THE ANALYSIS OF TRlHALOM£THAf£S

   IN DRINKING WATER BY LIQUID/LIQUID EXTRACTION
                   METHOD 501.2
                  November 1979
      Physical  and  Chemical Methods  Branch
Environmental Monitoring and  Support Laboratory
       Office of Research and Development
      U.S-. Environmental Protection  Agency
            Cincinnati,  Ohio   45268

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                                   FOREWORD

    This method has been prepared by the staff of the Environmental
Monitoring and Support Laboratory - Cincinnati, at the request of the Office
of Drinking Water, with cooperation from the Technical Support Division, OOW
and the Municipal  Environmental Research Laboratory.  Their comments and
suggestions on updating the SeptemDer 9, 1977, Interim Method as well as
those of the Health Effects Research Laboratory are gratefully acknowledged.

    The procedure  represents the current state-of-the-art, but as time
progresses, improvements are anticipated.  Users are encouraged to identify
problems and assist in updating the method by contacting the Environmental
Protection Agency, Environmental Monitoring and Support Laboratory,
Cincinnati, Ohio  45268.

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                      Analysis  of  Trihalomethanes in Drinking
                        Water  by  Liquid/Liquid Extraction

  1.   Scope
      1.1   This  method (1,2)  is applicable only to the determination of four
           trihalomethanes,  i.e.,  chloroform,  brcmodichloromethane,
           chlorodibrcmomethane, and  bromoform in finished drinking water,
           drinking water during intermediate  stages  of treatment,  and  the  raw
           source water.
     1.2   For compounds other  than the above-mentioned trihalomethanes, or
           for other sample sources, the analyst must  demonstrate the useful-
          ness of the method by collecting precision  and  accuracy  data on
          actual samples as described in (3) and provide  qualitative
          confirmation of  results  by_Gas Chromatography/Mass Spectrometry
          (GC/MS)  (4).
     1.3   Qualitative  analyses  using  GC/MS or the purge and trap metnod (5)
          must be  performed to  characterize each raw source water if peaxs
          appear as interferences  in  the  raw  source analysis.
     1.4   The method has been shown to be  useful  for  the trihalometnanes over
          a concentration range from  approximately  0.5 to  200  ug/L.   Actual
          detection limits  are  highly dependent  upon  the characteristics of
          the gas chromatographic  system used.
2.  Summary
    2.1  Ten milliliters of sample are extracted one  time with  2 ml  of
          solvent.   Three. vl of the extract are  then  injected  into  a  gas

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          chromato graph  equipped  with  a  linearized  electron capture detector
          for separation  and  analysis.
     2.2  The extraction  and  analysis  time  is  10  to 50  minutes  per sample
          depending upon  the  analytical conditions  cnosen.   (See  Taole  1  ana
          Figures 1, 2,  and 3.)
     2.3  Confirmatory evidence is obtained using dissimilar columns and'
          temperature programming.  Wh/»n component  concentrations  are
          sufficiently high (>50 ug/l), halogen specific detectors may be
          employed for improved specificity.
     2.4  Unequivocal  confirmatory analyses at high levels  (>50 ug/L) can oe
          performed  using GC/MS in place of the electron capture detector.
          At levels  below 50 ug/L, unequivocal  confirmation can only be per-
          formed by  the purge  and  trap  technique using GC/MS (4, 5).
     2.5  Standards  dosed into organic  free water and the samples are
          extracted  and analyzed in an  identical  manner in order to comperi-
          sate for possible extraction  losses.
     2.6   The concentration of each trihalomethane is summed and reported  as
          total  trihalomethanes in ug/L.
3.   Interferences
     3.1   Impurities contained in  the extracting  solvent usually account  for
          the majority  of the  analytical  proolems.   Solvent  blanks should  De
          analyzed before a new bottle  of  solvent  is used to extract samples.
          Indirect daily  checks on  the  extracting  solvent are obtained  by
         monitoring the  sample blanks  (6.4.10).   Whenever  an interference  is
         noted  in the  sample  blank, the  analyst  should  reanalyze  the
         extracting solvent.   The  extraction solvent  should be  discarded
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     whenever a high level  (>10  ug/L)  of  interfering compounds are
     traced to it.  Low  level  interferences  generally can de removed  DV
     distillation or column chromatography  (6);  however, it is generally
     more economical to obtain a new  source  of  solvent or select  one  of
     the approved alternative  solvents  listed  in  Section 5.1.
     Interference free solvent is defined as a  solvent containing  less
     than 0.4 ug/L individual  trihalomethane interference.   Protect
     interference-free solvents by storing in a non-laboratory  area
     known to be free of organochlorine solvents.   Subtracting  blank
     values is not recommended.
3.2  Several instances of accidental sample contamination have  oeen
     attributed to diffusion of volatile organics through the  septum
     seal on the sample bottle during shipment and  storage.  The sample
     blank (6.4.10)  is used to monitor for this problem.
3.3  This liquid/liquid extraction technique efficiently extracts  a wide'
     boiling range of non-polar organic compounds and,  in addition,
     extracts the polar organic components of the sample witn varying
     efficiencies.  In order to perform the trihalomethane  analysis as
     rapidly as possible with sensitivities in the  low  ug/L  range, it is
     necessary to use the semi-specific electron capture detector and
     chromatographic columns which have relatively  poor  resolving power.
     Because of these concessions, the probability  of  experiencing
     chromatograpnic interferences is high.  Trihalomethanes are
     primarily products of the chlorination process  and  generally do not
     appear in the raw source water.  The absence of  peaks  in the raw
                                 -3-

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         source water  analysis  with retention times similar to the trinalc-
         methanes  is generally  adequate evidence of an interference-free
         finished  drinking water  analysis.   Because of these possible inter-
         ferences,  in  addition  to  each finished drinking water analysis,  a
         representative  raw  source water (6.4.5) must be analyzed.   When
         potential  interferences  are  noted  in the raw source water  analysis,
         the alternate chromatographic columns must be used  to reanalyze  the
         sample set.   If  interferences are  still noted, qualitative
         identifications  should be performed  according to Sections  2.3  and
         2.4.  If  the  peaks  are confirmed to  be other than trihalomethanes
         and add significantly  to  the total  trihalomethane value  in the
         finished  drinking water  analysis,  then the sample set must be
         analyzed  by the  purge  and trap method (5).
4.  Apparatus                                                •     •   •
    4.1  Extraction vessel"- A  15  mL  total  volume glass vessel  with a Teflon
         lined screw-cap  is  required  to efficiently extract  the samples.
         4.1.1  For samples  that  do not form  emulsions 10"mL~sc~r'ew-cap"
                flasks with  a Teflon  faced  septum (total  volume is  ml.)  are
                recommended.
                Flasks and caps -  Pierce -  #13310 or equivalent
                Septa  -  Teflon  silicone - Pierce #12718 or equivalent.
         4.1.2  For samples  that  form emulsions (turbid source water) 15  mL
                screw  cap centrifuge  tubes  with a Teflon cap liner  are
                recommended.
                Centrifuge tube - Corning 8062-15 or equivalent.
    4.2  Sampling  containers -  40 ml  screw  cap sealed with Teflon faced
         silicone  septa.
                                       -4-

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       Vials and caps - Pierce #13075 .or. equivalent.
       Septa - Pierce #12722 or equivalent.
  4.3  Micro syringes - 10, 100 UL.
  4.4  Micro syringe - 25  uL with a 2-inch oy 0.006-inch needle - ,amil:cn
       702N  or equivalent.
  4.5  Syringes  -  10 ml  glass  hypodermic with Luerlok  tip (2 each).
  4.6  Syringe  valve - 2-way with  luer ends (2 each) - Hamilton
       #86570-1FM1 or equivalent.
 4.7   Pipette - 2.0 ml.  transfer.
 4.3   Glass stoppered volumetric  flasks  - 10  and  100  ml.
 4.9  Gas chromatograph with  linearized  electron  capture detector.
       (Recommended option - temperature  programmaDle.  See Section 4.12).
 4.10 Column A -.4 mm ID x 2m long glass  packed with.3% SP-1000 on
      Supelcoport  (100/120 mesh) operated  at 50°C with 60 mL/min flow.
      (See Figure  1  for  a  sample chrcmatogram and Table 1 for retention
      data).
4.11  Column  Bf- 2 m ID x  2m  long glass packed with  10% squalane  on
      Chromosorto WAW (30/100 mesh) operated at 67°C with  25  mt/min
      flow.  This  column is  recommended as the primary analytical
      column.   Trichloroethylene,  a common raw source  water  contaminate,
      coelutes with  bromodichloromethane.  (See  Figure 2  for  a  sample
      chromatogram and Table 1 for retention  data.)
4.12  Column C - 2 mm ID x 3m  long  glass  packed  with 6i OY-11/4% SP-2100
      on Supelcoport  (100/120 mesh)  temperature  program 45°C  for 12
     minutes, then  program  at l°/minute  to 70°C with  a 25 mL/min

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                 (See  Figure  3  for a sample chromatogram and Taole  I  for
         retention data.)
    4.13 Standard storage containers  -  15  ml amber screw-cap septjm  oof.'.es
         with Teflon  faced silicone septa.
         Bottles and  caps - Pierce *19830  or equivalent.
         Septa - Pierce #12716 or equivalent.
5.   Reagents
    5.1  Extraction  solvent - (See 3.1).
         Recommended  - Pentane3
         Alternative  - hexane,  methyl eyelohexane or 2,2,4-trimethylpentane.
         aPentane has  been  selected as the best solvent for this analysis
         because it elutes,  on  all of  the columns, well before any  of the
         trihalomethanes.   Hi^h  altitudes or laboratory temperatures  in
         excess  of 75°F  may make the use of this solvent impractical.  For
         these reasons,  alternative  solvents are acceptable; however,  the
         analyst may experience  baseline variances in the elution areas of
         the  trihalomethanes  due  to  coelution of these solvents.  The  degree
         of difficulty appears to  be dependent upon the design  and condition
         of the  electron capture  detector.   Such problems  should be
         insignificant when concentrations  of the  coeluting  trihalomethane
         are  in  excess of 5 ug/l.
   5.2  Methyl  alcohol - ACS Reagent  Grade
   5.3  Free and combined chlorine reducing  agents  -  Sodium thiosulfate  ACS
        Reagent Grade - sodium sulfite ACS  Reagent  Grade.
   5.4  Activated carbon - Filtrasorb - 200,  available  from Calgon
        Corporation,  Pittsburgh, PA, or equivalent.
                                    -6-

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    5.5  Standards:13
         5.5.1  Sromofonti 965 - available  from Aldrich Chemical
         5.5.2  Bromodichloromethane 975 - available from Aldricn Chemical
                Company.
         5.5.3  Chlorodibromomethane - available from Columbia Chemical,
                Incorporated, Columbia, S.C.
         5.5.4  Chloroform 99% - available from Aldrich Chemical  Company.
    5.6  Organic-free  water - Organic-free water is defined as water free  af
         interference  when employed in the procedure described herein.
         5.6.1   Organic-free water is generated by passing tap water through
                a  carbon filter bed containing carbon.   Change the  activated
                carbon  whenever the concentration of any triha 1 onethane
                exceeds 0.4  ug/L.
        '5.6.2   A  Mill.ipore  Super-Q Water System or its  equivalent may be
                used to generate organic-free deionized  water.
         5.6.3   Organic-free water may also be prepared  by boiling water for
                15 minutes.   Subsequently,  wlvile  maintaining  the  temperature
                at 90 C,  bubble  a  contaminant free  inert  gas  througn  the
                water at  100 mL/minute  for  one hour.  'While  still hot,
                transfer  the water to  a narrow mouth  screw cap bottle with a
                Teflon  seal.
         5.6.4   Test organic  free  water each day  it  is used  by analyzing it
                according  to  Section  7.
   a precautionary measure,  all standards  must be checked for purity by
boiling  point determinations  or GC/MS  assays.
                                      -7-

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5.7  Standard stock solutions
     5.7.1   Fill  a 10.0 ml ground glass stoppered volumetric flask witn
            approximately 9.8 ml of methyl alcohol.
     5.7.2   Allow the flask  to stand unstoppered about 10 minutes or
            until  all  alcohol  wetted surfaces dry.
     5.7.3   Weigh  the unstoppered flask to the nearest 0.1  mg.
     5.7.4   Using  a  100  UL syringe,  immediately add 2 to  3  drops  of  the
            reference  standard to the flask,  then reweigh.   3e  sure  that
            the reference standard  falls  directly into the  alcohol with-
            out contacting the neck  of the flask.
     5.7.5   Dilute to volume,  stopper,  then mix  by  inverting  the  flask
            several times.
     5.7.6   Transfer the standard solution  to  a  dated  and labeled  15 ml
            screw-cap bottle witn a  TefVon  cap  liner.               '
            NOTE:    Because of tne toxicity of trihalomethanes, it is
                   necessary  to prepare primary dilutions in a hood.
                   It is.furtfl^r recomnenoed.that.a NIOSH/MESA-approved
                   toxic gas rtsoir»tor be used when the analyst
                   handles  Mgn concentrations of such materials.
    5.7.7  Calculate the concentration in micrograms per microliter
           from the net  gain m ««ignt.
    5.7.8  Store  the solution  *t 43:.
           NOTE:    All  standard solutions prepared  in methyl  alcohol
                   are stable  u0 to  4 «««ks when stored under these
                   conditions.  They snould be discarded  after  that
                  •time  has  elapsed.
                                    -4-

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5.3  Aqueous calibration standard precautions
     5.3.1   In order to prepare accurate aqueous standard solutions,  the
            following precautions .rust be observed:
            a. Do not inject more than 20 UL of alcoholic standards into
               100 mL of organ.ic-free water.
            b. Use a 25 UL  Hamilton  702N microsyringe or equivalent.
               (Variations  in needle  geometry will  adversely affect tne
               ability  to  deliver  reproducible volumes  of methanolic
               standards  into water.)
            c.  Rapidly  inject tne  alcoholic  standard  into the'expanded
               area  of  the  filled  volumetric  flask.   Remove  the  needle
               as  fast  as possible after  injection.
          - d. Mix aqueous  standards by  inverting the flask  three times
              only.
           e. Discard the  contents contained  in the neck of the flask.
              Fill  the sample synng« from the standard  solution con-
              tained in tne  e*o*ided area of  the flask as directed in
              Section 7.
           f. Never use pip«ts to 11 lute or transfer samples and
              aqueous standards.
           g. Aqueous standards, «nen stored with a headspace,  are not
              stable and snould s« discarded after  one hour.  Aqueous
              standards can bf starts according to  Sections  6.4.9  and  -
              7.2.
                               .9.

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5.9  Calibration standards
     5.9.1  Prepare, from the standard stock  solutions, a multicomponent
            secondary dilation mixture in methyl alcohol so that a 20 uL
            injection into 100 ml of organic-free water will generate a
            calibration standard which produces a response close (* 25%)
            to that of the unknown.  (See 8.1).
     5.9.2  Alternative calibration procedure
            5.9.2.1 Construct a calibration curve for each trihalo-
                    methane containing a minimum of 3 different concen-
                    trations.  Two of the concentrations must  bracket
                    each unknown.
     5.9.3  Extract and analyze the aqueous calibration standards in the
            same manner as the unknowns.
     5.9.4  Other calibration procedures (7) which require the delivery
            of less than 20 uL of methanolic standards to 10.0 ml
            volumes of water contained in the sample syringe are
            acceptable only if the methanolic standard is delivered by
            the solvent flush technique (8).
5.10 Quality Check Standard Mixture
     5.10.1  Prepare, from the standard stock solutions, a secondary
            dilution mixture in methyl alcohol that contains 10.0 ng/ui.
            of each compound.  (See 5.7.6 and 5.7.3).
     5.10.2  Daily, prepare and analyze a 2.0 ug/L aqueous dilution  from
            this mixture by dosing 20.0 uL into 100 ml of organic-free
            water (See Section 8.1).
                               -10-

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•   Sample Collection  and Handling
   6.1   The sample  containers should have a total volume of at  least 25 ,,L.
        6.1.1   Narrow-nouth  screw-cap bottles  with tne TFE fluorocarbon
               faced  silicons septa cap liners are strongly
   6.2   Glassware Preparation
        6.2.1  Wash all  sample bottles, TFE  seals,  and extraction  flasks  in
              detergent.  Rinse with tap water and finally with distilled
              water.
       6.2.2  Allow the bottles and seals to air dry, then place  in an
              I05°C oven for 1 hour, then allow to cool  in an area known
              to  be free of  organics.
              NOTE:    Oo not heat  the TFE  seals  for'extended  periods of
                      time (>l hou»  because the  siHcone  layer  slowly'
                      degrades at  105°C.
      6.2.3  'When cool,  seal  the bottles using the TFE  seals  that *ill oe
             used for seaVlhg'the ""sample's". "  "'""   '''
 6.3  Sample stabilization - A chemical reducing agent (Section 5.3) is
      added to all  samples in order to arrest the formation of additional
      trihalcmethanes after  sample collection  (7,9) and  to eliminate t.ie
      possibility of  free chlorine reacting with  impurities in tne
      extraction  solvent to  form  interfering organohalides.  DO  NOT ADD
      THE REDUCING  AGENT TQ  SAMPLES AT  COLLECTION TIME WHEN DATA FM
     MAXIMIM  TRIHALOHETHAME  FORMATION  IS DESIRED.  If chemical
     stabilization is employed, then the reagent is  also  added  to the
     blanks.  The  chemical  agent  (2.5  to 3  mg/40 ml)  is added in
                                     -11-

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     crystalline form  to  the  empty  sample  Dottle  just prior to snipping
     to the sampling site.  If  chemical-stabilizator! is  not employed at
     sampling time then the reducing .agent is  added  just before
     extraction..
6.4  Sample Collection
     6.4.1  Collect all samples in duplicate.
     6.4.2  Fill  the sample bottles in such a manner  that no air bubbles
            pass  through the  sample as the bottle is  filled.
     6.4.3  Seal  the bottle so that no air bubbles are entrapped in  it.
     6.4.4  Maintain the hermetic seal on  the sample  bottle until
            analysis.
     6.4.5  The raw source water sample history should resemble the
            finished drinking  water.  The average retention time of the
            finished drinking  water .within the water  plant should be
            taken  into  account when sampling the raw  source water.
     6.4.6  Sampling from  a water tap.
            6.4.6.1  Turn on the water  and allow the  system to flush
                    until  the  temperature of the water has staoilized.
                    Adjust the flow to about 500 mt/minute and  collect
                    duplicate  samples  from the flowing stream.
     6.4.7  Sampling from  an open  body of water.
            6.4.7.1  Fill a 1-quart wide-flwuth  bottle  with sample from a
                    representative area.   Carefully  fill  duplicate
                    sample bottles from the 1-quart  bottle as  in 6.4.
                                -12-

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,.4.,  ,f a ch^ical  reducing agent has  b^added^to the^e

         ._ ^_ ^ -  -£-511  with s3inp16 3ust v-u
       WM>^IAC_ Till  fti**11 **~ r
       ottles, f1ll
       bottle,  and  shake  vigorously for 1 .nnutt.
. 4 9  Sealing  practice for  sept™ seal sere- cap bottles.
       r  ,.   Pen the -tie ana «„ -  overflo-ing.   PU-  °"  •

               seal upon the convex sample -niscus and seal  the
               bottle  by screvln, the cap on tightly.
        649.2Invert  the  s^le and  lightly tap the cap on a  sol,*
         "      surf»ce.   The absence  of  entrapped  air  indicates a
                su«essfUl seal.  If bubbles are present, open  the
                bottle,  add a f. additional drops of sa-nple,  then
                reseal bottle as above.
  a A in Samole blanks
  "      TlO,      Pr.p« — 1. create  at  t,e  labo.a^
                      by filling and sealing ,«p1. bottle with
                       organic-free water just prior to shipping the
                       sample  bottles  to  the sampling site.
                                  i- « to  be stabilized, add an
          6.4.10.2     If the sample is to  be
                       identical amount of reducing agent to the
                       blanks.
           ..4.10.3    Ship the blanks to and f*. the sampling site
                        along with the sample bottles.
                                -13-

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                 6.4.10.4     Store the blanics and the samples, colle*
                              a given site (sample set), together in
                              protected area known to oe free from
                              contamination.   A sample set is defined
                              the samples collected at a given site  (
                              a water treatment plant, duplicate raw :
                              water,  duplicate finished water and the
                              duplicate sample blanks comprise the sar
                              set).
    6.5   When  samples  are collected  and stored under these conditions
          measurable  loss  of  trihalomethanes  has  been detected over  e;
          periods  of  time  (7).   It is recommended that the samples be
          analyzed within  14  days  of  collection.
7.  Extraction  and Analysis
    7.1   Remove the  plungers from two  10-mL  syringes and attach a clc
          syringe  valve  to each.
    7.2   Open  the sample  bottle0  (or standard) and carefully pour the
          -ample into one  of  the  syringe barrels  until  it overflows.  Re
          the plunger and  compress  the  sample.  Open  the  syringe valve  a
          vent  any residue air  while  adjusting  the  sample volume to  1C
          Close  the valve.
    7.3   Fill  the second  syringe  in  an  identical manner  from the same
          bottle.  This  syringe is  reserved for a replicate analysis  (
          and 8.4).
clf for any reason the  chemical  reducing agent has not been  added to
 sample,  then  it  must be  added just  prior to  analyses  at the rate of
 3 mg/40  mL or  by adding  1 mg  directly to the  sample in  the  extracior
                                      -14-

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     7.4   Pipette  2.0 ml  of  extraction  solvent into a clean extraction flasx.
     7.5   Carefully  inject the  contents of  the syringe into the extraction
          flask.
     7.5   Seal with  a Teflon  faced  septum.
     7.7   Shake vigorously for  1 minute.
     7.3   Let stand  until the phases  separate  (-  60 seconds).
          7.8.1  If  the phases  do not separate  on  standing then
                centrifugation can be  used  to  facilitate  separation.
     7.9  Analyze  the sample by injecting 3.0  uL  (solvent  flush
         technique, (8)) of the upper  (organic)  phase  into  the gas
         chromatograph.
8.  Analytical  Quality Control
    8.1  A 2 ug/L quality check standard. (See  5.10) should  be  extracted and
         analyzed each day before any  samples  are  analyzed'.  Instrument-
         status checks and lower limit of detection estimations based upon
         response factor calculations  at 5  times the noise  level  are
         obtained from these data.   In addition, the data obtained from the
         quality check standard can be used to estimate the concentration of
         the unknowns.  From this information  the  appropriate  standards can
         be determined.
    8.2  Analyze the sample  blank and  the raw  source water  to  monitor for
         potential interferences  as described  in Sections 3.1, 3.2, and 3.3.
    8.3  Spiked samples
         8.3.1   For those laboratories analyzing more than  10  samples a day,
                each 10th sample  analyzed should be a laboratory-generated
                                        -15-

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           spike which closely duplicates the average finished
           water in trihalomethane composition  and concentration.
           Prepare the spiked sample  in organic-free water  as described
           in 5.9.
    3.3.2  En those laboratories  analyzing  less  than  10  samples  daily,
           each  time the  analysis  is  performed,  analyze  at  least one
           laboratory generated  spike sample which closely  duplicates
           the  average finished  drinking  water  in  trihalomethane
           composition and concentration.  Prepare the  spiked sample  in
           organic-free  water  as described  in  Section 5.9.
     8.3.3  Maintain  an up-to-date log on  the accuracy and precision
           data collected in Sections 8.3 and 8.4.  If results  are
           significantly different than those cited in Section  10.1,
     • -  •  the  analyst should check out the entire analysis scheme to
            determine why the laboratory's 'precision and accuracy "limits
            are  greater.
8.4  Randomly select and  analyze  10*  of all samples in duplicate.
8.5  Analyze all samples  in  duplicate  wnich appear to deviate more than
     30% from any established norm.
8.6  Quarterly,  spike an  EMSl-Cincinnati  trihalomethane  quality  control
     sample  into organic-free water  and analyze.
     8.6.1   The results  of the  EMSL  trihalomethane quality  control
             sample  should agree  within 20%  of  the  true  value for each
             trihalomethane.  If  they do not,  the analyst must check each
             step io the  standard generation procedure to solve  the
             problem.
                               -L6-

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     3.7  [t is important that the analyst be aware of  the  linear response
          characteristics of the electron capture system  that  is utilized.
          Calibration curves should be generated and rechecked quarterly for
          each  trihalomethane over the concentration range encountered in the
          samples  in order to confirm the linear response range of the system.
          Quantitative data  cannot be calculated from non-linear responses.
          Whenever non-linear responses  are  noted,  the analyst must  dilute
          the sample for  re analysis..
    8.8   Maintain a record  of  the retention  times  for each  trihalomethane
          using  data gathered from spiked  samples and  standards.
          8.8.1  Daily calculate  the  average  retention  time  for each
                trihalomethane and the  variance encountered  for  the  analyses.
                                             /
         8.8.2  If  .individual trihalomethane retention  time  varies by'more
              •  than  lOt over- an  eight  hour  period or does not fall  within
                lOt of an established norm,  the .system  is "out of control."
                The source of_jretentipn data variation must  be corrected
                before acceptable data can be generated.
9.  Calculations
    9.1  Locate each  trihalomethane in the sample chromatogram by comparing
         the retention time  of the suspect peak  to the data gathered in
         8.8.1.  The retention time of the suspect peak must fall'within the
         limits established  in 8.8.1  for a single column identification.
    9.2  Calculate the concentration  of each trihalomethane by comparing the
         peak  heights or peak areas of the samples to those of the
         standards.  Round off  the data to the nearest ug/L or two
         significant Figures.
                                        -17-

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         Concentration,  U9/U

    9.3  Calculate  the  total tri ha lome thane concentration (TTHM) by summing
         the 4  individual  trihalomethane concentrations in ug/L:

TTHM (ug/L) « (cone.  CHC^Hconc. CHBrClj) ""(cone. CH8r2Cl Hconc.CHS^)

    9.4  Calculate  the  limit of  detection (LOO)  for each trihalomethane not
         detected using  the  following criteria:
         LOO  (ug/L)  -     (3TT    x -(2 ug/L)
        where:
              8 »  peak  height  (mm)  of  2 ug/L quality check standard
              A »  5  times  the  noise level  in mm at the e^act retention  time
              of the trihalomethane or- the base line displacement in mm from
              theoretical  zero  at  tn«  exact retention time for the  trihalo-
              methane.  -  :--...._.... -... : ____ _ - -: ....... ._..__-  -    ------
              ATT  «  attenuation  factor.
    9.5  Report the  results  obtained  fry*  the  lower limit  of detection
         estimates along  with  th«  d«ti *zr the samples.
10. Precision and  Accuracy
    10.1 Single lab  precision  and  accuricy.  The data in Table II were
         generated by  spiking  organ ic-frtt water with trihalomethanes as
         described in  5.9.  The  mixtures ««r«  analyzed by the analyst as
         true unknowns.
                                               -18-

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                                   REFERENCES


 1.  Mieure,  J.  P.,  "A Rapid  and  Sensitive Method  for Determining Volatile
    Organohalides  in Water,"  Journal  AWMA.  69_,  60,  1977.

 2.  Reding,  R., et  al.  "THM's  in  Drinking Water:  Analysis  by  LIE  and
    Comparison  to Purge  and  Trap",  Organics Analysis in Water  and
    Wastewater, STP 686  ASTM,  1979.

 3.  "Handbook for Analytical Quality  Control  in Water and Wastewater
    Laboratories," Analytical Quality Control Laboratory, National Environ-
    mental Research Center, Cincinnati,  Ohio, June  1972.

 4.  Budde, W.L., J.W. Eichelberger, "Organic Analysis Using Gas
    Chroma to graphy-Mass  Spectrometry," Ann  Arbor  Science, Ann Arbor,
    Michigan, 1979.
5.
     "The Analysis of Trihalomethanes  in  Finished Water by the Purge and Trap
    Method," Environmental Monitoring  and  Support Laboratory, Environmental
    Research Center, Cincinnati, Ohio, 45268, May 15, 1979.
6.  Richard, J.J.; G.A. Junk, "Liquid Extraction for Rapid Determination of
    Halomethanes in Water," Journal AWWA. 69_, 62, January 1977.

7.  Brass, H.J., et al., "National Organic Monitoring Survey:  Sampling and
    Purgeable Organic Compounds, Drinking water Quality Through Source  •
    Protection," R. B. Pojasek, Editor, Ann Arbor Science,"?. 398, 1977.

8.  White, L.D., et al .  "Convenient Optimized Method for the Analysis of
    Selected Solvent Vapors in Industrial Atmosphere," AIHA Journal, Vol.
    31, p. 225, 1970.

9.  Kopfler, F.C., et al . "GC/MS 3*t«mnnation of Volatiles for the National
    Organics Reconnaissance Survey ;iORS} or Drinking Water,  Identification
    and Analysis of Organic Pollutirts  m *ater,* L. H. Keith, Editor, Ann
    Arbor Science, p. 87, 1976.
                                                                 1071B
                                                                   298

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Trihalomethane
              TABLE I

Retention Times for Trihalomethanes


         Retention  Time,  Minutes
Column A
Chloroform 1.0
Sromodichloromethane 1.5
Chlorodibromomethane 2.6
(di bromoch loromethane)
Bromoform 5.5
Column 8
1.3
2.5d
5.6
10.9
Column C
4.9
11.0
23.1
39.4
dOn this column,-trichloroethylene,  a common raw  source water contaminate,
 coelutes with bromodichloromethane.
                                   Table  II
                   Single Laboratory Accuracy  and Precision
Compound
CHC13
CHC13
CHBrCl?
CHBrCb
CHBrpCl
CHSr^l
CHBr3
CH8r3
Dose Level
uq/L
9.1
69
1.2
12
2.7
17
2.9
14
Number of
Samples
5
3
5
2
5
3
5
3
Mean
ug/L
10
73
1.3
15
2.0
16
2.2
16
Precision
Relative
Standard
Deviation, 5
11
5.3
9.8
1.4
17
9.9
10
12
Accuracy
Percent
Recovery
110
106
108
125
74
94
76
114

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0 -l	2	-4
                     COLUMN PACX1NG:  37.SP-1CCO
                     CARRIES GAS;  57, CH* IN ARGCN
                     CARRIES PLOW:  6C3 ML/MIN.
                     COLUMN TEM?5RATUR£  5Q'C
                     OETSaCR:  SLKTRON  CAPTURE
    RETENTION TIMS  IN  MINUTSS
1  PINJKWPH
                                EXTRACT

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  bU
  Z
uu
                                     to
                                       .
        COLUMN PACKING:
          SQUALANE CARRIER
       PLOW: 2Sml/min COLUMN
           TEMPERATURE: 67
  o
  ce
  O
    V024X
Urf

O

O
ce

5
O

o

0
                                  at
                                  O
                               256X
             5   6   7
             TIME (min)
           3
10
FIGURE 2. EXTRACT OF STANDARD

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COLUMN PACKING: 67, OV. 11 + 47, SP-2ICO
g CARRIER FlOW: 25 m!/min
2 TSMP6RATURE PROGRAM: 45°C-12 M1NUTSS
0 . 1-VMINUTE TO 70
G
a
2 «
vu ° 2 u-



< 1 = is
= U • wu >
M
0
ce
IIOltOFOftM
— I.I.I TRICIIIOI
VI
1
I
1!
2 2 S
- ^
• uy
1§ §1
>- G ^ Q
uj *Z CS «
— * O *
* 1 i
i
I
JU 1

= 2
w o
1 *
g
I ' A
i i i i j
5 10 15 20 25 30 35 40 45
          TIME (min)



FIGURE 3. EXTRACT OF STANDARD

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