 to
      120 days and display the spread  in data points.

             7.8.2    Report all raw, tabulated, and plotted data.  Recommended
      methods for collecting and  presenting information are described  in the
      documents listed under Step 6.1  and  in related agency guidance manuals.

             7.8.3    Summarize the  raw test results as follows:

             1.       Percent change in thickness.

             2.       Percent change in mass.

                                  9090A -  5                      Revision 1
                                                                  July 1992

-------
             3.       Percent   change  in  area  (provide  length   and   width
                      dimensions).

             4.       Percent  retention of physical properties.

             5.       Change,  in  points,  of hardness  reading.

             6.       The  modulus of elasticity calculated  in  pounds-force per
                      square inch.

             7.       Percent  volatiles of unexposed and exposed liner material.

             8.       Percent   extractables  of  unexposed  and  exposed  liner
                      material.

             9.       The  adhesion value, determined in  accordance  with ASTM
                      D413, Step  12.2.

             10.      The  pressure and  time elapsed at the  first appearance of
                      water  through the  flexible  membrane   liner  for  the
                      hydrostatic resistance test.

      7.9    The  following  additional   procedures  are  suggested  in  specific
situations:

             7.9.1    For  the  generation of  a synthetic leachate,  the  Agency
      suggests the use of  the  Toxicity Characteristic Leaching Procedure (TCLP)
      that was  finalized  in  the  Federal Register  on June 29,  1990,  Vol.  55,
      No. 126, p. 26986.

             7.9.2    For  semi crystal line membrane  liners,  the Agency suggests
      the determination of the potential for environmental stress cracking.  The
      test that can be used to make this determination is either ASTM D1693 or
      the National Institute of Standards and Technology Constant Tensile Load.
      The evaluation  of the  results should be  provided  by an  expert  in this
      field.

             7.9.3    For  field seams, the Agency suggests the determination of
      seam strength in shear and  peel modes.  To determine seam strength in peel
      mode, the test ASTM  D413 can be used.  To determine seam  strength in shear
      mode for  nonreinforced  FMLs,  the  test ASTM  D3083  can  be used,  and for
      reinforced FMLs, the test ASTM D751,  Grab Method, can be used at a speed
      of 12 in.  per minute.  The evaluation of the results should be provided by
      an expert in this field.

8.0  QUALITY CONTROL

      8.1    Determine  the mechanical  properties of  identical nonimmersed and
immersed liner samples in  accordance with the standard methods for the specific
physical property  test.   Conduct mechanical  property tests on nonimmersed and
immersed liner samples prepared from the same sample  or lot of material  in the
same manner and run under  identical  conditions.  Test liner samples immediately
after they are removed from the room temperature test solution.


                                   9090A  - 6                       Revision 1
                                                                  July 1992

-------
9.0  METHOD PERFORMANCE
      9.1    No data provided.
10.0  REFERENCES
1.    None required.
                                  9090A - 7                       Revision 1
                                                                  July 1992

-------
            Table t.   Physical testing of e*ปsed
                                                       in llner-wuto Itcpld oepatlblllty test
Tjpe of cnpaund and
construction
Tensile properties Betted
Type of vectavn
Cross! Inked or wlcanlzed
ASTMD412
Tharaplastlc
ASTM063B
Duetto! 1b
Seal crystal line
ASTMD63B
Durtte1lb
Fabric-reinforced9
ASIป407bl. MsthodB
1-ln. wlda strip and 2- In. Jaw
              Ntatorof
              $wedof test
              Values to to reported
                                          3 In each dlractlon
                                          20101
                                          Tensile strength, psl
                                          Elongation at break. 1
                                          Tensile sat after break.
                                          Stress at 100 and 2001
                                            elongation, pst
3 In aach direction
20 Ipa
Tamil* strength, pst
Elongation at break. 1
Tensile set after break.
Stress at 100 and 2001
  elongation, pst
  tO
  O
 I

CO
            Mxftilus of elasticity Mtnod

              Tjpeof
              Mater of spocleans
              3>eadof test
              Values reported
             Tear resistance Mtnod
  Type of *>ect
  Mater of spec lewis
  ^>eadof test
  Values reported

Puncture resistance avtted
                                          ASTM0624

                                          Diet
                                          3 In aach direction
                                          20 tpi
                                          Stress, ppl

                                          FT>6 101C. Nothod 2066
ASTN1004
                                                                           3 In each direction
                                                                           20 Ipa
                                                                           Stress, ppt

                                                                           FINS 101C. Method 2066
3 In each direction
Zip-
Tensile strength at yield, psl
Elongation at yield, X
Tensile set at break, psl
Elongation at break, psl
Tensile set after break. I
Stress at 100 and 200%
  elongation, psl

AS1N DBB2. Method A

Strip: O.S In. wide and 6. In long
  at a 2 In. Jaw separation
2 In each direction
0.2 HM
Greatest slope of Initial stress -
  strain curve,  psl

AS1M 01004
                               2 In each direction
                               21pป
                               Mntaua stress, ppl

                               FTMS 101C. Method 2066
                                                                                                                                   separation
                                                                                                                                 3 In each direction
                                                                                                                                 12 Ipa
                                                                                                                                 Tensile at fArtc break, ppi
                                                                                                                                 Elongation at fabric break, 1
                                                                                                                                 Tensile at ultlnte break, ppl
                                                                                                                                 Elongation at ultleate break, ppl
                                                                                                                                 Tensile set after break. I
                                                                                                                                 Stress at 100 and 200X
                                                                                                                                   elongation, psl
                                    FTMS 101C. Method 2066
Tjpa of yeclean
Mater of vectaans
Speed of test
Values reported


2 In. sqare
2
201p>
Gage. .11
Stress, lb
Elongation, In.
2 In. square
2
20 Ipa
Gage. ซ1I
Stress. lb
Elongation. In.
2 In. sqare
2
20 Ipa
Gage, artl
Stress. lb
Elongation. In.
2 In. sojiare
2
20 Ipx
Gage. .11
Stress. lb
Elongation. In.
ID O
VO 3
r\>
               •Can to thermoplastic,  crossl Inked, or vulcanized i
               bSee Figure 4.
                tear resistance test Is iwiaainrtBl for fatelc-ratnforcad sheetings In the taecrston study.
               •Saaa as AS1M 0624. Die C.

-------
                                   TABLE 2.
                   POLYMERS USED IN FLEXIBLE MEMBRANE LINERS
Thermoplastic Materials  (TP)
CPE   (Chlorinated polyethylene)8
      A  family  of  polymers  produced  by  a chemical  reaction of  chlorine on
      polyethylene.   The resulting  thermoplastic elastomers contain 25 to 45%
      chlorine by weight  and 0 to 25% crystallinity.
CSPE  (Chlorosulfonated polyethylene)8
      A  family of  polymers that are produced  by the  reaction of polyethylene
      with chlorine and  sulfur  dioxide,  usually containing 25 to 43% chlorine
      and 1.0 to 1.4% sulfur.   Chlorosulfonated polyethylene is also known as
      hypalon.
EIA (Ethylene interpolymer alloy)8
      A  blend of  EVA  and polyvinyl  chloride  resulting  in  a  thermoplastic
      elastomer.
PVC (Polyvinyl chloride)8
      A  synthetic  thermoplastic polymer  made  by polymerizing  vinyl  chloride
      monomer or  vinyl chloride/vinyl acetate monomers.    Normally  rigid and
      containing 50% of plasticizers.
PVC-CPE  (Polyvinyl  chloride - chlorinated polyethylene alloy)8
      A blend of polyvinyl chloride and chlorinated polyethylene.
TN-PVC (Thermoplastic nitrile-polyvinyl chloride)8
      An  alloy  of  thermoplastic unvulcanized  nitrile  rubber  and  polyvinyl
      chloride.
Vulcanized Materials (XL)
Butyl  rubber8
      A synthetic rubber based on isobutylene and a  small amount of isoprene to
      provide sites for vulcanization.
aAlso supplied reinforced with fabric.
                                   9090A  -  9                       Revision 1
                                                                  July 1992

-------
                             TABLE 2. (Continued)
EPDM (Ethylene propylene diene monomer)3'
      A synthetic elastomer based on  ethylene, propylene, and a small amount of
      nonconjugated diene to provide sites for vulcanization.

CM    (Cross-linked chlorinated polyethylene)

      No definition available by EPA.

CO, ECO (Epichlorohydrin polymers)8

      Synthetic rubber, including two epichlorohydrin-based elastomers that are
      saturated, high-molecular-weight aliphatic  polyethers with chloromethyl
      side chains.  The two  types  include homopolymer  (CO)  and a copolymer of
      epichlorohydrin and ethylene oxide (ECO).

CR (Polychloroprene)8

      Generic name for a  synthetic rubber based  primarily  on  chlorobutadiene.
      Polychloroprene is also known as neoprene.


Semicrvstalline Materials (CX)

HOPE - (High-density polyethylene)

      A polymer prepared by the low-pressure polymerization of ethylene as the
      principal monomer.

HOPE - A (High-density polyethylene/rubber alloy)

      A blend of high-density polyethylene and rubber.

LLDPE (Liner low-density polyethylene)

      A low-density polyethylene  produced  by the copolymerization of ethylene
      with various alpha olefins in the presence of suitable catalysts.

PEL (Polyester elastomer)

      A segmented thermoplastic copolyester elastomer containing recurring long-
      chain ester units derived from dicarboxylic acids and long-chain glycols
      and  short-chain  ester  units  derived  from  dicarboxylic  acids  and  low-
      molecular-weight diols.
8Also supplied reinforced with fabric.
bAlso supplied as a thermoplastic.
                                  9090A - 10                      Revision 1
                                                                  July 1992

-------
                             TABLE 2. (Continued)
PE-EP-A (Polyethylene ethylene/propylene alloy)
      A blend of polyethylene and ethylene  and  propylene polymer resulting in a
      thermoplastic elastomer.
T-EPDM (Thermoplastic EPDM)
      An ethylene-propylene  diene monomer  blend resulting  in  a  thermoplastic
      elastomer.
                                  9090A -  11                       Revision  1
                                                                  July  1992

-------
   FIGURE  1.  SUGGESTED  PATTERN FOR CUTTING TEST SPECIMENS FROM
NONREINFORCED CROSSLINKED OR THERMOPLASTIC IMMERSED LINER SAMPLES.
       Puncture test specimens
                                 test specimens
                                               Volatljes test specimen
Tensile test specimens
                                                            Hot to scale
                            9090A - 12
Revision 1
July 1992

-------
FIGURE 2.   SUGGESTED PATTERN  FOR CUTTING TEST SPECIMENS FROM
        FABRIC REINFORCED IMMERSED LINER SAMPLES.

        NOTE:  TO AVOID EDGE EFFECTS, CUT SPECIMENS
       1/8  -  1/4 INCH IN FROM EDGE OF IMMERSED SAMPLE.
                                             VoUtlln test  specimen
Puncture ttst specimens
                                  Ply tdheslon ttst specimens
                                  Tensile  test  specimens

                                                            Not to
                          9090A - 13
Revision 1
July 1992

-------
FIGURE 3.   SUGGESTED PATTERN  FOR  CUTTING TEST SPECIMENS FROM
          SEMICRYSTALLINE IMMERSED LINER SAMPLES.

        NOTE:  TO AVOID EDGE EFFECTS,  CUT  SPECIMENS
      1/8  TO  1/4  INCH  IN  FROM EDGE OF  IMMERSED SAMPLE.
                  Modulus of elasticity
                     ttst specimens
      Tensile ttst specimens
                                    Volitllts ttst sptclMn
                                           Puncture ttst specimens
                      ttst specimens
                                                          HOC tO
                       9090A  -  14
Revision 1
July 1992

-------
FIGURE 4.  DIE FOR TENSILE DUMBBELL (NONREINFORCED LINERS)
             HAVING THE FOLLOWING DIMENSIONS:

t
1
wo
1
1











N

s



1
\
w
t
1

LQ

X

V

















        W  - Width of narrow section
        L  - Length of narrow section
        WO - Width overall
        LO - Length overall
        G  - Gage length
        D  - Distance between gaps
0.25
1.25
inches
inches
0.625 inches
  50
  00
2.00
inches
inches
inches
                        9090A -  15
      Revision  1
      July  1992

-------
                       METHOD  9090A
COMPATIBILITY  TEST FOR WASTES AND MEMBRANE  LINERS
              START
        7.1  Obtain sample
         of  waste fluid
        7.2 Perform tests
          on unexposed
        samples of liner
           material
        7.3 Cut pieces  of
       lining material  for
       each test condition
         7.4 Label  test
          specimens and
         expose to  waste
             fluid
   7.5  Determine
 membrane physical
 properties at 30
day intervals (30,
 60.  90. 120 days)
7.6 To  test exposed
specimens, measure
 gauge  thickness,
 mass,  length,  and
       width
 7.7 Perform tests
on exposed samples
  7  8 Report and
  evaluate data
                                      STOP
                        9090A  - 16
                                 Revision  1
                                 July  1992

-------
                                 METHOD  9095

                          PAINT FILTER LIQUIDS  TEST
1.0  SCOPE AND APPLICATION

     1.1  This method 1s used to determine  the  presence of free liquids  1n  a
representative sample of waste.

     1.2  The method 1s used to  determine  compliance with 40 CFR 264.314 and
265.314.

2.0  SUMMARY OF METHOD

     2.1  A predetermined amount of material 1s  placed In a paint filter.  If
any portion of the material  passes  through  and drops from the filter within
the 5-m1n test period, the material is deemed to contain free liquids.


3.0  INTERFERENCES

     3.1  Filter media were  observed  to  separate  from  the  filter cone on
exposure to alkaline materials.    This  development  causes no problem 1f the
sample  is not disturbed.


4.0  APPARATUS AND MATERIALS

     4.1  Conical paint filter;  Mesh number 60  (fine meshed size).  Available
at local paint stores such as  Sherwin-Williams and Glidden for an approximate
cost of $0.07 each.

     4.2  Glass funnel;   If the  paint  filter, with the waste, cannot sustain
Its weight on the ring stand,  then  a fluted glass funnel or glass funnel  with
a mouth large enough to allow  at  least  1  in. of the filter mesh to protrude
should  be used to support the  filter.    The  funnel 1s to be fluted or have a
large open mouth 1n order to   support  the paint filter yet not interfere with
the movement, to the graduated cylinder, of the liquid that passes through the
filter  mesh.

     4.3  Ring stand and  ring, or tripod.

     4.4  Graduated cylinder or beaker;  100-mL.


5.0  REAGENTS

     5.1  None.
                                   9095 -  1
                                                         Revision
                                                         Date  September 1986

-------
6.0  SAMPLE COLLECTION,  PRESERVATION,  AND HANDLING

     6.1  All samples must be collected according to the directions  in  Chapter
Nine of this manual.

     6.2  A 100-mL or 100-g  representative  sample  is required for the test.
If it is  not  possible  to  obtain  a  sample  of  100  mL  or  100 g  that is
sufficiently representative of  the  waste,  the  analyst  may use larger size
samples in multiples of  100  mL  or  100  g,  i.e.,  200,   300,  400 mL or g.
However, when larger samples are  used,  analysts shall divide the sample into
100-mL or 100-g portions and  test  each  portion  separately.  If any  portion
contains free liquids, the entire sample is considered to have free liquids.

7.0  PROCEDURE

     7.1  Assemble  test apparatus as shown in Figure 1.

     7.2  Place sample in the filter.  A funnel may be used to provide support
for the paint filter.

     7.3  Allow sample to drain for 5 min  into the graduated cylinder.

     7.4  If any  portion  of  the  test   material  collects  in the graduated
cylinder in  the 5-min  period,  then  the  material  is deemed to contain free
liquids for  purposes of 40 CFR 264.314 and 265.314.


8.0  QUALITY CONTROL

     8.1  Duplicate samples  should be analyzed on  a routine basis.


9.0  METHOD  PERFORMANCE

     9.1  No data provided.


10.0   REFERENCES

     10.1  None required.
                                   9095 - 2
                                                         Revision      0
                                                         Date  September 1986

-------
MINC STAND —-
                                             FUNNEL
                                                PAINT FILTER
                                     .^-GRADUATED CYLINDER
            Figure 1.  Paint filter test apparatus.
                           9095 - 3
                                                  Revision       0
                                                  Date  September  1986

-------
       METHOD 9095

PAINT FILTER LIQUIDS TEST
    f      Start     J
7.1

Assemble test
apparatus

7.2



Place sample In
filter

7.3



Allow
cample to drain
into graduated
cylinder
     Did any teat
    material collect
     in graduated
       cylinder?
7.4
to cor
llqulc
CFR 21
Material
is deemed
itain free
Is; see 40
54.314 or
!6S.314
   f     Stop      J
 9095 -  4
                           Revision       0
                           Date  September 1986

-------
                                  METHOD 9096

                      LIQUID RELEASE TEST (LRT)  PROCEDURE


1.0   SCOPE AND APPLICATION

      1.1    The  Liquid Release Test  (LRT)  is  a laboratory  test designed to
determine whether or  not  liquids  will  be released from sorbents when they are
subjected to overburden pressures in a landfill.

      1.2    Any  liquid-loaded sorbent that  fails  the EPA Paint Filter Free
Liquids Test (PFT)  (SW-846  Method 9095),  may be assumed to release liquids in
this test.  Analysts  should ensure that the material in question will pass the
PFT before performing the LRT.

2.0   SUMMARY OF METHOD

      2.1    A representative  sample of the liquid-loaded sorbent, standing 10
cm high in the device,  is placed  between twin stainless steel screens and two
stainless-steel grids,  in a device capable  of  simulating  landfill overburden
pressures.  An absorptive filter paper  is placed on  the  side of each stainless-
steel grid opposite the sample (i.e.. the stainless-steel screen separates the
sample and the  filter  paper, while the stainless-steel  grid  provides a small air
gap to  prevent wicking  of liquid from  the  sample onto the filter paper).   A
compressive force of  50 psi  is applied to the  top  of  the  sample.   Release of
liquid is indicated when a visible wet  spot  is observed  on either filter paper.

3.0   INTERFERENCES

      3.1    When  testing sorbents  are loaded  with  volatile  liquids  (e.g..
solvents),  any released  liquid migrating  to  the  filter  paper  may  rapidly
evaporate.  For this reason,  filter  papers should  be examined  immediately after
the test has been conducted.

      3.2    It is  necessary to thoroughly clean, and  dry  the stainless-steel
screens prior to testing  to  prevent  false positive  or false negative results.
Material caught in screen holes may impede liquid transmission through the screen
causing false negative results.  A stiff bristled brush, like those used to clean
testing sieves, may be used to dislodge material  from holes  in  the  screens.  The
screens should  be ultrasonically cleaned with a laboratory detergent, rinsed with
deionized water,  rinsed with acetone, and thoroughly dried.

      When sorbents containing oily substances are tested,  it may be  necessary
to use solvents (e.g., methanol or methylene chloride) to remove any oily residue
from the screens  and from the sample holder surfaces.

      3.3    When placing  the  76  mm screen  on top  of  the  loaded  sample  it is
important to ensure that no sorbent is  present on top of the screen to contact
the filter paper and  cause  false positive results.   In addition,  some sorbent
residue may adhere to container sidewalls and contact the filter as the sample

                                   9096 - 1                        Revision 0
                                                                  September 1994

-------
compresses under load, causing wet spots on  the  edges  of the filter.  This type
of false positive may be avoided by carefully centering the 76 mm filter paper
in the device prior to initiating the test.

      3.4    Visual examination  of the sample may  indicate that  a release is
certain  (e.g.,  free standing  liquid  or a  sample  that flows  like  a liquid),
raising  concern  over  unnecessary clean-up  of the  LRT device.  An  optional  5
minute Pre-Test,  described in Appendix A of this  procedure, may  be  used to
determine whether or not an LRT must be performed.

4.0   APPARATUS AND MATERIALS

      4.1    LRT Device (LRTD):  A device capable of applying 50 psi  of pressure
continuously to the top of a confined, cylindrical  sample (see Figure 1).  The
pressure is applied by a piston on the top of the sample.  All  device components
contacting  the  sample (i.e.,  sample-holder, screens,  and  piston)  should be
resistant to attack by substances being tested.   The LRTD consists of two basic
components, described below.

             4.1.1    Sample holder:  A rigid-wall cylinder, with a  bottom plate,
      capable of holding a 10 cm high by 76 mm diameter sample.

             4.1.2    Pressure Application  Device:    In  the  LRTD  (Figure  1),
      pressure is  applied  to  the  sample  by a pressure rod pushing against  a
      piston that lies directly over the sample.  The  rod may  be pushed against
      the piston  at  a set pressure using pneumatic,  mechanical,  or hydraulic
      pressure.   Pneumatic pressure application  devices should be equipped with
      a pressure gauge accurate to within +1  psi, to  indicate when the desired
      pressure has been attained and whether or  not  it  is adequately maintained
      during the  test.   Other types  of  pressure  application  devices  (e.g.,
      mechanical  or  hydraulic) may  be used if  they  can apply the specified
      pressure continuously over the  ten minute testing time.   The pressure
      application device must  be  calibrated by  the  manufacturer,  using a load
      cell or similar device placed under the piston,  to ensure that 50 + 1 psi
      is applied  to  the  top  of  the sample.  The pressure  application device
      should be  sufficiently rugged  to deliver consistent  pressure  to the sample
      with repeated use.

      4.2    Stainless-Steel  Screens:  To separate the sample from the filter,
thereby preventing false positive results from particles falling on the filter
paper.  The screens  are made of stainless steel and have hole diameters of 0.012
inches with 2025 holes per square inch.  Two diameters of screens  are used:  a
larger (90 mm) screen  beneath  the  sample  and  a  smaller (76  mm) screen that is
placed on top of the sample in the sample-holding cylinder.

      4.3    Stainless-Steel  Grids:    To  provide  an air   gap  between  the
stainless-steel  screen and filter paper,  preventing false positive results from
capillary action.  The grids are  made  of 1/32" diameter, woven, stainless steel
wire cut to two diameters, 90 mm and 76 mm.
                                   9096 - 2                       Revision 0
                                                                  September 1994

-------
      4.4     Filter Papers:   To detect released liquid.  Two sizes, one 90 mm
and one  76  mm,  are placed on the side of the screen opposite the sample.  The
76 mm diameter filter paper has the outer 6 mm cut away except 3  conical points
used for centering the paper (see Figure 2).  Blue, seed-germination filter paper
manufactured by Schleicher and Schuell (Catalog Number 33900) is suitable. Other
colored, absorptive papers may be used as long  as they provide sufficient wet/dry
contrast for the  operator  to  clearly  see a wet spot.

      4.5     Spatula:   To  assist  in  loading and  removing  the sample.

      4.6     Rubber or  wooden mallet:  To tap the sides of the device to settle
and level the sample.

5.0   REAGENTS

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

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

      5.3    Acetone.

6.0   SAMPLE COLLECTION, PRESERVATION AND HANDLING

      6.1    All  samples  should  be  collected  using  a  sampling  plan  that
addresses the  considerations  discussed in "Test  Methods  for Evaluating Solid
Wastes (SW-846)."  The sampling  plan should be designed  to detect  and sample any
pockets of liquids that  may be present in a container  (i.e., in the bottom or top
of the container).

      6.2    Preservatives should not be added to  samples.

      6.3    Samples should be tested as soon  as  possible  after collection, but
in no case  after more  than three  days after collection.   If  samples  must be
stored,  they can be stored in  sealed  containers  and maintained under dark, cool
conditions  (temperature ranging between 35ฐ and 72ฐ  F).   Samples should not be
frozen.

7.0   PROCEDURE

      The procedure  below was developed for the original  LRTD,  manufactured by
Associated Design and Manufacturing Company  (ADM).  Procedures for other LRTDs,
along with evidence for  equivalency to the ADM device, should be supplied by the
manufacturer.
                                   9096 - 3                       Revision 0
                                                                  September 1994

-------
      7.1    Disassemble  the  LRTD and make sure that all  parts  are clean and
dry.

      7.2    Invert the sample-holding cylinder and place the large stainless-
steel screen, the large stainless-steel grid, then a 90 mm filter paper on the
cylinder base (bottom-plate side).

      7.3    Secure the bottom plate  (plate with a hole in the center and four
holes located on  the  outer circumference)  to the flange on  the  bottom of the
sample-holding cylinder using four knob screws.

      7.4    Turn  the sample  holder  assembly  to  the  right-side-up  position
(bottom-plate-side down).  Fill the sample holder with a representative sample
until the sample height measures  10 cm (up  to the etched line in the cylinder).

      7.5    Tap the  sides of the sample holder with a rubber or wooden mallet
to remove air pockets and to settle and level the sample.

      7.6    Repeat  filling,  and tapping  until  a sample  height of  10  cm is
maintained after tapping.

      7.7    Smooth the top of the sample with  a spatula to create a horizontal
surface.

      7.8    Place the small stainless-steel screen, then the small  stainless-
steel grid on top of the sample.

             NOTE:  Prior  to placing  the  stainless-steel   grid  on top  of the
             screen, make sure that no sorbent material  is on the grid side of
             the stainless-steel   screen.

      7.9    Place the 76 mm filter paper  on  top  of the small  stainless-steel
grid, making sure the filter paper is  centered in the device.

      7.10   Using the piston handle (screwed into the top  of the piston) lower
the piston  into  the  sample holder until it  sits  on top of  the  filter paper.
Unscrew and remove the handle.

      7.11   Place the loaded sample holder into position on the baseplate and
lock into place with two toggle clamps.

      7.12   Place the pressure application device on top of the sample-holder.
Rotate the device to lock it into place and insert the safety key.

      7.13   Connect air lines.

      7.14   Initiate rod movement and pressure application by pulling the air-
valve lever toward the operator and note time on data  sheet.  The pressure gauge
at the top of the  pressure  application device  should  read  as specified in the
factory calibration record for  the particular device.  If not, adjust regulator
to attain the specified pressure.

                                   9096 -  4                       Revision 0
                                                                  September 1994

-------
      NOTE: After pressure application, the air lines can be disconnected, the
      toggle  clamps can  be  released,  and  the  LRTD can  be set  aside  for  10
      minutes  while other LRTDs  are pressurized.   LRTD pressures  should  be
      checked  every 3  minutes to ensure that the  specified pressure is being
      maintained.   If the specified pressure is not being maintained to within
      +  5 psi,  the LRTD must  be  reconnected to  the  air  lines  and pressure
      applied  throughout the  10 minute test.

      7.15    After  10  minutes place the LRTD on  the  baseplate,  reconnect air
lines and toggle clamps, and turn off pressure  (retract the  rod) by pushing the
air-valve lever  away from the operator.  Note time on data  sheet.

      7.16    When the  air gauge reaches  0 psi,  disconnect the  air  lines and
remove the pressure-application device by removing  the safety key, rotating the
device, and lifting it away from the sample holder.

      7.17    Screw  the  piston handle into  the top  of the  piston.

      7.18    Lift out the piston.

      7.19    Remove the  filter  paper  and immediately  examine  it for wet spots
(wet area on  the filter  paper).   The presence  of a wet spot(s)  indicates a
positive test  (i.e., liquid release).  Note results on data sheet.

      7.20    Release toggle  clamps and  remove  sample holder  from baseplate.
Invert sample  holder onto suitable surface and remove the knob screws holding the
bottom plate.

      7.21    Remove the  bottom  plate  and immediately  examine  the filter paper
for wet  spots as described  in  Step 7.19.  Note  results on data  sheet.   Wet
spot(s) on either filter indicates a positive test.

8.0   QUALITY CONTROL

      8.1     Duplicate samples should be analyzed  every twenty samples or every
analytical  batch,   whichever  is more  frequent.    Refer  to  Chapter One  for
additional QC protocols.

9.0   METHOD PERFORMANCE

      9.1     Precision and accuracy data are not available  at this time.

10.0  REFERENCES

1.    Hoffman, P.,  G. Kingsbury,  B.  Lesnik,  M. Meyers, "Background Document for
the Liquid Release Test (LRT)  Procedure"; document submitted to the Environmental
Protection Agency by Research Triangle  Institute:   Research Triangle Park, NC
under Contract No.  68-01-7075, Work Assignment 76 and Contract No. 68-WO-0032,
Work Assignment  12.
                                   9096 - 5                       Revision 0
                                                                  September 1994

-------
FIGURE  1.
LRT DEVICE
     Pressure
   Application
      Device
     50  psi
                          Sample-Holding Cylinder

                             Filter

                              Separator Plate
 9096 - 6
Separator  Plate

Filter


Bottom Plate

    Revision 0
    September 1994

-------
76
   FIGURE 2.
DIAMETER FILTER  PAPER
         9096  -  7
                                   Revision 0
                                   September 1994

-------
         FIGURE  3.
GLASS GRID SPECIFICATIONS.
0.25 inchf
glass rodt
      i. Sen-*
      1.7cm
                                •^
                               4.0 cm
          9.7 cm
         9096  - 8
                                                           Revision 0
                                                           September 1994

-------
            FIGURE 4.
POSITIONING OF DYE ON GLASS  PLATE
         Methylene Blue
         Anthraquinone
                                            7.5 cm
                 7.5 cm
             9096  -  9
Revision 0
September 1994

-------
                                    METHOD 9096
                    LIQUID  RELEASE TEST  (LRT)  PROCEDURE
START
                                 J
7.6 Add mori
   •ample
                    7 .1  Di*a**amble
                    LRTD to en*ure
                    cleanline** and
                        dryne**
                       7.2 Place
                     *creen, grid
                      and filter
                       paper on
                     cylinder bate
                      7.3  Secure
                     •ample holder
                       7.4  - 7.5
                     Fill cylinder
                     xith (ample;
                     tap to remove
                         air
                  7.8 Place
               •tainle**-*teel
               and grid on top
                  ox *ample
                  7.9 Place
                filter paper
                 on grid and
                center in the
                   device
                 7.10 Lower
                 piston into
                •ample holder
                 7.11 Place
                •ample holder
                on baซe plate
                 and ซecure
                  7.12 Lock
                  preซ*ure
                device on top
                  of *ample
                   holder
                                         7 .13 Connect
                                           air  line*
 7.14 Pre**uriie
   LRTD and
   maintain
 preปซure for 10
    minute*
  7.15 - 7.16
 Depre**urize
  and remove
   LRTD from
 •ample holder
  7.18 Remove
    pi*ton
  7.19 -  7.21
Di*a**emble  and
 check filter
 paper for wet
    ซpot(.)
C    STOP      J
                                     9096  -  10
                                                      Revision  0
                                                      September 1994

-------
                                  APPENDIX A

                         LIQUID RELEASE TEST PRE-TEST

1.0   SCOPE AND APPLICATION

      1.1    The LRT Pre-Test is an optional,  5 minute laboratory test designed
to determine whether or  not  liquids will  be definitely released from sorbents
before applying the LRT.   This test is  performed to prevent unnecessary cleanup
and possible damage to the LRT device.

      1.2    This  test is  purely  optional  and completely up to the discretion
of the operator as to when it should be used.

2.0   SUMMARY OF METHOD

      A representative sample will  be loaded into a glass grid that  is placed on
a  glass  plate  already  stained with 2 dyes  (one water  soluble  and  one oil
soluble).  A second glass plate will be placed on  top and  a 2 Ib. weight placed
on top for 5 minutes.  At the end of  5 minutes the base  of  the glass grid is
examined for  any  dye running  along the edges, this  would  indicate  a liquid
release.

3.0   INTERFERENCES

      A  liquid  release  can  be  detected at  lower Liquid Loading  Levels  with
extremely clean glassware.   The glass  plates  and  glass  grid should be cleaned
with a laboratory detergent,  rinsed with Deionized water, rinsed with acetone,
and thoroughly dried.

4.0   APPARATUS AND MATERIALS

      4.1    Glass Plate:  2 glass  plates measuring 7.5 cm x 7.5 cm.

      4.2    Glass Grid:   See Figure 3.

      4.3    Paint Brush:  Two small paint brushes for applying dyes.

      4.4    Spatula:  To assist in  loading the sample.

      4.5    Weight:  2.7 kg weight  to apply pressure to  the sample.

5.0   REAGENTS

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

      5.2    Methylene Blue dye in methanol.
                                   9096  -  11
Revision 0
September 1994

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      5.3    Anthraquinone dye in toluene.


6.0   SAMPLE COLLECTION, PRESERVATION AND HANDLING

      See LRT Procedure.

7.0   PROCEDURE

      7.1    Paint  one  strip,  approximately 1 cm wide,  of  methylene blue dye
across the center of  a  clean and dry glass plate (see  Figure  4).   The dye is
allowed to dry.

      7.2    Paint  one  strip,  approximately  1  cm wide, of anthraquinone dye
across the center of the same glass  plate  (see Figure 4).  This strip should be
adjacent to and parallel with the methylene blue strip.  The dye is allowed to
dry.

      7.3    Place the glass grid in the center of the dye-painted glass plate.

      7.4    Place a small amount of sample into the glass-grid holes, pressing
down gently until the holes are filled to slightly above the grid top.

      7.5    Place a second,  clean and dry, glass plate on top of  the sample and
grid.

      7.6    Place a 2.7 kg weight on top of the glass  for  5 minutes.

      7.7    After 5 minutes remove  the  weight and examine the base of the grid
extending beyond the sample holes  for any indication  of dyed  liquid.  The entire
assembly may be turned  upside down  for  observation.   Any indication of liquid
constitutes a release and the LRT does not need  to be performed.

8.0   QUALITY CONTROL

      8.1    Refer to Chapter One for specific quality  control  procedures.

9.0   METHOD PERFORMANCE

      9.1    Precision and accuracy data are not available  at this time.

10.0  REFERENCES

1.    Research Triangle  Institute.  "Background Document for the Liquid Release
      Test:   Single  Laboratory  Evaluation  and  1988  Collaborative  Study".
      Submitted to the Environmental  Protection Agency under  Contract No. 68-01-
      7075, Work Assignment  76 and Contract No. 68-WO-0032, Work Assignment 12.
      September 18,  1991.
                                  9096  -  12                       Revision 0
                                                                  September 1994

-------
          METHOD 9096
           APPENDIX A
       START
7.1  Paint methylene
   blue atrip on
    glasi; dry
     7.2 Paint
anthraquinone strip
 on glass parallel
to firat atrip;  dry
 7.3 Place grid in
  center  of glass
       plate
 7.4 Fill holea of
 grid with aample
 7.5 Place second
glasa plate on top
     of  sample
7.6 Apply weight on
glaaa  for 5 minutes
 7.7 Remove weight
 and check for *ซt
      apot(a)
       STOP
         9096  - 13
                          Revision  0
                          September 1994

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                                 METHOD 9100

                      SATURATED HYDRAULIC CONDUCTIVITY,
                    SATURATED LEACHATE CONDUCTIVITY,  AND
                           INTRINSIC PERMEABILITY
1.0  INTRODUCTION
     1.1  Scope and Application;   This  section presents methods available to
hydrogeologists and and geotechnical  engineers  for determining the saturated
hydraulic conductivity of earth materials  and  conductivity of soil liners to
leachate, as outlined by  the  Part  264  permitting rules for hazardous-waste
disposal facilities.  In addition,  a general technique to determine intrinsic
permeability is provided.  A  cross  reference  between the applicable part of
the RCRA Guidance Documents and  associated  Part 264 Standards and these test
methods is provided by Table A.

          1.1.1  Part 264 Subpart  F  establishes  standards  for ground water
     quality  monitoring  and  environmental   performance.    To  demonstrate
     compliance with these standards,  a  permit applicant must have knowledge
     of certain aspects of the hydrogeology  at the disposal facility, such as
     hydraulic conductivity, in order  to  determine  the compliance point and
     monitoring well locations and in  order  to develop remedial action plans
     when necessary.

          1.1.2  In this report,  the  laboratory  and  field methods that are
     considered the most appropriate to  meeting  the requirements of Part 264
     are given in sufficient  detail  to provide an experienced hydrogeologlst
     or geotechnical engineer  with  the  methodology  required to conduct the
     tests.  Additional laboratory  and  field  methods that may be applicable
     under certain conditions are included by providing references to standard
     texts and scientific journals.

          1.1.3  Included in this  report  are  descriptions  of field methods
     considered appropriate for estimating saturated hydraulic conductivity by
     single  well  or  borehole   tests.     The  determination  of  hydraulic
     conductivity by pumping or  injection  tests  is not included because the
     latter are considered appropriate for  well field design purposes but may
     not be appropriate for economically evaluating hydraulic conductivity for
     the purposes set forth in Part 264 Subpart F.

          1.1.4  EPA is  not  Including  methods  for  determining unsaturated
     hydraulic conductivity  at  this  time  because  the   Part 264 permitting
     standards do not require such determinations.

     1.2  Definitions;   This section provides  definitions  of  terms used in
the  remainderofthis  report.    These  definitions  are  taken  from U.S.
Government publications when possible.
                                  9100 -  1
                                                         Revision
                                                         Date  September 1986

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                                   TABLE A

               HYDRAULIC AND LINER CONDUCTIVITY DETERMINATION
                      METHODS FOR SURFACE IMPOUNDMENT,
                WASTE PILE,  AND LANDFILL COMPONENTS,  AS CITED
             IN RCRA GUIDANCE DOCUMENTS AND DESCRIBED IN SW-846
                                   Guidance Cite*              Corresponding
Surface Impoundments            Associated Regulation          SW-846 Section


Soil liner hydraulic            Guidance section D(2)(b)(l)           2.0
conductivity                    and D(2)(c)(l)/Section
                                264.221(a),(b)

Soil Uner leachate             Guidance section D(2)(b)(2)           2.11
conductivity                    and D(2)(c)(2)

Leak detection                  Guidance section C(2)(a)/            2.0
                                Section 264.222

Final cover drain               Guidance section E(2)(d)(l)           2.0
layer                           Section 264.228

Final cover low                 Guidance section E(2)(e)(2)(A)/      2.0
permeability layer              Section 264.228

General hydrogeologic           264 subpart F                        3.0
site investigation
1 RCRA Guidance Document:  Surface Impoundments, Liner Systems, Final Cover,
  and Freeboard Control.  Issued July, 1982.


                          (continued on next page)
                                  9100 - 2
                                                         Revision
                                                         Date  September 1986

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                             TABLE A (continued)
                                    Guidance Cite2              Corresponding
Waste Piles                        Associated Regulation        SW-846 Section


Soil liner hydraulic            Guidance section D(2)(b)(i)          2.0
conductivity                    and D(2)(c)(1)/
                                Section 264.251(a)(1)

Soil liner leachate             Guidance section D(2)(b)(ii)         2.11
conductivity                    and D(2)(c)(1i)

Leak detection                  Guidance section C(2)(a)/            2.0
system                          Section 264.252(a)

Leachate collection             Guidance section C(2)(a)/            2.0
and renewal system              Section 264.251(a)(2)

General hydrogeologic           264 subpart F                        3.0
site investigation
 2  RCRA Guidance Document:   Waste  Pile  Design,  Liner Systems.
   Issued  July,  1982.

                           (continued on  next page)
                                   9100 - 3
                                                          Revision      0
                                                          Date  September 1986

-------
                             TABLE A (continued)
Landf111s
      Guidance Cite3
     Associated Regulation
Corresponding
SW-846 Section
Soil liner hydraulic
conductivity

Soil liner leachate
conductivity

Leak detection
system

Leachate collection and
removal system

Final cover drain
layer

Final cover low
permeability layer

General hydrogeologic
site investigation
  Guidance section D(2)(b)(l)/         2.0
  Section 264.301(a)(l)

  Guidance section D(2)(b)(2)          2.11
   Guidance  section  C(2)(a)/             2.0
   Section 264.302(a)(3)

   Guidance  section  C(2)(a)/             2.0
   Section 264.301(a)(2)

   Guidance  section  E(2)(d)(l)/          2.0
   Section 264.310(a)(b)

   Guidance  section  E(2)(e)(2)(A)        2.0
   Section 264.310(a)(b)

   264 subpart F                        3.0
3 RCRA Guidance  Document:
Issued July,  1982.
Landfill   Design,   Liner Systems and Final  Cover.
                                   9100 - 4
                                                          Revision       0
                                                          Date  September  1986

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     1.2.1  Units:  This  report  uses consistent units in all  equations.
The symbols used are:

          Length = L,
          Mass   •= M, and
          Time   = T.

     1.2.2  Fluid  potential  or  head  (h):  A  measure of the potential
energy required to move fluid  from  a  point  in  the porous medium to a
reference point.  For virtually  all  situations  expected to be found in
disposal sites and in ground water systems, h is defined by the following
equation:

     h = hp + hz                                                  (1)

where:

     h  is the total fluid potential, expressed as a height of
        fluid above a reference datum, L;

     hp, the pressure potential caused by the weight of fluid
         above the point in question, L, is defined by hp = P//KJ,

          where:

          P  is the fluid pressure at the point  in question, ML~^T~2,

          p  is the fluid density at the prevailing temperature, ML~3,
               and

          g  is the acceleration of gravity,  LT~2; and

      hz  is the height of the  point  in question  above  the  reference
      datum,  L.

      By  knowing  hp  and  hz  at  two  points along  a flow path  and by  knowing
 the distance between  these  points,   the   fluid potential gradient  can be
 determined.

      1.2.3   Hydraulic potential or  head:    The  fluid  potential when water
 is the fluid.

      1.2.4   Hydraulic conductivity:   The   fluid  potential  when water is
 the fluid.   The  generic term,  fluid conductivity,  is discussed below in
 1.2.5.

      1.2.5   Fluid conductivity (K):   Defined  as  the volume  of fluid at
 the prevailing  density  and dynamic  viscosity   that   will  move in  a unit
 time under  a unit fluid potential   gradient through  a unit area measured
 at right angles  to  the  direction  of  flow.    It is a  property  of both the
 fluid and the porous  medium as shown  by the following equation:
                              9100 - 5
                                                     Revision
                                                     Date  September 1986

-------
     K - SJfl ;                                                         (2)

where:

     K  is the fluid conductivity, IT"1;

     k  is the intrinsic permeability,  a  property  of the porous medium
        alone, L^; and

     u  is the dynamic viscosity of the fluid at the prevailing
        temperature, ML~1 T~l.

The fluid conductivity of a  porous  material  is also defined by Darcy's
law, which states that  the  fluid  flux  (q)  through a porous medium is
proportional to the first power  of  the  fluid potential across the unit
area:

     q = J = -KI                                                     (3)

where:

     q = the specific fluid flux, LT'l,

     Q is the volumetric fluid flux, L3!'1,

     A is the cross-sectional area, L2, and

      I is the fluid potential gradient, Lฐ.

Darcy's  law  provides  the  basis  for  all  methods  used  to determine
hydraulic conductivity  in this report.   The range of validity of Darcy's
law  is discussed  in Section 1.5  (Lohman, 1972).

      1.2.6  Leachate conductivity:  The  fluid conductivity when  leachate
is the fluid.

      1.2.7  Aquifer:  A geologic formation,  group of formations, or part
of a formation  capable  of  yielding   a  significant amount  of ground water
to wells or springs  (40 CFR 260.10).

      1.2.8  Confining  layer:   By strict definition,  a body of  impermeable
material  stratigraphically adjacent to  one   or more  aquifers.   In nature,
however,  its  hydraulic  conductivity   may   range   from nearly zero to some
value distinctly   lower  than   that   of the aquifer.    Its conductivity
relative  to that   of   the  aquifer it  confines   should  be specified  or
indicated   by  a   suitable  modifier,   such  as   "slightly permeable"  or
 "moderately permeable"  (Lohman,  1972).

      1.2.9  Transm1ss1y1ty, T  [L2,  I"1]:   The   rate  at which water of the
prevailing  kinematic  viscosity is transmitted through a  unit width of the
aquifer under  a   unit   hydraulic  gradient.    Although  spoken  of as a
                              9100 - 6
                                                     Revision
                                                     Date  September 1986

-------
     property of the aquifer,  the  term  also Includes the saturated thickness
     of the aquifer and  the  properties  of  the  fluid.     It 1s  equal  to an
     Integration of the hydraulic conductivities  across the saturated part of
     the aquifer perpendicular to the flow paths (Lohman,  1972).

     1.3  Temperature and  viscosity  corrections;    By  using  Equation (2),
corrections to conditions different from  those prevailing during the test can
be made.  Two types of  corrections  can  commonly be made: a correction for a
temperature that varies from the test temperature, and a correction for fluids
other than that used for the test.  The temperature correction 1s defined by:

               K  u
     where:
                                                              #
          the subscript f refers to field conditions, and

          the subscript t refers to test conditions.

Most temperature  corrections  are  necessary  because  of  the  dependence of
viscosity on temperature.    Fluid  density  variations  caused by temperature
changes are usually very  small  for  most liquids. The temperature correction
for water can be significant.    Equation  (4)  can  also be used to determine
hydraulic conductivity if fluids other  than  water  are used.  It is assumed,
however, when using  Equation  (4)  that  the  fluids  used  do  not alter the
intrinsic permeability of the  porous  medium  during  the test.  Experimental
evidence shows that this alteration  does  occur  with a wide range of organic
solvents (Anderson and Brown,  1981).    Consequently,  it is recommended that
tests be run  using  fluids,  such  as  leachates,  that  might  occur at each
particular site.   Special  considerations  for  using  non-aqueous fluids are
given in Section 3.3 of this report.


     1.4  Intrinsic permeability  (k) :  Rearrangement  of Equation 2 results in
a definition of intrinsic permeability:
Since this  is a property of the  medium alone, if fluid properties change, the
fluid conductivity must  also  change  to  keep  the  intrinsic permeability a
constant.   By using measured  fluid  conductivity, and values of viscosity and
density  for the fluid at  the  test temperature, intrinsic permeability can be
determined.

     1.5 Range   of  validity  of   Darcy's    law;    Determination  of  fluid
conductivities using both laboratory   and  field methods requires assuming the
validity of Darcy's law.  Experimental evidence has shown that deviations from
the  linear  dependence  of  fluid   flux on  potential  gradient exist for both
extremely low and extremely high   gradients   (Hillel, 1971;  Freeze and Cherry,
1979).   The  lower  limits  are   the  result  of  the  existence of threshold


                                   9100 - 7
                                                         Revision      0
                                                         Date  September  1986

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gradients required to Initiate flow  (Swartzendruber,  1962).   The upper limits
to the validity of Darcy's law  can  be estimated by the requirements that the
Reynolds number, Re,  In  most  cases  be  kept  below  10  (Bear, 1972).   The
Reynolds number Is defined by:
          Re =                                                             (6)

     where:

          d 1s some characteristic dimension of the system, often represented
            by the median grain size diameter, DSQ, (Bouwer, 1978), and
          q  1s the fluid flux per unit area, LT'1.

 For most  field situations, the Reynolds  number  1s less than one, and Darcy's
 law 1s  valid.  However, for  laboratory  tests 1t may be possible to exceed the
 range of  validity by   the  Imposition  of  high  potential gradients.  A rough
 check on  acceptable   gradients  can  be  made  by  substituting Darcy's law 1n
 Equation  (6)  and using an  upper limit of 10 for Re:

           T
                /*D50

      where:

           K  is the approximate  value  of  fluid conductivity determined at
             gradient I.

 A more correct check on  the validity   of Darcy's  law or the  range of gradients
 used to determine fluid   conductivity is  performed  by measuring the conduc-
 tivity at three different gradients.   If  a plot  of fluid flux  versus gradient
 is linear, Darcy's law can be considered to be  valid for the test conditions.

      1.6    Method  Classification;       This   report  classifies  methods  of
 determining   fluid  conductivity  into  two divisions:  laboratory  and field
 methods.  Ideally, and  whenever  possible, compliance with Part 264 disposal
 facility requirements should be evaluated by using field methods that test the
 materials under 1n-s1tu  conditions.    Field methods can usually provide more
 representative values than  laboratory   methods  because  they test a larger
 volume  of  material, thus  integrating  the   effects  of   macrostructure and
 heterogeneities.  However, field methods  presently available to determine the
 conductivity of compacted fine-grained  materials 1n reasonable times require
 the tested interval to  be  below  a   water table  or  to be fairly thick, or
 require excavation of the material  to  be  tested  at  some  point  in the test.
 The  Integrity  of  liners  and  covers   should  not  be  compromised  by  the
 installation of  boreholes  or  piezometers  required   for   the tests.  These
 restrictions generally lead to the  requirement that the  fluid  conductivity of
 Uner and cover materials must be  determined  in the  laboratory.   The  transfer
 value of laboratory data to field  conditions   can be maximized for liners and
 covers because it is possible to reconstruct relatively accurately the desired
                                   9100 - 8
                                                          Revision
                                                          Date  September 1986

-------
field conditions 1n  the  laboratory.    However,   field conditions  that  would
alter the values determined 1n the  laboratory  need to be addressed 1n permit
applications.  These conditions Include those that would Increase conductivity
by the formation of mlcrocracks  and  channels by repeated wetting and drying,
and by the penetration of roots.

          1.6.1  Laboratory methods  are  categorized  1n  Section  2.0 by the
     methods used to apply  the  fluid  potential  gradient across the sample.
     The discussion of the theory, measurement, and computations for tests run
     under constant and  falling-head  conditions  is  followed  by a detailed
     discussion of tests using specific  types of laboratory apparatus and the
     applicability  of  these   tests   to  remolded  compacted,  fine-grained
     uncompacted, and coarse-grained  porous  media.    Section 2.3 provides a
     discussion of the special  considerations for conducting laboratory tests
     using non-aqueous permeants.    Section  2.10  gives  a discussion of the
     sources  of  error  and  guidance   for  establishing  the  precision  of
     laboratory  tests.    Laboratory  methods  may  be  necessary  to measure
     vertical fluid conductivity.  Values  from field tests reflect effects of
     horizontal and vertical conductivity.

           1.6.2  Field methods  are discussed  in Section 3.0 and are limited to
     those requiring  a  single  bore  hole  or  piezometer.  Methods  requiring
     multiple bore holes   or  piezometers  and  areal  methods are  Included by
     reference.  Because of the difficulties  1n determining fluid conductivity
     of  in-place   liner  and  cap  materials  under  field  conditions without
     damaging their   integrity,  the  use  of field  methods for fine-grained
     materials will be generally  restricted  to  naturally occurring  materials
     that  may serve as a barrier  to fluid movement.  Additional field methods
     are  referenced   that   allow   determination   of  saturated   hydraulic
     conductivity  of  the  unsaturated  materials above  the shallowest water
     table.  General  methods  for fractured media   are given In Section 3.8.  A
     discussion  of   the   Important    considerations   in  well  Installation,
     construction, and development  1s   Included   as an  introduction to Section
     3.0.
 2.0  LABORATORY METHODS

      2.1   Sample  collection   for  laboratory  method;      To   assure  that  a
 reasonable assessment 1s made of fieldconditionsat  a disposal  site, a  site
 investigation plan should be  developed  to   direct sampling  and  analysis.   This
 plan  generally  requ1res$the   professional   judgement  of  an   experienced
 hydrogeologist or geotechnical   engineer.    General  guidance  1s  provided for
 plan development in the Guidance  Manual   for  Preparation  of  a Part  264  land
 Disposal  Facility Permit Application  (EPA,  in  press).The  points  listed below
 should be followed:

 o    The  hydraulic conductivity of a  soil Uner  should be determined either
      from samples that are processed  to  simulate the actual Uner,  or from  an
      undisturbed sample of the complete liner.
                                   9100 - 9
                                                          Revision      0
                                                          Date  September 1986

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o    To obtain undisturbed samples, the thin-walled tube sampling method (ASTM
     Method  #  D1587-74)  or  a   similar   method  may  be  used.    Samples
     representative of each 11ft of the  liner should be obtained, and used in
     the analyses.  If actual undisturbed  samples are not used, the soil used
     1n liner  construction  must  be  processed  to  represent accurately the
     liner's Initial water content and bulk  density.  The method described in
     Section 2.7.3 or ASTM Method #0698-70  (ASTM,  1978) can be used for this
     purpose.

o    For purpose of  the  general  site  investigation, the general techniques
     presented in ASTM method #0420-69 (ASTM,  1978) should be followed.  This
     reference establishes  practices  for  soil  and  rock  investigation and
     sampling,  and  incorporates   various   detailed   ASTM  procedures  for
     Investigation, sampling, and material classification.

     2.2  Constant-head methods:   The  constant-head  method   is  the simplest
method of determining hydraulic  conductivity  of  saturated soil  samples.  The
concept of  the constant-head method   is schematically  Illustrated  in Figure 1.
The  Inflow  of fluid is maintained  at a  constant   head  (h) above a datum and
outflow  (Q)  is measured  as  a  function  of  time   (t).   Using  Darcy's law, the
hydraulic conductivity can  be  determined  using  the  following equation after
the  outflow rate  has become constant:

                K  =  QL/hA,                                                   (8)

     where:

                K  =  hydraulic conductivity,  LT"1;

                L  =  length of sample,  L;

                A  =  cross-sectional  area  of sample,  L^;

                Q  =  outflow rate, L^T'l;  and

                h  =  fluid head difference across the sample,  L.

 Constant-head methods  should be restricted to tests on media having high fluid
 conductivity.

      2.3  Falling-head methods;   A schematic  diagram of the apparatus  for the
 falling-head method is shown in Figure 2.    The head of inflow fluid decreases
 from hj to \\2 as  a function  of  time (t)  in a standpipe directly connected to
 the specimen.   The fluid  head  at  the   outflow  1s maintained constant.  The
 quantity of outflow can be measured  as   well  as the quantity of Inflow.  For
 the setup shown in  Figure  2a,   the  hydraulic conductivity can be determined
 using the following equation:

           v   2.3 aL,      hO
           K = -At—Iog10 h  '
                                   9100 - 10
                                                          Revision
                                                          Date  September 1986

-------
                            WATER SUPPLY
OVERFLOW
TO MAINTAIN
CONSTANT HEAD
                                         OMAOUATIIO
                                         C VLINOE R
   Figure 1.—Principle of  the constant head method
                    9100 - 11
                                         Revision     0
                                         Date  September 1986

-------
      STANDPIPE-
OVERFLOW^-  _,
              ^T^
(a)
                                 OVERFLOW
                                               (b)
    Figure 2.—Principle of  the falling head method
               using a small (a)  and large  (b)  standpipe,
                      9100 - 12
                                           Revision      p
                                           Date  September 1986

-------
     where:

          a  = the cross-sectional  area of the standplpe,  L2;

          A  = the cross-sectional  area of the specimen,  L2;

          L  = the length of the specimen, L;  and

          t  = elapsed time from ti to t2, T.

For the setup in Figure 2b, the  term  a/A in Equation (9)  is replaced by 1.0.
Generally, falling-head methods are  applicable  to fine-grained soils because
the testing  time can be accelerated.

     2.4  General test considerations;

          2.4.1  Fluid  supplies  to  be  used:    For  determining  hydraulic
     conductivity and leachate  conductivity,  the  supplies of permeant fluid
     used should be de-a1red.  A1r  coming  out  of solution in the sample can
     significantly reduce the measured  fluid  conductivity.   Deairing can be
     achieved by boiling the water supply  under a vacuum,  bubbling helium gas
     through the supply, or both.

               2.4.1.1  Significant reductions  in  hydraulic conductivity can
          also  occur  in  the  growth  and  multiplication  of microorganisms
          present in the sample.  If it is desirable to prevent such growth, a
          bactericide or fungicide, such as  2000 ppm formaldehyde or 1000 ppm
          phenol (Olsen and Daniel, 1981), can be added to the fluid supply.

               2.4.1.1  Fluid used for  determining  hydraulic conductivity in
          the laboratory should never be distilled water.  Native ground water
          from the aquifer underlying  the  sampled  area or water prepared to
          simulate the native ground water chemistry should be used.

          2.4.2  Pressure and Fluid  Potential  Measurement:  The equations in
     this report are all dimenslonally correct; that is, any consistent set of
     units may be used for length, mass, and time.  Consequently, measurements
     of pressure and/or fluid  potential  using  pressure gages and manometers
     must be reduced  to  the  consistent  units  used  before applying either
     Equation 8 or 9.  Pressures or  potentials should be measured to within  a
     few  tenths of one percent of the gradient applied across the sample.

     2.5  Constant-head test with conventional permeameter;

          2.5.1  Applicability:  This method   covers  the determination of  the
     hydraulic   conductivity  of  soils  by  a  constant-head  method  using  a
     conventional permeameter.    This   method  1s  recommended  for disturbed
     coarse-grained  soils. If  this  method  1s  to  be  used for fine-grained
     soils,  the  testing time may be prohibitively  long.  This method was  taken
     from the  Engineering  and  Design,   Laboratory  Soils Testing Manual  (U.S.
     Army,  1980).   It parallels  ASTM  Method  D2434-68  (ASTM.1978).  The ASTM
                                   9100 -  13
                                                         Revision      0
                                                         Date  September  1986

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method gives extensive discussion of sample preparation and applicability
and should be  reviewed  before  conducting  constant-head  tests.  Lambe
(1951)  provides  additional   information   on  sample  preparation  and
equipment procedures.

     2.5.2  Apparatus:  The apparatus 1s shown schematically in Figure 3.
It consists of the following:

     1.  A permeameter cylinder having  a  diameter  at least 8 times the
         diameter of the largest particle of the material to be tested;

     2.  Constant-head filter tank;

     3.  Perforated metal disks and circular wire to support the sample;

     4.  Filter materials such as Ottawa sand, coarse sand, and gravel of
         various gradations;

     5.  Manometers connected to the top and bottom of the sample;

     6.  Graduated cylinder, 100-mL capacity;

     7.  Thermometer;

     8.  Stop watch;

     9.  Deal red water;

     10.  Balance sensitive  to 0.1 gram; and

     11.  Drying oven.

      2.5.3   Sample preparation:

      1.  Oven-dry  the sample.  Allow  it to cool,  and weigh to  the nearest
         0.1 g.   Record  the oven-dry   weight  of  material.  The  amount of
         material  should  be  sufficient   to  provide   a  specimen in the
         permeameter having a  minimum  length  of  about one to  two times
         the diameter of the specimen.

      2.   Place a  wire screen,  with  openings  small enough to retain the
          specimen,  over  a perforated  disk  near the  bottom  of  the
         permeameter above  the   Inlet.    The  screen  opening  should be
         approximately equal to  the 10 percent size of the specimen.

      3.  Allow deal red water to  enter  the water inlet of the  permeameter
          to a  height of about   1/2  1n.  above  the bottom of  the screen,
          taking care that no air bubbles  are trapped under the screen.
                              9100 - 14
                                                     Revision
                                                     Date  September 1986

-------




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                         9100 - 15
                                             Revision     0
                                             Date  September 1986

-------
4.  Mix the material  thoroughly  and  place  1n  the permeameter to
    avoid segregation.  The material  should  be dropped just at the
    water surface, keeping the water surface about 1/2 1n. above the
    top of the  soil  during  placement.    A  funnel  or a spoon 1s
    convenient for this purpose.

5.  The  placement  procedure  outlined   above  will  result  1n  a
    saturated specimen of uniform  density  although 1n a relatively
    loose condition.  To produce  a  higher density 1n the specimen,
    the sides of  the  permeameter  containing  the  soil sample are
    tapped uniformly  along  Its  circumference  and  length  with a
    rubber  mallet  to  produce  an  increase  1n  density; however,
    extreme caution should be  exercised  so  that fines are not put
    Into  suspension  and  segregated  within  the  sample.    As an
    alternative to  this procedure, the  specimen may be placed using
    an appropriate  sized funnel  or  spoon.  Compacting the specimen
    in layers is  not  recommended,  as  a  film  of dust which might
    affect the permeability  results may  be formed at the surface of
    the compacted layer.  After placement, apply a vacuum to the top
    of the specimen and permit water to enter the evacuated specimen
    through the base  of the  permeameter.

 6.  After the specimen has   been  placed, weigh the  excess material,
    if  any,  and  the  container.     The  specimen  weight  1s  the
    difference between the original weight  of  sample and the weight
    of the excess material.   Care   must be taken so  that  no material
    is lost during  placement of the specimen.  If there  1s evidence
    that material has been   lost,  oven-dry  the specimen and weigh
    after the test  as a check.

 7.  Level the top of  the  specimen,  cover with  a wire screen similar
    to that  used  at the   base,   and fill  the  remainder  of the
    permeameter with  a filter material.

 8.  Measure the   length   of   the  specimen,   inside  diameter of the
    permeameter,  and  distance between   the  centers  of  the manometer
    tubes  (L) where they  enter  the  permeameter.

 2.5.4 Test procedure:

 1.  Adjust the  height  of   the  constant-head  tank to  obtain the
    desired hydraulic gradient.     The hydraulic gradient should be
    selected so   that the   flow  through  the  specimen  1s  laminar.
    Hydraulic gradients ranging  from   0.2  to  0.5  are recommended.
    Too  high a hydraulic  gradient   may cause  turbulent  flow and also
    result in piping  of   soils.     In  general,  coarser  soils require
    lower  hydraulic  gradients.     See  Section  1.5   for  further
    discussion of excessive  gradients.

 2.  Open valve A  (see Figure 3a)   and record the initial piezometer
    readings after  the flow   has  become  stable.    Exercise care in
    building up heads in  the permeameter so that the specimen Is not
    disturbed.

                        9100 -  16
                                                Revision     0
                                                Date  September 1986

-------
     3.  After allowing a few  minutes  for  equilibrium conditions to be
         reached, measure by means  of  a graduated cylinder the quantity
         of discharge corresponding to  a  given  time Interval.  Measure
         the piezometric heads (hj and  h2)  and the water temperature in
         the permeameter.

     4.  Record  the  quantity   of   flow,  piezometer  readings,  water
         temperature, and the time interval  during which the quantity of
         flow was measured.

     2.5.5  Calculations:    By  plotting  the  accumulated  quantity  of
outflow versus time on  rectangular  coordinate  paper,  the slope of the
linear  portion  of  the  curve  can  be  determined,  and  the hydraulic
conductivity can be calculated using  Equation  (8).    The value of h in
Equation (8) 1s the difference between hi and \\2*

2.6  Falling-head test with conventional permeameter;

     2.6.1  Applicability:  The  falling-head  test  can  be used for all
soil types, but 1s usually most widely applicable to materials having low
permeability.  Compacted, remolded, fine-grained soils can be tested with
this method.  This  method  presented  1s  taken from the Engineering and
Design, Laboratory Soils Testing Manual  (U.S. Army, 1980).

     2.6.2  Apparatus:    The  schematic   diagram  of  the  falling-head
permeameter 1s shown   in  Figure  3b.    The  permeameter consists of the
following equipment:

     1.  Permeameter cylinder, a  transparent   acrylic  cylinder  having  a
         diameter at least 8  times the diameter of  the  largest  particles;

     2.  Porous  disk;

     3.  Wire  screen;

     4.  Filter  materials;

     5.  Manometer;

     6.  Timing  device;  and


     2.6.3  Sample  Preparation:    Sample  preparation  for  coarse-grained
soils  is similar to  that  described  previously   1n   Section 2.4.3.   For
fine-grained soils,  samples  are   compacted to  the desired density  using
methods described 1n ASTM Method  D698-70.

     2.6.4  Test Procedure:

     1.  Measure and record  the height  of  the specimen,  L,  and  the cross-
         sectional  area  of the specimen, A.
                              9100 - 17
                                                     Revision
                                                     Date   September  1986

-------
     2.   With valve B open  (see  Figure   3b),   crack  valve  A,  and  slowly
         bring  the  water  level   up  to  the   discharge  level  of  the
         permeameter.

     3.   Raise the head of  water  in  the  standpipe  above  the discharge
         level of the permeameter.    The  difference   in  head  should not
         result in  an  excessively  high  hydraulic  gradient  during the
         test.  Close valves A and B.

     4.   Begin the test by opening  valve  B.     Start the timer.   As the
         water flows through the specimen,  measure and record  the  height
         of water in the standpipe above  the discharge level,  hi, at time
         ti, and the height  of  water above  the discharge level, h2 at
         time t2.

     2.6.5  Calculation*.  From the test  data,  plot the logarithm of head
versus time on rectangular coordinate paper,  or use semi-log paper.  The
slope  of  the  linear   part   of   the    curve  is  used  to   determine
Iogio(hi/h2)/t.  Calculate the hydraulic  conductivity using  Equation (9).

2.7  Modified compaction permeameter method;

     2.7.1  Applicability:  This  method   can  be  used  to  determine the
hydraulic conductivity of  a  wide  range  of  materials.    The method is
generally used for remolded fine-grained   soils.  The method is generally
used under constant-head conditions.   The method was taken  from Anderson
and Brown, 1981, and EPA   (1980).    It  should be noted that this  method
method of Section 2.9.

     2.7.2  Apparatus:  The apparatus is  shown  in Figure 4 and consists
of equipment  and accessories as follows:

     1.  Soil  chamber, a compaction mold having a diameter 8 times  larger
         than the  diameter  of   the  largest  particles  (typically, ASTM
         standard mold, Number CN405, is  used);

     2.  Fluid chamber, a. compaction mold sleeve having the same diameter
         as  the  soil chamber;

     3.  2-kg hammer;

     4.  Rubber  rings  used for  sealing purposes;

     5.  A  coarse  porous  stone  having higher permeability than the tested
         sample;

     6.  Regulated  source  of compressed  air; and

     7.  Pressure  gage or  manometer to  determine   the  pressure on  the
         fluid chamber.
                              9100 -  18
                                                    Revision
                                                    Date  September 1986

-------
                         TO REGULATED PRESSURE SOURCE AND
                         PRESSURE GAGE OR MANOMETER USED TO
                         MEASURE H .
                                 PRESSURE RELEASE VALVE
                                              TOP PLATE
                                               RUBBER "0' RING SEALS
                                              BASE PLATE
                           I— POROUS STONE
                              OUTFLOW TO VOLUMETRIC MEASURING DEVICE.

                              PRESSURE SHOULD BE ATMOSPHERIC OR ZERO
                              GAGE PRESSURE
Figure  4.—Modified compaction  permeameter.
            Note: h  in Equation  8 is the difference
            between  the regulated inflow pressure
            and the  outflow pressure.  Source:
            Anderson and Brown,  1981.
                       9100 - 19
                                            Revision     0
                                            Date  September 1986

-------
    2.7.3  Sample preparation:
    1.  Obtain sufficient  representative  soil  sample.    Air  dry the
        sample at room temperature.  Do not oven dry.
    2.  Thoroughly mix the selected  representative sample with water to
        obtain a desired moisture  content.
    3.  Compact the  sample to  the  desired density within the mold  using
        the  method described as  part of ASTM Method D698-70.
    4.  Level the surface of   the  compacted   sample with straight  edge,
        weigh and determine the  density of the sample.
    5.  Measure the  length and diameter of the sample.
    6.  Assemble the apparatus,  make sure  that there  are no leaks, and
        then connect the pressure  line to the  apparatus.
    2.7.4  Test procedure:
    1.  Place sufficient volume  of water  in the fluid  chamber  above the
        soil chamber.
    2.  Apply air pressure gradually  to  flush water through the sample
        until no air bubbles   in  the  outflow are observed.   For  fine-
        grained  soils,  the saturation may  take several  hours to several
        days, depending on the applied pressure.
    3.  After the sample is   saturated,  measure and record  the quantity
        of outflow  versus time.
    4.  Record  the  pressure  reading  (h) on   the top of  the fluid chamber
        when each reading is  made.
    5.   Plot the   accumulated  quantity   of   outflow   versus  time  on
        rectangular coordinate paper.
    6.  Stop taking readings  as  soon as the  linear position  of  the  curve
         is defined.
     2.7.5  Calculations:  The  hydraulic   conductivity  can be  calculated
using  Equation  (8).
2.8  Triaxial-cell  method with back pressure:
     2.8.1  Applicability:   This  method  is  applicable  for all soil  types,
but especially  for fine-grained,  compacted,   cohesive  soils  in  which full
fluid  saturation of the sample  is  difficult  to  achieve.   Normally,  the
test is run under constant-head conditions.
                             9100 - 20
                                                    Revision
                                                    Date  September 1986

-------
     2.8.2  Apparatus:  The apparatus is similar to conventional  triaxial
apparatus.  The schematic diagram of this apparatus is shown in Figure 5.

     2.8.3  Sample preparation:  Disturbed  or undisturbed samples can be
tested.  Undisturbed samples must be  trimmed  to the diameter of the top
cap and base of the triaxial  cell.  Disturbed samples should be prepared
in the mold using either  kneading  compaction for fine-grained soils, or
by  the  pouring  and  vibrating  method  for  coarse-grained  soils,  as
discussed in Section 2.5.3.

     2.8.4  Test procedure:

     1.  Measure the dimensions and weight of the prepared sample.

     2.  Place one of the prepared specimens on the base.

     3.  Place a rubber membrane  in  a membrane stretcher, turn both ends
         of the membrane over  the  ends  of  the  stretcher, and apply a
         vacuum to the  stretcher.    Carefully  lower  the stretcher and
         membrane over the  specimen.   Place the specimen and release the
         vacuum on the membrane stretcher.  Turn the  ends of the membrane
         down around the base  and  up  around the specimen cap and fasten
         the ends with 0-rings.

     4.  Assemble the triaxial chamber   and  place  it in position in the
         loading device.  Connect  the tube from the pressure reservoir to
         the base of the triaxial  chamber.    With valve C  (see Figure 5)
         on the  pressure   reservoir  closed  and  valves  A  and B open,
         increase  the  pressure   inside the  reservoir,  and  allow the
         pressure fluid to  fill the triaxial  chamber.  Allow a few drops
         of the pressure fluid to  escape through the  vent valve  (valve B)
         to insure complete filling  of   the  chamber with fluid.  Close
         valve A and the vent  valve.

     5.  Place saturated filter paper  disks  having  the same diameter as
         that of the specimen  between the specimen and the base and cap;
         these disks will also facilitate  removal of the specimen after
         the test.  The drainage   lines   and the porous inserts should be
         completely saturated  with deaired  water.    The drainage  lines
          should be as short as possible and made of  thick-walled, small-
         bore tubing  to insure minimum elastic changes in volume due  to
          changes in pressure.  Valves in the drainage lines  (valves  E, F,
          and G  in Figure 5)  should  preferably  be   of a type which will
          cause  no discernible  change   of  internal  volume  when operated.
         While mounting the  specimen   in  the   compression chamber,  care
          should be exercised  to   avoid   entrapping   any  air  beneath  the
          membrane or  between the  specimen and the  base and  cap.
                              9100 - 21
                                                     Revision
                                                     Date  September 1986

-------
                                                            >-*
-------
6.  For ease and  uniformity  of  saturation,  as  well  as to allow
    volume changes  during  consolidation  to  be  measured with the
    burette, specimens  should  be  completely  saturated before any
    appreciable   consolidation   is   permitted;   therefore,   the
    difference between the  chamber  pressure  and the back pressure
    should not exceed 5 psi during  the saturation phase.  To insure
    that a specimen is not  prestressed during the saturation phase,
    the back pressure  must  be  applied  in  small increments, with
    adequate time between increments  to permit equalization of pore
    water pressure throughout the specimen.

7.  With all valves  closed,  adjust  the  pressure  regulators to a
    chamber pressure of about 7 psi  and  a back pressure of about 2
    psi.  Now open  valve  A  to  apply  the  preset pressure to the
    chamber fluid and simultaneously open  valve F to apply the back
    pressure through the specimen cap.  Immediately open valve G and
    read and record the pore  pressure  at  the  specimen base.  When
    the measured pore  pressure  becomes essentially constant, close
    valves  F and G and record the burette reading.

8.  Using the technique described   in  Step  3,  increase the  chamber
    pressure and the  back  pressure   in increments, maintaining the
    back pressure at about  5  psi  less  than the chamber pressure.
    The size of each  increment  might  be   5,   10,  or  even  20 psi,
    depending on the compressibility   of  the  soil specimen  and the
    magnitude of the desired  consolidation  pressure.   Open  valve  G
    and measure  the  pore  pressure   at  the  base immediately upon
    application of each  increment   of  back  pressure and observe the
    pore pressure until  it  becomes essentially constant.   The time
    required  for  stabilization of  the  pore pressure may  range from  a
    few minutes to several  hours   depending  on the permeability of
    the soil.   Continue   adding   increments  of  chamber  pressure and
    backpressure  until,   under  any   increment,  the pore  pressure
    reading  equals   the   applied   back  pressure immediately upon
    opening valve G.

 9.  Verify  the  completeness  of   saturation  by   closing valve F and
     increasing  the chamber pressure by  about  5 psi.   The  specimen
    shall not be  considered completely saturated unless  the  increase
    in pore  pressure   immediately equals   the   increase  in chamber
    pressure.

10.  When  the  specimen  is   completely saturated,  increase the chamber
    pressure  with the  drainage   valves  closed to attain the desired
    effective consolidation  pressure   (chamber   pressure  minus back
    pressure).  At zero  elapsed  time,  open  valves E and  F.

11.   Record  time,  dial   indicator  reading,   and  burette  reading at
    elapsed times of 0,  15, and  30 sec,  1,  2, 4,  8,  and 15  min, and
     1, 2, 4,  and  8 hr,   etc.     Plot the dial  indicator  readings and
                         9100 - 23
                                                Revision
                                                Date  September 1986

-------
        burette readings on an arithmetic scale versus elapsed time on a
        log scale.  When the  consolidation curves indicate that primary
        consolidation is complete, close valves E and F.

   12.  Apply a pressure to burette  B  greater  than that 1n burette A.
        The difference between  the  pressures  in  burettes  B and A 1s
        equal to the head  loss   (h);  h  divided  by  the height of the
        specimen after consolidation (L) is the hydraulic gradient.  The
        difference between the two pressures  should be kept as small as
        practicable, consistent with  the  requirement  that the rate of
        flow be  large  enough  to  make  accurate  measurements  of the
        quantity of flow within   a  reasonable  period of time.  Because
        the difference  in  the   two  pressures  may  be  very  small in
        comparison to the pressures  at  the  ends  of the specimen, and
        because the head loss must be maintained constant throughout the
        test, the difference between  the  pressures within the burettes
        must be measured  accurately;  a  differential  pressure gage is
        very useful  for  this  purpose.    The  difference  between the
        elevations of  the  water within  the  burettes  should also be
        considered  (1 in. of water = 0.036 psi of pressure).

    13.  Open valves D and F.    Record  the burette readings at any zero
        elapsed time.    Make  readings  of   burettes  A  and  B  and of
        temperature  at  various  elapsed  times   (the  interval between
        successive  readings depends  upon  the  permeability of the soil
        and the dimensions of  the   specimen).    Plot arithmetically the
        change  1n   readings  of   both   burettes   versus   time.  Continue
        making  readings  until   the  two  curves  become parallel  and
        straight   over   a  sufficient    length    of  time to  determine
        accurately the  rate of  flow as   Indicated  by the  slope of the
        curves.

     2.8.5  Calculations:  The   hydraulic   conductivity  can be  calculated
using Equation  (8).

2.9  Pressure-chamber permeameter method:

     2.9.1  Applicability:     This  method   can   be   used  to   determine
hydraulic  conductivity  of  a   wide   range  of  soils.     Undisturbed and
disturbed  samples  can be tested  under falling-head conditions  using this
method.  This method is  also   applicable to both  coarse- and  fine-grained
soils, including remolded,  fine-grained  materials.

     2.9.2  Apparatus:   The  apparatus,  shown  in Figure  6,  consists  of

     1.  Pressure  chamber;

     2.  Standpipe;

     3.  Specimen  cap and base; and

     4.  Coarse porous plates.
                             9100 - 24
                                                    Revision      0
                                                    Date  September 1986

-------
     ,-tevfciNC tuti
                               COADUATCD
                               STAND*! ปf
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Figure 6.-
—Pressure'chamber for hydraulic
 conductivity.
 Source:  U.S. Army Corps of Engineers,
  1980.
               9100 - 25
                                      Revision      0
                                      Date  September 1986

-------
    The apparatus  is capable of applying confining pressure to simulate field
    stress conditions.

         2.9.3   Sample preparation:  The  sample preparation of disturbed and
    undisturbed  conditions  can be prepared  in the chamber and enclosed within
    the rubber membrane,  as discussed  in Section 2.8.4.

         2.9.4   Test procedure:

         1.   By  adjusting the  leveling bulb,  a confining pressure  1s applied
              to  the sample such  that   the   stress conditions represent field
              conditions.   For  higher  confining  pressure, compressed air may
              be  used.

         2.   Allow the  sample  to  consolidate  under the applied  stress until
              the end of primary consolidation.

         3.   Flush water  through   the  sample  until   no  indication  of air
              bubbles  is observed.   For  higher  head of water,  compressed air
              may be used.

         4.   Adjust the head of water  to attain a desired hydraulic gradient.

         5.   Measure  and record the head   drop   1n   the standpipe  along with
              elapsed  time until the plot of  logarithm of head  versus time  is
              linear for more than  three consecutive  readings.

         2.9.5  Calculations:   The   hydraulic  conductivity  can be  determined
     using  Equation (9).

     2.10  Sources of error  for  laboratory  test for hydraulic conductivity;
There  are   numerouspotentialsourcesoferror1n  laboratorytests  for
hydraulic  conductivity.    Fixed-wall   permeameters   may   have   problems with
sidewall  leakage, causing higher values  of hydraulic conductivity.   Flexible-
membrane  permeameters  may  yield   misleadingly   low  values  for  hydraulic
conductivity  when  testing  with   a  leachate  that   causes   contraction   and
shrinkage cracks in the sample  because  the membrane shrinks with the sample.
Table B summarizes some potential   errors  that  can   occur.   01 sen and Daniel
(1981) provide a more  detailed  explanation  of  sources  of these errors  and
methods to minimize them.   If  the hydraulic conductivity does not fall  within
the expected range for the  soil   type,  as  given in Table C, the measurement
should be repeated after  checking the source of error in Table B.
                                  9100 - 26
                                                         Revision      0
                                                         Date  September 1986

-------
                                   TABLE B

                SUMMARY OF PUBLISHED DATA ON POTENTIAL ERRORS
                             IN USING DATA FROM
              LABORATORY PERMEABILITY TESTS ON SATURATED SOILS
                    Measured K
    Source of Error (References)
Too Low or Too High?
1.   Voids formed in sample preparation
     (01 sen and Daniel, 1981).

2.   Smear zone formed during trimming
     (Olsen and Daniel, 1981).

3.   Use of distilled water as a
     permeant (Fireman, 1944; and
     Wilkinson, 1969).

4.   Air in sample (Johnson, 1954)

5.   Growth of micro-organisms
     (Allison, 1947).

6.   Use of excessive hydraulic
     gradient (Schwartzendruber, 1968;
     and Mitchell and Younger, 1967).

7.   Use of temperature other than the
     test temperature.

8.   Ignoring volume change due to
     stress change, with no confining
     pressure used.

9.   Performing laboratory rather
     than in-situ tests (Olsen and
     Daniel, 1981),

10.  Impedance caused by the test
     apparatus, including the
     resistance of the screen or
     porous stone used to support
     the sample.
        High


        Low



        Low

        Low


        Low



        Low or High


        Varies



        High



        Usually Low
        Low
                                  9100 - 27
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                                                         Date  September 1986

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                                   TABLE C

       HYDRAULIC CONDUCTIVITIES ESTIMATED FROM GRAIN-SIZE DESCRIPTIONS
                              (In Feet Per Day)


Grain-Size Class or Range            Degree of Sorting         Silt Content
From Sample Description            Poor   Moderate Well   Slight  Moderate  High
Fine-Grained Materials
Clay
Silt, clayey
Silt, slightly sandy
Silt, moderately sandy
Silt, very sandy
Sandy silt
Silty sand
Sands and gravel s(!)
Very fine sand
Very fine to fine sand
Very fine to medium sand
Very fine to coarse sand
Very fine to very coarse sand
Very fine sand to fine gravel
Very fine sand to medium gravel
Very fine sand to coarse gravel
Fine sand
Fine to medium sand
Fine to coarse sand
Fine to very coarse sand
Fine sand to fine gravel
Fine sand to medium gravel
Fine sand to coarse gravel
Medium sand
Medium to coarse sand
Medium to very coarse sand
Medium sand to fine gravel
Medium sand to medium gravel
Medium sand to coarse gravel
Coarse sand
Coarse to very coarse sand
Coarse sand to fine gravel
Coarse sand to medium gravel
Coarse sand to coarse gravel





Less than .001
1 - 4
5
7-8
9-11
11
13

13
27
36
48
59
76
99
128
27
53
57
70
88
114
145
67
74
84
103
131
164
80
94
116
147
184

20 27
27
41-47
-
-
-
-
-
40 53
67
65-72
-
-
-
-
80 94
94
98-111
-
-
-
107 134
134
136-156
-
-

23
24
32
40
51
67
80
107
33
48
53
60
74
94
107
64
72
71
84
114
134
94
94
107
114
134

19
20
27
31
40
52
66
86
27
39
43
47
59
75
87
51
57
61
68
82
108
74
75
88
94
100

13
13
21
24
29
38
49
64
20
30
32
35
44
57
72
40
42
49
52
66
82
53
57
68
74
92
     Reduce  by  10  percent  if  grains  are  subangular.
     Source:  Lappala  (1978).
                                     (continued)
                                   9100 -  28
                                                          Revision
                                                          Date   September  1986

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                                TABLE C (Continued)
Grain-Size Class or Range            Degree of Sorting         Silt Content
From Sample Description            Poor   Moderate Well    Slight  Moderate  High


Sands and Gravels(*)
Very coarse sand
Very coarse sand to fine
Very coarse sand to medi

gravel
urn gravel
Very coarse sand to coarse gravel
Fine gravel
Fine to medium gravel
Fine to coarse gravel
Medium gravel
Medium to coarse gravel
Coarse gravel






107
134
1270
207
160
201
245
241
294
334
147
214
199-227
-
214
334
289-334
231
468
468
187
-
-
-
267
-
-
401
-
602
114
120
147
160
227
201
234
241
294
334
94
104
123
132
140
167
189
201
243
284
74
87
99
104
107
134
144
160
191
234
    Reduce by  10 percent  if grains are subangular.
    Source:  Lappala  (1978).
                                   9100 - 29
                                                          Revision
                                                          Date  September  1986

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     2.11  Leachate conductivity using laboratory  methods;    Many primary and
secondary leachates found  at  disposal   sites  may  be  nonaqueous liquids or
aqueous fluids of high ionic  strength.    These fluids may significantly alter
the intrinsic permeability of the  porous  medium.   For example,  Anderson and
Brown  (1981)  have  demonstrated   increases  in  hydraulic  conductivity  of
compacted clays of as much as two  orders  of magnitude after the  passage of a
few pore volumes  of  a  wide  range  of  organic  liquids.   Consequently, the
effects of leachate  on  these  materials  should  be  evaluated by laboratory
testing.  The  preceding  laboratory  methods  can  all  be  used  to determine
leachate conductivity by using the following guidelines.

          2.11.1  Applicability:  The  determination  of leachate  conductivity
     may be  required  for  both  fine-grained  and  coarse-grained materials.
     Leachates may either  increase  or  decrease  the hydraulic conductivity.
     Increases are of concern for compacted  clay liners, and decreases are of
     concern for drain materials.  The applicability sections of the preceding
     methods should be used  for  selecting  an  appropriate test for leachate
     conductivity.  The use  of  the  modified compaction method (Section 2.7)
     for determining leachate  conductivity  is  discussed  extensively in EPA
     Publication SW870 (EPA  1980).

          2.11.2   Leachate used:  A supply  of  leachate must be obtained that
     is as   close  in  chemical  and  physical  properties  to the anticipated
     leachate  at the disposal site  as  possible.   Methods for obtaining such
     leachate  are beyond   the  scope   of  this  report.    However,  recent
     publications  by  EPA    (1979)   and   Conway   and  Malloy   (1981)  give
     methodologies for  simulating  the  leaching  environment  to obtain such
     leachate.   Procedures   for  deal ring  the   leachate  supply   are given 1n
     Section 2.4.  The importance  of preventing bacterial growth in leachate
     tests will  depend on the expected  conditions  at  the  disposal  site.  The
     chemical  and physical   properties   that   may   result  in   corrosion,
     dissolution,  or encrustation   of   laboratory   hydraulic   conductivity
     apparatus  should  be    determined    prior   to    conducting  a leachate
     conductivity  test.   Properties   of  particular   importance are  the pH and
     the  vapor pressure of   the   leachate.     Both  extremely acidic and  basic
     leachates may corrode   materials.     In   general,   apparatus  for leachate
     conductivity  tests  should   be  constructed   of   Inert  materials,  such as
     acrylic plastic,  nylon,  or Teflon.     Metal  parts   that  might  come in
     contact with  the leachate  should be  avoided.   Leachates with  high  vapor
     pressures may require  special  treatment.  Closed  systems for  fluid supply
     and  pressure  measurement,   such  as   those   in the modified tr1axial-cell
     methods,  should  be  used.

           2.11.3  Safety:   Tests  involving   the  use   of   leachates should be
     conducted under  a vented  hood,  and  persons conducting the  tests should
     wear appropriate   protective  clothing   and eye  protection.   Standard
     laboratory  safety procedures   such  as   those  as  given by Manufacturing
     Chemists Association (1971)  should  be followed.

           2.11.4  Procedures:     The  determination   of  leachate  conductivity
     should  be conducted  immediately  following  the determination  of hydraulic
                                   9100 - 30
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                                                          Date   September  1986

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    conductivity  (Anderson and Brown, 1981).   This procedure maintains fluid
    saturation of the sample,  and  allows  a  comparison of the leachate and
    hydraulic conductivities under the same  test conditions.  This procedure
    requires modifications of test operations as described below.

         2.11.5  Apparatus:  In addition to  a  supply reservoir for water as
    shown  1n  Figures  3  through  6,  a  supply  reservoir  for  leachate 1s
    required.  Changing the Inflow  to  the  test cell from water to leachate
    can be accomplished by  providing  a  three-way  valve 1n the Inflow line
    that 1s connected to each of the reservoirs.

         2.11.6  Measurements:  Measurements  of  fluid potential and outflow
    rates  are the same for  leachate conductivity and hydraulic conductivity.
    If the leachate does not alter  the Intrinsic permeability of the sample,
    the criteria  for the time required  to  take measurements is the same for
    leachate  conductivity  tests   as   for  hydraulic  conductivity  tests.
    However, 1f significant changes  occur  in  the  sample by the passage of
    leachate, measurements should be taken until  either the shape of a curve
    of conductivity versus pore volume can  be defined, or until the leachate
    conductivity  exceeds   the   applicable   design   value  for  hydraulic
    conductivity.

         2.11.7   Calculations:   If  the  leachate  conductivity approaches a
    constant value, Equations  (8) and  (9)  can  be used.  If the conductivity
    changes continuously because of the action of the leachate, the following
    modifications should be made.   For constant-head tests, the conductivity
    should be determined by continuing  a  plot of outflow volume versus time
    for the constant   rate  part  of   the  test  conducted  with  water.  For
    falling-head  tests, the  slope of the logarithm of head versus time should
    be continued.

              2.11.7.1   If  the   slope  of  either  curve  continues to change
          after  the  flow  of   leachate  begins,  the   leachate  is altering the
          Intrinsic  permeability  of  the sample.   The  leachate  conductivity  in
          this case  is  not  a  constant.    In  this case,  values  of the  slope  of
          the  outflow  curve  to use  in  Equation  (8) or  (9) must  be taken as the
          tangent   to   the   appropriate  outflow   curve   at   the  times   of
          measurement.
3.0  FIELD METHODS

     This section discusses methods  available  for the determination of fluid
conductivity under field conditions.  As most of these tests will  use water as
the testing fluid, either natural formation water or water added to a borehole
or piezometer, the term hydraulic conductivity  will be used for the remainder
of this section.   However,  if  field  tests  are  run with leachate or other
fluids, the methods are equally applicable.

     The  location  of  wells,  selection   of  screened  intervals,  and  the
appropriate tests that are to be conducted depend upon the specific site under
                                  9100 - 31
                                                         Revision
                                                         Date  September 1986

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Investigation.   The  person  responsible  for  such  selections  should  be a
qualified hydrogeologist or geotechnical  engineer  who  is experienced in the
application of established principles  of  contaminant hydrogeology and ground
water hydraulics.  The following are given as general  guidelines.

          1.  The bottom of the screened  interval  should be below the lowest
              expected water level.

          2.  Wells should be screened in  the  lithologic units that have the
              highest  probability   of   either   receiving  contaminants  or
              conveying them down gradient.

          3.  Wells up gradient and down  gradient of sites should be screened
              in the same lithologic unit.

Standard  reference  texts   on   ground   water  hydraulics  and  contaminant
hydrogeology that should be  consulted  include:   Bear (1972), Bouwer (1978),
Freeze and Cherry (1979), Stallman  (1971), and Walton (1970).

     The success of  field  methods  in  determining hydraulic conductivity is
often determined by the design,  construction,  and development of the well or
borehole used for the tests.  Details of these methods are beyond the scope of
this report; however, important considerations  are  given in Sections 3.1 and
3.2.  Detailed discussions of well  installation, construction, and development
methods are given by  Bouwer,  pp.  160-180   (1978), Acker (1974), and Johnson
(1972).

     The  methods  for  field  determination  of  hydraulic  conductivity  are
restricted to well or  piezometer   type  tests applicable below existing water
tables.  Determinations  of  travel  times  of  leachate and dissolved solutes
above the water  table  usually  require  the  application of unsaturated flow
theory and methods which are beyond the scope of this report.

     3.1  Well-construct!on considerations:    The  purpose  of  using properly
constructed wells for hydraulicconductivity  testing  is to assure that test
results  reflect  conditions   in   the  materials  being  tested,   rather  than
conditions caused by well construction.     In  all  cases, diagrams showing  all
details of the actual  well  or  borehole   constructed  for the  test should be
made.  Chapter 3  of  the   U.S.  EPA,   RCRA  Ground Water Monitoring Technical
Enforcement Guidance Document  (TEGD) should be consulted.

           3.1.1  Well  Installation methods:    Well   installation methods  are
      listed   below   in   order  of   preference  for  ground  water testing  and
     monitoring.  The order was  determined  by the need  to minimize side-wall
     plugging by drilling  fluids   and   to   maximize  the  accurate detection of
      saturated zones.   This order  should  be used  as a guide,  combined  with  the
     judgment of an  experienced  hydrogeologist  in selecting a drilling  method.
      The combined uses   of wells   for  hydraulic conductivity testing, water-
      level  monitoring,   and water-quality  sampling   for organic contaminants
      were  considered in  arriving at the ranking.
                                   9100 - 32
                                                          Revision
                                                          Date  September 1986

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     1.   Hollow-stem auger;

     2.   Cable tool;

     3.   A1r rotary;

     4.   Rotary drilling with non-organic drilling fluids;

     5.   A1r foam rotary; and

     6.   Rotary with organic-based drilling fluids.

Although the  hollow  stem-auger  method  1s  usually  preferred  for the
Installation of most shallow  wells  (less  than  100 feet), care must be
taken 1f the tested zone Is very fine.  Smearing of the borehole walls by
drilling action can effectively seal  off  the borehole from the adjacent
formation.  Scarification can be used to remedy this.

     3.1.2  Wells requiring well screens:    Well screens placed opposite
the Interval to be  tested  should  be  constructed of materials that are
compatible with the fluids to be encountered.  Generally an Inert plastic
such as PVC is  preferred  for  ground  .water contamination studies.  The
screen slot size should  be  determined  to  minimize the Inflow of fine-
oral ned material to  the  well  during  development  and testing.  Bouwer
(1978) and Johnson  (1972) give  a  summary  of guidelines for sizing well
screens.

          3.1.2.1  The annul us between the  well  screen and the borehole
     should be filled  with  an  artificial  gravel  pack or sand filter.
     Guidelines for sizing these  materials  are given by Johnson (1972).
     For very  coarse  materials,  it  may  be  acceptable  to  allow the
     materials from the tested zone to collapse around the screen forming
     a natural gravel pack.

          3.1.2.2  The  screened   Interval   should   be  Isolated  from
     overlying  and  underlying  zones  by  materials  of  low  hydraulic
     conductivity.  Generally, a short bentonite plug 1s placed on top of
     the material surrounding the screen,  and  cement grout 1s placed in
     the borehole to the next  higher  screened  Interval  (in the case of
     multiple screen wells), or  to  the  land  surface for single screen
     wells.

          3.1.2.3   Although  considerations  for   sampling  may  dictate
     minimum  casing  and  screen  diameters,  the recommended guideline is
     that wells to  be tested by pumping, balling,  or injection  in coarse-
     grained  materials   should  be  at   least  4-1nches  Inside diameter.
     Wells  to be used for testing materials of low hydraulic conductivity
     by  sudden  removal  or Injection of   a known volume of  fluid should be
     constructed with as small  a  casing diameter  as possible to maximize
     measurement resolution  of  fluid  level  changes.  Casing sizes of  1.25
     to  1.50  inches usually allow  this   resolution  while enabling the
     efficient  sudden withdrawal of water for these  tests.
                              9100 - 33
                                                     Revision       0
                                                     Date   September  1986

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          3.1.3   Wells not requiring well  screens:     If  the  zone  to  be  tested
     1s  sufficiently Indurated  that  a well   screen  and casing are  not required
     to  prevent  caving in,  it  is  preferable  to  use  a  borehole open to the  zone
     to  be  tested.     These  materials   generally  are  those  having  low  to
     extremely low hydraulic conductivities.     Consolidated  rocks having  high
     conductivity because of the   presence  of  fractures  and  solution openings
     may also be  completed  without  the  use   of  a  screen and  gravel pack.
     Uncased  wells  may   penetrate   several    zones   for   which  hydraulic
     conductivity tests are to be run.   In these cases,  the  zones of interest
     can be isolated by the use of inflatable packers.

     3.2  Well development;  For wells  that are constructed  with  well screens
and gravel packs, and for all   wells  in  which drilling  fluids have been  used
that may have penetrated the  materials  to be  tested, adequate development  of
the well is required to  remove  these  fluids   and to remove the  fine-grained
materials from the zone around the well  screen.  Development  is carried out  by
methods  such  as  intermittent  pumping,  jetting   with   water,  surging, and
bailing.  Adequate  development  is  required  to assure  maximum communication
between fluids in the borehole and the  zone to be  tested.  Results from tests
run in wells that are inadequately  developed  will Include an error caused  by
loss of fluid potential  across  the  undeveloped zone, and computed hydraulic
conductivities will be lower than the actual value.  Bouwer  (1978) and Johnson
(1975) give further details on well development including methods  to determine
when adequate development has  occurred.    The  U.S.  EPA TEGD should also  be
consulted.

     3.3  Data interpretation and  test  selection   considerations;  Hydraulic
conductivity may be determined in  wells  that  are either cased or uncased  as
described in Section 3.1.  The tests all Involve disturbing the existing fluid
potential in the tested zone by  withdrawal  from or injection of fluid into a
well, either  as  a  slug  over  an  extremely  short  period  of  time, or by
continuous withdrawal or injection  of  fluid.    The hydraulic conductivity is
determined by measuring the response  of  the  water  level or pressure in the
well as a function  of  time  since  the  start  of  the  test.  Many excellent
references are available that give the  derivation  and use of the  methods that
are outlined below, including Bouwer  (1978), Walton  (1969), and Lohman (1972).

          3.3.1  The selection of a  particular  test method and data analysis
     technique requires the consideration of the purposes of the test, and the
     geologic framework in which the  test  is  to  be  run.   Knowledge of the
     stratigraphic  relationships of the zone  to  be tested and both overlying
     and underlying materials should always be used to select appropriate test
     design and data interpretation methods.

          3.3.2  The equations given  for  all computational methods given here
     and in the  above  references  are  based  on idealized models comprising
     layers of materials of  different  hydraulic  conductivities.  The water-
     level response caused by disturbing the system  by the addition or removal
     of water can be  similar  for  quite  different  systems.  For example, the
     response of  a water-table  aquifer  and  a  leaky,  confined aquifer to
                                  9100 - 34
                                                         Revision      0
                                                         Date  September 1986

-------
    pumping   can   be   very   similar.    Consequently,  1t  1s  not considered
    acceptable practice  to obtain data from a hydraulic conductivity test and
    interpret the type of  hydraulic   system  present  without  supporting
    geologic  evidence.

          3.3.3  The primary  use  of   hydraulic   conductivity  data from tests
    described subsequently will  usually be  to aid  In  siting monitoring wells
    for facility  design  as well  as for compliance with Subpart F of  Part 264.
    As  such,  the  methods are  abbreviated to provide  guidance in determining
    hydraulic conductivity only.  Additional  analyses   that may be possible
    with some methods to define  the  storage properties of the aquifer  are not
    included.    The   U.S.   EPA  TEGD has  an   expanded  discussion   on  the
    relationship  between K tests and siting  design (Chapter  1) and  should  be
    consulted.

          3.3.4   The well test methods are  discussed  under the following two
    categories:   1) methods  applicable   to coarse-grained materials  and tight
    to extremely tight materials  under   confined   conditions; and  2)  methods
    applicable  to unconflned materials of moderate permeability.   The single
    well tests  integrate the  effects of  heterogeneity and  anlsotropy.  The
     effects of  boundaries such as  streams or  less  permeable materials  usually
     are not detectable with  these  methods because  of the small portion of the
     geologic unit that is tested.

     3.4  Single well  tests;   The tests  for determining hydraulic  conductivity
with a single wellaredTscussed   below  based  on  methods  for  confined and
unconfined conditions.  The methods are   usually called slug  tests because the
test involves  removing  a  slug  of  water  instantaneously   from  a well  and
measuring the recovery of water in   the   well.   The method was first developed
by Hvorslev (1951), whose analysis  did not consider the effect of  fluid stored
in the well.  Cooper and others  (1967)  developed a method that considers  well
bore storage.  However, their method  only  applied  to wells  that are open  to
the entire zone to be tested and  that  tap confined aquifers.  Because of the
rapid water-level  response  1n  coarse   materials,   the  tests  are generally
limited to zones with a transmissivity  of less than about 70  cm^/sec (Lohman,
1972).  The method  has  been  extended  to  allow  testing of extremely tight
formations by Bredehoeft  and  Papadopulos  (1980).     Bouwer  and Rice (1976)
developed a method for analyzing slug tests for unconflned aquifers.

          3.4.1   Method for  moderately  permeable  formations  under confined
     conditions:

               3.4.1.1  Applicability;  This  method  is applicable for testing
          zones to which the entire zone  is   open  to the well  screen or open
          borehole.  The  method  usually  is   used  in  materials of moderate
          hydraulic  conductivity  which    allow  measurement   of   water-level
          response over a period of  a  hour  to  a  few days.  More permeable
          zones  can  be  tested  with  rapid  response  water-level  recording
          equipment.  The method assumes  that  the  tested zone  is uniform in
          all radial directions from the test  well.   Figure 7 illustrates the
          test geometry for this method.
                                  9100 - 35
                                                         Revision
                                                         Date  September 1986

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                              WELL CASING
                              WELL SCREEN
                               x CONFINING LAYER
Figure  7.—Geometry and variable definition for
            slug tests  in confined  aquifers.
                   9100 - 36
                                        Revision     0
                                        Date  September 1986

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     3.4.1.2  Procedures;  The slug  test  1s  run by utilizing some
method of removing or adding a  known  volume of water from the well
bore 1n a very short time  period  and measuring the recovery of the
water level 1n the  well.    The  procedures  are  the same for both
unconfined and confined aquifers.  Water Is most effectively removed
by using a bailer that  has  been  allowed  to fill and stand 1n the
well for a sufficiently long period  of time so that any water-level
disturbance caused by the Insertion  of the bailer will have reached
equilibrium.  In permeable materials,  this  recovery time may be as
little as a few minutes.   An alternate method of effecting a sudden
change 1n water level Is  the  withdrawal  of a weighted float.  The
volume of water displaced can  be computed using the known submersed
volume of the float and Archimedes' principle (Lohman, 1972).

     Water-level  changes  are  recorded  using  either  a  pressure
transducer and a strip chart recorder,  a weighted steel tape, or an
electric water-level probe.    For  testing permeable materials that
approach or exceed 70  cm^/sec, a rapid-response transducer/recorder
system 1s usually used  because  essentially full recovery may occur
1n a few minutes.   Because  the rate of water-level response decays
with time,  water-level  or  pressure  changes  should  be  taken at
increments that are approximately equally spaced in the logarithm of
the time since fluid withdrawal.  The test should be continued until
the water level in the well has  recovered to at least 85 percent of
the initial pre-test value.

     3.4.1.3  Calculations;  Calculations  for determining hydraulic
conductivity  for  moderately  permeable  formations   under confined
conditions can be made using the following procedure:

1.  Determine the transmisslvity of  the  tested zone by plotting the
    ratio  h/h0 on an arithmetic  scale against time since removal of
    water  (t) on a  logarithmic   scale.   The  observed fluid potential
    1n the well  during  the  test   as   measured   by   water  level or
    pressure  is h,  and   the  fluid   potential  before  the instant of
    fluid withdrawal is  h0.   The  data  plot is superimposed  on type
    curves, such  as  those  given   by   Lohman   (1972),  Plate 2, or
    plotted from Appendix  A, with  the h/h0 and time axes coincident.
    The  data  plot 1s moved  horizontally  until the data fits one of
    the  type  curves.  A  value of time on the data  plot corresponding
    to a dlmenslonless time  (/O  on   the  type curve plot 1s  chosen,
    and  the transmissivity 1s computed from  the following:
                                                                (10)


      where:

           rc 1s  the  radius  of the  casing  (Lohman,  p.  29  (1972)).
                         9100 - 37
                                                Revision
                                               Date  September  1986

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    The  type  curves  plotted  using  data   1n  Appendix A are not to be
    confused  with  those  commonly referred to as  "Theis Curves" which
    are  used  for pumping tests  in confined aquifers  (Lohman, 1972).
    The  type  curve  method   is  a   general  technique of  determining
    aquifer parameters when   the   solution  to   the descriptive  flow
    equation  involves more   than   one   unknown   parameter.   Although
    both the  storage  coefficient   and   transmissivity of the tested
    interval  can be  determined  with the type curve method  for  slug
    tests,  determination of  storage coefficients is beyond the scope
    of this report.   See Section   3.4.1.4  for further discussion of
    the storage coefficient.

          If  the data in Appendix  A are used, a type curve  for  each
    value of  a  is  prepared by   plotting  F(a,/7) on the arithmetic
    scale and dimensionless   time   (/?)   on  the  logarithmic  scale of
    semi-log  paper.

2.  Determine   the    hydraulic   conductivity    by   dividing   the
    transmissivity (T)  calculated  above  by  the  thickness of the
    tested zone.

     3.4.1.4  Sources of  error;     The  errors   that   can   arise  in
conducting slug tests can beof   three types:   those resulting  from
the well  or  borehole  construction;   measurement   errors;  and  data
analysis error.

Well construction and development errors;   This method assumes  that
the entire thickness of the  zone  of  interest   is  open to  the  well
screen or boreholes and that flow is principally radial.   If this  is
not the case, the computed  hydraulic  conductivity may be  too high.
If the well  is  not  properly  developed,  the computed conductivity
will be too  low.

Measurement  errors;  Determining or recording the fluid level  in the
boreholeandthe  time    of   measurement  incorrectly  can  cause
measurement  errors.  Water  levels  should be measured to an accuracy
of at least  1  percent  of the   initial  water-level   change.   For
moderately permeable  materials,    time  should  be  measured with an
accuracy of  fractions of minutes,  and,  for more permeable materials,
the time should be  measured   in   terms  of  seconds or fractions of
seconds.   The  latter  may require  the  use  of  a rapid-response
pressure transducer and recorder  system.

Data  analysis  errors;   The type curve procedure requires matching
the data tooneof a family   of  type  curves,  described by the
parameter  , which  is a measure   of the storage in the well bore and
aquifer.   Papadopulos and others   (1973)  show  that an  error of two
orders  of  magnitude in  the  selection  of    would result in an  error
of  less than 30 percent in the  value  of transmissivity determined.
Assuming no  error in  determining   the   thickness of the  zone tested,
this   is   equivalent to  a   30   percent  error  in  the   hydraulic
conductivity.

                         9100 - 38
                                                Revision      0
                                                Date  September  1986

-------
     3.4.2  Methods  for  extremely   tight   formations  under  confined
conditions:

          3.4.2.1  Applicability;  This  test  is applicable to materials
     that have low to  extremely  low  permeability such as silts,  clays,
     shales, and indurated lithologic units.    The test has been used to
     determine hydraulic conductivities  of  shales  of  as  low as 10~10
     cm/sec.

          3.4.2.2  Procedures;   The  test  described  by  Bredehoeft and
     Papadopulos (1980) andmodified  by  Neuzil  (1982) is conducted by
     suddenly pressurizing a packed-off zone  in  a portion of a borehole
     or well.  The test  1s  conducted  using  a  system such as shown in
     Figure 8.  The system is filled  with water to a level assumed to be
     equal to the prevailing  water  level.    (This  step is required if
     sufficiently large times have not  elapsed since the drilling of the
     well to allow full recovery of water levels.)  A pressure transducer
     and recorder are used to monitor  pressure changes in the system for
     a period prior to the  test  to obtain pressure trends preceding the
     test.  The system is  pressurized  by  addition of a known volume of
     water with a high-pressure pump.  The valve is shut and the pressure
     decay is monitored.  Neuzil's  modification  uses two packers with a
     pressure transducer below the bottom  packer to measure the pressure
     change in the cavity and one  between the two packers to monitor any
     pressure change caused by leakage around the bottom packer.

          3.4.2.3  Calculations;  The modified  slug test as developed by
     Bredehoeft and Papadopulos  (1980)  considered compresslve storage of
     water in the borehole.  These  authors considered that the volume of
     the packed-off borehole did not change  during the test and that all
     compressive storage  resulted  in  compression  of  water  under the
     pressure pulse.   Neuzil   (1980)  demonstrated  that under some test
     conditions this is not a  valid  assumption.  The computational from
     either Lohman, Plate 2 (1972) or plotted from data given in Appendix
     A as described in  Section  3.4.1.3.    The  values  of time  (t) and
     dimensionless time (/J) are  determined  in  the same manner as  for the
     conventional tests.   If  compression  of  water only  is considered,
     transmissivity  is  computed  by   replacing   rc  by  the  quantity
     (VwCw/>g/ir) in Equation 10:


                0(VU Cu pj*)2
           T -   P  W  p                                             (10)

     where:

           Vy  is the volume of water  in the  packed-off cavity, L3;

           CN  is the compressibility of water, U^M"1;

           p   is the density of  water, ML"3;  and

           g   is the acceleration of gravity, LT~2.

                             9100 - 39
                                                    Revision       0
                                                    Date  September 1986

-------
                   Valve
  Pressure Gage
     System Filled
     with Water ซv
       Pump
             Pressure Gage
       Land Surface
                              Initial Head
                       ? - ? -in Tested — ? - ? —
                    Casing      Interval
        ------ ,
        'WellPoint
              __j
    to--
Tested ^
                                                           Pump
                            ^ Tight     	
                            11. FormatiorQrinnnnr
                (a)
                         (b)
Figure 8.—Schematic diagram for pressurized slug
            test method in unconsolidated  (a)  and
            consolidated  (b)  materials.  Source:
            Papadopulos and  Bredehoeft, 1980.
                     9100 - 40
                                           Revision      0
                                           Date  September 1986

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     If the compresslve storage 1s altered  by changing the volume of the
     packed-off cavity  (V),  then  the  combined  compressibility of the
     water and the  expansion of the cavity  (C0) is used.  C0 1s computed
     by measuring the volume of water  injected during pressurization  (AV)
     and  the pressure change  (AP) for  the pressurization:


         co  -w                                                 (11)
     (Neuzll, p. 440  (1982)).  Use  of  C0  requires an accurate method  of
     metering the volume  of water Injected  and the volume  of  the cavity.

         3.4.2.4   Sources of  error;   The   types of errors 1n this method
     are  the  same as  those  for   th~e   conventional slug  test.   Errors may
     also arise  by   inaccurate  determination of  the   cavity  volume and
     volume of water injected.   An  additional assumption that 1s  required
     for  this method is  that the   hydraulic properties  of  the  Interval
     tested  remain  constant  throughout  the   test.   This assumption can
     best be  satisfied  by limiting  the initial pressure  change  to  a  value
     only  sufficiently  large  enough  to  be  measured  (Bredehoeft and
     Papadopulos,  1980).

     3.4.3   Methods for moderately  permeable materials under unconflned
conditions:

          3.4.3.1   Applicability;   This  method  1s   applicable  to  wells
     that fully or partiallypenetrate  the interval  of Interest (Figure
     9).   The hydraulic  conductivity  determined will  be principally the
     value  in the horizontal  direction  (Bouwer and Rice, 1976).

          3.4.3.2  Procedures;  A general   method for testing cased  wells
     that partly or fully penetrate  aquifers  that have a water table  as
     the upper boundary of the zone  to be tested was developed by Bouwer
     and Rice (1976).  The  geometry  and dimensions  that are required  to
     be known for  the  method  are  shown  in  Figure  9.    The test  is
     accomplished by effecting a sudden  change in fluid potential in the
     well  by  withdrawal  of  either  a  bailer  or  submerged  float  as
     discussed in Section 3.4.1.2.    Water-level changes can be monitored
     with either a pressure transducer and recorder,  a wetted steel  tape,
     or  an  electric   water-level   sounder.     For  highly  permeable
     formations,  a  rapid-response  transducer  and  recorder  system Is
     required.   The resolution of the transducer should be about 0.01 m.

          3.4.3.3  Calculations;      The   hydraulic   conductivity   1s
     calculated using the following equation from Bouwer and Rice (1976),
     in the notation of this report:


              r,,2 In R"/r     Yrt
                        * In ^                                      (12)
                 2Let
                             9100 - 41
                                                    Revision      0
                                                    Date  September 1986

-------
            WELL CASING
(•) CASED WITH SCREEN
(b) CASED. NO SCREEN, NO
   CAVITY ENLARGEMENT
(c) OPEN BOREHOLE
 Figure  9.—Variable definitions  for slug  tests in
             unconfined  materials.  Cased wells are
             open  at the bottom.
                           9100 - 42
                                                 Revision      0
                                                 Date  September 1986

-------
         where rc, rw, Le, t, Y,  and  K  have been previously defined or are
         defined 1n Figure  8a.    Y0  1s  the  value  of Y Immediately after
         withdrawal of the slug of water.   The term "R is an effective radius
         for wells that do not  fully  penetrate the aquifer that is computed
         using the following equation given by Bouwer and Rice (1976):


                            ..      A + B ln[(H -L )/r ] ,1 -1
                         	1J:	1+ 	.  ฐ—ฃ	SL 'y             (13}
                          In (L/rJ           (L/r )        I,            u<3;
                              W  W             G  W         J

         If the quantity  (H0-Lw)/rw) is larger than 6, a value of 6 should be
         used.

         For wells  that  completely  penetrate  the  aquifer,  the following
         equation is  used:

                                              -1
                                                                         (14)

          (Bouwer, 1976).  The values of  the  constants A,  B, and C are given
         by Figure 10 (Bouwer and Rice, 1976).

         For both cases,  straight-line portions  of plots of the logarithm of
         Y or  Y0/Y against  time  should be  used to  determine the  slope,
          (In Y0/Y)/t.

         Additional   methods  for  tests   under  unconfined  conditions  are
         summarized by  Bower   (1976)  on  pages  117-122.   These methods are
         modifications  of the   cased-well  method  described above that apply
         either to an uncased borehole  or  to  a well or piezometer  in which
         the diameter of  the casing and the borehole are the same  (Figures ,9b
         and 9c.)

               3.4.3.4  Sources  of error;    The  method  assumes that flow of
         water from above is negligible.    If this assumption cannot be met,
         the conductivities  may  be  1n  error.    Sufficient  flow  from the
          unsaturated  zone by  drainage  would result  in a high conductivity
          value.   Errors caused  by  measuring  water levels  and recording time
          are  similar  to those discussed  in Sections 3.4.1.4 and 3.4.2.4.

     3.5  Multiple well  tests;   Hydraulic  conductivity can  also be determined
by conventional pumpingtests   in  which  water   is continuously withdrawn or
injected using  one well, and  the water-level response  is  measured over time 1n
or near more observation wells.   The  observation wells must  be  screened  in the
same strata as  the injection   or  pumping  well.   These methods generally test
larger portions of aquifers  than  the  single  well  tests discussed 1n Section
3.4.  For some circumstances  these  tests  may  be  appropriate in obtaining data
to use in satisfying requirements of   Part  264  Subpart  F.   However,  the large
possibility for non-uniqueness  in interpretation,  problems  involved 1n pumping
contaminated fluids,   and  the   expense   of  conducting   such  tests  generally
                                  9100 - 43
                                                         Revision
                                                         Date  September 1986

-------
 A
and
 C
   12
  10
                10
50  100
500  1000
5000
 Figure  10.  —Curves  defining coefficients A, B,
               and  C  in equations  13  and 14 as
               a  function of the ratio L/rw.
               Source:  Bower and Rice, 1976.
                    9100 - 44
                                        Revision      0
                                        Date  September  1986

-------
preclude their use in  problems  of  contaminant  hydrogeology.  The following
references give excellent  discussions  of  the  design  and interpretation of
these tests:  Lohman (1972), Stallman (1971), and Walton (1970).

     3.6  Estimates of  hydraulic  conductivity  for coarse-grained materials;
The characterization of ground  water  flow  systems  to satisfy the Intent of
Part 264 Subpart  F  is  preferably  done  with  flow  nets  based on borehole
measurements rather than relying on interpolation from grain-size analyses.

     An empirical approach that has  been  used  by the U.S. Geological Survey
(Lappala, 1978) in several studies  relates conductivity determined by aquifer
testing to grain-size, degree of sorting  and  silt content.  Table C provides
the estimates of hydraulic conductivity.

     Although estimates of K from analysis of grain-size and degree of sorting
do provide a rough check on  test  values  of K, repeated slug tests provide a
better check on the accuracy of results.

     3.7  Consolidation tests:  As originally defined by Terzagi (Terzaghi and
Peck,  1967)  the   coefficient   of   consolidation   (Cv)  of  a  saturated,
compressible, porous medium is related to the hydraulic conductivity by:
          Cv •

     where:

          K is the hydraulic conductivity, LT~;

          p is the fluid density, ML~3;

          g is the gravitational constant, LT~2; and

          a is the soil's compressibility, LM'iT2.

The compressibility can be determined  in  the  laboratory with several types of
consolidometers,  and  is a  function  of  the   applied  stress and the previous
loading  history.  Lambe (1951) describes the testing procedure.

          3.7.1   The  transfer value of results from this testing procedure is
      influenced by the extent to  which the laboratory loading simulates field
      conditions and by the consolidation  rate.   The laboratory loadings will
      probably  be less  than  the   stress  that   remolded  clay   liner  will
      experience;  therefore,  the  use   of  an   already  remolded  sample in the
      consolidometer   will  probably  produce   no  measurable  results.    This
      suggests  that the test  is of  little utility in determining the hydraulic
      conductivity of  remolded or  compacted,   fine-grained soils.   Second, the
      consolidation rate determines  the   length  of the  testing period.  For
      granular  soils,  this  rate is  fairly  rapid.   For fine-grained soils, the
      rate may  be  sufficiently   slow   that  the  previously described methods,
                                   9100 - 45
                                                          Revision
                                                          Date   September  1986

-------
     which  give  faster results,   will   be  preferable.  Cohesive  soils  (clays)
     must  be  trimmed  from  undisturbed  samples   to  fit   the  mold,  while
     cohesionless   sands  can   be  tested  using  disturbed,   repacked  samples
     (Freeze and Cherry, 1979).

          3.7.2   In general, EPA believes  that consolidation  tests  can  provide
     useful  information  for  some  situations,  but  prefers the previously
     described methods  because  they  are  direct   measurements  of hydraulic
     conductivity.      Hydraulic   conductivity    values  determined    using
     consolidation tests are not to be used  in permit applications.

     3.8  Fractured media:  Determining  the hydraulic properties of fractured
media is always  adifficult  process.    Unlike   the  case with  porous media,
Darcy's Law is not strictly applicable  to flow through fractures,  although it
often can be  applied  empirically  to  large  bodies  of  fractured rock that
incorporate many fractures.    Describing  local   flow conditions in fractured
rock  often  poses   considerable   difficulty.      Sowers  (1981)  discusses
determinations of hydraulic conductivity  of  rock.   This reference should be
consulted for guidance  in analyzing flow through fractured media.

          3.8.1  Fine-grained sediments, such  as  glacial tills, are commonly
     fractured in both  saturated  and  unsaturated  settings.  These fractures
     may be sufficiently  interconnected  to  have  a significant influence on
     ground water flow, or  they may  be  of  very limited connection and be of
     little practical significance.

          3.8.2  Frequently, a laboratory test of  a small sample of clay will
     determine hydraulic conductivity to be  on  the  order of 10~8 cm/sec.  A
     piezometer test of the  same  geologic  unit  over an interval containing
     fractures may determine a hydraulic  conductivity on the order of perhaps
     10-5 or 10-6 cm/sec.   To   assess the extent of fracture interconnection,
     and  hence  the  overall  hydraulic  conductivity  of  the  unit,  several
     procedures can be  used.  Closely spaced piezometers can be  installed; one
     can be used as an  observation  well  while water is added to or withdrawn
     from the other.  Alternately, a  tracer might be added to one piezometer,
     and the second  could  be   monitored.    These  and  other  techniques are
     discussed by Sowers  (1981).

          3.8.3   For  situations  that may involve flow through fractured media,
     1t  is  Important  to note in  permit applications that an apparent hydraulic
     conductivity determined by  tests on  wells  that intersect  a  small number
     of  fractures may be  several  orders  others  of magnitude lower or higher
     than  the value required  to describe  flow  through  parts of the ground
     water  system  that   Involve  different  fractures  and  different stress
     conditions from  those  used  during the test.


4.0  CONCLUSION

     4.1  By  following  laboratory  and  field methods  discussed or referenced  in
this report,  the  user should   be  able  to determine the  fluid conductivity  of
materials  used  for  liners,  caps,   and  drains at waste-disposal  facilities,  as


                                   9100 -  46
                                                          Revision       0
                                                          Date  September  1986

-------
well as materials composing the  local  ground  water  flow system.  If fluid-
conductivity  tests  are  conducted  and  Interpreted  properly,  the  results
obtained  should  provide  the  level  of  information  necessary  to  satisfy
applicable requirements under Part 264.


5.0  REFERENCES

1.   Acker, W. L., Ill, Basic Procedures  for Soil Sampling and Core Drilling,
Acker Drill Co., 246 p., 1974.

2.   Allison, I.E., Effect  of  Microorganisms  on  Permeability of Soil under
Prolonged Submergence, Soil Science,  63, pp. 439-450  (1947).
                                                   i
3.   American Society  for Testing  and  Materials  >(ASTM), Annual  Book of ASTM
Standards, Part  19, 1978.

4.   Anderson,   D.,  and  K.  W.   Brown,  Organic  Leachate   Effects  on   the
Permeability of  Clay Liners,  iji   Proceedings   of  Solid Waste Symposium, U.S.
EPA, p.  119-130,  1981.

5.   Bear, J., Dynamics of  Fluids  1n  Porous Media, American  Elsevler, 764  p.,
1972.

6.   Bouwer, H.,   and  R.   C.   Rice,  A Slug   Test   for Determining  Hydraulic
Conductivity of  Unconflned  Aquifers   with  Completely or Partially Penetrating
Wells, Water Resources Research,  12, p. 423-428 (1976).

7.   Bredehoeft,  J. D., and S.  S.  Papadopulos,  A Method for Determining  the
Hydraulic  Properties of Tight Formations, Water Resources  Research,  16,  p.233-
238 (1980).

8.   Conway, R.  A., and   B.  C.  Malloy,  eds., Hazardous  Solid Waste Testing:
First  conference,  ASTM Special  Technical  Publication  760,  1981.

9.   Cooper, H.  H., J. D.   Bredehoeft,  and   I.  S.  Papadopulos,  Response of a
Finite Diameter  Well   to  an  Instantaneous   Charge   of Water, Water  Resources
Research,  3, p.  263-269  (1967).

10. Dakessian,   S.,   et  al.,  Lining  of  Waste   Impoundment  and   Disposal
Facilities, Municipal  Environment Research   Laboratory, U.S. EPA, Cincinnati,
OH, EPA-530/SW-870C, pp.  264-269,  1980.

11. Fireman,  M.,  Permeability  Measurements   on Disturbed Soil  Samples, Soil
Science, 58, pp.  337-355  (1944).

12. Freeze, R.  A.,  and J.  A.  Cherry,  Ground  Water,  Prentice  Hall, 604  p.,
1979.
                                   9100 - 47
                                                          Revision
                                                          Date  September 1986

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13.  Gordon, B.B., and,  M.  Forrest,  Permeability  of Soil Using Contaminated
Permeant, iji Permeability and  Ground  Water  Contaminant Transport, ed. T. F.
Zimmie and C. 0. R1ggs,  ASTM  Special  Technical Publication 746, p. 101-120,
1981.

14.  Hlllel, D., Soil and Water, Academic Press, 288 p., 1971.

15.  Hvorslev,  M.  J.,  Time  Lag  and  Soil  Permeability  1n  Ground  Water
Observations, U.S. Army Corps of  Engineers Waterways Experiment Station Bull.
36, 1951.

16.  Johnson, A.  I., Symposium  on  Soil  Permeability, ASTM STP 163, American
Society of Testing and Materials, Philadelphia, pp. 98-114, 1954.

17.  Johnson, E.  E., Inc., Ground Water and Wells, Johnson Division, UOP,
440 p.,  1975.

18.  Lappala, E.  G., Quantitative Hydrogeology of the Upper Republican  Natural
Resources District,  Southwest Nebraska, U.S. Geological Survey Water Resources
Investigations  78-38.

19.  Lambe,  T.  W., Soil Testing  for Engineers, John Wiley, N.Y.,  1951.

20.  Lohman,  S.  W.,   Ground   Water    Hydraulics,  U.S.  Geological   Survey
Professional  Paper 708, 70 p.,  1972.

21.  Lohman,  S. W.,  et   al.,   Definitions   of   Selected   Ground Water Terms  -
Revisions and  Conceptual  Refinements,   U.S.   Geological  Survey Water Supply
Paper  1988,  1972.

22.  Manufacturing Chemists   Association,   Guide  for  Safety  in the  Chemical
Laboratory,  Van Nostrand,  Reinhold  Co,  N.Y.,  1971.

23.  Mitchell,  A.K., and  J.  S.  Younger,  Permeability  and  Capillarity of Soils,
ASTM STP 417,  American   Society   for   Testing  and   Materials, Philadelphia,
pp.106-139,  1967.

24.  Neuzil,  C.   E.,   On Conducting   the  Modified  'Slug1   Test  in  Tight
Formations,  Water Resources  Research, 18(2),  pp. 439-441  (1982).

25.  01 sen,  R.  E.,  and D. E. Daniel,  Measurement of the Hydraulic Conductivity
of Fine-Grained Soils, 1_n  Permeability  and  Ground  Water Transport,  ed.  T.F.
Zimmie and  C. 0.  Riggs,  ASTM Special  Publication 746,  p.  18-64,  1981.

26.   Papadopulos, S. S.,  J.   D.   Bredehoeft,   and  H.   H.   Cooper, Jr., On the
Analysis of  'Slug   Test'  Data,   Water  Resources  Research,   9,  p. 1087-1089
 (1973).

27.   Schwartzendruber, D.,  The  Applicability  of  Darcy's   Law,  Soil Science
Society of  America  Proceedings,  32(1),  pp.  11-18 (1968).
                                   9100 - 48
                                                          Revision
                                                          Date  September 1986

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28.  Sowers,  G.  F.,  Rock  Permeability  or  Hydraulic  Conductivity  --  An
Overview, Jhi Permeability and Ground Water Transport, ed. T. F. Zlmrnle and Co.
0. R1ggs, ASTM Special Technical Publication 746, 1981.

29.  Stallman, R.  W.,  Aquifer-Test  Design,  Observation  and Data Analysis,
TWRI, Chap. Bl, Book 3,  U.S.  Geological  Survey, U.S. Govt. Printing Office,
Washington, D.C., 1971.

30.  Terzaghl, K., and R. B. Peck, Soil Mechanics 1n Engineering Practice, 2nd
ed., John Wiley & Sons, N.Y., 729 p., 1967.

31.  Walton, W. C., Ground  Water  Resource  Evaluation,  McGraw Hill, 664 p.,
1970.

32.  Wilkinson, W. B., In S1tu  Investigation  1n Soils and Rocks, British and
Geotechnlcal Society, Institution  of  C1v1l  Engineers,  London, pp. 311-313,
1969.

33.  U.S.  Army  Corps  of   Engineers,  Laboratory  Soil  Testing,  Waterways
Experiment  Station,  Vlcksburg,  Mississippi,   Publication  EM 1110-2-2-1906,
1970.

34.  U.S. Environmental  Protection  Agency,  Hazardous  Waste  Guidelines and
Regulations  (proposed), Federal Register,  Part IV, Dec.  18,  1978.

35.  U.S.   Environmental  Protection  Agency,  RCRA  Ground  Water   Monitoring
Technical Enforcement Guidance  Document, Draft Final.
                                   9100 - 49
                                                          Revision
                                                          Date  September 1986

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                        METHOD 9100  (Part)

             HYDRAULIC COONDUCTIVITV OF SOIL SAMPLES:

         CONSTANT-HEAD TEST WITH CONVENTIONAL PEPMEAMETER
a.s.3
                                                        o
 Oven-dry ปno
 weigh sample
2.5.3
                                                    2.5.4
           Open
          valve A;
   stabilize flow;
    obtain initial
       piezometer
        readings
 Admit de-airea
    water to
  permeameter
                                                    2.5.4
    Allow flow to
        reach
     eaullibrulm
2.5.31
        Place
       specimen
In permeameter.
taking care to
      avoid
   segregat ion
2.5.3
2.5.4 I

         Record
   quantity of flow.
piezometrlc readings.
and water temperature
    over an Interval
        of time
       Obtain
     weight and
     dimensions
    of specimen
                                                    2.5.S
            Plot
          outflow
          ve time:
   obtain slope of
    linear portion
         of curve
2.5.4  Adjust
       halght
     of tank to
 obtain desired
     hydraulic
     gradient
                                                    2.5.51
         Calculate
      conductivity
           using
      Equation (a)
    0
  (      stop      J
                       9100 - 50
                                                  Revision       0
                                                  Date   September 1986

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                          METHOD 9100

              HYDRAULIC CONDUCTIVITY OF SOIL SAMPLES:

          FALLING-HEAD TEST WITH CONVENTIONAL PERMEAMETEH
CED            O
 2.5.3
  Oven-dry end
  weigh sample
 2.5.3
                        2.6.4
                             o
                               Slowly
      bring water
  up  to discharge
      level of
     permeameter
       Admit
  de-elred water
  to permeanieter
 2.5.3
                      2.6.4
                                                2.6.4
  Record water
  temperature
Raise head of water
 In stardplpe above
 discharge level of
    permeameter
        Place
       specimen
 In  permeameter.
    taking care
      to avoid
    segregation
2.E.5
       Plot
  head ve time;
obtain slope of
 linear portion
     of curve
                      2.6.4
Open valve B:  Record
 height of water  In
   stardplpe above
 discharge level  at
   times t,  and t,
 2.5.31
  Obtain weight
  and dimensions
   of specimen
                                                2.6.5
    Calculate
   conductivity
      using
   Equation (9)
                        (
    o
                   9100 - 51
                                           Revision      0
                                           Date   September 1986

-------
                               METHOD 91OO

                 HYDRAULIC CONDUCTIVITY OF SOIL SAMPLES:

                  MODIFIED COMPACTION PARAMETER METHOD
   2.7.3
                                                           o
          Air dry
          sample:
    mix with water
      for desired
        moisture
         content
2.7.3
                                                       2.7.4
          Flush
     water through
   sample until It
      Is saturated
Compact sample:  level
 the surface,  weigh.
    and determine
  density:  measure
 length and density
   2.7.3
                                                    2.7.4
  Record quantity of
   outflow VG time:
  record pressure at
times out is measured
       Assemble
      apparatus
   2.7.4
                                                    2.7.4
    Plot cumulative
outflow vs time:  stop
 when linear protlon
 of curve is defined
    Place  water  in
    fluid  chamber
                                                       2.7.5
         Calculate
      conductivity
          using
      equation (8)
      Q
  f     Stop      J
                        9100 - 52
                                                   Revision       0
                                                   Date   September  1986

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                                            METHOD 9tOO

                              HYDRAULIC CONDUCTIVITY OF SOIL SAMPLES:

                              TRIAXIAL CELL METHOD WITH BACK PRESSURE
                                                           o
       Trim sample
       to diameter
     of top cap of
     trlaxial cell
   2.8.4
                                 o
                                                    Z. 8. 4
                                                      Saturate specimen
                                                     by applying chamber
                                                      pressure and back
                                                      pressure In small
                                                         Increments
                                                                       No
        Does
        pore
   pressure Incr.
    immediately -
       chamber
      pressure
        incr.
                             2.8.4  Maintain
                                    minimum
                                   head loss
                             corns Istent with
                               a measureable
                                  flow rate
                                                                              2.6.4
Open valves 0 and F:
   record burette
    readings and
  temperature as a
  function of time
          Measure
         dimension
         •nd weigh
        of sample:
    place specimen
         on base
                                                    2.6.4
  Increase chamber
 pressure to attain
  desired effective
ancolidation pressure
   2.8.41
   Secure membrane
    over specimen
                                                                                 2.6.4
   Determine flow
  rate from slope
     of curves
                                                    2.6.4
 Open valves E and F;
 record and plot dial
indicator and burette
    readings as a
   function of time
2.8.4
  Assemble trlaxlal
chamber and fill with
fluid:  insert filter
     paper disks
                                                                                 2.8.5
        Calculate
     conductivity
         using
     Equation (8)
       0
       O
                                        9100  - 53
                                                                   Revision       0
                                                                   Date   September  1986

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                                                         METHOD 9100

                                           HYDRAULIC CONDUCTIVITY OF SOIL SAMPLES:

                                              PRESSURE-CHAMBER PARAMETER METHOD
       Trim sample
       to diameter
     of top cap of
     trlaxlal cell
                                                           o
   2.8.41 Measure
        'dimension
         and weigh
        of sample;
    place specimen
         on base
   2.8.4
   Secure membrane
    over specimen
2.8.4
  Assemble trlaxlal
chamber and fill with
fluid:  insert filter
     paper disks
       o
                                                       2.9.4   Apply
                                                             confining
                                                           pressure by
                                                             adjusting
                                                         leveling held
                                                       or compress air
                                                       2.9.4
Allow sample to
  consolidate
2.9.4
        Flush
        •ample
     with water
   until no air
    bubbles are
      observed
                                                       2.9.4
        Adjust
       head of
       water to
 attain desired
     hydraulic
      gradient
    O
                              o

2.94.
p
he
in st
as f
of


ecord
ad drop
andpipe
unction
time
Is log vs  time
 linear for  >3
  consecutive
   readings?
      Calculate
   conductivity
       using
   Equation  (9)
                                          9100 - 54
                                                                     Revision       0
                                                                     Date   September  1986

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                             METHOD 9100

                HYDRAULIC CONDUCTIVITY OF SOIL SAMPLES:

FIELD METHODS FOR  EXTREMELY TIGHT FORMATIONS UNDER CONFINED CONDITIONS
       Start
  3.4.2.2
           Fill
         borehole
    with water  to
       prevailing
      water  level
  3.4.2.2   Add  a
           known
      '  volume  of
     water  with a
    high—pressure
         pump
  3.4.2.2
     Shut  valve
    and  monitor
   pressure decay
    Has  pressure
   reached 85X of
      initial
      value?
     o

3.4.2.3
tronem
of test
uslr
curve

3.4.2.2
for
in vc
pat
(

3.4.2.3
Condi
transml
by thick
testc


Oetei —
mine
Lsetvity
,ed zone
ig type
! method

Correct
changes
ilume of
:ked-of f
:avlty

Deter-
mine
ictivlty
Lseivity
cnesE of
•d zone

f     Stop      J
                        9100 - 55
                                                   Revision       0
                                                   Date   September 1986

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                             METHOD 9100
                  HYRAULIC CONDUCTIVITY OF SOIL SAMPLES
FIELD METHODS FOR MODERATELY PERMEABLE MATERIALS UNDER UNCONFINED CONDITIONS
3. 4. a. a

Rapidly
remove a volume
of water from
the well bore
3
4.3.8

Record
watei — level
Changes over
time
3.4.3.3
condi
using i
Bouwer e
(<
Calcu-
late
jctlvity
iquatlon
ind Rice
1976)
                          f     Stop      }
                         9100 -  56
                                                 Revision       p
                                                 Date  September 1986

-------
                               METHOD 910C

                  HYDRAULIC CONDUCTIVITY OF SOIL SAMPLES:

FIELD METHOD FOR  MODERATELY PERMEABLE FORMATIONS UNDER CONFINED CONDITIONS
                                  Start
3
.4.1.2

Rapidly
remove a volume
O' water from
the well bore

3
.4.1.2



Record
water-level
changes over
time
                                 Has  water
                            level reached 65X
                                of Initial
                                  value?
                              transmlssIvlty
                              of  tested  zone
                                 using  type
                               Curve method
                                Determine
                             conductivity by
                                dividing
                            tranซmlsslvlty by
                              thickness of
                              tested  zone
                        9100 - 57
                                                   Revision       0
                                                   Date  September 1986

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                                 METHOD 9310

                         GROSS ALPHA AND GROSS BETA
1.0  SCOPE AND APPLICATION

     1.1  This method covers the  measurement  of  gross  alpha and gross  beta
particle activities in surface and ground waters.

     1.2  The method is applicable to the measurement of alpha emitters having
energies above 3.9 mega electron volts  (MeV) and beta emitters having maximum
energies above 0.1 MeV.

     1.3  The  minimum  limit  of  concentration   to  which  this  method  is
applicable   depends   on   sample   size,   counting-system  characteristics,
background, and counting time.

     1.4  Because, in this method for  gross alpha and gross beta measurement,
the radioactivity of  the  sample  is  not  separated  from  the solids of the
sample, the  solids  concentration  is  very  much  a  limiting  factor in the
sensitivity of the method for any given  water sample.  Also, for samples with
very low concentrations of radioactivity, it  1s essential to analyze as large
a  sample aliquot as is needed to give reasonable times.

     1.5  The largest sample aliquot  that  should  be counted for gross alpha
activity 1s that  size  aliquot  which  gives  a  solids  density thickness of
5  mg/cm^ in the counting  planchet.    For  a 2-1n. diameter counting planchet
(20 crn^), an aliquot containing 100  mg  of nitrated dissolved solids would be
the maximum aliquot  size  for  that  sample  which  should  be evaporated and
counted  for gross alpha activity.

     1.6  When the concentration of  total  solids   (TS)  is known for a given
water  sample and the alpha background  and  the  counting efficiency of a given
counting system are  known,  the  counting  time  that  1s  needed to meet the
required sensitivity   (3  pCi/L)  can  be  determined  by  equations  given in
Appendix C.

     1.7  For the counting of gross beta activity in a water sample, the TS is
not as limiting as for  gross  alpha  activity   because beta particles are not
stopped  in solids as  easily  as  are  alpha  particles.   Very often a single
sample aliquot is evaporated and counted  for  both gross alpha and gross beta
activity.  In that case,  the  sample  aliquot   size  would be dictated by the
solids limitations for alpha  particles.    For  water  samples that are to be
counted  for gross beta activity, equations  in   Appendix C can also be used to
determine the necessary counting  time  to  meet  a sensitivity for gross beta
activity  (4 pC1/L).

     1.8  Radionuclides   that  are  volatile   under  the  sample  preparation
conditions of this method will not be  measured.  In some areas of the country
the nitrated water solids   (sample  evaporated   with nitric acid present) will
                                   9310 -  1
                                                          Revision      0
                                                          Date  September 1986

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not remain at a constant weight after  being  dried at 105*C for 2 hr and then
exposed to the atmosphere before  and  during counting.  Other radioactivities
(such as some chemical  forms  of  radloiodlne)  may  also  be lost during the
sample evaporation and drying at 105*C.   Those types of water samples need to
be heated to a dull red heat for a few minutes to convert the salts to oxides.
Sample  weights  are  then  usually  sufficiently  stable  to  give consistent
counting rates, and a correct counting  efficiency can then be assigned.  Some
radioactivities, such as the  cesium  radioisotopes,  may be lost when samples
are heated to a dull  red  color.    Such  losses  are limitations of the test
method.

     1.9  This method  provides  a  rapid  screening  measurement  to indicate
whether specific  analyses  are  required.    When  the  gross  alpha particle
activity exceeds 5 pCi/L, the same  or  an equivalent sample shall be analyzed
for alpha-emitting radium isotopes (Method 9315) or an alternative measurement
of radium-226 alpha emission  (Standard  Methods  for the Examination of Water
and Wastewater, 15th edition, Method  705  or  706, respectively).  Gross beta
particle emissions exceeding  15  pC1/L  in  a  sample  shall  be analyzed for
strontium-89 and cesium-134 (Standard Methods for the Examination of Water and
Wastewater, 15th edition, Methods 704  and  709, respectively).  If gross beta
activity exceeds 50 pC1/L, the   identity of the major radioactive constituents
must be evaluated and the appropriate organ and total body doses determined.


2.0  SUMMARY OF METHOD

     2.1  An aliquot of  a  preserved  water  sample  is  evaporated to  a small
volume  and  transferred quantitatively  to   a  tared  2-1n.  stainless steel
counting planchet.  The  sample  residue  is dried to constant weight, rewelghed
to determine dry   residue  weight,  and  then  counted  for  alpha and/or beta
radioactivity.

     2.2  Counting  efficiencies for   both  alpha   and  beta particle activities
are  selected according to the amount  of sample sol Ids  from counting efficiency
vs.  sample sol Ids  standard curves.


3.0  INTERFERENCES

     3.1  Moisture  absorbed by  the  sample   residue  is  an  interference  because
it obstructs counting and  self-absorption   characteristics.     If a sample is
counted  in an   internal  proportional  counter,  static  charge   on the sample
residue  can cause  erratic counting, thereby  preventing  an  accurate count.

     3.2  Nonunlformity  of the  sample residue in  counting planchet Interferes
with the  accuracy  and precision of the method.

     3.3  Sample density on  the planchet   area   should   be   not more  than 10
mg/cm2  for gross alpha and not  more than 20  mg/cm2 for gross beta.
                                   9310 - 2
                                                         Revision      0
                                                         Date  September  1986

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     3.4  When  counting  alpha  and  beta  particle  activity  by  a gas-flow
proportional counting  system,  counting  at  the  alpha plateau discriminates
against beta  particle  activity,  whereas  counting  at  the  beta plateau is
sensitive to alpha  particle  activity  present  in  the  sample.  This latter
effect should be determined and compensated  for during the calibration of the
specific instrument being used.


4.0  APPARATUS AND MATERIALS

     4.1  Gas-flow proportional counting system, or

     4.2  Scintillation detection system, or

     4.3  Stainless steel counting planchets.

     4.4  Electric hot plate.

     4.5  Drying oven.

     4.6  Drying lamp.

     4.7  Glass desiccator.

     4.8  Glassware.

     4.9  Analytical balance.


5.0  REAGENTS

     5.1  All chemicals  should  be  of   "reagent-grade" or equivalent whenever
they are commercially available.

     5.2  Distilled or deionized  water   (Type   II)  having a resistance value
between 0.5 and 2.0 megaohms  (2.0 to 0.5 mhos)/cm at 25ฐC.

     5.3  Nitric acid. 1 N:   Mix  6.2  ml  16 N  HN03 (cone.) with deionized or
distilled water and dilute to 100 ml.


6.0  SAMPLE COLLECTION,  PRESERVATION, AND HANDLING

     6.1  All samples must have  been collected  in a manner which addresses the
considerations discussed in  Chapter Nine of  this manual.

     6.2  It  is recommended  that samples  be  preserved at the time of collec-
tion by adding enough 1  N HN03 to the  sample   to  bring it to pH 2  (15 mL 1 N
HN03 per liter  of  sample   is   usually  sufficient).    If  samples are to be
collected without  preservation,  they   should   be  brought  to  the laboratory
within 5 days and then   preserved  and   held  in  the original "container for a
minimum of  16 hr before  analysis or transfer of  the sample.


                                  9310 - 3
                                                         Revision      0
                                                         Date  September 1986

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     6.3  The container choice should be  plastic rather than glass  to prevent
loss due to breakage during transportation and handling.


7.0  PROCEDURE

     7.1  Calibration;

          7.1.1  For absolute  gross  alpha  and  gross  beta measurement,  the
     detectors must  be  calibrated  to  obtain  the  ratio  of  count rate to
     disintegration rate.    Amer1c1um-24l  (used  for  alpha  activity 1n  the
     collaborative test of this method)  has  higher alpha particle energy  and
     rad1um-226  radlonuclldes  but  1s  close  to  the  energy  of  the alpha
     particles emitted  by  naturally  occurring  thorlum-228  and rad1um-224.
     Standards should be prepared  In  the  geometry  and  weight ranges to be
     encountered 1n these gross  analyses.    It 1s, therefore, the prescribed
     radlonucllde  for  gross  alpha   calibration.     NBS  or  NBS-traceable
     amerldum-241 1s available from Standard Reference Materials Catalog,  NBS
     Special Publications 260,  U.S.  Department  of  Commerce (1976) and from
     Quality Assurance Branch,  EMSL-LV,  P.O.  Box  15027,  Las Vegas, Nevada
     89114.

          7.1.2  Stront1um-90  and  ceslum-137  have   both  been  used  quite
     extensively as standards for gross  beta activity.  Standard solutions of
     each of these radlonuclldes are readily available.  Cesium 1s volatile at
     elevated temperatures  (above 450*C).   Some water supplies have dissolved
     sol Ids  (salts)  that,  when  converted   to  nitrate  salts,  are  quite
     hygroscopic and need to be converted to  oxides by heating to red heat to
     obtain sample allquots that  are  weight-stable.  Sample weight stability
     1s essential to gross  alpha  and  gross  beta measurements to ensure the
     accuracy of the self-absorption counting efficiency factor to be used for
     the samples.  Stront1um-90 In equilibrium with its daughter yttr1um-90 1s
     the prescribed radionucllde for gross beta calibrations.

           7.1.3  For each counting instrument  to  be  used,  the analyst should
     prepare separate alpha and  beta  particle self-absorption graphs showing
     water sample residue   weight   (mg)   vs.  the  efficiency  factor  (cpm/dpm),
     using standard alpha and beta emitter  solutions   and tap water.  For the
     alpha graph  standard,   alpha   activity  is   added to   varying   sizes of
     allquots of tap water  such  that  the   aliquot   residue weight  is varied
     between 0 and  100 mg  (for a 2-in.  counting planchet).   A similar graph 1s
     prepared with  standard beta activity and tap-water allquots,  varying the
     residue weight between 0 and 300   mg  (for   a 2-in.  planchet).   If it 1s
     planned to  use water-sample aliquot  volumes  that  always contain  100 mg of
     dried water solids,   then  only  the efficiency   factor for that residue
     weight needs to  be  established.

           7.1.4  Tap  water allquots,  with added  americium-241  or stront1um-90
     standard,  should be acidified  with a  few   ml  16 N  HN03,  evaporated  to a
     small volume  in  a  beaker on a  hot plate,  transferred  quantitatively 1n 5-
     mL portions or less to a tared counting planchet,  evaporated  to dryness,
     and finally dried  at  105*C  for  1   hr  (or   flamed to a red  heat if dried


                                  9310 - 4
                                                          Revision      0
                                                          Date  September 1986

-------
     solids appear  to  be  noticeably  hygroscopic).     Weight-stable  aliquot
     residues should then be alpha  and/or  beta counted until  at least 10,000
     total counts have been accumulated.   A single set of reference standards
     prepared 1n  this  way  can  be  used  for  each   counting Instrument for
     separate graph preparations and can be stored for reverlflcation whenever
     needed.

     7.2 Transfer to a beaker  an  aliquot  of  water  sample of a volume that
contains no more than 100 mg (for  alpha only or alpha and beta determination)
or 200 mg (for beta only determination)  of total water solids.  Evaporate the
aliquot to near dryness  on  a  hot  plate.    If  water  samples are known or
suspected to contain chloride salts,  those chloride salts should be converted
to nitrate salts before the sample residue is transferred to a stainless steel
planchet  (chlorides  will  attack  stainless  steel  and ' Increase  the sample
solids, and no correction can be made for those added solids).  Chloride salts
can be converted to nitrate salts by adding  5-mL portions of 16 N HN03 to the
sample residue and evaporating to  near  dryness.  (Two treatments are  usually
sufficient.)  Add 10 ml  1  N  HN03  to  the  beaker and swirl to dissolve the
residue.  Quantitatively transfer  the  aliquot  concentrate 1n small portions
(not more than 5 ml at a  time)  to a tared planchet,  evaporating each  portion
to dryness.

     7.3  Dry the sample residue in a drying  oven at 105*C for at least 1 hr,
cool in a  desiccator,  weigh,  and  count.    Store  the  sample residue in a
desiccator until ready for counting.

     7.4  Some types  of  water-dissolved  solids,  when  converted to  nitrate
salts, are quite hygroscopic even after being  dried  at 105*C for 1 hr.  When
such hygroscopic salts are present with samples that are put Into an automatic
counting  system, those  samples  gain  weight  while  they  are  waiting to be
counted,  and Inaccurate  counting  data  result.    When  there is evidence of
hygroscopic salts 1n sample counting planchets, 1t 1s recommended that  they be
flamed to a dull red heat with  a  Meeker  burner for a few minutes to convert
the nitrate salts to oxides before weighing  and counting.  (It 1s possible to
have a loss of cesium during the flaming of the samples.)

     7.5  Count for  alpha  and  beta  activity  at  their  respective voltage
plateaus.  If the sample is to  be recounted for reverification, store 1t in a
desiccator.
     NOTE:  As long as counting chambers are capable of handling the same size
            planchet, alpha and  beta  activities  can  be determined at their
            respective   voltage   plateaus   in   the   designated   counting
            Instruments.   Keep the planchet  in  the desiccator until ready to
            count because  vapors from  moist  residue  can damage detector and
            window and  can  cause  erratic  measurements.     If  the gas-flow
            internal proportional counter  does not discriminate for the higher
            energy alpha pulses at the  beta  plateau, the alpha activity must
            be   subtracted  from  the   beta  plus  alpha  activity.    This is
            particularly  Important for  samples with high alpha activity.
                                   9310 - 5
                                                         Revision      0
                                                         Date  September 1986

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7.6  Calculations;

     7.6.1  Calculate the alpha radioactivity by the following equation:


               Alpha (pd/liter) = jj^

     where:

          A = net alpha count  rate  (gross  alpha  count  rate minus the
              background count rate) at the alpha voltage plateau;

          C = alpha efficiency  factor,  read  from  the graph (Paragraph
              7.1.3) of efficiency  vs.  mg  of  water  sol Ids per cm2 of
              planchet area, cpm/dpm);

          V = volume of sample aliquot (ml); and

       2.22 = conversion factor from dpm/pC1.


      7.6.2  Calculate the beta  radioactivity by the following equations:

          7.6.2.1  If  there  are   no  significant  alpha counts when the
      sample 1s  counted at   the  alpha  voltage plateau, the beta activity
      can  be determined from the following equation:
                Beta  (pC1/Hter)  =
      where:
           B =  net  beta  count  rate  (gross alpha count rate minus the
               background  count  rate at the beta voltage plateau),

           D =  beta efficiency factor, read from the graph (Paragraph
               7.1.3)  of efficiency vs. mg of water solids per cm2 of
               planchet  area,  (cpm/dpm).

           V =  volume  of sample  aliquot (ml).

        2.22 =  conversion  factor from dpm/pd.


      7.6.3  When counting  beta radioactivity  1n  the presence of alpha
 radioactivity  by  gas-flow proportional  counting  systems   (at the beta
 plateau),  alpha particles are also  counted.  Because  alpha  particles  are
 more readily absorbed by  increasing sample thickness than beta particles,
 the  alpha/beta  count  ratios   vary  with   Increasing sample thickness.
 Therefore, 1t  is necessary to   prepare  a   calibration curve by counting
 standards  containing  amer1cium-24l with  increasing thickness of solids on
                              9310 - 6
                                                     Revision
                                                     Date  September 1986

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the alpha plateau and then  on  the  beta plateau,  plotting the ratios  of
the two counts vs. density thickness.  The alpha amplification factor (E)
from that curve 1s used to correct  the amplified alpha count on the beta
plateau.  When  significant  alpha  activity  is  indicated by the sample
count at the alpha voltage plateau,  the  beta activity of the sample can
be determined by counting  the  sample  at  the  beta voltage plateau and
calculating the activity from the following equation:
               Beta (pel/liter) • 
-------
9.0  METHOD PERFORMANCE

     9.1  In a  collaborative  study  of  two  sets  of  paired  water samples
containing known additions  of  radlonuclldes,  15 laboratories determined the
gross alpha  activity  and  16  analyzed  gross  beta  activity.   The samples
contained simulated water  minerals  of  approximately  350 mg fixed sol1ds/L.
The alpha results of one laboratory were rejected as outliers.

     The average recoveries of added gross alpha activity were 86,  87, 84, and
82%.  The precision (random error) at  the 95% confidence level was 20 and 24%
for the two sets  of  paired  samples.    The  method  was biased low, but not
seriously.

     The average recoveries of added  gross  beta  activity were 99, 100, 100,
and 100%.  The precision (random error) at the 95% confidence level was 12 and
18% for the two sets of paired samples.  The method showed no bias.
10.0  REFERENCES

     10.1  None required.
                                   9310 - 8
                                                         Revision
                                                         Date  September 1986

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                                            METHOD 9310

                                    GROSS ALPHA AND GROSS BETA
 7. 1
   Calibrate using
   Am-241 for gross
• lone activity:  Sr-go
 or Cs-137 for gross
    bata activity
   7.1.3
       Prepare
       separate
     alpha and
  beta particle
•elf—absorption
      graphs
   7.1.4
  Does water
 ample contain
   chloride
    •alts?
                                                                                    o
                                                                                 7.6. 1
                                                                              Calculate alpha
                                                                               radioactivity
                                     Add
                                    HNOj:
                             swirl:  transfer
                             each  aliquot  to
                              tard planchet;
                                avaporate
          Acidify
         tap water
     aliguots with
   HNOi; evaporate:
      transfer to
       planchet
   7.1.4
                              7.3
                                                   7.6.Z
                                                   •^-M>MซJ


                                                    Calculate  bete
                                                    radioactivity
  Dry •ample
residue:  weigh
  and count
                                                  f      Stop       j
         Evaporate
          and  dry:
      count  alpha.
     beta residue
    for  reference
      •tandard
    7.2
        i  Transfer
        aliquot  of
      water  sample
        to beaker;
        •vaporate
                         Flame to a dull
                            red neat
                                  9310 - 9
                                                             Revision       0
                                                             Date   September  1986

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                                 METHOD 9315

                       ALPHA-EMITTING RADIUM ISOTOPES
1.0  SCOPE AND APPLICATION

     1.1  This method  covers  the  measurement  of  the  total  soluble alpha-
emitting radioisotopes of radium,  namely  radium-223,  radium-224,  and radium-
226, in surface and ground waters.

     1.2  Although the method does not  always give an  accurate  measurement of
the radium-226 content of  the  sample  (when  other radium alpha emitters are
present), it can be  used  to  screen  samples.    When the total radium alpha
activity of a drinking water sample is  greater than 5  pC1/L,  then the radium-
226 analysis 1s required.   If  the  level  of rad1um-226 exceeds 3 pC1/L, the
sample must also be measured for rad1um-228 (Method 9320).

     1.3  Because this method provides for the separation of radium from other
water-dissolved sol Ids in  the  sample,  the  sensitivity  of  the method is a
function  of  sample  size,   reagent   and  Instrument  background,  counting
efficiency, and counting time.

     1.4  Absolute measurement can be  made  by calibrating the alpha detector
with standard radium-226 in the geometry obtained with the final precipitate.


2.0  SUMMARY OF METHOD

     2.1  The radium  1n  the surface water  or ground water sample 1s collected
by  coprecipitatlon with  barium   and   lead  sulfate  and purified by repredpi-
tation  from EDTA  solution.  Citric acid  is added to the water sample to assure
that complete Interchange occurs  before  the  first  precipitation step.  The
final BaS04 precipitate,  which   Includes  radium-226, radium-224, and radium-
223, 1s alpha counted to determine the total disintegration rate of the radium
isotopes.

     2.2 The   radium activities  are   counted  1n  an   alpha   counter   where
efficiency for  determining radium-226 has  been  calibrated with a standard of
known radium-226  activity.  By making a correction for  the Ingrowth of  alpha
activity in  radium-226 for the  elapsed  time  after   separation,  one can
determine radium  activity 1n  the sample.    Because some  daughter  Ingrowth can
occur before  the  separated radium 1s  counted,  it 1s necessary to make  activity
corrections for the  count rate.   A table of  ingrowth factors for various  times
after radium  separation  is provided  in Paragraph 7.14.
                                                        t

3.0 INTERFERENCES

     3.1  Inasmuch as the radlochemical  yield  of  the  radium activity  1s  based
on  the  chemical yield of the BaS04   precipitate, the presence  of significant
natural barium  in the sample  will result 1n  a  falsely  high chemical yield.


                                  9315 - 1
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                                                          Date  September  1986

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     3.2  Radium   Isotopes   are    separated   from   other   alpha-emitting
radlonuclldes by this method.
     3.3  The alpha count of the  separated  radium  must be corrected for Its
partially Ingrown alpha-emitting daughters.

4.0  APPARATUS AND MATERIALS
     4.1  Alpha  scintillation  or  a  gas-flow  proportional  alpha  particle
counting system with low background ซ1 cpm).
     4.2  Stainless steel counting planchets.
     4.3  Electric hot plate.
     4.4  Drying oven and/or drying lamp.
     4.5  Glass desiccator.
     4.6  Analytical balance.
     4.7  Centrifuge.
     4.8  Glassware.
5.0  REAGENTS
     5.1  Distilled or delonlzed water (Type II).
     5.2  Acetic acid. 17.4  N: glacial CHaCOOH (cone.), sp. gr. 1.05, 99.8%.
     5.3  Ammonium  sulfate,  200 mg/mL:   Dissolve  20 g  (NH^SCty 1n a minimum
of water and dilute to 100 ml.
     5.4  Barium carrier, 16 mg/mL, standardized:
          5.4.1  Dissolve 2.846 g  BaCl2-2H20 1n  water,  add 0.5 mL 16 N HN03,
     and dilute to  100 mL with water.
          5.4.2  To perform  standardization  (1n  triplicate):   Pipette 2.0 mL
     carrier solution Into a centrifuge  tube containing  15 mL water.  Add  1 mL
     18 N HgSOA with  stirring and  digest  precipitate   1n a water bath for 10
     m1n.   Cool, centrifuge, and  decant  the   supernatant.  Wash precipitate
     with 15 mL water.   Transfer  the   precipitate  to a tared  stainless steel
     planchet  with  a'minimum of   water.     Dry  under Infrared lamp, store 1n
     desiccator, and weigh as BaSCty.
     5.5  Citric acid.  1 M:  Dissolve  19.2 g WsOffyO  In water and dilute to
 100  mL.
                                   9315 - 2
                                                         Revision
                                                         Date  September 1986

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     5.6  EDTA reagent,  basic (0.25 M):    Dissolve  20 g  NaOH  1n  750 mL water,
heat  and  slowly  add   93   g  d1sodium  ethylened1n1tr1loacetate  d1hydrate
(Na2CioHu08N2*2H20).  Heat and  stir  until   dissolved;  filter through coarse
filter paper and dilute to 1 liter.

     5.7  Lead carrier,  15 mg/mL:  Dissolve 2.397 g Pb(N03)2 1n water, add  0.5
mL 16 N HN03, and dilute to 100 mL with water.

     5.8  Sodium hydroxide, 6 N:  Dissolve 24 g NaOH 1n 80 mL  water and dilute
to 100 mL.

     5.9  Sulfurlc add. 18 N:   Cautiously  mix  1 volume 36  N H2S04  (concen-
trated) with 1 volume of water.

     5.10 Sulfurlc add. 0.1 N:   Mix  1  volume  18  N ^04  with 179 volumes
of water.


6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

     6.1  All samples must have been collected 1n a manner which  addresses  the
considerations discussed 1n Chapter Nine of this manual.

     6.2  It  1s  recommended  that  samples  be  preserved  at  the   time   of
collection by adding enough 1 N HN03 to the  sample to bring It to pH  2  (15 mL
1 N HN03 per liter of  sample  1s  usually  sufficient).   If samples are  to be
collected without  preservation,  they  should  be  brought  to the  laboratory
within 5 days and then  preserved  and  held  1n  the original container  for a
minimum of 16 hr before analysis or transfer of the sample.

     6.3  The container choice should be  plastic rather than  glass to prevent
loss due to breakage during transportation and handling.


7.0  PROCEDURE

     7.1  Calibration;

          7.1.1  The  counting   efficiency  for   radium  alpha  particles with
     barium  sulfate  carrier  present  must   be   determined  using  a standard
      (known) radium alpha  activity and 32  mg of  barium carrier as 6aS04 (same
     carrier amount  used 1n   samples).    This   1s  done with spiked distilled
     water samples, and the procedure  for  regular samples 1s followed.   Note
     the  time of the Ra-BaS04 precipitation.

          7.1.2  The radium alpha  counting   efficiency,   E,  1s calculated as
      fol1ows;

                     E  (cpm/dpm)  = ^-j
                                   9315 - 3
                                                         Revision
                                                         Date  September 1986

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         where:

            C  =  sample  net  cpm (gross  counts minus background divided
                by the  counting time in  minutes).

            A  =  dpm of  rad1um-226 added  to sample.

            I  =  Ingrowth factor for the  elapsed time  from Ra-BaS04,
                precipitation to midpoint of counting time.
     7.2  To a 1,000-mL surface water  or  ground  water  sample,  add 5 ml 1  M
            1 mL lead carrier, and 2.0 ml barium carrier,  and heat to boiling.
     7.3  Cautiously, with vigorous stirring,  add 20  ml 18 N ^04.   Digest 5
to 10 m1n and let the  mixed BaS04-PbS04 precipitate settle overnight.  Decant
and discard supernate.

     7.4  Transfer the precipitate to a  centrifuge tube with a minimum amount
of 0.1 N H2S04.  Centrifuge and discard supernate.

     7.5  Wash the precipitate twice with 0.1 N ^$04.  Centrifuge and discard
washes.

     7.6  Dissolve the precipitate by adding 15 mL basic EDTA reagent; heat in
a hot-water bath and add a few drops 6 N NaOH until solution Is complete.

     7.7  Add 1 ml (NH4)2S04  (200  mg/mL)  and  stir  thoroughly.  Add 17.4 N
        dropwlse until precipitation begins and then add 2 ml extra.   Digest 5
to 10 mln.

     7.8  Centrifuge, discard the supernate, and record time.
     NOTE:  At this point, the  separation  of  the BaSCty 1s complete, and the
          Ingrowth of radon (and daughters) commences.

     7.9  Wash the BaS04 precipitate with 15 ml water, centrifuge, and discard
wash.

     7.10  Transfer the precipitate to a tared stainless steel planchet with a
minimum of water and dry under Infrared lamps.
     NOTE:  Drying should be rapid, but not too vigorous, to minimize any loss
          of radon-222 that has already grown Into the precipitate.

     7.11  Cool, weigh, and store In desiccator.

     7.12  Count 1n  a  gas-flow  Internal  proportional  counter  or an alpha
scintillation  counter to determine the alpha activity.
                                   9315 - 4
                                                          Revision
                                                         Date   September  1986

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    7.13  Calculation;

          7.13.1   Calculate  the   rad1um-226  concentration,  D   (which  would
    Include  any  rad1um-224  and rad1um-223 that 1s present), 1n plcocurles per
    liter as follows:
                    D
                          2.22  xExVxRxI


          where:

            C = net count rate, cpm.

            E = counter efficiency,  for rad1um-226 1n BaS04 predetermined
                for this procedure (see Paragraph 7.1.2).

            V = liters of sample used.

            R - fractional chemical  yield.

            I = Ingrowth correction factor (see Paragraph  7.14).

         2.22 = conversion factor from dpm/pC1.


     7.14  It  1s  not  always   possible   to  count  the  BaSCty  precipitate
Immediately after separation;  therefore,  corrections  must  be   made for the
Ingrowth of  the  rad1um-226  daughters  between  the  time  of separation and
counting, according to the following table:

          Hours from separation            Ingrowth correction
              to counting                        factor

                   0                              1.00
                   1                              1.02
                   2                              1.04
                   3                              1.06

                   4                              1.08
                   5                              1.10
                   6                              1.12

                  24                              1.49
                  48                              1.91
                  72                              2.25

                  96                              2.54
                 120                              2.78
                 144                              2.99

                 192                              3.29
                 240                              3.51
                                  9315 - 5
                                                         Revision
                                                         Date  September 1986

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8.0  QUALITY CONTROL
     8.1  All quality control data should be maintained and available for easy
reference or Inspection.
     8.2  Employ a minimum  of  one  blank  per  sample  batch to determine 1f
contamination or any memory effects are occurring.
     8.3  Run one duplicate sample for  every  10 samples.  A duplicate sample
1s a sample brought through the whole sample-preparation process.
     8.4  Spiked samples or standard reference materials shall be periodically
employed to ensure that  correct  procedures  are  being followed and that all
equipment 1s operating properly.
9.0  METHOD  PERFORMANCE
     9.1  No data provided.
10.0   REFERENCES
     10.1  None required.
                                   9315 - 6
                                                          Revision
                                                          Date  September 1986

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                              METHOD 9315

                    ALPHA-EMITTING RADIUM  ISOTOPES
  7. 1. J
        Calibrate
    detectors for
     radium (lob*
      measurement
7.Z
                             7.6
     Dissolve
   precipitate
 In EOTA;  heat:
    •dd NปOH
Add C,H.cv Hto.
and barium carrie
  to water sample
  heat to Dolling
7.3
                             7.7
  Cool.  weigh.
  and ctore in
   aaalccator
Add  CNH4>zS04:
   • tlr;   aao
CHjCOOM;  digact
  Add HiSOซ whil*
 stirring:  digest:
   precipitate:
 discard supernste
                                                       7.12
 Uae counter to
determine alpha
   activity
                             7.8
    Centrifuge:
     discard
    suparnate:
   record time
    Centrifuge:
      discard
     supernate
                                                       7.13.1
   Calculate
   raajium-226
 concentration
 7.9
     I Mash
       BSS04
   precipitate:
   centrifuge:
  dlacnard wash
         Maoh
     precipitate:
     centrifuge:
   discard Mashes
                                                       7.14
       Correct
   for ingrowth
  of redium-226
    daughtera
                             7.101
      Transfer
    precipitate
   to planchat:
        dry
                                                     f      Start      1
                       9315 -  7
                                                  Revision        o
                                                  Date  September 1986

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PART II   CHARACTERISTICS
                           Revision      0
                           Date  September 1986

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                                 CHAPTER SEVEN

                    INTRODUCTION AND REGULATORY  DEFINITIONS
7.1  IGNITABILITY

      7.1.1  Introduction

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

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

      7.1.2  Regulatory Definition

      The following definitions  have  been  taken  nearly verbatim  from the RCRA
regulations  (40  CFR 261.21) and  the  DOT  regulations  (49  CFR งง  173.300 and
173.151).

      Characteristics Of Iqnitabilitv Regulation

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

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

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

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

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

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      lonitable Compressed Gas

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

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

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

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

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

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

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

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

      Oxidizer (as defined in 49 CFR  173.151)

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

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7.2   CORROSIVITY

      7.2.1  Introduction

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

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

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

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

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

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

      7.2.2  Regulatory Definition

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

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

            a.  It is aqueous  and has a pH < 2 or > 12.5, as determined by a pH
                meter  using either  the  test  method  specified in this  manual
                (Method 9040)  or  an equivalent  test  method  approved  by  the
                Administrator under  the procedures set forth in Sections 260.20
                and  260.21.

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

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7.3   REACTIVITY

      7.3.1  Introduction

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

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

      7.3.2  Regulatory Definition

            7.3.2.1    Characteristic  Of Reactivity Regulation

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

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

            2.   It reacts  violently  with  water.

            3.   It forms potentially explosive  mixtures  with water.

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

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

            6.   It is capable  of detonation or  explosive  reaction  if it  is
                subjected  to  a  strong  initiating source  or  if  heated  under
                confinement.
                                  SEVEN  - 4                        Revision  2
                                                                   Septenterl994

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            7.  It is readily capable of detonation or explosive decomposition
                or reaction at standard temperature and pressure.

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


      7.3.3  Interim Guidance For Reactive Cyanide

            7.3.3.1    The current EPA guidance level  is:

            Total releasable cyanide:  250 mg HCN/kg waste.

            7.3.3.2    Test Method to Determine Hydrogen Cyanide Released from
                       Wastes

1.0   SCOPE AND APPLICATION

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

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

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

2.0   SUMMARY OF METHOD

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

3.0   INTERFERENCES

      3.1   Interferences  are undetermined.

4.0   APPARATUS AND MATERIALS (See Figure 1)

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

      4.2   Gas scrubber - 50 mL calibrated scrubber

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

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


                                   SEVEN -  5                       Revision  2
                                                                   Septenter 1994

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      4.5   Flexible   tubing   -   For  connection   from   nitrogen  supply  to
apparatus.

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

      4.7   Rotometer  - For monitoring nitrogen gas flow rate.

      4.8   Analytical balance - capable of weighing to 0.001 g.

5.0   REAGENTS

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

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

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

      5.4   Cyanide reference  solution,  (1000 mg/L).   Dissolve  approximately
2.5 g of KOH and 2.51  g  of  KCN in  1 liter  of reagent  water.  Standardize with
0.0192N AgN03.   Cyanide concentration in  this solution should be 1 mg/mL.

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

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

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

6.0   SAMPLE COLLECTION, PRESERVATION AND HANDLING

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

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

                                   SEVEN  -  6                       Revision 2
                                                                   Septennber 1994

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characteristics  of the  waste which  may affect  the rate  of release  of the
hydrocyanic acid.  Storage of samples should be under refrigeration and in the
dark.

      6.3   Testing should be performed  In a ventilated hood.

7.0   PROCEDURE

      7.1   Add  50 ml  of  0.25N NaOH  solution  (Step  5.6)  to  a  calibrated
scrubber and dilute with reagent water to obtain an adequate depth of liquid.

      7.2   Close  the system  and adjust the flow rate  of nitrogen,  using the
rotometer.  Flow should be 60 mL/min.

      7.3   Add 10 g of the waste to be tested to the system.

      7.4   With the  nitrogen flowing,  add  enough  sulfuric acid to  fill the
flask half full.  Start the 30 minute test period.

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

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

      7.6   After  30 minutes,   close  off  the  nitrogen   and  disconnect  the
scrubber.   Determine the amount  of cyanide  in  the scrubber  by  Method 9010,
Chapter Five, starting with Step 7.2.7 of the method.

NOTE: Delete  the  "C"  and  "D"   terms  from  the  spectrophotometric  procedure
      calculation  and the  "E"   and  "F"  terms from  the   titration  procedure
      calculation  in  Method  9010.    These  terms  are  not necessary for the
      reactivity  determination   because  the terms  determine  the  amount  of
      cyanide in the entire sample,  rather  than  only in the aliquot taken for
      analysis.

8.0   CALCULATIONS

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

            X = Concentration of HCN in diluted scrubber solution (mg/L)
                   (This is obtained from Method 9010.)

            L = Volume of solution in scrubber (L)

            W = Weight of waste used (kg)

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

                                                         X • L
            R = specific rate of release (mg/kg/sec.)  = 	
                                                         W • S

            Total releasable HCN (mg/kg) = R x S

                                  SEVEN  -  7                        Revision 2
                                                                   September 1994

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9.0   METHOD PERFORMANCE

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

10.0  REFERENCES

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

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                                      FIGURE  1.

             APPARATUS TO DETERMINE HYDROGEN CYANIDE RELEASED FROM WASTES
      Flowmeter
N, In
                    Reaction Flask
                                                                    Gas Scrubber
                                                    Waste Sample
                                     SEVEN - 9
Revision 2
September 1994

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      7.3.4 Interim Guidance For Reactive Sulfide

            7.3.4.1    The current EPA guidance level  is:

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

1.0   SCOPE AND APPLICATION

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

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

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

2.0   SUMMARY OF METHOD

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

3.0   INTERFERENCES

      3.1   Interferences are undetermined.

4.0   APPARATUS AND MATERIALS (See Figure 2)

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

      4.2   Gas scrubber - 50 mL calibrated scrubber.

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

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

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

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

      4.7   Rotometer - For monitoring nitrogen gas flow rate.

      4.8   Analytical balance - capable of weighing to 0.001 g.

5.0   REAGENTS

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

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

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

      5.4   Sulfide reference  solution  -  Dissolve 4.02 g  of  Na2S  •  ShU) in
1.0 L of  reagent water.   This solution  contains  570  mg/L hydrogen sulfide.
Dilute  this  stock solution  to cover the  analytical  range required (100-570
mg/L).

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

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


6.0   SAMPLE COLLECTION, PRESERVATION AND HANDLING

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

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

      6.3   Testing should be performed in a ventilated hood.


                                  SEVEN - 11                       Revision 2
                                                                   September 1994

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7.0   PROCEDURE

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

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

      7.3   Add 10 g of the waste to be tested to the system.

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

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

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

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

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

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


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

            L = Volume of solution in scrubber (L)

            W = Weight of waste used (kg)

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

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

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9.0   METHOD PERFORMANCE

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

10.0  REFERENCES

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

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                                      FIGURE 2.

             APPARATUS TO DETERMINE HYDROGEN SULFIDE  RELEASED FROM WASTES
                                      Stirrer
      Flowmeter
N2ln
                    Reaction Rask
                                                                    Gas Scrubber
                                                    Waste Sample
                                    SEVEN - 14
Revision 2
Septenter 1994

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7.4   TOXICITY CHARACTERISTIC LEACHING PROCEDURE

      7.4.1 Introduction

      The  Toxicity Characteristic  Leaching  Procedure  (TCLP)  is  designed  to
simulate  the  leaching  a waste  will  undergo  if  disposed of  in a  sanitary
landfill.   This  test is designed  to simulate  leaching that takes place  in a
sanitary  landfill  only.   The extraction  fluid  employed is a function  of the
alkalinity  of the  solid phase  of  the  waste.    A  subsample  of  a  waste  is
extracted with the appropriate buffered acetic acid solution for 18 ฑ 2 hours.
The extract obtained from the TCLP  (the  "TCLP  extract")  is then  analyzed  to
determine   if  any  of  the  thresholds  established   for the   40   Toxicity
Characteristic (TC)  constituents  (listed  in  Table 7-1)  have been  exceeded  or
if the treatment  standards  established for the constituents listed  in  40 CFR
ง268.41 have  been met for the Land  Disposal  Restrictions  (LDR) program.   If
the TCLP extract contains any one of the TC constituents in an  amount equal  to
or  exceeding   the concentrations  specified  in  40  CFR  ง261.24,  the  waste
possesses  the  characteristic of toxicity  and  is a  hazardous  waste.   If the
TCLP   extract   contains  LDR   constituents   in   an  amount  exceeding   the
concentrations specified  in  40 CFR  ง268.41,  the treatment standard  for  that
waste  has not been  met, and  further  treatment  is  necessary  prior to  land
disposal.

      7.4.2 Summary of Procedure

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

      1.   Separation Procedure

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

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

      2.   Particle Size Reduction

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

      3.   Extraction of Solid Material

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

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

      4.  Final Separation of the Extraction from the Remaining Solid

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

      5.  Testing  (Analysis) of TCLP Extract

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

      7.4.3 Regulatory Definition

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

      Under  the  Land  Disposal  Restrictions  program,  a  restricted   waste
identified  in 40  CFR ง268.41 may be  land  disposed  only if  a TCLP extract of
the waste  or a TCLP extract  of the treatment  residue  of the waste  does  not
exceed the  values shown  in  Table  CCWE  of  40  CFR  ง268.41  for  any  hazardous
constituent listed in  Table CCWE for that  waste.   If a  waste contains  <0.5%
filterable  solids, the waste itself,  after  filtering,  is  considered  to  be  the
extract for the purposes  of analysis.
                                  SEVEN - 16                       Revision  2
                                                                   Septwter 1994

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                            TABLE 7-1.
MAXIMUM CONCENTRATION OF CONTAMINANTS FOR TOXICITY CHARACTERISTIC

Contaminant
Arsenic
Barium
Benzene
Cadmium
Carbon tetrachloride
Chlordane
Chlorobenzene
Chloroform
Chromium
o-Cresol
m-Cresol
p-Cresol
Cresol
2,4-D
1,4-Dichlorobenzene
1,2-Dichloroethane
1,1-Dichloroethylene
2,4-Dinitrotoluene
Endrin
Heptachlor (and its hydroxide)
Hexachlorobenzene
Hexachloro-l,3-butadiene
Hexachloroethane
Lead
Lindane
Mercury
Methoxychlor
Methyl ethyl ketone
Nitrobenzene
Pentachlorophenol
Pyridine
Selenium
Silver
Tetrachl oroethyl ene
Toxaphene

SEVEN - 17

Regulatory Level
(ซg/L)
5.0
100.0
0.5
1.0
0.5
0.03
100.0
6.0
5.0
200. O1
200. O1
200. O1
200. O1
10.0
7.5
0.5
0.7
0.132
0.02
0.008
0.132
0.5
3.0
5.0
0.4
0.2
10.0
200.0
2.0
100.0
5.02
1.0
5.0
0.7
0.5
(continued)
Revision 2
September 1994

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                                   Table 7-1
                                  (continued)
                                                 Regulatory Level
Contaminant
Trichloroethylene                                       0.5
2,4,5-Trichlorophenol                                 400.0
2,4,6-Trichlorophenol                                   2.0
2,4,5-TP (Silvex)                                       1.0
Vinyl chloride                                          0.2
llf o-, m-,  and p-cresol  concentrations  cannot be  differentiated,  the total
cresol (0026) concentration  is  used.   The regulatory level of total cresol  is
200 mg/L.

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

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                             FIGURE 3.

  TOXICITY CHARACTERISTIC  LEACHATE  PROCEDURE FLOWCHART
   Separata
 liquids fro*
•olid. Kith 0.6
-  0.8 un glau
 fibar filtar
   Saparata
 liquid* from
solid* ซith 0.6
-  0.8 ua gUซa
 fibar filtar
                                                     Solid
    Diicatd
    •olida
                         Extract •/
                      appropriata fluid
                     1) Bottla aitractor
                      for non-volatilai
                      2) ZHE daviea for
                          volatila*
    Raduca
 particla tiza
  to <9 5 mm
                           SEVEN -  19
                     Revision 2
                     Septaiter 1994

-------
                                   FIGURE  3
                                 (continued)
Diicard
•olid*
Solid
   Separate
 ••tract from
•olidt "/ 0.6
 0.8  un glaปป
 fiber filter
 Meaaure amount of
liquid and analyze
  (ma thematiea11y
 combine retull •/
 reiult of extract
    analytn)
              I
            liquid
Liquid   /compatible  "V No
           •ith the
           ••tract?
                                               Combine
                                              extract •/
                                             liquid phase
                                               of "atte
                                  SEVEN -  20
                                                               Revision  2
                                                               Septaiter 1994

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                                 CHAPTER EIGHT

                    METHODS FOR DETERMINING CHARACTERISTICS
      Methods for determining the characterisitics of Ignitability  for  liquids,
Corrosivity for liquids,  and  Toxicity are included.   Guidance for determining
Toxic Gas Generation is found in Chapter Seven, Sections 7.3.3 and 7.3.4.
                                   EIGHT  -  1                       Revision 1
                                                                  September 1994

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8.1   Ignitability

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

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                                 METHOD 1010

        PENSKY-MARTENS CLOSED-CUP METHOD FOR DETERMINING IGNITABILITY


1.0  SCOPE AND APPLICATION

     1.1  Method 1010 uses the  Pensky-Martens  closed-cup tester to determine
the flash point of liquids Including  those  that  tend to form a surface film
under test conditions.    Liquids  containing non-filterable,  suspended solids
shall also be tested using this method.


2.0  SUMMARY OF METHOD

     2.1  The sample  1s  heated  at  a  slow,  constant  rate  with continual
stirring.  A small flame is  directed  into  the cup at regular Intervals with
simultaneous  Interruption  of  stirring.    The  flash  point  1s  the lowest
temperature at which application of the test flame Ignites the vapor above the
sample.


     For further information on  how  to  conduct  a  test by this method, see
Reference 1 below.


3.0  METHOD PERFORMANCE

     3.1  The Pensky-Martens and Setaflash Closed Testers were evaluated using
five industrial waste mixtures and  p-xylene.    The results of this study are
shown below in *F along with other data.

                        Pensky-
     Sample             Martens           Setaflash

        I2             143.7 +  1.5        139.3 + 2.1
        22             144.7 +  4.5        129.7 + 0.6
        32              93.7 +  1.5         97.7 + 1.2
        42             198.0 +  4.0        185.3 + 0.6
        52             119.3 +  3.1        122.7 + 2.5
     p-xylene2         81.3 +  1.1         79.3 + 0.6
     p-xylene3         77.7 +  0.5a

     Tanker oil       125, 135
     Tanker oil       180, 180
     Tanker oil       110, 110
     DIBK/xylene      102  + 4b               107

     ^75/25 v/v analyzed by four laboratories.
     a!2 determinations over five-day  period.
                                   1010 -  1
                                                         Revision
                                                         Date  September 1986

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4.0  REFERENCES

1.   D 93-80, Test Methods  for  Flash  Point by Pensky-Martens Closed Tester,
American Society for Testing and Materials, 1916 Race Street, Philadelphia, PA
19103, 04.09, 1986.

2.   Umana, M., Gutknecht, W.f Salmons, C.t et al., Evaluation of Ignitability
Methods (Liquids), EPA/600/S4-85/053, 1985.

3.   Gaskill, A., Compilation and Evaluation  of RCRA Method Performance Data,
Work Assignment No. 2, EPA Contract No. 68-01-7075, September 1986.
                                   1010 - 2
                                                          Revision
                                                          Date  September 1986

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                                 METHOD 1020A

           SETAFLASH CLOSED-CUP METHOD FOR DETERMINING IGNITABILITY
1.0  SCOPE AND APPLICATION

      1.1    Method 1020 makes use of the Setaflash Closed Tester to determine
the flash point of liquids that have  flash points between 0ฐ and 110'C (32ฐ and
230ฐF) and viscosities lower than 150 stokes at 25ฐC (77ฐF).

      1.2    The procedure may be used to determine whether a material will or
will not flash  at a specified temperature or to determine the finite temperature
at which a material will flash.

      1.3    Liquids that  tend  to  form  surface films  under test conditions or
those  that  contain  non-filterable   suspended solids  shall  be  tested  for
ignitability using Method 1010 (Pensky-Martens Closed-Cup).

2.0  SUMMARY OF METHOD

      2.1    By means of a syringe, 2-mL of sample is introduced through a leak-
proof entry port into the tightly closed Setaflash Tester or directly into the
cup which has been brought to within 3ฐC (5ฐF) below the expected flash point.

      2.2    As a flash/no-flash test, the expected  flash-point temperature may
be a specification (e.g.,  60ฐC).  For specification  testing, the temperature of
the apparatus  is raised to the  precise  temperature  of the specification flash
point by slight adjustment of the temperature dial.  After 1 minute,  a test flame
is applied inside the cup and note is  taken as to whether the test sample flashes
or not.  If a repeat test is necessary,  a fresh sample should be used.

      2.3    For  a  finite flash management,  the temperature  is  sequentially
increased through the  anticipated  range,  the test  flame being  applied  at 5ฐC
(9"F) intervals until  a flash is observed.   A repeat determination is then made
using a fresh sample,  starting the  test  at the  temperature  of the last interval
before the flash point of the material and making tests  at increasing 0.5ฐC (1ฐF)
intervals.

      For further information  on how to conduct a  test with  this  method,  see
Reference 1 below.

3.0  METHOD PERFORMANCE

      See Method 1010.

4.0  REFERENCES

1.    D-3278-78,  Test  Method for Flash Point  of Liquids  by  Setaflash  Closed
Tester,  American  Society  for  Testing  and  Materials,   1916  Race  Street,
Philadelphia, PA 19103.

2.    Umana, M.,  Gutknecht, W.,  Salmons, C., et al., Evaluation of Ignitability
Methods (Liquids),  EPA/600/S4-85/053, 1985.

                                   1020A - 1                       Revision 1
                                                                  July 1992

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3.    Gaskill, A., Compilation and Evaluation of RCRA Method Performance Data,
Work Assignment No. 2, EPA Contract No. 68-01-7075,  September 1986.
                                   1020A - 2                       Revision 1
                                                                  July 1992

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8.2   Corrosivity

      The following method  is  found  in Section 8.2:


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

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                                 METHOD 1110

                          CORROSIVITY TOWARD STEEL
1.0  SCOPE AND APPLICATION

     1.1  Method 1110 is used to measure
aqueous and nonaqueous liquid wastes.
                                          the corroslvlty toward steel  of both
2.0  SUMMARY OF METHOD

     2.1  This test exposes coupons of SAE Type 1020 steel  to the liquid waste
to be evaluated and, by  measuring  the  degree  to  which  the coupon has been
dissolved, determines the corroslvlty of the waste.
3.0  INTERFERENCES

     3.1  In laboratory  tests,  such  as
coupons 1s usually reproducible to within
corrosion rates  may  occasionally  occur
surfaces become passlvated.   Therefore,
corrosion rate should be made.
                                           this  one,  corrosion  of duplicate
                                           10%.  However, large differences 1n
                                           under  conditions  where  the metal
                                          at least duplicate determinations of
4.0  APPARATUS AND MATERIALS

     4.1  An apparatus should be  used,  consisting  of  a  kettle or flask of
suitable size  (usually 500 to 5,000  mL), a reflux condenser, a thermowell and
temperature regulating device, a heating  device (mantle, hot plate, or bath),
and a specimen support system.  A typical  resin flask set up for this type of
test is shown  in Figure 1.

     4.2  The  supporting  device  and   container  shall  be  constructed  of
materials that are not affected by, or cause contamination of, the waste under
test.

     4.3  The method of supporting  the  coupons  will vary with the apparatus
used for conducting  the  test,  but  it  should  be  designed to Insulate the
coupons from  each  other  physically  and  electrically  and  to Insulate the
coupons from any metallic container or  other  device  used 1n the test.  Some
common support materials include glass, fluorocarbon, or coated metal.
     4.4  The shape and form of the
with the waste.
                                     coupon support should ensure free contact
                                  1110 - 1
                                                         Revision      0
                                                         Date  September 1986

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                                       Jl
     Figure 1.  Typical  resin  flask  that  can  be  used  as a versatile and
convenient apparatus to conduct simple  immersion tests.   Configuration of the
flask top is such that more  sophisticated  apparatus can be added as required
by the specific test being conducted.   A  =  thermowell, B = resin flask, C =
specimens hung on supporting device,  D = heating mantle,  E = liquid interface,
F = opening in flask for  additional   apparatus  that may be required,  and G =
reflux condenser.
                                  1110 - 2
                                                         Revision      0
                                                         Date  September  1986

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     4.5  A circular specimen of SAE  1020  steel   of  about 3.75 cm (1.5 1n.)
diameter  is  a  convenient  shape  for   a  coupon.    With  a  thickness  of
approximately 0.32 cm (0.125  in.)  and  a 0.80-cm (0.4-1n.)-d1ameter hole for
mounting, these specimens will readily pass through a 45/50 ground-glass joint
of a distillation kettle.  The  total  surface  area of a circular specimen is
given by the following equation:

          A = 3.14/2(D2-d2) + (t)(3.14)(D) + (t)(3.14)(d)

     where:

          t = thickness.
          D = diameter of the specimen.
          d = diameter of the mounting hole.

If the hole is completely covered  by  the  mounting support, the last term in
the equation, (t)(3.14)(d), is omitted.

          4.5.1  All coupons should be  measured  carefully to permit accurate
     calculation of the exposed areas.  An area calculation accurate to +1% 1s
     usually adequate.

          4.5.2  More uniform results may  be  expected 1f a substantial layer
     of metal is removed from the  coupons prior to testing the corrosivlty of
     the waste.  This can be accomplished by chemical treatment (pickling), by
     electrolytic removal, or by grinding  with  a  coarse abrasive.  At least
     0.254 mm (0.0001 in.) or  2-3  mg/cm2  should  be removed.  Final surface
     treatment should include  finishing  with  #120  abrasive paper or cloth.
     Final cleaning consists  of  scrubbing  with bleach-free scouring powder,
     followed by rinsing in distilled  water  and then in acetone or methanol,
     and finally by air-drying.   After   final  cleaning, the coupon should be
     stored  in a desiccator until used.

          4.5.3  The minimum  ratio of  volume  of  waste  to area of the metal
     coupon  to be used  in  this test  1s 40 ml/cm2.


5.0  REAGENTS

     5.1  Sodium hydroxide (NaOH),  (20%):  Dissolves  200 g  NaOH 1n  800 ml  Type
 II water and mix well.

     5.2 Z1nc dust.

     5.3 Hydrochloric  add  (HC1):   Concentrated.

     5.4 Stannous  chloride  (SnCl2).

     5.5 Antimony  chloride
                                   1110 - 3
                                                          Revision
                                                          Date  September  1986

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6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

     6.1  All samples should be collected using a sampling plan that address
the considerations discussed in Chapter Nine of this manual.


7.0  PROCEDURE

     7.1  Assemble the test apparatus as described 1n Paragraph 4.0, above.

     7.2  Fill the container with the appropriate amount of waste.

     7.3  Begin agitation at a rate  sufficient  to  ensure that the liquid is
kept well mixed and homogeneous.

     7.4  Using the heating device, bring the temperature of the waste to 55*C
(130*F).

     7.5  An accurate  rate of corrosion  1s not required; only a determination
as to whether the rate of corrosion  Is  less than or greater than 6.35 nun per
year is required.  A 24-hr test period should be ample to determine whether or
not the rate of corrosion 1s >6.35 mm per year.

     7.6  In order to  determine  accurately  the  amount  of material lost to
corrosion, the  coupons  have  to  be  cleaned  after  Immersion  and prior to
weighing.  The  cleaning  procedure  should  remove  all products of corrosion
while, removing a minimum of sound metal.  Cleaning methods can be divided into
three general categories:  mechanical, chemical, and electrolytic.

          7.6.1  Mechanical cleaning  Includes  scrubbing, scraping, brushing,
     and  ultrasonic procedures.    Scrubbing  with  a  bristle  brush and mild
     abrasive 1s the most popular of  these  methods.   The others are used in
     cases of heavy corrosion as  a  first  step 1n removing heavily encrusted
     corrosion products prior to  scrubbing.    Care  should be taken to avoid
     removing sound metal.

          7.6.2  Chemical cleaning implies  the  removal  of material from the
     surface of  the coupon  by dissolution  In an appropriate solvent.  Solvents
     such as acetone,  dichloromethane,   and  alcohol  are   used to  remove  oil,
     grease, or  resinous materials and   are  used prior to  immersion to  remove
     the  products of   corrosion.     Solutions   suitable for removing corrosion
     from the steel coupon  are:

                    Solution                    Soaking Time    Temperature

           20% NaOH  +  200 g/L zinc dust             5 min           Boiling

                      or

     Cone.  HC1  + 50 g/L SnCl2 + 20  g/L  SbCl3     Until  clean       Cold
                                   1110 - 4
                                                          Revision      0
                                                          Date  September 1986

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          7.6.3   Electrolytic  cleaning   should  be  preceded  by  scrubbing to
     remove  loosely adhering corrosion   products.   One method of electrolytic
     cleaning  that  can  be  employed  uses:
          Solution:                        50  g/L

          Anode:                           Carbon  or lead

          Cathode:                         Steel coupon

          Cathode current density:         20  amp/cm2 (129 amp/1n.2)

          Inhibitor:                      2 cc organic  Inhibitor/liter

          Temperature:                    74* C (165*F)

          Exposure Period:                3 m1n.

     NOTE:  Precautions must be  taken  to ensure good  electrical  contact with
     the coupon to avoid  contamination  of  the  cleaning solution with easily
     reducible metal Ions and to  ensure  that Inhibitor decomposition has not
     occurred.    Instead  of  a  proprietary  Inhibitor,  0.5  g/L  of either
     dlorthotolyl thlourea or quinolln eth Iodide  can be used.

     7.7  Whatever treatment 1s employed to  clean  the coupons, Its effect 1n
removing sound metal should be  determined  by  using  a blank (I.e., a coupon
that has not been exposed to  the  waste).   The  blank  should be cleaned along
with the test coupon and  Its  waste  loss subtracted from that calculated for
the test coupons.

     7.8  After corroded  specimens  have  been  cleaned  and  dried, they are
rewelghed.  The weight loss 1s employed as the principal  measure of corrosion.
Use of weight loss as  a  measure  of corrosion requires making the assumption
that all weight loss has been  due  to generalized corrosion and not localized
pitting.  In order to  determine  the  corrosion   rate  for the purpose of this
regulation, the following formula 1s used:


          Corrosion Rate  (mmpy) -


     where:    weight loss 1s 1n milligrams,
               area 1n square centimeters,
               time 1n hours, and
               corrosion  rate 1n millimeters per year  (mmpy).


8.0  QUALITY CONTROL

     8.1  All quality control data should be filed  and available for auditing.

     8.2  Duplicate samples should be analyzed on a routine  basis.
                                   1110 - 5
                                                         Revision
                                                         Date  September 1986

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9.0  METHOD PERFORMANCE

     9.1  No data provided.


10.0  REFERENCES

1.   National  Association  of   Corrosion  Engineers,  "Laboratory  Corrosion
Testing of Metals for  the  Process  Industries/ NACE Standard TM-01-69 (1972
Revision),  NACE, 3400 West Loop South, Houston, TX 77027.
                                   1110 - 6
                                                         Revision
                                                         Date  September  1986

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                              METHOD itSO

                       CORROSIVITY TOWARD STEEL
C
  7.1
  Aaaenola test
    apparatus
  7.2
  Fill container
    with waste
  7.3
     Agitate
  7.4
       Heat
    o
                                                        7.6
       Clean
       coupons
 by necnenlcal.
chemical ana/or
  electrolytic
    methods
 7.7  I  Check
      i  effect
    of cleaning
   treatment on
 removing sound
       metal
                                                        7.8
   Determine
 corroaion rate
                                                     (      Stop       J
     o
                       1110 - 7
                                                   Revision        0
                                                   Date   September 1986
                                        •fr U.S. GOVERNMENT pRINTIMrs OFFICE:! 993-342-139/83251

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8.3   Reactivity

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

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8.4   Toxicity

      The  following methods are found  in  Section 8.4:
             Method 1310A:     Extraction  Procedure  (EP) Toxicity Test  Method
                               and Structural  Integrity Test
             Method 1311:      Toxicity  Characteristic Leaching Procedure
                                    EIGHT - 5                       Revision- 1
                                                                    September 1994
*U.S. G.P.O.;1995-386-824:33251

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                                 METHOD 1310A

                EXTRACTION PROCEDURE (EP) TOXICITY TEST METHOD
                         AND  STRUCTURAL  INTEGRITY  TEST
1.0  SCOPE AND APPLICATION

      1.1    This  method is  an  interim method  to  determine whether  a waste
exhibits the characteristic of Extraction Procedure Toxicity.

      1.2    The procedure  may  also be used to  simulate  the leaching  which a
waste may  undergo  if  disposed of  in  a  sanitary landfill.   Method  1310  is
applicable to liquid, solid, and multiphase samples.

2.0  SUMMARY OF METHOD

      2.1    If a representative sample of the waste contains > 0.5% solids, the
solid phase of the  sample is  ground  to pass  a  9.5 mm sieve and extracted with
deionized water which is  maintained at a pH of 5 + 0.2, with acetic acid.  Wastes
that contain <  0.5% filterable solids are, after filtering, considered to be the
EP  extract  for this method.   Monolithic  wastes which can be formed  into a
cylinder  3.3 cm  (dia) x 7.1  cm,  or from which  such  a  cylinder can  be formed
which is representative  of the waste,  may be evaluated  using  the  Structural
Integrity Procedure instead of being ground to pass a 9.5-mm sieve.

3.0  INTERFERENCES

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

4.0  APPARATUS AND MATERIALS

      4.1    Extractor - For purposes  of this test, an acceptable extractor is
one  that will  impart sufficient  agitation  to  the  mixture  to  (1)  prevent
stratification of the sample and extraction fluid and (2) ensure  that all sample
surfaces are continuously brought into contact with well-mixed extraction fluid.
Examples of suitable extractors  are  shown in  Figures  1-3 of  this method and are
available from: Associated  Designs  & Manufacturing  Co.,  Alexandria,  Virginia;
Glas-Col Apparatus Co., Terre Haute,  Indiana;  Millipore, Bedford, Massachusetts;
and Rexnard, Milwaukee, Wisconsin.

      4.2    pH  meter  or  pH  controller  -  Accurate to  0.05  pH  units  with
temperature compensation.

      4.3    Filter holder - Capable  of supporting a  0.45-jim filter membrane and
of withstanding the pressure needed to accomplish separation.  Suitable filter
holders range from  simple vacuum units to  relatively complex systems  that can
exert up to  5.3  kg/cm  (75  psi)  of  pressure.  The type of filter  holder used
depends upon the properties  of the mixture to be filtered.   Filter holders known
to EPA and deemed suitable for use are listed in Table 1.
                                   1310A  -  1                       Revision 1
                                                                  July 1992

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      4.4    Filter  membrane -  Filter membrane  suitable  for  conducting  the
required  filtration  shall  be  fabricated  from  a material  that  (1)   is  not
physically changed by the waste  material  to be filtered and (2) does not absorb
or leach the chemical species for which a waste's  EP extract will be  analyzed.
Table 2 lists filter media  known  to  the  agency  to be  suitable for solid waste
testing.

             4.4.1     In cases  of doubt  about physical  effects on the filter,
      contact the filter manufacturer to determine  if the  membrane  or  the
      prefilter  is  adversely  affected   by   the   particular  waste.    If  no
      information is  available,  submerge  the filter in  the waste's liquid phase.
      A filter  that  undergoes  visible physical  change  after 48  hours (i.e.,
      curls, dissolves, shrinks, or swells)  is unsuitable for use.

             4.4.2     To test for absorption or leaching  by  the filter:

                       4.4.2.1   Prepare  a standard  solution of  the  chemical
             species of interest.

                       4.4.2.2  Analyze  the  standard  for  its  concentration of
             the chemical species.

                       4.4.2.3   Filter  the  standard  and  reanalyze.    If  the
             concentration  of the filtrate  differs from that  of  the  original
             standard, then the filter membrane leaches or absorbs one or more
             of the  chemical  species and is not usable in this test method.

      4.5    Structural integrity tester - A device meeting the specifications
shown in Figure 4 and having a 3.18-cm (1.25-in) diameter hammer weighing 0.33
kg (0.73 Ib) with a free fall  of 15.24  cm (6  in) shall be used.  This device is
available  from  Associated  Design and Manufacturing  Company,  Alexandria,  VA
22314, as Part No. 125, or it may be fabricated to meet these specifications.

5.0  REAGENTS

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

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

      5.3    Acetic  acid  (0.5N), CHปCOOH.    This can  be made  by  diluting
concentrated glacial  acetic acid (17.5N)  by adding 57 ml glacial acetic acid to
1,000 mL of water and diluting to 2 liters.  The glacial acetic acid must be of
high purity and monitored for impurities.

      5.4    Analytical standards should  be prepared according to the applicable
analytical methods.


                                   1310A  - 2                       Revision 1
                                                                  July 1992

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6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

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

      6.2    Preservatives must not be added to samples.

      6.3    Samples can be refrigerated if it  is determined that refrigeration
will not affect the integrity of the sample.

7.0  PROCEDURE

      7.1    If the waste does not contain any  free  liquid, go to Step 7.9.  If
the sample is liquid or multiphase,  continue as follows.  Weigh filter membrane
and prefilter to ฑ  0.01 g.  Handle membrane and  prefilters with blunt curved-tip
forceps or vacuum tweezers, or by applying suction with a pipet.

      7.2    Assemble  filter  holder,  membranes,  and prefilters  following the
manufacturer's instructions.  Place the 0.45-jitn membrane on the support screen
and add  prefilters in  ascending  order of  pore  size.    Do not  prewet  filter
membrane.

      7.3    Weigh out a representative subsample of the waste (100 g minimum).

      7.4    Allow  slurries  to stand,  to permit the  solid  phase  to  settle.
Wastes that settle slowly may be centrifuged prior to filtration.

      7.5    Wet the filter with  a  small  portion  of the liquid phase from the
waste or from the  extraction mixture.   Transfer  the remaining  material  to the
filter holder and apply vacuum or gentle pressure (10-15 psi) until all  liquid
passes through the filter.  Stop filtration when air or pressurizing gas moves
through the  membrane.   If  this  point is not  reached  under vacuum  or  gentle
pressure, slowly increase  the  pressure in 10-psi increments to  75  psi.   Halt
filtration when liquid flow stops.  This liquid will constitute part or all of
the extract (refer  to Step 7.16).  The  liquid should be refrigerated until time
of analysis.

NOTE:  Oil samples or samples containing oil  are treated  in exactly the same way
      as any other  sample.   The liquid portion of  the  sample  is filtered and
      treated as part of the EP extract.   If the  liquid portion of the sample
      will not  pass  through the  filter  (usually  the  case with  heavy  oils or
      greases),  it should be carried through the EP extraction as a solid.

      7.6    Remove the  solid  phase and filter media and, while not allowing
them to dry,  weigh  to + 0.01 g.  The wet weight of the residue is determined by
calculating the weight difference between the weight of the filters (Step 7.1)
and the weight of the solid phase and the filter media.

      7.7    The waste will  be handled differently from this point on, depending
on whether it contains  more or  less  than 0.5% solids.  If the sample appears to
have < 0.5% solids, determine the percent solids exactly  (see Note below) by the
following procedure:


                                  1310A  - 3                       Revision 1
                                                                  July 1992

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             7.7.1     Dry the filter and residue at 80ฐC until  two successive
      weighings yield the same value.

             7.7.2     Calculate  the  percent  solids,   using  the  following
      equation:
                  weight of           tared weight
               filtered solid    -    of filters
                 and filters
                 initial weight of waste material
x 100  = % solids
NOTE: This  procedure  is  used  only  to determine  whether the  solid must  be
      extracted or whether it can be discarded unextracted.  It is not used in
      calculating the amount  of water or acid to use in the extraction step.  Do
      not extract solid  material  that has been dried at 80ฐC.  A new sample will
      have  to  be used  for  extraction  if a  percent  solids determination  is
      performed.

      7.8    If the solid constitutes < 0.5% of the waste,  discard  the solid and
proceed immediately to Step 7.17, treating the liquid phase as the extract.

      7.9    The solid  material  obtained  from Step 7.5 and all  materials that
do not contain free liquids shall be evaluated for  particle size.  If the solid
material has a surface area per g of material > 3.1 cm2 or  passes through a 9.5-
mm (0.375-in.) standard  sieve,  the operator shall  proceed  to Step  7.11.  If the
surface area is smaller  or the particle  size  larger than  specified above, the
solid material  shall be prepared for extraction by crushing, cutting, or grinding
the material so  that  it passes through a  9.5-mm  (0.375-in.) sieve  or,  if the
material is  in  a  single piece, by subjecting the  material  to  the "Structural
Integrity Procedure" described in Step 7.10.

      7.10   Structural  Integrity  Procedure (SIP)

             7.10.1    Cut a 3.3-cm diameter  by  7.1-cm long  cylinder from the
      waste material.  If the waste has been treated using a fixation process,
      the waste may be cast in  the  form of a cylinder and allowed to cure for 30
      days prior to testing.

             7.10.2    Place  waste into sample holder and  assemble the tester.
      Raise  the hammer  to its  maximum height and  drop.   Repeat  14 additional
      times.

             7.10.3    Remove  solid material  from  tester and  scrape off any
      particles adhering to sample holder.   Weigh  the  waste to the nearest 0.01
      g and transfer it to the extractor.

      7.11   If the  sample contains > 0.5% solids, use the wet weight  of the
solid phase (obtained in Step 7.6)  to calculate the amount  of liquid and acid to
employ for extraction by using the following equation:

                                 W  = Wf - Wt
                                   1310A  -  4                       Revision 1
                                                                  July 1992

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where :

      W = Wet weight in g of solid to be charged to extractor.

      Wf = Wet weight in g of filtered solids and filter media.

      Wt = Weight in g of tared filters.

If the waste does not  contain  any  free  liquids,  100 g of the material will be
subjected to the extraction procedure.

      7.12   Place the appropriate amount of material  (refer  to Step 7.11) into
the extractor and add 16 times its weight with water.

      7.13   After the solid material  and water are placed in  the extractor, the
operator  shall  begin  agitation  and  measure the  pH  of  the solution  in the
extractor.  If the pH is > 5.0,  the  pH  of the solution should be decreased to 5.0
ฑ 0.2 by  slowly  adding 0.5N acetic acid.   If the  pH  is  < 5.0,  no acetic acid
shou.ld be added.  The pH of the  solution  should be monitored, as described below,
during the course of the extraction, and, if the pH rises  above 5.2, 0.5N acetic
acid should be added to bring  the  pH  down  to 5.0 ฑ 0.2.   However, in no event
shall the aggregate  amount of acid  added to the solution exceed 4 ml of acid per
g of solid.  The mixture should be agitated for 24 hours and maintained at 20-
40ฐC (68-104ฐF) during this time.  It is recommended that the operator monitor
and adjust the pH during the course of the  extraction with  a  device such as the
Type 45-A pH Controller,  manufactured  by  Chemtrix,   Inc.,  Hillsboro,  Oregon
97123,  or its equivalent, in conjunction with a metering pump and reservoir of
0.5N acetic  acid.    If  such a system is  not available,  the following manual
procedure shall be employed.

NOTE: Do not add acetic acid too quickly.  Lowering the pH to below the target
      concentration  of  5.0 could affect  the  metal  concentrations in  the
      leachate.

             7.13.1    A pH meter  should be  calibrated in accordance with the
      manufacturer's specifications.

             7.13.2    The  pH  of  the  solution  should  be  checked,  and,  if
      necessary, 0.5 N acetic  acid should be manually  added to  the extractor
      until the pH reaches 5.0  ฑ 0.2.  The pH  of the solution  should be adjusted
      at 15-, 30-, and 60-minute intervals, moving to the next longer interval
      if the pH does not have to be adjusted > 0.5 pH units.

             7.13.3    The adjustment  procedure should be continued for at least
      6 hours.

             7.13.4    If, at the end of the 24-hour extraction period, the pH
      of the solution is not below  5.2 and  the maximum  amount of acid  (4 ml per
      g of solids) has not  been  added,  the pH  should  be  adjusted  to 5.0 + 0.2
      and the extraction continued for an additional 4 hours, during which the
      pH should be adjusted at 1-hour intervals.
                                   1310A  -  5                       Revision 1
                                                                  July 1992

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      7.14   At the end of the extraction period, water should be added to the
extractor in an amount determined by the following equation:
where:
                                V  =  (20)(W)  -  16(W)  - A
      V = ml water to be added.
      W = Weight in g of solid charged to extractor.

      A = ml of 0.5N acetic acid added during extraction.

      7.15   The  material  in  the  extractor  should  be  separated
component liquid and solid phases in the following manner:
                                                               into  its
             7.15.1    Allow slurries  to  stand to  permit  the solid  phase to
      settle  (wastes  that  are slow  to settle  may be  centrifuged  prior to
      filtration) and set up the filter apparatus  (refer to Steps 4.3 and 4.4).

             7.15.2    Wet the filter with a small portion of the liquid phase
      from the waste  or from the extraction mixture.   Transfer  the remaining
      material to the filter holder  and apply  vacuum or gentle pressure   (10-
      15 psi) until  all  liquid passes through the  filter.  Stop filtration when
      air or pressurizing gas moves through the membrane.  If this point is not
      reached under vacuum or gentle pressure,  slowly increase the pressure in
      10-psi increments to 75 psi.  Halt filtration when liquid flow stops.

      7.16   The liquids resulting from Steps 7.5 and 7.15 should be combined.
This combined liquid (or waste  itself,  if it has < 0.5%  solids,  as noted in Step
7.8) is the extract.

      7.17   The extract is then prepared and analyzed  using  the appropriate
analytical methods described in Chapters Three and Four of this manual.
NOTE:
If the EP extract  includes  two  phases,  concentration  of contaminants is
determined  by  using a  simple weighted  average.   For  example:    An EP
extract  contains  50  ml  of  oil   and  1,000  ml  of   an  aqueous  phase.
Contaminant  concentrations  are determined  for each  phase.    The  final
contamination concentration is taken to be:
               50  x  contaminant cone.
                           in oil
                                       1,000  x  contaminant cone
                                                 of aqueous phase
NOTE:
                                  1050

In  cases  where  a contaminant  was  not  detected,  use  the  MDL  in  the
calculation.  For example,  if the  MDL in the oily phase is 100 mg/L and 1
mg/L in the  aqueous phase, the reporting limit would be 6 mg/L (rounded to
the nearest mg).   If  the regulatory  threshold  is 5 mg/L, the waste may be
EP toxic and results of the analysis are inconclusive.
                                   1310A  -  6
                                                            Revision 1
                                                            July 1992

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8.0  QUALITY CONTROL
      8.1    All  quality  control  data should be maintained  and available for
easy reference or inspection.
      8.2    Employ  a  minimum of one  blank  per sample batch  to  determine if
contamination or any memory effects are occurring.
      8.3    All  quality  control  measures  described  in Cnapter One and in the
referenced analytical methods should be followed.
9.0  METHOD PERFORMANCE
      9.1    The data tabulated in Table 3 were obtained from records of state
and contractor laboratories and are intended to show the precision  of the entire
method (1310 plus analysis method).
10.0  REFERENCES
1.    Rohrbough,  W.G.;  et  al.  Reagent  Chemicals.  American Chemical  Society
Specifications. 7th ed.; American Chemical  Society: Washington, DC, 1986.
2.    1985 Annual  Book of ASTM Standards. Vol. 11.01; "Standard Specification for
Reagent Water"; ASTM: Philadelphia, PA, 1985; D1193-77.
3.    Gaskill, A., Compilation and Evaluation of RCRA Method Performance Data,
Work Assignment No. 2,  EPA Contract No. 68-01-7075, September 1986.
                                   1310A  - 7                       Revision 1
                                                                  July 1992

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                    TABLE  1.   ERA-APPROVED FILTER HOLDERS
      Manufacturer
Size
Model No.
Comments
Vacuum Filters
      Gel man
      Nalgene
      Nuclepore
      Millipore
Pressure Filters
      Nuclepore
 47 mm
500 mL
      Micro Filtration
      Systems
      Millipore
47 mm
47 mm

142 mm
142 mm

142 mm
4011
44-0045
410400
XX10 047 00

425900
302300

YT30 142 HW
Disposable   plastic   unit,
including prefilter,  filter
pads, and reservoir;  can be
used when solution is to be
analyzed    for    inorganic
constituents.
                                   1310A  - 8
                                         Revision 1
                                         July 1992

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                    TABLE 2.   ERA-APPROVED FILTRATION MEDIA
      Supplier
 Filter to be used
for aqueous systems
 Filter to be used
for organic systems
      Coarse prefilter
      Gel man
      Nuclepore
      Millipore
      Medium prefliters
      Gel man
      Nuclepore
      Millipore
      Fine prefilters
      Gel man
      Nuclepore
      Millipore
      Fine filters (0.45 urn)
      Gel man
      Pall
      Nuclepore
      Millipore
      Selas
  61631, 61635
  210907, 211707
  AP25 035 00,
  AP25 127 50

  61654, 61655
  210905, 211705
  AP20 035 00,
  AP20 124 50

  64798, 64803
  210903, 211703
  AP15 035 00,
  AP15 124 50

  63069, 66536

  NX04750, NX14225
  142218
  HAWP 047 00,
  HAWP 142 50
  83485-02,
  83486-02
   61631, 61635
   210907, 211707
   AP25 035 00,
   AP25 127 50
   210905,  211705
   AP20 035 00,
   AP20 124 50
   64798,  64803
   210903,  211703
   APIS 035 00,
   APIS 124 50
   60540 or 66149,
   66151
   1422188
   FHUP 047 00,
   FHLP 142 50
   83485-02,
   83486-02
Susceptible to decomposition by certain polar organic  solvents.
                                   1310A  - 9
                                       Revision 1
                                       July 1992

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                   TABLE 3.   PRECISIONS OF EXTRACTION-ANALYSIS
                         PROCEDURES FOR SEVERAL ELEMENTS
Element
Arsenic



Barium



Cadmium








Sample Matrix
1.
2.
3.

1.

2.
3.
1.

2.


3.
4.
5.

Auto fluff
Barrel sludge
Lumber treatment
company sediment
Lead smelting emission
control dust
Auto fluff
Barrel sludge
Lead smelting emission
control dust
Wastewater treatment
sludge from
electroplating
Auto fluff
Barrel sludge
Oil refinery
tertiary pond sludge
Analysis
Method
7060
7060
7060

6010

7081
7081
3010/7130

3010/7130


7131
7131
7131

Laboratory
Replicates
1.8,
0.9,
28,

0.12

791,
422,
120,

360,


470,
1100
3.2,

1.5 M9/L
2.6 M9/L
42 mg/L

, 0.12 mg/L

780 M9/L
380 M9/L
120 mg/L

290 mg/L


610 M9/L
, 890 M9/L
1.9 M9/L

Chromium
Mercury
1. Wastewater treatment         3010/7190
    sludge from
    electroplating
2. Paint primer                  7191
3. Paint primer filter           7191
4. Lumber treatment              7191
    company sediment
5. Oil refinery                  7191
    tertiary pond sludge

1. Barrel sludge                 7470
2. Wastewater treatment          7470
    sludge from
    electroplating
3. Lead smelting emission        7470
    control dust
1.1, 1.2 mg/L


61, 43 Mg/L

0.81, 0.89 mg/L
0.15, 0.09
1.4, 0.4
                                                                  0.4, 0.4 M9/L
                                  1310A - 10
                                                Revision 1
                                                July 1992

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                               TABLE 3 (Continued)
Element
Lead
Sample Matrix
1.
2.
3.
4.
5.
Lead smelting emission
control dust
Auto fluff
Incinerator ash
Barrel sludge
Oil refinery
tertiary pond sludge
Analysis
Method
3010/7420
7421
7421
7421
7421
Laboratory
Replicates
940, 920 mg/L
1540, 1490/ug/
1000, 974 jug/
2550, 2800 M9/
31, 29 M9/L
Nickel
Chromium(VI)
1. Sludge
2. Wastewater treatment
    sludge from
    electroplating

1. Wastewater treatment
    sludge from
    electroplating
 7521
3010/7520
 7196
2260, 1720
130, 140 mg/L
18, 19 Mg/L
                                  1310A -  11
                                                Revision 1
                                                July 1992

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          FIGURE 1.
          EXTRACTOR
                         5.0—H
^" *

-------
                                                                2-Liter Plastic or Glass Bottles
                     1/15-Horsepower Electric Motor
  CO

  o
  J>
                                                            Screws for Holding Bottles
                                                                                                                         o
                                                                                                                         73
CL, 73
Vฃ>
ro

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                                                   FIGURE 3.
                                                EPRI  EXTRACTOR
        l-Gallon Plastic
        or Glass Bottle
Hinged Cover
                                                                           Foam Bonded to Cover
Totally Enclosed
Fan Cooled Motor
30 rpm, 1/8 HP
                                                                                       Box Assembly
                                                                                       Plywood Construction
                                                1310A -  14
                                            Revision 1
                                            July 1992

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    FIGURE 4.
COMPACTION TESTER
                                m   Combined Weight
                                   0.33 kg (0.73 Ib)
                               Sample
                                   Elastomeric
                                   Sample Holder
   1310A  -  15
Revision 1
July  1992

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                               METHOD 1310A
          EXTRACTION PROCEDURE  (EP)  TOXICITY  TEST  METHOD
                    AND STRUCTURAL  INTEGRITY  TEST
 7.1 Weigh filter
   membrane and
    prefliter
7.2  Assemble  filter
holder, membranes,
  and  prefi1ters
   7.3 Weigh out
subsample of waste
7.4  Let solid  phase
settle: centrifuge
   if  necessary
                                       7.5 Filter  out
                                      liquid phase and
                                       refrigerate it
7.6 Weigh net solid
      phase
 7.7.1 Dry filter
    and weigh
  7.7.2 Calculate
  percent solids
                               1310A -  16
    7.7 Does
   waste appear
    to contain
      <0.5*
     soilds?
                                 Revision 1
                                 July 1992

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                     METHOD 1310A
                      (Continued)
7.8 Discard solids
              Area  >
              3.1 cm2/g
Area  <  3.1
cm2/g or
par ticle
size  >  9.5
mm sieve
                                 Material is
                                 in single
                                 place
                        7.10.1  Cut or cast
                        cylinder  from waste
                           material for
                            Structural
                        Integrity Procedure
         7.9 Prepare
        material for
        eMtraction by
     crushing, cutting.
         or grinding
                          7 10.2  Assemble
                        tester; drop hammer
                             IS times
                        7 .10.3 Remove solid
                         material; weigh;
                            transfer to
                             ex tractor
                     1310A  -  17
                   Revision  1
                   July  1992

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                                         METHOD  1310A
                                          (Continued)
                                                                         7.15 Allow slurries
                                                                          to stand; set  up
                                                                          filter apparatus;
                                                                               filter
  7.11  Calculate
 amount of  liquid
and acid to use for
    extraction
7.12  Place material
into  extractor; add
  deionized water
7.11  Use  100 g of
  material for
   extraction
    procedure
   7.16 Combine
   liquids from
 Sections 7.S and
7.15  to analyze for
   contaminants
                         7 .13  Agitate for 24
                          hours and monitor
                           pH  of  solution
                                                    7.17 Obtain
                                                 analytical method
                                                 from Chapters 3 and
                                                         4
                         7  13  Calibrate and
                           adjust  pH meter
                                                    7.18 Compare
                                                      ex t ract
                                                 concentration to
                                                      maximum
                                                    contamina tion
                                                 limits to determine
                                                    EP toxicity
                           7.14  At end of
                         extraction period,
                         add deionized water
                                                       STOP
                                         1310A  - 18
                                                          Revision 1
                                                          July  1992

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                                  METHOD  1311

                  TOXICITY CHARACTERISTIC LEACHING PROCEDURE
1.0  SCOPE AND APPLICATION

       1.1   The TCLP is designed to determine  the mobility of both organic and
inorganic analytes present in liquid, solid, and multiphasic wastes.

       1.2   If  a total  analysis  of the  waste demonstrates that  individual
analytes are not present in the waste, or that  they are present but at such low
concentrations that  the appropriate regulatory  levels  could not possibly be
exceeded, the TCLP need not be run.

       1.3   If  an  analysis of  any one of the  liquid  fractions of  the TCLP
extract indicates that a regulated compound is present at such high  concentra-
tions that, even after accounting for dilution from the other fractions of the
extract, the concentration would be above the regulatory level  for that compound,
then the waste  is  hazardous  and it is  not  necessary  to  analyze  the  remaining
fractions of the extract.

       1.4   If an analysis of extract obtained using a bottle extractor shows
that the concentration of any  regulated  volatile analyte exceeds the regulatory
level for that compound, then the waste is hazardous and extraction using the ZHE
is not necessary.  However, extract  from a  bottle  extractor  cannot  be used to
demonstrate that the  concentration of volatile compounds  is below the regulatory
level.

2.0    SUMMARY OF METHOD

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

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

      2.3    If compatible (i.e., multiple phases will  not form on combination),
the initial liquid phase of the waste is added  to the liquid extract,  and these
are analyzed together.  If incompatible,  the liquids are analyzed separately and
the  results are mathematically  combined  to yield  a volume-weighted  average
concentration.
                                    1311-.  1                       Revision 0
                                                                 July 1992

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3.0   INTERFERENCES

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

4.0   APPARATUS AND MATERIALS

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

      4.2    Extraction Vessels

             4.2.1    Zero-Headspace Extraction Vessel  (ZHE).   This device is
      for use only when the waste is being tested for the mobility of volatile
      analytes (i.e., those listed in Table  1).  The ZHE  (depicted in Figure 2)
      allows  for liquid/solid separation within  the device,  and  effectively
      precludes headspace.  This  type of vessel allows for initial liquid/solid
      separation, extraction, and final extract filtration without opening the
      vessel (see Section 4.3.1).   The vessels  shall have an internal volume of
      500-600 ml, and be  equipped to accommodate a 90-110 mm filter. The devices
      contain VITON*1 0-rings which should  be replaced  frequently.  Suitable ZHE
      devices known to EPA are identified in Table 3.

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

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

             Some ZHEs use gas pressure  to actuate the ZHE piston, while  others
      use mechanical  pressure  (see  Table  3).   Whereas the volatiles procedure
      (see  Section  7.3)  refers  to  pounds  per  square inch  (psi), for the
      mechanically  actuated  piston,  the  pressure   applied   is  measured  in
      torque-inch-pounds.  Refer  to the manufacturer's  instructions as  to the
      proper conversion.
     1 VITON* is a trademark of Du Pont.
                                    1311-  2                      Revision 0
                                                                 July 1992

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

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

      4.3    Filtration Devices:   It  is  recommended that all filtrations  be
performed in a hood.

             4.3.1    Zero-Headspace Extractor Vessel (ZHE): When the waste is
      evaluated for volatiles, the zero-headspace extraction  vessel described in
      Section 4.2.1  is  used  for filtration.   The device  shall   be capable  of
      supporting  and  keeping  in place the  glass  fiber  filter and be  able  to
      withstand the pressure needed to accomplish .separation (50  psi).

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

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

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

                                    1311- 3                       Revision  0
                                                                 July 1992

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

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

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

             4.6.1    If a waste contains  an aqueous  liquid phase or if a waste
      does not contain a significant amount of nonaqueous liquid (i.e., <1% of
      total waste),  the TEDLAR* bag or a 600 ml syringe should be  used to collect
      and combine the initial liquid and solid extract.

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

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

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

      4.8     Laboratory  Balance:   Any  laboratory balance accurate  to within
ฑ0.01 grams may be  used (all  weight measurements are to be within + 0.1 grams).

      4.9     Beaker  or Erlenmeyer  flask, glass, 500 ml.

      4.10   Watchglass,  appropriate diameter  to  cover beaker or Erlenmeyer
flask.
       TEDLAR* is a registered trademark of Du  Pont.
                                    1311- 4                      Revision 0
                                                                 July 1992

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      4.11   Magnetic stirrer.

5.0  REAGENTS

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

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

             5.2.1    Reagent water for  volatile extractions may be generated
      by passing  tap water  through a  carbon filter  bed containing  about 500
      grams of activated carbon (Calgon Corp.,  Filtrasorb-300 or equivalent).

             5.2.2    A  water  purification   system   (Millipore   Super-Q  or
      equivalent) may also be used  to  generate reagent  water  for  volatile
      extractions.

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

      5.3    Hydrochloric acid (IN), HC1,  made  from ACS reagent grade.

      5.4    Nitric acid (IN), HN03, made  from  ACS  reagent  grade.

      5.5    Sodium hydroxide  (IN),  NaOH,  made  from ACS reagent grade.

      5.6    Glacial acetic acid,  CH3CH2OOH,  ACS  reagent grade.

      5.7    Extraction fluid.

             5.7.1    Extraction fluid #  1:    Add 5.7  ml  glacial  CH3CH2OOH  to
      500 ml of  reagent water (See  Section 5.2), add 64.3 ml  of  IN NaOH, and
      dilute to a volume of 1  liter.   When correctly  prepared,  the  pH of this
      fluid will  be 4.93 ฑ 0.05.

             5.7.2    Extraction fluid # 2: Dilute 5.7 ml glacial  CH3CH2OOH with
      reagent water  (See Section 5.2)  to  a volume of  1  liter.   When correctly
      prepared, the pH of this fluid will  be  2.88 + 0.05.


                                    1311-  5                      Revision 0
                                                                 July 1992

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


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

6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

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

      6.2    The TCLP may place  requirements  on  the minimal  size  of the field
sample, depending upon the physical state or states of the waste and the analytes
of concern.   An  aliquot  is needed for preliminary  evaluation of which extraction
fluid is to be used for the nonvolatile analyte extraction procedure.  Another
aliquot may  be needed to actually conduct the nonvolatile extraction (see Section
1.4  concerning  the  use of this  extract  for  volatile organics).   If volatile
organics are of  concern, another aliquot may be needed.   Quality control measures
may  require  additional  aliquots.   Further,  it is always  wise to  collect more
sample just  in case something goes wrong with  the  initial  attempt to conduct the
test.

      6.3    Preservatives shall not be added to samples before extraction.

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

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

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

7.0   PROCEDURE

      7.1    Preliminary Evaluations
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      Perform preliminary  TCLP  evaluations on  a  minimum 100 gram  aliquot of
waste.  This aliquot may not actually undergo TCLP extraction.  These preliminary
evaluations include:  (1) determination of the percent solids (Section 7.1.1);
(2) determination of whether  the waste contains  insignificant  solids  and is,
therefore, its own extract  after filtration  (Section 7.1.2); (3) determination
of whether  the  solid portion  of the  waste  requires particle  size reduction
(Section 7.1.3);  and (4)  determination  of which of the two extraction fluids are
to be used for the nonvolatile TCLP extraction of the waste (Section 7.1.4).

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

                      7.1.1.1   If the  waste will obviously yield no liquid when
             subjected  to  pressure filtration (i.e.,  is  100%  solids) proceed to
             Section 7.1.3.

                      7.1.1.2   If  the  sample   is   liquid   or  multiphasic,
             liquid/solid  separation  to make  a preliminary  determination of
             percent solids is  required.  This  involves the  filtration device
             described  in  Section 4.3.2 and  is outlined  in  Sections  7.1.1.3
             through 7.1.1.9.

                      7.1.1.3   Pre-weigh the  filter and the container that will
             receive the filtrate.

                      7.1.1.4   Assemble the  filter holder  and filter following
             the manufacturer's instructions.   Place the filter on the support
             screen and secure.

                      7.1.1.5   Weigh  out a  subsample  of the waste  (100 gram
             minimum) and record the weight.

                      7.1.1.6   Allow  slurries  to stand  to  permit the  solid
             phase  to  settle.   Wastes  that  settle slowly may  be centrifuged
             prior to filtration.  Centrifugation is to be used only as an aid
             to filtration.  If  used, the liquid should be decanted and filtered
             followed by filtration of the solid  portion  of  the waste through
             the same filtration system.

                      7.1.1.7   Quantitatively transfer  the waste sample to the
             filter holder (liquid and solid  phases).  Spread the waste sample
             evenly over the surface of the filter. If filtration of the waste
             at 4 ฐC reduces the amount of expressed liquid over what would be
             expressed at room temperature then allow the sample to warm up to
             room temperature in the device before filtering.

NOTE:        If waste material  (>1% of original  sample weight)  has obviously
             adhered  to the  container used  to  transfer  the  sample to  the
             filtration  apparatus,  determine  the weight  of this residue and


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             subtract it from the sample weight determined  in Section 7.1.1.5 to
             determine the weight of the waste sample that will  be filtered.

                      Gradually apply vacuum  or  gentle pressure  of  1-10  psi,
             until air or pressurizing gas moves through  the  filter.   If this
             point is not reached under  10 psi, and if no additional liquid has
             passed through  the filter in any 2 minute interval, slowly increase
             the pressure in 10 psi increments to a maximum of  50 psi.   After
             each incremental  increase of 10  psi, if the  pressurizing gas has
             not  moved  through  the filter,  and  if  no additional liquid has
             passed through  the  filter  in any  2 minute interval, proceed to the
             next 10 psi increment.  When the pressurizing gas  begins to move
             through the filter,  or when liquid flow has ceased at  50 psi (i.e..
             filtration does not  result  in any additional filtrate within any 2
             minute period), stop the  filtration.

NOTE:        Instantaneous application of high pressure can degrade  the glass
             fiber filter and  may cause premature plugging.

                      7.1.1.8    The material  in the filter holder  is defined as
             the solid phase of the waste, and the  filtrate is  defined as the
             liquid phase.

NOTE:        Some wastes,  such  as  oily wastes  and some  paint  wastes,  will
             obviously contain some material  that appears  to be a  liquid.  Even
             after  applying vacuum  or pressure filtration,   as   outlined  in
             Section 7.1.1.7,  this  material  may not filter.   If  this  is the
             case, the material  within  the  filtration  device is  defined  as a
             solid.  Do  not replace the original  filter  with a  fresh  filter
             under any circumstances.   Use  only one filter.

                      7.1.1.9    Determine the weight of  the  liquid  phase  by
             subtracting the  weight of  the  filtrate  container  (see Section
             7.1.1.3) from the total weight  of the  filtrate-filled container.
             Determine the  weight  of  the solid  phase  of  the waste  sample  by
             subtracting the weight of the  liquid phase from the weight of the
             total waste sample,  as determined in Section  7.1.1.5 or 7.1.1.7.

                      Record  the  weight  of   the  liquid  and  solid  phases.
             Calculate the percent solids as follows:

                        Weight of solid (Section  7.1.1.9)
Percent solids =  	  x 100
                  Total weight of waste (Section  7.1.1.5 or 7.1.1.7)


             7.1.2    If the percent  solids  determined in Section  7.1.1.9  is
      equal to or greater than  0.5%,  then  proceed either to  Section  7.1.3  to
      determine whether the solid material  requires particle size reduction or
      to Section 7.1.2.1  if  it is noticed that a small amount of the filtrate is
      entrained in wetting of the filter.   If the percent  solids determined in
      Section 7.1.1.9 is less than 0.5%, then proceed  to  Section  7.2.9 if the

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      nonvolatile TCLP  is to  be  performed and  to Section  7.3  with  a  fresh
      portion of the waste if the volatile TCLP is to be performed.

                      7.1.2.1   Remove the  solid  phase and  filter from  the
             filtration apparatus.

                      7.1.2.2   Dry the filter and solid phase at  100  +  20 ฐC
             until two  successive  weighing  yield the same value within  + 1%.
             Record the final weight.

NOTE:        Caution should be taken to ensure that the subject solid will  not
             flash upon  heating.   It  is  recommended  that  the drying  oven be
             vented to a hood or other appropriate device.

                      7.1.2.3   Calculate the percent dry solids  as follows:

                        (Wt.  of dry waste + filter) - tared wt. of filter
Percent dry solids =	 x 100
                        Initial wt. of waste (Section 7.1.1.5 or  7.1.1.7)

                      7.1.2.4   If the percent dry solids  is  less  than  0.5%,
             then proceed  to Section  7.2.9 if the nonvolatile TCLP is  to be
             performed,  and  to  Section  7.3  if  the  volatile TCLP  is  to  be
             performed.  If the percent dry solids is greater than  or equal to
             0.5%, and if the nonvolatile TCLP is  to be performed, return to the
             beginning of this  Section  (7.1) and,  with a  fresh  portion of waste,
             determine whether  particle  size reduction  is  necessary (Section
             7.1.3)  and  determine the  appropriate extraction fluid (Section
             7.1.4).  If only the volatile TCLP is to be  performed, see the note
             in Section 7.1.4.

             7.1.3    Determination of whether the  waste requires particle size
      reduction (particle  size  is  reduced during  this step):   Using the  solid
      portion of the waste, evaluate the solid for particle  size.  Particle size
      reduction is  required, unless the  solid has a  surface  area  per  gram of
      material equal to or greater than 3.1  cm2, or is smaller than 1 cm in its
      narrowest dimension  (i  .e., is capable of passing through a  9.5 mm (0.375
      inch) standard  sieve).   If the  surface area  is smaller or  the particle
      size larger than described above, prepare the solid portion of the waste
      for extraction  by crushing,  cutting,  or  grinding  the waste  to a surface
      area or particle size as  described  above.   If the  solids are prepared for
      organic  volatiles  extraction,  special  precautions  must  be  taken  (see
      Section 7.3.6).

NOTE: Surface area criteria are meant for filamentous (e.g., paper, cloth,  and
      similar)  waste materials.   Actual  measurement of  surface  area is  not
      required, nor is it recommended.  For materials that do not obviously meet
      the  criteria,  sample  specific  methods  would need  to  be developed  and
      employed to measure  the  surface  area.  Such  methodology is  currently not
      available.
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             7.1.4    Determination of  appropriate  extraction fluid:   If the
      solid content of the waste  is  greater than or equal to 0.5%  and  if the
      sample will  be extracted  for nonvolatile  constituents  (Section  7.2),
      determine  the  appropriate  fluid  (Section  5.7)  for  the  nonvolatiles
      extraction as follows:

NOTE:        TCLP  extraction  for volatile  constituents  uses only  extraction
             fluid  #1 (Section  5.7.1).    Therefore,  if  TCLP  extraction  for
             nonvolatiles is  not required,  proceed to Section 7.3.

                      7.1.4.1   Weigh out a small subsample of the solid phase
             of the waste, reduce the solid (if necessary)  to  a particle size of
             approximately 1  mm in diameter or less, and transfer 5.0 grams of
             the  solid  phase of the waste to a  500  ml beaker  or  Erlenmeyer
             flask.

                      7.1.4.2   Add 96.5 ml of  reagent  water to the  beaker,
             cover with  a watchglass, and stir  vigorously for 5 minutes using a
             magnetic stirrer.  Measure and record the pH.  If the pH is <5.0,
             use extraction fluid #1.  Proceed to Section 7.2.

                      7.1.4.3   If the  pH  from  Section  7.1.4.2  is  >5.0,  add
             3.5 ml IN HC1, slurry  briefly,  cover  with a watchglass, heat to 50
             ฐC, and  hold at  50 ฐC for 10 minutes.

                      7.1.4.4   Let the  solution  cool to  room temperature and
             record the  pH.   If the pH is <5.0,  use extraction fluid  #1.  If the
             pH is >5.0, use  extraction fluid #2.  Proceed to Section 7.2.

             7.1.5    If  the  aliquot of the waste  used  for the preliminary
      evaluation  (Sections 7.1.1  -  7.1.4)  was determined to  be 100% solid at
      Section  7.1.1.1,  then   it  can be  used for  the  Section  7.2  extraction
      (assuming  at least 100  grams  remain),  and the Section  7.3  extraction
      (assuming at least 25 grams remain).   If  the aliquot was subjected to the
      procedure in Section 7.1.1.7, then another aliquot shall be used for the
      volatile extraction procedure  in  Section 7.3.   The  aliquot of the waste
      subjected to the procedure  in Section 7.1.1.7 might be appropriate for use
      for  the  Section  7.2  extraction   if  an  adequate  amount  of   solid  (as
      determined  by  Section   7.1.1.9)  was  obtained.    The  amount of  solid
      necessary is dependent  upon whether a sufficient amount  of  extract will be
      produced to support the  analyses.  If an adequate amount of solid remains,
      proceed to Section 7.2.10 of the nonvolatile TCLP extraction.

      7.2    Procedure When Volatiles are not Involved

      A minimum sample size of 100 grams (solid and liquid phases)  is recommend-
ed.  In some cases,  a larger  sample  size may be  appropriate, depending on the
solids content of the waste sample  (percent solids,  See Section 7.1.1), whether
the initial liquid phase of the waste will  be miscible with the aqueous extract
of the  solid,  and whether inorganics,  semivolatile  organics,  pesticides, and
herbicides are all analytes of concern.  Enough solids should be generated for
extraction such that the volume of TCLP extract will be sufficient to  support all

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of the analyses required.  If the amount of extract generated by a single TCLP
extraction will not be sufficient to  perform all of the analyses, more than one
extraction may be performed and the extracts from each combined and aliquoted for
analysis.

             7.2.1    If the waste will obviously yield no liquid when subjected
      to pressure  filtration (i.e.. is 100% solid,  see Section  7.1.1), weigh out
      a subsample  of the waste (100 gram minimum) and proceed to Section 7.2.9.

             7.2.2    If  the sample  is  liquid  or  multiphasic,  liquid/solid
      separation is required.  This involves the filtration device described in
      Section 4.3.2 and is outlined in Sections 7.2.3 to 7.2.8.

             7.2.3    Pre-weigh the container that will receive the filtrate.

             7.2.4    Assemble  the   filter  holder  and filter following  the
      manufacturer's instructions.  Place the filter on the support screen and
      secure.  Acid wash  the filter  if evaluating  the mobility of metals (see
      Section 4.4).

NOTE:        Acid  washed  filters  may be  used for  all  nonvolatile extractions
             even  when metals are not of concern.

             7.2.5    Weigh out a subsample of the waste (100 gram minimum) and
      record  the  weight.   If the waste  contains  <0.5%  dry  solids  (Section
      7.1:2), the  liquid portion of the waste,  after filtration, is defined as
      the TCLP extract. Therefore, enough of the  sample should be filtered so
      that  the amount  of filtered   liquid will  support all  of  the  analyses
      required of  the TCLP  extract.  For wastes  containing >0.5%  dry  solids
      (Sections 7.1.1 or 7.1.2),  use  the percent solids information obtained in
      Section 7.1.1 to determine the  optimum sample size (100 gram minimum) for
      filtration.   Enough solids  should be generated by filtration to support
      the analyses to be performed on the TCLP extract.

             7.2.6    Allow  slurries  to  stand  to permit  the solid  phase  to
      settle.  Wastes that settle  slowly may be centrifuged prior to filtration.
      Use  centrifugation only  as an  aid  to  filtration.     If  the waste  is
      centrifuged,  the  liquid  should be  decanted  and  filtered  followed  by
      filtration of the solid portion of the  waste through  the same filtration
      system.

             7.2.7    Quantitatively transfer the waste sample (liquid and solid
      phases) to the filter  holder (see Section 4.3.2). Spread  the waste sample
      evenly over  the surface of  the  filter.  If filtration  of the waste at 4 ฐC
      reduces  the  amount  of expressed liquid over what would  be  expressed at
      room temperature,  then allow the sample to warm up to room temperature in
      the device before filtering.

NOTE:        If waste material  (>1% of the original  sample weight) has obviously
             adhered  to  the  container used  to  transfer  the  sample to  the
             filtration  apparatus, determine  the weight of this  residue  and


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             subtract it from the  sample weight determined in Section 7.2.5, to
             determine the weight  of the waste sample that will  be filtered.

             Gradually apply vacuum  or gentle pressure of 1-10 psi, until air or
      pressurizing gas moves through the filter.   If this point  is not reached
      under 10 psi,  and  if no additional  liquid has passed  through the filter in
      any 2 minute interval, slowly increase the  pressure in 10  psi  increments
      to a maximum of 50 psi.  After each incremental  increase of 10 psi, if the
      pressurizing gas  has not moved through  the filter,  and  if no  additional
      liquid has passed through  the  filter  in  any 2 minute interval,  proceed to
      the  next  10 psi  increment.   When the  pressurizing gas begins  to  move
      through the filter, or when the liquid  flow has  ceased  at  50  psi (i .e..
      filtration does not result  in any additional  filtrate within  a 2 minute
      period), stop the filtration.

NOTE:        Instantaneous application of  high pressure  can degrade the glass
             fiber filter and may  cause  premature plugging.

             7.2.8    The material in  the filter holder is defined as the solid
      phase  of  the  waste,  and  the  filtrate  is defined  as the  liquid phase.
      Weigh  the  filtrate.  The  liquid phase may now be either  analyzed  (See
      Section 7.2.12) or stored at 4 "C  until  time  of analysis.

NOTE:        Some wastes,  such as  oily wastes  and some  paint wastes,  will
             obviously contain some  material that appears  to be a liquid.  Even
             after  applying vacuum  or  pressure  filtration,  as  outlined  in
             Section 7.2.7,  this material may  not filter.  If this is the case,
             the material  within the filtration device is defined as a solid and
             is carried through the extraction as a solid.  Do not replace the
             original filter with  a fresh filter  under any circumstances.   Use
             only one filter.

             7.2.9    If  the waste  contains   <0.5% dry  solids  (see  Section
      7.1.2), proceed to Section 7.2.13.   If the waste contains >0.5% dry solids
      (see Section 7.1.1 or 7.1.2),  and  if  particle  size reduction of the solid
      was needed in Section 7.1.3, proceed  to Section 7.2.10.   If the waste as
      received passes a 9.5 mm sieve, quantitatively  transfer the solid material
      into  the  extractor bottle  along  with the filter  used  to  separate the
      initial liquid from the solid phase,  and proceed to Section 7.2.11.

             7.2.10   Prepare the  solid  portion of the waste for extraction by
      crushing, cutting, or  grinding  the waste to  a surface  area  or particle
      size  as described in  Section  7.1.3.   When  the surface  area  or particle
      size  has  been appropriately altered, quantitatively  transfer  the solid
      material into  an extractor bottle.  Include the  filter used to separate the
      initial liquid from the solid phase.

NOTE:        Sieving  of the  waste  is  not normally required.   Surface  area
             requirements are meant  for filamentous .(e.g., paper,  cloth) and
             similar waste materials.  Actual measurement of  surface area is not
             recommended.  If sieving is necessary,  a Teflon  coated sieve should
             be used to avoid contamination of the  sample.

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manipulation of these materials should be done when cold (4  ฐC) to minimize loss
of volatiles.

             7.3.1    Pre-weigh the  (evacuated)  filtrate  cojlection container
      (See Section  4.6)  and set aside.   If using a  TEDLAR1" bag,  express all
      liquid from the ZHE device  into the  bag, whether  for the initial or final
      liquid/solid separation, and take an  aliquot from the  liquid in the bag
      for analysis.   The  containers  listed  in Section 4.6  are  recommended for
      use under the conditions stated in Sections 4.6.1 -  4.6.3.

             7.3.2    Place the ZHE piston within the body  of  the ZHE  (it may be
      helpful  first  to moisten  the  piston  0-rings  slightly with extraction
      fluid).   Adjust the piston within  the ZHE body to  a height  that  will
      minimize the distance the piston will have to move once  the ZHE  is charged
      with sample (based upon sample size requirements determined from Section
      7.3, Section  7.1.1  and/or 7.1.2).   Secure the  gas  inlet/outlet  flange
      (bottom  flange) onto the ZHE body  in  accordance with the manufacturer's
      instructions.  Secure the glass fiber filter between the support screens
      and set  aside.  Set liquid inlet/outlet flange (top  flange)  aside.

             7.3.3    If the waste  is 100% solid  (see Section 7.1.1), weigh out
      a subsample (25 gram maximum) of  the waste, record weight, and proceed to
      Section  7.3.5.

             7.3.4    If the waste contains < 0.5% dry solids (Section 7.1.2),
      the liquid  portion  of waste,  after  filtration,  is  defined  as the  TCLP
      extract.   Filter enough of  the  sample so  that the amount  of filtered
      liquid will  support all  of the volatile analyses required.   For  wastes
      containing  > 0.5%  dry solids (Sections  7.1.1  and/or 7.1.2), use the
      percent  solids  information obtained  in Section 7.1.1  to determine the
      optimum  sample size to charge into the ZHE.  The recommended sample size
      is as follows:

                      7.3.4.1    For wastes containing < 5% solids  (see Section
             7.1.1),  weigh  out  a 500  gram  subsample of waste  and record the
             weight.

                      7.3.4.2    For wastes containing > 5% solids  (see Section
             7.1.1),  determine the amount  of waste to  charge  into the-ZHE as
             follows:

                                            25
Weight of waste to charge ZHE =  	   x  100
                                  percent solids (Section  7.1.1)

             Weigh out  a  subsample of the  waste of the appropriate size and
             record the weight.

             7.3.5    If  particle  size reduction of the solid  portion  of the
      waste  was required  in Section  7.1.3,  proceed  to   Section  7.3.6.    If
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      particle size  reduction  was not required  in  Section 7.1.3,  proceed  to
      Section 7.3.7.

             7.3.6    Prepare the waste for extraction by crushing, cutting,  or
      grinding the solid portion of the waste  to a surface area or particle size
      as described in Section 7.1.3.  Wastes and appropriate reduction equipment
      should  be  refrigerated,  if  possible,  to  4  ฐC prior  to particle  size
      reduction.    The  means used to  effect  particle size reduction  must  not
      generate heat  in and  of  itself.  If reduction  of  the  solid  phase of the
      waste is necessary,  exposure of the waste to  the atmosphere  should  be
      avoided to the extent possible.

NOTE:        Sieving of the waste is not recommended due  to the possibility that
             volatiles may be lost.  The use of  an appropriately graduated ruler
             is  recommended  as   an   acceptable  alternative.    Surface  area
             requirements  are  meant  for  filamentous  (e.g., paper,  cloth)  and
             similar waste materials.  Actual  measurement of surface area is not
             recommended.

             When  the  surface area  or  particle  size  has  been  appropriately
      altered, proceed to Section 7.3.7.

             7.3.7    Waste slurries  need not be  allowed to stand to permit the
      solid phase to settle.  Do not  centrifuge wastes prior to filtration.

             7.3.8    Quantitatively   transfer  the entire  sample  (liquid  and
      solid phases) quickly to the ZHE.   Secure the  filter and support screens
      onto the top flange  of the device  and  secure  the top flange  to the ZHE
      body in accordance  with the manufacturer's  instructions.  Tighten all ZHE
      fittings and place the device in the  vertical  position (gas inlet/outlet
      flange on the bottom). Do not attach the  extract collection device to the
      top plate.

NOTE:        If waste  material  (>1%  of original sample weight)  has obviously
             adhered to the  container used to  transfer  the  sample to the ZHE,
             determine the weight of this  residue   and  subtract  it  from  the
             sample weight determined in Section 7.3.4 to determine the weight
             of the waste  sample that will  be filtered.

             Attach  a  gas  line to the gas inlet/outlet  valve  (bottom flange)
      and, with the liquid inlet/outlet valve (top flange) open, begin applying
      gentle pressure of 1-10 psi  (or more if necessary) to force all headspace
      slowly out  of  the  ZHE device  into a hood.  At the  first  appearance  of
      liquid from  the  liquid inlet/outlet  valve, quickly close the  valve and
      discontinue  pressure.   If filtration   of  the waste  at 4  ฐC  reduces  the
      amount of expressed  liquid over what  would be  expressed at room tempera-
      ture, then allow the  sample to  warm up  to room temperature in the device
      before filtering.  If the waste is 100% solid (see Section 7.1.1), slowly
      increase the  pressure  to  a maximum   of  50 psi  to  force  most  of  the
      headspace out  of the device and proceed to Section 7.3.12.
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             7.2.11   Determine the amount  of extraction fluid to  add  to the
      extractor vessel as follows:

                      20 x percent solids (Section 7.1.1) x weight of waste
                              filtered  (Section 7.2.5 or 7.2.7)
Weight of         =  	
extraction fluid                            100

             Slowly add this amount of appropriate extraction fluid (see Section
      7.1.4) to the extractor vessel.  Close the extractor bottle tightly (it is
      recommended that Teflon tape be used  to  ensure  a  tight  seal), secure in
      rotary agitation  device,  and rotate  at 30 +  2 rpm for  18  +  2  hours.
      Ambient temperature (i.e., temperature of room in which  extraction takes
      place) shall be maintained at 23 ฑ2 ฐC during the extraction period.

NOTE:        As agitation continues, pressure  may build up within the extractor
             bottle for some types of wastes (e.g.,  limed or calcium carbonate
             containing waste may evolve gases  such  as carbon dioxide).   To
             relieve excess pressure,  the extractor bottle may be periodically
             opened (e.g., after 15 minutes, 30 minutes,  and 1 hour) and vented
             into a hood.

             7.2.12   Following  the   18+2  hour  extraction,  separate  the
      material   in  the extractor  vessel  into  its  component  liquid  and  solid
      phases by filtering through a  new glass  fiber filter,  as  outlined in
      Section 7.2.7.  For final  filtration of  the TCLP extract, the glass fiber
      filter may be changed,  if  necessary, to facilitate  filtration.  Filter(s)
      shall  be  acid-washed (see  Section  4.4)  if  evaluating  the  mobility of
      metals.

             7.2.13   Prepare the TCLP extract as follows:

                      7.2.13.1    If  the  waste  contained no  initial  liquid
             phase, the filtered liquid material obtained from Section 7.2.12 is
             defined as the TCLP extract.   Proceed to Section  7.2.14.

                      7.2.13.2    If compatible (e.g., multiple phases will not
             result on combination), combine the filtered liquid resulting from
             Section 7.2.12 with the initial liquid phase of the waste obtained
             in Section  7.2.7.   This combined  liquid is defined  as  the  TCLP
             extract.  Proceed to Section 7.2.14.

                      7.2.13.3    If the  initial liquid  phase  of the waste, as
             obtained from Section 7.2.7,  is not or may not be compatible with
             the filtered liquid resulting from Section 7.2.12,  do not combine
             these liquids.  Analyze these liquids, collectively defined as the
             TCLP extract, and combine the results mathematically, as described
             in Section 7.2.14.

             7.2.14   Following collection of  the TCLP  extract,  the pH  of the
      extract should be recorded.   Immediately  aliquot and preserve the extract
      for  analysis.   Metals  aliquots  must  be  acidified with nitric acid to

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      pH <2.   If precipitation  is  observed  upon addition of nitric  acid  to  a
      small  aliquot of the extract, then the remaining  portion  of the extract
      for metals  analyses shall not  be acidified  and  the  extract  shall  be
      analyzed as soon as  possible.   All  other aliquots must be  stored  under
      refrigeration (4 ฐC) until analyzed.   The TCLP extract  shall be prepared
      and analyzed according to appropriate analytical methods. TCLP extracts to
      be analyzed for metals shall  be acid  digested except in those instances
      where  digestion causes loss of metallic analytes.   If an analysis of the
      undigested extract  shows that the concentration of any regulated metallic
      analyte exceeds the regulatory level, then the  waste  is hazardous and
      digestion of the extract  is not necessary.  However, data on undigested
      extracts  alone  cannot be used to  demonstrate  that  the waste is  not
      hazardous.   If the individual  phases  are to  be analyzed separately,
      determine the volume of the  individual  phases (to + 0.5%),  conduct the
      appropriate analyses, and combine the  results mathematically by using  a
      simple volume-weighted average:

                                        (V,) (C,) -f  (V2)  (C2)
      Final  Analyte Concentration  =  	
                                              V  +  V
                                              V1  +  V2

      where:

      V,  = The volume of the first phase (L).
      C,  = The concentration of the analyte of concern in the first phase (mg/L).
      V2  = The volume of the second phase (L).
      C2  = The concentration of the analyte  of concern  in  the second phase
           (mg/L).

             7.2.15   Compare the  analyte  concentrations  in  the  TCLP extract
      with the  levels  identified  in  the appropriate  regulations.    Refer to
      Section 8.0 for quality assurance requirements.

      7.3    Procedure When Volatiles are Involved

      Use  the  ZHE  device  to  obtain  TCLP  extract for  analysis of  volatile
compounds only.  Extract resulting from the  use of the ZHE shall not be used to
evaluate the mobility of nonvolatile analytes  (e.g., metals, pesticides, etc.).

      The ZHE device has approximately a 500 mL internal capacity.  The ZHE can
thus accommodate a maximum of 25 grams of solid (defined as that fraction of a
sample from which no additional  liquid may be  forced out by an applied pressure
of 50 psi), due  to  the  need to add an  amount of  extraction  fluid equal  to 20
times the weight of the solid phase.

      Charge the ZHE with sample only  once and do  not open the device until the
final extract (of the solid) has been collected.  Repeated  filling  of the ZHE to
obtain 25 grams of solid is not permitted.

      Do  not allow  the  waste,  the initial  liquid  phase,  or  the extract  to be
exposed to the atmosphere for any more time than is absolutely necessary.  Any


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             7.3.9    Attach  the  evacuated  pre-weighed  filtrate  collection
      container to  the  liquid inlet/outlet valve  and  open  the valve.   Begin
      applying gentle pressure  of 1-10 psi to  force  the liquid phase  of the
      sample into the filtrate collection  container.   If no additional  liquid
      has passed through the  filter  in  any 2 minute  interval,  slowly increase
      the pressure  in 10  psi  increments to a maximum  of 50 psi.   After each
      incremental  increase of  10 psi, if no additional liquid has passed through
      the filter in  any  2 minute interval,  proceed to the  next 10 psi increment.
      When liquid flow has ceased such that continued pressure filtration at 50
      psi does not result in any additional filtrate  within  a 2 minute period,
      stop the  filtration.   Close the  liquid inlet/outlet  valve,  discontinue
      pressure to the piston,  and disconnect  and weigh  the filtrate collection
      container.

NOTE:        Instantaneous application  of  high  pressure  can  degrade the glass
             fiber filter and may cause premature plugging.

             7.3.10   The material in the  ZHE is defined as  the solid phase of
      the waste and the  filtrate is defined as  the liquid phase.

NOTE:        Some wastes,  such  as  oily wastes  and  some  paint wastes,  will
             obviously contain some material that appears to be a liquid.  Even
             after applying pressure filtration,  this material will not filter.
             If this is  the case, the material  within the filtration device is
             defined as  a solid and is carried through the TCLP extraction as a
             solid.

             If the original  waste  contained  <0.5% dry solids  (see  Section
      7.1.2), this  filtrate  is  defined as the  TCLP  extract and  is  analyzed
      directly.  Proceed to Section 7.3.15.

             7.3.11   The liquid phase  may now  be either analyzed immediately
      (See Sections 7.3.13 through  7.3.15)  or   stored at  4 ฐC under  minimal
      headspace conditions  until  time  of  analysis.   Determine the  weight of
      extraction fluid #1 to add to the ZHE as  follows:

                               20 x percent solids (Section  7.1.1) x weight
                                of waste filtered (Section 7.3.4 or 7.3.8)
Weight of extraction fluid =  	
                                                 100

             7.3.12   The following Sections detail  how to add the appropriate
      amount of  extraction fluid  to the  solid material within  the ZHE  and
      agitation of the  ZHE  vessel.   Extraction fluid #1  is  used  in  all  cases
      (See Section 5.7).

                      7.3.12.1   With the  ZHE  in the vertical position,  attach
             a line  from  the  extraction  fluid reservoir to  the liquid  in-
             let/outlet valve.   The line used  shall contain fresh  extraction
             fluid and  should  be preflushed with  fluid to  eliminate any  air
             pockets in the line.  Release  gas  pressure on the ZHE piston (from
             the gas inlet/outlet  valve),  open the  liquid inlet/outlet  valve,

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                                                                 July 1992

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             and begin  transferring  extraction fluid  (by  pumping or  similar
             means)  into the ZHE.  Continue pumping extraction  fluid  into the
             ZHE until  the  appropriate amount of fluid has been introduced into
             the device.

                      7.3.12.2   After  the extraction  fluid  has been  added,
             immediately close the liquid inlet/outlet valve and disconnect the
             extraction fluid line.  Check the ZHE  to ensure that all  valves are
             in  their  closed  positions.   Manually  rotate  the  device  in  an
             end-over-end fashion 2  or  3  times.   Reposition  the ZHE  in  the
             vertical   position with  the   liqu'id  inlet/outlet  valve  on  top.
             Pressurize the ZHE to 5-10  psi (if necessary)  and slowly  open the
             liquid inlet/outlet valve to bleed out any headspace (into a hood)
             that may  have  been  introduced due to the  addition  of  extraction
             fluid.  This bleeding shall  be done quickly  and shall be stopped at
             the first appearance of liquid from the  valve.   Re-pressurize the
             ZHE with 5-10 psi and check all ZHE  fittings to  ensure that they
             are closed.

                      7.3.12.3    Place the ZHE in the rotary agitation appara-
             tus (if it is  not already there) and  rotate at 30 + 2 rpm for 18 +
             2 hours.   Ambient temperature (i.e.,  temperature of room  in which
             extraction occurs) shall  be maintained at 23  +  2 ฐC during agita-
             tion.

             7.3.13   Following the  18+2 hour  agitation  period,  check the
      pressure behind  the  ZHE piston by quickly  opening  and closing  the gas
      inlet/outlet  valve and noting the escape of  gas.   If the pressure has not
      been maintained  (i.e., no gas release observed),  the  device is  leaking.
      Check the ZHE for leaking as specified in Section  4.2.1, and perform the
      extraction again with a new sample of waste.  If the pressure  within the
      device has been maintained, the material  in  the  extractor vessel  is once
      again separated into  its component liquid and solid phases.  If the waste
      contained an  initial  liquid phase,  the liquid may be  filtered  directly
      into the same filtrate collection container (i.e., TEDLAR* bag) holding the
      initial  liquid  phase  of the  waste.   A  separate  filtrate  collection
      container must be used  if combining would  create multiple phases,  or there
      is  not  enough volume  left  within the   filtrate collection  container.
      Filter through the glass fiber filter, using the ZHE  device as discussed
      in Section 7.3.9.   All  extract shall  be  filtered and  collected  if the
      TEDLAR" bag is  used,  if the  extract  is  multiphasic,  or  if the  waste
      contained an  initial  liquid phase  (see Sections  4.6  and 7.3.1).

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

             7.3.14   If the original  waste contained  no initial  liquid phase,
      the filtered liquid material obtained from  Section  7.3.13  is  defined as
      the TCLP extract.   If the waste contained  an initial  liquid  phase, the
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                                                                 July 1992

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      filtered liquid  material  obtained from  Section  7.3.13 and  the initial
      liquid phase (Section 7.3.9) are collectively defined as the TCLP extract.

             7.3.15   Following collection  of  the  TCLP  extract,  immediately
      prepare the extract for analysis  and store with minimal headspace at 4 ฐC
      until analyzed.  Analyze the TCLP  extract according to the  appropriate
      analytical   methods.     If  the  individual  phases  are  to  be  analyzed
      separately  (i.e.,  are  not  miscible),   determine  the  volume  of  the
      individual  phases (to 0.5%), conduct the appropriate  analyses, and combine
      the results mathematically by using a simple volume-weighted average:
                              (VJ  (C,)  +  (V2) (C2)
      Final Analyte
      Concentration                  V,+ V2

      where:

      V, = The volume of the first phases (L).
      C, = The concentration of the analyte of concern in the  first phase (mg/L)
      V2 = The volume of the second phase (L).
      C2 = The concentration of the analyte  of concern in the second phase
             7.3.16   Compare the  analyte  concentrations in the  TCLP extract
      with  the  levels identified  in  the  appropriate  regulations.    Refer to
      Section 8.0 for quality assurance requirements.

8.0  QUALITY ASSURANCE

      8.1    A minimum of one blank (using the same extraction fluid as used for
the samples) must be analyzed  for every  20  extractions that have been conducted
in an extraction vessel.

      8.2    A  matrix spike  shall  be  performed  for each  waste type  (e.g.,
wastewater treatment sludge, contaminated soil,  etc.) unless  the result exceeds
the regulatory level and  the data are  being used solely to demonstrate that the
waste property exceeds the regulatory  level.  A minimum of one matrix spike must
be analyzed for each  analytical  batch.   As a minimum,  follow the matrix spike
addition guidance provided  in each analytical method.

             8.2.1    Matrix spikes are  to  be added after filtration of the TCLP
      extract and before  preservation.  Matrix spikes should  not be added prior
      to TCLP extraction of the sample.

             8.2.2    In  most  cases,  matrix   spikes  should  be added  at  a
      concentration equivalent to the corresponding  regulatory level.   If the
      analyte concentration is  less  than  one half the  regulatory  level,  the
      spike concentration may be  as low as one half  of  the  analyte  concentra-
      tion, but may not be not less than five  times the method detection limit.
      In order to avoid differences in matrix effects, the matrix  spikes must be


                                   1311- 19                      Revision 0
                                                                 July 1992

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      added  to  the  same  nominal volume  of TCLP  extract as  that which  was
      analyzed for the unspiked sample.

             8.2.3    The  purpose  of  the  matrix  spike  is  to  monitor  the
      performance of the analytical methods  used,  and  to determine  whether
      matrix interferences exist.   Use of  other  internal  calibration  methods,
      modification of the  analytical methods,  or use of  alternate analytical
      methods may be needed to accurately measure the analyte concentration in
      the TCLP  extract  when  the recovery  of  the matrix  spike is below  the
      expected analytical method performance.

             8.2.4    Matrix spike  recoveries are  calculated  by the following
      formula:

      %R (%Recovery) = 100 (X8 -  XJ/K

      where:
      X8 = measured  value for  the spiked  sample,
      Xu = measured  value for  the unspiked  sample,  and
      K = known value of the spike in the sample.

      8.3    All quality control measures described in the appropriate analytical
methods shall be followed.

      8.4    The  use of  internal  calibration quantitation  methods shall  be
employed for a metallic contaminant if:  (1) Recovery of the contaminant from the
TCLP extract  is not at  least  50% and the  concentration does  not  exceed  the
regulatory level, and (2) The concentration of the contaminant measured in the
extract is within 20% of the appropriate regulatory level.

             8.4.1.    The method of  standard additions shall be employed as the
      internal calibration quantitation method for each  metallic contaminant.

             8.4.2    The  method of standard   additions  requires  preparing
      calibration standards in the  sample matrix rather  than  reagent  water or
      blank  solution.    It requires  taking  four identical  aliquots  of  the
      solution and adding known amounts of standard to three of these aliquots.
      The forth aliquot is the unknown.   Preferably,  the first addition should
      be prepared so that  the  resulting  concentration is approximately 50% of
      the expected concentration of  the sample.   The  second and third additions
      should be prepared so that the concentrations are  approximately 100% and
      150% of the expected concentration of the sample.   All  four aliquots are
      maintained at  the  same  final  volume  by adding reagent  water or  a  blank
      solution, and may need dilution adjustment  to maintain the signals in the
      linear range of the  instrument technique. All four aliquots are analyzed.

             8.4.3    Prepare a plot, or subject  data to linear regression, of
      instrument signals or external-calibration-derived concentrations as the
      dependant  variable  (y-axis) versus concentrations  of the  additions of
      standard as the independent variable (x-axis).  Solve for the  intercept of
                                   1311- 20                      Revision 0
                                                                 July 1992

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      the abscissa (the  independent variable, x-axis) which  is the concentration
      in the unknown.

             8.4.4    Alternately, subtract the instrumental signal or external -
      calibration-derived concentration of the  unknown  (unspiked)  sample from
      the instrumental signals or external-calibration-derived concentrations of
      the standard  additions.    Plot  or subject to  linear regression  of  the
      corrected instrument  signals  or external-calibration-derived  concentra-
      tions as the dependant variable versus the independent variable.  Derive
      concentrations for unknowns using the  internal calibration curve as if it
      were an external  calibration curve.
      8.5
periods:
Samples must  undergo TCLP extraction  within the following  time
SAMPLE MAXIMUM HOLDING TIMES [Days]




Volatiles
Semi-volatiles
Mercury
Metals, except
mercury
From:
Field
collection
To:
TCLP
extraction
14
14
28
180
From:
TCLP
extraction
To:
Preparative
extraction
NA
7
NA
NA
From:
Preparative
extraction
To:
Determinative
analysis
14
40
28
180


Total
elapsed
time
28
61
56
360
NA = Not applicable


If sample holding  times  are exceeded,  the values obtained  will  be considered
minimal  concentrations.    Exceeding the  holding time  is  not  acceptable  in
establishing that a waste does not exceed the regulatory level.  Exceeding the
holding  time  will  not  invalidate characterization   if  the  waste  exceeds  the
regulatory level.


9.0   METHOD PERFORMANCE

      9.1    Ruggedness. Two ruggedness studies have been performed  to determine
the effect of various perturbations on specific elements of the TCLP protocol.
Ruggedness testing determines  the sensitivity of small  procedural variations
which might be expected to occur during routine laboratory application.

             9.1.1    Metals - The following  conditions were used when leaching
      a waste for metals analysis:
                                   1311- 21
                                                    Revision 0
                                                    July 1992

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Varying Conditions
Liquid/Solid ratio
Extraction time
Headspace
Buffer n acidity
Acid-washed filters
Filter type
Bottle type
19:1 vs. 21:1
16 hours vs. 18 hours
20% vs. 60%
190 meq vs. 210 meq
yes vs. no
0.7 /tun glass fiber vs. 0.45 /urn
vs. polycarbonate
borosilicate vs. flint glass
             Of the  seven method variations examined, acidity of the extraction
      fluid had the  greatest impact on the results.   Four of 13 metals from an
      API separator  sludge/electroplating waste (API/EW)  mixture  and two  of
      three metals from an  ammonia lime  still  bottom waste were extracted  at
      higher levels  by the more acidic buffer.   Because of the sensitivity to pH
      changes,  the method requires that  the extraction fluids  be  prepared  so
      that the  final  pH  is  within  + 0.05  units  as specified.

             9.1.2    Volatile Organic Compounds - The following conditions were
      used when leaching a  waste for VOC  analysis:
Varying Conditions
Liquid/Solid ratio
Headspace
Buffer n acidity
Method of storing extract
Aliquotting
Pressure behind piston
19:1 vs. 21:1
0% vs. 5%
60 meq vs. 80 meq
Syringe vs. Tedlarฎ
bag
yes vs. no
0 psi vs. 20 psi
             None of the parameters had a significant effect on the results of
      the ruggedness test.

      9.2    Precision. Many TCLP precision (reproducibility) studies have been
performed, and  have  shown  that,  in  general,  the  precision  of  the TCLP  is
comparable to or exceeds that of  the EP toxicity test and that method precision
is adequate.  One of the more significant contributions to poor precision appears
to be related to sample homogeneity and inter-laboratory variation (due to the
nature of waste materials).
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             9.2.1    Metals -  The results of a multi-laboratory study are shown
      in Table  6,  and indicate that a  single  analysis  of a waste  may  not be
      adequate for waste characterization and identification requirements.

             9.2.2    Semi-Volatile  Organic  Compounds  -  The  results  of two
      studies are  shown  in Tables 7 and  8.   Single  laboratory  precision was
      excellent with greater than 90 percent  of  the  results  exhibiting  an RSD
      less than 25 percent.  Over 85  percent of all individual compounds in the
      multi-laboratory study fell in the RSD  range of 20  -  120  percent.  Both
      studies concluded that the TCLP provides  adequate precision.   It was also
      determined that the high acetate content of the extraction fluid did not
      present problems (i.e., column degradation of the  gas chromatograph) for
      the analytical conditions used.

             9.2.3    Volatile   Organic  Compounds   -    Eleven   laboratories
      participated in a collaborative study of the use of the  ZHE with two waste
      types which were  fortified with  a mixture of VOCs.   The  results  of the
      collaborative study are shown in Table 9.  Precision  results for VOCs tend
      to occur  over a considerable  range.   However, the range and  mean RSD
      compared very closely  to  the same collaborative study  metals  results in
      Table 6.  Blackburn and Show concluded that at the 95% level  of signifi-
      cance:  1) recoveries among laboratories were statistically similar,  2)
      recoveries did not vary significantly between the two sample types, and 3)
      each laboratory showed the same  pattern  of recovery for each  of the two
      samples.

10.0  REFERENCES

1.    Blackburn,  W.B.  and  Show,  I.    "Collaborative Study  of the  Toxicity
Characteristics Leaching Procedure (TCLP)." Draft Final Report, Contract  No. 68-
03-1958, S-Cubed, November 1986.

2.    Newcomer,  L.R.,  Blackburn, W.B., Kimmell,  T.A.    "Performance  of the
Toxicity Characteristic Leaching Procedure."  Wilson Laboratories, S-Cubed, U.S.
EPA, December 1986.

3.    Williams, L.R.,  Francis,  C.W.; Maskarinec, M.P., Taylor  D.R.,, and Rothman,
N.  "Single-Laboratory Evaluation of Mobility Procedure for Solid Waste."  EMSL,
ORNL, S-Cubed, ENSECO.
                                   1311- 23                      Revision 0
                                                                 July 1992

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                                   Table 1.
                              Volatile  Analytes1'2
Compound                                                      CAS No.
Acetone
Benzene
n-Butyl alcohol
Carbon disulfide
Carbon tetrachloride
Chlorobenzene
Chloroform
1,2-Dichloroethane
1,1-Dichloroethylene
Ethyl acetate
Ethyl benzene
Ethyl ether
Isobutanol
Methanol
Methylene chloride
Methyl ethyl ketone
Methyl isobutyl ketone
Tetrachl oroethyl ene
Toluene
1,1,1,-Trichloroethane
Trichloroethylene
Tri chl orof 1 uoromethane
l,l,2-Trichloro-l,2,2-trifluoroethane
Vinyl chloride
Xylene
67-64-1
71-43-2
71-36-3
75-15-0
56-23-5
108-90-7
67-66-3
107-06-2
75-35-4
141-78-6
100-41-4
60-29-7
78-83-1
67-56-1
75-09-2
78-93-3
108-10-1
127-18-4
108-88-3
71-55-6
79-01-6
75-69-4
76-13-1
75-01-4
1330-20-7
1  When testing for any or all of these analytes, the zero-headspace
  extractor vessel shall be used instead of the bottle extractor.

2  Benzene, carbon tetrachloride, chlorobenzene, chloroform,
  1,2-dichloroethane, 1,1-dichloroethylene, methyl ethyl ketone,
  tetrachloroethylene, and vinyl chloride are toxicity characteristic
  constituents.
                                   1311- 24                      Revision 0
                                                                 July 1992

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                                   Table 2.
                     Suitable Rotary Agitation Apparatus1
Company
Location
    Model No.
Analytical Testing and
  Consulting Services,
  Inc.
Associated Design and
  Manufacturing Company
Warrington, PA
 (215) 343-4490
Alexandria, VA
(703) 549-5999
Environmental Machine and
  Design, Inc.

IRA Machine Shop and
  Laboratory

Lars Lande Manufacturing
Mi Hi pore Corp.
Lynchburg, VA
(804) 845-6424

Santurce, PR
(809) 752-4004

Whitmore Lake,
(313) 449-4116
Bedford, MA
(800) 225-3384
    4-vessel extractor (DC20S)
    8-vessel extractor (DC20)
   12-vessel extractor (DC20B)
   24-vessel extractor (DC24C)
    2-vessel
    4-vessel
    6-vessel
    8-vessel
   12-vessel
   24-vessel
MI
          (3740-2-BRE)
          (3740-4-BRE)
          (3740-6-BRE)
          (3740-8-BRE)
          (3740-12-BRE)
          (3740-24-BRE)
    8-vessel (08-00-00)
    4-vessel (04-00-00)

    8-vessel (.011001)
10-vessel
 5-vessel
 6-vessel
(10VRE)
(5VRE)
(6VRE)
    4-ZHE or
    4 2-liter bottle
        extractor (YT310RAHW)
1  Any device  that rotates the extraction vessel in an end-over-end fashion at  30
+ 2 rpm is acceptable.
                                   1311- 25
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                                 July 1992

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                                   Table 3.
                  Suitable Zero-Headspace Extractor Vessels1
Company
Location
Model No.
Analytical Testing &
  Consulting Services, Inc,
Associated Design and
  Manufacturing Company
Lars Lande Manufacturing2
Millipore Corporation
Environmental Machine
and Design, Inc.
Gelman Science
Warrington, PA
(215) 343-4490
Alexandria, VA
(703) 549-5999
Whitmpre Lake, MI
(313) 449-4116
Bedford, MA
(800) 225-3384
Lynchburg, VA
(804) 845-6424
Ann Arbor, MI
(800) 521-1520
C102, Mechanical
Pressure Device
3745-ZHE, Gas
Pressure Device
ZHE-11, Gas
Pressure Device
YT30090HW, Gas
Pressure Device
VOLA-TOX1, Gas
Pressure Device
15400 Gas Pressure
Device
1 Any device that meets the specifications listed in Section 4.2.1  of the method
is suitable.
2 This device uses a 110 mm filter.
                                   1311- 26
                                 Revision 0
                                 July 1992

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                                   Table 4.
                           Suitable Filter Holders1
                                                 Model/
Company
Nucleopore Corporation
Micro Filtration
Systems
Location
Pleasanton, CA
(800) 882-7711
Dublin, CA
(800) 334-7132
(415) 828-6010
Catalogue No.
425910
410400
302400
311400
Size
142 mm
47 mm
142 mm
47 mm
Millipore Corporation        Bedford,  MA        YT30142HW         142 mm
                             (800)  225-3384     XX1004700         47 mm


1  Any device capable  of separating  the liquid from the solid phase of the waste
is suitable, providing that it is chemically compatible with the waste and the
constituents to be analyzed.  Plastic devices (not listed above)  may be used when
only  inorganic  analytes are  of  concern.   The  142 mm  size filter  holder  is
recommended.
                                   1311- 27                      Revision 0
                                                                 July 1992

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                                   Table  5.
                            Suitable Filter  Media1
Company
Millipore Corporation
Nucleopore Corporation
Whatman Laboratory
Products, Inc.
Micro Filtration
Systems
Gelman Science
Location
Bedford, MA
(800) 225-3384
Pleasanton, CA
(415) 463-2530
Clifton, NJ
(201) 773-5800
Dublin, CA
(800) 334-7132
(415) 828-6010
Ann Arbor, MI
(800) 521-1520
Model
AP40
211625
GFF
GF75
66256 (90mm)
66257 (142mm)
Pore
Size
(M"i)
0.7
0.7
0.7
0.7
0.7
1  Any filter  that  meets the  specifications  in Section 4.4  of the Method  is
suitable.
                                   1311- 28
Revision 0
July 1992

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               Table  6.  Multi-Laboratory TCLP Metals, Precision

Waste
Ammonia
Lime Still
Bottoms



API/EW
Mixture




Fossil
Fuel Fly
Ash
v


Extraction
Fluid
#1
#2
#1
n
n
n
#1
n
n
n
n
n
n
n
n
n
n
n

Metal
Cadmium

Chromium

Lead

Cadmium

Chromium

Lead

Cadmium

Chromium

Lead


X
0.053
0.023
0.015
0.0032
0.0030
0.0032
0.0046
0.0005
0.0561
0.105
0.0031
0.0124
0.080
0.093
0.017
0.070
0.0087
0.0457

S
0.031
0.017
0.0014
0.0037
0.0027
0.0028
0.0028
0.0004
0.0227
0.018
0.0031
0.0136
0.069
0.067
0.014
0.040
0.0074
0.0083

%RSD
60
76
93
118
90
87
61
77
40
17
100
110
86
72
85
57
85
18
%RSD Range = 17 - 118
Mean %RSD = 74
NOTE: X = Mean results from 6-12 different laboratories
      Units = mg/L
      Extraction Fluid #1 = pH 4.9
                       #2 o pH 2.9
                                   1311- 29
Revision 0
July 1992

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             Table  7.   Single-Laboratory Semi-Volatiles, Precision

Waste
Ammonia
Lime Still
Bottoms





















API/EW
Mixture







Compound
Phenol

2-Methyl phenol

4-Methyl phenol

2, 4-Dimethyl phenol

Naphthalene

2-Methyl naphthalene

Dibenzofuran

Acenaphthylene

Fluorene

Phenanthrene

Anthracene

Fluoranthrene

Phenol

2,4-Dimethylphenol

Naphthalene

2-Methyl naphthalene

Extraction
Fluid
#1
#2
#1
n
n
n
n
n
n
n
n
#2
#1
n
n
n
n
n
#i
n
n
n
n
#2
n
n
n
n
n
n
n
n

X
19000
19400
2000
1860
7940
7490
321
307
3920
3827
290
273
187
187
703
663
151
156
241
243
33.2
34.6
25.3
26.0
40.7
19.0
33.0
43.3
185
165
265
200

S
2230
929
297
52.9
1380
200
46.8
45.8
413
176
44.8
19.3
22.7
7.2
89.2
20.1
17.6
2.1
22.7
7.9
6.19
1.55
1.8
1.8
13.5
1.76
9.35
8.61
29.4
24.8
61.2
18.9

%RSD
11.6
4.8
14.9
2.8
17.4
2.7
14.6
14.9
10.5
4.6
15.5
7.1
12.1
3.9
12.7
3.0
11.7
1.3
9.4
3.3
18.6
4.5
7.1
7.1
33.0
9.3
28.3
19.9
15.8
15.0
23.1
9.5
%RSD Range =1-33
Mean %RSD = 12
NOTE: Units = /xg/L
      Extractions were performed in triplicate
      All results were at least 2x the detection limit
      Extraction Fluid #1 = pH 4.9
                       n = pH 2.9
                                   1311- 30
Revision 0
July 1992

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              Table 8.  Multi-Laboratory Semi-Volatiles, Precision
Waste
Ammonia Lime
Still Bottoms (A)
API/EW
Mixture (B)
Fossil Fuel
Fly Ash (C)
Compound
BNAs
BNAs
BNAs
Extraction
Fluid
n
n
#1
#2
#1
n
X
10043
10376
1624
2074
750
739
S
7680
6552
675
1463
175
342
%RSD
76.5
63.1
41.6
70.5
23.4
46.3
Mean %RSD = 54
NOTE:
Units =
X = Mean results from 3-10 labs
Extraction Fluid #1 = pH 4.9
                 n = pH 2.9

%RSD Range for Individual Compounds
  A, #1                 0 -  113
  A, #2                28 -  108
  B, #1                20 -  156
  B, n                49 -  128
  C, n                36 -  143
  C, n                61 -  164
                                   1311- 31
                                                           Revision 0
                                                           July 1992

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              Table 9.  Multi-Laboratory (11 Labs) VOCs, Precision
Waste
Mine
Tailings

















Ammonia
Lime Still
Bottoms
















Compound
Vinyl chloride
Methylene chloride
Carbon disulfide
1,1-Dichloroethene
1,1-Dichloroethane
Chloroform
1,2-Dichloroethane
2-Butanone
1,1,1 -Tri chl oroethane
Carbon tetrachloride
Trichloroethene
1 , 1 , 2-Tri chl oroethene
Benzene
1,1,2 , 2-Tetrachl oroethane
Toluene
Chlorobenzene
Ethyl benzene
Tri chl orof 1 uoromethane
Acrylonitrile
Vinyl chloride
Methylene chloride
Carbon disulfide
1,1-Dichloroethene
1,1-Dichloroethane
Chloroform
1,2-Dichloroethane
2-Butanone
1,1,1 -Tri chl oroethane
Carbon tetrachloride
Trichloroethene
1,1, 2-Tri chl oroethene
Benzene
1,1, 2, 2-Tetrachl oroethane
Toluene
Chlorobenzene
Ethyl benzene
Tri chl orof 1 uoromethane
Acrylonitrile
X
6.36
12.1
5.57
21.9
31.4
46.6
47.8
43.5
20.9
12.0
24.7
19.6
37.9
34.9
29.3
35.6
4.27
3.82
76.7
5.00
14.3
3.37
52.1
52.8
64.7
43.1
59.0
53.6
7.10
57.3
6.7
61.3
3.16
69.0
71.8
3.70
4.05
29.4
S
6.36
11.8
2.83
27.7
25.4
29.2
33.6
36.9
20.9
8.2
21.2
10.9
28.7
25.6
11.2
19.3
2.80
4.40
110.8
4.71
13.1
2.07
38.8
25.6
28.4
31.5
39.6
40.9
6.1
34.2
4.7
26.8
2.1
18.5
12.0
2.2
4.8
34.8
%RSD
100
98
51
127
81
63
70
85
100
68
86
56
76
73
38
54
66
115
144
94
92
61
75
49
44
73 .
67
76
86
60
70
44
66
27
17
58
119
118
%RSD Range =17-144
Mean %RSD = 75
NOTE: Units = M9/L
                                   1311- 32
Revision 0
July 1992

-------
        Motor
     (30ฑ 2 rpm)
Extraction Vessel Holder









             Figure 1.   Rotary Agitation Apparatus
   Top Flange

Support Screen-
            Filter
    Support Screen'
                       Liquid Inlet/Outlet Valve
       Viton o-rings
Bottom Flange—*{_
  Pressurized Gas •
  Inlet/Outlet Valve
                       .'-;.-•.  .Sample
                              Piston
                               Gas
Pressure
 Gauge
           Figure 2.  Zero-Headspace Extractor (ZHE)

                            1311-  33
                          Revision 0
                          July  1992

-------
                            METHOD 1311

         TOXICITY CHARACTERISTIC  LEACHATE PROCEDURE
   Separate
 liquids from
solids with 0.6
-  0.8 um glass
 fiber filter
   Separate
 liquids from
solids with 0.6
-  0.8 um glass
 fiber filter
   Discard
   solids
                         Must the
                         solid be
                          milled?
                                                   Solid
En tract ป/
appropriate fluid
1) Bottle extractor
for non- vola ti les
2) 2HE device for
volatiles



Reduce
particle size
to <9 . 5 mm

                             1311-  34
                    Revision 0
                    July  1992

-------
            METHOD 1311  (CONTINUED)

TOXICITY  CHARACTERISTIC  LEACHATE PROCEDURE

Discard
sol ids
Solid


Separate
extract from
solids w/ 0.6 -
0 . 8 urn glass
fiber filter
Liquid Sw
V
Store
at
1 iquid
4 C
                               Is
                              1iquid
                            compatible
                              ith the
                             extract?
 Measure amount of
liquid and analyze
  (math etna tical 1 y
 combine result w/
 result of extract
    analysis)
                              Combine
                            extract w/
                           liquid phase
                             of waste
                              Analyze
                              1 iquid
                               STOP
                    1311-  35
         Revision  0
         July  1992

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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
Vine!and, 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. Cassidy 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      0
                                                         Date  September 1986

-------
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 - Manville  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

-------
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
Mllford, MA  01757
(617) 478-2000
(800) 252-4752

Whatman  Laboratory  Products,  Inc.
Clifton, NJ  07015
(201) 773-5800
                                 COMPANIES - 3
                                                          Revision
                                                          Date   September  1986

                                     U. S. GOVERNMENT PRINTING OFFICE :  1986 O - 169-934

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