EPA
United States Environmental Protection Agency
Office of Water Regulations and Standards
Industrial Technology Division
Office of Water
July 1989
Method 1618: Organo-halide Pesticides,
Organo-phosphorus Pesticides, and
Phenoxy-acid Herbicides by Wide Bore
Capillary Column Gas Chromatography
with Selective Detectors

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Introduction
Method  1618  was   developed  by  the  Industrial  Technology
Division   (ITD)   within   the  United   States   Environmental
Protection Agency's  (USEPA)  Office  of Water Regulations  and
Standards (OURS) to provide  improved precision and accuracy of
analysis of pollutants in aqueous and solid matrices.   The ITD
is responsible  for  development  and promulgation of nationwide
standards  setting   limits  on pollutant  levels   in industrial
discharges.

Method 1618 is a wide bore  capillary column gas chromatography
method  for analysis  of  organo-halide  and  organo-phosphorus
pesticides, phenoxy-acid herbicides  and  herbicide esters,  and
other  compounds  amenable to  extraction  and analysis  by wide
bore capillary column gas chromatography with halogen-specific
and organo-phosphorus detectors.

Questions concerning  the method or  its  application  should be
addressed to:

W. A. Telliard
USEPA
Office of Water Regulations and Standards
401 M Street SU
Washington, DC  20460
202/382-7131

OR

USEPA OURS
Sample Control Center
P.O. Box 1407
Alexandria, Virginia  22313
703/557-5040
Publication date:  July 1989

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Method 1618   Revision  A     July  1989
Organo-halide  Pesticides, Organo-phosphorus  Pesticides, and
Phenoxy-acid  Herbicides  by Wide  Bore Capillary Column
Gas  Chromatography  with Selective Detectors
       1   SCOPE AND APPLICATION

      1.1   This method is designed to meet the survey
           requirements of the USEPA ITD.  The method
           is  used  to determine  the  organo-halide
           pesticides  and poI/chlorinated  biphenyls
           (PCB's), the organo-phosphorus pesticides,
           and   the   phenoxyacid  herbicides   and
           herbicide  esters,  associated  with   the
           Clean  Water Act  (as  amended 1987);  the
           Resource Conservation  and Recovery Act (as
           amended     1986);     the    Comprehensive
           Environmental  Response,  Compensation  and
           Liability Act (as amended 1986);  and other
           compounds   amenable   to   extraction   and
           analysis by automated, wide bore capillary
           column   gas   Chromatography  (GC)   with
           halogen   specific  and  organo-phosphorus
           detectors.

      1.2   The  chemical compounds listed in Tables  1
           •  3  may  be  determined  in  waters,  soils,
           sediments,  and  sludges  by  this  method.
           The  method  is  a consolidation  of  EPA
           Methods  608,  608.1,  614,  615,  617,  622,
           and   701.     For  waters,   the   sample
           extraction  and  concentration  steps  are
           essentially the same as in these methods.
           However,  the  extraction and concentration
           steps  have  been extended  to other sample
           matrices.  The method  should be applicable
           to other pesticides and  herbicides.   The
           quality assurance/quality control require-
           ments  in Section 8.6  of  this method  give
           the  steps   necessary  to  determine  its
           applicability.

      1.3   When this method is applied  to analysis of
           unfamiliar   samples,   compound   identity
           shall   be  supported   by   at  least   one
           additional  qualitative  technique.    This
           method describes analytical  conditions for
           a  second gas  chromatographic  column  that
           can  be used to  confirm measurements  made
           with   the    primary   column.        Gas
           chromatography-mass   spectrometry   (GCMS)
           can  be   used   to confirm  compounds  in
           extracts  produced by  this  method  when
           analyte  levels are sufficient.

      1.4   The  detection limits  of this method are
           usually   dependent   on   the   level   of
        interferences  rather  than  instrumental
        limitations.   The  limits  in  Tables A  •  6
        typify  the  minimum quantities that  can be
        detected with no interferences present.

  1.5    This  method is for  use  by  or  under  the
        supervision of analysts experienced in the
        use of  a  gas  chromatograph  and  in  the
        interpretation  of   gas    chromatographic
        data.    Each  laboratory  that   uses  this
        nethod  must  demonstrate  the ability  to
        generate  acceptable   results  using   the
        procedure in Section 8.2.

    2    SUMMARY OF METHOD

  2.1    Extraction

2.1.1    The percent  solids content of a sample is
        determined.

2.1.2    Aqueous samples containing 1  -  30 percent
        solids  •-  The  sample  is  diluted  to  one
        percent  solids,   if  necessary.     The
        pesticides  and PCB's are extracted from a
        one liter sample  with methylene chloride
        using   continuous   extraction techniques.
        For the herbicides,  the  pH of  the sample
        is raised to 12 -  13 to  hydrolyze esters,
        the sample  is back-extracted   to  remove
        basic and neutral species, the pH is then
        reduced to  less than 2, and  the sample is
        extracted  with   diethyl    ether   using
        separatory  funnel  techniques.

2.1.3    Samples containing greater  than  30 percent
        solids  --  The sample is  extracted  with
        acetonitrile  and  then methylene chloride
        using ultrasonic techniques.   The extract
        is back extracted  with two  percent (w/v)
        sodium  sulfate  in  reagent  water to remove
        water  soluble interferences  and residual
        acetonitrile.   Samples in which phenoxy-
        acid herbicides are to be determined are
        acidified prior to extraction.

  2.2    Concentration  and  cleanup -- For samples
        in which pesticides  are  to be determined,
        each extract  is dried over sodium sulfate,
        concentrated   using   a   Kuderna-Danish
        evaporator,   cleaned   up   (if   necessary)
        using gel permeation Chromatography (GPC),

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      and/or  adsorption  chromatography,  and/or
      solid   phase   extraction,   and  then   re-
      concentrated to one ml.  Sulfur  is  removed
      from  the   extract,   if  required.     For
      samples  in  which  the herbicides are to be
      determined,  each  extract  is  dried  over
      acidified sodium sulfate and  the acids  are
      derivatized  to  form  the  methyl   esters.
      The solution  containing the methyl esters
      is   cleaned   up   (if   necessary)  using
      adsorption chromatography and  concentrated
      to one ml.

2.3   Gas chromatography  --  A one uL aliquot of
      the  extract   is  injected  into  the   gas
      chromatograph  (GC).    The compounds   are
      separated  on  a  wide  bore,  fused silica
      capillary   column.      The   organo-halide
      compounds,   including   the    derivatized
      phenoxy-acid  herbicides,  are  detected by
      an electron  capture,  microcoulometric, or
      electrolytic  conductivity  detector.    The
      phosphorus   containing   compounds    are
      detected   using   a    flame    photometric
      detector.

2.4   Identification of a pollutant  (qualitative
      analysis)  is  performed by  (1) comparing
      the GC  retention  times of the compound on
      two dissimilar columns  with the  respective
      retention times  of  an authentic standard,
      and  (2) comparing  the  concentrations of
      the compound determined on  the primary  and
      confirmatory   GC   systems.      Compound
      identity  is  confirmed  when the retention
      times   and   amounts   agree  within  their
      respective windows.

2.5   Quantitative   analysis   is  performed  by
      using an authentic standard  to produce a
      calibration  factor  or  calibration curve,
      and   using   the   calibration  data   to
      determine the  concentration of  a pollutant
      in the  extract.   The concentration in  the
      sample   is  calculated  using   the  sample
      weight or volume and the extract volume.

2.6   The  quality of  the  analysis  is   assured
      through   reproducible   calibration    and
      testing of the extraction and  GC systems.

  3    CONTAMINATION AND INTERFERENCES

3.1   Solvents,  reagents,  glassware,  and other
      sample   processing   hardware   may  yield
      artifacts    and/or    elevated   baselines
      causing   misinterpretation    of    chroma-
      tograms.     All   materials  used   in   the
      analysis shall be  demonstrated to be free
      from interferences under the  conditions of
      analysis  by  running  method  blanks   as
      described in Section 8.5.

3.2   Glassware  and,  where  possible,   reagents
      are cleaned  by solvent  rinse  and  baking  at
      450  °C for  one  hour minimum in a  muffle
      furnace  or   kiln.   Some  thermally  stable
      materials,   such   as   PCBs,  may  not   be
      eliminated by  this treatment and  thorough
      rinsing with acetone and  pesticide quality
      hexane may be required.

3.3   Specific   selection    of  reagents  and
      purification  of  solvents by distillation
      in all-glass systems may  be required.

3.4   Interference by  phthaiate esters can  pose
      a major problem  in pesticide  analysis  when
      using   the   electron   capture   detector.
      Phthalates    usually   appear    in   the
      chromatogram as  large,  late eluting  peaks.
      Phthalates  may  be  leached  from   common
      flexible plastic  tubing and  other plastic
      materials during the extraction and  clean-
      up   processes.      Cross-contamination   of
      clean  glassware   routinely  occurs   when
      plastics  are  handled  during extraction,
      especially  when  solvent   wetted  surfaces
      are    handled.        Interferences    from
      phthalates   can    best  be  minimized   by
      avoiding  the  use  of  plastics  in  the
      laboratory,  or by  using a microcoulometric
      or electrolytic conductivity  detector.

3.5   The  acid  forms   of  the  herbicides  are
      strong  acids   that  react   readily   with
      alkaline substances and can be lost  during
      analysis.   Glassware and glass  wool  must
      be  acid rinsed  with  dilute hydrochloric
      acid   and  the   sodium  sulfate  must   be
      acidified with sulfuric acid  prior to use.

3.6   Organic acids  and  phenols  cause  the  most
      direct  interference with the herbicides.
      Alkaline    hydrolysis    and    subsequent
      extraction   of   the  basic   solution  can
      remove many  hydrocarbons  and esters  that
      may  interfere with the  herbicide analysis.

3.7   Interferences  coextracted   from  samples
      will  vary   considerably   from  source  to
      source, depending  on  the diversity of the
      site   being   sampled.       The   cleanup
      procedures  given  in  this  Method can  be
      used    to    overcome   many    of   these
      interferences,  but  unique  samples  may
      require additional cleanup to achieve the
      minimum levels given in Tables 4-6.

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      SAFETY
                                                                APPARATUS AND MATERIALS
4.1   The  toxicity  or  carcinogenic!ty  of each
      compound  or  reagent  used  in  this  method
      has   not    been    precisely   determined;
      however,  each chemical  compound should be
      treated   as   a  potential   health  hazard.
      Exposure  to these  compounds   should  be
      reduced to  the  lowest possible level.  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  sheets
      should  also be  made   available  to  all
      personnel   involved  in   these  analyses.
      Additional    information   on    laboratory
      safety can be found in References  1-3.

4.2   The  following  compounds  covered  by this
      method have  been tentatively classified as
      known  or   suspected  human or  mammalian
      carcinogens:  4,4'-DDD,  4,4'-DDT,  the BHCs
      and the  PCBs.  Primary  standards  of these
      compounds shall be  prepared in a hood, and
      a NIOSH/MESA approved toxic gas  respirator
      should  be  worn when  high concentrations
      are handled.

4.3   Diazomethane is a  toxic  carcinogen which
      can  decompose  or  explode  under  certain
      conditions.    Solutions  decompose rapidly
      in the presence of  solid materials such as
      copper   powder,  calcium   chloride,  and
      boiling  chips.    The  following  operations
      may cause explosion:  heating above  90 °C;
      use  of grinding  surfaces  such  as  ground
      glass  joints,  sleeve bearings,  and glass
      stirrers;  and storage near alkali metals.
      Diazomethane shall  be used only  behind a
      safety  screen  in  a  well  ventilated hood
      and  should   be  pipetted  with  mechanical
      devices only.

4.4   Mercury vapor is highly  toxic.   If mercury
      is used for  sulfur  removal, all  operations
      involving mercury  shall  be performed in a
      hood.

4.5   Unknown    samples    may   contain   high
      concentrations     of     volatile    toxic
      compounds.    Sample containers  should be
      opened  in a  hood  and handled with  gloves
      that will prevent exposure.  The oven used
      for  sample   drying  to  determine  percent
      moisture  should be located in  a  hood so
      that vapors  from samples  do  not  create a
      health hazard in the  laboratory.
     5.1   Sampling   equipment    for    discrete   or
           composite sampling.

   5.1.1   Sample bottles and caps

 5.1.1.1   Liquid   samples   (waters,    sludges   and
           similar  materials that  contain less  than
           five  percent  solids)  --  Sample  bottle,
           amber  glass,  1   liter or  1  quart,  with
           screw cap.

 5.1.1.2   Solid  samples (soils, sediments,  sludges,
           filter    cake,    compost,    and    similar
           materials  that   contain  more  than  five
           percent  solids)  --  Sample  bottle,  wide
           mouth, amber  glass, 500 mL minimum.

 5.1.1.3   If   amber  bottles   are  not   available,
           samples shall be  protected from light.

 5.1.1.4   Bottle  caps  --  Threaded  to  fit  sample
           bottles.  Caps shall  be  lined with  Teflon.

 5.1.1.5   Cleaning

5.1.1.5.1   Bottles  are  detergent  water washed,  then
           solvent  rinsed  or baked at 450 °C  for one
           hour minimum  before use.

5.1.1.5.2   Liners  are  detergent water  washed,  then
           reagent  water  and   solvent   rinsed,  and
           baked  at  approx 200  °C   for  one  hour
           minimum prior to  use.

   5.1.2   Compositing   equipment  --    Automatic   or
           manual  compositing   system   incorporating
           glass   containers   cleaned   per   bottle
           cleaning    procedure    above.       Sample
           containers  are kept  at  0  -  4 °C  during
           sampling.    Glass or Teflon tubing  only
           shall  be  used.    If  the sampler  uses  a
           peristaltic   pump,  a  minimum  length  of
           compressible  silicone rubber  tubing may be
           used  in the  pump only.   Before use,  the
           tubing  shall  be  thoroughly  rinsed  with
           methaneI,  followed  by  repeated  rinsings
           with   reagent water   to minimize  sample
           contamination.   An integrating flow meter
           is  used to collect proportional  composite
           samples.

     5.2   Equipment for determining percent moisture

   5.2.1   Oven,   capable    of    being   temperature
           controlled at 110 ±5  *C.

   5.2.2   Dessicator
                                                        5.2.3   Crucibles, porcelain

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  5.2.4   Weighing pans, aluminum

    5.3   Extraction equipment

  5.3.1   Equipment for ultrasonic extraction

5.3.1.1   Sonic disrupter  -- 375  watt  with pulsing
          capability  and 1/2  or 3/4  in.  disrupter
          horn  (Ultrasonics,  Inc.  Model  375C,  or
          equivalent).

5.3.1.2   Sonabox  (or  equivalent),  for  use  with
          disrupter.

  5.3.2   Equipment for liquid-liquid extraction

5.3.2.1   Continuous   liquid-liquid  extractor
          Teflon  or  glass  connecting  joints  and
          stopcocks  without  lubrication,   1.5-2
          liter capacity (Hershberg-Wolf Extractor,
          Cat-Glass, Costa Mesa, California, 1000 or
          2000    ml    continuous    extractor,    or
          equivalent).

5.3.2.2   Round-bottom  flask,  500 ml,  with heating
          mantle.

5.3.2.3   Condenser, Graham, to fit extractor.

5.3.2.4   pH    meter,    with    combination   glass
          electrode.

5.3.2.5   pH  paper,  wide range  (Hydrion Papers,  or
          equivalent).

  5.3.3   Separatory funnels  --  250,  500,  1000, and
          2000 ml, with Teflon stopcocks.

  5.3.4   Filtration apparatus

5.3.4.1   Glass powder funnels -- 125 - 250 ml

5.3.4.2   Filter  paper  for  above  (Whatman 41,  or
          equivalent)

  5.3.5   Beakers

5.3.5.1   1.5 - 2 liter, calibrated to one liter

5.3.5.2   400 - 500 mL

  5.3.6   Spatulas -- Stainless steel or Teflon

  5.3.7   Drying column -- 400 mm x 15 to 20 mm i.d.
          Pyrex chromatographic column equipped with
          coarse glass frit or glass wool plug.

5.3.7.1   Pyrex glass  wool   --  Solvent  extracted or
          baked at 450 °C for one hour minimum.

    5.4   Evaporation/concentration apparatus
   5.4.1

 5.4.1.1




 5.4.1.2
 5.4.1.3


 5.4.1.4


 5.4.1.5

5.4.1.5.1



5.4.1.5.2


   5.4.2



   5.4.3




   5.4.4



     5.5

   5.5.1

   5.5.2

     5.6

   5.6.1




 5.6.1.1
          Kuderna-Danish (K-D) apparatus

          Evaporation  flask  --  500  ml  (Kontes  K-
          570001-0500,  or  equivalent),  attached  to
          concentrator  tube  with springs (Kontes  K-
          662750-0012).

          Concentrator  tube  --  10  ml,  graduated
          (Kontes K-570050-1025, or equivalent)  with
          calibration   verified.      Ground  glass
          stopper  (size  19/22  joint)  is   used  to
          prevent evaporation of extracts.

          Snyder column --  Three ball macro  (Kontes
          K-503000-0232, or equivalent).

          Snyder column -- Two ball micro (Kontes  K-
          469002-0219, or equivalent).

          Boiling chips

          Glass or  silicon carbide  --  Approx 10/40
          mesh,  extracted  with  methylene   chloride
          and baked at 450 "C for one hr minimum.
          Teflon   (optional)
          methylene chloride.
Extracted   with
          Water bath -- Heated, with concentric  ring
          cover, capable  of  temperature control  (±2
          °C), installed  in a fume hood.

          Nitrogen  evaporation  device  --   Equipped
          with heated bath that can be  maintained at
          35   -   40   °C   (N-Evap,    Organomation
          Associates, Inc., or equivalent).

          Sample vials -- Amber glass,  1 - 5 ml  with
          Teflon-lined screw or crimp cap, to fit GC
          autosampler.

          Balances

          Analytical -- Capable of weighing 0.1 rug.

          Top loading --  Capable of weighing 10 mg.

          Apparatus for sample cleanup.

          Automated  gel   permeation   chromatograph
          (Analytical    Biochemical    Labs,     Inc,
          Columbia, MO, Model  GPC Autoprep 1002,  or
          equivalent).

          Column  --  600  -  700  mn x  25  mm  i.d.,
          packed with  70 g of  SX-3 Bio-beads  (Bio-
          Rad   Laboratories,   Richmond,    CA,    or
          equivalent).

5.6.1.2   Syringe, 10 ml, with Luer fitting.

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5.6.1.3   Syringe  filter  holder,   stainless  steel,
          and glass  fiber  or Teflon filters (Gelman
          Acrodisc-CR, 1-5 micron, or equivalent).

5.6.1.4   UV  detectors  --  254-mu, preparative  or
          semi-prep flow cell:  (Isco, Inc., Type 6;
          Schmadzu, 5  mm path length; Beckman-Altex
          152U,  8  uL  micro-prep   flow  cell,   2  mm
          path; Pharmacia  UV-1,  3  mm flow cell; LDC
          Milton-Roy   UV-3,   monitor   #1203;   or
          equivalent).

  5.6.2   Vacuum  system  and  cartridges  for   solid
          phase extraction (SPE)

5.6.2.1   Vacuum system  --  Capable of achieving 0.1
          bar  (house  vacuum, vacuum pump,  or  water
          aspirator), with vacuum gauge.

5.6.2.2   VacElute       Manifold        (Analytichem
          International, or  equivalent).

5.6.2.3   Vacuum  trap --  Hade  from 500 ml sidearm
          flask  fitted   with  single  hole  rubber
          stopper and glass  tubing.

5.6.2.4   Rack  for  holding  50  ml   volumetric flasks
          in the manifold.

5.6.2.5   Column  --  Mega Bond  Elut,  Non-polar, C18
          Octadecyl,   10    g/60    ml    (Analytichem
          International   Cat.   No.   607H060,   or
          equivalent).

  5.6.3   Chromatographic  column  -- 400 mm  x  22 mm
          i.d., with Teflon  stopcock and coarse frit
          (Kontes K-42054, or equivalent).

  5.6.4   Sulfur removal  tubes  --  40 • 50 mL bottle
          or test tube with  Teflon  lined screw cap.

    5.7   Centrifuge apparatus

  5.7.1   Centrifuge  --  Capable of rotating  500 ml
          centrifuge  bottles  or  15  mL centrifuge
          tubes at 5,000 rpm minimum

  5.7.2   Centrifuge  bottles -- 500 ml,  with  screw
          caps, to fit centrifuge

  5.7.3   Centrifuge  tubes  -- 12-15 mL,  with  screw
          caps, to fit centrifuge

  5.7.4   Funnel, Buchner, 15 cm.

5.7.4.1   Flask, filter, for use with Buchner funnel

5.7.4.2   Filter  paper,  15  cm  (Whatman  #41,  or
          equivalent).

    5.8   Oerivatization  apparatus  --  Diazald kit
           with clear  seal  joints  for  generation of
           diazomethane    (Aldrich   Chemical    Co.
           210,025-0, or equivalent).

     5.9   Miscellaneous glassware

   5.9.1   Pipettes,  glass,  volumetric,  1.00,  5.00,
           and 10.0 mL

   5.9.2   Syringes,  glass,  with  Luerlok  tip,  0.1,
           1.0 and 5.0 mL.  Needles for syringes, two
           inch, 22 gauge.

   5.9.3   Volumetric flasks, 10.0, 25.0, and 50.0 mL

   5.9.4   Scintillation  vials,  glass,  20 -  50 mL,
           with Teflon-lined screw caps.

    5.10   Gas  chromatographs  --  Two GC's  shall  be
           employed.   Both  shall  have  split less or
           on-column simultaneous automated  injection
           into  separate  capillary  columns with  a
           halide    specific    detector   or    flame
           photometric detector at  the end  of each
           column,     temperature     program    with
           isothermal  holds,  data  system  capable of
           recording  simultaneous  signals  from the
           two detectors,  and  shall  meet  all of the
           performance specifications in Section 14.
  5.10.1
5.10.1.1
5.10.1.2
5.10.1.3
  5.10.2
GC columns  --  Bonded phase  fused silica
capillary

Primary for organo-halide  compounds -- 30
±3  m  x  0.5   ±0.05   mm  i.d.  DB-608,  or
equivalent).

Primary for organo-phosphate  compounds --
DB-1 (or  equivalent)  with  same dimensions
as column for organo-halide compounds.

Confirmatory  --  DB-1701,  or  equivalent,
with same dimensions as primary column.

Data system -- Shall collect and record GC
data,  store  GC runs  on magnetic  disk or
tape, process GC data, compute peak areas,
store calibration data including retention
times and calibration factors, identify GC
peaks  through  retention  times,  compute
concentrations, and generate reports.
5.10.2.1   Data  acquisition  --  GC  data  shall  be
           collected   continuously   throughout   the
           analysis  and  stored  on  a  mass  storage
           device.

5.10.2.2   Calibration factors and calibration curves
           -- The data system shall be used to record
           and maintain lists of calibration factors,
           and    multi-point    calibration    curves

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           (Section  7).    Computations  of  relative
           standard    deviation    (coefficient    of
           variation)    are    used    for    testing
           calibration   linearity.     Statistics  on
           initial (Section 8.2) and ongoing (Section
           14.6)  performance shall  be  computed and
           maintained.

5.10.2.3   Data  processing  -- The  data system shall
           be  used  to search,  locate,  identify, and
           quantify the compounds of interest in each
           GC  analysis.   Software  routines  shall be
           employed  to compute  and record retention
           times  and  peak  areas.     Displays  of
           chromatograms and  library comparisons are
           required to verify results.

  5.10.3   Detectors

5.10.3.1   Halide  specific  --   Electron capture  or
           electrolytic  conductivity (Hicoulometric,
           Hall,  O.I.,  or  equivalent),  capable  of
           detecting   8   pg  of   aldrin  under  the
           analysis conditions given in Table 4.

5.10.3.2   Flame photometric  --  Capable of detecting
           11  pg  of  ma I athi on under   the  analysis
           conditions given in Table 5.

  5.10.4   Chromatographs may be configured in one of
           two  ways:    (1)    Two  halide  specific
           detectors  (HSD's) in  one  GC; two  flame
           photometric   detectors   (FPD's)   in  the
           other.     With   this  configuration,  the
           primary   and  confirmatory   columns  and
           detectors  are in  the  same GC. (2) One HSD
           and  one   FPD  in  each  GC.    With  this
           configuration,  the  primary  columns  and
           detectors  are in one GC, the confirmatory
           columns and detectors are in the other.

       6   REAGENTS AND STANDARDS

     6.1   Sample preservation  --  Sodium thiosulfate
           (ACS), granular.

     6.2   pH adjustment

   6.2.1   Sodium hydroxide -- Reagent grade.

 6.2.1.1   Concentrated solution (10N)  -- Dissolve 40
           g NaOH in  100 ml reagent water.

 6.2.1.2   Dilute  solution  (0.1H)  --  Dissolve 4  g
           NaOH in 1  liter of reagent water.

   6.2.2   Sulfuric acid (1 + 1) -- Reagent grade, 6N
           in  reagent  water.  Slowly add 50 ml H.SO,
           (specific  gravity  1.84) to  50 ml reagent
           water.
6.2.3   Potassium  hydroxide  ••  37  w/v  percent.
        Dissolve 37 g KOH  in 100 mL  reagent water.

  6.3   Solution drying and back extraction

6.3.1   Sodium  sulfate,  reagent  grade,  granular
        anhydrous  (Baker  3375,   or  equivalent),
        rinsed  with  methylene chloride  (20 mL/g),
        baked  at  450  °C  for  one  hour  minimum,
        cooled  in a  dessicator,  and  stored  in  a
        pre-cleaned  glass bottle  with  screw  cap
        which prevents moisture from entering.

6.3.2   Acidified  sodium  sulfate  --  Add  0.5  mL
        H.SO,  and  30  mL  ethyl  ether  to  100  g
        sodium  sulfate.    Mix  thoroughly.    Allow
        the   ether   to   evaporate   completely.
        Transfer  the  mixture  to a clean container
        and store at  110 ±5 °C.

6.3.3   Sodium  sulfate  solution  --  Two percent
        (w/v) in reagent water, pH adjusted to  8.5
        - 9.0 with KOH or  H2S04.

6.3.4   Sodium  sulfate,  reagent  grade,  powdered
        anhydrous  (Baker  73898,   or  equivalent),
        rinsed  with  methylene chloride  (20 mL/g),
        baked  at  450  °C  for  one  hour  minimum,
        cooled  in a  dessicator,  and  stored  in  a
        pre-cleaned  glass bottle  with  screw  cap
        which   prevents  moisture  from  entering.
        NOTE:   The powdered sodium sulfate is used
        only  in ultrasonic extraction of samples
        containing 30 percent  solids  or  greater,
        and  not  for drying  of  sample  extracts.
        Use  of  granular  sodium  sulfate during
        ultrasonic  extraction  may  lead  to  poor
        recovery of analytes.

  6.4   Solvents  --  Methylene  chloride,  hexane,
        ethyl    ether,    acetone,    acetonitrile,
        isooctane,    and   methanol;     pesticide
        quality;  lot  certified  to  be  free   of
        interferences.

6.4.1   Ethyl ether  must  be  shown  to be free  of
        peroxides before  it  is used,  as  indicated
        by  EM   Laboratories   Quant   Test  Strips
        (Scientific     Products    P1126-8,      or
        equivalent).   Procedures  recommended  for
        removal of peroxides are provided  with  the
        test  strips.   After  cleanup,  20 mL   of
        ethyl alcohol is  added to  each liter  of
        ether as a preservative.

  6.5   GPC   calibration  solution   --   Solution
        containing 300  mg/mL  corn  oil,  15  mg/mL
        bis(2-ethylhexyl)  phthalate,   1.4  mg/mL
        pentachlorophenol, 0.1 mg/mL perylene,  and
        0.5 mg/mL sulfur

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    6.6   Sample cleanup

  6.6.1   Florisil   •-  PR   grade,   60/100  mesh,
          activated  at 650 - 700  °C,  stored in the
          dark  in  glass container with Teflon-lined
          screw  cap.   Activate  at 130  °C  for  16
          hours  minimum immediately  prior  to use.
          Alternatively,  500  mg   cartridges  (J.T.
          Baker, or  equivalent) may be used.

  6.6.2   Solid phase  extraction

6.6.2.1   SPE   cartridge   calibration   solution  --
          2,4,6-trichlorophenol,    0.1    ug/mL   in
          acetone.

6.6.2.2   SPE    elution   solvent    -•    Methylene
          chloride:acetonitrile:hexane (50:3:47).

  6.6.3   Alumina, neutral,  Brockman  Activity I,  80
          -  200 mesh  (Fisher  Scientific Certified,
          or equivalent).   Heat  for 16 hours at 400
          -  450   °C.     Seal   and  cool  to  room
          temperature.   Add  7 percent  w/w  reagent
          water  and  mix for  10  -  12 hours.   Keep
          bottle tightly sealed.

  6.6.4   Silicic acid, 100 mesh

  6.6.5   Sulfur   removal    --    Mercury    (triple
          distilled),  copper  powder   (bright,  non-
          oxidized),   or  TEA  sodium   sulfite.    If
          mercury  is   used,  observe  the   handling
          precautions  in Section 4.

    6.7   Derivatization   --   Diazald  reagent   [N-
          methyl-(N-nitroso-p-toluene  sulfanamide)],
          fresh  and high  purity  (Aldrich   Chemical
          Co.)

    6.8   Reference  matrices

  6.8.1   Reagent  water   --   Water  in  which  the
          compounds  of  interest  and   interfering
          compounds  are not detected by this method.

  6.8.2   High  solids  reference matrix  -- Playground
          sand  or   similar  material   in which  the
          compounds  of  interest  and   interfering
          compounds  are not detected by  this method.
          May   be   prepared   by   extraction  with
          methylene  chloride and/or baking  at 450 °C
          for 4 hours  minimum.

    6.9   Standard   solutions    --    Purchased   as
          solutions  or mixtures  with certification
          to   their   purity,    concentration,   and
          authenticity,  or prepared  from  materials
          of  known  purity  and   composition.    If
          compound purity  is  96 percent or greater,
          the weight may be used  without correction
         to   compute   the  concentration   of  the
         standard.  When  not  being used, standards
         are stored in the dark at -20 to -10 °C in
         screw-capped vials with Teflon-lined lids.
         A mark  is  placed on  the vial at the level
         of   the   solution    so   that   solvent
         evaporation  loss can  be  detected.    The
         vials  are  brought  to  room   temperature
         prior   to   use.     Any   precipitate   is
         redissolved   and  solvent   is   added  if
         solvent loss has occurred.

  6.10   Preparation of  stock solutions -- Prepare
         in isooctane per the steps below.  Observe
         the safety precautions in Section 4.

6.10.1   Dissolve an  appropriate amount of assayed
         reference  material   in  solvent.     For
         example, weigh   10 mg  aldrin  in a  10 ml
         ground  glass  stoppered volumetric  flask
         and  fill  to  the  mark  with   isooctane.
         After the  aldrin is  completely dissolved,
         transfer the solution to a 15 ml vial  with
         Teflon-lined cap.

6.10.2   Stock standard solutions should be checked
         for  signs  of  degradation  prior  to  the
         preparation of  calibration or  performance
         test  standards.   Quality  control  check
         samples that  can be  used to determine the
         accuracy   of   calibration  standards  are
         available  from  the  USEPA,  Environmental
         Monitoring    and    Support     Laboratory,
         Cincinnati, Ohio 45268.

6.10.3   Stock standard solutions shall  be replaced
         after six  months,  or sooner if comparison
         with   quality   control   check  standards
         indicates a change in concentration.

  6.11   Secondary   mixtures    --    Using   stock
         solutions  (Section 6.10), prepare mixtures
         at the  levels required for calibration and
         calibration verification (Sections 7.3 and
         14.5),  for initial  and ongoing precision
         and  recovery  (Sections  8.2 and 14.6), and
         for   spiking   into   the   sample   matrix
         (Section 8.4).

  6.12   Surrogate spiking solutions

6.12.1   Chlorinated pesticides  --  Prepare dibutyl
         chlorendate at  a concentration of 2 ug/mL
         in acetone.

6.12.2   Phosphorus    containing   pesticides
         Prepare  tributyl phosphate  and triphenyl
         phosphate  each  at  a  concentration of   2
         ug/ml in acetone.

-------
 6.12.3   Phenoxyacid  herbicides  --  Prepare  2,4-
          dichlorophenyI acetic     acid     at     a
          concentration of 2 ug/mL in acetone.

   6.13   DDT and  endrin decomposition  solution  --
          Prepare a solution  containing  endrin at a
          concentration  of  1  ug/mL  and DDT at  a
          concentration of 2 ug/mL.

   6.14   Stability  of  solutions  --  All  standard
          solutions (Sections  6.9 - 6.13)  shall  be
          analyzed  within 48  hours of  preparation
          and  on  a  monthly   basis  thereafter  for
          signs  of  degradation.    Standards  will
          remain acceptable if the peak area  remains
          within ±15 percent of the area obtained in
          the initial analysis of the standard.

      7   SETUP AND CALIBRATION

    7.1   Configure the GC systems in one of  the two
          ways given in Section 5.10.4 and establish
          the operating conditions in Tables 4-5.

    7.2   Attainment of Method Detection Limit (MDL)
          and DDT/Endrin  decomposition requirements
          --  Determine   that  each  column/detector
          system meets the MDL's  (Tables  4-6) and
          that the organohalide systems meet  the DDT
          and  Endrin  decomposition  test  (Section
          14.4).

    7.3   Calibration

  7.3.1   Calibration     solutions     --      Prepare
          calibration  standards  at  a  minimum  of
          three   concentration   levels   for  each
          compound of  interest  by adding volumes  of
          one   or   more   stock   standards   to   a
          volumetric  flask  and  diluting to  volume
          with  hexane  or  isooctane.    The   lowest
          concentration  solution  should  be  at   a
          concentration near,  but above, the MDL's
          (Tables 4-6).  The highest concentration
          solution  should be  near,  but  below,  the
          maximum  linear  range  of  the  analytical
          system.  The other concentration(s) should
          be ideally equally spaced on a logarithmic
          scale  between  the   lowest   and    highest
          concentration   solutions.      The   ratio
          between    the    highest    and     lowest
          concentration  should be  100 or  greater.
          Note:    the  GC  retention  time   overlap
          between   analytes   requires   that   the
          compounds   separated   and  analyzed   as
          groups.     Divide   the  single  component
          analytes  into  three  or  four  calibration
          groups  each  for  the  organo-halide  and
          organo-phosphorus    compounds   with   an
          approximately equal number of analytes per
          group.   The compound  pairs  specified for
          GC  resolution  (Section 14.3)  shall  be in
          the  same group.    PCB 1254  or  1260 and
          Toxaphene are calibrated separately.

  7.3.2   Inject the  calibration solutions into the
          GC  column/detector pairs  appropriate for
          the  mixture,  beginning  with   the   lowest
          level  mixture  and   proceeding  to  the
          highest.   For each compound,  compute and
          store, as a function  of the concentration
          injected, the retention time and peak area
          on  each  column/detector   system (primary
          and confirmatory).  For the multicomponent
          analytes  (PCB's,  toxaphene),   store  the
          retention time and peak area for the five
          largest peaks.

  7.3.3   Retention time -- The polar nature of some
          analytes  causes  the  retention time  to
          decrease    as    the   quantity   injected
          increases.  To compensate  this effect, the
          retention time for compound identification
          is correlated with the analyte level.

7.3.3.1   If  the difference  between the maximum and
          minimum  retention  times  for  any compound
          is   less   than  five   seconds  over  the
          calibration  range,  the retention time for
          that  compound  can be  considered constant
          and an average retention  time may be used
          for compound identification.

7.3.3.2   Retention    time     calibration    curve
          (retention  time  vs  amount)  --  If  the
          retention  time  for  a  compound  in  the
          lowest  level standard  is more  than five
          seconds  greater  than  the  retention time
          for  the  compound  in  the highest   level
          standard,  a   retention  time  calibration
          curve shall  be used for identification of
          that compound.

  7.3.4   Calibration  factor   (ratio   of  area  to
          amount injected)

7.3.4.1   Compute   the  coefficient   of  variation
          (relative   standard  deviation)  of  the
          calibration  factor over   the  calibration
          range   for    each   compound   on   each
          column/detector system.

7.3.4.2   Linearity -- If the calibration  factor for
          any compound is constant (Cv < 20 percent)
          over  the  calibration  range,   an  average
          calibration  factor nay be used for that
          compound;    otherwise,    the    complete
          calibration  curve  (area   vs   amount)  for
          that compound shall be used.
8

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    7.4   Combined  OC   standards   --  To  preclude
          periodic analysis of all of the  individual
          calibration  groups  of  compounds (Section
          7.3.1), the GC systems are  calibrated with
          combined solutions  as  a final  step.   Not
          all  of the  compounds  in  these standards
          will be  separated by the  GC  columns used
          in  this  method.    Retention   times  and
          calibration  factors  are verified  for the
          compounds    that   are    resolved,    and
          calibration  factors  are obtained  for the
          unresolved  peaks.     These  combined  OC
          standards are prepared at the level of the
          mid-range calibration standard (7.3.1).

  7.4.1   Analyze the combined OC standards on their
          respective column/detector pairs.

7.4.1.1   For those compounds that exhibit a single,
          resolved GC peak, the retention  time shall
          be within ±5 seconds of the retention time
          of   the   peak   in   the   medium    level
          calibration standard  (Section 7.3.1), and
          the  calibration  factor using the primary
          column shall be  within ±20 percent of the
          calibration  factor  in  the  medium   level
          standard (Section 7.3.4).

7.4.1.2   For  the  peaks  containing   two or  more
          compounds, compute and store  the retention
          times  at  the peak maxima  on  both columns
          (primary   and    confirmatory),   and  also
          compute and  store the calibration factors
          on  both  columns.   These  results  will be
          used for calibration verification (Section
          14.2  and  14.5)  and  for  precision  and
          recovery studies (Section 14.6).

    7.5   Florisil   calibration   --   The  cleanup
          procedure  in Section 11  utilizes florisil
          colim  chromatography.     Florisil  from
          different  batches  or sources may  vary in
          adsorptive  capacity.   To  standardize the
          amount of  florisil  that is used,  the use
          of  the  lauric  acid value (Reference 4) is
          suggested.     The   referenced  procedure
          determines  the adsorption  of lauric acid
          (in   mg/g   of   florisil)   from   hexane
          solution.   The  amount  of  florisil  to be
          used  for  each  column  is calculated  by
          dividing 110 by  this ratio  and multiplying
          by 20 g.

      8   QUALITY ASSURANCE/QUALITY CONTROL

    8.1   Each  laboratory  that uses  this method is
          required   to   operate   a  formal  quality
          assurance  program  (Reference   5).    The
          minimum   requirements   of   this  program
          consist  of  en  initial  demonstration  of
        laboratory capability, an ongoing analysis
        of  standards   and   blanks   as  tests  of
        continued  performance,  and  analysis  of
        matrix  spike and  matrix  spike duplicate
        (HS/HSO)  samples to assess  accuracy and
        precision.     Laboratory  performance  is
        compared    to    established    performance
        criteria  to determine  if  the  results of
        analyses     meet      the      performance
        characteristics  of   the  method.    If the
        method  is  to  be   applied   routinely  to
        samples containing  high solids with very
        little  moisture  (e.g.,  soils, compost),
        the high  solids reference matrix (Section
        6.8.2)  is  substituted  for  the   reagent
        water  (Section  6.8.1)  in  all  performance
        tests, and the high  solids method (Section
        10) is used for these tests.

8.1.1   The   analyst   shall   make   an   initial
        demonstration of  the  ability to generate
        acceptable  accuracy  and  precision  with
        this method.   This  ability is  established
        as described in Section 8.2.

8.1.2   The  analyst is  permitted  to modify this
        method to improve separations or lower the
        costs   of   measurements,   provided  all
        performance  requirements are met.   Each
        time a modification  is made  to the method
        or  a  cleanup  procedure  is  added,  the
        analyst   is   required   to   repeat   the
        procedure  in Section  8.2  to  demonstrate
        method performance.

8.1.3   The  laboratory  shall   spike   all   samples
        with  at   least  one   surrogate compound to
        monitor method  performance.   This test is
        described in Section 8.3.  When results of
        these  spikes   indicate  atypical  method
        performance  for samples, the samples are
        diluted to bring method  performance within
        acceptable  limits (Section 17).

8.1.4   The laboratory shall, on an ongoing basis,
        demonstrate       through       calibration
        verification  and   the  analysis  of  the
        combined  OC standard  (Section  7.4)  that
        the analysis system  is in control.   These
        procedures are described in Sections  14.1,
        14.5, and 14.6.

8.1.5   The  laboratory  shall  maintain  records to
        define  the  quality  of   data  that  is
        generated.      Development    of  accuracy
        statements is described  in Section 8.4.

8.1.6   Analyses   of   blanks   are   required  to
        demonstrate  freedom  from  contamination.

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          The  procedures  and criteria  for analysis
          of a blank are described in Section 8.5.

  8.1.7   Other analytes  may be determined  by this
          method.  The  procedure  for establishing a
          preliminary quality control  limit  for  a
          new analyte is given in Section 8.6.

    8.2   Initial  precision  and   accuracy   --  To
          establish   the    ability   to   generate
          acceptable  precision  and  accuracy,  the
          analyst   shall    perform  the   following
          operations.

  8.2.1   For  analysis  of  samples  containing  low
          solids    (aqueous   samples),    extract,
          concentrate,  and  analyze one set  of four
          one-liter aliquots of reagent water spiked
          with  the  combined OC   standard  (Section
          7.4) according to the procedure in Section
          10.      Alternatively,    sets   of   four
          replicates  of the  individual  calibration
          groups  (Section 7.3) may be  used.   For
          samples  containing high  solids,  sets  of
          four 30  gram  aliquots  of  the  high  solids
          reference matrix are used.

  8.2.2   Using results  of the set of four analyses,
          compute  the average percent  recovery (X)
          and  the  coefficient of  variation  (Cv)  of
          percent recovery (s) for each compound.

  8.2.3   For  each  compound, compare  s and  X with
          the   corresponding  limits   for   initial
          precision  and accuracy  in  Tables  7-9.
          For coeluting compounds,  use the coeluted
          compound   with    the    least   restrictive
          specification    (largest   Cv  and   widest
          range).  If s  and X for all compounds meet
          the     acceptance    criteria,     system
          performance is  acceptable  and  analysis  of
          blanks  and  samples   may  begin.     If,
          however,  any  individual  s  exceeds  the
          precision  limit or  any  individual  X falls
          outside  the  range for  accuracy,  system
          performance   is   unacceptable   for   that
          compound.    In  this  case,   correct  the
          problem and repeat the  test.

    8.3   The  laboratory   shall  spike  all  samples
          with  at  least  one surrogate compound  to
          assess  method performance  on the  sample
          matrix.

  8.3.1   Analyze  each   sample   according   to  the
          method beginning in Section 10.

  8.3.2   Compute  the percent recovery  (P)   of  the
          surrogate compound(s).
  8.3.3   The  recovery  of  the  surrogate  compound
          shall  be within the  limits of  40 to  120
          percent.  If the recovery of any surrogate
          falls  outside  of  these   limits,  method
          performance   is  unacceptable   for   that
          sample,  and  the sample is complex.   Water
          samples  are  diluted,  and  smaller  amounts
          of   soils,   sludges,   and  sediments   are
          reanalyzed per  Section  17.

    8.4   Method   accuracy   and  precision   --   The
          laboratory shall  spike  (matrix  spike)  at
          least  ten percent  of the  samples from  a
          given   site   type    (e.g.,   influent   to
          treatment,   treated   effluent,    produced
          water,   river   sediment)    in    duplicate
          (MS/MSD).  If only  one  sample from a  given
          site  type is   analyzed,  two  aliquots  of
          that sample shall be  spiked.

  8.4.1   The  concentration   of  the  analytes spiked
          into  the MS/MSD  shall  be  determined  as
          follows.

8.4.1.1   If,  as   in   compliance  monitoring,    the
          concentration of a  specific analyte in the
          sample   is   being   checked  against   a
          regulatory   concentration    limit,    the
          spiking  level shall be  at that limit  or at
          one   to  five   times  higher   than    the
          background   concentration   determined   in
          Section  8.4.2,  whichever concentration  is
          larger.

8.4.1.2   If the  concentration  of an analyte in the
          sample   is  not   being  checked   against  a
          limit specific  to that  analyte,  the matrix
          spike shall be  at the concentration of the
          combined QC  standard (Section 7.4) or  at
          one   to  five   times  higher   than    the
          background    concentration,      whichever
          concentration is larger.

8.4.1.3   If  it   is  impractical   to  determine  the
          background  concentration  before   spiking
          (e.g.,   maximum holding  times   will   be
          exceeded), the  matrix spike concentration
          shall  be the   regulatory  concentration
          limit,  if any;  otherwise,  the  larger  of
          either five  times  the expected  background
          concentration or  at  the concentration  of
          the combined OC standard (Section 7.4).

  8.4.2   Analyze  one  sample  aliquot  to   determine
          the  background  concentration (B)  of   each
          analyte.  If necessary, prepare  a  standard
          solution appropriate  to produce  a  level  in
          the   sample   one   to   five  times    the
          background   concentration.     Spike    two
          additional   sample   aliquots    with    the
10

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8.4.3
standard  solution  and  analyze  them  to
determine the concentrations after spiking
(A)  of  each   analyte.     Calculate  the
percent  recovery  (P)  of  each  analyte  in
each aliquot:

P = 100 (A - B) / T

where T is the true value of the spike.

Compare  the  percent  recovery  for  each
analyte   with    the   corresponding   OC
acceptance criteria  in Tables 7-9.   If
any analyte  fails the acceptance criteria
for recovery,  the  sample  is  complex  and
must be diluted and reanalyzed per Section
17.

Determine  the  precision  of  the  MS/MSD
analyses  by  comparing   the  recoveries
calculated in 8.4.2 of each spiked analyte
in both  aliquots.   Calculate the relative
percent difference (RPD) of the recoveries
(not  the concentrations)  of  each analyte
with MS/MSD aliquots as:
        RPD
                      P   •  P
                       MS    MSP
                    
-------
          of  the analytes  of  interest into  samples
          may be  required  to  assess  the  precision
          and accuracy  of  the  sampling  and  sample
          transporting  techniques.

     9    SAMPLE    COLLECTION,    PRESERVATION,    AND
          HANDLING

   9.1    Collect   samples   in   glass   containers
          following conventional sampling  practices
          (Reference  6),   except  that   the   bottle
          shall  not be prerinsed with sample before
          collection.    Aqueous  samples  which  flow
          freely   are   collected  in   refrigerated
          bottles     using    automatic    sampling
          equipment.  Solid samples are  collected as
          grab samples  using wide nouth jars.

   9.2    Maintain  samples  at 0 - 4 °C from the time
          of  collection until  extraction.   If  the
          samples  will  not be  extracted within  72
          hours  of  collection,  adjust the  sample to
          a pH of 5.0  to 9.0 using sodium hydroxide
          or  suIfuric  acid solution.    Record  the
          volume  of acid or base used.   If residual
          chlorine  is  present   in  aqueous samples,
          add 80 mg sodium thiosulfate per liter of
          water.   EPA Methods 330.4 and 330.5 may be
          used   to    measure    residual   chlorine
          (Reference 7).

   9.3    Begin  sample extraction  within  seven days
          of  collection,  and  analyze all extracts
          within 40 days of extraction.

     10    SAMPLE  EXTRACTION AND CONCENTRATION

          Figure  1  outlines   the extraction  and
          concentration steps.   Samples  containing
          one percent  solids or less are extracted
          directly  using   continuous   liquid/liquid
          extraction   techniques  (Section  10.2.1).
          Samples containing one through  30  percent
          solids  are   diluted   to  the  one  percent
          level  with reagent water (Section  10.2.2)
          and     extracted     using      continuous
          liquid/liquid    extraction     techniques.
          Samples containing greater  than 30  percent
          solids  are  extracted  using   ultrasonic
          techniques    (Section    10.2.5).       For
          determination    of     the     phenoxy-acid
          herbicides,   a separate  sample  aliquot is
          extracted,  derivatized,  and  cleaned  up.
          The derivatized  extract may be  combined
          with the  organo-chlorine extract  for  gas
          chromatography.

   10.1    Determination of percent  solids
  10.1.1    Weigh  5  -  10 g  of  sample into  a tared
           beaker.    Record   the  weight  to  three
           significant figures.

  10.1.2    Dry overnight (12 hours minimum) at 110 *5
           °C, and cool in a dessicator.
  10.1.3   Determine percent solids as follows:

                        weight of dry sample
10.2.2.2
10.2.2.3
           X solids  =
                        weight of wet sample
                                     x  100
    10.2   Preparation of samples for extraction

  10.2.1   Samples  containing  one percent  solids or
           less  --  Pesticides  and  PCB  samples  are
           extracted   directly    using   continuous
           liquid/liquid    extraction    techniques;
           herbicides are  extracted  using separatory
           funnel techniques.

10.2.1.1   Shake  the  samples   to  ensure   thorough
           mixing  and measure  1.00  ±0.01   liter of
           each  sample  into a  separate  clean  1.5  -
           2.0  liter  beaker.   Measure a  separate one
           liter aliquot for each sample  to be  tested
           for the phenoxy-acid herbicides.

10.2.1.2   Spike  0.5  mL  of  the surrogate  spiking
           solution  (Section 6.12)  into  the  sample
           aliquot.  For the phenoxy-acid herbicides,
           spike  0.5  mL  of the  herbicide surrogate
           spiking   solution   into    the  herbicide
           aliquot.  Proceed to preparation of  the OC
           aliquots  for  low solids  samples  (Section
           10.2.3).

  10.2.2   Samples  containing   one   to  30  percent
           solids   --  Samples  are  diluted  to  one
           percent solids and then extracted.

10.2.2.1   Mix sample thoroughly.
Using the percent  solids found in 10.1.3,
determine the weight of  sample required to
produce  one  liter of  solution containing
one percent solids as follows:
           sample weight
                  1000 grams
                   X solids
Place  the  weight of  sample as determined
in  10.2.2.2 in  a clean  1.5  -  2.0  liter
beaker.   For the phenoxy-acid herbicides,
place  a   separate   aliquot  in  a   clean
beaker.  Discard all sticks, rocks,  leaves
and   other  foreign  material   prior  to
weighing.
12

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10.2.2.4   Bring the  sample aliquot(s) to  100  - 200
           mL volune with reagent water.

10.2.2.5   Spike 0.5  ml  of  the appropriate surrogate
           spiking solution  (Section  6.12)  into each
           sample aliquot.

10.2.2.6   Using  a clean metal  spatula,   break any
           solid portions of  the sample  into   small
           pieces.

10.2.2.7   Place the  3/4 in.  horn  on the  ultrasonic
           probe approx  1/2  in.  below the surface of
           each  sample   aliquot   and  pulse  at  50
           percent for  three minutes  at  full power.
           If  necessary,  remove  the  probe  from the
           solution and  break  any large pieces  using
           the  metal  spatula  or  a stirring  rod and
           repeat  the sonication.   Clean  the   probe
           with   methylene  chloride:acetone   (1:1)
           between   samples   to   preclude   cross-
           contamination.
10.2.2.8
  10.2.3
10.2.3.1
Bring the sample  volume  to 1.0 ±0.1 liter
with reagent water.

Preparation  of  OC  aliquots  for  samples
containing <30 percent solids.

For  each  sample  or  sample  lot  (to  a
maximum of 20) to be extracted at the same
time, place  two 1.0  lO.OI  liter aliquots
of reagent water  in  clean 1.5 - 2.0 liter
beakers.  For the phenoxy-aeid herbicides,
place two additional one  liter aliquots in
clean beakers.
10.2.3.2   To  serve as a blank,  spike  0.5 ml of  the
           pesticide   surrogate   spiking   solution
           (Section  6.12.1   and  6.12.2)  into   one
           reagent  water  aliquot, and  0.5 ml of  the
           herbicide   surrogate   spiking   solution
           (Section 6.12.3)  into  a  second   reagent
           water aliquot.

10.2.3.3   Spike  the  combined OC  standard  (Section
           7.4)  into  a  reagent water  aliquot.    For
           the  herbicides.   spike   the  herbicide
           standard into  the remaining reagent water
           aliquot.

10.2.3.4   If  a  matrix spike is  required,  prepare an
           aliquot  at  the concentrations  specified in
           Section  8.4.

  10.2.4   Stir  and  equilibrate all  sample  and  QC
           solutions  for 1  - 2  hours.    Extract  the
           samples  and QC aliquots per  Section 10.3.

  10.2.5   Samples  containing  30 percent solids  or
           greater
10.2.5.1    Nix the sample thoroughly

10.2.5.2    Weigh 30 ±0.3 grams into a clean 400 - 500
           ml beaker.   For the  herbicides,  weigh an
           additional two 30 gram aliquots into clean
           beakers.     Discard  all  sticks,  rocks,
           leaves and other foreign material prior to
           weighing.

10.2.5.3    Herbicide  acidification ••  Add 50  ml of
           reagent  water  to  one  of  the herbicide
           sample  aliquots and  stir  on  a  stirring
           plate  for  one hour minimum.   Using  a pH
           meter, determine and  record the sample pH
           while  stirring.    Slowly  add  HjSO^ while
           stirring  and  determine   and   record  the
           amount  of  acid  required  to  acidify the
           sample  to pH  <2.   Discard this aliquot.
           The  volune of  H.SO^  will  be  used during
           the  extraction of  the  samples in  Section
           10.4.6.

10.2.5.4   Spike 0.5  ml of the appropriate surrogate
           spiking  solution (Section  6.12)  into the
           pesticide and herbicide aliquots.

10.2.5.5    QC aliquots -- For each  sample or sample
           lot  (to  a maximum  of  20)  to be extracted
           at the  same time,  place  two 30 ±0.3  gram
           aliquots  of   the   high  solids  reference
           matrix in clean 400 - 500  ml beakers.  For
           the  herbicides,  place  three additional
           aliquots  in clean  beakers  and use one of
           these  to  determine  the  amount   of   acid
           required   for   acidification   per   step
           10.2.5.3.  Discard  this aliquot.

10.2.5.6   To serve  as a blank,  spike 0.5 ml of the
           pesticide    surrogate    spiking   solution
           (Section   6.12.1   and  6.12.2)  into  one
           aliquot   of  the  high  solids   reference
           matrix,   and  0.5   ml  of   the  herbicide
           surrogate    spiking   solution    (Section
           6.12.3)  into a second aliquot  of the  high
           solids reference matrix.

10.2.5.7   Spike  the  combined QC  standard  (Section
           7.4)  into a high  solids  reference matrix
           aliquot.    For the herbicides,  spike the
           herbicide  standard  into  the remaining  high
           solids  reference matrix aliquot.   Extract
           the  high solids samples per  Section 10.4.

    10.3   Extraction  of  low solids (aqueous)  samples

  10.3.1   Continuous  extraction of  pesticides/PCB's
           -• Place 100  •  150 ml methylene  chloride
           in each continuous  extractor and 200  - 300
           nL in each  distilling flask.
                                                                                                             13

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10.3.1.1
10.3.1.2
10.3.1.3
10.3.1.4
  10.3.2
Pour  the sample(s),  blank,  and  standard
atiquots  into  the extractors.   Rinse the
glass   containers  with  50   -   100  ml
methylene   chloride   and  add   to   the
respective extractors.  Include all solids
in the extraction process.

Extraction -- Adjust  the  pH  of the waters
in the  extractors to  5  - 9 with  NaOH or
H-SO, while monitoring with a pH meter.

Begin the extraction  by  heating  the flask
until the methylene  chloride  is  boiling.
When  properly  adjusted,  1-2 drops of
methylene chloride per  second will   fall
from  the condenser  tip  into  the  water.
Test  and  adjust  the pH of  the  waters
during   the  first   1-2  hours  of
extraction.   Extract for 18 - 24 hours.

Remove the  distilling flask,  estimate and
record  the  volume  of  extract  (to  the
nearest  100 ml),  and  pour  the  contents
through   a    prerinsed    drying    column
containing 7 to  10 cm of anhydrous sodium
sulfate  (acidified  sodium sulfate  for the
herbicides).   Rinse  the  distilling flask
with 30  - 50 ml  of methylene chloride and
pour  through  the  drying  column.    For
pesticide   extracts  and   for  herbicide
extracts  to  be  cleaned  up  using   GPC,
collect  the  solution  in a   500  ml  K-D
evaporator  flask  equipped  with  a 10 ml
concentrator  tube.     Seal,   label,   and
concentrate  per   Sections   10.5   through
10.7.
Hydrolysis
herbicides
and    back-extraction
of
10.3.2.1   Pour  the  sample  and  QC  atiquots  into
           separate  1.5  -  2  L  separator/ funnels.
           Add 250 g NaCl and shake to dissolve.

10.3.2.2   Add 17  ml  of 6 N  NaOH to each  separatory
           funnel and shake to mix thoroughly.  Check
           the pH  of  the sample  and QC aliquots and
           adjust  to  >12 if  required.   Periodically
           shake  the  aliquots  during a  1  -  2 hour
           hydrolysis period.

10.3.2.3   Rinse each  beaker  used for measurement of
           the sample  and QC aliquots  with 60 ml of
           nethylene chloride,  add to its  respective
           separator/  funnel,  and extract  the  sample
           by shaking the funnel  for  two minutes with
           periodic   venting   to    release    excess
           pressure.  Allow   the   organic  layer  to
           separate  from  the  water  phase   for  a
           minimum  of   10 minutes.    If  the emulsion
           interface between  layers  is more than one
           third the volume of the solvent  layer, the
           analyst must  employ mechanical  techniques
           to  complete  the  phase  separation.   The
           optimum technique depends upon the  sample,
           but  may  include  stirring,  filtration of
           the    emulsion   through    glass   wool,
           centrifugation, or other physical methods.
           Discard the methylene  chloride phase.   If
           the emulsion  cannot  be broken,  continuous
           liquid/liquid extraction techniques may be
           used.   Check and  adjust   the  pH  of  the
           sample to >12 with NaOH if  required.

10.3.2.4   Add  a second 60 ml  volume  of  methylene
           chloride  to  the sample bottle and repeat
           the  extraction procedure  a  second time,
           combining  the extracts in  the  Erlenmeyer
           flask.  Perform a  third extraction in the
           same manner.

  10.3.3   Extraction of the herbicides

10.3.3.1   Add 17 ml  of  12 N  H-SO^ to the  sample and
           OC  aliquots.     Seal   and   shake to  mix.
           Caution:        some    samples     require
           acidification  in a  hood  because  of  the
           potential for generating hydrogen sulfide.
           Check and adjust the pH of the sample to
           <2 if required.

10.3.3.2   Add  120  ml ethyl ether to  the sample and
           QC aliquots.  Seal and extract per  Section
           10.3.2.       Drain   the    aqueous   phase
           completely into the respective beaker used
           for measurement  of  aliquot  volume.   Drain
           the  ether phase into  500  ml  round-bottom
           flask containing approx  10 g of acidified
           sodium  sulfate  making certain   that  the
           amount of  water drained into the flask is
           minimized.  Periodically, shake  the round-
           bottom flask  to mix the ether solution and
           the drying agent.

10.3.3.3   Return the aqueous phase to the  separator/
           funnel, add  a 60 ml volume of ether, and
           repeat  the   extraction  a  second  time.
           Drain  the aqueous  phase  completely   into
           the beaker used for measurement  of  aliquot
           volume and the ether phase  into  the round-
           bottom flask.

10.3.3.4   Repeat   the  extraction  a  third  time,
           combining   the  ether   with   the   other
           extracts  in the round-bottom  flask.  Allow
           the  sodium sulfate  to remain  in  contact
           with  the  ether solution for  a minimum of
           two hours, periodically shaking  the round-
           bottom  flask  to nix  the  ether and  the
 14

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         drying agent.   Concentrate the extract to
         5 ml per Sections 10.5 through 10.7.

  10.4   Ultrasonic   extraction  of   high  solids
         aliquots

10.A.1   Add 60 g powdered (not granular)  anhydrous
         sodium sulfate to  the sample and  the QC
         alfquots.  Add 100  ±10 mL acetonitrile to
         each of  the  aliquots (Section 10.2.5) and
         nix thoroughly,  to  produce a  free-flowing
         mixture.

10.4.2   Place the  3/4 in.  horn  on the ultrasonic
         probe approx  1/2 in. below the surface of
         the solvent but above  the  solids  layer and
         pulse at  50 percent for  three minutes at
         full  power.    If  necessary,  remove the
         probe  from  the  solution  and break any
         large pieces using  a  metal spatula  or a
         stirring  rod  and  repeat  the sonication.
         Clean the  horn  with five percent  aqueous
         sodium   bicarbonate  immediately    after
         sonicating  any of  the herbicide aliquots
         to prevent acid damage to  the horn.

10.4.3   Decant   the   pesticide    and   herbicide
         extracts through filter  paper into 1000 -
         2000 mL separator/  funnels.

10.4.4   Repeat the extraction  and  filtration  steps
         (Sections  10.4.2 -  10.4.3) using a second
         100 *10 mL of  acetonitrile.

10.4.5   Repeat   the   extraction   step   (Section
         10.4.2)  using  100  ±10  crt  of   methylene
         chloride.  On  this  final extraction,  swirl
         the  sample or  QC  aliquot,  pour  into  its
         respective  filter  paper,  and  rinse  with
         methylene  chloride.    Record the  total
         extract volume.

10.4.6   For  each extract,  prepare 1.5-2  liters
         of  reagent  water  containing  two  percent
         sodium   sulfate.      For   the   pesticide
         extracts,  adjust the  pH   of  the  water to
         6.0  -  9.0  with NaOH  or   H.SO^.   For  the
         herbicide  extracts, adjust  the  pH  of  the
         water to <2.

10.4.7   Back  extract  each extract  three  times
         sequentially  with  500 nL  of  the  aqueous
         sodium   sulfate   solution,  returning  the
         bottom  (organic) layer  to  the separator/
         funnel   the    first  two   times    while
         discarding  the  top (aqueous) layer.   On
         the  final  back  extraction,  filter  each
         pesticide   extract   through   a   prerinsed
         drying   column  containing  7  to  10  cm
         anhydrous sodium sulfate  into  a 500 -  1000
         nL   graduated  cylinder.      Filter   the
         herbicide    extracts    similarly    using
         acidified  sodium  sulfate.    Record  the
         final extract volume.

10.4.8   Filter  the extracts  through  Whatman  *41
         paper  into 500  nL K-D  evaporator flasks
         equipped  with 10  mL  concentrator tubes.
         Rinse the graduated cylinder or centrifuge
         tube with 30  - 50 mL of methylene  chloride
         and  pour  through  the filter  to  complete
         the  transfer.   Concentrate  the  extracts
         per Sections  10.5 through 10.7.

  10.5   Concentration

10.5.1   Concentrate  the  extracts  in separate 500
         mL   K-D  flasks   equipped  with   10  mL
         concentrator  tubes.   Add  1  to  2 clean
         boiling chips to  the flask and  attach a
         three-ball  macro  Snyder  column.   Prewet
         the  column  by  adding  approx  one mL  of
         methylene chloride through the top.  Place
         the  K-D  apparatus in a  hot  water bath so
         that  the  entire  lower  rounded surface of
         the  flask is bathed with steam.   Adjust
         the vertical  position of the apparatus and
         the   water   temperature  as  required  to
         complete  the  concentration  in  15  to 20
         minutes.      At   the   proper   rate   of
         distillation,  the balls of the column will
         actively chatter but  the chambers  will not
         flood.

10.5.2   When  the  liquid  has  reached  an  apparent
         volume of one mL,  remove the K-D apparatus
         from  the  bath and  allow  the  solvent to
         drain and cool for at  least  10 minutes.

10.5.3   If  the extract is  to be cleaned  up using
         GPC,  remove  the  Snyder column  and  rinse
         the  flask  and its  lower  joint   into the
         concentrator   tube  with  1   -  2 mL  of
         methylene  chloride.   A 5 mL  syringe is
         recommended   for  this operation.   Adjust
         the  final  volume to  10  mL and proceed to
         GPC cleanup  in Section 11.

  10.6   Hexane   exchange   --   Extracts   to  be
         subjected   to  Florist I   or  silica  gel
         cleanup   and  extracts  that   have  been
         cleaned up are exchanged into hexane.

10.6.1   Remove     the    Snyder    column,    add
         approximately 50 nL of hexane and a clean
         boiling  chip,   and   reattach  the Snyder
         column.    Concentrate the  extract  as in
         Section  10.5 except  use hexane to prewet
         the  column.    The- elapsed  time  of  the
         concentration should  be 5 -  10 minutes.
                                                                                                           15

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 10.6.2    Remove the  Snyder  column and  rinse  the
          flask  and  Its   lower  joint  into   the
          concentrator tube  with  1  •  2  mL  of  hexane.
          Adjust the  final  volume  of  extracts  that
          have not  been cleaned  up by  GPC to 10  mL
          and those that have been  cleaned up by GPC
          to 5 ML  (the  difference  accounts  for  the
          50  percent   loss   in  the GPC  cleanup).
          Clean up  the extracts  using  the Florisil,
          silica   gel,    and/or   sulfur   removal
          procedures in Section 11.

   10.7    Herbicide extracts  --  These  extracts  are
          concentrated  to  5  -  10  mL  and   the
          herbicides are derivatized  per Section  12.

    11    CLEANUP AND  SEPARATION

   11.1    Cleanup procedures  nay  not  be necessary
          for  relatively  clean   samples  (treated
          effluents,   grounduater,  drinking   water).
          If  particular  circumstances  require  the
          use of a cleanup  procedure, the  analyst
          may use any or all of the procedures below
          or   any   other   appropriate   procedure.
          However,  the  analyst  shall  first  repeat
          the tests  in  Section  8.2 to demonstrate
          that the  requirements  of Section  8.2  can
          be met using  the  cleanup  procedure(s)  as
          an integral  part of  the method.   Figure 1
          outlines  the cleanup steps.

 11.1.1    Gel  permeation   chromatography  (Section
          11.2) removes many high  molecular weight
          interferents   that   cause   GC    column
          performance  to  degrade.    It is used  for
          all soil  and sediment  extracts  and may be
          used for  water extracts  that are  expected
          to contain  high molecular weight  organic
          compounds   (e.g.,   polymeric   materials,
          humic acids).

 11.1.2    The   solid   phase   extraction  cartridge
          (Section   11.3)   removes  polar   organic
          compounds such as  phenols.   It is  used for
          cleanup  of   organo-chlorine   and   organo-
          phosphate extracts.

 11.1.3    The Florisil column  (Section 11.4) allows
          for selected fractionation of the  organo-
          chlorine  compounds and  will also eliminate
          polar interferences.

 11.1.4    Alumina column cleanup (Section 11.5)  may
          also  be  used  for  cleanup of the  organo-
          chlorine  compounds.

 11.1.5    Elemental sulfur,   which  interferes  with
          the electron capture gas  chromatography of
          some of the pesticides and herbicides,  is
           removed using  GPC, mercury,  or activated
           copper.    Sulfur  removal   (Section  11.6)
           from  extracts   containing   organo-chlorine
           is  required  when sulfur  is  known  or
           suspected  to  be  present.    Mercury  and
           copper  should  not  be  used  for  sulfur
           removal from extracts  expected to contain
           the  organo-phosphorus  pesticides  because
           some  of  these  analytes  are  also removed
           (Reference 8).

    11.2   Gel permeation chromatography  (GPC)

  11.2.1   Column packing

11.2.1.1   Place 70 - 75 g of SX-3 Bio-beads in a 400
           - 500 ml beaker.

11.2.1.2   Cover  the beads  with methylene chloride
           and  allow to  swell  overnight  (12  hours
           minimum).

11.2.1.3   Transfer  the swelled  beads  to the column
           and pump  solvent  through  the  column, from
           bottom to  top,  at 4.5 -  5.5 mL/min prior
           to connecting the column to the detector.

11.2.1.4   After purging the column  with solvent for
           1-2  hours,   adjust  the   column  head
           pressure to 7 - 10 psig, and purge for 4  -
           5  hours  to remove air.    Maintain  a head
           pressure  of  7  -  10  psig.    Connect  the
           column to the detector.

  11.2.2   Column calibration

11.2.2.1   Load  5  mL  of   the calibration solution
           (Section 6.5) into the sample  loop.

11.2.2.2   Inject the calibration solution  and record
           the signal from the detector.  The elution
           pattern  will  be corn  oil,  bis(2-ethyl
           hexyl)    phthalate,    pentachlorophenol,
           perylene, and sulfur.

11.2.2.3   Set  the  "dump  time" to  allow >85 percent
           removal  of  the  corn  oil  and  >85 percent
           collection of the phthalate.

11.2.2.4   Set the "collect  time" to  the  peak minimum
           between perylene  and sulfur.

11.2.2.5   Verify    the    calibration    with    the
           calibration   solution   after   every   20
           extracts.  Calibration is verified if the
           recovery   of   the  pentachlorophenol   is
           greater  than 85  percent.   If calibration
           is  not  verified,  the  system  shall  be
           recalibrated    using    the   calibration
16

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 < 30% SOLIDS
                                   Percent Solids
            > 30% SOLIDS
       Dilute to 1% Solids
                                                                   1
ACN and CHgCLg Sonication
       CH CL2 Liquid/Liquid
           Extraction
   Kp Back Extraction
          Concentrate
                                                                   I
      Concentrate
          To Cleanup                                             To Cleanup

                    Method 1618 - Extraction and Concentration Steps
                                Gel Permeation Cleanup
ORGANOPHOSPHORUS
                                Solid Phase Extraction
          ORGANO-CHLORINE
            GCFPD
       Florisil
                                                             Remove Sulfur
                                                                GCHSD
                         Method 1618 - Cleanup and Analysis Steps
           FIGURE  1   Method 1618 -  Extraction, Cleanup,  and Analysis
                                                                                           17

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           solution,  and  the  previous  20  samples
           shall be re-extracted and cleaned up using
           the calibrated GPC system.

  11.2.3   Extract  cleanup  -•  GPC requires  that the
           column  not  be  over  loaded.    The  column
           specified in  this  method is  designed to
           handle  a maximum  of  0.5  gram  of  high
           molecular  weight  material   in  a   5  ml
           extract.    If  the   extract   is  known  or
           expected  to  contain  more than 0.5  gran,
           the  extract  is  split Into  fractions for
           GPC  end the  fractions  are  combined after
           elution  from  the  column.    The  solids
           content  of  the  extract  may  be  obtained
           gravimetricly by evaporating  the solvent
           from a 50 uL  aliquot.

11.2.3.1   Filter  the  extract  or  load  through  the
           filter   holder   to   remove  particulates.
           Load the 5.0 mL extract onto the column.

11.2.3.2   Elute  the extract  using  the calibration
           data   determined   in   Section   11.2.2.
           Collect the eluate in a clean 400 -  500 ml
           beaker.

11.2.3.3   Rinse  the sample loading  tube thoroughly
           with  methylene  chloride  between  extracts
           to prepare for the next sample.

11.2.3.4   If   a   particularly   dirty   extract  is
           encountered,   a  5.0 ml  methylene  chloride
           blank  shall be  run through  the system to
           check for carry-over.

11.2.3.5   Concentrate the extracts per Sections 10.5
           - 10.7.

    11.3   Solid phase extraction (SPE)

  11.3.1   Setup

11.3.1.1   Attach  the Vac-elute manifold  to a water
           aspirator or vacuum pump with the trap and
           gauge  installed  between  the  manifold and
           vacuum source.

11.3.1.2   Place  the SPE  cartridges  in the manifold,
           turn on the vacuum  source,  and adjust the
           vacuum  to 5 - 10 psia.

  11.3.2   Cartridge   washing   --  Pre-elute   each
           cartridge prior  to  use sequentially with
           10  it  portions each  of hexane, methanol,
           and  water  using vacuum  for  30  seconds
           after   each  eluant.    Follow  this  pre-
           elution with  1  mL  methylene chloride and
           three   10 ml  portions  of  the  elution
           solvent  (6.6.2.2)  using  vacuum  for five
           minutes   after   each   eluant.    Tap  the
           cartridge  lightly while  under  vacuum to
           dry between  eluants.    The three portions
           of  elution solvent may be  collected and
           used  as  a blank  if  desired.   Finally,
           elute  the cartridge  with  10  ml  each of
           methanol  and  water,  using  the vacuum for
           30 seconds after each eluant.

  11.3.3   Cartridge  certification -- Each cartridge
           lot must  be certified  to ensure recovery
           of  the  compounds of  interest  and removal
           of 2,4,6-trichlorophenol.

11.3.3.1   To  make   the   test   mixture,   add  the
           trichlorophenol solution (Section 6.6.2.1)
           to  the   combined   calibration  standard
           (Section  7.4).    Elute the  mixture  using
           the procedure in 11.3.4.

11.3.3.2   Concentrate  the  eluant  to   1.0  ml  and
           inject  1.0 uL of  the concentrated  eluant
           into the GC using the procedure  in Section
           13.   The   recovery of all organo-chlorine
           or  organo-phosphorus   analytes  (including
           the unresolved  GC peaks)  shall  be  within
           the  ranges   for  recovery  specified  in
           Tables  7-8,   and   the   peak  for
           trichlorophenol  shall  not  be detectable;
           otherwise   the   SPE   cartridge   is  not
           performing properly and the cartridge lot
           shall be rejected.

  11.3.4   Extract cleanup

11.3.4.1   After cartridge  washing (Section 11.3.2),
           release  the  vacuum  and  place  the  rack
           containing  the  50 ml  volumetric   flasks
           (Section  5.6.2.4)  in  the vacuum manifold.
           Reestablish the vacuum at 5 -  10 psia.

11.3.4.2   Using   a   pi pet   or   a  one   mL  syringe,
           transfer  1.0  mL of  extract  to  the SPE
           cartridge.  Apply vacuum for  five minutes
           to  dry  the cartridge.   Tap gently  to aid
           in drying.

11.3.4.3   Elute  each cartridge  into its  volumetric
           flask   sequentially   with   three   10  mL
           portions    of    the    elutions   solvent
           (6.6.2.2),  using vacuum  for  five minutes
           after  each portion.    Collect the eluants
           in  the  50  mL volumetric flasks.

11.3.4.4   Release the vacuum and remove  the  50 mL
           volumetric flasks.

11.3.4.5   Concentrate the  eluted extracts to  1.0 mL
           using  the  nitrogen  blow-down  apparatus.
           Adjust  the final  volume to 5 or  10 mL (per
           Section 10.6), depending on  whether  or not
 18

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         the extract was  subjected to GPC cleanup,
         and proceed to Section 13 for GC analysis.

  11.4   Florisil column

11.4.1   Place a  weight of  Florisil  (nominally 20
         B>  predetermined by  calibration (Section
         7.5) in a chromatographic column.  Tap the
         column to settle  the  Florisil  and add 1 -
         2  cm  of anhydrous  sodium sulfate  to the
         top.

11.4.2   Add 60 nL  of  hexane to  wet  and rinse the
         sodium sulfate and Florisil.   Just prior
         to exposure of the sodium sulfate layer to
         the air, (top the elution of the hexane by
         closing     the     stopcock      on     the
         chromatographic   column.     Discard  the
         eluate.

11.4.3   Transfer the concentrated extract (Section
         10.6.2)  onto   the column.    Complete the
         transfer with two 1-mL hexane rinses.

11.4.4   Place  a   clean   500   ml  K-D   flask  and
         concentrator tube under  the column.  Drain
         the column into the flask until  the  sodium
         sulfate  layer  is  nearly exposed.   Elute
         fraction  1 with 200  mL  of  six  percent
         ethyl ether  in hexane (v/v)  at a rate of
         approx 5  ni/min.   Remove the  K-D  flask.
         Elute fraction 2 with 200 ml of  15 percent
         ethyl ether in hexane (v/v)  into a  second
         K-D flask.   Elute fraction  3  with 200 ml
         of 50 percent ethyl ether in hexane (v/v).

11.4.5   Concentrate  the  fractions  as  in Section
         10.6,  except  use  hexane to  preuet  the
         column.  Readjust the final volume to 5 or
         10  ml as  in  Section 10.6,  depending on
         whether  the  extract was subjected to GPC
         cleanup, and analyze by  gas  chromatography
         per the procedure in Section 13.

  11.5   Alumina column

11.5.1   Reduce the volume of the extract to  0.5 nL
         and bring to 1.0 nL with acetone.

11.5.2   Add 3 g of activity III  neutral  alumina to
         a  10  nL chromatographic column.  Tap the
         column to settle  the alumina.

11.5.3   Transfer  the  extract  to  the  top  of the
         column and collect the  eluate  in a  clean
         10  nL   concentrator   tube.      Rinse  the
         extract  container with  1  -  2 nL  portions
         of  hexane  (to  a total volume of 9 mL) and
         add to  the alumina column.   Do not  allow
         the column to  go dry.
11.5.4   Concentrate  the  extract  to  1.0  mL  if
         sulfur  is to  be  removed,  or  adjust  the
         final volume to 5 or 10 mL  as in Section
         10.6, depending on whether the extract was
         subjected  to  GPC cleanup, and analyze by
         gas chromatography per Section 13.

  11.6   Sulfur  removal  --  Elemental  sulfur  will
         usually  elute  entirely  in fraction  1  of
         the Florisil column cleanup.

11.6.1   Transfer  the  concentrated extract  into a
         clean  concentrator tube  or Teflon-sealed
         vial.   Add 1  - 2  drops  of mercury or 100
         mg  of  activated  copper  powder  and  seal
         (Reference 9).    If  TBA sulfite  is used,
         add 1 mL  of  the TBA sulfite reagent and 2
         nL of isopropanol.

11.6.2   Agitate the contents of the vial  for 1 - 2
         hours  on  a  reciprocal  shaker.    If  the
         mercury  or copper appears  shiny, or if
         precipitated sodium  sulfite crystals from
         the  TBA sulfite  reagent  are present, and
         if the color remains unchanged, all sulfur
         has  been  removed;  if  not,   repeat  the
         addition and shaking.

11.6.3   If mercury or  copper  is used, centrifuge
         and  filter  the   extract  to   remove  all
         residual  mercury  or  copper.   Dispose of
         the  mercury waste properly.    Bring the
         final volume to 1.0  mL and analyze by gas
         chromatography   per   the   procedure  in
         Section 13.

11.6.4   If  TBA  sulfite  is  used,  add  5 mL  of
         reagent water and shake for  1  - 2 minutes.
         Centrifuge  and  filter  the  extract  to
         remove  all  precipitate.    Transfer  the
         hexane  (top)  layer  to a  sample  vial and
         adjust  the final  volume to  5  or  10 mL as
         in Section 10.6,  depending on whether the
         extract  was  subjected  to GPC  cleanup, and
         analyze  by gas chromatography per  Section
         13.

    12   ESTERIFICAT10N  OF  PHENOXY-ACID HERBICIDES

  12.1   Concentrate the extract  to approximately 5
         mL    per   Section   10.5   and    further
         concentrate  the  extract   to  near  dryness
         using   the  nitrogen   blowdown apparatus.
         Bring  the volume  to 5 nL with  isooctane.
         If desired, the extract nay  be transferred
         to a 10 nL sample vial  and stored at -20
         to -10  'C.
                                                                                                           19

-------
  12.2   Esterification  --   Observe   the   safety
         precautions   regarding   diazomethane   in
         Section 4.

12.2.1   Set   up   the   diazomethane   generation
         apparatus as given  in  the  instructions in
         the Diazald kit.

12.2.2   Transfer one mL of  the  isooctane solution
         (Section 12.1) to a clean vial and add 0.5
         •L of  met Hanoi and  3  ML  of  ether.   For
         extracts that have been cleaned up by GPC,
         use 2 H to account for the loss.

12.2.3   Add  two ML  of diazomethane  solution  and
         let  the  sample stand for  10  minutes with
         occasional swirling.  The  yellow color of
         diazomethane   should   persist  throughout
         this   period.      If   the  yellow   color
         disappears,  add  two mL   of  diazomethane
         solution   and  allow   to   stand,   with
         occasional   swirling,   for   another   10
         •inutes.  Colored  or complex  samples will
         require  at  least  4 mL of  diazomethane to
         ensure    complete   reaction   of    the
         herbicides.   Continue  adding  diazomethane
         in 2 mL  increments  until  the  yellow color
         persists  for  the  entire 10 minute  period
         or until 10  mL of  diazomethane solution
         has been added.

12.2.4   Rinse  the  inside  wall  of the  container
         with 0.2 - 0.5 mL of diethyl ether and add
         10 - 20 mg of silicic acid to react excess
         diazomethane.   Filter  through Whatman #41
         paper  into  a  clean  sample vial.   If  the
         solution  is colored or  cloudy,  evaporate
         to   near  dryness   using  the   nitrogen
         blowdown  apparatus,  bring  to 10 mL with
         hexane,  and proceed to  Section  11.3  for
         SPE cleanup.   If the solution is clear and
         colorless,  evaporate  to   near  dryness,
         bring to 1.0 mL with hexane and proceed to
         Section  13 for GC analysis.

    13   GAS CHROMATOGRAPHY

         Tables   4   through   6   summarize   the
         recommended  operating  conditions  for  the
         gas  chromatographs.    Included  in  these
         tables   are   the   retention  times  and
         estimated  detection  limits  that  can  be
         achieved under  these conditions.  Examples
         of the separations achieved by the primary
         and  confirmatory  columns  are  shown  in
         Figures  2 through 6.

  13.1   Calibrate   the system   as  described  in
         Section  7.
                                                            13.2   Combining pesticide and herbicide extracts

                                                          13.2.1   Pesticide  extracts  cleaned  up  by  solid
                                                                   phase  extraction  --  Combine  the  1.0  ml
                                                                   final  organo-chlorine  pesticide   extract
                                                                   (Section 11.3.4.5  or  11.5.4) with  the  1.0
                                                                   ml   final   herbicide   extract   (Section
                                                                   11.3.4.5   or  11.5.4   if  the  herbicide
                                                                   extract  required  cleanup;  Section  12.2.4
                                                                   if it did not).

                                                          13.2.2   Pesticide extracts cleaned up by  Florisil
                                                                   -- Combine 1.0 ml  of the  5.0 ml  or  10.0 ml
                                                                   pesticide  extract  (Section  11.4.5)  with
                                                                   the   1.0  ml   final   herbicide   extract
                                                                   (Section   11.3.4.5  or   11.5.4   if   the
                                                                   herbicide    extract   required    cleanup;
                                                                   Section 12.2.4 if  it did  not).

                                                            13.3   Set   the    injection   volume   on   the
                                                                   autosampler  to   inject   1.0  uL   of  all
                                                                   standards  and   extracts  of  blanks  and
                                                                   samples.

                                                            13.4   Set the data system or GC control  to start
                                                                   the   temperature   program   upon   sample
                                                                   injection, and begin data collection after
                                                                   the  solvent  peak  elutes.   Set  the  data
                                                                   system  to  stop data  collection after  the
                                                                   last  analyte is expected to elute  and to
                                                                   return   the   column   to    the   initial
                                                                   temperature.

                                                              14   SYSTEM AND LABORATORY PERFORMANCE

                                                            14.1   At the  beginning of each eight  hour shift
                                                                   during  which analyses  are  performed,  GC
                                                                   system  performance  and  calibration  are
                                                                   verified for all pollutants  and surrogates
                                                                   on all column/detector systems.   For these
                                                                   tests,   analysis   of   the   combined   OC
                                                                   standard  (Section  7.4)  shall  be  used to
                                                                   verify     all      performance     criteria.
                                                                   Adjustment   and/or   recalibration   (per
                                                                   Section  7)  shall  be performed until  all
                                                                   performance  criteria  are met.   Only after
                                                                   all   performance  criteria  are  met  may
                                                                   samples,   blanks,  and    precision   and
                                                                   recovery standards be analyzed.

                                                            14.2   Retention  times  -- The absolute retention
                                                                   times of  the peak maxima shall be within
                                                                   ±10  seconds  of  the retention times in the
                                                                   initial calibration (Section 7.4.1).

                                                            14.3   GC  resolution  --  Resolution  is  acceptable
                                                                   if the valley height between two peaks (as
                                                                   measured  from the baseline)  is less than
                                                                   10 percent of the  taller  of  the  two peaks.
20

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56   7   8   9   10  11   12  13  14  15  16   17   18   19   20  21   22  23  24   25
            FIGURE 2  Organochlorine Mix A [(A) DDB-608 and (B) DB-1701].
                                                                                 21

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    (B)
                  o
                  » i
    (A)
 56   7    8   9   10   11   12  13  14  15   16   17   18  19  20   21   22  23  24  25
                 FIGURE 3  Organochlorine Mix B [(A) DB-608 and (B) DB-1701].
22

-------
(B)-j
 (A)
      iupru[iHi|mT|inipmpTn|Miqun|uupiu|Hnpmfnupm[nn|iiii|iiu^
       6  7 6  9  10 11 12 13 14 15 16 17 18  19 20 21 22 23 24 25 26 27 28 26 30 31 32 33 3* 35 36 37 38 39 40 41 42 43 44 45 46 47 48 *9 50 51 52 53 54 55 56
                            FIGURE 4   Organophosphate Mix A [(A) DB-1  and (B) DB-1701).
                                                                                                                    23

-------
      (B)

           K.JL
                                <
                                |
                                                                            s
                                                                            £
m
i
                 I	AJ
     (A)
                                             I   I
                                    •o
                                   uu
         LJ
.-A...
   mlHUlM"!""!""!""!""!""!""!""!""!""!""!""!""!"1
    6  7 B 9 10 11 12 13 14 15 16 17 18 19 20
                               II 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 36 39 40 41 42 43 44 45 46 47 46 49 50 51 52 53 54 55 56
                    FIGURE 5  Organophosphate Mix B [(A) DB-1 and (B) DB-1701].
24

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 (B)
FIGURE 6  Phenoxy-acid Herbicides [(A) DB-608 and (B) DB-1701]
                                                                            25

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  14.3.1   Organo-halide compounds

14.3.1.1   Primary col inn  (DB-608)  --  DDT and endrin
           aldehyde.

14.3.1.2   Confirmatory column (DB-1701) -- Alpha and
           gamma chlordane.

  14.3.2   Organo-phosphorus compounds

14.3.2.1   Primary  column  (DB-1)  -•  Ma lath ion  and
           ethyl parathion.

14.3.2.2   Confirmatory column  (DB-1701)  -- Terbufos
           and diazinon.

    14.4   Decomposition of DDT and endrin

  14.4.1   Analyze  a total  of  2  ng  DDT  and 1  ng
           endrin  on   each  organo-chlorine  column
           using the  analytical  conditions specified
           in Table 4.

  14.4.2   Measure the total area of all peaks in the
           chromatogram.

  14.4.3   The  area  of peaks  other than  the sum of
           the  areas of   the  DDT  and endrin peaks
           shall be  less  than 20 percent  the sum of
           the areas of these two peaks.   If the area
           is  greater  than  this  sum,  the system is
           not  performing  acceptably  for  DDT  and
           endrin.   In  this case, the  GC  system that
           failed   shall   be    repaired   and   the
           performance  tests  (Sections 14.1  - 14.4)
           shall be  repeated until  the specification
           is   met.       Note:    DDT    and   endrin
           decomposition   are   usually   caused   by
           accumulations   of  particulates   in  the
           injector  and  in  the  front   end   of  the
           column.    Cleaning  and  silanizing  the
           injection port  liner,  and  breaking off a
           short  Section  of  the  front  end  of  the
           column   will    usually   eliminate   the
           decomposition problem.

    14.5   Calibration verification -• Calibration is
           verified  for   the  combined  OC  standard
           only.

  14.5.1   Inject  the  combined OC  standard  (Section
           7.4)

  14.5.2   Compute   the  percent   recovery  of  each
           compound  or  coeluting  compounds, based on
           the calibration data (Section 7.4).

  14.5.3   For  each compound  or  coeluted  compounds,
           compare   this   calibration   verification
           recovery with the corresponding limits for
           ongoing  accuracy in  Tables 7-9.   For
         coeluting  compounds,   use  the  coeluted
         compound   with   the   least   restrictive
         specification  (the widest  range).   If the
         recoveries  for  all  compounds  meet  the
         acceptance criteria, system performance  is
         acceptable  and  analysis  of  blanks  and
         samples  may  begin.    If,  however,  any
         recovery  falls  outside   the  calibration
         verification range,  system performance  is
         unacceptable for  that  compound.   In this
         case, correct  the problem and repeat the
         test,  or  recalibrate   (Section 7).     If
         verification  requirements  are  met,  the
         calibration is assumed to  be valid for the
         multicomponent    analytes    (PCB's    and
         toxaphene).

  14.6   Ongoing precision and recovery
14.6.1
14.6.2
14.6.3
14.6.4
Analyze the  extract of  the  precision and
recovery  standard   extracted  with  each
sample   lot    (Sections   10.2.3.3   and
10.2.5.7).
Compute  the  percent   recovery
analyte and coeluting compounds.
of  each
For each  compound or  coeluted compounds,
compare  the  percent  recovery  with  the
limits for ongoing recovery in Tables 7 -
9.     For  coeluted   compounds,   use  the
coeluted   compound    with    the    least
restrictive specification  (widest range).
If  all  analytes  pass,  the  extraction,
concentration,  and  cleanup  processes are
in  control  and  analysis   of  blanks  and
samples may proceed.   If,  however, any of
the analytes fail, these processes are not
in  control.    In  this event,  correct the
problem,  re-extract  the  sample  lot,  and
repeat the ongoing precision and  recovery
test.

Add results which pass the  specifications
in Section 14.6.3 to initial and  previous
ongoing data.   Update  OC charts to form a
graphic    representation   of   continued
laboratory   performance.      Develop   a
statement  of  laboratory data  quality for
each  analyte  by  calculating  the average
percent  recovery (R)  and  the   standard
deviation of percent recovery sr.  Express
the accuracy as a recovery  interval from R
- 2sr  to R * 2sr.  For example, if R  <= 95X
and sr = 5X, the  accuracy is 85 - 105X.
 26

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    15   QUALITATIVE DETERMINATION
  16   QUANTITATIVE DETERMINATION
  15.1    Qualitative determination  is accomplished
         by comparison  of  data from  analysis  of  a
         sample or blank with data from analysis of
         the  shift  standard  (Section  U.2),  and
         with data stored in the retention time and
         calibration  libraries (Section  7.3.3 and
         7.3.4.1).    Identification  is  confirmed
         when retention time  and  amounts  agree per
         the criteria below.

  15.2    For each  compound  on each column/detector
         system, establish  a  retention  time window
         ±20  seconds   on   either   side   of   the
         retention  time  in  the  calibration  data
         (Section 7.3.3).   For compounds  that have
         a retention  time  curve (Section 7.3.3.2),
         establish this  window as  the  minimum -20
         seconds and maxinun  +20  seconds.  For the
         multi-component    analytes,    use    the
         retention times of the five largest peaks
         in  the chromatogram  from  the  calibration
         data (Section 7.3.3).

15.2.1    Compounds not  requiring a  retention time
         calibration curve  --  If  a peak  from the
         analysis of a  sample or  blank  is within a
         window (as defined in Section 15.2) on the
         primary   column/detector   system,   it  is
         considered  tentatively   identified.     A
         tentatively    identified    compound    is
         confirmed when  (1) the retention time for
         the    compound    on   the   confirmatory
         column/detector   system    is   within  the
         retention time  window on that  system, and
         (2)  the  computed  amounts  (Section 16) on
         each  system   (primary  and  confirmatory)
         agree within a factor of three.

15.2.2    Compounds   requiring  a   retention  time
         calibration  curve  --  If  a  peak from the
         analysis of a  sample or  blank  is within a
         window (as defined in Section 15.2) on the
         primary   column/detector   system,   it  is
         considered  tentatively   identified.     A
         tentatively    identified    compound    is
         confirmed when  (1) the retention times on
         both  systems  (primary  and confirmatory)
         are  within  ±30  seconds  of  the retention
         times  for  the  computed  amounts  (Section
         16), as  determined  by  the retention time
         calibration  curve (Section  7.3.3.2), and
         (2)  the  computed  amounts  (Section 16) on
         each   system   (primary  and  confirmatory)
         agree within a factor of three.
16.1
16.2
16.3
16.4
16.5
Using  the  GC  data  system,  compute  the
concentration of  the analyte  detected in
the   extract   (in   ug/mL)   using   the
calibration  factor  or  calibration  curve
(Section 7.3.3.2).

Liquid    samples     --     Compute    the
concentration  in  the  sample  using  the
following equation:
       Cs  •


       where,
       Cs   «

       10   =
       Cex  •

       Vs   =
                    10 (Cex)
               (Vs)
         the concentration  in  the sample
         in ug/L.
         extract total volume  in ml.
         concentration in the  extract  in
         ug/mL.
         volume of sample extracted  in
         liters.
Solid samples -- Compute the concentration
in the solid phase of the sample using the
following equation:
       Cs  «    -

       where,
       Cs

       10
       Cex

       1000

       Us
       X solids
                       10 (Cex)
          1000 (Us) (X solids)
              concentration  in the  sample
              in ug/kg.
              extract  total  volume  in ml.
              concentration  in the  extract
              in ug/mL.
              used to  convert  grams to
              kilograms.
              sample weight  in grams.
              percent  solids as determined
              in Section  10.1.3.
 If   the  concentration   of   any   analyte
 exceeds   the   calibration  range  of   the
 system, the extract  is diluted by a  factor
 of 10, and a one uL  aliquot of the  diluted
 extract is analyzed.

 Two  or more PCB's  in a  given sample  are
 quantitated and reported  as total PCB.
16.6   Report  results  for  all  pollutants  found  in
       all   standards,  blanks,   and  samples   to
       three significant  figures.    Results for
       samples  that   have   been   diluted  are
       reported  at  the  least  dilute  level   at
       which  the   concentration   is   in  the
       calibration range.
                                                                                                          27

-------
      17   ANALYSIS OF COMPLEX SAMPLES

    17.1   Sane  samples   nay  contain  high  levels
           (>1000 ng/L) of the compounds of interest,
           interfering  compounds,  and/or  polymeric
           Materials.      Some   samples   may   not
           concentrate  to  10   »L  (Section  10.6);
           others nay overload the GC column and/or
           detector.

    17.2   The analyst  shall  attempt  to clean up all
           camples using  GPC  (Section 11.2),  and the
           SPE cartridge  (Section 11.3),  and samples
           for   the   organo-halide   compounds   by
           florisil (Section  11.4) or  alumina (11.5),
           and  sulfur  removal  (Section  11.6).    If
           these   techniques  do  not   remove   the
           interfering  compounds,  the  extract  is
           diluted by a factor of  10 and reanalyzed
           (Section 16.4).

    17.3   Recovery of surrogates --  In most samples,
           surrogate  recoveries  will  be  similar  to
           those from reagent water or from the high
           solids reference matrix.   If the surrogate
           recovery is outside the range specified in
           Section    8.3,   the   sample   shall   be
           reextracted  and   reanalyzed.     If   the
           surrogate  recovery is  still  outside  this
           range, the sample is  diluted  by  a factor
           of 10 and  reanalyzed (Section 16.4).

    17.4   Recovery   of  matrix   spikes  --  In  most
           samples, matrix spike  recoveries  will  be
           similar  to  those  from  reagent  water  or
           from the high solids reference matrix.  If
           the matrix spike  recovery  is outside the
           range  specified   in  Tables  7-9,  the
           sample shall be diluted by  a factor of 10,
           respiked,  and  reanalyzed.    If  the matrix
           spike recovery  is  still outside the range,
           the method does  not  apply  to  the sample
           being analyzed and the  result  may not be
           reported    for    regulatory   compliance
           purposes.

      18   METHOD PERFORMANCE
    18.1


REFERENCES

       1
Development of this method  is detailed in
Reference 10.
•Working  with  Carcinogens,"  DHEU,  PHS,
CDC,  NIOSH,   Publication 77-206,  (August
1977).

•OSHA Safety and Health Standards, General
Industry* OSHA 2206,  29 CFR 1910 (January
1976).
                                                     10
•Safety      in      Academic     Chemistry
Laboratories,"  ACS Committee  on Chemical
Safety (1979).

Mills,  P.   A.,   "Variation  of  Florisil
Activity:  Simple   Method  for  Measuring
Adsorbent   Capacity   and   Its  Use   in
Standardizing Florisil Columns," J. Assoc.
Off. Analytical Chemists, 51, 29 (1968).

"Handbook of Analytical Quality Control  in
Water and Wastewater Laboratories," USEPA,
EMSL, Cincinnati,  OH  45268, EPA-600/4-79-
019 (March 1979).

•Standard  Practice  for  Sampling  Water,"
ASTM  Annual  Book  of  Standards,   ASTM,
Philadelphia, PA, 76 (1980).

•Methods   330.4   and   330.5   for    Total
Residual     Chlorine,"     USEPA,      EMSL,
Cincinnati,  OH  45268,  EPA  600/4-70-020
(March 1979).

"Method  Development  and  Validation, EPA
Method 1618, Cleanup Procedures", Colorado
State     University,      Department      of
Environmental  Health,   Colorado Pesticide
Center, November 1988 and January 1989.

Goerlitz,  D.F., and  Law,  L.M. "Bulletin
for   Environmental   Contamination   and
Toxicology," 6, 9  (1971).

"Consolidated    GC    Method    for    the
Determination of ITD/RCRA  Pesticides  using
Selective  GC Detectors," Report Reference
32145-01,   Document   R70,   S-CUBED,   A
Division of  Maxwell Laboratories,  Inc,  PO
Box   1620,  La  Jolla,   CA,   92038-1620
(September 1986).
  28

-------
                     Table 1
ORGANO-HALIDE PESTICIDES DETERMINED BY WIDE BORE,
 FUSED SILICA CAPILLARY  COLUMN GAS  CHROMATOGRAPHY
          WITH HALIDE SPECIFIC DETECTOR
                                       Table 2
                ORGANO-PHOSPHORUS PESTICIDES DETERMINED BY WIDE BORE,
                   FUSED SILICA CAPILLARY COLUMN GAS CHROMATOGRAPHY
                           WITH FLAME PHOTOMETRIC DETECTOR
EGD
No.
089
102
103
105
104
434
433
441
091
431
094
093
092
432
478
090
095
096
097
098
099
435
100
101
437
439
430
438
436
112
108
109
106
110
107
111
440
113
442

Compound
Aldrin
alpha-BHC
beta-BHC
delta-BHC
gannia-BHC (Lindane)
Captafol
Captan
Carbophenothion
Chlordane
Chlorobenzilate
4,4<-DDD
4,4' -DDE
4, 4' -DDT
Dial late
Dichlone
Dieldrin
Endosulfan I
Endosulfan II
Endosulfan sulfate
Endrin
Endrin aldehyde
Endrin ketone
Heptachlor
Heptachlor epoxide
Isodrin
Kepone
Methoxychlor
Mi rex
Nitrofen (TOO
PCB-1016
PCB-1221
PCB-1232
PCB-1242
PCB-1248
PCB -1254
PCB-1260
PCNB (pentachloronitrobenzene)
Toxaphene
Trif luralin

CAS Registry
309-00-2
319-84-6
319-85-7
319-86-8
58-89-9
2425-06-1
133-06-2
786-19-6
57-74-9
510-15-6
72-54-8
72-55-9
50-29-3
2303-16-4
117-80-6
60-57-1
959-98-8
33213-65-9
1031-07-8
72-20-8
7421-93-4
53494-70-5
76-44-8
1024-57-3
465-73-6
143-50-0
72-43-5
2385-85-5
1836-75-5
12674-11-2
11104-28-2
11141-16-5
53469-21-9
12672-29-6
11097-69-1
11096-82-5
82-68-8
8001-35-2
1582-09-8
EGD
No.
468
453
461
469
443
479
471
460
450
455
449
452
458
467
463
446
454
447
464
474
475
456
444
470
459
448
457
465
473
477
476
472
466
445
451
462


NON

Compound
Azinphos ethyl
Azinphos methyl
Chlorfevinphos
Chlorpyrifos
Coumaphos
Crotoxyphos
Demeton
Diazinon
Dichlorvos
Dicrotophos
Dimethoate
Dioxathion
Disulfoton
EPN
Ethion
Famphur
Fensulfothion
Fenth i on
Hexamethylphosphoramide
Leptophos
Ma lath ion
Methyl pa rath ion
Mevinphos
Mooocrotophos
Naled
Parathion
Phorate
Phosmet
Phosphamidon
Sulfotepp
TEPP
Terbufos
Tetrachlorvinphos
Trichlorofon
Tricresylphosphate
Trimethylphosphate


-ITD ORGANO- PHOSPHATE COMPOUNDS

CAS Registry
2642-71-9
86-50-0
470-90-6
2921-88-2
56-72-4
7700-17-6
8065-48-3
333-41-5
62-73-7
141-66-2
60-51-5
78-34-2
298-04-4
2104-64-5
563-12-2
52-85-7
115-90-2
55-38-9
680-31-9
21609-90-5
121-75-5
298-00-0
7786-34-7
6923-22-4
300-76-5
56-38-2
298-02-2
732-11-6
13171-21-6
3689-24-5
107-40-3
13071-79-9
961-11-5
42-68-6
78-30-8
512-56-1


THAT CAN BE
                                                                       ANALYZED BY THIS METHOD
   NON-ITD ORGANO-HALIDE  COMPOUNDS  THAT CAN BE
             ANALYZED BY  THIS METHOD
      Compound

      Chloroneb
      Chloropropylate
      DBCP
      Dicofol
      Etridiazole
      Perthane (Ethylan)
      Propachlor
      Strobane
CAS Registry
   2675-77-6
   5836-10-2
     96-12-8
    115-32-2
   2593-15-9
     72-56-0
   1918-16-7
   8001-50-1
Comxxjnd
Bolster
Dichlorofenthion
Ethoprop
Merphos
Methyl Chlorpyrifos
Methyl trithion
Rormel
Su I prof os
Tokuthion
Trichloronate
CAS Registry
  35400-43-2
     97-17-6
  13194-48-4
    150-50-5
   5598-
    953-
    299-84-3
  35400-43-2
  34643-46-4
    327-98-0
13-0
17-3
                                                                                                           29

-------
                       Table 3
   PHENOXYACID  HERBICIDES DETERMINED BY WIDE BORE,
  FUSED SILICA CAPILLARY COLUMN GAS CHROMATOGRAPHY
            WITH  HALIDE SPECIFIC DETECTOR
EGD
NO.
481
480
482
483
Compound
2,4-D
Dinoseb
2,4,5-T
2,4,5-TP
CAS Registry
94-75-7
88-85-7
93-76-5
93-72-1
     NON-ITD PHENOXYACID HERBICIDES THAT CAN BE
               ANALYZED  BY  THIS  METHOD
      Compound                      CAS Registry
      Dalapon                              75-99-0
      2,4-DB (Butoxon)                     94-82-6
      Dicamba                           1918-00-9
      Dichlorprop                        120-36-5
      MCPA                                 94-74-6
      MCPP                                 93-65-2
30

-------
                   Table 4
GAS CHROMATOGRAPHY OF ORGANO-HALIDE PESTICIDES
EGD
No.
442
432

102
440
104
103
100
478
105
089
437
101

091
095
093
090
433
431
098
436
439
094
096
092
441
099
097
434
438
Retention Time (1)
Compound
Trif luralin
Dialtate-A
Diallate-B
alpha-BHC
PCNB
gamma-BHC (Lindane)
beta-BHC
Heptachlor
Dichlone
delta-BHC
Aldrin
Isodrin
Heptachlor epoxide
ganma-Chlordane
alpha-Chlordane
Endosulfan I
4,4'-DDE
Dieldrin
Captan
Chlorobenzi late
Endrin
Nitrofen (TDK)
Kepone
4.4'-DOO
Endosulfan II
4,4'-DOT
Carbophenothion
Endrin aldehyde
Endosulfan sulfate
Captafol
M i rex
OB-608
5
7
7
8
9
9
9
10
10
11
11
13
13
14
15
15
16
16
16
17
17
17
17
18
18
19
19
19
20
22
22
.16
.15
.42
.14
.03
.52
.86
.66
.80
.20
.84
.47
.97
.63
.24
.25
.34
.41
.83
.58
.80
.86
.92
.43
.45
.48
.65
.72
.21
.51
.75
DB-1701
8
8
8
9
9
10
13
11

14
12
13
15
16
16
15
16
17
17
18
18
19
25
19
19
20
20
21
22
23
21
.58
.05
.58
.45
.91
.84
.58
.56
(3)
.39
.50
.93
.03
.20
.48
.96
.76
.32
.32
.97
.06
.14
.03
.56
.72
.10
.21
.18
.36
.11
.82
HDL (2)
(ng/L)
50 est
45
32
6
6
11
7
5
(4)
5
8
13
12
9
8
11
10
6
(4)
25
4
13
(4)
5
8
12
50
11
7
(4)
4
EGD
No.
430
435
106
109
112
108
110
107
111




113





(1)

Retention Time (1)
Compound
Methoxychlor
Endrin ketone
PCS- 1242
PCS- 1232
PCB-1016
PCB-1221
PCS- 1248
PCB-1254
PCB-1260




Toxaphene





Columns: 30 m x
micron; DB-1701: 1.
DB-608
22.80
23.00






15.44
15.73
16.94
17.28
19.17
16.60
17.37
18.11
19.46
19.69

0.53 mm i
0 micron.
DB-1701
22.34
23.71






14.64
15.36
16.53
18.70
19.92
16.60
17.52
17.92
18.73
19.00

MDL (2)
(ng/L)
30
8






140




910





.d.; DB-608: 0.83

Conditions: 150 °C for 0.5 min, 150 -
°C per minute, 270 °C until endrin
elutes.

270 a 5
ketone
Carrier gas flow rate: approximately 7 mL/min.
(2)
(3)

(4)
40 CFR Part 136,
Detection limits
estimated to be 30
Appendix
for soils
- 100 times
Does not elute from DB-1701
tested.

Not recovered from

B (49 FR 43234).
(in ng/kg) are
this level.
column at level


water at levels tested.
                                                                        31

-------
                                                    Table 5
                               GAS CHROMATOGRAPHY OF ORGANO-PHOSPHORUS  PESTICIDES
EGO
No.
450
444
445
471

459
455
470
477
457
449

452
472
473
458
460



456



475
447
448
469

Retention Time (1)
Compound
Dichlorvos
Mevinphos
Trichlorofon
Demeton-A
Ethoprop
Naled
Dicrotophos
Honocrotophos
Sulfotepp
Phorate
Dimethoate
Demeton-B
Dioxathion
Terbufos
Phosphamidon-E
Disulfoton
Diazinon
Tributyl phosphate
(surr)
Phosphamidon-Z
Methyl parathion
0 i ch I orof ent h i on
Methyl chlorpyrifos
Ronnel
Malathion
Fenthion
Parathion (ethyl)
Chlorpyrifos
Trichloronate
DB-608
6
11
12
17
18
18
19
19
20
20
20
21
22
22
23
23
24
24

25
25
26
26
27
28
.56
.85
.69
.70
.49
.92
.33
.62
.04
.12
.59
.40
.24
.97
.70
.89
.03
.50

.88
.98
.11
.29
.33
.87
29.14
29
29
30
.29
.48
.44
DB-1701
9
16
18
20
21
23
26
29
23
23
29
25
26
24
29
27
26
17

32
32
28
29
30
33
32
34
32
32
.22
.20
.85
.57
.43
.00
.30
.24
.68
.08
.29
.52
.70
.55
.89
.01
.10
.20

.62
.12
.66
.53
.09
.49
.16
.61
.15
.12
MDL (2)
(ng/L)
4
74
150 (3)
19
7
18
81
85
6
10
27
21
121
26
28
32
38
-

116
18
6
13
11
11
22
10
4
14
EGD
No.
461
479

466

454

463

446
465
467
453
474
468


443

(1)

Retention
Compound
Chlorfevinphos
Crotoxyphos
Tokuthion
Tetrachlorvinphos
Merphos-B
Fensulfothion
Methyl trithion
Ethion
Sulprofos (Bolstar)
Famphur
Phosmet
EPN
Azinphos methyl
Leptophos
Azinphos ethyl
Triphenyl phosphate
(surr)
Coumaphos

Columns: 30 m x 0.53
DB-1701: 1.0 micron.
Time (1) MDL
(2)
DB-608 DB-1701 (ng/L)
32.05
32.65
33.30
33.40
35.16
36.58
36.62
37.61
38.10
38.24
41.24
41.94
43.33
44.32
45.55
47.68

48.02

mm i.d.;

36.08
37.58
37.17
37.85
37.37
43.86
40.52
41.67
41.74
46.37
48.22
47.52
50.26
47.36
51.88
40.43

56.44

2
81
2
12
18
104
10
13
6
27
14
9
9
14
22
-

24

DB-1: 1.5 micron;

Conditions: 110 °C for 0.5 min, 110 - 250



(2)
(3)


°C per minute, 250 °C
Carrier gas flow rate:


a 3
until coumaphos e lutes.
approximately 7 mL/min.

40 CFR Part 136, Appendix B (49
Estimated: Detection limits
ng/kg) are estimated
level.
to be 30


FR 43234).
for soils
- 100 times



(in
this

32

-------
                       Table 6
          GAS CHROMATOGRAPHY OF PHENOXY-ACID
                      HERBICIDES
EGO
No.
481
480
482
483






Compound
2,4-D
D i noseb
2,4, 5-T
2,4,5-TP (SHvex)
Dalapon
2,4-DB (Butoxon)
D i camba
Dichlorprop
MCPA
MCPP
Retention
DB-608
5.85

7.92
6.97

8.74
4.39
5.15
4.74
4.24
Time (1)
DB-1701
6.05

8.20
7.37

9.02
4.39
5.46
4.94
4.55
HDL (2)
(ng/L)
100
100 est
50
40
1000 est
50
110
40
90
56
(1)  Columns:     Same   as   for  the  organo-chlorine
     pesticides.   See Table 4.
     Conditions:   175 °C for  0.5 min, 175  -  270 3 5
     °C per minute.
     Carrier gas  flow rate:  approximately 7 mL/min.

(2)  40  CFR Part  136,  Appendix  B  (49 FR  43234).
     Detection   limits  for   soils   (in   ng/kg)  are
     estimated  to be  30  - 100  times  this  level.
                                                                                                            33

-------
                                                     Table 7
                      ACCEPTANCE CRITERIA FOR PERFORMANCE TESTS FOR  ORGANO-HALIDE  COMPOUNDS


                                                                       Acceptance Criteria
EGD
No.(1) Compound
089
102
103
105
104
434
433
441
091

431
094
093
092
432
478
090
095
096
097
098
099
435
100
101
437
439
430
438
436
112
108
109
106
110
107
111
440
113
442
Aldrin
alpha-BHC
beta-BHC
delta-BHC
gamma-BHC (Lindane)
Captafol (2)
Captan (2)
Carbophenoth i on
Chlordane-alpha
Chlordane-gamma
Chlorobenzilate
4,4'-DDD
4,4'-DDE
4,4'-DDT
Diallate
Oichlone (2)
Dieldrin
Endosulfan I
Endosulfan II
Endosulfan sulfate
Endrin
Endrin aldehyde
Endrin ketone
Heptachlor
Heptachlor epoxide
Isodrin
Kepone (2)
Methoxychlor
Mi rex
Nitrofen (TDK)
PCB-1016
PCB-1221
PCB-1232
PCB-1242
PCB-1248
PCB-1254
PCB-1260
PCNB
Toxaphene
Trif luralin
Spike
level
(ng/L)
100
100 '
100
100
100


1000
100
100
500
100
200
200
250

100
200
200
100
100
200
100
100
100
100

200
100
200






1000
100
5000
200
Initial
precision
and accuracy
Sec 8.2 (X)
s
12
10
10
24
10


10
10
13
19
12
13
19
16

11
14
19
17
13
13
25
12
13
15

19
23
22






20
11
20
12
X
82 -
57 -
66 -
60 -
66 -


63 -
79 -
32 -
58 -
69 -
66 -
86 -
44 -
79 -
66 -
41 -
78 -
50 -
17 -
0 -
36 -
78 -
63 -
69 -

50 -
25 -
15 -






82 -
49 -
82 -
32 -
Calibration
verification
Sec 14.5
(ug/mL)
108
135
130
122
112


141
122
140
118
117
114
112
120
110
140
133
142
130
149
149
126
104
117
113

136
155
139






112
129
112
148
79 -
69 -
85 -
79 -
75 -
70 -
49 -
79 -
73 -
79 -
54 -
77 -
81 -
77 -
70 -

48 -
78 -
76 -
70 -
5 -
86 -
68 -
80 -
79 -
71 -
47 -
47 -
78 -
59 -






79 -
78 -
68 -
47 -
113
108
102
103
119
107
114
102
102
113
129
109
121
118
124

115
119
119
109
117
117
135
114
117
126
134
128
114
142






126
101
134
134
Recovery
Sec 8.4
Ongoing
accuracy
Sec 14.6
R (%)
76 -
38 -
50 -
45 -
55 -


43 -
69 -
4 -
43 -
57 -
54 -
79 -
24 -

48 -
18 -
62 -
31 -
0 -
0 -
14 -
71 -
49 -
45 -

28 -
0 -
0 -






75 -
29 -
76 -
3 -

114
154
146
136
123


161
133
169
133
129
126
119
139

158
156
158
149
182
190
148
111
131
127

158
188
170






119
149
122
177
(1)  Reference numbers beginning with 0 or 1 indicate a pollutant quantified by the internal  standard method.

(2)  Not recovered.

-------
                                                    Table 8
                   ACCEPTANCE CRITERIA FOR PERFORMANCE TESTS FOR  ORGANO-PHOSPHORUS COMPOUNDS


                                                                      Acceptance Criteria
EGO
No.
468
453
461
469
443
479
471
460
450
455
449
452
458
467
463
446
454
447
464
474
475
456
444
470
459
448
457
465
473
477
476
472
466
445
451
462









Compound
Azinphos ethyl
Azinphos methyl
Chlorfevinphos
Chlorpyrifos
Coumaphos
Crotoxyphos
Demeton-S
Diazinon
Dichlorvos
Dicrotophos (1)
Dimethoate
Dioxathion
Disulfoton
EPN
Ethion
Famphur
Fensulfothion
Fenthion
Hexamethylphosphoramide (1)
Leptophos
Malathion
Methyl parathion
Mevinphos
Monocrotophos (1)
Naled
Parathion
Phorate
Phosmet
Phosphamidon-Z
Sulfotepp
TEPP (1)
Terbufos
Tetrachlorvinphos
Trichlorofon (1)
Tricresylphosphate
Trimethylphosphate (1)
Diehlorofenthion
Ethoprop
Merphos-B
Methyl chlorpyrifos
Methyl trithion
Rome I
Sulprofos (Bolster)
Tokuthion
Trichloronate
Spike
level

59 -
37 •
37 •
48 -
72 •
6 -
16 -
60 •
39 •
78 -
22 -
49 •
33 -
62 •
47 •
76 •
0 -
61 •
70 •
80 •
66 -
61 •
7 -
19 -
0 •
61 •
43 •
25 -
0 -
58 -
70 •
47 •
32 -
70 •
74 -
70 -
65 -
73 •
59 •
83 •
0 -
71 -
70 •
65 •
77 •
129
127
151
125
110
138
118
120
119
122
100
111
111
136
149
106
141
109
130
110
118
123
107
206
176
121
109
138
100
132
130
123
126
130
114
130
125
109
111
113
166
119
100
113
107
(1)  Not recovered.
                                                                                                           35

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                                                  Table 9
                    ACCEPTANCE CRITERIA FOR  PERFORMANCE TESTS FOR PHENOXY-ACID COMPOUNDS
                                                                     Acceptance Criteria




EGO
No. Compound



Spi ke
level
(ng/L)

Initial
precision
and accuracy
Sec 8.2 (X)
s X


Calibration
verification
Sec 14.5
(ug/mL)
Recovery
Sec 8.4
Ongoing
accuracy
Sec 14.6
R (%)
481      2,4-D
480     Dinoseb
482     2,4,5-T
483     2,4,5-TP (Silvex)
        Dalapon
        2,4-DB (Butoxon)
        Dicamba
        Dichlorprop
        MCPA
        MCPP
200

100
100

100
200
100
200
400
16

17
14

16
18
14
14
14
41 • 107

30 - 132
36 • 120

22 • 118
37 - 145
49 - 133
46 - 130
65 - 149
70 • 130

70 - 130
70 • 130

70 • 130
70 - 130
70 - 130
70 - 130
70 - 130
23 •  131

 5 -  158
15 -  141

 0 -  142
10 •  172
28 •  154
25 •  151
42 -  170
36

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