United Statn
Environrnonttl Protection
Agency
Of flee of Water and
Warn Management
Washington. DC 20460
SW-846
Revision B
July 1981
Solid Waite
Test Methods
for Evaluating Solid Waste

Physical/Chemical Methods
    Technical
       Update

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U.S. Environmental Protection Agency

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           TEST METHODS FOR EVALUATING SOLID WASTE

                  PHYSICAL/CHEMICAL METHODS

                       Technical Update
This manual (SW-846B) updates the Test Methods for Evaluating
  Solid Waste (SW-846), and was written by the Hazardous and
   Industrial Waste Division of the Office of Solid waste.
             U.S. ENVIRONMENTAL PROTECTION AGENCY
                          July 1981

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   This publication (SW-846B) is the second revision to Test Methods for
Evaluating Solid Waste (SW-846).  Any mention of commercial products in
the manual or this revision does not constitute''endorsement by the U.S.
Government.  Editing and technical content were the responsibilities of
the Hazardous and Industrial Waste Division, Office of Solid Waste.

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                              PREFACE
      Attached is the second revision, dated April 15,1981, to the
Environmental Protection Agency's manual, Test Methods for Evaluating
Solid Waste (SW-846).

     These attached pages should be inserted in the manual in place
of like-numbered pages or as entirely new pages, where appropriate.
The date on which the page was issued is printed in the upper right-hand
corner.  Modified sections are indicated in the contents by double
underscores.

     The Office of Solid Waste encourages comments and suggestions for
improving the utility or content of this manual.  Comments may be made
by telephoning 202-755-9187 or writing:


                     Manager, Waste Analysis Program
                     Office of Solid Waste
                     U.S. EPA (WH-562)
                     Washington, DC 20460

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                                          Revision B   4/15/81
                        Table of Contents
Section
          Introduction
  1.0     Evaluation Plan Design
  2.0     Chain of Custody Considerations
  3.0     Sampling Methodology
            3.1  Sampling Plan Design [Reserved]
            3.2  Sampling Equipment
            3.3  Sample Containers
            3.4  Sample Handling & Preservation [Reserved]
  4.0     Ignitability  (40 CFR 261.21)
  5.0     Corrosivity   (40 CFR 261.22)
  6.0     Reactivity    (40 CFR 261.23)
  7.0     Extraction Procedure Toxicity  (40 CFR 261.24)
            7.1  Regulations
            7.2  Separation Procedure
            7.3  Sample Size Reduction  [Reserved)
            7.4  Structural Integrity Procedure
            7.5  Extractors
  8.0     Analytical Methodology
          Gas Chromatographic Methods
            8.01  Volatile organics, general
            8.02  Volatile aromatics, selected ketones 6 ethers
            8.03  Acrolein, Acrylonitrile and Acetonitrile
            8.04  Phenols
            8.06  Semi-volatile organics, not otherwise specified
            8.08  Organochlorine pesticides and PCBs

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                                   Revision B   4/15/81
8.09  Nitroaromatics
8.10  Polynuclear Aromatic Hydrocarbons
8.11  Haloethers [Reserved]
8.12  Semi-volatile chlorinated hydrocarbons, Not Otherwise
      Specified
8.13  Chlorinated Dibenzo-p-dioxins [Reserved]
8.22  Organophosphorus pesticides
8.40  Chlorophenoxy acid pesticides
Gas Chromatographic/Mass Spectroscopy Methods
8.24  Volatile organics
8.25  Semi-volatile organics
8.27  Capillary Column GC/MS Metod for the Analysis of Wastes
High Performance Liquid Chromatographic Methods
8.30  Polynuclear Aromatic Hydrocarbons  [See method 8.10]
8.32  Carbamates [Reserved]
Atomic Absorption Spectrographic Methods
8.49  General Requirements
8.50  Antimony
8.51  Arsenic
8.52  Barium
8.53  Cadmium
8.54  Chromium
8.55  Cyanide
8.56  Lead
8.57  Mercury
8.58  Nickel
8.59  Selenium
8.60  Silver

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                                         Revision B   4/15/81
      Other Measurement Methods
        8.55  Titrimetric Method for Cyanide
        8.56  Microcoulometric Method for Total Organic Halide
        8.57  Titrimetric Method for Sulfides
      Sample Preparation/Introduction Techniques
        8.80  Direct Injection
        8.62  Headspace
        8.83  Purge and Trap
        8.84  Shake Out
        8.85  Sonication
        8.86  Soxhlet Extraction
 9.0  Interference Removal Procedures
        9.01  Liquid - Liquid Extraction
10.0  Quality Control/Quality Assurance
11.0  Suppliers
 Appendices
   I  "Samplers and Sampling Procedures for Hazardous Waste
      Streams", EPA-600/2-80-018
  II  Selected sections of "Methods for Chemical Analysis
      of Water and Wastes",  EPA-600/4-79-020,
 III  "Methods for Benzidine, Chlorinated Organic
      Compounds,  Pentachlorophenol and  Pesticides in Water and
      Wastewater"
  IV  Selected sections from the Federal Register,  "Guidelines
      Establishing Test Procedures for  the  Analysis of Pollutants;
      Proposed Regulations", 44 PR 69464-69567.

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                                        Revision B  4/15/81  -8."27-1


                         Method 8.27

   Capillary Column GC/MS method for the analysis of Wastes



Scope and Application

     This method may be used to determine the presence and
concentration of the volatile and extractable organic compounds
which are listed in Appendix VIII, 40 CFR 261.33 in wastes.  The
method employs capillary column gas chromatography-mass
spectrometry.  Quantitation can be performed in two ways depending
on the level of information required.

Summary of Method

     The waste is categorized by its physical makeup into one
of the following three classes.

        0 Liquid (either single or multi-phase systems)
        0 Solid
        0 Combination of Liquid and Solid

     Liquids are analyzed in their "as received" form except that
if more than one phase is present the organic and aqueous phases
are separated and the two phases analyzed separately.   The
organic phases are analyzed by direct injection onto the
capillary column using, either the split or splitless technique.
Aqueous phases are de/termined by a combination of the purge
and trap technique for volitiles and a series of extractions
for the base/neutrals and acids.  The extracted fractions
are then combined and analyzed as a single solution using
the splitless technique.
     Solids are analyzed using purge and trap technique for
volatiles and a soxhlet extraction for the extractables.
     Samples containing both liquid and solid phases are first
separated into their component liquid and solid phases
using centrifugation.  The separated phases are then analyzed
as either liquids or solids as described above.
     The components of the sample are quantitated in either
of two ways, depending on the degree of quantitation necessary.
The first way estimates concentration and assigns these
estimated concentrations into ranges.  Since this is not a
rigorous quantitative procedure it may only be used for
order of magnitude type estimates of concentration.  These
ranges are:

          Greater than 50%
          •Between 10 and 50%
          Between 1 and 10%
          Between 100 ppm and 1%
          Between 1 and 100 ppm

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                                        Revision B  4/15/81  8.27-2

For determining the precise concentration of a component in a
sample the method of standard additions is employed.

Procedure
     The analyst must first determine which category the
sample belongs to.

        0 If the sample is a liquid go to the section labled
          "Liquids" (1} of this procedure.
        0 If the sample is a solid go to the section labled
          "Solids" (II) of this procedure.
        0 If the sample contains both liquid and solid go to
          the section labled "Mixtures of Liquids and Solids"
          (III) of this procedure.

I,  Liquids

     The analyst should determine if more than one liquid
phase is present in the sample.  If more than one phase is
present the sample should be separated into its organic and
aqueous phases respectively.  This separation can be achieved
by using either gravity or cenrifugation.  The separated
phases should be weighed.  10.0 gm of well mixed sample
should be used.

   A.  Organic Liquids

       1. Summary
          Organic Liquids are injected directly onto the
          capillary column using either the split or splitless
          mode.  The liquid may be diluted if necessary to
          facilitate sample handling or to accomodate the
          linear range of the mass spectrometer.

       2. Apparatus and Materials
          a. Sample Vials - 10 dram vials with teflon lined caps
          b. Gas Chromatograph - Analytical system capable of
             split and splitless injections and all required
             accessories including column supplies, gases, etc.
          c. Column - 30m SE-30, SE-52, SE-54, or equivalent,
             .2 to .25mm internal diameter with a film thickness
             between .15 to .40u.
          d. Mass Spectrometer - Capable of scanning from 35 to
             450 daltons every 1 second or less.  The mass-
             spectrometer must be able to operate at 70
             volts for electron ionization and must produce
             a recognizable mass spectrum for 50 ng or less
             of DFTPP when the sample is introduced through
             the GC column.  The GC column should be directly
             interfaced (i.e. no separator) to the mass
             spectrometer through either an all glass or all
             glass lined system.  If a fused silica capillary
             column is used, the analyst is required to
             complete the interface by placing the end of

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                                Revision B  4/15/81  8.27-3


      the  column in the  ion source.

   e.  Computer System -  The computer system interfaced
      to the mass spectrometer should be  capable  of
      continuously acquiring mass  spectra for  the duration
      of the gas chromatographic program,  (about  1 hr.)
      All  data must be stored either within the data
      system or on line  mass storage devices such as
      disk or tape.  The system must have software
      available capable  of searching GC/MS runs for
      the  following:

         1) selected ion chromatograms
         2) total ion chromatograms
         3) reverse and  forward search for any compound
            from the EPA/NIH Mass  Spectral Data Base.

3. Reagents
   a.  Methylene chloride -  Pesticide quality
   b.  Ethyl Ether        -  "               "
   c.  Ethylacetate          n               "
   d.  Methanol           -  "               "
   e.  Standards - Standards can be made up as  necessary
      if appropriate reagents are  available.  Naphthalene-dg
      or phenanthrene-djo mav be  used as internal standards.

4. Calibration
   a.  The mass spectrometer is calibrated with either
      PFK or FC-43 oxver  the scan  range. The mass  spec-
      trometer should be scaned from 35 to 450 daltons
      in 2 sec or less.   50ng or  less of DFTPP should
      be injected in the splitless mode using  the
      conditions given in Table 8.27-1.
   b.  The DFTPP spectrum obtained  from the top of the
      chromatographic peak (backgroud subtracted)
      should meet the criteria listed in Table 8.24-2.

5. Sample Preparation
   a.  If the liquid can  be convieniently drawn into  a
      10 ul syringe, then no sample  preparation is
      necessary.  Weigh  1 gm of the  liquid into a
      a pre-tared 10 dram vial.  Add the internal
      standard at a level that would give 50 ng on
      column when injected.  (The  amount added will
      vary with split ratio)
   b.  If it is necessary to dilute the samplef a  weighed
      portion of the organic phase should be transfered
      to an appropriate  volumetric flask and diluted
      to volume with one of the solvents listed in
      the reagent section.  The internal standard is
      added at a level that would give 50 ng on column
      when injected prior to dilution.  Record the
      dilution volume.

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                              Revision B  4/15/81  8.27-4
Gas Chromatography/Mass spectrometry
a. Establish the chromatographic conditions given
   in table 8.27-1.
b. Set the Gas Chromatograph for either split
   or splitless injection depending on estimated
   concentration.  For example, an organic liquid
   that can be conveniently drawn up in a syringe
   can be analyzed using the split mode.  An oily
   sample that needs to be diluted to 1:100 might
   best be handled using the splitless mode.  If
   using the split mode, record the split ratio.
   Record both linear and volume column flow.
c. Inject sample, start the chromatographic program,
   and acquire data.  Record amount of sample
   injected. (1 to 5 ul when using split mode and
   1 to 2 ul when the splitless mode is employed).
d. Inject appropriate standards and acquire data using
   sample conditions as employed in c.

Qualitative and Quantitative Determination
a. A compound will be judged to have been identified
   if either three or more characteristic ions of
   the compound maximize within one scan of the
   apex of the peak and the integrated ion areas
   agree with a library or standard mass spectrum
   within + 20%; or, a reverse search yields a numerical
   value equivalent to the criteria stated above.
b. Samples can be quantitated in two ways.  The first
   is by the method of standard additions.  This
   method is always acceptable and must be used
   when the actual concentration is needed.  The
   second method is used when order of
   magnitude estimates of concentration are
   needed.  This is done by comparing the Total
   Ion Chromatogram of the compound in the sample
   with a standard.  For example, if 100 ng of
   benzene gives a total of 10,000 integrated area
   counts then a peak corresponding to toluene
   with 25,000 counts would be expected to correspond
   to about 250 ng.  When using this method the
   analyst should try to use standards which resemble
   the compounds in question as closely as possible.
   The internal standard is used as a method check.
   For example, if 50 ng of the internal standard
   normally gives 5000 integrated area counts,
   this condition should be met in the sample
   +20%
c. Example Calculation
   5 ul of a 5 rag/ml solution of benzene was injected
   with a split ratio of 100:1 to produce the

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                                Revision B  4/16/31  C.27-5


      chromatogram in figure  8.27-1.   The integrated
      area  of  the benzene  peak  from the  total  ion
      chromatogram was 7840 counts.   10  gm of  an
      organic  liquid  sample was disolved in methylene
      chloride in a volumetric  flask  to  a final volume
      of  100 ml.   5 ul of  this  solution  was injected
      with  the same split  ratio to  produce the chromatogram
      in  figure 8.27-2. The  integrated  area for
      benzene  in  this sample  was 4235 counts.  The
      peak  for toluene gave an  area of 4827 counts.
      The estimated concentration of  benzene and
      toluene  in  this sample  are:

      Benzene  Standard

         5  mg/ml  = 5  ug/ul

         5  ug/ul  x 5  ul =  25  ug injected

         7840  counts/25 ug =  313.6  counts/ug

      Benzene  in  Sample

         4235  counts/5 ul  injected  x  1 ug/ 313.6  counts  =

         13.5  ug/5 ul

         13.5  ug/5 ul x 1000  ul/ml  =

         2700  ug/ml

         2700  ug/ml x 100  ml/10 gm  dilution =  27000 ug/gm

         27000 ug/gm  =  27 mg/gm

         27 mg/gm x 1 gm/1000 mg =  .027  = 2.7%

         The sample is 2.7% benzene

      Toluene  in  sample

         By an analogus method  the  sample is calculated  to

         be 3.1%  toluene.

8.   Report
   a. Report the  results of each analysis giving
      the method  used to quantify each comound.
      Report the  scan number  of each  compound.
   b. Example:

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                                      Revision  B   4/15/81   8.27-6


Compound          Quantitation         Scan     Amount    Range
                  Method                 #

Benzene           Estimate/Benzene      500        2%      1-10%
Toluene           Estimate/Benzene      622        3%      1-10%

 B.  Aqueous Liquid

     1. S umma ry
        Aqueous liquids are analyzed by purge and trap and
        extraction methods given in Methods 8.83 and 8.84.
        After the aqueous sample is purged and traped and
        extracted by Methods 8.83 and 8.84 the traped material
        and the extracts {which have been combined) are
        analyzed by capillary column gas chromatography-mass
        spectrometry.

     2. Apparatus and Materials
        See the appropriate sections in Methods 8.83, 8.84, and
        the apparatus and materials section for organic liquids
        in this method

     3. Reagents
        See the appropriate sections in Methods 8.83, 8.84, and
        the reagents section for organic liquids in this method.

     4. Calibration
        a. The mass spectrometer is calibrated with PFK or
           PC-43 over the scan range of interest.  For the
           volatiles scan over the range 20 to 260 daltons,
           and scan over the range 35 to 450 daltons for
           the base/neutrals and acid extractables.  The
           scan rates should be 2 sec. or less.  50 ng or
           less of bromoflurobenzene or DFTPP should be injected
           for the volitiles and extractables respectively.
           Chromatographic conditions are given in Tables
           8.27-2 and 8.27-3.
        b. The specta obtained from the top of the chromatographic
           peak (background subtracted) should meet the criteia
           listed in Tables 8.24-2 and 8.24-3.

     5. Sample Preparation
        a. Follow the purge and trap and extraction methods
           given in Methods 8.83 and 8.84 of this manual
           for preparation of the sample.
        b. Base/neutral and acid extractable fractions
           may be combined and analyzed in a single GC/MS
           analysis.

     6. Gas Chromatography/Mass Spectrometry
        a. Establish the Chromatographic conditions described
           in Tables 8.27-2 or 8.27-3, whichever is appropriate.
        b. Set gas chromatograph in either the split or

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                                Revision B  4/15/81  8.27-7
      splitless mode.  If using the split mode record
      the split ratio.  Record both the linear and
      volume column flow.
   c. When analyzing volatiles it may be necessary to
      adjust desorption time or cool the first few
      cm of the column with a flurocarbon spray
      in order to maintain chromatographic resolution.
   d. Inject sample and acquire data, recording the amount
      injected. Follow the same procedure for any standards.

7. Quantitative and Qualitative Determination
   a. A compound can be qualitativly identified in either
      of two ways.  At least three characteristic ions  of the
      compound must maximize within one scan of the apex
      of the peak and the integrated ion areas agree with
      a library or standard mass spectrum within ± 20%;
      or, a reverse search yeilds  a numerical value
      equivalent to the criteria stated above.
   b. Samples can be quantitated in two ways.   The first
      is by the method of standard additions.   This
      method is always acceptable  and should be used
      when the exact concentration is needed.   The
      second method is to be used  only for order of
      magnitude estimates of concentartion.   This is
      done by comparing the Total  Ion Chromatogram of
      the compound in the sample with a standard.   For
      example, if 100 ng of benzene gives a total of
      10,000 integrated area counts then a peak corresponding
      to toluene with 25,000 counts would be expected
      to correspond to about 250 ng.   When using this
      method the analyst should try to use standards
      which resemble the compounds in question as
      closely as possible.  The internal standard is used
      as a method check.  For example, if 50 ng of
      the internal standard normally gives  5000 integrated
      area counts, this condition  should be met in
      the sample +20%
   c. Example Calculation
      A 10 gm sample contained 3.5 gm of organic liquid
      with a volume of 3.9 ml.   5  ul  of the organic
      liquid was injected with a split ratio of 100
      to 1.   The integrated area of benzene  gave 3582
      counts.   Benzene in the organic phase  is calculated:

          3582 counts/5 ul x 1 ug/313.6 counts = 11.4 ug/5 ul

          11.4 ug/5 ul x 1000 ul/ml = 2280  ug/ml

          the density is 3.5gm/3.9ml  = .9  gm/ml

          2280 ug/ml = 2.28mg/ml

          2.28mg/ml x Igm/lOOOmg x 1  ml/.9gm = .0025  =  .25%

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                                     Revision B  4/15/81  8.27-8


           The purge and trap analysis  of the aqueous phase
           was performed on 6.5 gm of liquid.  Benzene gave
           12562 counts.  The benzene in the aqueous phase
           is:

               12562 counts/6.5 gm x 1  ug/313.6 counts =

               40.0 ug/6.5 gm =  6.2 ppm

               This is insignificant compared to .25%

           The total amount of benzene  in the sample is
           calculated:

               .25% x .35 of total = .0875% or 875  ppm
      8. Report
        a. Report the results of each analysis giving
           each compound identified, the scan number, the
           quantity of the compound, and the method used
           to calculate that quantity.
        b. Example

Compound          Quantitation         Scan     Amount    Range
                  Method                 #

Benzene           Estimate/Benzene      687      875ppm  100ppm-l%

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                                        Revision B  4/15/81  8.27-9

II.  Solids

     Two samples of well mixed solid should be used in this
analysis.  One sample is used for the purge and trap analysis
of volatiles and one for soxhlet extraction analysis.

   A.  Purge and Trap Determination of Volatiles in Solids

       1. Summary
          An appropriate weight of sample (1-10 gm) is diluted
          with 10 ml of organic-free water.  The diluted
          sample is purged for 12 min. with inert gas at
          room temperature. The gaseous phase is passed
          through a sorbent trap where the organic compounds
          are concentrated.  The contents of the trap are
          desorbed into the GC/MS by heating and backflushing
          the trap.

       2. Apparatus and Materials
          a. See the apparatus section of Method 8.83 of this
             manual.
          b. Gas Chromatograph - Analytical system capable of
             split and splitless injections and all required
             accessories including column supplies, gases, etc.
          c. Column - 30m SE-30, SE-52, SE-54, or equivalent,
             .2 to ,25mm internal diameter with a film thickness
             between .15 to .40u.
          d. Mass Spectrometer - Capable of scanning from 20 to
             260 daltons every 1 second or less.  The MS must
             be able to operate at 70 volts for electron
             ionization and must produce a recognizable mass
             spectrum for 50 ng or less of BFB when the sample
             is introduced through the GC column.  The GC column
             should be directly interfaced (i.e. no separator)
             to the mass spectrometer through an all glass
             or all glass lined system.  If a fused silica
             capillary column  is used, the analyst is required
             to complete the interface by directly connecting
             the end of the column to the  ion source.
          e. Computer System - The computer system interfaced
             to the mass spectrometer should be capable of
             continuously acquiring mass spectra for the duration
             of the gas chromatographic program,  (about 1 hr.)
             All data must be  s,tored either within the data
             system or on line mass storage devices such as
             disk or tape.  The system must have software
             available capable of searching GC/MS runs for
             the following:

                1}  selected ion chromatograms
                2)  total ion chromatograms

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                                 Revision B  4/15/81  8.27-10
         3) reverse and forward search for any compound
            from the EPA/NIH Mass Spectral Data Base

3. Reagents - Standards as necessary  (See Methods 8.24,
              8.83, and I-A-3e of this Method)

4. Calibration
   a. The mass spectrometer is calibrated with either
      PFK or FC-43 over the scan range.   50ng or less of
      BFB should be injected in the splitless mode
      using the conditions given in table 8.27-3.
   b. The spectrum obtained from the top of the chro-
      matographic peak (backgroud subtracted) should
      meet the criteria listed in table 8.24-2.

5. Sample Preparation
   a. Weigh an appropriate sample into a pretared 10 to
      15 ml Teflon lined, screw-capped vial.
   b. Dilute the sample with 10 ml distilled water.
      Disperse the sample into the water.  Transfer
      the total sample to the purging device using a
      syringe with an 1/8 in. gauge Teflon needle.
      Seal the sample in the purging device.   Add
      the internal standard and purge with 40
      ml/min (He or N2) for 12 min. at room temperature.

6. Gas Chromatography/Mass spectrometry
   a. Establish the chromatographic conditions given
      in table 8.27-1.
   b. Set up the Gas Chromatograph for either split
      or splitless injection.  If using the split
      mode, record the split ratio, linear and volume
      column flow.
   c. The first few inches of the column should be
      cooled using flurocarbon spray.  Heat the trap
      to 200°C.  Backflush it for 4 min in the
      desorb mode into the gas Chromatograph.

7. Qualitative and Quantitative Determination
   a. A compound can be qualitativly identified in either
      of two ways.  At least three characteristic ions of the
      compound must maximize within one scan of the apex
      of the peak and the integrated ion areas agree with
      a library or standard mass spectrum within _+ 20%;
      or, a reverse search yeilds a value equivalent to
      the criteria stated above.
   b. Samples can be quantitated in two ways.  The first
      is by the method of standard additions.  This

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                           Revision B  4/15/81  8.27-11

method is always acceptable and should be used
when the exact concentration is needed.
The second method is to be used only for order
of magnitude estimates of concentration as
given on page 1 of this method.  This is done
by comparing the Total Ion Chromatogram of the
compound in the sample with a standard.  For
example, if 100 ng of benzene gives a total of
10,000 integrated area counts then a peak corresponding
to toluene with 25,000 counts would be expected
to correspond to about 250 ng.  When using this
method the analyst should try to use standards
which resemble the compounds in question as
closely as possible.  The internal standard is
used as a method check.  For example, if 50 ng
of the internal standard normally gives 5000
integrated area counts this condition should
be met in the sample ^20%.
Example Calculation
5.0 gm of a solid sample was mixed with 10 ml
water and purged and traped by the procedure
specified.  A splitless injection gave 29,043
integrated area counts for toluene.  1 ul of
a standard solution of Toluene 100 ug/ml gave
16,290 integrated counts.

   16290 counts/ 1 ul x 1000 ul/100 ug = 162900 counts/ug

   29043 counts/5 gm x 1 ug/162900 counts = .18 ug/5 gm

   .18 ug/5 gm = .036 ug/gm = .036 ppm

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                                Revision  B   4/15/81   8.27-12
8. Report
  a. Report the results of each analysis giving
     each compound identified,  the scan number, the
     quantity of the compound,  and the method used
     to calculate that quantity.
  b. Example

     The level of toluene in the sample is very low
     and for the purpose of this analysis is reported
     at less than 1 ppm

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                                    Revision B  4/15/81  8.27-13

B. Soxhlet Extraction for Solids

   1. Summary
      The sample is mixed with anhydrous sodium sulfate,
      placed in an extraction thimble or between two
      plugs of glass wool and extracted using methylene
      chloride.  The extract is reserved.  The remaining
      contents of the thimble are mixed with distilled
      water and the pH is adjusted to 2 or less.  This
      aqueous mixture is extracted with ethyl ether.
      The two extracts are dried, combined, and anaylzed
      in one GC/MS analysis.

   2. Apparatus and Materials
      a. Soxhlet extractor - 40 mm id, with 500 ml round-
         bottom flask.
      b. Kuderna-Danish Apparatus  [Kontes K-570000 or equivalent]
         with 3-ball snyder column
      c. Gas Chromatograph - Analytical system capable of
         split and splitless injections and all required
         accessories including column supplies, gases, etc.
      d. Column - 30m SE-30, SE-52, SE-54, or equivalent,
         .2 to .25mm internal diameter with a film thickness
         between .15 to .40u.
      e. Mass Spectrometer - Capable of scanning from 35 to
         450 daltons every 1 second or less.  The MS must
         be able to operate at 70 volts for electron
         ionization and must produce a recognizable mass
         spectrum for 50 ng or less of DFTPP when the sample
         is introduced through the GC column.  The GC column
         should be directly interfaced (i.e. no separator)
         to the mass spectrometer through an all glass
         or all glass lined system.  If a fused silica
         capillary column is used, the analyst  is required
         to complete the interface by directly connecting
         the end of the column to the ion source.
      f. Computer System - The computer system  interfaced
         to the mass spectrometer should be capable of
         continuously acquiring mass spectra for the duration
         of the gas chromatographic program, (about 1 hr.)
         All data must be stored within the data system.
         Mass storage devices such as disk or tape are
         accepable.  The system must have software available
         to allow searching GC/MS runs for the  following:
            1) selected ion chromatograms
            2) total ion chromatograms
            3) reverse and forward search for any compound
               from the EPA/NIH Mass Spectral Data Base

   3. Reagents
      a. Methylene chloride - Pesticide grade
      b. Ethyl Ether - Pesticide grade

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                                 Revision B  4/15/81  8.27-14

   c. Anhydrous Sodium Sulfate,  ACS grade, purified
      by heating at 400 C for 4  hr. in a shallow tray.

4. Calibration
   a. The mass spectrometer is calibrated with either
      PFK or FC-43 over the scan range.   50ng or less of
      DFTPP should be injected in the splitless mode
      using the conditions given in table 8.27-1.
   b. The DFTPP spectrum obtained from the top of  the
      chromatographic peak (backgroud subtracted)
      should meet the criteria listed in table 8.24-2.

5. Sample Preparation
   a. Blend 10.0 gm of the solid sample with 10.0  gm
      of anhydrous sodium sulfate.   Weigh this mixture
      to the nearest 0.1 gm.   Place in either a paper
      (pre-washed with methylene chloride and dried)
      or glass extraction thimble.
   b. Place the thimble in the extractor.  (If any
      problems arise when using  the thimble, i.e.  if
      the sample clogs the thimble, an alternative
      would be to place a plug of glass wool in the
      extraction chamber, transfer the sample into
      the chamber, then cover the sample with another
      plug of glass wool.)
   c. Place 250 ml of methylene  chloride into the  500 ml
      roundbottom flask, add  a boiling chip and attach
      the flask to the extractor.  Extract the sample
      for 16 hours.
   d. After the extraction is complete,  cool the extract;
      rinse extractor flask and  thimble with fresh
      solvent.  Combine the extract and rinse.
      Dry the extract by passing it through a 4 inch
      column of sodium sulfate that has been washed
      with solvent.  Collect  the dried extract
      in a 500 ml Kuderna-Danish (KD)  flask fitted with
      a 10 ml graduated concentartor tube.
      Empty the contents of the  thimble into a pre-weighed
      250 ml Erlinmeyer flask.   Add 100 ml distilled
      water to the flask.
   e. Adjust the pH to 2 or less with  sulfuric acid
      solution.  Extract three times with fresh 60 ml
      portions of ethyl ether.   Combine the three
      extracts and dry by passing through a 4 inch
      column of sodium sulfate.   Rinse column with
      fresh solvent.   The dried  extract is added to
      the KD.
   f. Evaporate the aqueous solution in the erlinmeyer
      flask to dryness; cool  the flask and weigh the
      residue.  Determine the weight difference between

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                               Revision B 4/15/81   8.27-15

   the residue in the erlinmeyer flask and the
   original sample.
g. Concentrate the dried extracts in the KD.  A
   level that would give a final concentration of
   about 1 mg/ml is generally appropriate for
   GC/MS.
h. The concentrated extract should be placed in a
   volumetric flask and made up to the appropriate
   volume.

Gas Chromatography/Mass spectrometry
a. Establish the chromatographic conditions given
   in table 8.27-1.
b. Set the Gas Chromatograph for either split
   or splitless injection.  If using the split
   mode, record the split ratio.  Record both
   liniar and volume column flow.
c. Inject sample and acquire data.  Record amount
   of sample injected. (2 to 5 ul for split
   and 1 to 2ul for splitless)
d. Inject appropriate standards and acquire data as
   in c.

Qualitative and Quantitative Determination
a. A compound can be qualitativly identified in either
   of two ways.  At least three characteristic ions of the
   compound must maximize within one scan of the apex
   of the peak and the integrated ion areas agree with
   a library or standard mass spectrum within + 20%;
   or, a reverse search yeilds a value equivalent to
   the criteria stated above.
b. Samples can be quantitated in two ways.  The first
   is by the method of standard additions.  This
   method is always acceptable and should be used
   when the exact concentration is needed.  The
   second method is to be used only for order of
   magnitude estimates of concentartion.  This is
   done by comparing the Total Ion Chromatogram of
   the compound in the sample with a standard.  For
   example, if 100 ng of benzene gives a total of
   10,000 counts then a peak corresponding to toluene
   with 25,000 counts would be expected to correspond
   to about 250 ng.  When using this method the
   analyst should try to use standards which resemble
   the compounds in question as closely as possible.
   The internal standard is used as a method check.
   For example, if 50 ng of the internal standard
   normally gives 5000 integrated area counts this
   condition should be met  in the sample +20%.
c. Example Calculation
   10 gm of solid sample was extracted with methylene
   chloride and ethyl ether as in the procedure. The

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                                       Revision B 4/15/81   8.27-16

           sample lost about 4 gm during the extraction.  The
           combined extracts were diluted to 500 ml with
           methylene chloride.  5 ul was injected with a
           split "ratio of 100 to 1.  Hexachlorobenzene was
           found in the extract with a total of 7,121
           total area counts.

           Dichlorobenzene was used as a standard

               5 ul x  1 mg/ml x 1 ml/1000 ul = 5 ug

               Total counts for Dichlorobenzene was 3760

               3760 counts/5 ug = 752 counts/ug

           Hexachlorobenzene in sample

               7121 counts/5 ul x 1 ug/752 counts = 9.47 ug/5 ul

               9.47 ug/5 ul x 1000 ul/1 ml x 500 ml = 947000ug

               947000 ug = .947 gm

               .947 gm/10 gm = .0947 = 9.5% hexachlorobenzene
      8. Report
        a. Report the results of each analysis giving
           each compound identified, the scan number, the
           quantity of the compound, and the method used
           to calculate that quantity.
        b. Example

Compound          Quantitation         Scan     Amount    Range
                  Method                 #

Hexachloro        Estimate/dichloro     693      9.5 %    1-10%
benzene               benzene

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                                        Revision B  4/15/81  8.27-17

III.   Mixtures of Liquids and Solids
     A 10 to 20 gm sample of well mixed waste is used.   The sample
is divided into its component phases and the procedures oulined
in sections I and II of this Method are employed for analysis.

   A.   Separation Procedure for Liquids and Solids

       1. Summary
          A 10 to 20 gm sample of the waste is separated into
          its component phases by centrifugation.  The  Liquid
          Phases are either decanted or pipeted for analysis
          using section I and the solid residue is analyzed
          using section II.

       2. Apparatus and Materials
          a. Centrifuge tubes - 10-20 ml pyrex glass or equivalent
             with ground glass stopper.
          b. Centrifuge -  Capable of 2400 RPM

       3. Reagents - Reserved

       4. Calibration - See calibration sections in parts
          I and II of this method

       5. Sample Preparation
          a. Alliquot a 10 to 20 gm sample of well mixed waste
             into a pre weighed cenrifuge tube.  Weigh.
          b. Place tube into centrifuge and spin at 2400 RPM
             for 15 min. or until the solids and liquid phases
             are separated.
          c. Pour off liquid phase and weigh.  Proceed  to section
             I of this method.
          d. Weigh remaining solids and proceed to section II of
             this method.  The purge and trap method for the
             determination of volatiles in solids may be
             omitted since the volatiles are determined in the
             liquid phase of the sample.

   B.   Report

       1. Report the results as a weighted average of the
          liquid phases and solid phase.
       2. Example calculation
          See sections I and II

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                                        Revision B  4/15/81  8.27-18
                    Table 8.27-1 (Liquids)

Column:   SE-30, SE-52, SE-54      (30 m)
Linear Flow Rate:  50 cm/sec H2 or 30 cm/sec He
Temperature Program:  Inject at 25°C then 50°C
                      Program 50° to 280° C at 8°/min
                      Hold at 280°C for 15 min.
                 Table 8.27-2  (Extractables)

Column:  SE-30, SE-52, SE-54    (30 m)
Linear Flow Rate:   50 cm/sec H2 or 30 cm/sec He
Temperature Program:  Inject at 50°C hold 2 min.
                      Program to 280°C at 8°C/min
                      Hold at 280°C for 15 min
                  Table 8.27-3  (Volatiles)

Column:   Same as 8.27-2
Linear Flow Rate:  Same as 8.27-2
Temperature Program:   Inject at 25 C (cool head of column with
                      flurocarbon spray) then to 50°C
                      Program 50°C to 200°C at 4°C/mir
                      Hold at 200°C for 10 min

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H/E. BEF, TOL
                  BECOHST.  GAS  CHECHIA HICHAM
                  DATE:
                  SAMPLE:
  RGC
                            Benzene  Standard
                                 7840 counts
                                                                                                                          10
                                                                                                                          CO
                                                                                                                          H-
                                                                                                                          0
                                                                                                                          3
                                  Y
SCAN
TRIE
200
3:20
4CO
6:40
 600
10:09
  I
 800
13:20
                                                                                                               cc
                                                                                                               M


                                                                                                               cc

                                                                                                               ISJ

                                                                                                               I
                          Figure  8.27-1

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VE. DEF. TOL
                BECONST. GAS CHROHATOGRAH
                DATE:           TIHE:
                SAMPLE:
                                                           SAMPLE RUN:
                                                           CALIB. RUM:
                                             SCANS  100 TO 1809
                                                                             8B.A. ,
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                                              Revision B   4/15/81   8.56-1
                              Method  8.56
                             TOTAL ORGANIC HALIDE
1.   Scope and Application
    1.1  This method is to be used for the determination  of  Total  Organic
         Hal ides as Cl" by carbon adsorption,  and requires that  all
         samples be run in duplicate.   Under conditions of duplicate
         analysis, the reliable limit  of sensitivity 1s 5 ug/L.  Organic
         halides as used in this method are defined as all organic species
         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.
    1.2  This is a microcoulometrlc-titration  detection method applicable to
         the determination of the compound class listed above in drinking
         and ground waters, as provided under  40 CFR 265.92.
    1.3  Any modification of this method, beyond those expressly permitted,
         shall be considered as major  modifications subject  to application
         and approval of alternate test procedures under  40  CFR  260.21.
    1.4  This method is restricted to  use by,  or under the supervision  of,
         analysts experienced in the operation of a pyrolys1s/m1crocolumeter
         and in the Interpretation of  the results.
2.   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 1s free of undlssolved solids, is passed through  a
         column containing 40 mg of activated  carbon.  The column  is  washed

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                                               Revision B   4/15/81   8.56-2
         to remove any trapped Inorganic halldes, and. 1s. ttien.D.vrolvzed to
         convert the adsorbed organohalides to a titratable species that can
         be measured by a microcoulometrlc detector.
3.  Interferences
    3.1  Method Interferences may be caused by contaminants, reagents,
         glassware, and other sample processing hardware.  All of these
         materials must be routinely demonstrated to be free from
         Interferences under the conditions of the analysis by 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, drain dry, and-heat In a muffle furnace at 400°C
                for 15 to 30 minutes.  Volumetric ware should not be heated
                1n 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  The use of high purity reagents and gases help to minimize
                Interference problems.
    3.2  Purity of the activated carbon must be verified before use.  Only
         carbon samples which register less than 1000 ng/40 mg should be
         used.  The stock of activated carbon should be stored in its
         granular form 1n 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 two-week supply

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                                                Revision  B  4/15/81   8.56-3

         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  This method is applicable to samples whose, inorganic-halide
         concentration does not exceed the organic-halide concentration by
         more than 20,000 times.
4.  Safety
    The toxicity or carcinogenicity of each reagent in this method has not
    been precisely defined; however, each chemical compound should be
    treated as a potential health hazard.  From this viewpoint, exposure to
    these chemicals must be reduced to the lowest possible level by whatever
    means available.  The laboratory is responsible for maintaining a
    current-awareness file of OSHA regulations regarding the safe handling
    of the chemicals specified  in this method.  A reference file of
    material-handling data sheets should also be made available to all
    personnel involved in the chemical analysis.
5.  Apparatus and Materials  (All specifications are suggested.  Catalog
    numbers are included for illustration only).
    5.1  Sampling equipment, for discrete or composite sampling
         5.1.1  Grab-sample bottle - Amber glass, 250-ml, fitted with
                Teflon-lined caps.  Foil may be substituted for Teflon if
                the sample is not corrosive.  If amber bottles are not
                available, protect samples from light.  The container must
                be washed and muffled at 400°C before use, to minimize
                contamination.

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                                          Revision B   4/15/81  8.56-4
5.2  Adsorption System
     5.2.1  Dohrmann Adsorption Module (AD-2), or equivalent,
            pressurized, sample and nitrate-wash reservoirs.
     5.2.2  Adsorption columns - pyrex, 5 cm long X 6-mm OD X 2-mm ID.
     5.2.3  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-haTide background should be 1000-mg Cl"
            equivalent or less.
     5.2.4  Cerafelt (available from Johns-Manville), or equivalent  -
            Form this material into plugs using a 2-mrn ID
            stainless-steel borer with ejection rod (available from
            Dohrmann) to hold 40 mg of GAC in the adsorption columns.
            CAUTION:  Do not touch this material with your fingers.
     5.2.5  Column holders (available from Dohrman).
     5.2.6  Volumetric flasks - 100-nt, 50-mL.
            A general schematic of the adsorption system is shown in
            Figure 1.
5.3  Dohrmann microcoulometric-titration system (MCTS-20 or DX-20),  or
     equivalent, containing the following components:
     5.3.1  Boat sampler.
     5.3.2  Pyrolysis furnace.
     5.3.3  Microcoulometer with integrator.
     5.3.4  Titration cell.
            A general description of the analytical system is shown  in
            Figure 2.
5.4  Strip-Chart Recorder.

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                                              Revision B   4/15/81  8.56-5
6.  Reagents
    6.1  Sodium sulfite - 0.1 M, ACS reagent grade (12.6 g/L).
    6.2  Nitric acid - concentrated.
    6.3  Nitrate-Wash Solution (5000 mg NO^/L) - Prepare a nitrate-wash
         solution by transferring approximately 8.2 gm of potassium nitrate
         into a 1-litre volumetric flask and diluting to volume with reagent
         water.
    6.4  Carbon dioxide - gas, 99.9% purity.
    6.5  Oxygen - 99.9% purity.
    6.6  Nitrogen - prepurified.
    6.7  7035 Acetic acid in water - Dilute 7 volumes of acetic acid with 3
         volumes of water.
    6.8  Trichlorophenol solution, stock (1 wL = 10 ug Cl") - Prepare a
         stock solution by weighing accurately 1.856 gm of trichlorophenol
         into a 100-mL volumetric flask.  Dilute to volume with methanol.
    6.9  Trichlorophenol solution, calibration (1 uL • 500 ng Cl") -
         Dilute 5 ml of the trichlorophenol stock solution to 100 ml with
         methanol.
    6.10 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 yL of the calibration solution.
    6.11 Trichlorophenol standard,  adsorption-efficiency  (100 ug C1"/L) -
         Prepare a adsorption-efficiency standard by  injecting  10 uL of
         stock solution  into  1 liter of reagent water.
    6.12 Reagent water - Reagent water is defined as  a water in which an

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                                               Revision B   4/15/81  8.56-6
          Interferent  1s  not observed  at  the method detection  limit of each
          parameter of Interest.
    6.13  Blank  standard  - The reagent water used to  prepare the calibration
          standard should be used as the  blank  standard.
7.  Calibration
    7.1   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 5% of the standard value.
    7.2   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 pyrolysis determinations.
          7.2.1  The nitrate-wash blank values are obtained on single columns
                packed with 40 mg of activated carbon.  Mash with the
                nitrate  solution as Instructed for sample analysis, and then
                pyrolyze the carbon.
    7.3   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 3% of the
         calibration-standard value.  Repeat analysis of the
          Instrument-calibration standard after each  group of eight pyrolysis
         determinations, and before resuming sample  analysis after cleaning
         or reconditioning the tltration cell  or pyrolysis system.
8.  Sample Preparation
    8.1  Special care should be taken in the handling of the sample to

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                                              Revision B   4/15/81   8.56-7
         minimize the loss of volatile organohalides.  The adsorption
         procedure should be performed simultaneously on duplicates.
    8.2  Reduce residual chlorine by the addition of sulfite (1 ml of O.-l  M
         per liter of sample).  Addition of sulflte should be done at the
         time of sampling 1f the analysis is 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.
    8.3  Adjust pH of the sample to approximately 2 with concentrated HNOj
         just prior to adding the sample to the reservoir.
9.  Adsorption Procedure
    9.1  Connect two columns in series, each containing 40 mg of
         100/200-mesh activated carbon.
    9.2  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 ug/L; 50 ml for 501 to 1000
         yg/L, and 25 ml for 1001 to 2000 ug/L.
    9.3  Wash the co.lumns-1n-series with 2 ml of the 5000-mg/L nitrate
         solution at a rate of approximately 2 mL/min to displace Inorganic
         chloride ions.
10. Pyrolysis Procedure
    10.1 The contents of each column is pyrolyzed separately.  After rinsing
         with the nitrate solution, the columns should be protected from the
         atmosphere and other sources of contamination until ready for
         further analysis.

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                                             Revision  B  4/15/81   8.56-8
    10.2  Pyrolysis  of  the  sample  1s  accomplished  In two  stages.  The
         volatile components  are  pyrolyzed  1n a CQg-rich  atmosphere at a
         low  temperature to assure the  conversion of  brominated
         trlhalomethanes to a titratable  species.  The less volatile
         components are then  pyrolyzed  at a high  temperature  in  an Og-rich
         atmosphere.
         NOTE:   The quartz sampling  boat  should have  been previously muffled
         at 800°C for  at least 2  to  4 minutes as  1n a previous analysis,
         and  should be cleaned of any residue by  vacuuming.
    10.3  Transfer the  contents of each  column to  the  quartz boat for
         individual analysis.
    10.4  If the Dohrmann MC-1 is  used for pyrolysis,  manual Instructions  are
         followed for  gas  flow regulation.   If the MCT-20 is  used, the
         information on the diagram  in  Figure 3 is used  for gas  flow
         regulation.
    10.5  Position the  sample  for  2 minutes  in the 200°C  zone  of  the
         pyrolysis  tube.   For the MCTS-20,  the boat  1s positioned just
         outside the furnace  entrance.
    10.6  After 2 minutes,  advance the boat  Into the 800°C zone  (center) of
         the  pyrolysis furnace.  This second and  final stage  of  pyrolysis
         may  require from  6 to 10 minutes to complete.
11.  Detection
    The effluent gases are directly  analyzed 1n the microcoulometric-titra-
    tion  cell.  Carefully  follow  manual instructions  for optimizing  cell
    performance.

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                                             Revision B  4/15/81   8.56-9
12. Breakthrough
    Because the background bias can be of such  an unpredictable nature,  it
    can be 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-percent of the two-column total measurement.  If the 10-percent
    figure is exceeded, one of three events can have happened.  Either the
    first column was overloaded and a legitimate measure of breakthrough was
    obtained - in which case taking a smaller sample may be necessary; or
    channeling or some other failure occurred - in which case the sample may
    need to be rerun; or a high, random, bias occurred and the result should
    be rejected and the sample rerun.  Because knowing which event has
    occurred may not be possible,  a sample analysis should be repeated often
    enough to gain confidence  in results.  As a general rule, any analyses
    that  is rejected should be repeated whenever  sample is available.  In
    the event that the second-column measurement  is equal to or less than
    the nitrate-wash blank value,  the second-column value should be
    disregarded.
 13. Quality Control
    13.1  Before  performing any analyses, the analyst must demonstrate the
          ability to  generate  acceptable  accuracy and precision  with  this
          procedure  by  the analysis of  appropriate quality-control check
          samples.
    13.2  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.

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                                               Revision B   4/15/81  8.56-10
     13.3  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 nature of the samples.  Field duplicates
          may be  analyzed to monitor the precision of the sampling
          technique.  Whenever possible, the laboratory should perform
          analysis of standard reference materials and participate in
          relevant performance-evaluation studies.
14. Calculations
    OX as Cl~ Is calculated using the following formula:
                    (cr c3) * (c2 - c3 ).  ug/L Total Organ1c Hal1de
                             5
    where:
    C-] » ug Cl~ on the first column in series
    Cy = U9 Cl" on the second column In series
    C., = predetermined, dally, average,  method-blank value
           (nitrate-wash blank for a 40-mg carbon column)
    V = the sample volume In L
15. Accuracy and Precision
    These procedures have been applied to a large number of drinking-water
    samples.  The results of these analysis are summarized in Tables I and
    II.
16. Reference
    Oressman, R.f Najar, G.,  Redzikowski, R.,  paper presented at the
    Proceedings of the American  Water  Works Association Water Quality
    Technology Conference,  Philadelphia,  Dec.  1979.

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                           Revision B   4/15/81   8.56-11



                   TABLE  I



PRECISION AND ACCURACY  DATA FOR MODEL COMPOUNDS
Model
Compound
CHC13
CHBrC12
CHBr2C1
CHBr3
Pentachlorophenol


Sample
A
B
C
Dose Dose Average Standard
wg/L as wg/L C1 % Recovery Deviation
98 88 89 14
160 106 98 9
155 79 86 11
160 67 111 8
120 80 93 9
TABLE II
PRECISION DATA ON TAP WATER ANALYSIS
Avg. halide Standard
ug Cl/L Deviation
71 4.3
94 7.0
191 6.1
No. of
Replicate;
10
11
13
11
7


No. of
Replicates
8
6
4

-------
N2
f
  SAMPLE
RESERVOIR
  (1 of 4)
                                      NITRATE WASH
                                      RESERVOIR
 GAG COLUMN 1
 GAC COLUMN 2
                                                                   50
                                                                   fO

                                                                   !-••
                                                                   in
                                                                   »-••
                                                                   O
                                                                   3

                                                                   00
            Figure 1. Adsorption Schematic
                                                                 en
                                                                 \
                                                                 00
                                                                   GO
                                                                   a\
                                                                   I
                                                                   M
                                                                   10

-------
                     SPARGING
                      DEVICE
TITRATION
PYROLYSIS
                                  BOAT
                                  INLET
       MICROCOULOMETER
       WITH INTEGRATOR
            STRIP CHART
             RECORDER
                                                 ADSORPTION
                                                   MODULE
          Figure 2.  CAOX Analysis System Schematic
                                                                       i—
                                                                       n>
                                                                       M-
                                                                       o
                                                                       3
                                                                       03
                                                                       00
                                                                       00
                                                                       •
                                                                       U1
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     SINGLE BOAT OUTLET
[CONNECT TO
  BOAT-INLET
   PORTS
           IIOiVENT   CAPPED
      —T	 "~
                                                    PYROLYSIS FURNACE
CO i SO ml/min  Oi 100 ml/min
CARRIER OUT  REAClANT OUT
    o           o
                                            "-MD
       CO> 10O ml/min
       AUXILIARY
          OUT
          Figure 3. Rear view plumbing schematic for MCTS-20 system.
                  Valve A is set for first-stage combustion. O2 venting
                  (push/pull valve out). Port B enters inner combustion
                  tube:  Port C enters outer combustion tube.
                                             H-
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                                       Revision B   4/15/81   8.57-1
                         Method 8.57

                           Sulfides

1.   Scope and Application
    1.1  This method is applicable to the measurement of total
         and dissolved sulfides in drinking, surface and saline
         waters, domestic and industrial wastes.
    1.2  Acid insoluble sulfides are not measured by this method.
         Copper sulfide is the only common sulfide in this class.
    1.3  This method is suitable for the measurement of sulfide
         in concentrations above 1 mg/1
2.   Summary of Method
    2.1  Excess iodine is added to a sample which may or may
         not have been treated with zinc acetate to produce zinc
         sulfide.  The iodine oxidizes the sulfide to sulfur
         under acidic conditions.  The excess iodine is back
         titrated with sodium thiosulfate or phenylarsine oxide.
3.   Comments
    3.1  Reduced sulfur compounds, such as sulfite, thiosulfate
         and hydrosulfite, which decompose in acid may yield erratic
         results.  Also, volatile iodine-consuming substances
         will give high results.
    3.2  Samples must be taken with a minimum of aeration.
         Sulfide may be volitilized by aeration and any ozygen
         inadvertently added to the sample may convert sulfide
         to an immeasurable form.
    3.3  If the sample is not preserved with zinc acetate, the
         analysis must start immediately.  Similarly, the
         measurement of dissolved sulfides must also be commenced
         immediately.
4.   Apparatus: Ordinary laboratory glassware
5.   Reagents
    5.1  Hydrochloric acid, HC1, 6N
    5.2  Standard iodine solution, ,0.0250 N: Dissolve 20 to 25 g
         KI in a little water in a 'liter volumetric flask and add
         3.2 g iodine.  Allow to dissolve.  Dilute to 1 liter and
         standardize against 0.0250 N sodium thiosulfate or
         phenylarsine oxide using a starch  indicator.
    5.3  Phenylarsine oxide 0.0250 N: commercially available.
    5.4  Starch indicator: commercially available.
    5.5  Procedure for standardization  (see Residual Chlorine-
         iodometric titration)
6.   Procedure
    6.1  Unprecipitated sample
         6.1.1  Place a known amount of standard iodine solution
                (5.2) into a 500 ml flask.  The amount should
                be estimated to be  in excess of the amount of
                sulfide expected.
         6.1.2  Add distilled water, if necessary, to bring the
                volume to approximately 20 ml.
         6.1.3  Add 2 ml of 6N HC1  (5.1)
         6.1.4  Pipet 200 ml of sample  into the flask, keeping
                the tip of the pipet below  the surface of the
                sample.
         6.1.5  If the iodine color disappears, add more iodine
                       O.S. Environmental Protection Agency
                       Region V, Library
                       230 South Dearborn Street
                                    ' >0604

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                                        Revision B   4/15/81    8.57-2
                until  the  color remains.  Record the total
                number of  milliliters of the standard iodine  used
                in performing steps 6.1.1 and 6.1.5.
         6.1.6  Titrate with reducing solution (0.0250 N sodium
                thiosulfate  or 0.0250 N phenylarsine oxide
                solution (5.3)} using the starch indicator  (5.4)
                until  the  blue color disappears.   Record the
                number of  milliliters used.
    6.2  Precipitated  samples
         6.2.1  Add  the reagents to the sample in the original
                bottle.  Perform steps 6.1.1, 6.1.3, 6.1.5, and
                6.1.6.
    6.3  Dewatered samples
         6.3.1  Return the glass fibre filter paper which con-
                tains  the  sample to the. original bottle.  Add
                200  ml of  distilled water.  Perform steps* 6.1.1,
                6.1.,3,  6.1.5,  and 6.1.6.
         6.3.2  The  calculations (7) should be based on the
                original sample put throug the filter.
7.  Calculations
    7.1  One ml of 0.0250  N  standard iodine solution (5.2)
         reacts with 0.4 mg  of sulfide present in the titration
         vessel.
    7.2  Use the formula

         mg/1 sulfide  = 400(A-B)/ml sample

         where:
                A=ml of  0.0250 N standard iodine solution (5.2)
                B=ml of  0.0250 N standard reducing sodium
                  thiosulfate or phenylarsine oxide solution  (5.3)

8.  Precision and Accuracy
    8.1  Precision and  accuracy for this method have not been
         determined.
                        U.S. Environmental Protection Agency
                        Region V, Library
                        230 South Dearborn Street
                        Chicago, Illinois  60604
                                            ana. GOVERNMENT PRINTING OFFICE 1911 Ml-DII/MI 1.1

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