United States
         Environmental Protection
         Agency
          Office of Water
          (4601)
EPA814-B-96-006
April 1996
 x>EPA
Reprints of EPA Methods for
Chemical Analyses under the
Information Collection Rule
EPA
814
B
96
006
c.2

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[EPA
 8 IT
 6
 16
1000
EPA814-B-96-006
April 1996
                              REPRINTS OF EPA METHODS FOR

                             CHEMICAL ANALYSES UNDER THE

                              INFORMATION COLLECTION RULE
                                    U S. EPA Headquarters Library
                                         Mail code 3201
                                    1200 Pennsylvania Avenue NW
                                      Washington DC 20460
                                 Informr.t!o:i Issources Center
                                 US EFA (3^04r
                                 401 M Street, SW
                                 Washington, DC 20460  '
                                    OFFICE OF WATER
                      OFFICE OF GROUND WATER AND DRINKING WATER
                               TECHNICAL SUPPORT DIVISION
                                  CINCINNATI, OHIO 45268
                                                             Printed on Recycled Paper

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                                DISCLAIMER

      The methods in this manual have been reviewed and printed previously by
the National Exposure Research Laboratory - Cincinnati, U.S. Environmental
Protection Agency {formerly the Environmental Monitoring Systems Laboratory -
Cincinnati, U.S. Environmental Protection Agency).  Mention of trade names or
commercial products  does not constitute endorsement or recommendation for use.

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                                ABSTRACT

      This publication, "Reprints of EPA Methods for Chemical Analyses under the
Information Collection Rule," is a compilation of EPA methods cited in 141.142
(b) (1) of the Information Collection Rule. The methods are reprinted from the
original manuals which were published by the National Exposure Research
Laboratory (formerly the Environmental Monitoring Systems Laboratory) -
Cincinnati.

      Method 300, "Determination of Inorganic Anions by Ion Chromatography,"
was originally published in "Methods for the Determination of Inorganic Substances
in Environmental Samples, " EPA/600/R-93/100, August 1993, PB94-121811.

      Method 350.1, "Determination of Ammonia Nitrogen by Semi-Automated
Colorimetry," was originally published in "Methods for the Determination of
Inorganic Substances in Environmental Samples," EPA/600/R-93/100, August
1993, PB94-121811.

      Method 551.1, "Determination of Chlorination Disinfection Byproducts,
Chlorinated Solvents, and Halogenated Pesticides/Herbicides in Drinking Water by
Liquid-Liquid Extraction and  Gas Chromatography with Electron-Capture Detection,"
was originally published in "Methods for the Determination of Organic Compounds
in Drinking Water - Supplement III," EPA/600/R-95/131, August 1995,
PB95-261616.

      Method 552.1, "Determination of Haloacetic Acids and Dalapon in Drinking
Water by Ion-Exchange Liquid-Solid Extraction and Gas-Chromatography with an
Electron Capture Detector,"  was originally published in "Methods for the
Determination of Organic Compounds in  Drinking Water - Supplement II,"
EPA/600/R-92/129, August 1992, PB92-207703.

      Method 552.2, "Determination of Haloacetic Acids and Dalapon in Drinking
Water by Liquid-Liquid Extraction, Derivatization and Gas Chromatography  with
Electron Capture Detection," was  originally published in "Methods for the
Determination of Organic Compounds in  Drinking Water - Supplement III,"
EPA/600/R-95/131, August 1995, PB95-261616.
                                     HI

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                            TABLE OF CONTENTS
Method
Number
300.0
350.1
551.1
552.1
552.2
Title

Disclaimer

Abstract .
Revision
                                                                            iii
Determination of Inorganic Anions       2.1
by Ion Chromatography

Determination of Ammonia Nitrogen     2.0
By Semi-Automated Colorimetry

Determination of Chlorination           1.0
Disinfection Byproducts, Chlorinated
Solvents, and Haiogenated Pesticides/
Herbicides in Drinking Water by
Liquid-Liquid Extraction and Gas
Chromatography with Electron-Capture
Detection

Determination of Haloacetic Acids and   1.0
Daiapon in Drinking Water by Ion-
Exchange Liquid-Solid Extraction and
Gas-Chromatography with an Electron
Capture Detector

Determination of Haloacetic Acids and   1.0
Daiapon in Drinking Water by Liquid-
Liquid Extraction, Derivatization and
Gas Chromatography with Electron
Capture Detection

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                     METHOD 300.0

DETERMINATION OF INORGANIC ANIONS BY ION CHROMATOGRAPHY
                      John  D.  Pfaff
               Inorganic Chemistry Branch
               Chemistry Research  Division
                      Revision 2.1
                      August 1993
      ENVIRONMENTAL MONITORING SYSTEMS LABORATORY
           OFFICE OF RESEARCH AND DEVELOPMENT
          U.S.  ENVIRONMENTAL PROTECTION AGENCY
                CINCINNATI, OHIO  45268
                        300.0-1

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                                METHOD 300.0

           DETERMINATION OF INORGANIC ANIONS BY ION CHRONATOGRAPHY
1.0  SCOPE AND APPLICATION

     1.1  This method covers the determination of the following inorganic
          anions:
             PART A.

             Bromide
             Chloride
             Fluoride
             Nitrate

             PART B.

             Bromate
             Chlorate
   Nitrite
   Ortho-Phosphate-P
   Sulfate
   Chlorite
     1.2  The matrices applicable to each method are shown below:

          A.    Drinking water,  surface water,  mixed  domestic  and industrial
               wastewaters,  groundwater,  reagent waters,  solids  {after
               extraction 11.7),  leachates (when no  acetic acid  is used).

          B.    Drinking water and reagent waters

     1.3  The single laboratory Method Detection Limit  (MDL defined in Sect.
          3.2) for the above analytes is  listed  in Tables 1A  and IB.   The  MDL
          for a specific matrix may differ from  those listed,  depending upon
          the nature of the  sample.

     1.4  Method A is recommended for drinking and wastewaters.   The
          multilaboratory ranges  tested for each anion  are as  follows:
                 Analvte

                 Bromide
                 Chloride
                 Fluoride
                 Nitrate-N
                 Nitrite-N
  mq/L

0.63 - 21.0
0.78 - 26.0
0.26 - 8.49
0.42 - 14.0
0.36 - 12.0
                 Ortho-Phosphate-P  0.69 -  23.1
                 Sulfate            2.85 -  95.0
                                   300.0-2

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     1.5  This method is recommended for use only by or under the supervision
          of analysts experienced in the use of ion chromatography and in the
          interpretation of the resulting ion chromatograms.

     1.6  When this method is used to analyze unfamiliar samples for any of
          the above anions, anion identification should be supported by the
          use of a fortified sample matrix covering the anions of interest.
          The fortification procedure is described in Sect. 11.6.

     1.7  Users of the method data should state the data-quality objectives
          prior to analysis.  Users of the method must demonstrate the ability
          to generate acceptable results with this method, using the
          procedures described in Sect. 9.0.

2.0  SUMMARY OF METHOD

     2.1  A small volume of sample, typically 2 to 3 ml, is introduced into
          an ion chromatograph.  The anions of interest are separated and
          measured, using a system comprised of a guard column,  analytical
          column, suppressor device, and conductivity detector.

     2.2  The main differences between Parts A and B are the separator columns
          and guard columns.  Sections 6.0 and 7.0 will elicit the
          differences.

     2.3  An extraction procedure must be performed to use this  method for
          solids (See 11.7).

     2.4  Limited performance-based method modifications may be  acceptable
          provided they are fully documented and meet or exceed  requirements
          expressed in Sect. 9.0, Quality Control.

3.0  DEFINITIONS

     3.1  CALIBRATION BLANK (CB)  A volume of reagent water fortified with
          the same matrix as the calibration standards, but without the
          analytes, internal standards, or surrogate analytes.

     3.2  CALIBRATION STANDARD (CAL)  A solution prepared from the primary
          dilution standard solution or stock standard "'solutions and the
          internal standards and surrogate analytes. 'The CAL solutions are
          used to calibrate the instrument response with respect to analyte
          concentration.

     3.3  FIELD DUPLICATES (FD)  Two separate samples collected at the same
          time and place under identical circumstances and treated exactly the
          same throughout field and laboratory procedures.  Analyses of field
          duplicates indicate the precision associated with sample collection,
          preservation and storage, as well as with laboratory procedures.

     3.4  INSTRUMENT PERFORMANCE CHECK SOLUTION (IPC)  A solution of one or
          more method analytes, surrogates, internal standards,  or other test

                                    300.0-3

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     substances used to evaluate the performance of the instrument system
     with respect to a defined set of criteria.

3.5  LABORATORY FORTIFIED BLANK (LFB) -- An aliquot of reagent water or
     other blank matrices to which known quantities of the method
     analytes are added in the laboratory.  The LFB is analyzed exactly
     like a sample, and its purpose is to determine whether the
     methodology is in control, and whether the laboratory is capable of
     making accurate and precise measurements.

3.6  LABORATORY FORTIFIED SAMPLE MATRIX (LFM) ~ An aliquot of an
     environmental sample to which known quantities of the method
     analytes are added in the laboratory.  The LFM is analyzed exactly
     like a sample, and its purpose is to determine whether the sample
     matrix contributes bias to the analytical results.  The background
     concentrations of the analytes in the sample matrix must be
     determined in a separate aliquot and the measured values in the LFM
     corrected for background concentrations.

3.7  LABORATORY REAGENT BLANK (LRB)  An aliquot of reagent water or
     other blank matrices that are treated exactly as a sample including
     exposure to all glassware, equipment, solvents, reagents, internal
     standards, and surrogates that are used with other samples.  The LRB
     is used to determine if method analytes or other interferences are
     present in the laboratory environment, the reagents, or the
     apparatus.

3.8  LINEAR CALIBRATION RANGE (LCR)  The concentration range over which
     the instrument response is linear.

3.9  MATERIAL SAFETY DATA SHEET (MSDS)  Written information provided by
     vendors concerning a chemical's toxicity, health hazards, physical
     properties, fire, and reactivity data including storage, spill, and
     handling precautions.

3.10 METHOD DETECTION LIMIT (MDL) -- The minimum concentration of an
     analyte that can be identified, measured and reported with 99%
     confidence that the analyte concentration is greater than zero.

3.11 PERFORMANCE EVALUATION SAMPLE (PE)  A solution of method analytes
     distributed by the Quality Assurance Research Division (QARD),
     Environmental Monitoring Systems Laboratory (EMSL-Cincinnati), U. S.
     Environmental Protection Agency, Cincinnati, Ohio, to multiple
     laboratories for analysis.  A volume of the solution is added to a
     known volume of reagent water and analyzed with procedures used for
     samples.  Results of analyses are used by QARD to determine
     statistically the accuracy and precision that can be expected when a
     method is performed by a competent analyst.  Analyte true values are
     unknown to the analyst.

3.12 QUALITY CONTROL SAMPLE (QCS)  A solution of method analytes of
     known concentrations that is used to fortify an aliquot of LRB or

                               300.0-4

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          sample matrix.  The QCS is obtained from a source external to the
          laboratory and different from the source of calibration standards.
          It is used to check laboratory performance with externally prepared
          test materials.

     3.13 STOCK STANDARD SOLUTION (SSS)  A concentrated solution containing
          one or more method analytes prepared in the laboratory using assayed
          reference materials or purchased from a reputable commercial source.

4.0  INTERFERENCES

     4.1  Interferences can be caused by substances with retention times that
          are similar to and overlap those of the anion of interest.  Large
          amounts of an anion can interfere with the peak resolution of an
          adjacent anion.  Sample dilution and/or fortification can be used to
          solve most interference problems associated with retention times.

     4.2  The water dip or negative peak that elutes near, and can interfere
          with, the fluoride peak can usually be eliminated by the addition of
          the equivalent of 1 mL of concentrated eluent (7.3 100X) to 100 mL
          of each standard and sample.

     4.3  Method interferences may be caused by contaminants in the reagent
          water, reagents, glassware, and other sample processing apparatus
          that lead to discrete artifacts or elevated baseline in ion
          chromatograms.

     4.4  Samples that contain particles larger than 0.45 microns and reagent
          solutions that contain particles larger than 0.20 microns require
          filtration to prevent damage to instrument columns and flow systems.

     4.5  Any anion that is not retained by the column or only slightly
          retained will elute in the area of fluoride and interfere.  Known
          coelution is caused by carbonate and other small organic anions.   At
          concentrations of fluoride above 1.5 mg/L,  this interference may not
          be significant, however, it is the responsibility of the user to
          generate precision and accuracy information in each sample matrix.

     4.6  The acetate anion elutes early during the chromatographic run.   The
          retention times of the anions also seem to differ when large amounts
          of acetate are present.  Therefore,  this method is not recommended
          for leachates of solid samples when  acetic acid is used for pH
          adjustment.

     4.7  The quantitation of unretained peaks should be avoided, such as low
          molecular weight organic acids (formate, acetate,  propionate etc.)
          which are conductive and coelute with or near fluoride and would
          bias the fluoride quantitation in some drinking and most waste
          waters.

     4.8  Any residual  chlorine dioxide present in the sample will  result in
          the formation of additional chlorite prior to analysis.  If any

                                   300.0-5

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           concentration of chlorine dioxide is suspected in the sample purge
           the sample with an inert gas (argon or nitrogen) for about five
           minutes or until no chlorine dioxide remains.
5.0  SAFETY

     5.1  The toxicity or carcinogenicity of each reagent used in this method
          have not been fully established.  Each chemical should be regarded
          as a potential health hazard and exposure should be as low as
          reasonably achievable.  Cautions are included for known extremely
          hazardous materials or procedures.

     5.2  Each 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
          Safety Data Sheets (MSDS) should be made available to all personnel
          involved in the chemical analysis.  The preparation of a formal
          safety plan is also advisable.

     5.3  The following chemicals have the potential to be highly toxic or
          hazardous, consult MSDS.

          5.3.1   Sulfuric acid (7.4)

6.0  Equipment and Supplies

     6.1  Balance  Analytical, capable of accurately weighing to the nearest
          0.0001 g.

     6.2  Ion chromatograph  Analytical system complete with ion chromato-
          graph and all required accessories including syringes, analytical
          columns, compressed gasses and detectors.

          6.2.1   Anion guard column: A protector of the separator column.  If
                  omitted from the system the retention times will be shorter.
                  Usually packed with a substrate the same as that in the
                  separator column.

          6.2.2   Anion separator column:  This column produces the separation
                  shown in Figures 1 and 2.

                  6.2.2.1   Anion analytical column (Method A):  The
                            separation shown in Figure 1 was generated using a
                            Dionex AS4A column (P/N 37041).  An optional
                            column may be used if comparable resolution of
                            peaks is obtained, and the requirements of Sect.
                            9.2 can be met.

                  6.2.2.2   Anion analytical column (Method B).  The
                            separation shown in Figure 2 was generated using a
                            Dionex AS9 column (P/N 42025).  An optional column
                            may be used if comparable resolution of peaks is

                                    300.0-6

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          6.2.3
          6.2.4
          obtained and the requirements of Sect. 9.2 can be
          met.

Anion suppressor device:  The data presented In this method
were generated using a Dionex anion micro membrane
suppressor (P/N 37106).

Detector ~ Conductivity cell: approximately 1.25 pL
internal volume, (Dionex, or equivalent) capable of
providing data as required in Sect. 9.2.
     6.3  The Oionex AI-450 Data Chromatography Software was used to generate
          all the data in the attached tables.  Systems using a strlpchart
          recorder and integrator or other computer based data system may
          achieve approximately the same MOL's but the user should demonstrate
          this by the procedure outlined in Sect. 9.2.

7.0  Reagents and Standards

     7.1  Sample bottles:  Glass or polyethylene of sufficient volume to
          allow replicate analyses of anions of interest.

     7.2  Reagent water:  Distilled or deionized water, free of the anions of
          interest.  Water should contain particles no larger than 0.20
          microns.

     7.3  Eluent solution (Method A and Method 8):  Sodium bicarbonate (CASRN
          144-55-8) 1.7 mM, sodium carbonate (CASRN 497-19-8) 1.8 mM.
          Dissolve 0.2856 g sodium bicarbonate (NaHC03)  and  0.3816 g  of sodium
          carbonate (Na2C03)  in reagent water  (7.2) and dilute to  2 L.

     7.4  Regeneration solution (micro membrane suppressor):  Sulfuric acid
          (CASRN-7664-93-9) 0.025N.  Dilute 2.8 ml cone,  sulfuric acid
          (H2S04) to 4 L with reagent water.

     7.5  Stock standard solutions, 1000 mg/L (1 mg/ml):   Stock standard
          solutions may be purchased as certified solutions  or prepared from
          ACS reagent grade materials (dried at 105C for 30 min) as  listed
          below.

          7.5.1   Bromide (Br")  1000 mg/L:   Dissolve  1.2876  g  sodium  bromide
                  (NaBr,  CASRN  7647-15-6) in reagent  water and dilute to 1 L.

          7.5.2   Bromate (Br03") 1000 mg/L:  Dissolve 1.1798g of  sodium
                  bromate (NaBrO,,  CASRN  7789-38-0) in  reagent water  and
                  dilute to 1 L.

          7.5.3   Chlorate (CIO,')  1000 mg/L:  Dissolve 1.2753g of sodium
                  chlorate (NaCIO,,  CASRN 7775-09-9)  in reagent water and
                  dilute to 1 L.
                                   300.0-7

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          7.5.4   Chloride (CL") 1000 mg/L:   Dissolve 1.6485 g sodium
                  chloride (NaCl, CASRN 7647-14-5) in reagent water and
                  dilute to 1 L.

          7.5.5   Chlorite (C102")  1000 mg/L:   Dissolve  1.3410g  of  sodium
                  chlorite (NaClO,, CASRN 7758-19-2)  in  reagent water and
                  dilute to 1 L.

          7.5.6   Fluoride (F")  1000 mg/L:   Dissolve  2.2100g sodium fluoride
                  (NaF, CASRN 7681-49-4)  in reagent water and dilute to 1 L.

          7.5.7   Nitrate (NO",-N)  1000 mg/L:   Dissolve  6.0679 g sodium
                  nitrate (NaN03, CASRN 7631-99-4) in reagent water and
                  dilute to 1 L.

          7.5.8   Nitrite (NO~,-N)  1000 mg/L:   Dissolve  4.9257 g sodium
                  nitrite (NaN02, CASRN 7632-00-0) in reagent water and
                  dilute to 1 L.

          7.5.9   Phosphate (PO=.-P)  1000 mg/L:   Dissolve  4.3937 g  potassium
                  phosphate (KH2PO,,  CASRN 7778-77-0)  in reagent water
                  and dilute to  1 1.

          7.5.10  Sulfate (SO/8)  1000 mg/L:   Dissolve  1.8141 g potassium
                  sulfate (K,S04, CASRN 7778-80-5) in  reagent water and
                  dilute to 1 L.

                  NOTE:  Stability of standards:  Stock standards  (7.5) are
                         stable  for  at least 1 month when stored at 4C.
                         Except  for  the chlorite  standard which  is only stable
                         for two weeks.  Dilute working standards  should be
                         prepared weekly, except  those that contain nitrite
                         and phosphate should be  prepared fresh daily.

     7.6  Ethylenediamine preservation solution:  Dilute 10 mL of
          ethylenediamine (99%)  (CASRN 107-15-3)  to 200 mL with reagent
         water. Use 1 mL of this dilution to each 1 L of sample taken.

8.0  Sample Collection. Preservation and Storage

     8.1  Samples should be collected in  plastic  or glass bottles.  All
          bottles must be thoroughly cleaned andirinsed with  reagent water.
          Volume collected should be sufficient to insure a representative
          sample, allow for replicate analysis, if required,  and minimize
          waste disposal.

     8.2  Sample preservation and holding times for the anions that can be
          determined by this method  are as follows:
          Analvte

          Bromate
Preservation

None required

     300.0-8
Holding Time

   28 days

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          Bromide
          Chlorate
          Chloride
          Chlorite
          Fluoride
          Nitrate-N
          Combined
      (Nitrate/Nitrite)
          Nitrite-N
          0-Phosphate-P
          Sulfate
None required
None required
None required
Cool to 4C
None required
Cool to 4C
cone. H2SO,.
to a pH 
Cool to 4C
Cool to 4C
Cool to 4C
 28  days
 28  days
 28  days
 immediately
 28  days
 48  hours
28 days

 48  hours
 48  hours
 28  days
          NOTE: If the determined value for the combined
                nitrate/nitrite exceeds 0.5 mg/L as N",  a resample
                must be analyzed for the individual concentrations
                of nitrate and nitrite.

     8.3  The method of preservation and the holding time for samples
          analyzed by this method are determined by the anions of interest.
          In a given sample, the anion that requires the most preservation
          treatment and the shortest holding time will  determine the preser-
          vation treatment.  It is recommended that all  samples be cooled to
          4C and held for no longer than 28 days for Method A and analyzed
          immediately in Method B.

          NOTE:   If the sample cannot be analyzed for chlorite within < 10
                  minutes, the sample may be preserved by adding 1 ml of the
                  ethylenediamine (EDA) preservation solution (7.6) to 1 L
                  of sample.  This will preserve the concentration of the
                  chlorite for up to 14 days. This addition of EDA has no
                  effect on bromate or chlorate, so they can also be
                  determined in a sample preserved with EDA.  Residual
                  chlorine dioxide should be removed from the sample
                  (per 4.8) prior to the addition of EDA.

9.0  QUALITY CONTROL

     9.1  Each laboratory using this method is required to operate a formal
          quality control (QC) program.  The minimum requirements of this
          program consist of an initial demonstration of laboratory
          capability, and the periodic analysis of laboratory reagent blanks,
          fortified blanks and other laboratory solutions as a continuing
          check on performance.  The laboratory is required to maintain per-
          formance records that define the quality of the data that are
          generated.

     9.2  INITIAL DEMONSTRATION OF PERFORMANCE

          9.2.1   The initial demonstration of performance is used to
                  characterize instrument performance (determination of LCRs
                  and analysis of QCS) and laboratory performance
                                   300.0-9

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              (determination of MDLs) prior to performing analyses by this
              method.

     9.2.2    Linear Calibration Range (LCR)  The LCR must be determined
              initially and verified every 6 months or whenever a
              significant change in instrument response is observed or
              expected.  The initial demonstration of linearity must use
              sufficient standards to insure that the resulting curve is
              linear.  The verification of linearity must use a minimum of
              a blank and three standards.  If any verification data
              exceeds the initial values by  10%, linearity must be
              reestablished.  If any portion of the range is shown to be
              nonlinear, sufficient standards must be used to clearly
              define the nonlinear portion.

     9.2.3    Quality Control Sample (QCS)  When beginning the use of
              this method, on a quarterly basis or as required to meet
              data-quality needs, verify the calibration standards and
              acceptable instrument performance with the preparation and
              analyses of a QCS.  If the determined concentrations are not
              within  10% of the stated values, performance of the
              determinative step of the method is unacceptable.  The
              source of the problem must be identified and corrected
              before either proceeding with the initial determination of
              MDLs or continuing with on-going analyses.

     9.2.4    Method Detection Limit (MDL)  MDLs must be established for
              all analytes, using reagent water (blank) fortified at a
              concentration of two to three times the estimated instrument
              detection limit/6'  To determine MDL values, take seven
              replicate aliquots of the fortified reagent water and
              process through the entire analytical method.  Perform all
              calculations defined in the method and report the
              concentration values in the appropriate units.  Calculate
              the MDL as follows:

                                MDL = (t) x (S)

             where, t = Student's t value for a 99% confidence level
                        and a standard deviation estimate with n-1
                        degrees of freedom [t = 3.14 for seven
                        replicates].

                    S = standard deviation of the replicate analyses.

             MDLs should be determined.every 6 months, when a new
              operator begins work or whenever there is a significant
              change in the background or instrument response.

9.3  ASSESSING LABORATORY PERFORMANCE
                              300.0-10

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9.3.1   Laboratory Reagent Blank (LRB) -- The laboratory must
        analyze at least one LRB with each batch of samples.  Data
        produced are used to assess contamination from the
        laboratory environment.  Values that exceed the MDL indicate
        laboratory or reagent contamination should be suspected and
        corrective actions must be taken before continuing the
        analysis.

9.3.2   Laboratory Fortified Blank (LFB)  The laboratory must
        analyze at least one LFB with each batch of samples.
        Calculate accuracy as percent recovery (Sect. 9.4.2).   If
        the recovery of any analyte falls outside the required
        control limits of 90-110%, that analyte is judged out of
        control, and the source of the problem should be identified
        and resolved before continuing analyses.

9.3.3   The laboratory must use LFB analyses data to assess
        laboratory performance against the required control limits
        of 90-110%.  When sufficient internal performance data
        become available (usually a minimum of 20-30 analyses),
        optional control limits can be developed from the percent
        mean recovery (x) and the standard deviation (S) of the mean
        recovery.  These data can be used to establish the upper and
        lower control limits as follows:

                    UPPER CONTROL LIMIT - x + 3S
                    LOWER CONTROL LIMIT - x - 3S

        The optional control limits must be equal to or better than
        the required control limits of 90-110%.  After each five to
        ten new recovery measurements, new control limits can  be
        calculated using only the most recent 20-30 data points.
        Also, the standard deviation (S) data should be used to
        establish an on-going precision statement for the level of
        concentrations included in the LFB.  These data must be kept
        on file and be available for review.

9.3.4   Instrument Performance Check Solution (IPC)  For all
        determinations the laboratory must analyze the IPC (a  mid-
        range check standard) and a calibration blank immediately
        following daily calibration, after every tenth sample  (or
        more frequently, if required) and at the end of the sample
        run.  Analysis of the IPC solution and calibration blank
        immediately following calibration must verify that the
        instrument is within  10% of calibration.  Subsequent
        analyses of the IPC solution must verify the calibration is
        still within  10%.  If the calibration cannot be verified
        within the specified limits, reanalyze the IPC solution.  If
        the second analysis of the IPC solution confirms calibration
        to be outside the limits, sample analysis must be
        discontinued, the cause determined and/or in the case  of
        drift, the instrument recalibrated.  All samples following

                         300.0-11

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             the last acceptable IPC solution must be reanalyzed.   The
             analysis data of the calibration blank and IPC solution  must
             be kept on file with the sample analyses data.

9.4  ASSESSING ANALYTE RECOVERY AND DATA QUALITY

     9.4.1   Laboratory Fortified Sample Matrix (LFH) -- The laboratory
             must add a known amount of analyte to a minimum of 10% of
             the routine samples.  In each case the LFM aliquot must  be a
             duplicate of the aliquot used for sample analysis.  The
             analyte concentration must be high enough to be detected
             above the original sample and should not be less than four
             times the MDL.  The added analyte concentration should be
             the same as that used in the laboratory fortified blank.

             9.4.1.1   If the concentration of fortification is less  than
                       25% of the background concentration of the matrix
                       the matrix recovery should not be calculated.

     9.4.2   Calculate the percent recovery for each analyte, corrected
             for concentrations measured in the unfortified sample, and
             compare these values to the designated LFM recovery range
             90-110%.  Percent recovery may be calculated using the
             following equation:
                               C8-C
x 100
             where,   R    percent recovery.
                      C8 *  fortified  sample  concentration.
                      C  -  sample background concentration.
                      s    concentration equivalent of analyte added to
                            sample.

     9.4.3   Until sufficient data becomes available (usually a minimum
             of 20 to 30 analysis), assess laboratory performance against
             recovery limits for method A of 80 to 120% and 75 to 125%
             for method B. When sufficient Internal performance data
             becomes available develop control limits from percent mean
             recovery and the standard deviation of the mean recovery.

     9.4.4   If the recovery of any analyte falls outside the designated
             LFM recovery range and the laboratory performance for that
             analyte is shown to be in control (Sect. 9.3), the recovery
             problem encountered with  the LFM is judged to be either
             matrix or solution related, not system related.

     9.4.5   Where reference materials are available, they should be
             analyzed to provide additional performance data.  The
                              300.0-12

-------
                  analysis of reference samples is a valuable tool for
                  demonstrating the ability to perform the method acceptably.

          9.4.6   In recognition of the rapid advances occurring in chromatog-
                  raphy, the analyst is permitted certain options, such as the
                  use of different columns and/or eluents, to improve the
                  separations or lower the cost of measurements.  Each time
                  such modifications to the method are made, the analyst is
                  required to repeat the procedure in Sect. 9.2.

          9.4.7   It is recommended that the laboratory adopt additional
                  quality assurance practices for use with this method.  The
                  specific practices that are most productive depend upon the
                  needs of the laboratory and the nature of the samples.
                  Field duplicates may be analyzed to monitor the precision of
                  the sampling technique.  When doubt exists over the
                  identification of a peak in the chromatogram,  confirmatory
                  techniques such as sample dilution and fortification, must
                  be used.  Whenever possible, the laboratory should perform
                  analysis of quality control check samples and participate in
                  relevant performance evaluation sample studies.

          9.4.8   At least quarterly, replicates of LFBs should be analyzed to
                  determine the precision of the laboratory measurements.   Add
                  these results to the on-going control  charts to document
                  data quality.

          9.4.9   When using Part B, the analyst should  be aware of the purity
                  of the reagents used to prepare standards.  Allowances must
                  be made when the solid materials are less than 99% pure.

10.0 Calibration and Standardization

     10.1 Establish ion chromatographic operating parameters equivalent to
          those indicated in Tables 1A or IB.

     10.2 For each analyte of interest, prepare calibration standards at a
          minimum of three concentration levels and a blank by adding
          accurately measured volumes of one or more stock standards  (7.5)  to
          a volumetric flask and diluting to volume with reagent water.   If
          a sample analyte concentration exceeds the calibration range the
          sample may be diluted to fall within the range.   If this  is not
          possible then three new calibration concentrations must be  chosen,
          two of which must bracket the concentration of the sample analyte of
          interest.   Each attenuation range of the instrument used  to analyze
          a sample must be calibrated individually.

     10.3 Using injections of 0.1 to 1.0 ml (determined  by injection  loop
          volume) of each calibration standard,  tabulate peak height  or area
          responses  against the concentration.   The results are  used  to
          prepare a  calibration curve for each analyte.   During  this  pro-
          cedure, retention times must  be recorded.

                                   300.0-13

-------
     10.4 The calibration curve must be verified on each working day,  or
          whenever the anion eluent is changed,  and after every 20
          samples.  If the response or retention time for any analyte  varies
          from the expected values by more than   10%,  the test must be
          repeated, using fresh calibration standards.   If the results are
          still more than  10%, a new calibration curve must be prepared
          for that analyte.

     10.5 Nonlinear response can result when the separator column capacity is
          exceeded (overloading).  The response  of the detector to the sample
          when diluted 1:1, and when not diluted, should be compared.   If the
          calculated responses are the same, samples of this total anionic
          concentration need not be diluted.

11.0 Procedure

     11.1 Tables 1A and IB summarize the recommended operating conditions for
          the ion chromatograph.  Included in these tables are estimated
          retention times that can be achieved by this method.  Other  columns,
          chromatographic conditions, or detectors may be used if the
          requirements of Sect. 9.2 are met.

     11.2 Check system calibration daily and, if required, recalibrate as
          described in Sect. 10.

     11.3 Load and inject a fixed amount of well mixed sample.  Flush
          injection loop thoroughly, using each  new sample.  Use the same size
          loop for standards and samples.  Record the resulting peak size in
          area or peak height units.  An automated constant volume injection
          system may also be used.

     11.4 The width of the retention time window used to make identifications
          should be based upon measurements of actual retention time varia-
          tions of standards over the course of  a day.   Three times the
          standard deviation of a retention time can be used to calculate a
          suggested window size for each analyte.  However, the experience of
          the analyst should weigh heavily in the interpretation of
          chromatograms.

     11.5 If the response for the peak exceeds the working range of the
          system, dilute the sample with an appropriate amount of reagent
          water and reanalyze.

     11.6 If the resulting chromatogram fails to produce adequate resolution,
          or if identification of specific anions is questionable, fortify the
          sample with an appropriate amount of standard and reanalyze.

          MOTE:   Retention time is inversely proportional to concentration.
                  Nitrate and sulfate exhibit the greatest amount of change,
                  although all anions are affected to some degree.  In some
                  cases this peak migration may  produce poor resolution or
                  identification.

                                   300.0-14

-------
     11.7 The following extraction should be used for solid materials.  Add an
          amount of reagent water equal to ten times the weight of dry solid
          material taken as a sample.  This slurry is mixed for ten minutes
          using a magnetic stirring device.  Filter the resulting slurry
          before injecting using a 0.45 n membrane type filter.  This can be
          the type that attaches directly to the end of the syringe.  Care
          should be taken to show that good recovery and identification of
          peaks is obtained with the user's matrix through the use of
          fortified samples.

     11.8 It has been reported that lower detection limits for bromate
          (=7 pg/L) can be obtained using a borate based eluent.  The use
          of  this eluent or other eluents that improve method performance may
          be considered as a minor modification of the method and as such
          still are acceptable.

     11.9 Should more complete resolution be needed between peaks the eluent
          (7.3) can be diluted.  This will spread out the run but will also
          cause the later eluting anions to be retained longer.  The analyst
          must determine to what extent the eluent is diluted.  This dilution
          should not be considered a deviation from the method.

12.0 DATA ANALYSIS AND CALCULATIONS

     12.1 Prepare a calibration curve for each analyte by plotting instrument
          response against standard concentration.  Compute sample
          concentration by comparing sample response with the standard curve.
          Multiply answer by appropriate dilution factor.

     12.2 Report only those values that fall  between the lowest and the
          highest calibration standards.  Samples exceeding the highest
          standard should be diluted and reanalyzed.

     12.3 Report results in mg/L.
     12.4 Report
NO '  as N
NO,  as N
HP04= as P
13.0 METHODS PERFORMANCE

     13.1 Tables 1A and 2A give the single laboratory (EMSL-Cincinnati)  MDL
          for each anion included in the method under the conditions listed.

     13.2 Tables 2A and 2B give the single laboratory (EMSL-Cincinnati)
          standard deviation for each anion included in the method in a
          variety of waters for the listed conditions.

     13.3 Multiple laboratory accuracy and bias data (S.)  and estimated  single
          operator values (S )  for  reagent, drinking  and waste water  using
                                   300.0-15

-------
          method A are given for each anion in Tables 3 through 9.  Data from
          19 laboratories were used for this data.

     13.4 Some of the bias statements, for example chloride and sulfate, may
          be misleading due to spiking small increments of the anion into
          large naturally occurring concentrations of the same anion.

14.0 POLLUTION PREVENTION

     14.1 Pollution prevention encompasses any technique that reduces or
          eliminates the quantity or toxicity of waste at the point of
          generation.  Numerous opportunities for pollution prevention exist
          in laboratory operation.  The EPA has established a preferred
          hierarchy of environmental management techniques that places
          pollution prevention as the management option of first choice.
          Whenever feasible, laboratory personnel should use pollution
          prevention techniques to address their waste generation.  When
          wastes cannot be feasibly reduced at the source, the Agency
          recommends recycling as the next best option.

     14.2 Quantity of the chemicals purchased should be based on expected
          usage during its shelf life and disposal cost of unused material.
          Actual  reagent preparation volumes should reflect anticipated usage
          and reagent stability.

     14.3 For information about pollution prevention that may be applicable to
          laboratories and research institutions, consult "Less is Better:
          Laboratory Chemical  Management for Waste Reduction," available from
          the American Chemical Society's Department of Government
          Regulations and Science Policy, 1155 16th Street N.W., Washington
          D.C.  20036, (202) 872-4477.

15.0 WASTE MANAGEMENT

     15.1 The Environmental Protection Agency requires that laboratory waste
          management practices be conducted consistent with all applicable
          rules and regulations.   Excess reagents, samples and method
          process wastes should be characterized and disposed of in an
          acceptable manner.   The Agency urges laboratories to protect the
          air,  water, and land by minimizing and controlling all releases from
          hoods and bench operations,  complying with the letter and spirit of
          any waste discharge  permit and regulations, and by complying with
          all  solid and hazardous waste regulations, particularly the
          hazardous  waste identification rules and land disposal
          restrictions.   For further information on waste management consult
          the "Waste Management Manual for Laboratory Personnel," available
          from the American Chemical  Society at the address listed in Sect.
          14.3.
                                   300.0-16

-------
16.0 REFERENCES

     1.
     5.



     6.

     7.
"Determination of  Inorganic Disinfection By-Products  by  Ion
Chromatography", J. Pfaff, C. Brockhoff.  J. Am. Water Works Assoc.,
Vol 82, No. 4, pg  192.

Standard Methods for the Examination of Water and Wastewater,
Method 4110B, "Anions by Ion Chromatography11, 18th Edition of
Standard Methods (1992).

Dionex, System 4000 Operation and Maintenance Manual, Dionex
Corp., Sunnyvale,  California 94086, 1988.

Method Detection Limit  (MDL) as described in "Trace Analyses for
Wastewater,11 J. Glaser, D. Foerst, G. McKee, S. Quave, W. Budde,
Environmental Science and Technology, Vol. 15, Number 12, page
1426, December, 1981.

American Society for Testing and Materials. Test Method for Anions
in Water by Chemically-Suppressed Ion Chromatography D4327-91.
Annual Book of Standards, Vol 11.01 (1993).

Code of Federal Regulations 40,  Ch. 1,  Pt. 136, Appendix B.

Hautman, D.P. & Bolyard, M. Analysis of Oxyhalide Disinfection By-
products and other Anions of Interest in Drinking Water by Ion
Chromatography.  Jour,  of Chromatog.,  602,  (1992),  65-74.
                                  300.0-17

-------
17.0 TABLES.  DIAGRAMS.  FLOWCHARTS AND VALIDATION DATA
          TABLE 1A.  CHROMATOGRAPHIC CONDITIONS AND  DETECTION  LIMITS
                     IN REAGENT WATER (PART A)

                                 *   RETENTION
ANALYTE
PEAK f
TIME(HIN)
MDL
mg/L
            Fluoride          1       1.2
            Chloride          2       1.7
            Nitrite-N         3       2.0
            Bromide           4       2.9
            Nitrate-N         5       3.2
            o-Phosphate-P     6       5.4
            Sulfate           7       6.9
        0.01
        0.02
        0.004
        0.01
        0.002
        0.003
        0.02
    Standard Conditions:

    Columns: as specified in 6.2.2.1
    Detector:  as specified in 6.2.4
    Eluent:  as specified  in 7.3
Pump Rate: 2.0 mL/min.
Sample Loop: 50 juL
    MDL calculated from data system using  a y-axis  selection  of
    1000 ns and with a stripchart recorder with  an  attenuator
    setting of 1 uMHO full  scale.

    *  See Figure 1
                                   300.0-18

-------
      TABLE IB.  CHROMATOGRAPHIC CONDITIONS AND DETECTION LIMITS
                 IN REAGENT WATER (PART B)
                                  RETENTION
ANALYTE
PEAK #
TIME(MIN)
NDL
mg/L
          Chlorite
          Bromate
          Chlorate
1
2
4
2.8
3.2
7.1
0.01
0.02
0.003
Standard Conditions:

Column: as specified in 6.2.2.2
Detector: as specified in 6.2.4
Eluent: as specified in 7.3
        * See Figure 2
               Pump Rate:  1.0 mL/min.
               Sample Loop:  50 fil
                Attentuation - 1
                y-axis - 500 ns
                               300.0-19

-------
TABLE 2A.  SINGLE-OPERATOR ACCURACY AND BIAS OF STANDARD ANIONS
                             (METHOD A)
ANALYTE
Bromide





Chloride





Fluoride





Nitrate- N





Nitrite- N





o-Phosphate- P




SAMPLE
TYPE
RW
DW
SW
WW
GW
SD
RW
DW
SW
WW
GW
SD
RW
DW
SW
WW
GW
SD
RW
DW
SW
WW
GW
SD
RW
DW
SW
WW
GW
SD
RW
DW
SW
WW
GW
KNOWN NUMBER MEAN STANDAR
CONC. OF RECOVERY DEVI ATI
fma/L) REPLICATES % (ma/Li
5.0
5.0
5.0
5.0
5.0
2.0
20.0
20.0
10.0
20.0
20.0
20.0
2.0
1.0
1.0
1.0
0.4
5.0
10.0
10.0
10.0
10.0
10. 0
10.0
10.0
10.0
5.0
5.0
10.0
2.0
10.0
10.0
10.0
10.0
10.0
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
99
105
95
105
92
82
96
108
86
101
114
90
91
92
73
87
95
101
103
104
93
101
97
82
97
121
92
91
96
98
99
99
98
106
95
0.08
0.10
0.13
0.34
0.34
0.06
0.35
1.19
0.33
5.2
1.3
0.32
0.05
0.06
0.05
0.07
0.07
0.35
0.21
0.27
0.17
0.82
0.47
0.28
0.14
0.25
0.14
0.50
0.35
0.08
0.17
0.26
0.22
0.85
0.33
                              300.0-20

-------
                          TABLE  2A  (CONT'D)
Sulfate            RW
                   DM
                   SW
                   ww
                   GW

  RW = Reagent Water
  DW = Drinking Water
  SW = Surface Water
20.0
50.0
40.0
40.0
40.0
7
7
7
7
7
 99
105
 95
102
112
0.40
3.35
1.7
6.4
3.2
WW - Mixed Domestic and Industrial  Wastewater
GW = Groundwater
SD = USEPA QC Solid (shale)
                               300.0-21

-------
TABLE 2B. SINGLE-OPERATOR ACCURACY AND BIAS OF BY-PRODUCT
                             (PART B)
NUMBER MEAN STANDARD
SAMPLE SPIKE OF RECOVERY DEVIATION
ANALYTE TYPE (mg/L) REPLICATES % (rog/L)
Bromate RW 5.0
1.0
0.1
0.05
DW 5.0
1.0
0.1
0.05
Chlorate RW 5.0
1.0
0.1
0.05
DW 5.0
1.0
0.1
0.05
Chlorite RW 5.0
1.0
0.1
0.05
DW 5.0
1.0
0.1
0.05
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
103
98
155
122
95
85
98
98
101
97
100
119
101
115
121
110
100
98
86
94
96
100
76
96
0.07
0.04
0.005
0.01
0.04
0.02
0.005
0.005
0.06
0.01
0.01
0.05
0.04
0.01
0.005
0.01
0.04
0.01
0.01
0.01
0.03
0.02
0.00
0.01
  RW = Reagent Water
  DW = Drinking Water
                               300.0-22

-------
TABLE 3.     MULTIPLE LABORATORY (n*19)
             DETERMINATION OF BIAS FOR FLUORIDE
WATER
Reagent





Drinking





Waste





AM'T ADDED
mg/L
0.26
0.34
2.12
2.55
6.79
8.49
0.26
0.34
2.12
2.55
6.79
8.49
0.26
0.34
2.12
2.55
6.79
8.49
AM'T FOUND
mg/L
0.25
0.29
2.12
2.48
6.76
8.46
0.24
0.34
2.09
2.55
6.84
8.37
0.25
0.32
2.13
2.48
6.65
8.27
st
0.08
0.11
0.07
0.14
0.20
0.30
0.08
0.11
0.18
0.16
0.54
0.75
0.15
0.08
0.22
0.16
0.41
0.36
S0
0.11

0.12

0.19

0.05

0.06

0.25

0.06

0.15

0.20

BIAS
%
-3.8
-14.7
0.0
-2.7
-0.4
-0.4
-7.7
0.0
-1.4
0.0
+0.7
-1.4
-3.8
-5.9
+0.5
-2.7
-2.1
-2.6
                  300.0-23

-------
TABLE 4.    MULTIPLE LABORATORY (n=19)
            DETERMINATION OF BIAS FOR CHLORIDE
WATER
Reagent





Drinking





Waste





AM'T ADDED
mg/L
0.78
1.04
6.50
7.80
20.8
26.0
0.78
1.04
6.50
7.80
20.8
26.0
0.78
1.04
6.50
7.80
20.8
26.0
AM'T FOUND
mg/L
0.79
1.12
6.31
7.76
20.7
25.9
0.54
0.51
5.24
6.02
20.0
24.0
0.43
0.65
4.59
5.45
18.3
23.0
st
0.17
0.46
0.27
0.39
0.54
0.58
0.35
0.38
1.35
1.90
2.26
2.65
0.32
0.48
1.82
2.02
2.41
2.50
So
0.29

0.14

0.62

0.20

1.48

1.14

0.39

0.83

1.57

BIAS
%
+1.3
+7.7
-2.9
-0.5
-0.5
-0.4
-30.8
-51.0
-19.4
-22.8
-3.8
-7.7
-44.9
-37.5
-29.4
-30.1
-11.8
-11.5
                  300.0-24

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TABLE 5. MULTIPLE LABORATORY (n=19)
         DETERMINATION OF BIAS FOR NITRITE - NITROGEN
HATER
Reagent





Drinking





Waste





AM'T ADDED
mg/L
0.36
0.48
3.00
3.60
9.60
12.0
0.36
0.48
3.00
3.60
9.60
12.0
0.36
0.48
3.00
3.60
9.60
12.0
AM'T FOUND
mg/L
0.37
0.48
3.18
3.83
9.84
12.1
0.30
0.40
3.02
3.62
9.59
11.6
0.34
0.46
3.18
3.76
9.74
12.0
st
0.04
0.06
0.12
0.12
0.36
0.27
0.13
0.14
0.23
0.22
0.44
0.59
0.06
0.07
0.13
0.18
0.49
0.56
So
0.04

0.06

0.26

0.03

0.12

0.28

0.04

0.10

0.26

BIAS
%
+2.8
0.0
+6.0
+6.4
+2.5
+0.6
-16.7
-16.7
+0.7
+0.6
-0.1
-3.1
-5.6
-4.2
+6.0
+4.4
+1.5
+0.3
                    300.0-25

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TABLE 6. MULTIPLE LABORATORY (n*19)
         DETERMINATION OF BIAS FOR BROMIDE
WATER
Reagent





Drinking





Waste





AM'T ADDED
mg/L
0.63
0.84
5.24
6.29
16.8
21.0
0.63
0.84
5.24
6.29
16.8
21.0
0.63
0.84
5.24
6.29
16.8
21.0
AM'T FOUND
mg/L
0.69
0.85
5.21
6.17
17.1
21.3
0.63
0.81
5.11
6.18
17.0
20.9
0.63
0.85
5.23
6.27
16.6
21.1
t
0.11
0.12
0.22
0.35
0.70
0.93
0.13
0.13
0.23
0.30
0.55
0.65
0.15
0.15
0.36
0.46
0.69
0.63
S0
0.05

0.21

0.36

0.04

0.13

0.57

0.09

0.11

0.43

BIAS
%
+9.5
+1.2
-0.6
-1.9
+1.6
+1.5
0.0
-3.6
-2.5
-1.7
+0.9
-0.4
0.0
+1.2
-0.2
-0.3
-1.0
+0.3
                     300.0-26

-------
TABLE 7.  MULTIPLE LABORATORY (n=19)
          DETERMINATION OF BIAS FOR NITRATE - NITROGEN
HATER
Reagent





Drinking





Waste





AM'T ADDED
mg/L
0.42
0.56
3.51
4.21
11.2
14.0
0.42
0.56
3.51
4.21
11.2
14.0
0.42
0.56
3.51
4.21
11.2
14.0
AM'T FOUND
mg/L
0.42
0.56
3.34
4.05
11.1
14.4
0.46
0.58
3.45
4.21
11.5
14.2
0.36
0.40
3.19
3.84
10.9
14.1
t
0.04
0.06
0.15
0.28
0.47
0.61
0.08
0.09
0.27
0.38
0.50
0.70
0.07
0.16
0.31
0.28
0.35
0.74
S0
0.02

0.08

0.34

0.03

0.10

0.48

0.06

0.07

0.51

BIAS
%
0.0
0.0
-4.8
-3.8
-1.1
+2.6
+9.5
+3.6
-1.7
0.0
+2.3
+1.6
-14.6
-28.6
-9.1
-8.8
-3.0
+0.4
                      300.0-27

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TABLE 8.  MULTIPLE LABORATORY (n=19)
          DETERMINATION OF BIAS FOR ORTHO-PHOSPHATE
WATER
Reagent





Drinking





Waste





AM'T ADDED
mg/L
0.69
0.92
5.77
6.92
18.4
23.1
0.69
0.92
5.77
6.92
18.4
23.1
0.68
0.92
5.77
6.92
18.4
23.1
AM'T FOUND
mg/L
0.69
0.98
5.72
6.78
18.8
23.2
0.70
0.96
5.43
6.29
18.0
22.6
0.64
0.82
5.18
6.24
17.6
22.4
t
0.06
0.15
0.36
0.42
1.04
0.35
0.17
0.20
0.52
0.72
0.68
1.07
0.26
0.28
0.66
0.74
2.08
0.87
S0
0.06

0.18

0.63

0.17

0.40

0.59

0.09

0.34

1.27

BIAS
'/.
0.0
+6.5
-0.9
-2.0
+2.1
+0.4
+1.4
+4.3
-5.9
-9.1
-2.2
-2.0
-7.2
-10.9
-10.2
-9.8
-4.1
-3.0
                        300.0-28

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TABLE 9.  MULTIPLE LABORATORY (n*19)
          DETERMINATION OF BIAS FOR SULFATE
WATER
Reagent





Drinking





Waste





AN'T ADDED
mg/L
2.85
3.80
23.8
28.5
76.0
95.0
2.85
3.80
23.8
28.5
76.0
95.0
2.85
3.80
23.8
28.5
76.0
95.0
AN'T FOUND
mg/L
2,83
3.83
24.0
28.5
76.8
95.7
1.12
2.26
21.8
25.9
74.5
92.3
1.89
2.10
20.3
24.5
71.4
90.3
st
0.32
0.92
1.67
1.56
3.42
3.59
0.37
0.97
1.26
2.48
4.63
5.19
0.37
1.25
3.19
3.24
5.65
6.80
So
0.52

0.68

2.33

0.41

0.51

2.70

0.24

0.58

3.39

BIAS
%
-0.7
+0.8
+0.8
-0.1
+1.1
+0.7
-60.7
-40.3
-8.4
-9.1
-2.0
-2.8
-33.7
-44.7
-14.7
-14.0
-6.1
-5.0
                           300.0-29

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Method A
Peak Ret. Time
1 1.17
2 1.73
3 2.02
2 4 2.95



1
I
5 3.20
6 5.38
7 6.92
7
5 A
I
i
Hi i V
JV ,J Y S^ J \^

I I II i
0 2 46 8
Minutes
Figure 1. Chromatogram showing separation using the AS4A column

Ion
F-
ci-
N02-
Br
NO,-
HPO^
so4J-








mg/L
2
20
2
2
10
2
60







                                    Method  B
                                                 Peak
                                                 1
                                                 2
                                                 3
                                                 4
Ret. Time
2.75
3.23
3.63
7.08
Ion
CI02-
Br03-
ci-
CI03-
              I
0246
                        Minutes
Figure 2. Chromatogram showing separation using the ASS column
mg/L
0.1
0.1
0.1
0.1
                                        300.0-30

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                          METHOD 350.1

DETERMINATION OF AMMONIA NITROGEN BY SENI-AUTOMATED COLORIHETRY
                   Edited by James W. O'Dell
                   Inorganic  Chemistry  Branch
                  Chemistry Research Division
                          Revision  2.0
                          August 1993
          ENVIRONMENTAL MONITORING SYSTEMS LABORATORY
              OFFICE OF RESEARCH AND DEVELOPMENT
             U.S. ENVIRONMENTAL PROTECTION AGENCY
                    CINCINNATI, OHIO  45268
                            350.1-1

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                                 METHOD 350.1

        DETERMINATION OF AMMONIA NITROGEN BY SEMI-AUTOMATED COLORIMETRY


 1.0  SCOPE AND APPLICATION

     1.1  This method covers the determination of ammonia in drinking, ground,
          surface, and saline waters, domestic and industrial wastes.

     1.2  The applicable range is 0.01 to 2.0 mg/L NH3 as N.   Higher
          concentrations can be determined by sample dilution.  Approximately
          60 samples per hour can be analyzed.

     1.3  This method is described for macro glassware; however, micro
          distillation equipment may also be used.

2.0  SUMMARY OF METHOD

     2.1  The sample is buffered at a pH of 9.5 with a borate buffer in order
          to decrease hydrolysis of cyanates and organic nitrogen compounds,
          and is distilled into a solution of boric acid.  Alkaline phenol and
          hypochlorite react with ammonia to form indophenol  blue that is
          proportional to the ammonia concentration.  The blue color formed is
          intensified with sodium nitroprusside and measured col orimetrically.

     2.3  Reduced volume versions of this method that use the same reagents
          and molar ratios are acceptable provided they meet the quality
          control and performance requirements stated in the method.

     2.4  Limited performance-based method modifications may be acceptable
          provided they are fully documented and meet or exceed requirements
          expressed in Sect. 9.0, Quality Control.

3.0  DEFINITIONS

     3.1  CALIBRATION BLANK (CB)   A volume of reagent water fortified with
          the same matrix as the calibration standards, but without the
          analytes, internal standards,  or surrogate analytes.

     3.2  CALIBRATION STANDARD (CAL)  --  A solution prepared from the primary
          dilution standard solution or  stock standard solutions and the
          internal standards and surrogate analytes.  The CAL solutions are
          used to calibrate the instrument response with respect to analyte
          concentration.

     3.3  INSTRUMENT PERFORMANCE CHECK SOLUTION (IPC)  A solution of one or
          more method analytes,  surrogates,  internal standards,  or other test
          substances used to evaluate the performance of the  instrument system
          with respect to a defined set  of criteria.
                                   350.1-2

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3.4  LABORATORY  FORTIFIED  BLANK  (LFB)  An aliquot of reagent water or
     other  blank matrices  to which known quantities of the method
     analytes  are  added  in the laboratory.  The LFB Is analyzed exactly
     like a sample,  and  its purpose  is to determine whether the
     methodology is  in control,  and  whether the laboratory is capable of
     making accurate  and precise measurements.

3.5  LABORATORY  FORTIFIED  SAMPLE MATRIX (LFM)  An aliquot of an
     environmental sample  to which known quantities of the method
     analytes  are  added  in the laboratory.  The LFM is analyzed exactly
     like a sample,  and  its purpose  is to determine whether the sample
     matrix contributes  bias to  the  analytical results.  The background
     concentrations  of the analytes  in the sample matrix must be
     determined  in a  separate aliquot and the measured values in the LFM
     corrected for background concentrations.

3.6  LABORATORY  REAGENT BLANK (LRB)   An aliquot of reagent water or
     other  blank matrices  that are treated exactly as a sample including
     exposure to all  glassware,  equipment, solvents, reagents, internal
     standards,  and  surrogates that  are used with other samples.  The LRB
     is used to  determine  if method  analytes or other interferences are
     present in  the  laboratory environment, the reagents, or the
     apparatus.

3.7  LINEAR CALIBRATION RANGE (LCR)   The concentration range over which
     the instrument response is  linear.

3.8  MATERIAL SAFETY  DATA  SHEET  (HSDS) - Written information provided by
     vendors concerning a  chemical's toxicity, health hazards, physical
     properties, fire, and reactivity data including storage,  spill, and
     handling precautions.

3.9  METHOD DETECTION LIMIT (MDL)  The minimum concentration of an
     analyte that can be identified,  measured and reported with 99%
     confidence  that  the analyte concentration is greater than zero.

3.10 QUALITY CONTROL SAMPLE (QCS)  A solution of method analytes of
     known concentrations  that is used to fortify an aliquot  of LRB or
     sample matrix.  The QCS is obtained from a source external  to the
     laboratory  and different from the source of calibration  standards.
     It is used  to check laboratory performance with externally prepared
     test materials.

3.11 STOCK STANDARD SOLUTION (SSS)  ~ A concentrated solution  containing
     one or more method analytes  prepared in the laboratory using assayed
     reference materials or purchased from a reputable commercial  source.
                              350.1-3

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 4.0   INTERFERENCES

      4.1  Cyanate, which may  be  encountered  in certain industrial effluents,
          will  hydrolyze to some extent even at the pH of 9.5 at which
          distillation  is  carried  out.

      4.2  Residual chorine must  be removed by pretreatment of the sample with
          sodium thiosulfate  or  other reagents before distillation.

      4.3  Method interferences may be caused by contaminants in the reagent
          water, reagents, glassware, and other sample processing apparatus
          that  bias  analyte response.

 5.0   SAFETY

      5.1  The toxicity  or  carcinogenicity of each reagent used in this method
          have  not been fully established.  Each chemical should be regarded
          as a  potential health  hazard and exposure should be as low as
          reasonably achievable.   Cautions are included for known extremely
          hazardous materials or procedures.

      5.2  Each  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
          Safety Data Sheets  (MSDS) should be made available to all personnel
          involved in the chemical  analysis.  The preparation of a formal
          safety plan is also advisable.

      5.3  The following chemicals  have the potential to be highly toxic or
          hazardous, consult MSDS.

          5.3.1   Sulfuric acid  (7.6)

          5.3.2   Phenol (7.7)

          5.3.3   Sodium nitroprusside (7.10)

6.0  EQUIPMENT AND SUPPLIES

     6.1  Balance - Analytical,  capable of accurately weighing to the nearest
          0.0001 g.

     6.2  Glassware - Class A volumetric flasks and pi pets as required.

     6.3  An all-glass distilling apparatus with an 800-1000-mL flask.

     6.4  Automated  continuous flow analysis equipment designed to deliver and
          react sample and reagents in the required order and ratios.

          6.4.1   Sampling device  (sampler)

          6.4.2   Multichannel pump

                                    350.1-4

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          6.4.3   Reaction unit or manifold

          6.4.4   Colorimetric detector

          6.4.5   Data recording device

7.0  REAGENTS AND STANDARDS

     7.1  Reagent water - Ammonia free:  Such water is best prepared by
          passage through an ion exchange column containing a strongly acidic
          cation exchange resin mixed with a strongly basic anion exchange
          resin.  Regeneration of the column should be carried out according
          to the manufacturer's instructions.

          NOTE 1:  All solutions must be made with ammonia-free water.

     7.2  Boric acid solution (20 g/L):  Dissolve 20 g H3B03  (CASRN  10043-35-
          3) in reagent water and dilute to 1 L.

     7.3  Borate buffer:  Add 88 ml of 0.1 N NaOH (CASRN 1310-73-2) solution
          to 500 ml of 0.025 M sodium tetraborate solution (5.0 g anhydrous
          Na2B40, [CASRN 1330-43-4] or 9.5 g Na2B40/10H20 [CASRN 1303-96-4]  per
          L) ana dilute to 1 L with reagent water.

     7.4  Sodium hydroxide, 1 N:  Dissolve 40 g NaOH in reagent water and
          dilute to 1 L.

     7.5  Dechlorinating reagents:  A number of dechlorinating reagents may be
          used to remove residual chlorine prior to distillation.  These
          include:

          7.5.1   Sodium thiosulfate:  Dissolve 3.5 g Na2S,03'5H20 (CASRN
                  10102-17-7) in reagent water and dilute to 1 L.  One mi. of
                  this solution will  remove 1 mg/L of residual chlorine in 500
                  mL of sample.

          7.5.2   Sodium sulfite:  Dissolve 0.9 g Na2S03 (CASRN 7757-83-7)  in
                  reagent water and dilute to 1 L. One ml removes 1 mg/L Cl
                  per 500 mL of sample.

     7.6  Sulfuric acid 5 N:  Air scrubber solution.   Carefully add 139 mL of
          cone, sulfuric acid (CASRN 7664-93-9) to approximately 500 mL of
          reagent water.  Cool  to room temperature and dilute to 1 L with
          reagent water.

     7.7  Sodium phenolate:  Using a 1-L Erlenmeyer flask, dissolve 83 g
          phenol (CASRN 108-95-2) in 500 mL of distilled water.  In small
          increments, cautiously add with agitation,  32 g of NaOH.
          Periodically cool flask under water faucet.   When cool, dilute to
          1 L with  reagent water.
                                   350.1-5

-------
      7.8  Sodium hypochlorite  solution:  Dilute 250 ml of a bleach solution
          containing 5.25% NaOCl  (CASRN 7681-52-9) (such as "Clorox") to 500
          ml with reagent water.  Available chlorine level should approximate
          2% to 3%.  Since "Clorox" is a proprietary product, its formulation
          is subject to change.   The analyst must remain alert to detecting
          any variation in this product significant to its use in this
          procedure.  Due to the  instability of this product, storage over an
          extended period should  be avoided.

      7.9  Disodium ethylenediamine-tetraacetate (EDTA) (5%):  Dissolve 50 g of
          EDTA (disodium salt) (CASRN 6381-92-6) and approximately six pellets
          of NaOH in 1 L of reagent water.

      7.10 Sodium nitroprusside (0.05%):  Dissolve 0.5 g of sodium
          nitroprusside (CASRN 14402-89-2) in 1 L of reagent water.

      7.11 Stock solution:  Dissolve 3.819 g of anhydrous ammonium chloride,
          NH4C1  (CASRN 12125-02-9),  dried at 105C,  in reagent water, and
          dilute to 1 L.  1.0 ml  = 1.0 mg NH3-N.

      7.12 Standard Solution A:  Dilute 10.0 ml of stock solution (7.11) to 1 L
          with reagent water.  1.0 ml = 0.01 mg NH3-N.

      7.13 Standard Solution B:  Dilute 10.0 ml of standard solution A (7.12)
          to 100.0 ml with reagent water.  1.0 mL = 0.001 mg NH3-N.

8.0   SAMPLE COLLECTION. PRESERVATION AND STORAGE

      8.1  Samples should be collected in plastic or glass bottles.  All
          bottles must be thoroughly cleaned and rinsed with reagent water.
          Volume collected should be sufficient to insure a representative
          sample, allow for replicate analysis (if required), and minimize
          waste disposal.

      8.2  Samples must be preserved with H2S04 to a pH <  2 and cooled to  4C
          at the time of collection.

     8.3  Samples should be analyzed as soon as possible after collection.  If
          storage is required, preserved samples are maintained at 4"C and may
          be held for up to 28 days.

9.0  QUALITY CONTROL

     9.1  Each laboratory using this method is required to operate a formal
          quality control (QC) program.  The minimum requirements of this
          program consist of an initial demonstration of laboratory
          capability,  and the periodic analysis of laboratory reagent blanks,
          fortified blanks and other laboratory solutions as a continuing
          check on performance.  The laboratory is required to maintain per-
          formance records that define the quality of the data that are
          generated.
                                    350.1-6

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9.2  INITIAL DEMONSTRATION OF PERFORMANCE

     9.2.1   The initial demonstration of performance is used to
             characterize instrument performance (determination of LCRs
             and analysis of QCS) and laboratory performance
             (determination of MDLs) prior to performing analyses by this
             method.

     9.2.2   Linear Calibration Range (LCR)  The LCR must be determined
             initially and verified every 6 months or whenever a
             significant change in instrument response is observed or
             expected.  The initial demonstration of linearity must use
             sufficient standards to insure that the resulting curve is
             linear.   The verification of linearity must use a minimum of
             a blank and three standards.  If any verification data
             exceeds  the initial  values by  10%, linearity must be
             reestablished.  If any portion of the range is shown to be
             nonlinear, sufficient standards must be used to clearly
             define the nonlinear portion.

     9.2.3   Quality  Control  Sample (QCS)  When beginning the use of
             this method,  on  a quarterly basis or as required to meet
             data-quality needs,  verify the calibration  standards and
             acceptable instrument performance with the  preparation and
             analyses of a QCS.   If the determined concentrations are not
             within  10% of  the  stated values,  performance of the
             determinative step of the method is unacceptable.   The
             source of the problem must be  identified and corrected
             before either proceeding with  the initial determination of
             MDLs or  continuing with on-going analyses.

     9.2.4   Method Detection Limit (MDL)  MDLs must be established for
             all  analytes,  using  reagent water (blank) fortified at a
             concentration of two to three  times the estimated  instrument
             detection limit.' *   To determine MDL values,  take seven
             replicate aliquots of the fortified reagent  water  and
             process  through  the  entire analytical  method.   Perform all
             calculations  defined in the method  and report  the
             concentration values in the appropriate units.   Calculate
             the  MDL  as follows:

                               MDL  = (t) x  (S)

             where, t = Student's t  value for a  99% confidence  level
                        and a standard  deviation  estimate with  n-1
                        degrees of freedom  [t  =  3.14  for  seven
                        replicates],

                   S = standard  deviation of the replicate analyses.
                              350.1-7

-------
             MDLs should be determined every 6 months,  when a new
             operator begins work or whenever there is  a significant
             change in the background or instrument response.
9.3  ASSESSING LABORATORY PERFORMANCE

     9.3.1   Laboratory Reagent Blank (LRB)  -- The laboratory must
             analyze at least one LRB with each batch of samples.   Data
             produced are used to assess contamination from the
             laboratory environment.   Values that exceed the MDL indicate
             laboratory or reagent contamination should be suspected and
             corrective actions must  be taken before continuing the
             analysis.

     9.3.2   Laboratory Fortified Blank (LFB)  The laboratory must
             analyze at least one LFB with each batch of samples.
             Calculate accuracy as percent recovery (Sect. 9.4.2).  If
             the recovery of any analyte falls outside the required
             control limits of 90-110%, that analyte is judged out of
             control, and the source  of the problem should be identified
             and resolved before continuing analyses.

     9.3.3   The laboratory must use  LFB analyses data to assess
             laboratory performance against the required control limits
             of 90-110%.  When sufficient internal performance data
             become available (usually a minimum of 20-30 analyses),
             optional control limits  can be developed from the percent
             mean recovery (x) and the standard deviation (S) of the mean
             recovery.  These data can be used to establish the upper and
             lower control limits as  follows:

                         UPPER CONTROL LIMIT = x + 3S
                         LOWER CONTROL LIMIT = x - 3S

             The optional control limits must be equal to or better than
             the required control limits of 90-110%.  After each five to
             ten new recovery measurements,  new control limits can be
             calculated using only the most recent 20-30 data points.
             Also, the standard deviation (S) data should be used to
             established an on-going  precision statement for the level of
             concentrations included  in the LFB.  These data must be kept
             on file and be available for review.

     9.3.4   Instrument Performance Check Solution (IPC)  For all
             determinations the laboratory must analyze the IPC (a mid-
             range check standard) and a calibration blank immediately
             following daily calibration, after every tenth sample (or
             more frequently, if required) and at the end of the sample
             run.  Analysis of the IPC solution and calibration blank
             immediately following calibration must verify that the
             instrument is within  10% of calibration.  Subsequent
             analyses of the IPC solution must verify the calibration is

                              350.1-8

-------
             still within  10%.  If the calibration cannot be verified
             within the specified limits, reanalyze the IPC solution.  If
             the second analysis of the IPC solution confirms calibration
             to be outside the limits, sample analysis must be
             discontinued, the cause determined and/or in the case of
             drift, the instrument recalibrated.  All samples following
             the last acceptable IPC solution must be reanalyzed.  The
             analysis data of the calibration blank and IPC solution must
             be kept on file with the sample analyses data.

9.4  ASSESSING ANALYTE RECOVERY AND DATA QUALITY

     9.4.1   Laboratory Fortified Sample Matrix (LFM)  The laboratory
             must add a known amount of analyte to a minimum of 10% of
             the routine samples.  In each case the LFM aliquot must be a
             duplicate of the aliquot used for sample analysis.  The
             analyte concentration must be high enough to be detected
             above the original sample and should not be less than four
             times the MDL.  The added analyte concentration should be
             the same as that used in the laboratory fortified blank.

     9.4.2   Calculate the percent recovery for each analyte, corrected
             for concentrations measured in the unfortified sample, and
             compare these values to the designated LFM recovery range
             90-110%.  Percent recovery may be calculate using the
             following equation:
                R =
CS-C
x 100
             where,   R  -  percent recovery.
                      Cs    fortified  sample concentration.
                      C  =  sample background  concentration.
                      s  =  concentration equivalent of analyte added  to
                            sample.

     9.4.3   If the recovery of any analyte falls outside the designated
             LFM recovery range and the laboratory performance for that
             analyte is shown to be in control  (Sect.  9.3),  the recovery
             problem encountered with  the LFM  is  judged to be either
             matrix or solution related,  not system related.

     9.4.4   Where reference materials are available,  they should  be
             analyzed to  provide additional  performance data.   The
             analysis of  reference samples is  a valuable tool  for
             demonstrating the ability to perform the  method  acceptably.
                              350.1-9

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10.0 CALIBRATION AND STANDARDIZATION

     10.1 Prepare a series of at least 3 standards, covering the desired
          range, and a blank by diluting suitable volumes of standard
          solutions (7.12, 7.13) to 100 ml with reagent water.

     10.2 Process standards and blanks as described in Sect. 11, Procedure.

     10.3 Set up manifold as shown in Figure 1.

     10.4 Prepare flow system as described in Sect, 11, Procedure.

     10.5 Place appropriate standards in the sampler in order of decreasing
          concentration and perform analysis.

     10.6 Prepare standard curve by plotting instrument response against
          concentration values.  A calibration curve may be fitted  to the
          calibration solutions concentration/response data using computer or
          calculator based regression curve fitting techniques.   Acceptance  or
          control limits should be established using the difference between
          the measured value of the calibration solution and the "true value"
          concentration.

     10.7 After the calibration has been established,  it must be verified by
          the analysis of a suitable QCS.  If measurements exceed  10% of the
          established QCS value, the analysis should be terminated  and the
          instrument recalibrated.  The new calibration must be  verified
          before continuing analysis.   Periodic reanalysis of the QCS is
          recommended as a continuing calibration check.

11.0 PROCEDURE

     11.1 Preparation of equipment:  Add 500 ml of reagent water to an 800-mL
          Kjeldahl  flask.  The addition of boiling chips that have  been
          previously treated with dilute NaOH will prevent bumping.  Steam out
          the distillation apparatus until  the distillate shows  no  trace of
          ammon i a.

     11.2 Sample preparation:   Remove  the residual chorine in the sample by
          adding dechlorinating agent  (7.5)  equivalent to the chlorine
          residual.   To 400 ml of sample add 1 N NaOH  (7.4),  until  the pH is
          9.5,  check the pH during addition  with a pH  meter or by use of a
          short range pH paper.

     11.3 Distillation:   Transfer the  sample,  the pH of which has been
          adjusted  to 9.5,  to  an 800-mL Kjeldahl  flask and add 25 ml of the
          borate buffer (7.3).   Distill  300  ml at the  rate of 6-10  mL/min.
          into  50 mL of 2% boric acid  (7.2)  contained  in a 500-mL Erlenmeyer
          flask.

          NOTE  4:   The condenser tip or an extension of the condenser tip must
          extend below the level of the boric  acid solution.

                                   350.1-10

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     11.4 Since the intensity of the color used to quantify the concentration
          is pH dependent, the acid concentration of the wash water and the
          standard ammonia solutions should approximate that of the samples.

     11.5 Allow analysis system to warm up as required.  Feed wash water
          through sample line.

     11.6 Arrange ammonia standards in sampler in order of decreasing
          concentration of nitrogen.  Complete loading of sampler tray with
          unknown samples.

     11.7 Switch sample line from reagent water to sampler and begin analysis.

12.0 DATA ANALYSIS AND CALCULATIONS

     12.1 Prepare a calibration curve by plotting instrument response
          against standard concentration.  Compute sample concentration by
          comparing sample response with the standard curve.  Multiply answer
          by appropriate dilution factor.

     12.2 Report only those values that fall between the lowest and the
          highest calibration standards.  Samples exceeding the highest
          standard should be diluted and reanalyzed.

     12.3 Report results in mg NH3-N/L.

13.0 METHOD PERFORMANCE

     13.1 In a single laboratory (EMSL-Cincinnati),  using surface water
          samples at concentrations of 1.41, 0.77, 0.59 and 0.43 mg NHj-N/L,
          the standard deviation was  0.005.

     13.2 In a single laboratory (EMSL-Cincinnati),  using surface water
          samples at concentrations of 0.16 and 1.44 mg NH3-N/L,  recoveries
          were 107% and 99%,  respectively.

     13.3 The interlaboratory precision and accuracy data in Table 1 were
          developed using a reagent water matrix.   Values are in mg NH3-N/L.

14.0 POLLUTION PREVENTION

     14.1 Pollution prevention encompasses  any technique that reduces or
          eliminates the quantity or toxicity  of waste at the point of
          generation.   Numerous opportunities  for pollution prevention exist
          in laboratory operation.   The EPA has established a preferred
          hierarchy of environmental  management techniques  that places
          pollution prevention as the management option of first choice.
          Whenever feasible,  laboratory personnel  should use pollution
          prevention techniques to address  their waste generation.   When
          wastes cannot be feasibly reduced at the source,  the Agency
          recommends recycling as the next  best option.
                                   350.1-11

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     14.2 The quantity of chemicals purchased should be based on expected
          usage during its shelf life and disposal cost of unused material.
          Actual reagent preparation volumes should reflect anticipated usage
          and reagent stability.

     14.3 For information about pollution prevention that may be applicable to
          laboratories and research institutions, consult "Less is Better:
          Laboratory Chemical Management for Waste Reduction," available from
          the American Chemical Society's Department of Government
          Regulations and Science Policy, 1155 16th Street N.W., Washington
          D.C. 20036, (202)872-4477.

15.0 WASTE MANAGEMENT

     15.1 The U.S. Environmental Protection Agency requires that laboratory
          waste management practices be conducted consistent with all
          applicable rules and regulations.  Excess reagents, samples and
          method process wastes should be characterized and disposed of in an
          acceptable manner.  The Agency urges laboratories to protect the
          air, water and land by minimizing and controlling all releases from
          hoods, and bench operations, complying with the letter and spirit of
          any waste discharge permit and regulations, and by complying with
          all solid and hazardous waste regulations, particularly the
          hazardous  waste identification rules and land disposal
          restrictions.  For further information on waste management consult
          the "Waste Management  Manual for Laboratory Personnel," available
          from the American Chemical Society at the address listed in Sect.
          14.3.

16.0 REFERENCES

     1.   Hiller,  A., and Van Slyke, D., "Determination of Ammonia in Blood,"
          J. Biol. Chem.  102. p. 499 (1933).

     2.   O'Connor, B., Dobbs, R.,  Villiers, B., and Dean. R., "Laboratory
          Distillation of Municipal  Waste Effluents," JWPCF 39, R 25 (1967).

     3.   Fiore, J., and O'Brien, J.E., "Ammonia Determination by Automatic
          Analysis," Wastes Engineering 33_, p. 352 (1962).

     4.   A Wetting Agent Recommended and Supplied by the Technicon
          Corporation for Use in AutoAnalyzers.

     5.   ASTM "Manual on Industrial Water and Industrial Waste Water," 2nd
          Ed., 1966 printing, p. 418.

     6.   Booth, R.L., and Lobring.  L.B., "Evaluation of the AutoAnalyzer II:
          A Progress Report" in Advances in Automated Analysis:  1972
          Technicon International Congress, Vol. 8, p. 7-10, Mediad
          Incorporated, Tarrytown,  N.Y., (1973).
                                   350.1-12

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7.   Standards Methods for the Examination of Water and Wastewater, 18th
     Edition, p. 4-77, Methods 4500 NH3 B and H (1992).

8.   Annual Book of ASTM Standards, Part 31, "Water," Standard D1426-
     79(C).

9.   Code of Federal Regulations 40, Ch. 1, Pt. 136, Appendix B.
                              350.1-13

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17.0 TABLES. DIAGRAMS. FLOWCHARTS. AND VALIDATION DATA
TABLE 1. INTERLABORATORY PRECISION AND ACCURACY DATA
NUMBER OF
VALUES
REPORTED
134
157
136
195
142
159
156
200
196
156
142
199
TRUE
VALUE
(T)
0.270
0.692
1.20
1.60
3.00
3.50
3.60
4.20
8.76
11.0
13.0
18.0
MEAN
(X)
0.2670
0.6972
1.2008
1.6095
3.0128
3.4991
3.5955
4.2271
8.7257
11.0747
12.9883
17.9727
RESIDUAL
FOR X
-0.0011
0.0059
0.0001
0.0076
0.0069
-0.0083
-0.0122
0.0177
-0.0568
0.0457
-0.0465
-0.0765
STANDARD
DEVIATION
(S)
0.0342
0.0476
0.0698
0.1023
0.1677
0.2168
0.1821
0.2855
0.4606
0.5401
0.6961
1.1635
RESIDUAL
FOR S
0.0015
-0.0070
-0.0112
0.0006
-0.0067
0.0165
-0.0234
0.0488
-0.0127
-0.0495
0.0027
0.2106
REGRESSIONS:  X = 1.003T - 0.003, S = 0.052T + 0.019
                                   350.1-14

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u
5

i
ii

     8
E
RUSSIE
                         g

                           8

                      350.1-15

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      METHOD 551.1
DETERMINATION OF CHLORINATION DISINFECTION BYPRODUCTS,
CHLORINATED SOLVENTS, AND HALOGENATED PESTICIDES/
HERBICIDES IN DRINKING WATER BY LIQUID-LIQUID
EXTRACTION AND GAS CHROMATOGRAPHY WITH ELECTRON-
CAPTURE DETECTION
                                 Revision 1.0
J.W. Hodgeson, A.L. Cohen - Method 551, (1990)

D.J. Munch (USEPA, Office of Water) and D.P. Hautman (International
           Consultants, Inc.) - Method 551.1, (1995)
                     NATIONAL EXPOSURE RESEARCH LABORATORY
                      OFFICE OF RESEARCH AND DEVELOPMENT
                     U.S. ENVIRONMENTAL PROTECTION AGENCY
                            CINCINNATI, OHIO 45268
                                    551.1-1

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                                 METHOD 551.1

 DETERMINATION OF CHLORINATION DISINFECTION BYPRODUCTS,  CHLORINATED  SOLVENTS,
   AND HALOGENATED PESTICIDES/HERBICIDES IN DRINKING WATER BY  LIQUID-LIQUID
      EXTRACTION AND GAS CHROMATOGRAPHY WITH ELECTRON-CAPTURE DETECTION


1.    SCOPE AND APPLICATION

     1.1  This method (1-9) is applicable to the determination of the
          following analytes in finished drinking water,  drinking water during
          intermediate stages of treatment,  and raw source water.  The
          particular choice of analytes from this list should be a function of
          the specific project requirements.

          Disinfection Byproducts fDBPsl;
                             Analvte                         CAS No.
          Trihalomethanes    Chloroform                      67-66-3
                             Bromodichloromethane            75-27-4
                             Bromoform                       75-25-2
                             Dibromochloromethane           124-48-1
          Haloacetonitriles  Bromochloroacetonitrile      83463-62-1
                             Dibromoacetonitrile           3252-43-5
                             Dichloroacetonitrile          3018-12-0
                             Trichloroacetonitrile          545-06-2
          Other DBPs         Chloral Hydrate                 75-87-6
                             Chloropicrin                    76-06-2
                             1,1-Di chloro-2-propanone       513-88-2
                              l,l,l-Trichloro-2-             918-00-3
                             propanone
          Chlorinated Solvents;
                             Carbon Tetrachloride            56-23-5
                              l,2-Dibromo-3-                 96-12-8
                             chloropropane  [DBCP]
                              1,2-Dibromoethane  [EDB]        106-93-4
                             Tetrachloroethylene            127-18-4
                              1,1,1-Trichloroethane           71-55-6
                              1,1,2-Trichloroethane           79-00-5
                             Trichloroethylene               79-01-6
                              1,2,3-Trichloropropane          96-18-4
          Pesticides/Herbicides:
                             Alachlor                     15972-60-8
                             Atrazine                      1912-24-9
                             Bromacil                       314-40-9
                             Cyanazine                    21725-46-2
                              Endrin                          72-20-8
      #                       Endrin Aldehyde               7421-93-4
                              Endrin Ketone                53494-70-5
                             Heptachlor                      76-44-8
                              Heptachlor  Epoxide            1024-57-3
                              Hexachlorobenzene              118-74-1
                                    551.1-2

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                             Hexachlorocyclopentadi ene      77-47-4
                             Lindane (gamma-BHC)             58-89-9
                             Metolachlor                 51218-45-2
                             Metribuzln                  21087-64-9
                             Methoxychlor                   72-43-5
                             Simazine                      122-34-9
                             Trifluralin                  1582-09-8

     1.2  This  analyte  list  includes  twelve commonly observed chlorination
         disinfection  byproducts  (3,4),  eight commonly used chlorinated
         organic  solvents and  sixteen  halogenated pesticides and herbicides.

     1.3  This  method  is  intended  as  a  stand-alone procedure for either the
         analysis of  only the  trihalomethanes (THMs)  or  for all the
         chlorination  disinfection  by-products (DBPs) with the chlorinated
         organic  solvents or as a procedure  for  the total analyte  list.  The
         dechlorination/preservation technique presented in section 8 details
         two different dechlorinating  agents.  Results for the THMs and  the
         eight solvents  may be obtained from the analysis of samples
         employing either dechlorinating agent.  (Sect. 8.1.2)

     1.4  After an analyte has  been  identified and quantitated  in an unknown
         sample with  the primary  GC  column  (Sect. 6.9.2.1) qualitative
         confirmation  of results  is  strongly recommended by gas
         chromatography/mass spectrometry (GC/MS)  (10,11), or  by GC analysis
         using a  dissimilar column  (Sect.  6.9.2.2).

     1.5  The experimentally determined method detection  limits  (MDLs)  (12)
         for the  above listed  analytes are  provided  in Tables  2 and 8.
         Actual HDL values  will vary according to the particular matrix
         analyzed and the specific  instrumentation employed.

     1.6  This  method  is  restricted  to  use by or  under the supervision of
         analysts experienced  in  the use of GC and in the interpretation of
         gas chromatograms.  Each analyst must demonstrate the ability to
         generate acceptable results with this method using the procedure
         described in Sect. 9.4.

     1.7  Methyl-t-butyl  ether (MTBE) is recommended  as the primary extraction
          solvent  in this method  since  it effectively  extracts  all  of  the
         target analytes listed  in  Sect. 1.1.  However,  due to safety
         concerns associated with MTBE and the current use of  pentane  by some
         laboratories for certain method analytes, pentane  is  offered  as an
         optional extraction solvent for all analytes except chloral  hydrate.
          If project requirements  specify the analysis of chloral  hydrate,
         MTBE  must be used  as the extracting solvent. This method includes
          sections specific  for pentane as an optional solvent.

2.   SUMMARY OF METHOD

     2.1  A 50  ml sample  aliquot  is extracted with  3  ml of MTBE or 5 ml of
          pentane.  Two /iL  of the  extract is then injected  into a  GC equipped
                                    551.1-3

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          with a fused silica capillary column and  linearized  electron  capture
          detector for separation and analysis.   Procedural  standard
          calibration is used to quantitate method  analytes.

     2.2  A typical sample can be extracted and analyzed by  this  method in  50
          min for the chlorination by-products/chlorinated solvents and 2 hrs.
          for the total analyte list.  Confirmation of the eluted compounds
          may be obtained using a dissimilar column (6.9.2.2)  or  by the use of
          GC-MS.  Simultaneous confirmation can be  performed using dual
          primary/confirmation columns installed in a single injection  port
          (Sect. 6.9.3) or a separate confirmation  analysis.

3.   DEFINITIONS

     3.1  INTERNAL STANDARD (IS)  A pure analyte(s) added to a  sample,
          extract, or standard solution in known amount(s) and used  to  measure
          the relative responses of other method analytes and surrogates that
          are components of the same sample or solution.  The internal
          standard must be an analyte that is not a sample component.

     3.2  SURROGATE ANALYTE (SA) -- A pure analyte(s), which is extremely
          unlikely to be found in any sample, and which is added  directly to a
          sample aliquot in known amount(s) before extraction or other
          processing and is measured with the same procedures used to measure
          other sample components. The purpose of a surrogate analyte  is to
          monitor method performance with each sample.

     3.3  LABORATORY DUPLICATES  (LD1 and LD2)  Two sample aliquots,  taken  in
          the laboratory from a  single sample bottle, and analyzed separately
          with  identical procedures.  Analyses of LD1 and LD2 indicate
          precision associated with  laboratory procedures, but not with  sample
          collection, preservation,  or storage procedures.   This method
          cannot utilize laboratory duplicates since sample extraction must
          occur in the sample vial and sample transfer  is not possible due to
          analyte volatility,

     3.4  FIELD DUPLICATES  (FD1  and  FD2)  Two separate  samples collected at
          the same time and place under identical circumstances  and  treated
          exactly the  same  throughout field and laboratory procedures.
          Analyses of  FD1 and FD2 give a measure of the precision associated
          with  sample  collection, preservation and storage, as well  as with
          laboratory procedures.  Since laboratory duplicates cannot be
          analyzed, the collection and analysis of field  duplicates  for  this
          method  is critical.

     3.5  LABORATORY REAGENT BLANK  (LRB) ~ An aliquot  of reagent water, or
          other blank  matrix, that  is treated exactly as  a sample including
          exposure to  all glassware, equipment, solvents, reagents,  internal
          standards, and  surrogates  that are  used with  other  samples.   The LRB
          is  used  to determine  if method analytes  or other  interferences are
          present  in the  laboratory  environment, the reagents, or the
          apparatus.
                                    551.1-4

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3.6  FIELD REAGENT  BLANK  (FRB)   Reagent water, or other blank matrix,
     that Is  placed in  a  sample container in the laboratory and treated
     as a sample  In all respects, Including shipment to  sampling  site,
     exposure to  sampling site  conditions, storage, preservation  and all
     analytical procedures.   The purpose of the FRB is to determine if
     method analytes  or other interferences are present  in the field
     environment.

3.7  LABORATORY FORTIFIED .BLANK (LFB)  An aliquot of reagent water, or
     other blank  matrix,  to which known quantities of the method  analytes
     are added in the laboratory.  The LFB is analyzed exactly like a
     sample,  and  its  purpose  is to determine whether the methodology is
     in control,  and  whether  the laboratory is capable of making  accurate
     and precise  analyte  quantitation at various concentrations including
     the required method  detection limit.

3.8  LABORATORY FORTIFIED SAMPLE MATRIX (LFM)  An aliquot of an
     environmental  sample to  which known quantities of the method
     analytes are added in the  laboratory.  The LFM is analyzed exactly
     like a sample,  and its purpose  is to determine whether the sample
     matrix contributes bias  to the  analytical results. The background
     concentrations of  the analytes  in the sample matrix must be
     determined in  a  separate aliquot and the measured values in  the LFM
     corrected for  background concentrations.

3.9  STOCK STANDARD SOLUTION  (SSS)  A concentrated solution containing
     one or more method analytes which is prepared in the laboratory
     using assayed  reference  materials or purchased as certified  from a
     reputable commercial  source.

3.10 PRIMARY  DILUTION STANDARD  SOLUTION (PDS)  A solution of several
     analytes prepared  in  the laboratory from stock standard solutions
     and diluted  as needed to prepare calibration solutions and other
     needed analyte solutions.

3.11 CALIBRATION STANDARD (CAL)   A solution prepared from the primary
     dilution standard  solution  or stock standard solutions and the
     internal standard(s)  and surrogate analyte(s).  The. CAL solutions
     are used to calibrate the  instrument response with respect to
     analyte  concentration.

3.12 QUALITY  CONTROL  SAMPLE (QCS) -- A solution of method analytes which
     is used  to fortify an aliquot of LRB or sample matrix.   The QCS is
     obtained from  a  source external  to the laboratory and different from
     the source of  calibration  standards.   It is used to check laboratory
     performance with externally prepared test materials.

3.13 LABORATORY PERFORMANCE CHECK SOLUTION (LPC) - A solution of
     selected method analytes,  surrogate(s),  internal  standard(s), or
     other test substances used  to evaluate the performance of the
     instrument system with respect to a defined set of method criteria.
                               551.1-5

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     3.14 METHOD DETECTION LIMIT (MDL)  The minimum concentration of an
          analyte that can be identified, measured and reported with 99%
          confidence that the analyte concentration is greater than zero.
          (Appendix B to 40 CFR Part 136)

     3.15 ESTIMATED DETECTION LIMIT (EDL)  Defined as either the MDL or a
          level of compound in a sample yielding a peak in the final extract
          with a signal to noise (S/N) ratio of approximately 5, whichever is
          greater.

     3.16 PROCEDURAL STANDARD CALIBRATION   A calibration method where
          aqueous calibration standards are prepared and processed (e.g.
          purged,extracted, and/or derivatized) in exactly the same manner as
          a sample.  All steps in the process from addition of sampling
          preservatives through instrumental analyses are included in the
          calibration.  Using procedural standard calibration compensates for
          any inefficiencies in the processing procedure.

4.   INTERFERENCES

     4.1  Impurities contained in the extracting solvent usually account for
          the majority of the analytical problems.  Each new bottle of solvent
          should be analyzed for interferences before use.  An interference
          free solvent is a solvent containing no peaks yielding data at > MDL
          (Tables 2 and 8) at the retention times of the analytes of interest.
          Indirect daily checks on the extracting solvent are obtained by
          monitoring the laboratory reagent blanks (Sect. 9.3).  Whenever an
          interference is noted in the reagent blank, the analyst should
          analyze the solvent separately to determine if the source of the
          problem is the solvent or another reagent.

     4.2  Glassware must be scrupulously cleaned (13).  Clean all glassware as
          soon as possible after use by thoroughly rinsing with the last
          solvent used in it.  Follow by washing with hot water and detergent
          and thoroughly rinsing with tap and reagent water.  Drain dry, and
          heat in an oven or muffle furnace at 400C for 1 hr.   Do not muffle
          volumetric ware but instead rinse three times with HPLC grade or
          better,acetone.  Thoroughly rinsing all glassware with HPLC grade or
          better acetone may be substituted for heating provided method blank
          analysis confirms no background interferant contamination is
          present.   After drying and cooling, seal and store all glassware in
         . a clean environment free of all potential contamination.  To prevent
          any accumulation of dust or other contaminants, store glassware
          inverted on clean aluminum foil or capped with aluminum foil.

     4.3  Commercial lots of the extraction solvents (both MTBE and pentane)
          often contain observable amounts of chlorinated solvent impurities,
          e.g., chloroform, trichloroethylene, carbon tetrachloride.  When
          present,  these impurities can normally be removed by double
          distillation.
                                    551.1-6

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     4.4  This liquid/liquid extraction technique efficiently extracts a wide
          boiling range of non-polar and polar organic components of the
          sample.  Thus, confirmation  is quite important, particularly at
          lower analyte concentrations.  A confirmatory column (6.9.2.2) is
          suggested for this purpose.  Alternatively, GC/MS may also be used
          for confirmation if sufficient concentration of analyte is present.

     4.5  Special care must be taken in the determination of endrin since it
          has been reported to breakdown to aldo and keto derivatives upon
          reaction with active sites in the injection port sleeve (14).  The
          active sites are usually the result of micro fragments of the
          injector port septa and high boiling sample residual deposited in
          the injection port sleeve or on the inner wall at the front of the
          capillary column.  The degradation of endrin is monitored using the
          Laboratory Performance Check Standard (Sect. 9.2).

     4.6  Interfering and erratic peaks have been observed in method blanks
          within the retention windows of metribuzin, alachlor, cyanazine and
          heptachlor.  These are believed to be due to phthalate
          contamination.  This contamination can be reduced by paying special
          attention to reagent preparation (See solvent rinsing the dry buffer
          and the dechlorination/ preservative salts, Sect. 7.1.7.5) and
          elimination of all  forms of plastic from the procedure (i.e.  HOPE
          bottles, plastic weighing boats, etc.).   After NaCl  or Na2S04 is
          muffled or phosphate buffer and dechlorination/preservative salts
          are solvent rinsed, they should be stored in sealed glass
          containers.  NaCl,  Na2S04,  phosphate buffer  and dechlorination/
          preservative salts should be weighed using glass beakers, never
          plastic weighing boats.
5.   SAFETY
     5.1  The toxicity and carcinogenicity of chemicals used in this method
          have not been precisely defined; each chemical  should be treated as
          a potential health hazard, and exposure to these chemicals should be
          minimized.  Each laboratory is responsible for maintaining awareness
          of OSHA regulations regarding safe handling of chemicals used in
          this method.   Additional references to laboratory safety are
          available (15-17) for the information of the analyst.

     5.2  The following have been tentatively classified as known or suspected
          human or mammalian carcinogens:

          Chloroform, l,2-Dibromo-3-chloropropane, 1,2-Dibromoethane,
          heptachlor, and hexachlorobenzene.

     5.3  The toxicity of the extraction solvent, MTBE, has not been well
          defined.  Susceptible individuals may experience adverse affects
          upon skin contact or inhalation of vapors.   Therefore, protective
          clothing and gloves should be used and MTBE should be used only in a
          chemical fume hood or glove box.  The same precaution applies to
          pure standard materials.

                                    551.1-7

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6.   EQUIPMENT AND SUPPLIES  (All specifications in Sections 6 and 7 are
     suggested.  Catalogue numbers are included for illustration only.)

     6.1  SAMPLE CONTAINERS - 60-mL screw cap glass vials (Kimble #60958A-16,
          Fisher #03-339-5E or equivalent) each equipped with size 24-400 cap
          and PTFE-faced septa (Kimble #73802-24400, Fisher #03-340-14A  or
          equivalent)."  Prior to use or following each use, wash vials and
          septa with detergent and tap water then rinse thoroughly with
          distilled water.  Allow the vials and septa to dry at room
          temperature, place only the vials in an oven and heat to 400C for
          30 min.  After removal  from the oven allow the vials to cool in an
          area known to be free of organics.  After rinsing caps with
          distilled water, rinse in a beaker with HPLC grade or better acetone
          and place in a drying oven at 80C for 1  hr.

     6.2  VIALS -. Autosampler, 2.0-mL vial with screw or crimp cap and a
          teflon faced septa.

     6.3  MICRO SYRINGES - 10 /iL, 25 ML,  50 /iL, 100 /iL, 250 pi, and 1000 fjl.

     6.4  PIPETTES - 3.0 mL or 5.0 ml, type A, TO,  glass.

     6.5  VOLUMETRIC FLASK - 10 mL, 100 mL, 250 mL, 500 mL glass stoppered.

     6.6  DISPOSABLE PASTEUR PIPETS - 9 inch, used for extract transfer.

     6.7  STANDARD SOLUTION STORAGE CONTAINERS - 30-mL Boston round, amber
          glass'bottles with TFE-lined caps or equivalent.

     6.8  BALANCE - Analytical, capable of accurately weighing to the nearest
          0.0001 g.

     6.9  GAS CHROMATOGRAPHY SYSTEM

          6.9.1  The GC must be capable of temperature programming and should
                 be equipped with a linearized electron capture detector
                 (ECD), fused silica capillary column, and on-column or
                 splitless injector (splitless mode, 30 sec. delay).  If
                 simultaneous confirmation is employed the GC must have a
                 second ECD. An auto-sampler/injector is desirable.

                 6.9.1.1  SPECIAL PRECAUTION:  During method development, a
                          problem was encountered with the syringe on the
                          autosampler.  The syringe plunger, after repeated
                          sample extract  injections, developed resistance when
                          withdrawn or inserted into the syringe barrel.  This
                          resistance was due to salt deposits in the syringe
                          barrel which were left behind following the
                          evaporation of hydrated MTBE. To minimize this
                          problem, a unique syringe wash procedure was
                          employed.  After sample injection, the syringe was
                          first rinsed three times with reagent water then

                                    551.1-8

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                 three  times  with  MTBE.   This  effectively removed all
                 the  residual  salt after  each  injection  from the
                 syringe  and  surmounted the  problem.   Some
                 autosampler  designs  may  not encounter this  problem
                 but  this precaution  has  been  mentioned  to alert  the
                 analyst.  When pentane was used  as  the extraction
                 solvent,  this was not a  problem.

6.9.2  Two  GC  columns  are recommended.   Column  A is  recommended  as
       the  primary analytical  column unless routinely occurring
       analytes  are  not  adequately resolved.  Column 8  is
       recommended for use as a confirmatory  column  when  GC/MS
       confirmation  is not sensitive enough or  unavailable.  Other
       GC columns or conditions may  be employed provided  adequate
       analyte resolution is  attained and all the  quality assurance
       criteria  established  in Sect. 9 are  met.

       6.9.2.1   Column A - 0.25 mm ID x  30  m  fused silica capillary
                 with chemically bonded methyl polysiloxane  phase
                 (J&W,  DB-1,  1.0 m film thickness or  equivalent).  As
                 a result  of  the different boiling  points  of MTBE
                 (b.p.  55C) and pentane  (b.p.  35C),  two different
                 GC oven  temperature  programs  are specified  in Table
                 1 for  MTBE and Table 12  for pentane.  Retention
                 times  for target  analytes were  slightly different
                 using  the pentane oven temperature program  but
                 elution  order, analyte resolution, and total
                 analysis  time were not effected.   Injector
                 temperature:  200C equipped with 4 mm ID
                 deactivated  sleeve with  wool  plug  (Restek #20781 for
                 HP GC's  or equivalent).  This sleeve  design was
                 found  to  give better analyte  response than  the
                 standard  2 mm sleeve.  DAtector temperature: 290C.

       6.9.2.2   Column B  - 0.25 mm ID x  30  m with chemically bonded
                 6 % cyanopropylphenyl/94 %  dimethyl  polysiloxane
                 phase  (Restek, Rtx-1301,  1.0 fun film  thickness or
                 equivalent).  The column oven was temperature
                 programmed exactly as indicated for  column A (Tables
                 1 and  12).   Injector and detector temperatures at
                 200C and 290C, respectively.   The  same
                 temperature program was  utilized to  allow for
                 simultaneous confirmation analysis.

6.9.3  To perform simultaneous confirmation from a single injection
       onto both the primary and confirmation columns, two  injector
       setups can be employed.

       6.9.3.1  Using  a two hole graphite ferrule  (Restek #20235, or
                equivalent) both columns can be inserted  into one
                 injection  port.  To ensure  the column ends are
                centered  in the injection port sleeve and not angled

                          551.1-9

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                          to the side, an inlet adaptor fitting is installed
                          at the base of the injection port (Restek #20633,  or
                          equivalent).  Use caution when installing columns  in
                          this manner to ensure the column does not break at
                          the base of the injector due to the two columns
                          twisting as the ferrule nut is tightened.  To
                          minimize this hazard, the ferrule nut can be reverse
                          twisted four to five times once the ferrule has been
                          seated.

                 6.9.3.2  An alternate procedure involves installing a 1 meter
                          portion of 0.25 mm deactivated, uncoated fused
                          silica capillary tubing (Restek #10043, or
                          equivalent) into the injector as a normal single
                          column is installed.  Then using a Y-press tight
                          union (Restek #20403 or equivalent) join the 1 meter
                          uncoated column to the primary and secondary
                          columns.  Using this procedure will reduce detection
                          limits when compared to the procedure outline in
                          6.9.3.1 since only one column is positioned in the  .
                          injection port to receive the injected sample
                          extract.

          6.9.4  The analyst is permitted to modify GC columns, GC conditions,
                 internal standard or surrogate compounds.  Each time such
                 method modifications are made, the analyst must repeat the
                 procedures in Sect. 9.4.
7.   REAGENTS AND STANDARDS

     7.1  REAGENTS
          7.1.1  MTBE - High purity grade. It may be necessary to double
                 distill the solvent if impurities are observed which coelute
                 with some of the more volatile compounds.

          7.1.2  Pentane (optional extraction solvent) - High purity grade. It
                 may be necessary to double distill the solvent if impurities
                 are observed which coelute with some of the more volatile
                 compounds.

          7.1.3  Acetone - High purity, demonstrated to be free of analytes.

          7.1.4  Methanol - High purity, demonstrated to be free of analytes.

          7.1.5  Sodium Chloride, NaCl - ACS Reagent Grade.  Before using a
                 batch of NaCl, place in muffle furnace, increase temperature
                 to 400C and hold for 30 min.   Store in a capped glass
                 bottle, not in a plastic container.

          7.1.6  Sodium Sulfate, Na^SC*  -  ACS Reagent Grade.   Before  using  a
                 batch of Na2S04,  place  in muffle  furnace,  increase

                                   551.1-10

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       temperature to 400C and hold  for 30  rain.
       glass bottle not in a plastic container.

7.1.7  Sample Preservation Reagents
Store in a capped
       7.1.7.1  Phosphate buffer - Used to lower the sample matrix
                pH to 4.8-5.5 in order to inhibit base catalyzed
                degradation of the haloacetonitriles (7), some of
                the chlorinated solvents, and to standardize the pH
                of all samples.  Prepare a dry homogeneous mixture
                of 1% Sodium Phosphate, dibasic (Na2HP04)/99%
                Potassium Phosphate, monobasic (KH2P04) by weight
                (example:  2 g NazHP04  and 198 g KH2P04 to yield a
                total weight of 200 g)  Both of these buffer salts
                should be in granular  form and of ACS grade or
                better.  Powder would  be ideal but would require
                extended cleanup time  as outlined below  in Sect.
                7.1.7.5 to allow for buffer/solvent settling.

       7.1.7.2  Ammonium Chloride, NH4C1, ACS Reagent Grade.   Used
                to convert free chlorine to monochloramine.
                Although this is not the traditional dechlorination
                mechanism, ammonium chloride is categorized as a
                dechlorinating agent in  this method.

       7.1.7.3  Sodium Sulfite, Na2S03, ACS  Reagent  Grade.  Used  as
                a dechlorinating agent for chloral  hydrate sample
                analysis.

       7.1.7.4  To simplify the addition of 6 mg of the
                dechlorinating agent to  the 60 ml vial,  the
                dechlorinating salt is combined with the phosphate
                buffer as a homogeneous  mixture.  Add  1.2 g of the
                appropriate dechlorinating agent to 200  g of the
                phosphate buffer.  When  1 g of the  buffer/
                dechlorinating agent mixture are added to the  60-mL
                sample vial, 6 mg  of the dechlorinating  agent  are
                included reflecting an actual concentration of 100
                mg/L.  Two separate mixtures are prepared, one
                containing ammonium chloride and the  other with
                sodium  sulfite.

       7.1.7.5  If background  contaminants  are detected  in the salts
                listed  in Sections 7.1.7.1  through  7.1.7.3, a
                solvent  rinse  cleanup  procedure may be required.
                These contaminants may coelute with some of  the  high
                molecular weight  herbicides  and pesticides.  These
                salts cannot be muffled since they  decompose when
                heated  to 400C.   This solvent rinsing procedure is
                applied  to  the homogeneous  mixture  prepared  in Sect.
                7.1.7.4.
                          551.1-11

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7.2
7.3
                NOTE:   If  a  laboratory  is  not conducting analyses
                for  the high molecular  weight herbicides and
                pesticides,  this cleanup may not  be required  if no
                interfering  peaks  are observed within the retention
                time window  (Sect.12.2) for any target  analytes in
                the  laboratory  reagent  blank.

                SOLVENT RINSE CLEANUP PROCEDURE

                Prepare two  separate homogeneous  mixtures of  the
                phosphate  buffer salts  (Sect. 7.1.7.1)  in a 500-mL
                beaker. To  one, add the correct  amount of  ammonium
                chloride and to the other  add the correct amount  of
                sodium sulfite.  Three  separate  solvents are  then
                used to rinse the  mixture.  (This solvent rinsing
                must be performed  in a  fume  hood  or glove box.)
                First, add approx.  100  ml  of methanol,  or enough  to
                cover  the  salt  to  a depth  of approx.  1  cm,  and using
                a clean spatula, stir the  solvent salt  mixture for  1
                minute. Allow  the buffer/solvent mixture to  settle
                for  1  minute and then decant the  methanol,  being
                careful not  to  pour off the  rinsed buffer.   It may
                be necessary to perform this procedure  up to  four
                times  with methanol.  NOTE:  By  softly lifting and
                tapping the  base of the beaker  against  the  fume hood
                counter surface, more of the  solvent  is brought to
                the  surface of  the buffer.  Next, perform the
                identical  procedure up  to  two  times using acetone.
                Finally, perform two  final rinses with  the
                appropriate extracting  solvent  (MTBE  or Pentane).
                After the  final solvent rinse,  place  the "wet"
                buffer on  a hot plate  at  approx.  60C for 30  minutes
                or until dry.   Stir the mixture every 5 minutes to
                aid  the evaporation of  excess  solvent.   Once dry,
                place the  buffer  in a  glass  bottle with either a
                ground glass stopper  or TFE  faced septum.

REAGENT WATER - Reagent water  is  defined as  purified water  which
does not contain any measurable quantities of any target analytes or
any other interfering species.

7.2.1  A Millipore Super-Q water  system or its equivalent may be
       used to generate deionized  reagent  water.   Distilled water
       that has been charcoal  filtered  may also be suitable.

7.2.2  Test reagent water each  day it  is used by analyzing  according
       to Sect. 11.

STOCK STANDARD SOLUTIONS  (SSS)- These solutions may be obtained as
certified solutions or prepared from neat-materials using the
following procedures:
                              551.1-12

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7.3.1  For analytes which are solids  in their pure form, prepare
       stock standard solutions  (1 mg/mL) by accurately weighing
       approximately 0.01 g of pure material in a 10-mL volumetric
       flask.  Dilute to volume with  acetone.  Due to the low
       solubility of simazine, this stock should be prepared at 0.5
       mg/mL by weighing 0.005 g diluted to volume with acetone in a
       10-mL volumetric flask.  Alternatively, simazine stock
       standard solutions may be prepared in ethyl acetate at
       approximately 0.01 g/10 ml.  Stock standard solutions for
       analytes which are liquid in their pure form at room
       temperature can be accurately  prepared in the following
       manner.

       7.3.1.1  Place about 9.8 mL of acetone into a 10-mL ground-
                glass stoppered volumetric flask.  Allow the flask
                to stand, unstoppered, for about 10 min to allow
                solvent film to evaporate from the inner walls of
                the volumetric flask, and weigh to the nearest 0.1
                mg.

       7.3.1.2  Use a 10-pL syringe and immediately add 10.0 jjl of
                standard material to the flask by keeping the
                syringe needle just above the surface of the
                acetone.  Caution should be observed to be sure that
                the standard material falls dropwise directly into
                the acetone without contacting the inner wall of the
                volumetric flask.

       7.3.1.3  Reweigh, dilute to volume, stopper,  then mix by
                inverting the flask several  times.  Calculate the
                concentration in milligrams per milliliter from the
                net gain in weight.  Final concentration should be
                between 0.800 - 1.50 mg/mL.

7.3.2  Larger volumes of standard solution may be prepared at the
       discretion of the analyst.  When compound purity is assayed
       to be 96% or greater, the weight can be used without
       correction to calculate the concentration of the stock
       standard.

7.3.3  Commercially prepared stock standards can be used at any
       concentration if they are certified by the manufacturer or by
       an independent source.   When purchasing commercially prepared
       stock standards,  every effort should be made to avoid
       solutions prepared in methanol (chloral  hydrate is an
       exception,  Sect.  7.3.3.1).  Methanol  can cause degradation of
       most of the haloacetonitriles.  In addition,  some commercial
       suppliers have reported instability with solutions of
       simazine and atrazine prepared in methanol  (18).  For these
       reasons, acetone should be used as the primary solvent for
       stock standard and primary dilution standard preparation and
                         551.1-13

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all sources of methanol  Introduction into these acetone
solutions should be eliminated.
7.3.4
7.3.5
7.3.6
7.3.3,1  It is extremely difficult to acquire chloral  hydrate
         in its pure form since it is classified as a
         controlled substance.  Consequently, if pure  chloral
         hydrate cannot be acquired,  a commercially prepared
         solution of this analyte (most often at 1.0 mg/mL)
         must be purchased.  Most manufactures provide
         certified chloral hydrate solutions in methanol.
         Since chloral  hydrate is unstable, standards  from a
         separate vendor must be utilized to confirm the
         accuracy of the primary supplier's solution.

Outside source stock solutions, which are independently
prepared or purchased from an outside source different from
the source for the original stock standard solutions,  must be
used as a means of verifying the accuracy of the original
stock standard solutions for all analytes.  Prepare a
dilution of both stocks in acetone and perform a final
dilution in MTBE such that each stock dilution is at the same
concentration.  Analyze as outlined in Section 11.3.  The
relative percent difference (RPD as defined below) between
the analytes' response (area counts)  from both solutions
should not exceed 25% for any one analyte.  The RPD must be
less than 20% for 90% or greater of the total number of
target analytes analyzed.
                         (DUP 1 - DUP 2)

                       ((DUP 1 + DUP 2) / 2)
                                        x 100
       7:3.4.1
         If this criteria cannot be met, a third outside
         source should be purchased and tested in the same
         manner.  When two sources of stock solutions agree,
         the accuracy of the stock solutions is confirmed.
         This should be done prior to preparing the primary
         dilution standards.

Stock Solution of Surrogate - Prepare a stock solution of the
surrogate standard in acetone by weighing approx. 0.010 g
decaf luorobiphenyl in a 10-mL volumetric flask.  When diluted
to volume this yields a concentration of 1.00 mg/mL. t
Alternate surrogate analytes may be selected provided they
are similar in analytical behavior to the compounds of
interest, are highly unlikely to be found in any sample, and
do not coelute with target analytes.

Stock Solution of Internal Standard (IS) - Use of an IS is
optional when MTBE is the extraction solvent but mandatory if
pentane is used.  This is due to the high volatility of
pentane when compared to MTBE (see boiling points, Sect.
                  551.1-14

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            6.9.2.1).  Prepare an internal standard stock solution of
            bromofluorobenzene (BFB)  in acetone.  Since this compound  is
            a liquid at room temperature, the procedure outlined in
            Sections 7.3.1.1 through  7.3.1.3 should be followed but add
            approximately 65 pi of neat BFB rather than 10 //L as
            specified in 7.3.1.2.  When diluted to volume this yields  a
            concentration near 10.0 mg/mL.  Alternate internal standard
            analytes may be selected  provided they are highly unlikely to
            be found in any sample and do not coelute with target
            analytes.

     7.3.7  Transfer the stock standard solutions into Teflon-lined screw
            cap amber bottles.  Store at 4C  or less  and protect from
            light.  Stock standard solutions should be checked frequently
            for signs of degradation  or evaporation,  especially just
            prior to preparing calibration standards from them.

     7.3.8  When stored in a freezer  at < -10Ct the THM stock standards
            have been shown to be stable for up to six months.  The other
            analyte stock standards,  with the exception of chloral
            hydrate, have been shown  to be stable for at least four
            months when stored in a freezer (<-10C).   Chloral hydrate
            stock standards, when stored in a freezer (<-10C), have been
            shown to be stable for two months,  however,  since freezers
            can hold at various temperatures below -10C,  fresh chloral
            hydrate standards should  be initially prepared weekly,  until
            the stability of this analyte is determined for a specific
            laboratory setting.

7.4  PRIMARY DILUTION STANDARDS (PDS) - Two separate groups of primary
     dilution standards must be prepared;  one set in  acetone for all  the
     method analytes except chloral  hydrate and the second set in
     methanol  for chloral  hydrate.  Although preparation of separate
     chloral hydrate standards may seem laborious, due to the stability
     problems encountered with this  analyte,  making fresh chloral  hydrate
     primary dilution standards is more efficient.  Prepare primary
     dilution standards by combining  and diluting stock standards in
     acetone (methanol  for chloral hydrate).   The primary dilution
     standards should be prepared such that when 25 //L of this primary
     dilution standard  are added  to  50 ml of buffered/dechlorinated
     reagent water (Sect 10.1.2), aqueous concentrations will bracket the
     working concentration range.  Store the primary  dilution standard
     solutions in vials or bottles,  with caps using TFE faced liners,  in
     a freezer (<-10C) with minimal headspace  and check frequently for
     signs of deterioration or evaporation,  especially just before
     preparing calibration standards.  The same comments on storage
     stability in Sect. 7.3.8 apply  to primary  dilution standards.

     7.4.1  SURROGATE PRIMARY DILUTION STANDARD - Dilute 500 ^L of  the
            surrogate stock solution to volume  with acetone in a 50-mL
            volumetric  flask.   This  yields a  primary  dilution standard at
            10.0 //g/mL.   Addition of 50 i/L of this standard to 50 ml  of

                              551.1-15

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            aqueous sample yields a final concentration in water of 10.0
            fjg/l.  This solution is fortified into the aqueous sample
            prior to extraction of all calibration standards (Sect.
            10.1.3), quality control samples (Sect. 9), laboratory
            reagent blanks (Sect. 9.3.1) and actual field samples (Sect.
            11.1.3) in the extraction set.

     7.4.2  INTERNAL STANDARD (IS) PRIMARY DILUTION STANDARD - Prepare a
            IS primary dilution standard at 100 //g/mL by diluting the
            appropriate amount of internal standard stock solution (500
            /jl if stock is 10.0 mg/mL) to volume with acetone in a 50-mL
            volumetric flask.  When 10 ^L of this solution are added to
            1,0 mL of extract, the resultant final concentration is 1.00
            /yg/mL,  The internal standard is used in order to perform an
            internal standard calibration and is added to an analytically
            precise volume of the extract following extraction.  This
            solution is added to all extracts.

     7.4.3  Reserve approximately a 10 mL aliquot of the same lot of both
            the acetone and methanol used in the preparation of the
            primary dilution standards.  When validating the accuracy of
            the calibration standards (Sect. 7.3.4), fortify a laboratory
            reagent blank with 25 //L of both the acetone and the methanol
            which was used to prepare the primary dilution standards.
            Analysis of this laboratory reagent blank will confirm no
            target analyte contamination in the solvents used to prepare
            the primary dilution standards.

7.5  LABORATORY PERFORMANCE CHECK SOLUTION (LPC) - To insure proper
     instrument performance,  a Laboratory Performance Check Solution is
     prepared.  This solution is prepared in MTBE for direct injection on
     the GC and is used to evaluate the parameters of instrument
     sensitivity, chromatographic performance,  column performance and
     analyte breakdown.  These parameters are listed in Table 7 along
     with the method analytes utilized to perform this evaluation, their
     concentration in MTBE and the acceptance criteria.  To prepare this
     solution at the concentrations listed in Table 7, a double dilution
     of the analyte stock solutions must be made.  First prepare a
     primary stock dilution mix at 1000 times the concentrations listed
     in Table 7, by adding the appropriate volume of each stock solution
     to a single 50-mL volumetric flask containing approximately 25 mL of
     MTBE.  Dilute to volume with MTBE.  Then the LPC working solution is
     prepared in MTBE by diluting 50 fjl of the  primary stock dilution mix
     in MTBE to 50-mL in a volumetric flask.  The best way to accomplish
     this is to add approximately 48 mL MTBE to the 50-mL volumetric
     flask and add 50 //L of the primary stock dilution mix, then dilute
     to volume with MTBE.   Store this solution  in a vial or bottle, with
     TFE faced cap,  in a freezer (<-10"C) with  minimal headspace and
     check frequently for signs of deterioration or evaporation.

     7.5.1  If a laboratory is not conducting analyses for the high
            molecular weight pesticides and herbicides, a modified LPC

                              551.1-16

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                 may be prepared.  This modified LPC can omit the endrin
                 analyte breakdown component as well as the resolution
                 requirement for bromacil and alachlor under column
                 performance.  In addition, substitute analytes in place of
                 lindane for the sensitivity check and
                 hexachlorocyclopentadiene for chromatographic performance can
                 be selected.  These substitute compounds must meet the same
                 criteria as listed in table 7 with the concentration for
                 sensitivity check near the substitute analyte's EDL and the
                 concentration for chromatographic performance near 50 times
                 the substitute analyte's EOL.  The column performance
                 criteria for resolution between bromodichloromethane and
                 trichloroethylene cannot be modified.

          7.5.2  If pentane is selected as an alternate extraction solvent the
                 LPC must also be prepared in pentane.

8.   SAMPLE COLLECTION. PRESERVATION. AND STORAGE *

     8.1  SAMPLE VIAL PREPARATION

          8.K1  To conduct analyses for the total  analyte list,  two sets of
                 60-mL vials must be prepared for sampling.  One set of vials,
                 prepared for the analysis of all  target analytes except
                 chloral hydrate, contains ammonium chloride as a
                 dechlorinating agent.   Due to concerns over low recoveries
                 for chloral hydrate in matrices preserved with ammonium
                 chloride (Sect.  8.1.2),  a separate sample set must be
                 collected and preserved with sodium sulfite.   Both sets of
                 vials are prepared as  follows.

                 8.1.1.1  Using the homogeneous  phosphate
                          buffer/dechlorinating  agent mixtures prepared in
                          Sect.  7.1.7.4,  0.60 g  of the appropriate mixture are
                          added to the  corresponding vials.

          8.1.2  If the sample assay is for only the THMs and/or solvents,
                 either dechlorinating  agent can be added.   However,  sodium
                 sulfite promotes the decomposition of the haloacetonitriles,
                 l,l-dichloro-2-propanone, l,l,l-trichloro-2-propanone  and
                 chloropicrin and therefore ammonium chloride  must be used as
                 the dechlorination reagent in their analysis.   In addition,
                 some fortified matrices,  dechlorinated with ammonium
                 chloride,  have displayed recoveries of chloral  hydrate which
                 have been  up to 50% lower than  expected,  when compared to the
                 same sample matrix dechlorinated  with sodium  sulfite.   In
                 other matrices,  recoveries have been consistent  regardless of
                 dechlorinating agent.   The reason  for these differences has
                 not been  determined.   Due to this  uncertainty,  a  separate
                 sample, dechlorinated  with 100  mg/L sodium sulfite must be
                 collected  for the analysis of chloral  hydrate.
     * See Addendum page 551.1-71
                                   551.1-17

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     8.1.3  The dechlorinating agents,  if not added within the
            homogeneous mixture of the  buffer, must be added to the
            sampling vials as a dry salt.  Solutions of the
            dechlorinating agents should not be used due to concerns over
            the stability of these salts dissolved in solution and the
            potential chemical interactions of aqueous solutions of these
            salts with the dry phosphate buffer.

     8.1.4  Samples roust contain either 100 mg/L ammonium chloride or
            sodium sulfite, as appropriate for the analysis being
            performed.  This amount will eliminate free chlorine residual
            in typical chlorinated drinking water samples.  If high
            chlorine doses are used, such as in a maximum formation
            potential test, additional dechlorinating reagent may be
            required.

8.2  SAMPLE COLLECTION

     8.2.1  Collect all samples in duplicate.  Fill sample bottles to
            just overflowing but take care not to flush out the buffer/
            dechlorination reagents.  No air bubbles should pass through
            the sample as the bottle is filled, or be trapped in the
            sample when the bottle is sealed.

     8.2.2  When sampling from a water tap, open the tap and allow the
            system to flush until the water temperature has stabilized
            (usually about 3-5 min).  Remove the aerator and adjust the
            flow so that no air bubbles are visually detected in the
            flowing stream.

     8.2.3  When sampling from an open body of water, fill a 1-quart
            wide-mouth glass bottle or  1-liter beaker with sample from a
            representative area, and carefully fill duplicate 60-mL
            sample vials from the container.

     8.2.4  The samples must be chilled to 4C on the day of collection
            and maintained at that temperature until analysis.  Field
            samples that will not be received at the laboratory on the
            day of collection must be packaged for shipment with
            sufficient ice to ensure they will be at 4C on arrival at
            the laboratory.  Synthetic ice (i.e. Blue ice) is not
            recommended.

8.3  SAMPLE STORAGE/HOLDING TIMES

     8.3.1  Store samples at 4C and extracts in a freezer (<-10C) until
            analysis.  The sample storage area must be free of organic
            solvent vapors.
                              551.1-18

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          8.3.2  Extract all samples within 14 days of collection and analyze
                 within 14 days following extraction. This applies to either
                 MTBE or pentane extracts). Samples not analyzed within these
                 time periods must be discarded and replaced.

9.   QUALITY CONTROL

     9.1  Each laboratory that uses this method is required to operate a
          formal quality control (QC) program.  Minimum QC requirements
          include the laboratory performance check standard, initial
          demonstration of laboratory capability,  method detection limit
          determination, analysis of laboratory reagent blanks, continuing
          calibration check standard, laboratory fortified sample matrices,
          field duplicates and monitoring surrogate and/or internal  standard
          peak response in each sample and blank.   Additional quality control
          practices may be added.

     9.2  ASSESSING INSTRUMENT SYSTEM - LABORATORY PERFORMANCE CHECK STANDARD
          (LPC).  Prior to any sample analyses, a  laboratory performance check
          standard must be analyzed.   The LPC sample contains compounds
          designed to indicate appropriate instrument sensitivity,  endrin
          breakdown, column performance (primary column),  and chromatographic
          performance.  LPC sample components and  performance criteria are
          listed in Table 7.  Inability to demonstrate acceptable instrument
          performance indicates the need for revaluation  of the instrument
          system.  The sensitivity requirement is  based on the Estimated
          Detection Limits (EDLs) published in this method.   If laboratory
          EDLs differ from those listed in this method, concentrations of the
          LPC standard must be adjusted to be compatible with the laboratory
          EDLs.  If endrin breakdown  exceeds 20 %,  the problem can  most likely
          be solved by performing routine maintenance on the injection port
          including replacing the injection port sleeve, and all  associated
          seals and septa.  If column or chromatographic performance criteria
          cannot be met, new columns  may need to be installed,  column flows
          corrected, or modifications adapted to the oven  temperature program.
          During early method development work, significant  chromatographic
          and column performance problems were observed while using  a DB-1
          column which had been used  for several years for drinking  water
          extract analysis.   By installing a new DB-1 column, these
          performance problems were overcome.   If  the columns to  be  used for
          this method have been used  for several years or  have had  extended
          use with extracts from harsh sample matrices (i.e.  wastewater,
          acidified sample extracts,  hazardous waste samples) it  may be
          difficult to meet the criteria established for this LPC standard and
          column replacement may be the best alternative.

     9.3  LABORATORY REAGENT BLANKS (LRB).   Before  processing any samples,  the
          analyst must analyze an LRB to demonstrate that  all glassware and
          reagent interferences are under control.   In addition,  each time a
          set of samples is  extracted or reagents  are changed,  a  LRB must be
          analyzed.   If the LRB produces a peak within the retention time
          window of any analyte (Sect.  12.2)  preventing the  quantitation   of

                                   551.1-19

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     that analyte, determine the source of the contamination and
     eliminate the interference before processing samples.  LRB samples
     must' contain the appropriate buffer for the target analytes
     (buffered/NH4Cl  dechlorinated and/or buffered/Na2S03 dechlorinated
     reagent water).

     9.3.1  Prepare the two LRBs in the appropriate buffered/
            dechlorinated reagent water.  Add 50 /;!_ of surrogate primary
            dilution standard (Sect. 7.4.1) to each blank and follow the
            procedure outlined in Sect. 11.2.

9.4  INITIAL DEMONSTRATION OF CAPABILITY (IDC)

     9.4.1  Preparation of the IDC Laboratory Fortified Blank (LFB).
            Select a concentration for each of the target analyte which
            is approximately 50 times the EDL or close to the expected
            levels observed in field samples.  Concentrations near
          '  analyte levels in Table 3.A are recommended.  Prepare a LFB
            by adding the appropriate concentration of the primary
            dilution standard (Sect. 7.4) to each of four to seven 50 ml .
            aliquots of buffered/NH4Cl  dechlorinated reagent water.
            Separate Na,S03 preserved matrices  need  not be analyzed
            (Sect. 9.4.1.1).   Analyze the aliquots according to the
            method beginning in Section 11.

            9.4.1.1  Chloral  hydrate is included in the buffered/NH4Cl
                     dechlorinated reagent water, containing all the
                     other target analytes since no matrix induced
                     recovery problems have been found from reagent water
                     preserved with NH4C1.

     9.4.2  Following procedural calibration standard analysis and
            subsequent instrument calibration, analyze a set of at least
            seven IDC samples and calculate'the mean percent recovery (R)
            and the relative standard deviation of this recovery (RSD).
            The percent recovery is determined as the ratio of the
            measured concentration to the actual fortified concentration.
            For each analyte, the mean recovery value must fall within
         '   the range of 80% to 120% and the RSD must not exceed 15 %.
            For those compounds that meet these criteria, performance is
            considered acceptable, and sample analysis may begin. For
            those compounds that fail these criteria, this procedure must
            be repeated using eight fresh samples until satisfactory
            performance has been demonstrated.

     9.4.3  The initial demonstration of capability is used primarily to
            preclude a laboratory from analyzing and reporting unknown
            samples without obtaining some experience with an unfamiliar
            method.  It is expected that as laboratory personnel gain
            experience with this method, the quality of data will improve
            beyond those specified in Sect. 9.4.2.
                              551.1-20

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          8.3.2  Extract all samples within 14 days of collection and analyze
                 within 14 days following extractidn. This applies .to either
                 MTBE or pentane extracts). Samples not analyzed within these
                 time periods must be discarded and replaced.

9.   QUALITY CONTROL

     9.1  Each laboratory that uses this method is required to operate a
          formal quality control (QC) program.  Minimum QC requirements
          include the laboratory performance check standard, initial
          demonstration of laboratory capability, method detection limit
          determination, analysis of laboratory reagent blanks, continuing
          calibration check standard, laboratory fortified sample matrices,
          field duplicates and monitoring surrogate and/or internal  standard
          peak response in each sample and blank.  Additional quality control
          practices may be added.

     9.2  ASSESSING INSTRUMENT SYSTEM - LABORATORY PERFORMANCE CHECK STANDARD
          (LPC).  Prior to any sample analyses, a laboratory performance check
          standard must be analyzed.  The LPC sample contains compounds
          designed to indicate appropriate instrument sensitivity, endrin
          breakdown, column performance {primary column),  and chromatographic
          performance.  LPC sample components and performance criteria are
          listed in Table 7.  Inability to demonstrate acceptable instrument
          performance indicates the need for reevaluation  of the instrument
          system.  The sensitivity requirement is based on the Estimated
          Detection Limits (EDLs) published in this method.   If laboratory
          EDLs differ from those listed in this method, concentrations of the
          LPC standard must be adjusted to be compatible with the laboratory
          EDLs.  If endrin breakdown exceeds 20 %,  the problem can most likely
          be solved by performing routine maintenance on the injection port
          including replacing the injection port sleeve,  and all associated
          seals and septa.   If column or chromatographic performance criteria
          cannot be met, new columns may need to be installed,  column flows
          corrected, or modifications adapted to the oven  temperature program.
          During early method development work, significant  chromatographic
          and column performance problems were observed while using  a DB-1
          column which had been used for several  years for drinking  water
          extract analysis.   By installing a new DB-1  column, these
          performance problems were overcome.   If the columns to be  used for
          this method have been used for several  years or  have had extended
          use with extracts  from harsh sample matrices (i.e.  wastewater,
          acidified sample extracts,  hazardous waste samples) it may be
          difficult to meet  the criteria established for this LPC standard and
          column replacement may be the best alternative.

     9.3  LABORATORY REAGENT BLANKS (LRB).   Before  processing any samples, the
          analyst must analyze an LRB to demonstrate that  all glassware and
          reagent interferences are under control.   In addition, each time a
          set of samples is  extracted or reagents are  changed,  a LRB must be
          analyzed.   If the  LRB produces a peak within the retention time
          window of any analyte (Sect.  12.2)  preventing the  quantitation  of

                                   551.1-19

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     that analyte, determine the source of the contamination and
    eliminate the interference before processing samples.  LRB samples
     must'contain the appropriate buffer for the target analytes
     (buffered/NH4GL dechlorinated and/or buffered/Na2S03 dechlorinated
     reagent water).

     9.3.1  Prepare the two LRBs in the appropriate buffered/
            dechlorinated reagent water.  Add 50 ^L of surrogate primary
            dilution standard (Sect. 7.4.1) to each blank and follow the
            procedure outlined in Sect. 11.2.

9.4  INITIAL DEMONSTRATION OF CAPABILITY (IDC)

     9.4.1  Preparation of the IDC Laboratory Fortified Blank (LFB).
            Select a concentration for each of the target analyte which
            is approximately 50 times the EDL or close to the expected
            levels observed in field samples.  Concentrations near
          '  analyte levels in Table 3.A are recommended.  Prepare a LFB
            by adding the appropriate concentration of the primary
            dilution standard (Sect. 7.4) to each of four to seven 50 ml .
            aliquots of buffered/NH4Cl  dechlorinated reagent water.
            Separate Na,SO,  preserved  matrices  need  not  be analyzed
            (Sect. 9.4.1.1).  Analyze the aliquots according to the
            method beginning in Section 11.

            9.4.1.1  Chloral hydrate is included in the buffered/NH4Cl
                     dechlorinated reagent water, containing all the
                     other target analytes since no matrix induced
                     recovery problems have been found from reagent water
                     preserved with NH4C1.

     9.4.2  Following procedural calibration standard analysis and
            subsequent instrument calibration, analyze a  set of at least
            seven IOC samples and calculate the mean percent recovery  (R)
            and the relative standard deviation of this recovery (RSD).
            The percent recovery is determined as the ratio of the
            (measured concentration to the actual fortified concentration.
          .t For each analyte, the mean recovery value must fall within
            the range of 80% to 120% and the RSO must not exceed 15 %.
            For those compounds that meet these criteria, performance  is
            considered acceptable, and sample analysis may begin. For
            those compounds that fail these criteria, this procedure must
            be repeated using eight fresh samples until satisfactory
            performance has been demonstrated.

     9.4.3  The initial demonstration of capability is used primarily  to
            preclude a laboratory from analyzing and reporting unknown
            samples without obtaining some experience with an unfamiliar
            method.  It is expected that as laboratory personnel gain
            experience with this method, the quality of data will improve
            beyond those specified in Sect. 9.4.2.
                              551.1-20

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     9.4.4  METHOD DETECTION  LIMITS  (MDL).  Prior to the analysis of  any
            field samples the method detection limits must be determined.
            Initially, estimate the concentration of an analyte which
            would yield a peak equal to 5 times the baseline noise and
            drift.  Prepare a primary dilution standard with analyte
            concentrations at 1000 times this level in acetone (or
            methanol for chloral hydrate).

            9.4.4.1  Prepare  a 500 ml aliquot of buffered/ammonium
                     chloride dechlorinated reagent water.  Fill a
                     minimum of seven replicate, 60-mL vials with 50 mL
                     of the buffered/dechlorinated (NH4C1)  reagent water.


            9.4.4.2  Fortify the 50 ml buffered/dechlorinated (NH4C1)
                     reagent water with 50 //L of both the MDL concentrate
                     prepared in acetone and the chloral hydrate MDL
                     concentrate in methanol.  Separate preparation of a
                     reagent water containing Na,S03 as  the
                     dechlorinating agent for chloral  hydrate MDL
                     determination is not necessary.  (See Sect. 9.4.1.1)

            9.4.4.3  Extract and analyze these samples as outlined in
                     Section 11.  MDL determination can then be performed
                     as discussed in Sect. 13.1.

9.5  LABORATORY FORTIFIED BLANK (LFB).  Since this method utilizes
     procedural calibration standards, which are fortified reagent water,
     there is no difference between the LFB and the continuing
     calibration check standard.  Consequently, there is not a
     requirement for the analysis of an LFB.  However,  the criteria
     established for the continuing calibration check standard (Sect.
     10.4) should be evaluated as the LFB.

9.6  LABORATORY FORTIFIED SAMPLE MATRIX (LFM).  The laboratory must add
     known concentrations of analytes to a minimum of 10% of the routine
     samples or one fortified sample per sample set,  whichever is
     greater,  for both NH4C1  and Na2S03 dechlorinated sample matrices.
     The concentrations should be equal  to or greater than the background
     concentrations in the sample selected for fortification.   Over time,
     samples from all  routine sample sources should be fortified.  By
     fortifying sample matrices and calculating analyte recoveries,  any
     matrix induced analyte bias is evaluated.  When  an analyte recovery
     falls outside the acceptance criteria outlined below,  a bias is
     concluded and that analyte for that matrix is reported to the data
     user as suspect.

     9.6.1  First, follow the procedure outlined in Sect.  11.1

     9.6.2  Next,  prepare the LFM by adding 50 //L of  an acetone based
            standard solution into the remaining 50 mL of the buffered/
            NH4C1  dechlorinated  sample matrix  in  the vial  in which  it  was

                              551.1-21

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            sampled.  This sample vial  will  have had the required amount
            of aqueous sample removed as specified in Sect.  11.1.2.   Add
            50 /Jl of surrogate primary dilution standard (Sect.  7.4.1)
            and follow procedure outlined in Sections 11 and 12.

     9.6.3  When chloral hydrate is being determined, prepare the LFM by
            adding 50 fjl of a methanol  based chloral hydrate standard
            solution into 50 ml of the buffered/Na2S03 dechlorinated
            sample matrix in the vial in which it was sampled.  Add 50 jj
            of surrogate primary dilution standard (Sect. 7.4.1) and
            follow procedure outlined in Sections 11 and 12.

     9.6.4  Calculate the percent recovery,  R, of the concentration for
            each analyte, after correcting the total measured
            concentration, A, from the fortified sample for the
            background concentration, B, measured in the unfortified
            sample, i.e.:
                             R = 100 (A - B) / C,

            where C is the fortifying concentration.  The recoveries of
            all analytes being determined must fall between 75 % and 125
            % and the recoveries of at least 90% of these analytes must
            fall between 80 % and 120 %.  This criteria is applicable to
            both external and internal standard calibrated quantitation.

     9.6.5  If a recovery falls outside of this acceptable range, a
            matrix induced bias can be assumed for the respective analyte
            and the data for that analyte in that sample matrix must be
            reported to the data user as suspect.

     9.6.6  If the unfortified matrix has analyte concentrations equal to
            or greater than the concentration fortified, a duplicate
            sample vial needs to be fortified at a higher concentration.
            If no such sample is available the recovery data for the LFM
           . sample should not be reported for this analyte to the data
            user.

9.7  FIELD DUPLICATES (FD1 and FD2).  The laboratory must analyze a field
     sample duplicate for a minimum of 10% of the total number of field
     samples or at least one field sample duplicate per sample set,
     whichever is greater.  Duplicate results must not reflect a relative
     percent difference (RPD as defined below) greater than 25% for any
     one analyte and the RPD for 90% of the analytes being determined
     must be less than 20%.
     RPD
              (FD1 - FD2)
            ((FD1 + FD2) / 2)
X 100
                              551.1-22

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     where F01 and FD2 represent the quantified concentration on an
     Individual analyte for the initial and duplicate field sample
     analysis, respectively.  If this criteria is not met the analysis
     must be repeated.  Upon repeated failure, the sampling must be
     repeated or the analyte out of control must be reported as suspect
     to the data user.

9.8  ASSESSING SURROGATE RECOVERY

     9.8.1  The surrogate analyte is fortified into the aqueous portion
            of all calibration standards, quality control samples and
            field samples.  By monitoring the surrogate response, the
            analyst generates useful quality control information from
            extraction precision through quantitative analysis.
            Deviations in surrogate recovery may indicate an extraction
            problem.  If using external standard calibration the
            surrogate retention time functions as a reference for
            identification of target analytes.

     9.8.2  Using the mean surrogate response from the calibration
            standard analyses (Cal-),  determine the  surrogate  percent
            recovery (%RECS) in  all  calibration standards,  LFBs,  and
            LFMs, and field samples.  This recovery is calculated by
            dividing the surrogate response from the sample (SamSR)  by
            the mean response from the initial calibration standards
            (Sect. 10.2 or 10.3) and multiplying by 100, as shown below.
                     % RECe
                                  Sam
                                     SR
                                x 100
                                  Cal
                                     SR
     9.8.3
Recoveries must fall within the range of 80% to 120%.  If a
sample provides a recovery outside of this range, the extract
must be reanalyzed.  If upon reanalysis, the recovery
continues to fall outside the acceptable range a fresh sample
should be extracted and analyzed.  If this is not possible
the data for all the analytes from this sample should be
reported to the data user as suspect due to surrogate
recovery outside acceptable limits.

If consecutive samples fail the surrogate response acceptance
criterion, immediately analyze a continuing calibration
standard.

9.8.3.1  If the continuing calibration standard provides a
         recovery within the acceptable range of 80% to 120%,
         then follow procedures itemized in Sect. 9.8.2 for
         each sample failing the surrogate response
         criterion.

9.8.3.2  If the check standard provides a surrogate recovery
         which falls outside the acceptable range or fails

                  551.1-23

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                     the acceptance criteria specified in Sect. 10.4 for
                     the target analytes, then the analyst must
                     recalibrate, as specified in Sect. 10.

9.9  ASSESSING THE INTERNAL STANDARD (IS)

     9.9.1  When using the internal standard calibration procedure, the
            analyst must monitor the internal standard response (peak
            area or peak height) of all samples during each analysis day.
            The internal standard response should not deviate from mean
            internal standard response of the past five continuing
            calibration standards by more than 20%.

     9.9.2  If > 20% deviation occurs with an individual extract,
            optimize instrument performance and inject a second aliquot
            of that extract.

            9.9.2.1  If the reinjected aliquot produces an acceptable
                     internal standard response, report results for that
                     aliquot.

            9.9.2.2  If a deviation of greater than 20% is obtained for
                     the reinjected extract, analysis of a calibration
                     check standard must be performed (Sect. 10.4).

     9.9.3  If consecutive samples fail this IS response acceptance
            criterion, immediately analyze a calibration check standard.

            9.9.3.1  If the check standard provides a response factor
                     (RF) within 20% of the predicted value for the
                     internal standard and the criteria for all the
                     target analytes as specified in Sect. .10.4 is met,
        ,9-           the previous sample(s) failing the IS response
                     criteria need to be reextracted provided the sample
                     is still available.  In the event that reextraction
                     is not possible, report results obtained from the
                     reinjected extract (Sect 9.9.2) but annotate as
                     suspect due to internal standard recovery being
                     outside acceptable limits.

            9.9.3.2  If the check standard provides a response factor
                     which deviates more than 20% of the predicted value
                     for the internal standard or the criteria for the
                     target analytes, as specified in Sect 10.4 are not
                     met, then the analyst must recalibrate, as specified
                     in Sect. 10.3 and all samples analyzed since the
                     previous calibration check standard need to be
                     reanalyzed.

9.10 CONFIRMATION COLUMN ANALYSIS.  If a positive result is observed on
     the primary column, a confirmation analysis should be performed
     using either the confirmation column or by GC/MS.

                              551.1-24

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     9.11  The laboratory may adapt additional  quality control  practices for
          use with this method.  The specific  practices that are most
          productive depend upon the needs of  the laboratory and the nature of
          the samples.   For example, field reagent blanks may be used to
          assess contamination of samples under site conditions,
          transportation and storage.

     9.12  Quality control samples (QCS) from an outside source, as defined in
          Sect.  3.12, should be analyzed at least quarterly.

10.  CALIBRATION AND STANDARDIZATION

     10.1  PREPARATION OF CALIBRATION STANDARDS

          10.1.1 Five calibration standards are required.  One should contain
                 the analytes at a concentration near to but greater than the
                 method detection limit (Table 2) for each compound; the
                 others should be evenly distributed throughout the
                 concentration range expected  in samples or define the working
                 range of the detector.  Guidance on the number of standards
                 is as follows:  A minimum of  three calibration standards are
                 required to calibrate a range of a factor of 20 in
                 concentration.  For a factor  of 50 use at least four
                 standards, and for a factor of 100 at least five standards.
                 For example, if the MDL is 0.1 ^g/L, and a sample
                 concentrations are expected to range from 1.0 p.g/1 to 10.0
                 M9/L,  aqueous standards should be prepared at 0.20 M9/U 0-80
                       2.0 M9/U 5.0 M9/U and 15.0 M9/L.
          10.1.2 As a means of eliminating any matrix effects due to the use
                 of the phosphate buffer and dechlorinating agents, the
                 procedural calibration standards are prepared in reagent
                 water which has been buffered to pH 4.8 - 5.5 and
                 dechlorinated with ammonium chloride.  To prepare this
                 buffered/dechlorinated reagent water, add 5.0 g of phosphate
                 buffer/dechlorinating agent (Sect 7.1.7.4, ammonium chloride
                 type) to 500 mL of reagent water (Sect. 7.2).

          10.1.3 Next, add 25 pi of the desired concentration primary dilution
                 standards (acetone and methanol based, Sect. 7.4) to a 50 ml
                 aliquot of the buffered/dechlorinated reagent water in a 60-
                 mL vial.  Use a 50-/iL micro syringe and rapidly inject 25 jiL
                 of the standard into the middle point of the water volume.
                 Remove the needle as quickly as possible after injection.
                 Next, add 50 juL of the surrogate standard solution (Sect.
                 7.4.1) in the same manner.  Mix by slowly and carefully
                 inverting the sample vial two times with minimal sample
                 agitation.  Aqueous standards must be prepared fresh daily
                 and extracted immediately after preparation (Section 11.2).

                 10.1.3.1 By including chloral hydrate into the total NHC1
                          analyte matrix, a separate calibration standard
                          analysis for Na2S03 preserved reagent water
                          fortified with chloral hydrate is avoided.  Chloral

                                   551.1-25

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                     hydrate  is  included  in the buffered/NH4Cl
                     dechlorinated  reagent water,  containing  all the
                     other target analytes since no matrix  induced
                     recovery problems  have been found from reagent water
                     preserved with NHC1. Warning! Do not attempt to
                     analyze   chloral hydrate  in field samples preserved
                     with NH4C1, low recoveries may result due to matrix
                     effects.

     10.1.4 CAUTION - DO NOT  prepare procedural calibration standards  in
            a volumetric flask and  transfer the sample to  an  extraction
            vial  either directly for weight determination  of  volume or
            into  a graduated  cylinder with a  subsequent  additional
            transfer into the extraction  vial.  Volatility experiments
            reflected as much as a  30 % loss  in volatile low  molecular
            weight analytes following such transfers.  All  fortified
            samples and field samples must be  extracted  in the vial  or
            bottle in which they were fortified and  collected.

10.2 EXTERNAL STANDARD CALIBRATION  PROCEDURE

     10.2.1 Extract and analyze  each calibration  standard according  to
            Section 11 and tabulate peak height or area  response versu's
            the concentration of the standard.  The  results are used to
            prepare a calibration curve for  each  compound by  plotting the
            peak height or area  response versus the  concentration.   This
            curve can be defined as either  first  or  second order.
            Alternatively, if the ratio of  response  to concentration
            {response factor) is constant over the working range (< 10%
            relative standard deviation,[RSD]), linearity through the
            origin can be assumed,  and the  average ratio or calibration
            factor can be used in place of  a calibration curve.

     10.2.2 Surrogate analyte recoveries must be  verified as  detailed  in
            Sections 9.8.

10.3 INTERNAL STANDARD (IS) CALIBRATION PROCEDURE

     10.3.1 Extract each calibration standard according to Section 11.
            Remove a 1.00 mL portion of the MTBE  or pentane extract from
            the sample extraction vial  and  place  this into a 2.0-mL
            autosampler vial.  To this extract,  add the 10 p.1 of the
            internal standard primary dilution standard, cap the vial  and
            analyze.  Following analysis, tabulate peak height or area
            responses against concentration for each compound and the
            internal standard.  Calculate relative response factor (RRF)
            for each compound using Equation 1.
                               551.1-26

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                  Equation  1

                           RRF
iAsl_LCisl
   (Ais}  (Ct)
                 where
                     = Response for the analyte to be measured
                     = Response for the internal  standard
                     = Concentration of the internal  standard (fig/I)
                     = Concentration of the analyte to be measured
                  If RF value  over  the working  range  is constant  (<  10%  RSO),
                  the  average  RF can  be used  for calculations.  Alternatively,
                  the  results  can be  used to  plot a calibration curve of
                  response versus analyte ratios, As/Ajs vs.  Cs.

     10.4 CONTINUING  CALIBRATION CHECK STANDARD    

          10.4.1  Preceding each analysis set,  after  every tenth  sample
                  analysis and after  the final  sample analysis, a calibration
                  standard should be  analyzed as a continuing calibration
                  check. These check  standards  should be at  two different
                  concentration levels to verify the  calibration  curve.  This
                  criteria is  applicable to both external and internal standard
                  calibrated quantitation.  Surrogate and internal standard
                  recoveries must be  verified as detailed in Sections 9.8 and
                  9.9, respectively.

          10.4.2  In order for the  calibration  to be  considered valid, analyte
                  recoveries for the  continuing calibration check standard must
                  fall between 75 % and 125 % for all the target  analytes.  The
                  recoveries of at  least 90% of the analytes determined must
                  fall between 80%  and 120%

          10.4.3  If this criteria  cannot be met, the continuing calibration
                  check standard is reanalyzed  in order to determine if the
                  response deviations observed  from the initial analysis are
                  repeated.  If this  criteria still cannot be met then the
                  instrument is considered out of calibration for those
                  specific analytes beyond the  acceptance range.  The
                  instrument needs  to be recalibrated and the previous samples
                  reanalyzed or those analytes out of acceptable range should
                  be reported as suspect to the data  user for all the
                  previously analyzed samples.

11.   PROCEDURE

  '   11.1 SAMPLE  PREPARATION

          11.1.1  Remove samples from storage and allow them to equilibrate to
                  room temperature.

                                   551.1-27

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     11.1.2 Remove the vial caps.  Remove a 10 ml volume of the sample.
            Check the pH of this 10 ml aliquot to verify that it is
            within a pH range of 4.5 and 5.5.   If the pH is out of this
            range a new sample must be collected.  Replace the vial caps
            and weigh the containers with contents to the nearest 0.1 g
            and record these weights for subsequent sample volume
            determination.  (See Sect. 11.2.4  for continuation of
            weighing and calculation of true volume).  Alternatively, the
            sample vials may be precalibrated by weighing in 50 ml of
            water and scoring the meniscus on the bottle.  This will
            eliminate the gravimetric step above and in Sect. 11.2.4.

     11.1.3 Inject 50pL of the surrogate analyte fortification solution
            (Sect. 7,4.1) into the sample.  The aqueous concentration of
            surrogate analyte must be the same as that used in preparing
            calibration standards (Sect. 9.1.3).  Mix by slowly and
            carefully inverting the sample vial two times with minimal
            sample agitation.

11.2 SAMPLE EXTRACTION

     11.2.1 WITH MTBE AS EXTRACTION SOLVENT

            11.2.1.1 After addition of the surrogate (Sect 11.1.3) add
                     exactly 3.0 roL of MTBE with a type A, TD, transfer
                     or automatic dispensing pipet.

            11.2.1.2 Add 10 g NaCl or 20 g Na2SOA to  the sample vial.
                     (See Section 13.7 for an important notice concerning
                     the use of NaCl when analyzing for DBFs.)  Recap and
                     extract the NaCl or Na2SO,  /MTBE/sample  mixture by
                     vigorously and consistently shaking the vial by hand
                     for 4 min.  Invert the vial and allow the water and
                     MTBE phases to separate (approx. 2 min).

                     If a series of samples are being prepared for
                     extraction using Na^SO^,  immediately after the
                     addition of the Na2S04, the sample  should be
                     recapped, agitated and placed in a secure horizontal
                     position with the undissolved Na,SO,  distributed
                     along the length of the vial.  If the vial is left
                     in a vertical position, while additional  samples
                     have solvent and salt added, the Na2S04  will
                     solidify in the bottom of the vial and it will not
                     dissolve during sample extraction.

                     NOTE:  Previous versions of this method call  for the
                     addition of the salt by "shaking the vial
                     vigorously" before the MTBE has been added.   Please
                     make a note that this procedural order has been
                     changed in an effort to minimize volatile analyte
                     losses.

                              551.1-28

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       11.2.1.3 By using a disposable Pasteur pipet (Sect. 6.2),
                transfer a portion of the solvent phase from the 60-
                ml vial to an autosampler vial (Sect. 6.2).  Be
                certain no water has carried over onto the bottom of
                the autosampler vial.  If a dual phase appears in
                the autosampler vial, the bottom layer can be easily
                removed and discarded by using a Pasteur pipet.  The
                remaining MTBE phase may be transferred to a second
                autosampler vial as a backup extract or for separate
                confirmation analysis.  Approximately 2.5 ml of the
                solvent phase can be conveniently transferred from
                the original 3 ml volume.

                11.2.1.3.1  If using  an  internal  standard
                            quantitation,  the  extract  transfer into
                            the autosampler  vial  must  be performed
                            in a quantitative  manner.   This may be
                            done using a  1.00  ml  syringe or a  2.00-
                            ml_ graduated  disposable  pipet  to
                            accurately transfer  1.00 ml of sample
                            extract  to the autosampler vial  where  10
                            fjl of internal standard  primary dilution
                            standard  (Sect.  7.4.2) solution can be
                            added.

11.2.2 WITH PENTANE AS EXTRACTION SOLVENT

       11.2.2.1 After addition of the surrogate (Sect 11.1.3)  add
                exactly 5.0 ml of pentane with a type A,  TO,
                transfer or automatic dispensing pipet.

       11.2.2.2 Add 20 g Na2S04 to the sample  vial.  Recap  and
                extract the Na2S04/pentane/sample mixture  by
                vigorously and consistently shaking  the vial by hand
                for 4 min.  Invert the vial  and allow the water and
                pentane phases to separate (approx.  2 min).  NOTE:
                Previous versions of this method call  for the
                addition of NaCl by "shaking the vial  vigorously"
                before the pentane has been added.   Please make a
                note that this procedural order has  been changed in
                an effort to minimize volatile analyte losses.  If a
                series of samples are being prepared for extraction,
                immediately after the addition of the Na2S04,  the
                sample should be recapped, agitated  and placed in a
                secure horizontal position with the  undissolved
                Na2S04  distributed along  the length  of the  vial.  If
                the vial is left in a vertical position,  while
                additional samples have  solvent and  salt added, the
                Na2SO,  will  solidify  in the  bottom of  the  vial  and
                it will not dissolve during sample extraction.
                         551.1-29

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            11.2.2.3 Using a disposable Pasteur pipet,  transfer a portion
                     of the solvent phase from the 60-mL vial  to an
                     autosampler vial.   Be certain no water has carried
                     over onto the bottom of the autosampler vial.  If a
                     dual phase appears in the autosampler vial, the
                     bottom layer can be easily removed and discarded
                     using a Pasteur pipet.  The remaining pentane phase
                     may be transferred to a second autosampler vial as a
                     backup extract or for separate confirmation
                     analysis.

                     11.2.2.3.1 The extract transfer into the
                                autosampler vial must be performed  in a
                                quantitative manner.  This may be done
                                using a 1.00-mL syringe or a 2.00-mL
                                graduated disposable pipet to accurately
                                transfer 1.00 ml of sample extract  to
                                the autosampler vial where 10 //L of
                                internal standard primary dilution
                                standard (Sect. 7.4.2) solution can be
                                added.

     11.2.3 Discard the remaining contents of the sample vial.  Shake off
            the last few drops with short, brisk wrist movements.

     11.2.4 Reweigh the empty vial with the original cap and calculate
            the net weight of sample by difference to the nearest 0.1 g
            (Sect. 11.1.2 minus Sect. 11.2.4).  This net weight (in
            grams) is equivalent to the volume of water (in ml)
            extracted, Vs.

     11.2.5 The sample extract may be stored in a freezer (<-10C)  for a
            maximum of fourteen days before chromatographic analysis but
            no more than 24 hours at room temperature (i.e. on an
            autosampler rack).  Due to the volatility of the extraction
            solvent, if the septum on a vial has been pierced, the crimp
            top or screw cap septum needs to be replaced immediately or
            the extract cannot be reanalyzed at a later time.

11.3 SAMPLE ANALYSIS

     11.3.1 The recommended GC operating conditions are described in
            6.9.2.1 and 6.9.2.2 along with recommended primary and
            confirmation columns.  Retention data for the primary and
            confirmation columns are given in Table 1.

     11.3.2 Inject 2 (tl of the sample extract and record the resulting
            peak response.  For optimum performance and precision,  an
            autosampler for sample injection and a data system for  signal
            processing are strongly recommended.
                              551.1-30

-------
12.  DATA ANALYSIS AND CALCULATIONS

     12.1 Identify sample components by comparison of retention times to
          retention data from the calibration standard analysis.  If the
          retention time of  an unknown compound corresponds, within limits
          (Sect.  12.2), to the retention time of a standard compound, then
          identification is  considered positive.

     12.2 The width of the retention time window used to make identifications
          should  be based upon measurements of actual retention time
          variations of standards over the course of a day.  Three times the
          standard deviation of a retention time can be used to calculate a
          suggested window size for a compound.  However, the experience of
          the analyst should weigh heavily in the interpretation of
          chromatograms.  Use the initial demonstration of capability
          retention time data as an initial means of determining acceptable
          retention time windows.  Throughout the development of this method a
          retention time window of 1.0 % of the total analyte retention time
          was used.

     12.3 Identification requires expert judgment when sample components are
          not resolved chromatographically, that is, when GC peaks obviously
          represent more than one sample component (i.e., broadened peak with
          shoulder(s) or valley between two or more maxima).  Whenever doubt
          exists  over the identification of a peak in a chromatogram,
          confirmation is suggested by the use of a dissimilar column or by
          GC-MS when sufficient concentrations of analytes are present.

     12.4 If the  peak response exceeds the linear range of the calibration
          curve,  the final  extract should be diluted with the appropriate
          extraction solvent and reanalyzed.  The analyst is not permitted to
          extrapolate beyond the concentration range of the calibration curve.

     12.5 Calculate the uncorrected concentrations (C;)  of each  analyte  in  the
          sample  from the response factors or calibration curves generated in
          Sect. 10.2.1 or 10.3.1.  do not use the daily calibration check
          standard to calculate amounts of method analytes in samples.

     12.6 Calculate the corrected sample concentration as:

                Concentration, (ig/L = Cf  x 50  ,
                                            Vs

          where the sample volume,  Vs  in  ml,  is  equivalent to  the  net sample
          weight  in grams determined in Sect.  11.1.2 and Sect. 11.2.4.

13.  METHOD PERFORMANCE

     13.1 In a single laboratory, analyte recoveries from reagent  water  with
          MTBE as the extracting solvent,  were determined at three
          concentration levels,  Tables 2A through 4B.  Results from the  lowest
          fortified level  were used to determine the analyte MOLs  (11)  listed

                                   551.1-31

-------
      In Table 2.  These MDLs along with the estimated detection limit
      (EDL) were determined in the following manner.  EDLs are provided
      for  informational purposes.

      13.1.1 For each analyte, calculate the mean concentration and the
            standard deviation of this mean between the seven replicates.
            Multiply the student's t-value at 99% confidence and n-1
            degrees of freedom (3.143 for seven replicates) by this
            standard deviation to yield a statistical estimate of the
            detection limit.  This estimate is the MDL.

      13.1.2 Since the statistical estimate is based on the precision of
            the analysis, an additional estimate of detection can be
            determined based upon the noise and drift of the baseline as
            well as precision.  This estimate, known as the "EDL" is
            defined as either the MDL or a level of compound in a sample
            yielding a peak in the final extract with a signal to noise
            (S/N) ratio of approximately 5, whichever is greater.

      13.1.3 These MDL determinations were conducted on both the primary
            (DB-1) and the confirmation (Rtx-1301) columns and are
            presented in Tables 2.A. through 2.D.

13.2 Analyte recoveries were also determined for reagent water with
     pentane as the extracting solvent.  Two concentration levels were
     studied and the results are presented in Tables 8 and 9.  Results
     from the lowest fortified level were used to determine the analyte
     MDLs (11) listed in Table 8.  These MDLs along with the estimated
     detection limit (EDL) were determined in a manner analogous to that
     described in Sect. 13.1.1 through 13.1.2.

13.3 In a single laboratory,  method precision and accuracy were evaluated
     using analyte recoveries from replicate buffered/dechlorinated (both
     NH4C1 and Na2S03) matrices with MTBE as the extracting solvent.  The
     matrices studied included; fulvic acid fortified reagent water and
     ground water displaying a high CaCO,  content.   The results for these
     are presented in Tables 3.A. through 6.B.  These matrices were
     fortified using outside source analyte solutions (except for the
     pesticides and herbicides) to assess accuracy and eight replicate
     analyses were conducted to assess precision.

13.4 Holding time studies were conducted for buffered/dechlorinated
     reagent water and tap water.  Holding studies were also conducted on
     MTBE sample extracts from these two matrices.  Results indicated
     that analytes were stable in these water matrices stored at 4C.

13.5 MTBE and pentane extracts holding studies indicated the analytes
     were stable for 14 days when stored in a freezer at <-10C.

13.6 Chromatograms of a fortified, buffered/NH4Cl  dechlorinated reagent
     water extract are presented as Figures 1 through 3.  In the
     chromatograms of Figures 1 and 2, the elution of the method analytes

                              551.1-32

-------
          from a MTBE extract can be seen on the primary DB-1 column and the
          confirmation Rtx-1301 column, respectively.  Figure 3 shows the
          elution of the method analytes from a pentane extract, using a
          modified temperature program, on the primary DB-1 column. Analyte
          numerical peak identification, retention time and fortified
          concentrations are presented for information purposes only in Tables
          10, 11 and 12 for Figures 1, 2 and 3, respectively.

     13.7 IMPORTANT NOTICE: All demonstration data presented in Section 17
          using MTBE as the extracting solvent, was obtained using NaCl as the
          salt.  A recent report (19) indicated elevated recoveries (via
          synthesis) of some brominated DBPs when NaCl was used in the
          extraction process, due to the inevitable presence of bromide
          impurities in the NaCl.  This phenomenon has been confirmed by the
          authors of this method in samples from chlorinated water systems
          that were not extracted immediately after the NaCl was added.
          Significant effects can be seen if extraction is delayed for as
          little as 15 minutes after the addition of the NaCl.   For this
          reason, the use of Na,SO,  is  strongly recommended  over NaCl for MTBE
          extraction of DBPs.  Although less method validation  data have been
          obtained for the Na2S04 option, sufficient data have been collected
          to indicate that it is equivalent or superior to NaCl  in salting out
          the method analytes, and has no observed negative effect on
          precision or accuracy.

14.  POLLUTION PREVENTION

     14.1 This method is a micro-extraction procedure which uses a minimal
          amount of extraction solvent per sample.  This microextraction
          procedure reduces the hazards involved with handling  large volumes
          of potentially harmful organic solvents needed for conventional
          liquid-liquid extractions.

     14.2 For information about pollution prevention that may be applicable to
          laboratory operations, consult "Less is Better:   Laboratory Chemical
          Management for Waste Reduction",  available from the American
          Chemical  Society's Department of Government Relations  and Science
          Policy, 1155 16th Street N.W., Washington,  D.C.  20036.

15.  WASTE MANAGEMENT

     15.1 Due to the nature of this method,  there is little need for waste
          management.   No large volumes of solvents or hazardous chemicals are
          used.   The matrices of concern are finished drinking water or source
          water.  However,  the Agency requires that laboratory waste
          management practices be conducted consistent with all  applicable
          rules and regulations, and that laboratories protect the air, water,
          and land  by minimizing and controlling  all  releases from fume hoods
          and bench operations.  Also,  compliance is required with any  sewage
          discharge permits and regulations,  particularly the hazardous waste
          identification rules and land disposal  restrictions.   For further
          information on waste management,  consult "The Waste Management

                                   551.1-33

-------
          Manual for Laboratory Personnel,"  also available from the American
          Chemical Society at the address in Sect.  14.2.

16.   REFERENCES

     1.    Glaze, W.W.,  Lin,  C.C., "Optimization of  Liquid-Liquid Extraction
          Methods for Analysis of Organics in Water",  EPA-600/S4-83-052,  U.S.
          Environmental  Protection Agency, January  1984.

     2.    Richard, J.J.,  Junk, G.A.,  "Liquid Extraction  for Rapid
          Determination  of Halomethanes in Water,"  Journal  AWWA. 69, 62,  1977.

     3.    Reding, R., P.S. Fair,  C.J.  Shipp, and H.J.  Brass,  "Measurement of
          Dihaloacetonitriles and Chloropicrin in Drinking Water",
          "  Disinfection  Byproducts:  Current Perspectives ",  AWWA,  Denver,CO
          1989.

     4.    Hodgeson,  J.W.,  Cohen,  A.L.  and Collins,  J.  P., "Analytical  Methods
          for Measuring  Organic Chlorination Byproducts"  Proceedings Water
          Quality Technology Conference (WQTC-16),  St.  Louis,  MO, Nov.  13-17,
          1988,  American  Water Works  Association, Denver, CO,  pp. 981-1001.

     5.    Henderson,  J.E., Peyton, G.R. and  Glaze,  W.H.  (1976).   In
          "Identification and Analysis of Organic Pollutants  in Water"  (L.H.
          Keith  ed.) PP  105-111.  Ann Arbor Sci. Publ.,  Ann  Arbor, Michigan.

     6.    Fair,  P.S., Barth,  R.C., Flesch, J.J.  and Brass,  H.,  "Measurement of
          Disinfection Byproducts in  Chlorinated Drinking Water," Proceedings
          Water  Quality Technology Conference (WQTC 15),  Baltimore, MD, None.
          15-20,  1987, American Water  Works  Association,  Denver, CO, pp 339-
          353

     7.    Trehy,  M.L. and Bieber, T.I. (1981).  In " Advances  in the
          Identification  and Analysis  of Organic Pollutants in Water II"  (L.H.
          Keith,  ed.) pp  941-975. Ann  Arbor  Sci. Publ,, Ann Arbor,  Michigan.

     8.    Oliver,  B.G.,  "Dihaloacetonitriles in Drinking  Water:  Algae and
          Fulvic Acid as  Precursors,"  Environ.  Sci.  Techno!.  17, 80, 1983.

     9.    Krasner,  S.W.,  Sclimenti, M.J.  and Hwang,  C.J., "Experience with
          Implementing a  Laboratory Program  to Sample  and Analyze for
          Disinfection By-products in  a National Study,"  Disinfection By-
          products:  Current  Perspectives.  AWWA,  Denver, CO,  1989.

     10.   Munch,  J.  W.,  "Method 525.2-Determination of Organic Compounds  in
          Drinking Water  by  Liquid-Solid  Extraction and Capillary Column
          Chromatography/  Mass Spectroraetry" in Methods for the Determination
          of Organic  Compounds in Drinking Water; Supplement  3  (1995).
          USEPA,  National  Exposure Research  Laboratory, Cincinnati, Ohio
          45268.
                                   551.1-34

-------
11.  Munch, J.W.,  "Method 524.2- Measurement of Purgeable Organic
     Compounds In Water by Capillary Column Gas Chromatography/ Mass
     Spectrometry" in Methods for the Determination of Organic Compounds
     in Drinking Water: Supplement 3  H995K  USEPA, National Exposure
     Research Laboratory, Cincinnati, Ohio 45268.

12.  Glaser, J.A., Foerst, D.L., McKee, G.D., Quave, S.A. and Budde, W.L.
     "Trace Analysis for Wastewaters", Environ. Sci. Techno!.. I_5, 1426,
     1981.

13.  ASTM Annual Book of Standards, Part 11, Volume 11.02, D3694-82,
     "Standard Practice for Preparation of Sample Containers and for
     Preservation," American Society for Testing and Materials,
     Philadelphia, PA, 1986.

14.  Bellar, T.A., Stemmer, P., Lichtenburg, J.J., "Evaluation of
     Capillary Systems for the Analysis of Environmental Extracts," EPA-
     600/S4-84-004, March 1984.

15.  "Carcinogens-Working with Carcinogens", Publication No. 77-206,
     Department of Health, Education, and Welfare, Public Health Service,
     Center for Disease Control, National Institute of Occupational
     Safety and Health, Atlanta, Georgia, August 1977.

16.  "OSHA Safety and Health Standards, General Industry", (29CFR1910),
     OSHA 2206, Occupational Safety and Health Administration,
     Washington, D.C. Revised January 1976.

17.  "Safety in Academic Chemistry Laboratories", 3rd Edition, American
     Chemical Society Publication, Committee on Chemical Safety,
     Washington, D.C., 1979.

18.  Cole, S., Henderson, D.  "Atrazine and Simazine - Product Redesign
     improves Stability".  The Reporter, Volume 13, No. 6, 1994, pg 12.
     Trade publication from Supelco, Inc.
                                                               t
19.  Xie, Yuefeng, "Effects of Sodium Chloride on DBP Analytical
     Results," Extended Abstract,  Division of Environmental  Chemistry,
     American Chemical Society Annual Conference, Chicago, IL, Aug. 21-
     26, 1995.
                              551.1-35

-------
TABLE 1.  RETENTION TIME DATA USING NTBE
Column Aa
Retention Time
ANALYTE minutes
Chloroform
1,1, 1-Trichloroethane
Carbon Tetrachloride
Tr i chl oroaceton i tri 1 e
Dichl Oroacetoni tri 1 e
Bromod i chl oromethane
Trichloroethylene
Chloral Hydrate
1 , 1-Di chl oro-2-Propanone
1,1, 2-Tri chl oroethane
Chloropicrin
Dibromochl oromethane
Bromochl oroacetoni tri 1 e
1,2-Dibromoethane (EDB)
Tetrachl oroethyl ene
1,1, 1-Trichloropropanone
Bromoform
Di bromoaceton i tr i 1 e
1,2, 3-Tr i chl oropropane
l,2-Dibromo-3-chloropropane (DBCP)
Hexachl orocycl opent ad i ene
Trifluralin
Simazine
Atrazine
Hexachl orobenzene
Lindane (gamma-BHC)
Metribuzin
Bromacil
7.04
8.64
9.94
10.39
12.01
12.42
12.61
13.41
14.96
19.91
23.10
23.69
24.03
24.56
26.24
27.55
29.17
29.42
30.40
35.28
40.33
45.17
46.27
46.55
47.39
47.95
50.25
52.09
Column Bb
Retention Time
minutes
7.73
7.99
8.36
10.35
25.21
15.28
11.96
NR c
20.50
25.01
23.69
26.32
29.86
26.46
24.77
28.47
30.36
32.77
31.73
36.11
39.53
45.43
48.56d
48.56d
46.47
49.68
53.92
59.60
                 551.1-36

-------
               TABLE 1.   RETENTION TIME DATA USING MTBE (cont'd)
                                           Column  Aa
                                       Retention  Time
                                                               Column Bb
                                                            Retention Time
ANALYTE
Alachlor
Cyanazine
Heptachlor
Metolachlor
Heptachlor Epoxide
Endrin
Endrin Aldehyde
Endrin Ketone
Methoxychlor
Surrogate:
minutes
52.25
53.43
53.72
55.44
58.42
64.15
65.46
72.33
73.53
36.35
minutes
54.38
59.89
53.15
57.07
59.05
65.24
71.56
81.28
76.73
36.28
  Decafluorobiphenyl
                                            31.00
                                                                 31.30
  Internal Standard:
  Bromofluorobenzene
(a)   Column A -     0.25 ram ID x 30 m fused silica capillary with chemically
                    bonded methyl polysiloxane phase (J&W, DB-1, 1.0 (tm film
                    thickness or equivalent).  The linear velocity of the
                    helium carrier is established at 25 cm/sec at 35C.
               The column oven is temperature programmed as follows:
               [1]  HOLD at 35C for 22 min
               [2]  INCREASE to 145C at 10C/min  and hold  at  145C for 2 min
               [3]  INCREASE to 225C at 20C/min  and hold  at  225C for 15 min
               [4]  INCREASE to 260C at 10C/min  and hold  at  260C for 30
                    min. or until all expected compounds have eluted.
               Injector temperature:  200C
               Detector temperature:.  290C
(b)  Column B -
                    0.25 mm ID x 30 m with chemically bonded 6 %
                    cyanopropylphenyl/94 % dimethyl polysiloxane phase
                    (Restek, Rtx-1301, 1.0 0m film thickness or equivalent).
                    The linear velocity of the helium carrier gas is
                    established at 25 cm/sec at 35C.
               The column oven is temperature programmed exactly as indicated
               for column A, above.  The same temperature program is utilized
               to allow for simultaneous confirmation analysis.
(c)
     There is no retention time for this analyte since it does not separate
     into a discreet peak on the Rtx-1301.
(d)  Atrazine and simazine coelute on the confirmation column.
                                   551.1-37

-------
   TABLE 2.A.
NHC1  PRESERVED
METHOD DETECTION LIMIT USING  MTBE
REAGENT WATER ON PRIMARY DB-1 COLUMN
ANALYTE
Alachlor
Atrazlne
Bromacil
Bromochl oroacetonltri 1 e
Bromodi chl oromethane
Bromoforra
Carbon Tetrachloride
Chloral Hydrate
Chloropicrin
Chloroform
Cyanazine
Dlbromoacetoni tri le
01 bromochl oromethane
1 , 2-D1 bromo-3-chl oropropane
1,2-Dibromoethane
Dichloroacetonitrile
1 , 1-Di chl oro-2-propanone
Endrin
Endrln Aldehyde
Endrin Ketone
Heptachlor
Heptachlor Epoxide
Hexachlorobenzene
Hexachl orocycl opentad 1 ene
Lindane (g-BHC)
Methoxychlor
Metolachlor
Metrlbuzin
Simazine
Fort.
Cone.,
//g/L
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.327
.633
.094
.010
.010
.010
.010
.025
.010
.050
.567
.010
.010
.010
.010
.010
.010
.016
.022
.016
.047
0.044
0
0
0
0
0
0
0
.006
.019
.009
.063
.219
.062
.625
Obser.3
Cone. ,
W/L
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.384
.764
.099
.011
.012
.018
.011
.029
.009
.054
.757
.016
.011
.020
.020
.009
.011
.023
.023
.016
.062
.050
.006
.019
.015
.057
.254
.100
.794
Avg,
%Rec.
117
121
105
110
120
180
110
116
90
108
134
160
110
200
200
90
110
144
105
100
132
114
100
100
167
90
116
161
127
%
2
3
10
5
7
8
6
5
7
34
13
12
4
15
12
4
6
2
2
5
43
1
5
31
9
4
3
12
5
RSD
.13
.56
.05
.42
.50
.12
.32
.61
.65
.04
.93
.78
.55
.15
.54
.28
.22
.57
.25
.14
.65
.64
.44
.81
.89
.85
.20
.45
.95
MDLb
//g/L
0
.025
0.082
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.030
.002
.003
.004
.002
.005
.002
.055
.316
.006
.001
.009
.008
.001
.002
.002
.002
.002
.081
.002
.001
.018
.004
.008
.024
.037
.142
EDLC
_j>g/L
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
500
324
055
009
005
006
004
Oil
014
075
685
010
007
009
008
0.005
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
007
Oil
010
020
081
030
006
022
016
046
146
037
431
                      551.1-38

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           TABLE 2.A.  METHOD DETECTION LIMIT USING MTBE (cont'd)
            NH^Cl PRESERVED REAGENT WATER ON PRIMARY DB-1 COLUMN
ANALYTE
Tetrachl oroethyl ene
Tri chl oroacetoni tri 1 e
1 , 1 , 1-Trichloroethane
1,1, 2-Tr i chl oroethane
Tri chl oroethyl ene
1,2, 3-Tr i chl oropropane
1 , 1 , 1-Trichl oro-2-propanone
Trifluralin
Surrogate ===>
Decaf 1 uorobyphenyl
(a) Based upon the analysis
(b) MDL designates the stati
Fort.
Cone. ,
0.
0.
0.
0.
0.
0.
0.
0.
10.
010
010
010
140
010
156
010
022
0
of eight
stically
Obser.8
Cone.,
//g/L
0.012
0.010
0.013
0.124
0.008
0.137
0.027
0.026
10.8
Avg.
%Rec.
120
100
130
89
80
88
270
118
108
replicate MTBE
derived MDL and

5
5
12
3
8
1
20
3
2
RSD
.04
.31
.35
.27
.68
.95
.53
.89
.38
sample
is cal

0
0
0
0
0
0
0
0

MDLb
.002
.002
.005
.012
.002
.008
.016
.003

extracts
culated

0
0
0
0
0
0
0
0

by
EDLC
.004
.004
.005
.040
.008
.028
.016
.010


     multiplying the standard deviation of the eight replicates by the
     student's t-value (2.998) appropriate for a 99% confidence level  and a
     standard deviation estimate with n-1 degrees of freedom.
(c)  Estimated Detection Limit (EDL)  Defined as either the  MDL or a level
     of compound in a sample yielding a peak in the final  extract with a
     signal to noise (S/N)  ratio of approximately 5, whichever is greater.
                                  551.1-39

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TABLE 2.B.  METHOD DETECTION LIMIT USING NTBE
NHAC1 PRESERVED REAGENT WATER
ANALYTE
Alachlor
Bromacil
Bromochl oroacetoni tri 1 e
Bromodichloromethane
Bromoform
Carbon Tetrachloride
Chloropicrin
Chloroform
Cyanazine
Dibromoacetoni tri 1 e
Di bromochl oromethane
l,2-Dibromo-3-chloropropane
1,2-Dibromoethane
Dichl oroacetoni tri 1 e
l,l-Dichloro-2-propanone
Endrin
Endrin Aldehyde
Endrin Ketone
Heptachlor
Heptachlor Epoxide
Hexachlorobenzene
Hexachlorocyclopentadiene
Lindane (g-BHC)
Methoxychlor
Metolachlor
Metribuzin
Simazine/Atrazine
Tetrachl oroethyl ene
Tri chl oroacetoni tri 1 e
Fort.
Cone. ,
//g/L
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
0
0
.109
.094
.010
,010
.010
.010
.010
.010
.189
.010
.010
.010
.010
.010
.010
.016
.022
.047
.016
.044
.006
.019
.009
.188
.219
.062
.26 e
.010
.010
ON
CONFIRMATION
Obser."
Cone.,
//g/L
0
0
0
0
0
0

0
0
0
0
0
0
0
0
0
0
0
0
0
0

0
0
0
0
1
0
0
.107
.134
.008
.012
.015
.011
NR d
.059
.279
.010
.021
.020
.039
.010
.009
.025
.034
.049
.018
.079
.006
NR
.011
.221 .
.280
.076
.619
.012
.006
Avg.
%Rec.
98
143
80
120
150
110
NR
590
148
100
210
200
390
100
90
156
155
104
113
180
100
NR
122
118
128
123
129
120
60
Rtx-1301 COLUMN
%RSD
1
11
9
4
29
18
.70
.65
.49
.34
.51
.70
HDL"
0
0
0
0
0
0
NR
2
7
4
29
9
6
4
11
4
22
5
3
84
16
.82
.56
.87
.30
.95
.44
.11
.65
.09
.45
.49
.79
.71
.47
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.005
.047
.002
.002
.013
.006
NR
.005
.063
.001
.018
.006
.007
.001
.003
.003
.023
.008
.002
.202
.003
NR
6
3
1
2
2
6
16
.09
.53
.45
.17
.48
.97
.01
0
0
0
0
0
0
0
.002
.023
.012
.005
.121
.002
.003
EDLC
//g/L
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.076
.071
.015
.006
.013
.006
.062
.008
.065
.007
.018
.024
.007
.003
.015
.015
.030
.047
.010
.202
.011
.327 .
.009
.041
.268
.013
.629
.003
.010
                   551.1-40

-------
          TABLE  2.B.   METHOD  DETECTION  LIMIT USING MTBE  (cont'd)
       NH.C1  PRESERVED REAGENT WATER ON CONFIRMATION  Rtx-1301 COLUMN
ANALYTE
1,1, 1-Trichl oroethane
1,1,2-Tri chl oroethane
Trichloroethylene
1,2, 3-Tri chl oropropane
1,1, 1-Trichl oro-2-propanone
Trifluralin
Fort.
Cone. ,
//g/L
0
0
0
0
0
0
.010
.140
.010
.156
.010
.022
Obser.a
Cone.,
0
0
0
0
0
0
.020
.133
.009
.160
.011
.024
Avg.
%Rec.
200
95
90
103
110
109
%RSD
19
3
13
3
7
3
.22
.40
.77
.11
.11
.07
MDLb
0
.012
0.014
0
0
0
0
.004
.015
.002
.002
EDLe
^9/L
0.
0.
0.
0.
0.
0.
012
020
007
114
010
006
Surrogate ->
Decafluorobyphenyl
10.0
10.6
106
1.78
(a)  Based upon the analysis of eight replicate MTBE sample extracts.
(b)  MDL designates the statistically derived MDL and is calculated by
     multiplying the standard deviation of the eight replicates by the
     student's t-yalue (2.998) appropriate for a 99% confidence level  and a
     standard deviation estimate with n-1 degrees of freedom.
(c)  Estimated Detection Limit (EDL) ~ Defined as either the  MDL or a
     level of compound in a sample yielding'a peak in the final extract
     with a signal  to noise (S/N) ratio of approximately 5, whichever is
     greater.
(d)  NR indicates Not Reported since their was no peak detected for the
     eight replicate MDL determination.
(e)  The concentration of atrazine and simazine were added together for
     this determination since these two peaks coelute on the confirmation
     column.
                                 551.1-41

-------
      TABLE 3.A.  PRECISION AND ACCURACY RESULTS USING MTBE"
NHAC1  PRESERVED FORTIFIED REAGENT WATER ON THE PRIMARY DB-l COLUMN
ANALYTE
Alachlor
Atrazine
Bromacil
Bromochl oroacetoni tri 1 e
Bromodi chl oromethane
Bromoform
Carbon Tetrachloride
Chloropicrin
Chloroform
Cyanazine
Di bromoaceton 1 tri 1 e
Dibromochl oromethane
1 , 2-Di bromo-3-chl oropropane
1 , 2-Di bromoethane
Di chl oroacetoni tri 1 e
1, l-Dichloro-2-propanone
Endrin
Endr in Aldehyde
Endrin Ketone
Heptachlor
Heptachlor Epoxide
Hexachl orobenzene
Hexachlorocyclopentadiene
Lindane (g-BHC)
Methoxychlor
Metolachlor
Metribuzin
Simazine
Tetrachl oroethyl ene
Tri chl oroacetoni tri 1 e
Fortified
Cone., //g/L
2.18
12.6
1.88
5.00
5.00
5.00
5.00
5.00
5.00
3.77
5.00
5.00
5.00
5.00
5.00
5.00
0.311
0.437
0.310
0.313
0.875
0.124
0.374
0.188
1.26
4.39
1.24
12.5
5.00
5.00
Mean Meas.
Cone., //g/L
2.40
12.4
1.85
5.69
4.94
5.07
5.07
5.32
5.10
3.89
5.78
4.87
5.11
4.96
5.35
5.08
0.337
0.503
0.319
0.351
0.968
0.137
0.368
0.199
1.48
4.89
1.21
13.1
5.07
5.73
%RSD
1.47
1.71
3.13
0.71
1.14
0,72
1.72
1.38
1.30
2.85
1.43
0.71
0.59
0.73
0.57
0.72
1.40
1.32
1.52
2.84
0.65
0.89
1.18
1.41
2.84
0.87
3.94
2.02
1.62
1.34
Percent
Recovery
110
98
98
114
99
101
101
106
102
103
116
97
102
99
107
102
108
115
103
112
111
110
98
106
117
111
97
105
101
115
                             551.1-42

-------
       TABLE 3.A.  PRECISION AND ACCURACY RESULTS USING HTBE" (cont'd)
     NH.C1 PRESERVED FORTIFIED REAGENT WATER ON THE PRIMARY DB-1 COLUMN
ANALYTE
1,1,1-Trichloroethane
1,1, 2-Tri chl oroethane
Trichloroethylene
1,2,3-Trichloropropane
1,1, l-Trichloro-2-propanone
Trifluralin
Fortified
Cone., fjq/L
5.00
2.80
5.00
3.12
5.00
0.439
Mean Meas.
Cone., //g/L
5.02
2.92
4.87
3.08
5.30
0.503
%RSD
1.22
0.91
1.48
0.62
0.81
1.09 -
Percent
Recovery
100
104
97
99
106
115
Surrogate -==>
Decaf1uorobyphenyl
10.0
10.4
1.93
104
(a)  Based upon the analysis of eight replicate MTBE sample extracts.
                                  551.1-43

-------
           TABLE 3.B.  PRECISION AND ACCURACY RESULTS USING MTBE *
     Na,SO, PRESERVED FORTIFIED REAGENT WATER ON THE PRIMARY DB-1 COLUMN
ANALYTE
Bromod 1 chl oromethane
Bromoform
Carbon Tetrachlorlde
Chloral Hydrate
Chloroform
Dlbromochl oromethane
1 , 2-Di bromo-3-chl oropropane
1,2-Dlbroinoethane
Tetrachloroethylene
1,1,1 -Tr 1 chl oroethane
Trichloroethylene
Fortified
Cone., uq/l
5.00
5.00
5.00
1.00
5.00
5.00
5.00
5.00
5.00
5.00
5.00
Mean Meas.
Cone., ;/g/L
4.91
5.05
5.08
0.93
4.96
4.83
5.07
4.90
5.06
5.01
4.81
%RSD
1.49
1.32
2.24
1.81
1.71
1.43
1.04
1.02
2.53
2.11
2.21
Percent
Recovery
98
101
102
93
99
97
101
98
101
100
96
Surrogate ===>
Decaf1uorobyphenyl
                                 10.0         10.2        1.88       102


(a)  Based upon the analysis of eight replicate MTBE sample extracts.
                                  551.1-44

-------
   TABLE 3.C.  PRECISION AND ACCURACY RESULTS USING MTBE*
NH4C1  PRESERVED FORTIFIED REAGENT WATER ON THE CONFIRMATION
                      Rtx-1301 COLUMN
ANALYTE
Alachlor
Bromacil
Bromochl oroaceton i tr i 1 e
Bromodlchloromethane
Bromoform
Carbon Tetrachloride
Chloropicrin
Chloroform
Cyanazine
D1 bromoacetoni tr i 1 e
01 bromochl oromethane
1 , Z-D1 bromo-3-chl oropropane
1,2-Dibromoethane
Di chl oroaceton i tr i 1 e
1 , 1-D1 chl oro-2-propanone
Endrin
Endrln Aldehyde
Endrin Ketone
Heptachlor
Heptachlor Epoxide
Hexachl orobenzene
Hexachlorocyclopentadiene
Lindane (g-BHC)
Methoxychlor
Metolachlor
Met ri buz in
Simazine/Atrazine
Tetrachl oroethy 1 ene
Tri chl oroaceton i tri 1 e
Fortified
Cone., //g/L
2.18
1.88
5.00
5.00
5.00
5.00
5.00
5,00
3.77
5.00
5.00
5.00
5.00
5.00
5.00
0.310
0.440
0.310
0.310
0.880
0.124
0.374
0.188
1.26
4.39
1.24
25.1 b
5.00
5.00
Mean Meas.
Cone., jjq/L
2.26
1.77
5.59
4.92
5.04
4.90
5.24
5.05
3.90
5.47
5.04
5.12
5.09
5.30
4.94
0.335
0.490
0.317
0.349
0.978
0.135
0.474
0.205
1.42
4.57
1.29
30.0
4.93
5.48
%RSO
0.81
3.50
0.86
1.02
0.73
1.72
1.20
1.20
2.30
0.58
0.90
0.54
1.82
0.55
0.70
2.08
2.13
1.63
1.06
0.80
0.59
7.19
0.75
2.30
3.43
1.15
1.11
1.65
1.31
Percent
Recovery
104
94
112
98
101
98
105
101
103
109
101
102
102
106
99
108
111
102
113
111
109
127
109
113
104
104
119
99
110
                         551.1-45

-------
       TABLE  3.C.   PRECISION AND  ACCURACY  RESULTS USING NTBE * (cont'd)
         NH,C1 PRESERVED FORTIFIED REAGENT WATER ON THE CONFIRMATION
                               Rtx-1301 COLUMN
ANALYTE
1 , 1 , 1-Tri chl oroethane
1 , 1 ,2-Trichl oroethane
Trichloroethylene
1,2, 3-Tri chl oropropane
1,1, 1-Tri chl oro-2-propanone
Trifluralin
Fortified
Cone., fjg/l
5.00
2.80
5.00
3.12
5.00
0.440
Mean Meas.
Cone., jjq/L
4.87
2.76
4.87
3.07
4.90
0.486
%RSD
1.66
1.52
1.52
0.88
0.89
0.93
Percent
Recovery
97
98
97
98
98
110
Surrogate ===>                   10.0         10.6        1.96        106
Decafluorobyphenyl

(a)  Based upon the analysis of eight replicate MTBE sample extracts.
(b)  Simazine and atrazine coelute on the confirmation coTumn and therefore
     there results were added together.
                                  551.1-46

-------
           TABLE 3.D.  PRECISION AND ACCURACY RESULTS USING NTBE *
        Na,SO,  PRESERVED  FORTIFIED  REAGENT  WATER ON  THE  CONFIRMATION
                              Rtx-1301 COLUMN
ANALYTE
Bromodichloromethane
Bromoform
Carbon Tetrachloride
Chloroform
Dibromochloromethane
1 , 2-Di bromo-3-chl oropropane
1,2-Dibromoethane
Tetrachl oroethyl ene
1,1,1-Trlchloroethane
Trlchl oroethyl ene
Fortified
Cone., fjq/l
5.00
5.00
5.00
5.00
5.00
5.00
5.00
5.00
5.00
5.00
Mean Meas.
Cone., //g/L
4.88
5.03
4.90
4.90
5.15
5.07
5.02
4.89
4.84
4.83
%RSD
1.53
1.19
2.27
1.58
1.78
0.94
0.82
2.47
2.18
2.06
Percent
Recovery
98
101
98
98
103
101
100
98
97
97
Surrogate ===>                   10.0          10.3        1.64
Decaf1uorobyphenyl
(a)  Based upon the analysis of eight replicate MTBE sample extracts.
103
                                  551.1-47

-------
       TABLE 4.A.   PRECISION AND ACCURACY RESULTS USING MTBE*
NH^CI  PRESERVED  FORTIFIED REAGENT WATER ON THE PRIMARY DB-1 COLUMN
ANALYTE
Alachlor
Atrazine
Bromacll
Bromochl oroacetoni tri 1 e
Bromodichloromethane
Bromoform
Carbon Tetrachloride
Chloropicrin
Chloroform
Cyanazine
Di bromoacetoni tri 1 e
Di bromochl oromethane
1 , 2-Dibromo-3-chl oropropane
1,2-Dibromoethane
Dichl oroacetoni tri 1 e
1 , 1-Di chl oro-2-propanone
Endrin
Endrin Aldehyde
Endrin Ketone
Heptachlor
Heptachlor Epoxide
Hexachl orobenzene
Hexachl orocycl opentadi ene
Lindane (g-BHC)
Methoxychlor
Metolachlor
Metribuzin
Simazine
Tetrachloroethylene
Trlchloroacetonitrile
Fortified
Cone., uq/l
0.436
2.520
0.376
0.250
0.250
0.250
0.250
0.250
0.250
0.754
0.250
0.250
0.250
0.250
0.250
0.250
0.062
0.087
0.062
0.063
0.175
0.025
0.075
0.038
0.252
0.878
0.248
2.500
0.250
0.250
Mean Meas.
Cone. , //g/L
0.515
2.994
0.376
0.281
0.276
0.260
0.299
0.285
0.264
0.761
0.276
0.266
0.261
0.274
0.268
0.261
0.073
0.108
0.062
0.059
0.206
0.030
0.074
0.047
0.298
1.056
0.264
2.960
0.263
0.29.1
%RSD
1.84
1.95
3.32
1.57
1.42
1.62
1.60
2.03
1.94
1.97
1.89
1.20
1.82
1.89
1.12
0.91
2.65
1.29
0.76
10.29
0.90
3.77
3.22
2.74
3.24
1.00
2.15
2.71
1.93
1.02
Percent
Recovery
118
119
100
113
110
104
120
114
105
101
110
106
104
110
107
105
117
123
100
93
118
120
99
125
118
120
107
118
105
116
                             551.1-48

-------
       TABLE 4.A.  PRECISION AND ACCURACY RESULTS USING MTBE1  (cont'd)
     NH.C1  PRESERVED FORTIFIED REAGENT WATER  ON  THE  PRIMARY  DB-1 COLUMN
* *
ANALYTE
1,1, 1-TMchloroethane
1,1, 2-THchl oroethane
Trlchloroethylene
1,2, 3-Tr1 chl oropropane
1,1, l-Tr1 chl oro-2-propanone
Trlfluralln
Fortified
Cone., jug/L
0.250
0.560
0.250
0.624
0.250
0.088
Mean Meas.
Cone., fjg/l
0.291
0.531
0.252
0.595
0.286
0.106
%RSD
3.65
0.85
1.20
0.83
3.72
1.50
Percent
Recovery
116
95
101
95
114
121
Surrogate >
Decafluorobyphenyl
                                 10.0          10.9         2.49       109


(a)  Based upon the analysis of eight  replicate  MTBE  sample extracts.
                                  551.1-49

-------
           TABLE  4.B.   PRECISION AND ACCURACY RESULTS USING NTBE*
     Na,SO, PRESERVED  FORTIFIED REAGENT WATER ON THE PRIMARY DB-1 COLUMN
ANALYTE
Bromodichloromethane
Bromoform
Carbon Tetrachloride
Chloral Hydrate
Chloroform
Di bromochl oromethane
1 , 2-Di bromo-3-chl oropropane
1,2-Dibromoethane
Tetrachl oroethyl ene
1,1, 1-Trichl oroethane
Trichl oroethyl ene
Fortified
Cone., fjg/l
0.250
0.250
0.250
0.250
0.250
0.250
0.250
0.250
0.250
0.250
0.250
Mean Meas.
Cone., fjg/l
0,270
0.257
0.287
0.258
0.248
0.261
0.258
0.243
0.256
0.276
0.246
%RSD
1.77
2.04
5.18
4.12
1.88
1.36
1.26
0.90
1.95
5.72
1.01
Percent
Recovery
108
103
115
103
99
105
103
97
102
110
98
                                 10.0          10.6         3.51        106


(a)  Based upon the analysis of eight  replicate MTBE sample extracts.
Surrogate =>
Decaf1uorobyphenyl
                                  551.1-50

-------
           TABLE  5.A.   PRECISION  AND  ACCURACY  RESULTS  USING  MTBEa
NH4C1  PRESERVED FORTIFIED FULVIC ACID ENRICHED REAGENT WATER6 ON THE PRIMARY
                                 DB-1  COLUMN
ANALYTE
Alachlor
Atrazlne
Bromacil
Bromochl oroacetoni tri 1 e
Bromodichloromethane
Bromoform
Carbon Tetrachloride
Chloropicrin
Chloroform
Cyanazine
D1 bromoaceton 1 tri 1 e
Di bromochl oromethane
1 , 2-Dibromo-3-chl oropropane
1,2-Dibromoethane
Dichl oroacetoni irile
l,l-Dichloro-2-propanone
Endrln
Endrin Aldehyde
Endrln Ketone
Heptachlor
Heptachlor Epoxide
Hexachl orobenzene
Hexachl orocycl opentadi ene
Lindane (g-BHC)
Methoxychlor
Metolachlor
Metribuzin
Simazine
Tetrachl oroethyl ene
Fortified
Cone., jjq/l
2.18
12.6
1.88
1.00
1.00
1.00
1.00
1.00
1.00
3.77
1.00
1.00
.1.00
1.00
1.00
1.00
0.311
0.437
0.310
0.313
0.875
0.124
0.374
0.188
1.26
4.39
1.24
12.5
1.00
Mean Meas.
Cone. , fjq/i
2.38
11.6
1.89
1.11
0.87
0.97
0.88
1.13
1.03
4.02
1.14
0.89
0.93
0.96
1.05
1.03
0.325
0.505
0.319
0.358
0.978
0.139
0.363
0.206
1.41
4.84
1.30
12.0
0.90
%RSD
1.57
2.31
3.33
1,51
1.93
1.50
3.91
2.49
2.47
3.99
1.61
1.78
1.37
1.58
0.98
0.90
3.50
1.99
2.62
5.45
1.28
1.82
3.55
1.79
4.78
1.27
2.08
1.09
4.02
Percent
Recovery
109
92
101
111
87
97
88
113
103
107
114
89
93
96
105
103
104
116
103
114
112
112
97
110
112
110
105
96
90
                                  551.1-51

-------
      TABLE 5.A.  PRECISION AND ACCURACY RESULTS USING NTBE * (cont'd)
 NH4C1  PRESERVED FORTIFIED  FULVIC ACID  ENRICHED REAGENT WATERb ON THE PRIMARY
   *                             DB-1 COLUMN
ANALYTE
Trichloroacetonitrile
1,1,1-Trichloroethane
1,1, 2-Trichl oroethane
Trichloroethylene
1,2, 3-Tr i chl oropropane
l,l,l-Trichloro-2-propanone
Trifluralin
Fortified
Cone., uq/L
1.00
1.00
2.80
1.00
3.12
1.00
0.439
Mean Meas.
Cone., fjq/l
1.11
0.96
2.81
0.93
2.92
1.10
0.517
%RSD
2.41
3.89
2.89
3.55
0.82
2.05
1.27
Percent
Recovery
111
96
100
93
93
110
118
Surrogate ===>                     10.0         10.4       1.84      104
Decafluorobyphenyl

(a)  Based upon the analysis of eight replicate MTBE sample extracts.
(b)  Reagent water fortified at 1.0 mg/L with fulvic acid extracted from
     Ohio River water.  Sample simulated high TOC matrix.
                                  551.1-52

-------
           TABLE 5.B.  PRECISION AND ACCURACY RESULTS USING KTBE *
 Na,S03 PRESERVED FORTIFIED FULVIC ACID ENRICHED REAGENT WATER ON THE PRIMARY
                                DB-1 COLUMN
ANALYTE
Bromodi chl oromethane
Bromoform
Carbon Tetrachloride
Chloral Hydrate
Chloroform
D1 bromochl oromethane
1 , 2-Di bromo-3-chl oropropane
1,2-Dibromoethane
Tetrachl oroethyl ene
1,1, 1-Trlchl oroethane
Trichl oroethyl ene
Fortified
Cone., fjg/l
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
1.00
Mean Meas.
Cone., //g/L
0.87
0.97
0.88
0.90
0.96
0.88
0.92
0.93
0.90
0.97
0.94
%RSD
1.13
1.28
1.71
0.95
1.51
1.25
0.98
1.01
2.07
1.57
1.62
Percent
Recovery
87
97
88
90
96
88
92
93
' 90
97
94
Surrogate ===>                     10.0         10.6       2.56      106
Decafluorobyphenyl

(a)  Based upon the analysis of eight replicate MTBE sample extracts.
(b)  Reagent water fortified at 1.0 mg/L with fulvic acid extracted from
     Ohio River water.  Sample simulated high TOC matrix.
                                  551.1-53

-------
TABLE 6.A.   PRECISION AND  ACCURACY  RESULTS  USING NTBE"
NH4C1  PRESERVED FORTIFIED GROUND WATER* ON THE PRIMARY
                      OB-1  COLUMN
ANALYTE
Alachlor
Atrazlne
Bromacll
Bromochl oroacetoni tri 1 e
Bromodichl oromethane
Bromoform
Carbon Tetrachloride
Chloropicrin
Chloroform
Cyanazlne
Di bromoacetoni tri 1 e
D1 bromochl oromethane
1 , 2-D1 bromo-3-chl oropropane
1,2-Dibromoethane
Dichloroacetonltrile
l,l-Dichloro-2-propanone
Endrin
Endrin Aldehyde
Endrin Ketone
Heptachlor
Heptachlor Epoxide
Hexachl orobenzene
Hexachlorocyclopentadiene
Lindane (g-BHC)
Hethoxychlor
Metolachlor
Hetribuzin
Simazine
Tetrachloroethylene
Unfort.
matrix
cone.,
V9/L
NO c
ND
NO
ND
1.70
20.1
ND
ND
0.571
ND
ND
6.00
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Fort.
Cone.,
//9/L
8.72
50.4
7.52
5.00
5.00
5.00
5.00
5.00
5.00
15.1
5.00
5.00
5.00
5.00
5.00
5.00
1.24
1.75
1.24
1.25
3.50
0.50
1.50
0.75
5.04
17.6
4.96 .
50.0
5.00
Mean
Meas.
Cone.,
/*/L
9.01
46.7
6.53
5.74
6.68
24.8
4.99
5.29
5.73
15.4
5.84
11.1
5.04
4.87
5.29
5.01
1.32
1.91
1.22
1.33
3.67
0.509
1.41
0.773
5.60
18.2
4.85
48.3
4.97
%RSD
2.93
3.30
7.81
1.38
2.59
1.61
6.65
3.59
3.68
6.07
1.59
1.89
1.64
1,90
1.52
1.30
4.81
2.36
3.77
4.46
2.92
3.42
3.70
1.91
5.86
3.06
6.15
3.30
6.29
Percent
Recovery
103
93
87
115
100
95
100
106
103
102
117
102
101
97
106
100
106
109
98
106
105
103
94
103
111
103
98
97
99
                       551.1-54

-------
       TABLE 6.A.   PRECISION AND ACCURACY RESULTS  USING  HTBE* (cont'd)
           NH,C1 PRESERVED FORTIFIED  GROUND WATERb ON THE PRIMARY
                                 DB-1  COLUMN
ANALYTE
Trichloroacetonitrlle
1,1, 1-Trichl oroethane
1,1, 2-Tri chl oroethane
Trichloroethylene
1,2,3-Trichloropropane
1,1, 1-Tr i chl oro-2-propanone
Trlfluralin
Unfort.
matrix
cone.,
*/g/L
ND
1.77
ND
ND
0.340
ND
ND
Fort.
Cone.,
W/l
5.00
5.00
11.2
5.00
12.5
5.00
1.76
Mean
Meas.
Cone.,
W/L
5.59
6.62
10.4
4.74
12.5
5.21
1.94
%RSD
4.89
4.60
2.98
5.78
3.92
1.58
3.38
Percent
Recovery
112
97
93
95
97
104
110
Surrogate =>                          10.0      10.4      2.25    104
Decafluorobyphenyl

(a)  Based upon the analysis of eight replicate MTBE sample extracts.
(b)  Chlorinated ground water from a water source displaying a hardness of
     460 mg/L as CaC03.
(c)  ND Indicates not detected above the EDL.
                                  551.1-55

-------
           TABLE 6.B.  PRECISION AND ACCURACY RESULTS USING MTBE*
     Na,SO, PRESERVED  FORTIFIED  GROUND WATERb ON THE PRIMARY DB-1 COLUMN
ANALYTE
Bromodichloromethane
Bromoform
Carbon Tetrachloride
Chloral Hydrate
Chloroform
Di bromochl oromethane
1 , 2-Dibromo-3-chl oropropane
1,2-Dibromoethane
Tetrachl oroethy 1 ene
1,1, 1-Trichloroethane
Trlchloroethylene
Unfort.
matrix
cone.,
jug/L
1.77
20.5
NO c
NO
0.600
6.16
NO
ND
ND
1.91
ND
Fort.
Cone.,
M/L
5.00
5.00
5.00
2.00
5.00
5.00
5.00
5.00
5.00
5.00
5.00
Mean
Meas.
Cone.,
jug/L
6.64
24.6
4.99
1.84
5.22
11.0
5.01
4.79
4.95
6.73
4.69
%RSD
1.70
1.63
2.72
1.38
1.89
1.53
1.19
1.86
2.49
3.18
2.38
Percent
Recovery
97
82
100
92
92
98
100
96
99
96
94
Surrogate ===>
Decafluorobyphenyl
10.0
10.1
8.71    101
(a)  Based upon the analysis of eight replicate MTBE sample extracts.
(b)  Chlorinated ground water from a water source displaying a hardness of
     460 mg/L as CaC03.
(c)  ND Indicates Not Detected above the detection limit.
                                  551.1-56

-------
           TABLE 7.  LABORATORY PERFORMANCE CHECK SOLUTION
Parameter
Instrument
Sensitivity
Chromatographic
Performance
Col umn
Performance

Analyte
Breakdown
Analyte
lindane
(gamma-BHC)
Hexachlorocyclopentadiene
Bromodichloromethane
Trichloroethylene
Bromacil
Alachlor
Endrin
Cone.,
//g/mL
in MTBE
or pentane
0.000200
0.0200
0.0300
0.0300
0.0830
0.0830
0.0300
Acceptance
Criteria
Detection of
Analyte;
Signal to
Noise > 3
PGF between
0.80 and 1.15"
Resolution >
0.50b
Resolution >
0.50
%BDC < 20 %
     PGF = Peak Gaussian Factor. Calculated using the equation:
           1.83 x W(l/2)
     PGF =     ................ ----
     where W(l/2) is the peak width at half height and W(l/10) 1s the
     peak width at tenth height.

     Resolution between the two peaks as defined by the equation:
           t
     R - -----
           W
     where t 1s the difference in elution times between the two peaks and
     W is the average peak width, at the baseline, of the two peaks.

     %BD - Percent Breakdown.  Endrin breakdown calculated using the
     equation.
            (AREA Endrin Ketone + AREA Endrin Aldehyde)
                                                                  X 100
          (AREA Endrin Ketone + AREA Endrin Aldehyde + AREA Endrin)
Note:     If laboratory EDL's differ from those listed in this method,
          concentrations of the LPC standard must be adjusted to be
          compatible with the laboratory EDL's.
                              551.1-57

-------
   TABLE 8.  METHOD DETECTION LIMIT USING PENTANE
NH4C1  PRESERVED REAGENT WATER ON PRIMARY DB-1 COLUMN
ANALYTE
Alachlor
Atrazine
Bromacil
Bromochl oroaceton i tr i 1 e
Bromodi chl oromethane
Bromoform
Carbon Tetrachloride
Chloropicrin
Chloroform
Cyanazine
Di bromoacetoni tr i 1 e
01 bromochl oromethane
1 , 2-Di bromo-3-chl oropropane
1,2-Dibromomethane
Dichloroacetonitrile
i;i-Dichloro-2-propanone
Endrln
Endrln Aldehyde
Endrln Ketone
Heptachlor
Heptachlor Epoxide
Hexachl orobenzene
Hexachloropentadlene
Lindane (g-BHC)
Methoxychlor
Metolachlor
Metribuzin
Simazine
Tetrachl oroethyl ene
Fort.
Cone.
//9/L
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.109
.633
.094
.040
.040
.040
.040
.040
.040
.189
.040
.040
.040
.040
.040
.040
.016
.022
.016
.016
.044
.0062
.040
.0094
.063
.219
.062
.625
.040
Observ.b
Cone.
//9/L
0.
0
0
0
0
0
0
0
0
0.
0
0
0
0
0
0
0
0
0
0.
0
0
0
0
0
0
0
0
0
095a
.663
.058
.047
.054
.033
.060
.045
.110
170a
.046
.050
.053
.053
.037
.042
.019
.023
.014
Olla
.045
.008
.022
.006
.069
.267
.076
.662
.052
Avg.
%Rec.
87
105
62
118
135
83
150
113
275
90
115
125
133
133
93
105
119
105
88
69
102
129
55
64
110
122
123
106
130
%RSD
5.
5.
21.
3.
42.
20.
27.
4.
24.
13.
3.
5.
5.
19.
20.
4.
4.
5.
9.
18.
5.
9.
24.
91.
12.
10.
18.
9.
5.
37
00
44
61
05
60
76
25
36
37
84
48
39
85
09
86
69
52
50
14
02
56
42
20
76
35
15
42
33
MDLe
//9/L
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.015
.099.
.037
.005
.068
.020
.050
.006
.080
.068
.005
.008
.009
.032
.022
.006
.003
.004
.004
.006
.007
.002
.016
.017
.026
.083
.041
.187
.008
EDLd
V9/L
0
0
.050
.390
0.330
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.026
.068
.035
.050
.023
.080
.200
.030
.026
.017
.032
.042
.022
.016
.022
.020
.009
.016
.002
.016
.017
.066
.172
.041
.420
.016
                      551.1-58

-------
          TABLE 8.  METHOD DETECTION LIMIT USING PENTANE (cont'd)
            NH4C1 PRESERVED REAGENT WATER ON PRIMARY DB-1 COLUMN
ANALYTE
Tri chl oroacetoni tri 1 e
1,1, 1-Tri chl oroethane
1 , 1 ,2-Trichl oroethane
Tr 1 chl oroethyl ene
1,2,3-Trichloropropane
1,1, 1-TMchl oro-2-propanone
Trifluralin
Fort.
Cone.
//g/L
0.040
0.040
0.140
0.040
0.156
0.040
0.040
Observ.b
Cone.
W/L
0.048
0.058
0.141
0.064
0.151
0.045
0.021
Avg.
%Rec.
120
145
101
160
97
113
53
%RSD
2.79
4.26
4.01
21.80
3,54
3.65
19.28
MDLC
//9/L
0.004
0.007
0.017
0.042
0.016
0.005
0.012
EDLd
//g/L
0.014
0.017
0.052
0.042
0.116
0.024
0.012
Surrogate =>
Decafluorobyphenyl
10.0
11.2  112
3.98
(a)  Quantitated from confirmation column due to baseline interference on
     primary column.
(b)  Based upon the analysis of eight replicate pentane sample extracts.
(c)  MDL designates the statistically derived MDL and is calculated by
     multiplying the standard deviation of the eight replicates by the
     student's t-value (2.998) appropriate for a 99% confidence level  and  a
     standard deviation estimate with n-1 degrees of freedom.
(d)  Estimated Detection Limit (EDL)  Defined as either the  MDL or a level
     of compound in a sample yielding a peak in the final  extract with a
     signal to noise (S/N) ratio of approximately 5, wbv never is greater.
                                  551.1-59

-------
            TABLE 9.  PRECISION AND ACCURACY RESULTS*
                          USING PENTANE
NH4C1  PRESERVED FORTIFIED REAGENT WATER ON THE PRIMARY DB-1 COLUMN
ANALYTE
Alachlor
Atrazine
Bromacil
Bromochl oroacetonl tr i 1 e
Bromodichloromethane
Bromoform
Carbon Tetrachloride
Chloropicrin
Chi orof orm
Cyanazine
D1 bromoacetoni tr 11 e
Dlbromochloromethane
1 , 2-Di bromo-3-chl oropropane
1,2-Dibromoethane
Dichloroacetonitrile
1 , 1-D1 chl oro-2-propanone
Endrin
Endrin Aldehyde
Endrin Ketone
Heptachlor Epoxlde
Heptachlor
Hexachlorobenzene
Hexachlorocyclopentadiene
Llndane (g-BHC)
Methoxychl or
Metolachlor
Metribuzin
Simazlne
Tetrachl oroethyl ene
Fortified
Cone., /yg/L
2.18
12.6
1.88
5.00
5.00
5.00
5.00
5.00
5.00
3.77
5.00
5.00
5.00
5.00
5.00
5.00
0.311
0.437
0.310
0.875
0.313b
0.124
0.374
0.188
1.26
4.39
1.24
12.5
5.00
Mean Meas.
Cone., jjg/L
1.98 b
12.0
1.74
4.63
4.46
4.81
4.61
4.51
4.95
4.00 b
4.80
4.23
4.73
4.69
4.73
4.78
0.312
0.443
0.311
0.866
0.30
0.123
0.384
0.176
1.28
4.42
1.34
12.5
4.46
%RSD
5.09
3.09
2.95
3.18
4.07
2.76
4.14
2.46
2.90
2.59
2.87
3.38
3.00
2.54
3.39
3.04
2.61
2.29
2.10
2.11
3.47
2.51
3.30
10.23
3.03
2.36
2.13
2.20
3.67
Percent
Recovery
91
95
93
93
89
96
92
90
99
106
96
85
95
94
95
96
100
101
100
99
97
99
103
94
102
101
108
100
89
                            551.1-60

-------
            TABLE 9.  PRECISION AND ACCURACY RESULTS' (cont'd)
                              USING PENTANE
    NH4C1  PRESERVED FORTIFIED REAGENT WATER ON THE PRIMARY DB-1 COLUMN
ANALYTE
Tri chl oroacetoni tri 1 e
1,1,1-Trichloroethane
1,1, 2-Tri chl oroethane
Trichloroethylene
1,2,3-Trichloropropane
1, 1, l-Trichloro-2-propanone
Trifluralin
Surrogate===>
Decaf 1 uorobyphenyl
Fortified
Cone., ^g/L
5.00
5.00
2.80
5.00
3.12
5.00
0.439
10.0
Mean Meas.
Cone., fjq/i
5.07
4.70
2.62
4.84
3.13
4.88
0.446
10.7
%RSD
4.02
3.39
2.03
2.98
1.76
2.80
2.74
1.88
Percent
Recovery
101
94
93
97
100
98
102
107
(a)
Based upon the analysis of eight replicate pentane sample extracts.
(b)      Quantitated from confirmation column due to baseline interference
        on primary column.
                                551.1-61

-------
TABLE 10.  ANALYTE PEAK IDENTIFICATION, RETENTION TIMES,
 CONCENTRATIONS  AND  CONDITIONS  USING  NTBE  FOR  FIGURE  1
     NH,C1  PRESERVED  FORTIFIED REAGENT WATER ON THE
                   PRIMARY  DB-1  COLUMN
Retention
PEAK Time3
1 ANALYTE minutes
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
Chloroform
1,1, 1-Tri chl oroethane
Carbon Tetrachloride
Tri chl oroacetoni tri le
Dichl oroacetoni tri 1 e
Bromodichloromethane
Trichloroethylene
Chloral Hydrate
1 , 1-Dichl oro-2-Propanone
1,1, 2-Tri chl oroethane
Chloropicrin
Di bromochl oromethane
Bromochl oroacetoni tri 1 e
1,2-Dibromoethane (EDB)
Tetrachl oroethyl ene
1,1, 1-Tri chl oropropanone
Bromoform
Dibromoacetonitrile
1,2, 3-Tri chl oropropane
1 , 2-Di bromo-3-chl oropropane (DBCP)
Surrogate: Decaf luorobiphenyl
Hexachl orocycl opentad i ene
Trlfluralin
Simazine
Atrazine
Hexachl orobenzene
Lindane (gamma-BHC)
Metribuzin
7.04
8.64
9.94
10.39
12.01
12.42
12.61
13.41
14.96
19.91
23.10
23.69
24.03
24.56
26.24
27.55
29.17
29.42
30.40
35.28
36.35
40.33
45.17
46.27
46.55
47.39
47.95
50.25
Cone.
m/i
5.00
5.00
5.00
5.00
5.00
5.00
5.00
5.00
5.00
44.8
5.00
5.00
5.00
5.00
5.00
5.00
5.00
5.00
50.0
5.00
10.0
28.0
7.04
200
200
1.98
30.1
19.9
                        551.1-62

-------
           TABLE 10.  ANALYTE PEAK IDENTIFICATION, RETENTION TIMES,
        CONCENTRATIONS AND CONDITIONS USING MTBE FOR FIGURE 1  (cont'd)
                NH,C1  PRESERVED  FORTIFIED REAGENT  WATER ON THE
                              PRIMARY DB-1 COLUMN
PEAK
#
29
30
31
32
33
34
35
36
37
38
NOTE:
ANALYTE
Bromacil
Alachlor
Cyanazine
Heptachlor
Metolachlor
Heptachlor Epoxide
Endrin
Endrin Aldehyde
Endrin Ketone
Methoxychlor
Bromofluorobenzene (ret.
standard was not Included
Retention
Time8
minutes
52.09
52.25
53.43
53.72
55.44
58.42
64.15
65.46
72.33
73.53
time 31.00 min.) as the
in this chromatogram.
Cone.
//g/L
30.1
34,9
60.4
5.00
70.0
14.0
5.00
7.00
4.96
20.1 	
ThternaT
(a)  Column A -
     0.25 mm ID x 30 m fused silica capillary with chemically
     bonded methyl polysiloxane phase  (J&W, DB-1, 1.0 fm  film
     thickness or equivalent).  The linear velocity of the
     helium carrier is established at  25 cm/sec at 35C.
The column oven is temperature programmed as follows:
[1]  HOLD at 35C for 22 min
[2]  INCREASE to 145C at 10C/min and  hold  at  145C for 2 min.
[3]  INCREASE to 225C at 20C/min and  hold  at  225C for 15
     min.
[4]  INCREASE to 260C at 10C/min and  hold  at  260C for 30
     min. or until all expected compounds have eluted.
Injector temperature:  200C
Detector temperature:  290C
                                   551.1-63

-------
FIGURE I.  FORTIFIED REAGENT WATER EXTRACT USING HTBE ON PRIHARY DB-1 COLUMN






















i




S






1










21
23


IS
u1 M
fill



45 SI



3











i

i


5




a

u
17
11 1,""
r
1 "
,
i , ll .IT
- .,.....!.. . ! . . . . 1 . . _ ^ 1 - - - J , .
11 IS a 25 31 35 
MINUTES
34
* 33
| 31
ll
31
ll. ll

SS 41  71 75 M 6
MINUTES
                                  551'. 1-64

-------
TABLE 11.  ANALYTE PEAK IDENTIFICATION, RETENTION TIMES,
  CONCENTRATIONS AND  CONDITIONS USING MTBE FOR FIGURE 2
     NH,C1  PRESERVED  FORTIFIED  REAGENT WATER  ON THE
                  CONFIRMATION  RtX-1301
PEAK
f
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
Retention
Time*
ANALYTE minutes
Chloroform
1,1, 1-Tri chl oroethane
Carbon Tetrachloride
Trichloroacetoni tri 1 e
Trichloroethylene
Bromodichloromethane
1 , 1-Dichl oro-2-Propanone
Chloroplcrin
Tetrachl oroethyl ene
1,1, 2-Trichloroethane
Dichloroacetoni tri 1 e
Dibromochloromethane
1,2-Di bromoethane (EDB)
1,1, 1-THchl oropropancne
Bromochl oroacetoni tri 1 e
Bromoform
1 , 2 ,3-Tri chl oropropane
Oi bromoaceton i tr i 1 e
1,2-Di bromo-3-chl oropropane (DBCP)
Surrogate: Decaf luorobiphenyl
Hexachl orocycl opentadi ene
Trifluralin
Hexachl orobenzene
Atrazine/Simazine
Lindane (gamma-BHC)
Heptachlor
Metribuzin
7.73
7.99
8.36
10.35
11.96
15.28
20.50
23.69
24.77
25.01
25.21
26.32
26.46
28.47
29.86
30.36
31.73
32.77
36.11
36.28
39.53
45.43
46.47
48.56
49.68
53.15
53.92
Cone.
//9/L
5.00
5.00
5.00
5.00
5.00
5.00
5.00
5.00
5.00
44.8
5.00
5.00
5.00
5.00
5.00
5.00
50.0
5.00
5.00
10.0
28.0
7.04
1.98
400
30.1
5.00
19.9
                        551.1-65

-------
           TABLE 11.  ANALYTE PEAK IDENTIFICATION, RETENTION TINES,
        CONCENTRATIONS AND CONDITIONS USING MTBE FOR FIGURE 2 (cont'd)
                NH4C1  PRESERVED  FORTIFIED  REAGENT WATER ON  THE
                             CONFIRMATION  Rtx-1301
      PEAK
       f    ANALYTE
                                  Retention
                                    Time8        Cone.
                                   minutes       fjg/L
28
29
30
31
32
33
34
35
36
NOTE:
Alachlor
Metolachlor
Heptachlor Epoxide
Bromacil
Cyanazine
Endrin
Endrin Aldehyde
Methoxychlor
Endrin Ketone
Bromof 1 uorobenzen
54.38
57.07
59.05
59.60
59.89
65.24
71.56
76.73
81.28
e (ret. time 31.30 min.) as th<
34.9
70.0
14.0
30.1
60.4
5.00
7.00
20.1
4.96 	
B" internal
(a)  Column B -
standard was not included in this chromatogram.

     0.25 mm ID x 30 m with chemically bonded 6 %
     cyanopropylphenyl / 94 % dimethyl polysiloxane phase
     (Restek, Rtx-1301, 1.0 pm film thickness or equivalent).
     The linear velocity of the helium carrier gas is
     established at 25 cm/sec at 35C.
The column oven is temperature programmed as follows:
The column oven is temperature programmed as follows:
[1]  HOLD at 35C for 22 min
[2]  INCREASE to 145C at 10C/min  and hold  at  145C for 2  min
[3]  INCREASE to 225C at 20C/min  and hold  at  225C for 15 min
[4]  INCREASE to 260C at 10C/min  and hold  at  260C for 30
     min. or until all expected compounds have eluted.
Injector temperature:  200C
Detector temperature:  290PC
                                   551.1-66

-------
FIGURE 2.
COLUMN
FORTIFIED REAGENT WATER EXTRACT USING MTBE OK CONFIRMATION Rtx-1301
                                          12
                                                        If
                                            U
                                               IS
                                                '   II
                                                 17
                                                  21
                                                   I
                  II      IS      21      25       31      35      It
                                 MINUTES
        22
           T
        JL_b_L
                                    M
       45      51      55       it            71      75      II       15
                                 MINUTES
                               551.1-67 '

-------
TABLE 12.  ANALYTE PEAK IDENTIFICATION, RETENTION TINES, CONCENTRATIONS
               AND CONDITIONS USING PENTANE FOR FIGURE 3
            NH4C1 PRESERVED FORTIFIED REAGENT WATER ON THE
                          PRINARY DB-1 COLUMN
Retention
PEAK Time"
1 ANALYTE minutes
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
Chi orof orm
1,1, 1-Tr 1 chl oroethane
Carbon Tetrachloride
Trichloroacetonitrile
Di chl oroacetonl tri 1 e
Bromodi chl oromethane
Trichloroethylene
1 , 1-Dichl oro-2-Propanone
1,1, 2-Tri chl oroethane
Chloropicrin
01 bromochl oromethane
Bromochl oroacetonl tri 1 e
1,2-Dibromoethane (EDB)
Tetrachl oroethyl ene
1,1, 1-Tr 1 chl oropropanone
Bromoform
Dibromoacetonltrile
1,2, 3-Tr 1 chl oropropane
Internal Standard: Bromof 1 uorobenzene
l,2-Dibromo-3-chl oropropane (DBCP)
Surrogate: Decaf luorobiphenyl
Hexachl orocycl opent ad 1 ene
Trifluralin
Simazine
Atrazine
Hexachl orobenzene
Lindane (gamma-BHC)
8.41
10.26
11.56
12.03
13.53
13.73
13.89
15.60
18.57
20.49
21.03
21.25
22.03
24.75
27.94
30.97
31.45
32.82
33.60
38.34
39.48
43.92
49.04
50.08
50.37
51.11
51.66
Cone.
09/L
5.00
5.00
5.00
5.00
5.00
5.00
5.00
5.00
44.8
5.00
5.00
5.00
5.00
5.00
5.00
5.00
5.00
50.0
1.00 fjq/ml in
pentane extract
5.00
10.0
28.0
7.04
200
200
1.98
30.1
                                551.1-68

-------
   TABLE  12.   ANALYTE PEAK IDENTIFICATION, RETENTION TINES, CONCENTRATIONS
              AND CONDITIONS USING  PENTANE FOR  FIGURE  3  (cont'd)
                NH4C1  PRESERVED FORTIFIED REAGENT WATER ON THE
                              PRIMARY DB-1 COLUMN
PEAK
#
28
29
30
31
32
33
34
35
36
37
38
ANALYTE
Metribuzin
Bromacil
Alachlor
Cyanazine
Heptachlor
Metolachlor
Heptachlor Epoxide
Endrin
Endrin Aldehyde
Endrin Ketone
Methoxychlor
Retention
Time*
minutes
53.95
55.72
55.87
57.04
57.21
59.13
62.50
68.00
69.25
75.74
76.98
Cone.
W/L
19.9
30.1
34.9
60.4
5.00
70.0
14.0
5.00
7.00
4.96
20.1
(a)   Column A -
     0.25 mm ID x 30 m fused silica capillary with  chemically
     bonded methyl polysiloxane phase  (J&W, DB-1, 1.0 /im  film
     thickness or equivalent).  The linear velocity of  the
     helium carrier is established at  25 cm/sec at  35C.
The column oven is temperature programmed as follows:
[1]  HOLD at 15C for 0 min
[2]  INCREASE to 50C at 2C/min  and  hold  at  50C  for  10 min
[3]  INCREASE to 225C at 10C/min and  hold  at  225C for 15 min
[4]  INCREASE to 260C at 10C/min and  hold  at  260C for 30
     min. or until all expected compounds have eluted.
Injector temperature:  200C
Detector temperature:  290C
                                   551.1-69

-------
   FIGURE 3.
COLUMN
FORTIFIED REAGENT MATER EXTRACT USING PENTANE ON PRIMARY DB-1



1


J

ft

5 11


a n

23
1 JS 21

45 SI

J
t
* u *

n
21
s ; . M
u " w
1 1Z,/ I I
1 "M IS
 1 1 1 "
{ n A 11 .Alii

15 a K * 15 41
MINUTES
u

11
3t"
111 ill n ,
i |  - - - !    - f  - **ir-'l-ri'1 n I I I
55 M 15 71 75 H 15
MINUTES
                                   551.1-70

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                           ADDENDUM TO METHOD 551.1

      ERA Method 551 (a previous version of Method 551.1) used a 40 ml sample
collection vial and a 35 ml sample volume.  The sample volume used in EPA
Method 551.1 was increased to 50 ml and the sample collection vial was
increased to a 60 ml size.  This increase in sample volume permitted the use
of sufficient extracting solvent to fill two autosampler vials with the final
extract.  Using a smaller sample size and less solvent may not provide a
sufficient volume of extract to do this with all types of autosamplers.
Although filling two vials is not required by the method, laboratories may
find this a prudent practice.

      Many laboratories have large supplies of 40 ml sample containers already
in stock.  Laboratories may use these bottles for sample collection, and may
extract a 35 ml sample if the sample volume to reagent ratios (such as solvent
to sample ratios, concentration of buffer, etc.) are maintained as specified
in EPA Method 551.1.  However, laboratories are encouraged to analyze 50 mL
samples as specified in the 551.1 version of the method.
                                 551.1-71

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-------
METHOD 552.1
DETERMINATION OF HALOACETIC ACIDS AND DALAPON IN
DRINKING WATER BY ION-EXCHANGE LIQUID-SOLID
EXTRACTION AND GAS CHRONATOGRAPHY WITH AN
ELECTRON CAPTURE DETECTOR
                         Revision 1.0
                         August 1992



                      Jlmnle M. Hodgeson

         David  Becker  (Technology Applications Inc.)
         ENVIRONMENTAL MONITORING SYSTEMS LABORATORY
              OFFICE OF RESEARCH AND DEVELOPMENT
             U.S. ENVIRONMENTAL PROTECTION AGENCY
                    CINCINNATI, OHIO 45268
                           552.1-1

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                                 METHOD 552.1

                DETERMINATION OF HALOACETIC ACIDS AND DALAPON
           IN DRINKING HATER BY ION-EXCHANGE LIQUID-SOLID EXTRACTION
            AND GAS CHROMAT06RAPHY WITH ELECTRON CAPTURE DETECTION
1.  SCOPE AND APPLICATION
    1.1
    1.2
    1.3
    1.4
    1.5
This 1s a gas chromatographic (GC) method (1) applicable to the
determination of the listed halogenated acetic acids In drinking
water, ground water, raw water and water at any Intermediate
treatment stage.  In addition, the chlorinated herbicide, Dalapon,
is determined using this method.
          Analvte

          Monochloroacetic Acid
          Dichloroacetic Acid
          Trichloroacetic Acid
          Monobromoacetic Acid
          Bromochloroacetic Acid
          Dibromoacetic Acid
          Dalapon
                               Chemical Abstract Services
                                    Registry Number

                                         79-11-8
                                         79-43-6
                                         76-03-9
                                         79-08-3
                                       5589-96-3
                                        631-64-1
                                         75-99-0
This is a liquid-solid extraction method and 1s designed as a
simplified alternative to the liquid-liquid extraction approach of
Method 552 for the haloacetlc acids.  This method also provides a
much superior technique for the determination of the herbicide,
dalapon, compared to the complex herbicide procedure described in
Method 515.1.  The procedure also represents a major step in the
Incorporation of pollution prevention in methods development, in
that the use of large volumes of organic solvents Is eliminated.

This method 1s applicable to the determination of the target
analytes over the concentration ranges typically found In drinking
water (2, 3), subject to the method detection limits (MDL) listed in
Table 2.  The MDLs observed may vary according to the particular
matrix analyzed and the specific Instrumentation employed.  The
haloacetic acids are observed ubiquitously in chlorinated supplies
at concentrations ranging from < 1 to > 50 pg/L.

Reduced analyte recoveries may be observed in high ionic strength
matrices, particularly waters containing elevated sulfate concentra-
tions.  Improved recoveries may be obtained by sample dilution at
the expense of higher MDLs.  This effect Is discussed more exten-
sively in Sect. 4.2.

Tribromoacetic acid has not been Included because of problems
associated with stability and chromatography with this method.
                                    552.1-2

-------
          Mixed bromochloroacetic adds have recently been synthesized.
          Bromochloroacetic add is present in chlorinated supplies and method
          validation data are provided here.  Commercial standards are now
          available for this compound.  The mixed trihalogenated acids may
          also be present.  These are not included because of current problems
          with purity and the chromatography for these compounds.

    1.6   This method is designed for analysts skilled in extract concentra-
          tion techniques, derivatization procedures and the use of GC and
          interpretation of gas chromatograms.

    1.7   When this method is used for the analyses of waters from unfamiliar
          sources, analyte identifications must be confirmed by at least one
          additional qualitative technique, such as gas chromatography/mass
          spectrometry (GO/MS) or by GC using dissimilar columns.

2.  SUMMARY OF METHOD

    2.1   A 100-mL volume of sample is adjusted to pH 5.0 and extracted with a
          preconditioned miniature anion exchange column.  NOTE:  The use of
          liquid-solid extraction disks is certainly permissible as long as
          all the quality control criteria specified in Sect. 9 of this method
          are met.  The analytes are eluted with small allquots of acidic
          methanol and esterified directly in this medium after the addition
          of a small volume of methyl-tert-butyl ether (MTBE) as co-solvent.
          The methyl esters are partitioned into the MTBE phase and identified
          and measured by capillary column gas chromatography using an elec-
          tron capture detector (GC/ECD).

3.  DEFINITIONS

    3.1   INTERNAL STANDARD (IS)  A pure analyte(s) added to a sample,
          extract, or standard solution in known amount(s)  and used to measure
          the relative responses of other method analytes and surrogates that
          are components of the same sample or solution.  The internal stan-
          dard must be an analyte that 1s not a sample component.

    3.2   SURROGATE ANALYTE (SA)  A pure analyte(s), which Is extremely
          unlikely to be found in any sample, and which is  added to a sample
          aliquot in known amount(s) before extraction or other processing and
          Is measured with the same procedures used to measure other sample
          components.  The purpose of the SA is to monitor  method performance
          with each sample.

    3.3   LABORATORY DUPLICATES (LD1 AND LD2) - Two aliquots of the same
          sample taken in the laboratory and analyzed separately with identi-
          cal procedures.  Analyses of LD1 and LD2 indicate the precision
          associated with laboratory procedures, but not with sample collec-
          tion, preservation, or storage procedures.

    3.4   FIELD DUPLICATES (FD1 AND FD2)  Two separate samples collected at
          the same time and place under identical circumstances and treated

                                     552.1-3

-------
      exactly the same throughout field and laboratory procedures.
      Analyses of FD1 and FD2 give a measure of the precision associated
      with sample collection, preservation and storage, as well as with
      laboratory procedures.

3.5   LABORATORY REAGENT BLANK (LRB)  An aliquot of reagent water or
      other blank matrix that are treated exactly as a sample including
      exposure to all glassware, equipment, solvents, reagents, internal
      standards, and surrogates that are used with other samples.  The LRB
      is used to determine if method analytes or other interferences are
      present in the laboratory environment, the reagents, or the appara-
      tus.

3.6   FIELD REAGENT BLANK (FRB) -- An aliquot of reagent water or other
      blank matrix that is placed in a sample container in the laboratory
      and treated as a sample in all respects, including shipment to the
      sampling site, exposure to sampling site conditions, storage,
      preservation and all analytical procedures.  The purpose of the FRB
      Is to determine if method analytes or other interferences are
      present in the field environment.

3.7   LABORATORY FORTIFIED BLANK (LFB)  An aliquot of reagent water or
      other blank matrix to which known quantities of the method analytes
      are added in the laboratory.  The LFB is analyzed exactly like a
      sample, and Us purpose is to determine whether the methodology is
      In control, and whether the laboratory is capable of making accurate
      and precise measurements.

3.8   LABORATORY FORTIFIED SAMPLE MATRIX (LFM)  An aliquot of an envi-
      ronmental sample to which known quantities of the method analytes
      are added in the laboratory.  The LFM is analyzed exactly like a
      sample, and its purpose is to determine whether the sample matrix
      contributes bias to the analytical results.  The background concen-
      trations of the analytes in the sample matrix must be determined in
      a separate aliquot and the measured values in the LFM corrected for
      background concentrations.

3.9   STOCK STANDARD SOLUTION (SSS)  A concentrated solution containing
      one or more method analytes prepared in the laboratory using assayed
      reference materials or purchased from a reputable commercial source.

3.10  PRIMARY DILUTION STANDARD SOLUTION (PDS)  A solution of several
      analytes prepared in the laboratory from stock standard solutions
      and diluted as needed to prepare calibration solutions and other
      needed analyte solutions.

3.11  CALIBRATION STANDARD (CAL)  A solution prepared from the primary
      dilution standard solution and stock standard solutions of the
      internal standards and surrogate analytes.  The CAL solutions are
      used to calibrate the instrument response with respect to analyte
      concentration.
                                552.1-4

-------
    3.12  QUALITY CONTROL SAMPLE (QCS)  A solution of method analytes of
          known concentration which is used to fortify an aliquot of LRB or
          sample matrix.  The QCS is obtained from a source external to the
          laboratory and different from the source of calibration standards.
          It 1s used to check laboratory performance with externally prepared
          test materials.

4.  INTERFERENCES

    4.1   Method interferences may be caused by contaminants in solvents,
          reagents, glassware and other sample processing apparatus that lead
          to discrete artifacts or elevated baselines in gas chromatograms.
          All reagents and apparatus must be routinely demonstrated to be free
          from significant interferences under the conditions of the analysis
          by analyzing laboratory reagent blanks as described in Sect. 9.2.

          4.1.1   For each set of samples analyzed, the reagent blank concen-
                  tration values exceeding 0.1 fig/I should be subtracted from
                  the sample concentrations.  A persistent reagent blank of
                  approximately 1 pg/L was observed for bromochloroacetic acid
                  (BCAA) on the primary DB-1701 column.  The background was
                  clean on the DB-210 confirmation column and the MDL for BCAA
                  in Table 2 was determined using this column.

          4.1.2   Glassware must be scrupulously cleaned (4).  Clean all
                  glassware as soon as possible after use by thoroughly rins-
                  ing with the last solvent used in it.  Follow by washing
                  with hot water and detergent and thorough rinsing with tap
                  water, dilute acid,  and reagept water.  Drain and heat in an
                  oven or muffle furnace at 400 C for 1  hr.   Do not  heat
                  volumetric ware.   Thermally stable materials such as PCBs
                  may not be eliminated by this treatment.  Thorough rinsing
                  with reagent grade acetone may be substituted for the heat-
                  ing.  After drying and cooling, store glassware in a clean
                  environment to prevent any accumulation of dust or other
                  contaminants.  Store inverted or capped with aluminum foil.

          4.1.3   The use of high purity reagents and solvents helps to mini-
                  mize interference problems.   Purification of solvents by
                  distillation in all-glass systems may be required.  The
                  extraction solvent,  MTBE, may need to be redistilled.

    4.2   The major potential interferences in this ion-exchange procedure are
          other naturally occurring ions in water sources, principally sul-
          fate.  This is the only ion  thus far demonstrated as an interfer-
          ence, when present at concentrations possibly occurring in drinking
          water sources.  Sulfate as an effective counter ion displaces the
          haloacids from the column when present at concentrations above 200
          mg/L.  Table 4 illustrates this effect for fortified reagent water
          containing 500 mg/L and 400  mg/L of Na2S04 and NaCl respectively
          (approximately 3.7 millimole (mM) in both cases).   Markedly reduced
          recoveries are observed for  all  analytes in the presence of high
                                    552.1-5

-------
      concentrations of sulfate.  Reduced recoveries may be observed for
      the monohaloacetic acids in very high ionic strength waters, as
      illustrated for the sample with 400 mg/L NaCl.  However, normal
      recoveries were observed from a water sample containing the same
      molar concentration of CaCl2.   The only preventive measure currently
      available for high ionic strength waters is sample dilution.
      Dilution by a factor of 5 will suffice in the vast majority of
      cases, although a factor of 10 may be required in a few extreme
      sites (e.g. western waters with sulfate > 1000 mg/L).  The HOLs will
      still be approximately 1 pg/l for a dilution factor of 5.  However,
      for many chlorinated supplies the monohaloacetic acids may occur at
      concentrations near 1 /ig/L.  In any event, this is the recommended
      method to determine dalapon.

4.3   The acid forms of the analytes are strong organic acids which react
      readily with alkaline substances, and can be lost during sample
      preparation.  Glassware must be acid rinsed with 1:9 hydrochloric
      acid: water prior to use to avoid analyte losses due to adsorption.

4.4   Organic acids and phenols, especially chlorinated compounds, are the
      most direct potential interferences with the determination.  The
      procedure includes a methanol wash step after the acid analytes are
      adsorbed on the column.  This step eliminates the potential for
      interferences from neutral or basic, polar organic compounds present
      in the sample.

4.5   Interfering contamination may occur when a sample containing low
      concentrations of analytes is analyzed immediately following a
      sample containing relatively high concentrations of analytes.
      Routine between-sample rinsing of the sample syringe and associated
      equipment with MTBE can minimize sample cross-contamination.  After
      analysis of a sample containing high concentrations of analytes, one
      or more injections of HT6E should be made to ensure that accurate
    ,  values are obtained for the next sample.

4.6   Matrix interferences may be caused by contaminants that are coex-
      tracted from the sample.  The extent of matrix interferences will
      vary considerably from source to source, depending upon the water
      sampled.  Tentative identifications should be confirmed using the
      confirmation column specified in Table 1 or by the use of gas
      chromatography with mass spectrometric detection.
5.1   The toxicity or carcinogenicity of each reagent used in this method
      has not been precisely defined; however, each chemical compound must
      be treated as a potential health hazard.  From this viewpoint,
      exposure to these chemicals must be minimized.  The laboratory is
      responsible for maintaining a current awareness file of OSHA regula-
      tions regarding the safe handling of the chemicals specified in this
      method.  A reference file of material data handling sheets should
      also be made available to all personnel involved in the chemical

                                552.1-6

-------
          analysis.  Additional references to laboratory safety are available
          and have been Identified (5-7) for the Information of the analyst.

    5.2   The toxiclty of the extraction solvent, MTBE, has not been well
          defined.  Susceptible Individuals may experience adverse affects
          upon skin contact or Inhalation of vapors.  For such Individuals a
          mask may be required.  Protective clothing and gloves should be used
          and MTBE should be used only in a chemical fume hood or glove box.

6.  EQUIPMENT AND SUPPLIES

    6.1   SAMPLE CONTAINERS  Amber glass bottles, approximately 250 ml,
          fitted with Teflon-lined screw caps.  At least 200 ml of sample
          should be collected.

    6.2   GAS CHROMATOGRAPH (GC)  Analytical system complete with GC
          equipped for electron capture detection, spllt/splitless capillary
          Injection, temperature programming, differential  flow control,  and
          with all required accessories including syringes, analytical col-
          umns, gases and strip-chart recorder.   A data system is recommended
          for measuring peak areas.  The gases flowing through the electron
          capture detector should be vented through the laboratory fume hood
          system.

    6.3   PRIMARY GC COLUMN  DB-1701 or equivalent bonded,  fused silica
          column, 30 m x 0.32 mm ID,  0.25 pi film thickness.   Another type of
          column may be used if equivalent or better separation of analytes
          can be demonstrated.

    6.4   CONFIRMATORY GC COLUMN - DB-210 or equivalent bonded,  fused silica
          column, 30 m x 0.32 mm ID,  0.50 pm film thickness.   Another type of
          column may be used if equivalent or better separation of analytes
          can be demonstrated.

    6.5   PASTEUR PIPETS,  GLASS DISPOSABLE

    6.6   pH METER  Wide range with the capability of accurate  pH measure-
          ments at pH 5  0.5.

    6.7   15-mL amber colored bottles with Teflon-lined screw caps.

    6.8   LIQUID-SOLID EXTRACTION VACUUM MANIFOLD - Available from a number
          of suppliers.

    6.9   LSE CARTRIDGES (1 ml) AND FRITS - Also available from  a number of
          suppliers.  The  use of LSE  disks instead of cartridges  is permissi-
          ble as long as all  the quality control  criteria in  Sect. 9 of this
          method are met.

    6.10  75-mL RESERVOIRS PLUS ADAPTERS - Available from J.  T.  Baker,  Cat.
          No.  7120-03 and  Cat. No.  7122-00.
                                    552.'1-7

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    6.11  GRADUATED CONICAL CENTRIFUGE TUBES WITH TEFLON-LINED SCREW CAPS (15
          mL).

    6.12  SCREW CAP CULTURE TUBES  Suggested size 13 x 100 mm.

    6.13  BLOCK HEATER  Capable of holding screw cap culture tubes In Sect.
          6.12.

    6.14  VORTEX MIXER

7.  REAGENTS AND STANDARDS

    7.1   REAGENT WATER  Reagent water is defined as a water in which an
          Interference Is not observed at the MDL of each analyte of Interest.

          7.1.1   A Milllpore Super-Q water system or its equivalent may be
                  used to generate deionized reagent water.  Distilled..water
                  that has been passed through granular charcoal may also be
                  suitable.

          7.1.2   Test reagent water each day it is used by analyzing accord-
                  ing to Sect. 11.
    7.2

    7.3
    7.4
    7.5


    7.6

    7.7

    7.8
METHANOL -- Pesticide quality or equivalent.

METHYL-TERT-BUTYL ETHER -- Nanograde, redistilled in glass if
necessary.  Ethers must be demonstrated to be free of peroxides.
One test kit (EM Quant Test Strips), is available from EM Science,
Gibbstown, NJ.  Procedures for removing peroxides from the ether are
provided with the test strips.  Ethers must be periodically tested
(at least monthly) for peroxide formation during use.  Any reliable
test kit may be used.

SODIUM SULFATE  (ACS) granular, anhydrous.  Heat in a shallow tray
at 400C for a minimum of 4 hr to remove phthalates and other
interfering organic substances.  Alternatively, extract with methy-
lene chloride in a Soxhlet apparatus for 48 hr.

SODIUM HYDROXIDE (NaOH), IN  Dissolve 4 g ACS grade in reagent
water in a 100-mL volumetric flask and dilute to the line.

1,2,3-TRICHLOROPROPANE, 99+%  For use as the internal standard.

2-BROMOPROPIONIC ACID  For use as a surrogate compound.

10X Na?S04/H20  (BY WEIGHT)  SOLUTION  Dissolve lOg NazS04 in 90 g
reagent water.
    7.9   10X H2S04/MeOH SOLUTION   Prepare a solution containing 10 mL H2S04
          in 90 mL methanol.
                                    552.1-8

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    7.10  IN HCl/MeOH  Prepare a solution containing 8.25 ml HC1 (ACS grade)
          with 91.75 ml methanol.

    7.11  AG-1-X8 ANION EXCHANGE RESIN - Rinse resin with three consecutive
          500-mL aliquots of deionized water and store in deionized water.
          Available from Biorad, Richmond, CA.

    7.12  ACETONE  ACS reagent grade or equivalent.

    7.13  AMMONIUM CHLORIDE  ACS reagent grade or equivalent.

    7.14  SODIUM SULFITE  ACS reagent grade or equivalent.

    7.15  STOCK STANDARD SOLUTIONS

          7.15.1  Analytes and Surrogates (Table 1)  Prepare at 1 to 5 mg/mL
                  in MTBE.

          7.15.2  Internal Standard Fortifying Solution  Prepare a solution
                  of 1,2,3-trichloropropane at 1 mg/mL by adding 36 j*L of the
                  neat material (Sect. 7.6) to 50 ml of MTBE.  From this stock
                  standard solution, prepare a primary dilution standard at 10
                  mg/L by the addition of 1 ml to 100 ml MTBE.

          7.15.3  Surrogate Standard Fortifying Solution  Prepare a surro-
                  gate stock standard solution of 2-bromopropionic acid at a
                  concentration of 1 mg/mL by accurately weighing approximate-
                  ly 10 mg of 2-bromopropionic acid, transferring it to a 10-
                  mL volumetric, and diluting to the mark with MTBE.   Prepare
                  a primary dilution standard at a concentration of 2.5 0g/mL
                  by diluting 250 pL of the stock standard to 100 ml with
                  methanol.

8.  SAMPLE COLLECTION. PRESERVATION AND STORAGE

    8.1   Grab samples must be collected in accordance with conventional
          sampling practices (9) using amber glass containers with TFE-lined
          screw-caps and capacities in excess of 100 mL.

          8.1.1   Prior to shipment to the field, to combine residual chlo-
                  rine, add crystalline ammonium chloride (NH4C1)  to  the
                  sample container in an amount to produce a concentration of
                  100 mg/L in the sample.  Alternatively, add 1.0 mL of a
                  10 mg/mL aqueous solution of NH4C1  to the sample bottle for
                  each 100 mL of sample bottle capacity Immediately prior to
                  sample collection.  Granular ammonium chloride may also be
                  added directly to the sample bottle.

          8.1.2   After collecting the sample in the bottle containing the
                  dechlorination reagent, seal  the bottle and agitate for 1
                  min.
                                     552.1-9

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          8.1.3
          8.1.4
Samples must be iced or refrigerated at 4C  and maintained
at these conditions away from light until  extraction.
Holding studies performed to date have suggested  that,  in
samples dechlorinated with NH,C1,  the analytes are  stable
for up to 28 days.  Since stability may be matrix dependent,
the analyst should verify that the prescribed preservation
technique is suitable for the samples under study.

Extract concentrates (Sect. 11.3.6) should be stored at 4C
or less away from light in glass vials with Teflon-lined
caps.  Extracts should be analyzed within 48 hrs  following
preparation.
9.  QUALITY CONTROL

    9.1   Minimum quality control (QC) requirements are initial demonstration
          of laboratory capability, determination of surrogate compound
          recoveries in each sample and blank, monitoring internal standard
          peak area or height in each sample and blank, analysis of laboratory
          reagent blanks, laboratory fortified blanks, laboratory fortified
          sample matrices, and QC samples.  Additional QC practices are
          recommended.

    9.2   LABORATORY REAGENT BLANKS (LRB) - Before processing any samples,
          the analyst must analyze at least one LRB to demonstrate that all
          glassware and reagent interferences are under control.  In addition,
          each time a set of samples is extracted or reagents are changed, a
          LRB must be analyzed.  If within the retention time window (Sect.
          11.4.4) of any analyte, the LRB produces an interference signifi-
          cantly in excess of that anticipated (Sect. 4.1.1), determine the
          source of contamination and eliminate the interference before
          processing samples.

    9.3   INITIAL DEMONSTRATION OF CAPABILITY

          9.3.1   Select a representative fortified concentration for each of
                  the target analytes.  Concentrations near level 2 (Table 4)
                  are recommended.  Prepare 4 to 7 replicate laboratory forti-
                  fied blanks by adding an appropriate aliquot of the primary
                  dilution standard or another certified quality control
                  sample.  Be sure to add the internal standard, 1,2,3-tri-
                  chloropropane, and the surrogate compound, 2 bromopropionic
                  acid, to these samples (See Sect. 11).  Analyze the LFBs
                  according to the method beginning in Sect. 11 and calculate
                  mean recoveries and standard deviation for each analyte.

          9.3.2   Calculate the mean percent recovery, the standard deviation
                  of the recoveries, and the MDL (10).  For each analyte, the
                  mean  recovery value, expressed as a percentage of the true
                  value, must fall in the range of 70-130% and the standard
                  deviation should be less than 30%.  For those compounds that
                  meet these criteria, performance is considered acceptable

                                   552.1-10

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              and sample analysis may begin.  For those compounds that
              fall these criteria, this procedure must be repeated using a
              minimum of four fresh samples until satisfactory performance
              has been demonstrated.  Maintain this data on file to demon-
              strate Initial capabilities.

      9.3.3   The Initial demonstration of capability is used primarily to
              preclude a laboratory from analyzing unknown samples via a
              new, unfamiliar method prior to obtaining some experience
              with It.  As laboratory personnel gain experience with this
              method, the quality of data should improve beyond those re-
              quired here.

      9.3.4   The analyst is permitted to modify GC columns, GC condi-
              tions, detectors, extraction techniques, concentration
              techniques (i.e., evaporation techniques), Internal standard
              or surrogate compounds.  Each time such method modifications
              are made, the analyst must repeat the procedures In Sect.
              9.3.1 and also analyze a laboratory fortified matrix sample.

9.4   ASSESSING SURROGATE RECOVERY
      9.4.1
      9.4.2
              When surrogate recovery from a sample or blank Is < 70% or
              > 130X, check (1) calculations to locate possible errors,
              (2) standard solutions for degradation, (3) contamination,
              and (4) instrument performance.  If those steps do not
              reveal the cause of the problem, reanalyze the extract.

              If the extract reanalysis fails the 70-130% recovery crite-
              rion, the problem must be identified and corrected before
              continuing.  It may be necessary to extract another aliquot
              of sample.
      9.4.3
              If the extract reanalysis meets the surrogate recovery
              criterion, report only data for the reanalyzed extract.
              sample extract continues to fail the recovery criterion,
              report all data for that sample as suspect.
                                                                       If
      9.4.4
              Develop and maintain control charts on surrogate recovery as
              described 1n Sect. 9.6.2.  Charting of surrogate recoveries
              1s an especially valuable activity, since these are present
              In every sample and the analytical results will form a
              significant record of data quality.

9.5   ASSESSING THE INTERNAL STANDARD

      9.5.1   When using the Internal standard calibration  procedure
              prescribed In this method, the analyst is expected to moni-
              tor the IS response (peak area or peak height) of all sam-
              ples during each analysis day.  The IS response for any
              sample chromatogram should not deviate from the dally cali-
              bration standard IS response by more than 30%.
                                552.1-11

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      9.5.2   If > 30% deviation occurs with an individual extract, opti-
              mize instrument performance and inject a second aliquot of
              that extract.

              9.5.2.1   If the reinjected aliquot produces an acceptable
                        internal standard response, report results for
                        that aliquot.

              9.5.2.2   If a deviation of greater than 30% is obtained for
                        the reinjected extract, analysis of the samples
                        should be repeated beginning with Sect. 11, pro-
                        vided the sample is still available.  Otherwise,
                        report results obtained from the reinjected ex-
                        tract, but annotate as suspect.

      9.5.3   If consecutive samples fail the IS response acceptance
              criteria, immediately analyze a medium calibration standard.

              9.5.3.1   If the calibration standard provides a response
                        factor (RF) within 20% of the predicted value,
                        then follow procedures itemized in Sect. 9.5.2 for
                        each sample failing the IS response criterion.

              9.5.3.2   If the check standard provides a response factor
                        which deviates more than 20% of the predicted
                        value, then the analyst must recalibrate (Sect.
                        10).

9.6   LABORATORY FORTIFIED BLANK

      9.6.1   The laboratory must analyze at least one laboratory forti-
              fied blank (LFB) sample with every 20 samples or one per
              sample set (all samples extracted within a 24-hr period),
              whichever is greater.  Fortified concentrations near level 2
              (Table 4) are recommended.  Calculate percent recovery (R).
              If the recovery of any analyte falls outside the control
              limits (see Sect. 9.6.2), that analyte is judged out of
              control, and the source of the problem should be identified
              and resolved before continuing analyses.

      9.6.2   Prepare control charts based on mean upper and lower control
              limits, R  3 SR.  The initial demonstration of capability
              (Sect. 9.3) establishes the initial limits.  After each 4-6
              new recovery measurements, recalculate R and S. using all
              the data, and construct new control limits.  When the total
              number of data points reach 20, update the control limits by
              calculating R and SR using only the most recent 20 data
              points.  At least quarterly, replicates of LFBs should be
              analyzed to determine the precision of the laboratory mea-
              surements.  Add these results to the ongoing control charts
              to document data quality.
                              552.1-12

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9.7   LABORATORY FORTIFIED SAMPLE MATRIX

      9.7.1   Chlorinated water supplies will usually contain significant
              background concentrations of several method analytes, espe-
              cially dichloroacetic acid (DCAA) and trichloroacetic acid
              (TCAA).  The concentrations of these acids may be equal to
              or greater than the fortified concentrations.  Table 6
              illustrates the relatively poor accuracy and precision which
              may be anticipated when a large background must be subtract-
              ed.  The water supply used in the development of this method
              contained only moderate concentrations of DCAA and TCAA.
              For many supplies, the concentrations may be so high that
              fortification may lead to a final extract with instrumental
              responses exceeding the linear range of the electron capture
              detector.  If this occurs, the extract must be diluted.  In
              spite of these problems, sample sources should be fortified
              and analyzed as described below.   Poor accuracies and high
              precisions across all analytes likely indicate the presence
              of interfering ions, especially sulfate, and the requirement
              for sample dilution.

      9.7.2   The laboratory must add known concentrations of analytes to
              a minimum of 10% of samples or one sample per sample set,
              whichever Is greater.  The concentrations should be equal  to
              or greater than the background concentrations in the sample
              selected for fortification.  Ideally, the concentration
              should be the same as that used for the laboratory fortified
              blank (Sect.  9.6).  Over time,  samples from all  routine
              sample sources should be fortified.

      9.7.3   Calculate the mean percent recovery, R,  of the concentration
              for each analyte,  after correcting the total  mean measured
              concentration, A,  from the fortified sample for the back-
              ground concentration, B, measured in the unfortified sample,
              i.e.:

                        R - 100  (A - B) / C,

              where C Is the fortifying concentration.  Compare these
              values to control  limits appropriate for reagent water data
              collected in  the same fashion (Sect. 9.6).

      9.7.4   If the analysis of the unfortified sample reveals the ab-
              sence of measurable background  concentrations,  and the added
              concentrations are those specified in Sect.  9.6,  then the
              appropriate control  limits would  be  the  acceptance limits  in
              Sect.  9.6.

      9.7.5   If the sample contains measurable background  concentrations
              of analytes,  calculate mean recovery of  the  fortified con-
              centration, R,  for each such  analyte after correcting for
              the background concentration  (Sect.  9.7.3).   Compare these

                               552.1-13.

-------
              values to reagent water recovery data, R*, at comparable
              fortified concentrations from Tables 2, 4, and 5.  Results
              are considered comparable if the measured recoveries fall
              within the range,

                        R  3SC,

              where Sc is the estimated percent relative standard devia-
              tion in the measurement of the fortified concentration.  By
              contrast to the measurement of recoveries in reagent water
              (Sect. 9.6.2) or matrix samples without background (Sect.
              9.7.3), the relative standard deviation, Sc,  must be ex-
              pressed as the statistical sum of variation from two
              sources, the measurement of the total concentration as well
              as the measurement of background concentration.  In this
              case, variances, defined as S ,  are additive  and Sc can be
              expressed as,
or
(Sa2
                                           Sb2)1/2,
              where S  and Sb are the  percent  relative standard deviations
              of the total measured concentration and the background
              concentration respectively.  The value of S  may be estimat-
              ed from the mean measurement of A above or from data at
              comparable concentrations from Tables 2, 4, and 5.  Like-
              wise, Sb can be measured from repetitive measurements of the
              background concentration or estimated from comparable con-
              centration data from Tables 2, 4, and 5.

      9.7.6   If the recovery of any such analyte falls outside the desig-
              nated range, and the laboratory performance for that analyte
              is shown to be in control (Sect. 9.6), the recovery problem
              encountered with the fortified sample is judged to be matrix
              related, not system related.  The result for that analyte in
              the unfortified sample is labeled suspect/matrix to inform
              the data user that the results are suspect due to matrix
              effects.

9.8   QUALITY CONTROL SAMPLE (QCS) -- At least quarterly, analyze a QCS
      from an external source.  If measured analyte concentrations are not
      of acceptable accuracy, check the entire analytical procedure to
      locate and correct the problem source.

9.9   The laboratory may adapt additional QC practices for use with this
      method.  The specific practices that are most productive depend upon
      the needs of the laboratory and the nature of the samples.  For
      example, field or laboratory duplicates may be analyzed to assess
      the precision of the environmental measurements or field reagent
                                552.1-1

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          blanks may be used to assess contamination of samples under site
          conditions, transportation and storage.

10. CALIBRATION AND STANDARDIZATION

    10.1  Establish GC operating parameters equivalent to the suggested
          specifications in Table 1.  The GC system must be calibrated using
          the internal standard (IS) technique.  Other columns or conditions
          may be used if equivalent or better performance can be demonstrated.

    10.2  INTERNAL STANDARD CALIBRATION PROCEDURE -- This approach requires
          the analyst to select one or more internal standards which are
          compatible In analytical behavior with the method analytes.  For the
          single laboratory precision and accuracy data reported in Tables
          2-9, one internal standard, 1,2,3-trichloropropane, was used as a
          concentration of 0.4 ng/ml in the final 5.0-mL concentrate.

          10.2.1  Prepare separate stock standard solutions for each analyte
                  of interest at a concentration of 1-5 mg/mL in MTBE.  Method
                  analytes may be obtained as neat materials or ampulized
                  solutions (> 99% purity) from a number of commercial suppli-
                  ers.

          10.2.2  Prepare primary dilution standard solutions by combining and
                  diluting stock standard solutions with methanol.  As a
                  guideline to the analyst, the primary dilution standard
                  solution used in the validation of this method is described
                  here.  Stock standard solutions were prepared in the 1-2
                  mg/mL range for all analytes and the surrogate.  Aliquots of
                  each stock standard solution (approximately 50-250 /zL) were
                  added to 100-mL methanol to yield a primary dilution stan-
                  dard containing the following approximate concentrations of
                  analytes:
                  Honochloroacetic acid
                  Monobromoacetic add
                  Dalapon
                  Dichloroacetic acid
                  2-Bromopropionic acid
                  Trichloroacetic acid
                  Bromochloroacetic acid
                  Dibromoacetic acid
Concentration, ua/ml

         3
         2
         2
         3
         1
         1
         2
         1
                  The primary dilution standards are used to prepare calibra-
                  tion standards, which comprise at least three concentration
                  levels (optimally five) of each analyte with the lowest
                  standard being at or near the MOL of each analyte.  The
                  concentrations of the other standards should define a range
                  containing the expected sample concentrations or the working
                  range of the detector.
                                   552.1-15

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        10.2.2.1  Calibration standards  Calibration is performed
                  by extracting procedural standards,  i.e.;  forti-
                  fied reagent water.   A five-point calibration
                  curve may be prepared by fortifying  a 100- ml re-
                  agent water samples  at pH 5 with 20, 50, 100, 250,
                  and 500 til of the primary dilution standard pre-
                  pared above.  Alternatively, three levels  of cali-
                  bration solutions may be prepared.  Analyze each
                  calibration standard in triplicate according to
                  the procedure outlined in Sect.  11.   In addition,
                  a reagent water blank must be analyzed in  tripli-
                  cate.

10.2.3  Include the surrogate analyte, 2-bromopropionic acid,
        within the calibration standards prepared  in Sect. 10.2.2.

10.2.4  Inject 2 0L of each standard and calculate the relative
        response for each analyte (RRa)  using the  equation:

                       *^**  !

        where     A, is the peak area  of the analyte.
                  A{8 the peak area of the internal  standard.

        Generate a calibration curve of RR. versus analyte concen-
        tration of the standards expressed in equivalent pg/L in the
        original aqueous sample.  The working calibration curve must
        be verified daily by measurement of one or more calibration
        standards.  If the response for any analyte falls outside
        the predicted response by more than 15%, the calibration
        check must be repeated using a freshly prepared calibration
        standard.  Should the retest fail, a new calibration curve
        must be generated.

        A data system may be used to collect the chromatographic
        data, calculate response factors, and calculate linear or
        second order calibration curves.
          10.2.5
          10.2.6
11. PROCEDURE

    11.1  PREPARATION AND CONDITIONING OF EXTRACTION COLUMNS

          11.1.1  Preparation  Place 1 mL liquid-solid extraction cartridges
                  (Sect. 6.9) onto the vacuum manifold.  Place frits into the
                  tubes and push down to place them flat on the bottom.  Add
                  the AG-1-X8 resin solution dropwise to the tubes with a
                  Pasteur pipet until there is a solid layer of resin 10 mm in
                  height.  Add reagent water and apply vacuum to settle out
                  the suspended resin particles.  Do not allow the resin to go
                  dry.  At this point extraction of samples can begin or the
                  columns can be stored for later use by maintaining the resin
                  under water and sealing the top with aluminum foil.

                                    552.1-16

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      11.1.2  Conditioning --  Attach adapters and 75-mL reservoirs to the
              liquid-solid extraction cartridges.  To condition the col-
              umns, add to the reservoirs and pass the following series of
              solvents in 10-mL aliquots through the resin under vacuum:
              methanol, reagent water, 1 M HCl/MeOH, reagent water, 1 H
              NaOH, and reagent water.  The conditioning solvents should
              pass through the resin at the rate of = 2 mL/min. without
              allowing the resin bed to dry and the sample should be added
              (Sect. 11.2.3) immediately after the last reagent water
              aliquot.

11.2  SAMPLE EXTRACTION AND ELUTION

      11.2.1  Remove the samples from storage (Sect. 8.1.3) and allow them
              to equilibrate to room temperature.

      11.2.2  Adjust the pH of a 100-mL sample to 5  0.5 using 1:2 H2S04
              water and check the pH with a pH meter or narrow range pH
              paper.

      11.2.3  Add 250 pi of the surrogate primary dilution standard (Sect.
              7.15.3) to each sample

      11.2.4  Transfer the 100-mL sample to the reservoir and apply a
              vacuum  to extract the sample at the rate of * 2 mL/min.

      11.2.5  Once the sample has completely passed through the column add
              10 mL MeOH to dry the resin.

      11.2.6  Remove the reservoirs and adapters, disassemble the vacuum
              manifold and position screw cap culture tubes (Sect.  6.12)
              under the columns to be eluted.  Reassemble the vacuum
              manifold, add 4 mL 10% H2S04/methanol to the column and
              elute at the rate of approximately 1.5 mL/min.   Turn  off the
              vacuum and remove the culture tubes containing the eluants.

11.3  SOLVENT PARTITION

      11.3.1  Add 2.5 mL MTBE to each eluant and agitate in the vortex
              mixer at a low setting for about 5 sec.

      11.3.2  Place the capped culture tubes in the heating block (Sect.
              6.13) at 50C and maintain for 1 hr.   At this stage,  quanti-
              tative methyl ation of all  method analytes is attained.

      11.3.3  Remove the culture tubes from the heating block and add to
              each tube 10 mL of 10% by weight of sodium sulfate in re-
              agent water (Sect.  7.8).   Agitate each solution for 5-10 sec
              In the vortex mixer at a high setting.

      11.3.4  Allow the phases to separate  for approximately 5 min. Trans-
              fer the upper MTBE layer to a 15-mL graduated conical cen-

                                 552.1-17

-------
          11.3.5
trifuge tube (Sect. 6.11) with a pasteur pipet.  Repeat the
extraction two more times with approximately 1 ml HTBE each
time.  Combine the MTBE sample extracts In the graduated
centrifuge tube.

Add 200 fil of the Internal standard fortifying solution
(Sect. 7.15.2) to each extract and add MTBE to each to a
final volume of 5 ml.
          11.3.6  Transfer a portion of each extract to a vial and analyze
                  using GC-ECD.  A duplicate vial should be filled from excess
                  extract.  Analyze the samples as soon as possible.  The
                  sample extract may be stored up to 48 hr If kept at 4C or
                  less away from light In glass vials with Teflon-lined caps.

    11.4  GAS CHROMATOGRAPHY
          11.4.1
Table 1 summarizes recommended GC operating conditions and
retention times observed using this method.  Figure 1 illus-
trates the performance of the recommended column with the
method analytes.  Other GC columns, chromatographic condi-
tions, or detectors may be used if the requirements of Sect.
9.3 are met.
          11.4.2
          11.4.3
          11.4.4
Calibrate the system daily as described in Sect. 10.
standards and extracts must be in MTBE.
                  The
Inject 2 0L of the sample extract.
peak size in area units.
Record the resulting
          11.4.5
The width of the retention time window used to make Identi-
fications should be based upon measurements of actual reten-
tion time variations of standards over the course of a day.
Three times the standard deviation of a retention time can
be used to calculate a suggested window size for a compound.
However, the experience of the analyst should weigh heavily
in the interpretation of chromatograms.

If the response for the peak exceeds the working range of
the system, dilute the extract and reanalyze.
12. DATA ANALYSIS AND CALCULATIONS

    12.1  Calculate analyte concentrations in the sample and reagent blanks
          from the response for the analyte relative to the internal standard
          (RR.)  using the equation in Sect.  10.2.4.

    12.2  For samples processed as part of a set where recoveries falls
          outside of the control limits established in Sect. 9, results for
          the affected analytes must be labeled as suspect.
                                     552;1-18

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13.
        MEPPD
   13.1 In a single laboratory  (EMSL-Cincinnati) , recovery and precision data
        were obtained at three corcentrations in reagent water  (Tables 2, 4, and
        5) .  In addition,  recovery and precision data were obtained at a medium
             nitration  for  high  ionic  strength  reagent water  (Table  3) ,
14.
15.
16.
        dechlorinated tap water, high humectant ground water, and an ozonated
        surface water (Tables 6-9).  The MDL (10}  data are given in Table 2.
                  HREVHfi'XOf
   14.1 This method utilizes the new LSE technology which requires the use of
        very small quantities of organic solvents.  This feature eliminates the
        hazards involved with the use of large volumes of potentially harmful
        organic solvents  needed for  conventional liquid-liquid  extractions.
        This method also uses acidic methanol as the  derivatizing reagent in
        place of the highly toxic diazomethane. These features make this method
        much safer for use  by the analyst  in the laboratory and much  less
        harmful to the environment.

   14.2 For information about pollution prevention that may be applicable to
        laboratory operations, consult  "Less is Better:  laboratory  Chemical
        Management for Waste Reduction11 available from the American  Chemical
        Society's Department of Government. Relations arse! Science  Policy,  1155
        16th Street N.W.,  Washington,  D.C.  20036.
   15.1 It is the laboratory's responsibility to comply with all federal, state
        and local regulations governing the waste management,  particularly the
        hazardous waste identification rules and land disposal restrictions.  It
        is also the laboratory's responsibility to protect the air,  water, and
        land by  minimizing and controlling  all  releases from fume hoods and
        bench operations.  Compliance is also required with any sewage discharge
        permits and regulations.  For further information on waste management,
        consult  "The Waste Management Manual for Laboratory  Personnel," !"
        available from the American Chemical Society at the address  in Section
        14.2.
    1.
        Hbdgeson, J. W. , Collins, J. D. , and Becker, D. A. , "Advanced Techniques
        for the Measurement of Acidic Herbicides and Disinfection Byproducts in
        Aqueous  Samples,"  Proceedings of  the 14th Annual  EPA Conference  on
        Analysis of Pollutants in the Environment, Norfolk, VA. , May 8-9, 1991.
        Office  of  Water  Publication No.  821-R-92-001,  U.S.  Fjwironmental
        Protection Agency, Washington, DC,  pp 165-194.
                                   552.1-19

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2.  Uden, P.C. and Miller, J.W., J. Am. Water Works Assoc. 75,  1983,  pp.
    524-527.

3.  Fair. P.S., Barth, R.C., Flesch, J. J. and Brass, H.  "Measurement of
    Disinfection By-products in Chlorinated Drinking Water,"  Proceedings
    Water Quality Technology Conference (WQTC-15), Baltimore, Maryland,
    November 15-20, 1987, American Water Works Association, Denver, CO,
    pp. 339-353.

4.  ASTM Annual Book of Standards, Part 31, D3694, "Standard Practice for
    Preparation of Sample Containers and for Preservation," American
    Society for Testing and Materials, Philadelphia, PA, p. 679, 1980.

5.  "Carcinogens-Working with Carcinogens," Publication No. 77-206,
    Department of Health, Education, and Welfare, Public Health Service,
    Center for Disease Control, National Institute of Occupational Safety
    and Health, Atlanta, GA, August 1977.

6.  "OSHA Safety and Health Standards, General Industry,"  (29CFR1910),
    OSHA 2206, Occupational Safety and Health Administration, Washington,
    D.C.  Revised January 1976.

7.  "Safety In Academic Chemistrv Laboratories," 3rd Edition, American
    rhami^>i.. Society Publication, Committee on Chemical Safety, Washing
    ton, D.C., 1979.

8.  Hodgeson, J.W. and Cohen, A.L. and Collins, J.D., "Analytical  Methods
    for Measuring Organic Chlorination By-products," Proceedings Water
    Quality Technology Conference  (WQTC-16), St.  Louis, MO,  Nov. 13-17,
    1988, American Water Works  Association, Denver,  CO, pp.  981-1001.

9.  ASTM Annual Book of Standards,  Part 31, D3370,  "Standard Practice  for
    Sampling Water," American Society  for  Testing  and Materials, Philadel-
    phia, PA, p. 76,  1980.

10. Glaser, J. A., Foerst,  D. L., McKee,  G. D., Quave,  S.  A. and Budde,  W.
    L., Environ. Sci. Techno!.  15,  1981,  pp.  1426-1435.
                                552.1-20

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17. TABLES, DIAGRAMS, FLOWCHARTS, AND VALIDATION DATA
            TABLE 1.   RETENTION DATA AND CHRONATOGRAPHIC CONDITIONS
Analyte
Monochloroacetic Add (MCAA)
Monobromoacetic Add (MBAA)
Dal apon
Dichloroacetic Add (DCAA)
2-Bromoprop ionic add (b)
Trichloroacetlc Acid (TCAA)
1,2,3-Trlchloropropane (a)
Bromochloroacetic Acid (BCAA)
Dibromoacetic Acid (DBAA)
Retention Time.
Column A
5.16
7.77
8.15
8.37
8.80
11.43
12.62
12.92
15.50
m1n.
Column B
9.44
11.97
11.97
11.61
12.60
13.34
12.91
14.20
16.03
  Column A:  DB-1701, 30 m x 0.32 mm i.d., 0.25 |im film thickness,
             Injector Temp. - 200C, Detector Temp.   260C,  Helium
             Linear Velocity - 27 cm/sec, Splitless injection with 30 s
             delay

  Program:   Hold at 50C for 10 min,  to 200C  at  10C/min. and hold 5
             min., to 230'C at 10C/min. and hold 5 min.

  Column B:  DB-210, 30 m x 0.32 mm i.d., 0.50 pi film thickness,
             Injector Temp. - 200C, Detector Temp.  * 260C,  Linear
             Helium Flow  25 cm/sec, splitless injection with 30 s
             delay.

  Program:   Hold at 50C for 10 min.,  to 200< at 10C/min and hold 5
             min., to 230 at 10C/min. and hold 5 min.

  (a)  Internal Standard

  (b)  Surrogate Compound

                                 552.1-21

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                     TABLE 2.  ANALYTE RECOVERY AND PRECISION DATA
                               AND METHOD DETECTION LIMITS"
                               LEVEL 1 IN REAGENT WATER
Fortified
Cone.
Analyte pg/L
Monochloroacetlc Add
Honobromoacetic Add
Dlchloroacetic Add
2-Bromoprop1on1c Ac1db
Trlchloroacetlc Add
Bromochloroacetlc acid
D1bromoacet1c Add
Dalapon
1.5
1.0
1.5
0.05
0.50
1.0
0.50
1.0
Mean
Meas.
Cone.
M9/L
1.47
0.73
1.65
0.47
0.30
0.75
0.29
0.81
Std.
Dev.
W/L
0.07
0.08
0.14
0.03
0.02
0.03
0.03
0.10
Rel.
Std.
Dev., %
4.6
7.9
7,7
5.6
4.0
3.4
6.4
12
Mean
Recovery
%
98
73
110
94
60
75
58
81
Method
Detection
Limit
M9/L
0.21
0.24
0.45
0.08
0.07
0.10
0.09
0.32
"Produced  by  analysis  of seven  allquots  of fortified  reagent water  (Reference  10).

b Surrogate Compound
                                         552'. 1-22

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                     TABLE 3.  RECOVERY AND PRECISION DATA IN HIGH
                                IONIC STRENGTH MATERS
                                  MEAN  RECOVERY    RSD8
Fortified
Cone.
Analyte pg/l
Monochloroacetic Acid
Monobromoacetic Acid
Dichloroacetic Acid
2-Bromoprop ionic Acid
Trichloroacetic Acid
Bromochloroacetic Acid
Dibromoacetic Acid
Dal apon
7.
5.
7.
2.
2.
5.
2.
5.
5
0
5
5
5
0
5
0
Reagent Reagent Water +
Water (RW) 500 mg/L Na2S04b
109 
83 
107 
108 
101 i
101 
93 
93 
1.5
18
3.6
1.8
0.4
2.6
1.9
1.9

5.0  10
59  2.4
32  0.3
8  3.0
85  0.7
40  22
57  5.3
Reagent Water +
400 mg/L NaClfa
46
50
114
137
64
107
89
99








10
13
0
2
11
3
5
1


.1
.1

.5
.0
.7
a  Based on the analysis of three replicate samples.

b  Molar concentration of added salt 1s 3.7 tnM in both cases.
                                        552,1-23

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                    TABLE 4.   ANALYTE RECOVERY AND PRECISION DATA*
                               LEVEL 2  IN REAGENT WATER
Analyte
Monochloroacetlc Add
Monobromoacetic Add
Dichloroacetlc Add
2-Bromopropionic Ac1db
Trlchloroacetlc Add
Bromochloro acetic Add
Dibromoacetlc Add
Dal apon
Fortified
Cone.
M9/L
7.5
5.0
7.5
2.5
2.5
5.0
2.5
5.0
Mean
Heas.
Cone.
M9/L
7.73
3.95
8.06
2.57
2.32
5.22
2.41
4.03
Std.
Dev.
H9/L
0.18
0.65
0.16
0.06
0.14
0.12
0.09
0.36
Rel.
Std.
Dev., X
2.3
16
2.0
2.4
5.8
2.2
3.4
7.5
Mean
Recovery
%
103
79
108
103
93
104
96
97
* Produced by the analysis of seven aliquots of fortified reagent water.
b Surrogate Compound
                                       552.1-24

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                    TABLE 5.   ANALYTE RECOVERY AND PRECISION DATA*
                               LEVEL 3  IN REAGENT WATER
Analyte
Monochloroacetlc Add
Monobromoacetlc Add
Dlchloroacetic Add
2-Bromopropionic Add
Trichloroacetlc Add
Bromochloroacetlc Add
D1bromoacet1c Add
Dal apon
Fortified
Cone.
W/L
15.0
10.0
15.0
5.0
5.0
10.0
5.0
10.0
Mean
Meas.
Cone.
W/L
14.5
7.82
15.1
4.98
4.89
10.3
4.85
9.02
Std.
Dev.
M/L
0.15
0.68
6.09
0.08
0.07
0.25
0.04
0.16
Rel.
Std.
Dev., %
1.0
8.4
0.6
1.5
1.4
2.4
0.7
1.8
Mean
Recovery
%
99
78
101
100
98
103
97
90
' Produced by the analysis of seven aliquots of fortified reagent water.
                                         552.1-25

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                    TABLE 6.  ANALYTE RECOVERY AND PRECISION DATA1
                                DECHLORINATED TAP WATER
Fortified
Cone.
Analyte ftg/l
Monochloroacetlc Acid
Honobromoacetic Acid
Dlchloroacetic Acid
2-Bromoproplonic Ac1dc
THchloroacetic Acid
Brofflochloroacetic Acid
Dibromoacetic Acid
Dal apon
7.5
5.0
7.5
7.5
2.5
5.0
2.5
5.0
Meanb
Meas.
Cone.
MI/L
5.70
4.57
5.62
2.22
1.48
5.70
2.42
4.69
Std.
Dev.
W/L
0.63
0.45
0.76
0.16
0.42
0.92
0.13
0.21
Rel.
Std.
Dev., X
11
9.8
14
7.2
28
16
5.4
4.5
Mean
Recovery
%
76
91
75
89
59
114
97
94
a Produced by the analysis of seven aliquots  of fortified dechlorinated tap water.
b Significant background concentrations (> 5-15 M9/L)  have  been  subtracted from these
values for dichloroacetic add, trichloroacetic acid,  bromochloroacetic  acid,  and
dibromoacetic acid.
c Surrogate Compound
                                          552.1-26

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                    TABLE 7.   ANALYTE RECOVERY AND PRECISION DATA*
                            HIGH HUMIC CONTENT GROUND WATER
Analyte
Monochl oroacet i c Ac 1 d
Monobromoacetlc Acid
Dichl oroacet 1c Add
2-Bromoprop1on1c Ac1db
Trichl oroacet ic Acid
Bromochl oroacet 1c Acid
Dlbronoacetlc Add
Dalapon
Fortified
Cone.
W/L
7.5
5.0
7.5
2.5
2.5
5.0
2.5
5.0
Mean
Meas.
Cone.
M9/L
3.55
2.21
7.60
1.83
2.37
5.53
2.58
4.92
Std.
Dev.
A9/L
0.32
0.21
0.08
0.09
0.12
0.16
0.13
Q.29
Rel.
Std.
Dev., %
8.9
11
1.1
4.9
5.1
2.9
5.0
6.0
Mean
Recovery
X
47
44
101
73
95
111
103
90
* Produced by the analysis of seven aliquots of fortified high humic content ground
  water.

b Surrogate Compound
                                       552.1-27

-------
                    TABLE  8.  ANALYTE RECOVERY AND PRECISION DATA8
                      HIGH HUMIC CONTENT GROUND WATER DILUTED 1:5
Analyte
Monochloroacetic Acid
Monobromoacetlc Add
Dichloroacetic Acid
2-Bromopropionic Acidb
Trichloroacetic Acid
Bromochloroacetic Acid
Dibromoacetic Acid
Dal apon
Fortified
Cone.
M/L
1.5
1.0
1.5
0.5
0.5
1.0
0.5
1.0
Mean
Meas.
Cone.
0g/L
1.50
0.97
1.89
0.49
0.28
0.43
0.30
0.88
Std.
Dev.
W/L
0.17
0.06
0.16
0.01
0.03
0.07
0.02
0.12
Rel.
Std.
Dev., %
11
6.2
8.5
2.0
11
16
6.7
14
Mean
Recovery
%
100
97
126
98
56
43
60
88
* Produced by the analysis of seven aliquots of fortified high hunric content ground
  water diluted 1:5.

b Surrogate Compound
                                       552.1-28

-------
                    TABLE 9.  ANALYTE RECOVERY AND PRECISION DATA*
                                 OZONATED RIVER WATER
Analyte
Honochloroacetic Acid
Monobrorao acetic Acid
Dichlorpacetic Acid
2-Bromopropionic Acidb
Trichloroacetic Acid
Bromochloroacetic Acid
Dibromoacetic Acid
Oalapon
Fortified
Cone.
W/L
7.5
5.0
7.5
2.5
2.5
5.0
2.5
5.0
Mean
Meas.
Cone.
M9/L
6.22
4.28
7.09
2.31
2.65
5.20
2.36
5.08
Std.
Dev.
ng/i
0.91
0.34
0.22
0.09
0.13
0.18
0.09
0.17
Rel.
Std.
Dev., X
15
7.9
3.1
3.7
4.9
3.5
3.8
3.4
Mean
Recovery
%
83
86
94
92
106
104
94
102-
" Produced by the analysis of seven aliquots of fortified ozonated river water.
b Surrogate Compound
                                        552.1-29

-------
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                            ppt 3U9^*o*o[qDOfflOjg
                            ppl 91483C
-------
METHOD.552.2
DETERMINATION OF HALOACETIC ACIDS AND DALAPON IN DRINKING WATER
BY LIQUID-LIQUID EXTRACTION, DERIVATIZATION AND GAS
CHROMATOGRAPHY WITH ELECTRON CAPTURE DETECTION.
                                 Revision 1.0
J.W. Hodgeson (USEPA), J. Collins and  R.E. Earth (Technology Applications
Inc.) - Method 552.0, (1990)

J.W. Hodgeson (USEPA), D. Becker (Technology Applications Inc.) - Method
552.1, (1992)

D.J. Munch, J.W. Munch (USEPA) and A.M. Pawlecki (International Consultants,
Inc.), Method 552.2, Rev. 1.0, (1995)
                     NATIONAL EXPOSURE RESEARCH LABORATORY
                      OFFICE OF RESEARCH AND DEVELOPMENT
                     U.S. ENVIRONMENTAL PROTECTION AGENCY
                            CINCINNATI, OHIO 45268
                                    552.2-1

-------
          METHOD 552.2  DETERMINATION  OF HALOACETIC ACIDS AND DALAPON
         IN DRINKING MATER BY LIQUID-LIQUID EXTRACTION, DERIVATIZATION
            AND GAS CHROMATOGRAPHY WITH ELECTRON CAPTURE DETECTION
1.   SCOPE AND APPLICATION
     1.1
     1.2
     1.3
     1.4
This is a gas chromatographic (GC) method (1-8) applicable to the
determination of the listed halogenated acetic acids in drinking
water, ground water, raw source water and water at any intermediate
treatment stage.  In addition, the chlorinated herbicide, Dalapon,
may be determined using this method.
               Analvte

          Bromochloroacetic Acid (BCAA)
          Bromodichloroacetic Acid (BOCAA)
          Chlorodibromoacetic Acid (CDBAA)
          Dalapon
          Dibromoacetic Acid (DBAA)
          Dichloroacetic Acid (DCAA)
          Monobromoacetic Acid (MBAA)
          Monochl.oroacetic Acid (MCAA)
          Tribromoacetic Acid (TBAA)
          Trichloroacetic Acid (TCAA)
                                  Chemical Abstract Services
                                         Registry Number

                                             5589-96-3
                                            7113-314-7
                                             5278-95-5
                                               75-99-0
                                              631-64-1
                                               79-43-6
                                               79-08-3
                                               79-11-8
                                               75-96-7
                                               76-03-9
This method is applicable to the determination of the target
analytes over the concentration ranges typically found in drinking
water (1,2,4).  Experimentally determined method detection limits
(MDLs) for the above listed analytes are provided in Table 2.
Actual MDLs may vary according to the particular matrix analyzed and
the specific instrumentation employed.  The haloacetic acids are
observed ubiquitously in chlorinated drinking water supplies at
concentrations ranging from <1 to >50 /*g/L.

This method is designed for analysts skilled in liquid-liquid
extractions, derivatization procedures and the use of GC and
interpretation of gas chromatograms.  Each analyst must demonstrate
the ability to generate acceptable results with this method using
the procedure described in Section 9.3.

When this method is used for the analyses of waters from unfamiliar
sources, it is strongly recommended that analyte identifications be
confirmed by GC using a dissimilar column or by GC/MS if
concentrations are sufficient.
2.   SUMMARY OF METHOD

     2.1  A 40-mL volume of sample is adjusted to pH <0.5 and extracted with
          4-mL of methyl-tert-butyl-ether (MTBE).  The haloacetic acids that
          have been partitioned into the organic phase are then converted to
                                    552.2-2

-------
          their methyl esters by the addition of acidic methanol followed by
          slight heating.  The acidic extract 1s neutralized by a back-
          extraction with a saturated solution of sodium bicarbonate and the
          target analytes are identified and measured by capillary column gas
          chromatography using an electron capture detector (GC/ECD).
          Analytes are quantitated using procedural standard calibration.

3.   DEFINITIONS

     3.1  INTERNAL STANDARD (IS)  A pure analyte(s) added to a sample,
          extract, or standard solution in known amount(s) and used to measure
          the relative responses of other method analytes and surrogates that
          are components of the same sample or solution.  The internal
          standard must be an analyte that is not a sample component.

     3.2  SURROGATE ANALYTE (SA)  A pure analyte(s), which is extremely
          unlikely to be found in any sample, and which is added to a sample
          aliquot in known amount(s) before extraction or other processing and
          is measured with the same procedures used to measure other sample
          components.  The purpose of the SA is to monitor method performance
          with each sample.

     3.3  LABORATORY DUPLICATES (LD1 AND LD2)  Two aliquots of the same
          sample designated as such in the laboratory.  Each aliquot is
          extracted, derivatized and analyzed separately with identical
          procedures.  Analyses of LD1 and LD2 indicate the precision
          associated with laboratory procedures, but not with sample
          collection, preservation, or storage procedures.

     3.4  FIELD DUPLICATES (FD1 AND FD2) -- Two separate samples collected at
          the same time and place under identical circumstances and treated
          exactly the same throughout field and laboratory procedures.
          Analyses of FD1 and FD2 give a measure of the precision associated
          with sample collection, preservation and storage, as well as with
          laboratory procedures.

     3.5  LABORATORY REAGENT BLANK (LRB)  An aliquot of reagent water or
          other blank matrix that are treated exactly as a sample including
          exposure to all glassware, equipment, solvents,' reagents, internal
          standards, and surrogates that are used with other samples.  The LRB
          is used to determine if method analytes or other interferences are
          present in the laboratory environment, the reagents, or the
          apparatus.

     3.6  FIELD REAGENT BLANK (FRB)  An aliquot of reagent water or other
          blank matrix that is placed in a sample container in the laboratory
         .and treated as a sample in all respects, including shipment to the
          sampling site, exposure to sampling site conditions, storage,
          preservation and all analytical procedures.  The purpose of the FRB
          is to determine if method analytes or other interferences are
          present in the field environment.
                                    552.2-3

-------
3.7  LABORATORY FORTIFIED BLANK (LFB)  An aliquot of reagent water or
     other blank matrix to which known quantities of the method analytes
     are added in the laboratory.  The LFB is analyzed exactly like a
     sample, and its purpose is to determine whether the methodology is
     in control, and whether the laboratory is capable of making accurate
     and precise measurements.

3.8  LABORATORY FORTIFIED SAMPLE MATRIX (LFM) -- An aliquot of an
     environmental sample to which known quantities of the method
     analytes are added in the laboratory.  The LFM is analyzed exactly
     like a sample, and its purpose is to determine whether the sample
     matrix contributes bias to the analytical results.  The background
     concentrations of the analytes in the sample matrix must be
     determined in a separate aliquot and the measured values in the LFM
     corrected for background concentrations.

3.9  STOCK STANDARD SOLUTION (SSS)  A concentrated solution containing
     one or more method analytes prepared in the laboratory using assayed
     reference materials or purchased from a reputable commercial source.

3.10 PRIMARY DILUTION STANDARD SOLUTION (PDS) -- A solution of several
     analytes prepared in the laboratory from stock standard solutions
     and diluted as needed to prepare calibration solutions and other
     needed analyte solutions.

3.11 CALIBRATION STANDARD (CAL) -- A solution prepared from the primary
     dilution standard solution and stock standard solutions of the
     internal standards and surrogate analytes.  The CAL solutions are
     used to calibrate the instrument response with respect to analyte
     concentration.

3.12 QUALITY CONTROL SAMPLE (QCS)  A solution of method analytes of
     known concentration which is used to fortify an aliquot of reagent
     water or sample matrix.  The QCS is obtained from a source external
     to the laboratory and different from the source of calibration
     standards. It is used to check laboratory performance with
     externally prepared test materials.

3.13 LABORATORY PERFORMANCE CHECK SOLUTION (LPC)  A solution of
     selected method analytes used to evaluate the performance of the
     instrumental system with respect to a defined set of method
     criteria.

3.14 METHOD DETECTION LIMIT (MDL)  The minimum concentration of an
     analyte that can be identified, measured and reported with 99%
     confidence that the analyte concentration is greater than zero.

3.15 MATERIAL SAFETY DATA SHEET (MSDS) -- Written information provided by
     vendors concerning a chemical's toxicity, health hazards, physical
     properties, fire and reactivity data including storage, spill, and
     handling precautions.
                               552.2-4

-------
     3.16 ESTIMATED DETECTION LIMIT  (EDL)  Defined as either the MDL or a
          level of a compound in a sample yielding a peak in the final extract
          with a signal to noise (S/N) ratio of approximately 5, whichever is
          greater.

     3.17 PROCEDURAL STANDARD CALIBRATION  A calibration method where
          aqueous calibration standards are prepared and processed (e.g.
          purged, extracted and/or derivatized) in exactly the same manner as
          a sample.  All steps in the process from addition of sampling
          preservatives through instrumental analyses are included in the
          calibration.  Using procedural standard calibration compensates for
          any inefficiencies in the  processing procedure.

     3.18 CONTINUING CALIBRATION CHECK (CCC) -- A calibration standard con-
          taining one or more method analytes, which is analyzed periodically
          to verify the accuracy of  the existing calibration curves or re-
          sponse factors for those analytes.

4.   INTERFERENCES

     4.1  Method interferences may be caused by contaminants in solvents,
          reagents, glassware and other sample processing apparatus that lead
          to discrete artifacts or elevated baselines in chromatograms.  All
          reagents and apparatus must be routinely demonstrated to be free
          from interferences under the conditions of the analysis by analyzing
          laboratory reagent blanks  as described in Section 9.5.  Subtracting
          blank values from sample results is not permitted.

          4.1.1  Glassware must be scrupulously cleaned.  Clean all glassware
                 as soon as possible after use by thoroughly rinsing with the
                 last solvent used in it.  Follow by washing with hot water
                 and detergent and thorough rinsing with tap water and reagent
                 water.  Drain and heat in an oven or muffle furnace at 400C
                 for 1 hr.  Do not heat'volumetric ware but instead rinse
                 three times with HPLC grade or better acetone.   Thorough
                 rinsing with reagent grade acetone may be substituted for the
                 heating provided method blank analysis confirms no background
                 interferant contamination is present.   Thermally stable
                 materials such as PCBs may not be eliminated by these treat-
                 ments.  After drying and cooling, store glassware in a clean
                 environment free of all  potential contamination.   To prevent
                 any accumulation of dust or other contaminants, store glass-
                 ware inverted or capped with aluminum foil.               :

          4.1.2  The use of high purity reagents and solvents helps to mini-
                 mize interference problems.   Each new bottle of solvent
                 should be analyzed before use.   An interference free solvent
                 is a solvent containing no peaks yielding data  at > MDL
                 (Table 2) and at the retention times of the analytes of
                 interest.  Purification of solvents by distillation in all-
                 glass systems may be required.
                                   552.2-5

-------
     4.2  Interfering contamination may occur when a sample containing low
          concentrations of analytes is analyzed immediately following a
          sample containing relatively high concentrations of analytes.
          Routine between-sample rinsing of the sample syringe and associated
          equipment with MTBE can minimize sample cross-contamination.  After
          analysis of a sample containing high concentrations of analytes, one
          or more injections of MTBE should be made to ensure that accurate
          values are obtained for the next sample.

     4.3  Matrix interferences may be caused by contaminants that are coex-
          tracted from the sample.  The extent of matrix interferences will
          vary considerably from source to source, depending upon the water
          sampled.  Analyte identifications should be confirmed using the
          confirmation column specified in Table 1 or by GC/MS if the concen-
          trations are sufficient.

     4.4  Bromochloroacetic acid coelutes with an interferant on the DB-1701
          confirmation column.  The interferant has been tentatively identi-
          fied as dimethyl sulfide.  However, because of the difference in
          peak shapes, the peak for the ester of BCAA tends to "ride on" the  .
          interferant peak and quantitative confirmation can be performed by
          manual integration that includes only the peak area of the target
          ester.

     4.5  Methylation using acidic methanol results in a partial decarboxyl-
          ation of tribromoacetic acid (8).  Therefore a substantial peak for
          bromoform will be observed in the chromatograms.  Its elution does
          not, however, interfere with any other analytes.  Furthermore, this
          demonstrates the need for procedural standards to establish the
          calibration curve by which unknown samples are quantitated.
5.   SAFETY
     5.1  The toxicity or carcinogenicity of each reagent used in this method
          has not been precisely defined; however, each chemical  compound must
          be treated as a potential health hazard.  From this viewpoint,
          exposure to these chemicals must be minimized.  The laboratory is
          responsible for maintaining a current awareness file of OSHA regula-
          tions regarding the safe handling of the chemicals specified in this
          method.  A reference file of material safety data sheets should also
          be made available to all personnel involved in the chemical analy-
          sis.  Additional references to laboratory safety are available and
          have been identified (9-11) for the information of the analyst.

     5.2  The toxicity of the extraction solvent, MTBE, has not been well
          defined.  Susceptible individuals may experience adverse affects
          upon skin contact or inhalation of vapors.  Therefore protective  
          clothing and gloves should be used and MTBE should be used only in a
          chemical fume hood or glove box.  The same precaution applies to
          pure standard materials.
                                    552.2-6

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6.   APPARATUS AND EQUIPMENT

     6.1  SAMPLE CONTAINERS  Amber glass bottles, approximately 50 mL,
          fitted with Teflon-lined screw caps.

     6.2  EXTRACTION VIALS  60 mL clear glass vials with teflon-lined screw
          caps.

     6.3  VIALS -- Autosampler, 2.0 mL vials with screw or crimp cap and a
          teflon-faced seal.

     6.4  STANDARD SOLUTION STORAGE CONTAINERS  10-20 ml amber glass vials
          with teflon lined-screw caps.

     6.5  GRADUATED CONICAL CENTRIFUGE TUBES WITH TEFLON-LINED SCREW CAPS -
          15-mL with graduated 1 mL markings.

     6.6  BLOCK HEATER (or SAND. BATH) -- Capable of holding screw cap conical
          centrifuge tubes in Section 6.4.

     6.7  PASTEUR PIPETS  Glass, disposable.

     6.8  PIPETS  2.0 mL and 4.0 mL, type A, TO, glass.

     6.9  VOLUMETRIC FLASKS  5 ml, 10 mL.

     6.10 MICRO SYRINGES  10 fit, 25 0L, 50 fil, 100 /iL, 250 fil, 500 /d. and
          1000 /iL.

     6.. 11 BALANCE  analytical, capable of weighing to 0.0001 g.

     6.12 GAS CHROMATOGRAPH  Analytical system complete with gas chromato-
          graph equipped for electron capture detection, split/splitless
          capillary or direct injection, temperature programming, differential
          flow control,  and with all required accessories including syringes,
          analytical columns, gases and strip-chart recorder.   A data system
          is recommended for measuring peak areas.  An autoinjector is recom-
          mended for improved precision of analyses.  The gases flowing
          through the electron capture detector should be vented through the
          laboratory fume hood system.

     6.13 PRIMARY GC COLUMN -- DB-5.625 [fused silica capillary with chemical-
          ly bonded (5% phenylj-methylpolysiloxane)] or equivalent bonded,
          fused silica column, 30m x 0.25mm ID, 0.25 pm film thickness.

     6.14 CONFIRMATION GC COLUMN  DB-1701 [fused silica capillary with
          chemically bonded (14% cyanopropylphenyl)-methylpolysiloxane)] or
          equivalent bonded,  fused silica column,  30 m x 0.25  mm ID, 0.25 /im
          film thickness.
                                   552.2-7

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7.   REAGENTS AND STANDARDS

     7.1  REAGENT WATER  Reagent water is defined as a water in which an
          interference is not observed > to the MDL of each analyte of inter-
          est.

          7.1.1  A Millipore Super-Q water system or its equivalent may be
                 used to generate deionized reagent water.   Distilled water
                 that has been passed through granular charcoal may also be
                 suitable.

          7.1.2  Reagent water is monitored through analysis of the labora-
                 tory reagent blank (Section 9.5).

     7.2  SOLVENTS

          7.2.1  METHYL-TERT-BUTYL ETHER  High purity, demonstrated to be
                 free of analytes and interferences, redistilled in glass if
                 necessary.

          7.2.2  METHANOL  High purity, demonstrated to be free of
                 analytes and interferences.

          7.2.3  ACETONE -- High purity, demonstrated to be free of analytes
                 and interferences.

     7.3  REAGENTS

          7.3.1  SODIUM SULFATE, Na2S04    (ACS)  granular,  anhydrous.   If
                 interferences are observed, it may be necessary to heat the
                 sodium sulfate in a shallow tray at 400C  for up to 4 hr.  to
                 remove phthalates and other interfering organic substances.
                 Alternatively, it can be extracted with methylene chloride in
                 a Soxhlet apparatus for 48 hr.  Store in a capped glass
                 bottle rather than a plastic container.

          7.3.2  COPPER II SULFATE PENTAHYDRATE, CuS04"5H20 -- ACS re-
                 agent grade.

          7.3.3  SODIUM BICARBONATE, NaHC03   ACS reagent  grade.

          7.3.4  AMMONIUM CHLORIDE, NH^Cl  ACS reagent grade, used to
                 convert free chlorine to monochloramine. Although this
                 is not the traditional dechlorination mechanism, ammoni-
                 um chloride is categorized as a dechlorinating agent in
                 this method.

     7.4  SOLUTIONS

          7.4.1  10% H2S04/METHANOL SOLUTION  Use caution when prepar-
                 ing sulfuric acid solutions.  To prepare a 10% solution,
                 add 5 mL sulfuric acid dropwise  (due to heat evolution)

                                    552.2-8

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     7.4.2
to 20-30 ml methanol contained in a 50.0 ml volumetric
flask that has been placed in a cooling bath.  Then
dilute to the 50.0 ml mark with methanol.

SATURATED SODIUM BICARBONATE SOLUTION  Add sodium
bicarbonate to a volume of water, mixing periodically
until the solution has reached saturation.
7.5  STANDARDS

     7.5.1  1,2,3-TRICHLOROPROPANE, 99+% -- For use as the internal
            standard.  Prepare an internal standard stock standard solu-
            tion of 1,2,3-trichloropropane in MTBE at a concentration of
            approximately 1 mg/mL.  From this stock standard solution,
            prepare a primary dilution standard in MTBE at a concentra-
            tion of 25 fig/ml.

     7.5'.2  2,3-OIBROMOPROPIONIC ACID, 99+% -- For use as a surrogate
            compound.  Prepare a surrogate stock standard solution of
            2,3-dibromopropionic acid in MTBE at a concentration of
            approximately 1 mg/mL.  From this stock standard solution,
            prepare a primary dilution standard in MTBE at a concentra-
            tion of 10 ng/ml.

     7.5.3  STOCK STANDARD SOLUTION (SSS)

            Prepare separate stock standard solutions for each analyte of
            interest at a concentration of 1-5 mg/mL in MTBE.  Method
            analytes may be obtained as neat materials or ampulized
            solutions (> 99% purity) from a number of commercial suppli-
            ers.  These stock standard solutions shcald be stored at -
            10C and protected from light.   They are stable  for at least
            one month but should be checked frequently for signs of
            evaporation.

            7.5.3.1. For analytes which are solids in their pure form,
                     prepare stock standard solutions by accurately
                     weighing approximately 0.01 to 0.05 grams of pure
                     material in a 10.0 ml volumetric flask.  Dilute to
                     volume with MTBE.  When a compound purity is assayed
                     to be 96% or greater, the weight can be used without
                     correction to calculate the concentration of the
                     stock standard.

            7.5.3.2. Stock standard solutions for analytes which are
                     liquid in their pure form at room temperature can
                     be accurately prepared in the following manner.

            7.5.3.3. Place about 9.8 mL of MTBE into a 10.0 mL volumetric
                     flask.   Allow the flask to stand, unstoppered, for
                     about 10 minutes to allow solvent film to evaporate
                              552.2-9

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                from the inner walls of the volumetric,  and weigh to
                the nearest 0.1 mg.

       7.5.3.4. Use a 10 fil syringe and immediately add  10.0 /*L of
                standard material  to the flask by keeping the
                syringe needle just above the surface of the MTBE.
                Be sure that the standard material  falls dropwise
                directly into the MTBE without contacting the inner
                wall of the volumetric.

       7.5.3.5. Reweigh, dilute to volume, stopper, then mix by
                inverting the flask several times.   Calculate the
                concentration in milligrams per milliliter from the
                net gain in weight.

7.5.4  PRIMARY DILUTION STANDARD (PDS)  Prepare the primary
       dilution standard solution by combining and diluting stock
       standard solutions with MTBE (the surrogate stock standard
       solution was prepared in Section 7.5.2).  This primary
       dilution standard solution should be stored at -10C and
       protected from light.  It is stable for at least  one month
       but should be checked before use for signs of evaporation.
       As a guideline to the analyst, the primary dilution standard
       solution used in the validation of this method is described
       below.

                                  Concentration. ug/mL

       Monochloroacetic acid                60
       Monobromoacetic acid                 40
       Dalapon                              40
       Dichloroacetic acid                  60
       Trichloroacetic acid                 20
       Bromocnloroacetic acid               40
       Dibromoacetic acid                   20
       Bromodichloroacetic acid             40
       Chlorodibromoacetic acid            100
       Tribromoacetic acid                 200
       2,3-Dibromopropionic acid (surr.)   100

       This primary dilution standard is used to prepare calibration
       standards, which comprise five concentration levels of each
       analyte with the lowest standard being at or near the MDL of
       each analyte.  The concentrations of the other standards
       should define a range containing the expected sample
       concentrations or the working range of the detector.
       NOTE:  When purchasing commercially prepared standards, solu-
       tions prepared in methanol must not be used because it has
       been found that the haloacetic acids are subject to
       spontaneous methylation when stored.in this solvent (12).

                         552.2-10

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                 Furthermore, tribromoacetic acid has been found to be unsta-
                 ble  in methanol because it undergoes decarboxylation when
                 stored in this solvent.

                 7,5.4.1. Include the surrogate analyte, 2,3-dibromopropionic
                          acid, within the primary dilution standard prepared
                          in Section 7.5.4.  By incorporating the surrogate
                          into the primary dilution standard, it is diluted
                          alongside the target analytes in the standard
                          calibration curve.  This is done so that the peaks
                          for the surrogate and the ester of chlorodibromo-
                          acetic acid, which elute fairly closely, are
                          relatively close in size and adequate resolution is
                          therefore insured.  Furthermore, if a sample should
                          have a very large concentration of chlorodibromo-
                          acetic acid, it may be impossible to obtain an
                          accurate measurement of surrogate recovery.  If this
                          happens, reextraction with a higher surrogate
                          concentration would be an option.

          7.5.6  LABORATORY PERFORMANCE CHECK STANDARD (LPC)  A low level
                 calibration standard can serve as the LPC standard.

8-   SAMPLE COLLECTION. PRESERVATION AND STORAGE

     8.1  SAMPLE VIAL PREPARATION

          8.1.1  Grab samples must be collected in accordance with conven-
                 tional sampling practices (13) using amber glass containers
                 with TFE-lined screw-caps and capacities of at least 50 ml.

          8.1.2  Prior to shipment to the field, add crystalline or granular
                 ammonium chloride (NH4C1)  to  the  sample  container  in  an
                 amount to produce a concentration of 100 mg/L in the sample.
                 For a typical  50 mL sample, 5 mg of ammonium chloride is
                 added.

                 NOTE:  Enough ammonium chloride must be added to the sample
                 to convert the free chlorine residual  in the sample matrix to
                 combined chlorine.  Typically,  the ammonium chloride
                 concentration here will  accomplish that.   If high doses of
                 chlorine are used,  additional  ammonium chloride may be re-
                 quired.

     8.2  SAMPLE COLLECTION

          8.2.1  Fill  sample bottles to just overflowing  but take care not to
                 flush out the ammonium chloride.

          8.2.2  When sampling from a water tap,  open the tap and allow the
                 system to flush until  the water temperature has stabilized
                 (usually about 3-5  minutes).   Remove the aerator so that no

                                   552.2-11

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                 air bubbles can be visibly detected and collect samples  from
                 the flowing system.

          8.2.3  When sampling from an open body of water,  fill  a 1-quart
                 wide-mouth bottle or 1-liter beaker with sample from a
                 representative area, and carefully fill sample  vials from the
                 container.

          8.2.4  After collecting the sample in the bottle containing the
                 ammonium chloride, seal  the bottle and agitate  by hand for 1
                 min.

     8.3  SAMPLE STORAGE/HOLDING TIMES

          8.3.1  Samples must be iced or refrigerated at 4C  and maintained at
                 these conditions away from light until extraction.  Synthetic
                 ice (i.e., blue ice) is not recommended.  Holding studies
                 performed to date have suggested that, in samples preserved
                 with NH/C1,  the analytes are stable for up to 14 days.   Since
                 stability may be matrix dependent, the analyst  should verify
                 that the prescribed preservation technique is suitable for
                 the samples under study.

          8.3.2  Extracts (Section 11.2.7) must be stored at  4C or less  away
                 from light in .glass vials with Teflon-lined  caps.  Extracts
                 must be analyzed within 7 days from extraction  if stored at
                 4C or within 14 days if stored at -10C or  less.

9.   QUALITY CONTROL

     9.1  Each laboratory that uses this method is required to operate a
          formal quality control (QC) program.  Minimum quality  control
          requirements are monitoring the laboratory performance check stan-
          dard, initial demonstration of laboratory capability,  performance of
          the method detection limit study, analysis of laboratory reagent
          blanks and laboratory fortified sample matrices,  determination of
          surrogate compound recoveries in each sample and blank, monitoring
          internal standard peak area or height in each sample,  blank and CCC,
          and analysis of QC samples.  Additional QC practices may be added.

     9.2  LABORATORY PERFORMANCE CHECK STANDARD (LPC)

          At the beginning of an analysis set, prior to any calibration
          standard or sample analysis and after an initial solvent analysis, a
          laboratory performance check standard must be analyzed.  This check
          standard insures proper performance of the GC by evaluation of the
          instrument parameters of detector sensitivity, peak symmetry, and
          peak resolution.  It furthermore serves as a check.on the continuity
          of the instrument's performance.  In regards to sensitivity, it
          allows the analyst to ascertain that this parameter has not changed
          drastically since the analysis of the MDL study.  Inability to
          demonstrate acceptable instrument performance indicates the need for

                                   552.2-12

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     re-evaluation of the instrument system.
     Table 8.
Criteria are listed in
     9.2.1  The sensitivity requirement is based on the EDLs published in
            this method.  If laboratory EDLs differ from those listed in
            Table 2, concentrations of the LPC standard may be adjusted
            to be compatible with the laboratory EDLs.

     9.2.2  If column or chromatographic performance cannot be met, one
            or more of the following remedial actions should be taken.
            Break off approximately 1 meter of the injector end of the
            column and re-install, install a new column, adjust column
            flows or modify the oven temperature program.

9.3  INITIAL DEMONSTRATIONS CAPABILITY (IDC)

     9.3.1  Calibrate for each analyte of interest as specified in
            Section 10.  Select a representative fortification
            concentration for each of the target analytes.
            Concentrations near those in Table 4 are recommended.
            Prepare 4-7 replicates laboratory fortified blanks by adding
            an appropriate aliquot of the primary dilution standard or
            quality control  sample to reagent water.  (This reagent water
            should  contain ammonium chloride at the same  concentration
            as that specified for samples as per Section 8.1.2.)  Analyze
            the LFBs according to the method beginning in  Section 11.

     9.3.2  Calculate the mean percent recovery and the standard devia-
            tion of the recoveries.   For each analyte, the mean recovery
            value, expressed as a percentage of the true value, must fall
            in the range of 80-120% and the relative standard deviation
            should be less than 20%.   For those compounds  that meet these
            criteria,  performance is  considered acceptable and sample
            analysis may begin.  For  those compounds that  fail  these
            criteria,  this procedure  must be repeated using 4-7 fresh
            samples until  satisfactory performance has been demonstrated.
            Maintain these data on file to demonstrate initial
            capabilities.

     9.3.3  Furthermore,  before processing any samples,  the analyst must
            analyze at least one laboratory reagent blank  to demonstrate
            that all  glassware and reagent interferences are under
            control.

     9.3.4  The initial  demonstration of capability is used primarily  to
            preclude a laboratory from analyzing unknown samples via a
            new,  unfamiliar  method prior to obtaining some experience
            with it.   As  laboratory  personnel  gain experience with this
            method,  the quality of data should improve beyond those re-
            quired here.
                              552.2-13

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     9.3.5  The analyst is permitted to modify GC columns, GC conditions,
            internal standard or surrogate compounds.  Each time such
            method modifications are made, the analyst must repeat the
            procedures in Section 9.3.1 through Section 9.3.4 and Sect.
            9.4.

9.4  METHOD DETECTION LIMIT STUDY (MDL)

     9.4.1. Prior to the analysis of any field samples, the method
            detection limits must be determined.  Initially, estimate the
            concentration of an analyte which would yield a peak equal to
            5 times the baseline noise and drift.  Prepare seven
            replicate laboratory fortified blanks at this estimated
            concentration with reagent water that contains ammonium
            chloride at the same concentration as that specified for
            samples as per Section 8.1.2.  Analyze the LFB's according to
            the method beginning in Section 11.

     9.4.2. Calculate the mean recovery and the standard deviation for
            each analyte.  Multiply the student's t value at 99% confi-
            dence and n-1 degrees of freedom (3.143 for seven replicates)
            by this standard deviation to yield a statistical estimate of
            the detection limit.  This calculated value is the MDL.

     9.4.3. Since the statistical estimate is based on the preci-  sion
            of the analysis, an additional estimate of detection can be
            determined based upon the noise and drift of the baseline as
            well as precision.  This estimate is the EDL (Table 2).

9.5  LABORATORY REAGENT BLANKS (LRB)   Each time a set of samples is
     extracted or reagents are changed, a LRB must be analyzed.  If the
     LRB produces an interferant peak within the retention time window
     (Section 12.3} of any analyte that would prevent the determination
     of that analyte or a peak of concentration greater than the MDL for
     that analyte, the analyst must determine the source of contamination
     and eliminate the interference before processing samples.  Field
     samples of an extraction set associated with an LRB that has failed
     the specified criteria are considered suspect.

     NOTE:  Reagent water containing ammonium chloride at the same
     concentrations as in the samples (Section 8.1.2) is used to prepare
     the LRB.

9.6  LABORATORY FORTIFIED BLANK (LFB) -- Since this method utilizes
     procedural calibration standards,, which are fortified reagent water,
     there is no difference between the LFB and the continuing
     calibration check standard.  Consequently, the analysis of an LFB is
     not required (Section 10.2).
                              552.2-14

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9.7  LABORATORY  FORTIFIED  SAMPLE  MATRIX  (LFM)

     9.7.1  Chlorinated water  supplies will  usually  contain  significant
            background concentrations of several  method  analytes,  espe-
            cially dichloroacetic acid  (DCAA)  and trichloroacetic  acid
            (TCAA).   The concentrations  of these  acids may be  equal  to or
            greater  than the fortified concentrations.   Relatively poor
            accuracy and precision may be anticipated when a large
            background must be subtracted.   For many samples,  the  concen-
            trations may be so high  that fortification may lead  to a
            final extract  with instrumental  responses exceeding  the
            linear range of the electron capture  detector.   If this
            occurs,  the extract must be  diluted.   In spite of  these
            problems, sample sources should  be fortified and analyzed as
            described below.   By  fortifying  sample matrices and  calcu-
            lating analyte recoveries, any matrix induced analyte  bias is
            evaluated.

     9.7.2. The  laboratory must add  known concentrations of analytes to
            one  sample per extraction set or a minimum of 10%  of the
            samples,  whichever is greater.   The concentrations should be
            equal to or greater than the background  concentrations in the
            sample selected for fortification.  If the fortification
            level is less  than the background concentration, recoveries
            are  not  reported.   Over  time, samples from all routine sample
            sources  should be  fortified.

     9.7.3  Calculate the  mean percent recovery,  R,  of the concentration
            for  each analyte,  after correcting the total mean measured
            concentration. A,  from the fortified  sample for the  back-
            ground concentration, B, measured in  the unfortified sample,
            i.e.:

                      R = 100 (A - B) / C,

            where C  is the fortifying concentration.  In order for the
            recoveries to  be considered  acceptable,  they must fall
            between  70% and 130%  for all the target  analytes.

     9.7.4  If a recovery  falls outside  of this acceptance range, a
            matrix induced bias can be assumed for the respective analyte
            and  the  data for that analyte must be reported to the data
            user as  suspect due to matrix effects.

9.8  ASSESSING SURROGATE RECOVERY

     The surrogate analyte is  fortified  into the aqueous portion of all
     continuing calibration standards,  samples and laboratory reagent
     blanks.  The surrogate is  a means of assessing method performance in
     every analysis  from extraction to final  chromatographic performance.
                              552.2-15

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     9.8.1  When surrogate recovery from a sample,  blank or CCC is < 70%
            or > 130%, check (1) calculations to locate possible errors,
            (2) standard solutions for degradation, (3) contamination,
            and (4) instrument performance.  If those steps do not reveal
            the cause of the problem, reanalyze the extract.

     9.8,2  If the extract reanalysis meets the surrogate recovery
            criterion, report only data for the reanalyzed extract.

     9.8.3  If the extract reanalysis fails the 70-130% recovery
            criterion, the analyst should check the calibration by
            analyzing the most recently acceptable continuing calibration
            check standard.  If the CCC fails the criteria of Section
            10.2.1, recalibration is in order per Section 10.1.  If the
            CCC is acceptable, it may be necessary to extract another
            aliquot of sample.  If the sample re-extract also fails the
            recovery criterion, report all data for that sample as
            suspect.

9.9  ASSESSING THE INTERNAL STANDARD

     9.9.1. The analyst must to monitor the IS response (peak area or
            peak height) of all injections during each analysis day.
            A mean IS response should be determined from the five point
            calibration curve.  The IS response for any run should not
            deviate from this mean IS response by more than 30%.  It is
            also acceptable if the IS response of a injection is within
            15% of the daily continuing calibration standard IS response.

     9.9.2  If a deviation greater than this occurs with an individual
            extract, optimize instrument performance and inject a second
            aliquot of that extract.

            9.9.2.1  If the reinjected aliquot produces an acceptable
                     internal standard response, report results for that
                     aliquot.

            9.9.2.2  If a deviation of greater than 30% is obtained for
                     the reinjected extract, the analyst should check the
                     calibration by analyzing the most recently
                     acceptable CCC.  If the CCC fails the criteria of
                     Section 10.2.1, recalibration is in order per
                     Section 10.1.  If the CCC is acceptable, analysis of
                     the sample should be repeated beginning with Section
                     11, provided the sample is still available.  Oth-
                     erwise, report results obtained from the reinjected
                     extract, but annotate as suspect.

9.10 QUALITY CONTROL SAMPLE (QCS) ~ At least quarterly, analyze a QCS
     from an external source.  If measured analyte concentrations are not
     of acceptable accuracy, check the entire analytical procedure to
     locate and correct the problem source.

                              552.2-16

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     9.11 The laboratory may adapt additional QC practices for use with this
          method.  The specific practices that are most productive depend upon
          the needs of the laboratory and the nature of the samples.  For
          example, field or laboratory duplicates may be analyzed to assess
          the precision of the environmental measurements or field reagent
          blanks may be used to assess contamination of samples under site
          conditions, transportation and storage.

10.   CALIBRATION AND STANDARDIZATION

     10.1 INITIAL CALIBRATION CURVE

          10.1.1 Calibration is performed by extracting procedural standards,
                 i.e.; fortified reagent water,  by the procedure set forth in
                 Section 11.  A five-point calibration curve is to be prepared
                 by diluting the primary dilution standard into MTBE at the
                 appropriate levels.  The desired amount of each MTBE
                 calibration standard is added to separate 40 ml aliquots of
                 reagent water to produce a calibration curve ranging from the
                 detection limit to approximately 50 times the detection
                 limit.  (These MTBE calibration standards should be prepared
                 so that 20 //L or less of the solution is added the water
                 aliquots.)  Also, the reagent water used for the procedural
                 standards contains ammonium chloride at the same concentra-
                 tion as that in the samples as per Section 8.1.2.

          10.1.2 Establish GC operating parameters equivalent to the suggested
                 specifications in Table 1.  The GC system must be calibrated
                 using the internal standard (IS) technique.  Other columns or
                 conditions may be used if equivalent or better performance
                 can be demonstrated.

          10.1.2 Five calibration standards are  required. The lowest should
                 contain the analytes at a concentration near to but greater
                 than the MDL (Table 2) for each compound. The others should
                 be evenly distributed throughout the concentration range
                 expected in the samples.

          10.1.3 Inject 2 /iL of each calibration standard extract and tabulate
                 peak height or area response and concentration for each
                 analyte and the internal  standard.

          10.1.4 Generate a calibration curve by plotting the area ratios
                 (Aa/Ais) against the concentration Ca of the five calibration
                 standards where

                          Aa is  the peak area of the  analyte.
                          Ajs is the  peak area of the internal standard.
                          C  is  the concentration  of  the  analyte.
                                   552.2-17

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            This curve can be defined as either first or second order.
            Also, the working calibration curve must be verified daily  by
            measurement of one or more calibration standards (Section
            10.2).  If the response for any analyte falls outside the
            predicted response by more than 30%, the calibration check
            must be repeated using a freshly prepared calibration stan-
            dard.  Should the retest fail, a new calibration curve must
            be generated.

     10.1.5 Alternately, an average relative response factor can be
            calculated and used for quantitation.  Relative response
            factors are calculated for each analyte at the five
            concentration levels using the equation below:
            RRF
                  
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          10.2.2 If this criteria cannot be met, the continuing calibration
                 check standard extract is re-injected in order to determine
                 if the response deviations observed from the initial analysis
                 are repeated.  If this criteria still cannot be met, a second
                 CCC should be extracted and analyzed or a CCC that has
                 already been analyzed and has been found to be acceptable
                 should be run.  If this second CCC fails, then the instrument
                 is considered out of calibration and needs to be
                 recalibrated.
11.   PROCEDURE

     11.1 SAMPLE EXTRACTION
          11.1.1 Remove the samples from storage (Sect. 8.3.1) and allow them
                 .to equilibrate to room temperature.

          11.1.2 Place 40 ml of the water sample into a precleaned 60 ml glass
                 vial with a teflon-lined screw cap using a graduated
                 cylinder.

          11.1.3 Add 20 /j(L of surrogate standard (10.0 jug/ml 2,3-dibromo-
                 propionic acid in MTBE per Section 7.5.2).

                 NOTE:  When fortifying an aqueous sample with either
                 surrogate or target analytes contained in MTBE,  be sure that
                 the needle of the syringe is well  below the level of the
                 water.  After injection, cap the sample and invert once.
                 This insures that the standard solution is mixed well  with
                 the water.

          11.1.4 Adjust the pH to less than 0.5 by adding at least 2 mL of
                 concentrated sulfuric acid.   Cap,  shake and then check the pH
                 with a pH meter or narrow range pH paper.

          11.1.5 Quickly add approximately 2  g of copper II sulfate
                 pentahydrate and shake until  dissolved.   This colors the
                 aqueous phase blue and therefore allows for the  analyst to
                 better distinguish between the aqueous phase and the organic
                 phase in this micro extraction.

          11.1.6 Quickly add 16 g of muffled  sodium sulfate and shake for 3 to
                 5  minutes until  almost all  is dissolved.   Sodium sulfate Is
                 added to increase the ionic  strength of the aqueous phase and
                 thus further drive the haloacetic  acids  into the organic
                 phase.   The addition of this  salt  and the  copper II sulfate
                 should be done quickly so that the heat  generated from the
                 addition of the  acid (Section 11.1.4)  will  help  dissolve the
                 salts.
                                   552.2-19

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     11.1.7 Add 4.0 ml MTBE and place on the mechanical  shaker for  30
            minutes.  (If hand-shaken, two minutes is  sufficient  if
            performed vigorously).

     11.1.8 Allow the phases to separate for approximately 5 minutes.

11.2 METHYLATION

     11.2.1 Using a pasteur pipet,  transfer approximately 3 ml of the
            upper MTBE layer to a 15 ml graduated conical  centrifuge
            tube.

     11.2.2 Add 1 ml 10% sulfuric acid in methanol to  each centrifuge
            tube.

     11.2.3 Cap the centrifuge tubes and place in the  heating block (or
            sand bath) at 50C and  maintain for 2 hr.   The vials  must  fit
            snugly into the heating block to ensure proper heat transfer.
            At this stage,  methylation of the method analytes is  at-
            tained.

     11.2.4 Remove the centrifuge tubes from the heating block (or sand
            bath) and allow them to cool before removing the caps.

     11.2.5 Add 4 ml saturated sodium bicarbonate solution to each
            centrifuge tube in 1 ml increments.  Exercise caution when
            adding the solution because the evolution  of C02 in this
            neutralization reaction is rather rapid.

     11.2.6 Shake each centrifuge tube for 2 minutes.   As the neutral-
            ization reaction moves  to completion, it is important to
            continue to exercise caution by venting frequently to release
            the evolved C02.

     11.2.7 Transfer exactly 1.0 ml of the upper MTBE  layer to an auto-
            sampler vial.  A duplicate vial should be  filled using the
            excess extract.

     11.2.8 Add 10 pi of internal standard to the vial to be analyzed.
            (25 pg/wl 1,2,3-trichloropropane in MTBE per Section 7.5.1).

     11.2.9 Analyze the samples as  soon as possible.  The sample extract
            may be stored up to 7 days if kept at 4C  or less or up to 14
            days if kept at -10C or less.  Keep the extracts away from
            light in amber glass vials with Teflon-lined caps.

11.3 GAS CHROMATOGRAPHY

     11.3.1 Table 1 summarizes recommended GC operating conditions and
            retention times observed using this method.  Figure 1 illus-
            trates the performance  of the recommended  primary column with
            the method analytes.  Figure 2 illustrates the performance of

                              552.2-20

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                 the recommended confirmation column with the method analytes.
                 Concentrations of the analytes of these chromatograms are
                 those listed in Table 4 for the fortified reagent water
                 samples.  Other GC columns or chromatographic conditions may
                 be used if the requirements of Section 9 are met.

          11.3.2 Calibrate the system (Section 10.1) or verify the existing
                 calibration by analysis of a CCC daily as described in
                 Section 10.2.
          11.3.3 Inject 2 /zL of the sample extract.
                 sizes in area or height units.
Record the resulting peak
          11.3.4 If the response for the peak exceeds the working range of the
                 system, dilute the extract, add an appropriate additional
                 amount of internal standard and reanalyze.  The analyst must
                 not extrapolate beyond the calibration range established.

12.  DATA ANALYSIS AND CALCULATIONS

     12.1 Identify sample components by comparison of retention times to
          retention data from the calibration standard analysis.  If the
          retention time of an unknown peak corresponds, within limits (Sec-
          tion 12.2), to the retention time of a standard compound, then the
          identification is considered positive.  Calculate analyte concentra-
          tions in the samples and reagent blanks from the calibration curves
          generated in Section 10.1.

     12.2 If an average relative response factor has been calculated (Sect
          10.1.5), analyte concentrations in the samples and reagent blanks
          are calculated using the following equation:

               (Aa)(Cis)

           9   (Ajs)(RRF)

     12.3 The width of the retention time window used to make identifications
          should be based upon measurements of actual retention time varia-
          tions of standards over the course of a day.  Three times the
          standard deviation of a retention time can be used to calculate a
          suggested window size for a compound.  However, the experience of
          the analyst should weigh heavily in the interpretation of
          chromatogram.

13.  METHOD PERFORMANCE

     13.1 In a single laboratory, recovery and precision data were obtained at
          three concentrations in reagent water (Tables 3 and 4).   The MDL and
          EDL data are given in Table 2.   In addition, recovery and precision
          data were obtained at a medium concentration for dechlorinated tap
          water (Table 5),  high ionic strength reagent water (Table 6) and
          high humectant ground water (Table 7).

                                   552.2-21

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14.  POLLUTION PREVENTION

     14.1 This method utilizes a micro-extraction procedure which requires the
          use of very small quantities of organic solvents. This feature
          reduces the hazards involved with the use of large volumes of poten-
          tially harmful organic solvents needed for conventional liquid-
          liquid extractions.  This method also uses acidic methanol as the
          derivatizing reagent.

     14.2 For information about pollution prevention that may be applicable to
          laboratory operations consult "Less is Better:  Laboratory Chemical
          Management for Waste Reduction" available from the American Chemical
          Society's Department of Government Relations and Science Policy,
          1155 16th Street N.W., Washington, D.C. 20036.

15.  WASTE MANAGEMENT

     15.1 Due to the nature of this method there is little need for waste
          management.  No large volumes of solvents or hazardous chemicals are
          used.  The matrices of concern are finished drinking water or source
          water.  However, the Agency requires that laboratory waste manage-
          ment practices be conducted consistent with all applicable rules and
          regulations, and that laboratories protect the air, water, and land
          by minimizing and controlling all releases from fume hoods and bench
          operations.  Also compliance is required with any sewage discharge
          permits and regulations, particularly the hazardous waste identifi-
          cation rules and land disposal restrictions.  For further informa-
          tion on waste management, consult "The Waste Management Manual for
          Laboratory Personnel" also available from the American Chemical
          Society at the address in Sect. 14.2.

16.  REFERENCES

     1.   Quimby, B.D., Delaney, M.F., Uden. P.C. and Barnes, R.M.  Anal.
          Chem. 52, 1980, pp. 259-263.

     2.   Uden, P.C. and Miller, J.W., J. Am. Water Works Assoc. 15, 1983, pp.
          524-527.

     3.   Hodgeson, J.W. and Cohen, A.L. and Collins, J.D., "Analytical
          Methods for Measuring Organic Chlorination Byproducts", Proceedings
          Watejr Quality Technology Conference (WQTC-16), St. Louis, MO, Nov.
          13-17, 1988, American Water Works Association, Denver, CO, pp. 981-
          1001.

     4.   Fair. P.S., Barth, R.C., "Comparison of the Microextraction
          Procedure and Method 552 for the Analysis of HAAs and
          Chlorophenols", Journal AWWA, November, 1992, pp. 94-98.
                                   552.2-22

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5.   Chinn, R. and Krasner, S.  " A Simplified Technique  for the Measure-
     ment of Halogenated Organic Acids  in Drinking Water by Electron
     Capture Gas Chromatography". Presented at the 28th  Pacific Confer-
     ence on Chemistry  and Spectroscopy, Pasadena, CA, October, 1989

6.   Hodgeson, J. W., Collins,  J. D., and Becker, D. A., "Advanced Tech-
     niques for the Measurement of Acidic Herbicides and Disinfection
     Byproducts in Aqueous Samples," Proceedings of the  14th Annual EPA
     Conference on Analysis of  Pollutants in the Environment, Norfolk,
     VA., May 8-9, 1991.  Office of Water Publication No. 821-R-92-001,
     U.S. Environmental Protection Agency, Washington, DC, pp 165-194.

7.   Shorney, Holly L.  and Randtke, Stephen J., "Improved Methods for
     Haloacetic Acid Analysis", Proceedings Water Quality Technology
     Conference, San Francisco, CA, November 6-10, 1994, American Water
     Works Association, pp 453-475.

8.   Peters, Rund J.B., Erkelens, Corrie, De Leer, Ed W.B. and De Galan,
     Leo, "The Analysis of Halogenated Acetic Acids in Dutch Drinking
     Water",  Wat. Res., Vol.25, No.4, 1991, Great Britain, pp 473-477.

9.   "Carcinogens-Working with  Carcinogens", Publication No. 77-206,
     Department of Health, Education, and Welfare, Public Health Service,
     Center for Disease Control, National Institute of Occupational
     Safety and Health, Atlanta, Georgia, August 1977.

10.  "OSHA Safety and Health Standards, General Industry", (29CFR1910),
     OSHA 2206, Occupational Safety and Health Administration, Washing-
     ton, D.C.  Revised January 1976.

11.  "Safety In Academic Chemistry Laboratories",  3rd Edition, American
     Chemical Society Publication, Committee on Chemical Safety, Washing-
     ton, D.C., 1979.

12.  Xie, Yuefeng, Reckhow, David A., and Rajan,  R.V., "Spontaneous
     Methylation of Haloacetic Acids in Methanolic Stock Solutions",
     Environ. Sci. Technol., Vol.27, No.6,  1993,  pp!232-1234.

13.  ASTM Annual  Book of Standards,  Part 31, D3370,  "Standard  Practice
     for Sampling Water", American Society for Testing and Materials,
     Philadelphia, PA, p. 76,  1980.

14.  ASTM Annual  Book of Standards,  Part 31, D3694,  "Standard  Practice
     for Preparation of Sample Containers and for Preservation", American
     Society for Testing and Materials, Philadelphia,  PA, p. 679,  1980.

15.  Glaser, J. A.,  Foerst, D. L., McKee, G. 0.,  Quave,  S.  A.  and Budde,
     W. L.,  Environ.  Sci. Technol. 15,  1981, pp.  1426-1435.
                              552.2-23

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                                     552.2-24

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                                        552.2-25

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            TABLE 1.  RETENTION DATA AND CHROMATOGRAPHIC CONDITIONS
Analyte
Monochloroacetic Acid (MCAA)
Monobromoacetic Acid (MBAA)
Dichloroacetic Acid (OCAA)
Dalapon
Trichloroacetic Acid (TCAA)
Bromochloroacetic Acid (BCAA)
1,2,3-Trichloropropane (I.S.)
Dibromo acetic Acid (DBAA)
Bromodichloroacetic acid (BOCAA)
Chlorodibromoacetic acid (CDBAA)
2,3-Dibromopropionic acid (SURR)
Tribromoacetic Acid (TBAA)
Retention Time.
Column A
13.03
17.15
17.80
19.08
22.67
23.15
23.70
31.38
32.18
41.57
41.77
49.22
min.
Column B
13.70
17.33
17.88
17.73
20,73
22.87
22.35
30.27
28.55
38.78
39.72
47.08
Column A:  DB-5.625, 30 m x 0.25 mm  i.d., 0.25 tun  film  thickness,
           Injector Temp. = 200C, Detector Temp. = 260C,  Helium
           Linear Velocity -  24 cm/sec at 35C,  Splitless  injection
           with 30 s delay

Program:   Hold at 35C for 10 min, ramp to 75*C at 5C"/roin. and hold
           15 min., ramp to 100"C  at  5C/min. and  hold  5 min,  ramp to
           135C at 5C/min.  and hold 2 min.

Column B:  DB-1701, 30 m xo0.25 mm i.d., 0.25 /zm film thickness,  Injec-
           tor Temp.  200C,  Detector Temp. * 260C, Linear Helium
           Velocity = 25 cm/sec at 35"C, splitless  injection with 30 s
           delay.

Program:   Hold at 35*C for 10 min, ramp to 75'C at 5C/min. and hold
           15 min., ramp to 100C  at  5t"/min. and  hold  5 min,  ramp to
           135"C at 5C/nrin.  and hold 0 min.
                                552.2-26

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                     TABLE 2.   ANALYTE ACCURACY AND PRECISION DATA
                               AND METHOD DETECTION LIMITS0
                               LEVEL 1 IN REAGENT WATER
Analyte
MCAA
MBAA
DCAA
Dalapon
TCAA
BCAA
DBAA
BDCAA
CDBAA
TBAA
Fortified
Cone.
M9/L
0.600
0.400
0.600
0.400
0.200
0.400
0.200
0.400
1.00
2.00
Mean
Meas.
Cone.
W/L
0.516
0.527
0.494
0.455
0.219
0.498
0.238
0.357
1.19
1.91
Std.
Dev.
W/L
0.087
0.065
0.077
0.038
0.025
0.080
0.021
0.029
0.149
0.261
Rel.
Std.
Dev., %
17
12
16
8.4
11
16
8.8
8.1
12
14
Method
Detection
Limit"
W/L
0.273
0.204
0.242
0.119
0.079
0.251
0.066
0.091
0.468
0.820
Estimated
Detection
Limit6
W/L
0.60
0.20
0.24
0.40
0.20
0.25
0.20
0.40
0.75
1.5
a Produced  by  analysis  of seven  aliquots  of fortified  reagent water.

b The MDL is a statistical estimate of the detection limit.   To determine the MDL  for
each analyte, the standard deviation of the mean concentration of the seven replicates
is calculated.  This standard deviation is then multiplied by the student's t-value at
99% confidence and n-1 degrees of freedom  (3.143 for seven replicates).  The result is
the MDL.

c The EDL is defined as either the MDL or a level  of a compound in a sample yielding a
peak in the final extract with a signal to noise (S/N) ratio of approximately 5,
whichever is greater.
                                       552.2-27

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                    TABLE 3.   ANALYTE ACCURACY AND PRECISION DATA"
                               LEVEL 2  IN REAGENT WATER
Fortified
Cone.
Analyte ng/i
Monochloroacetic Acid
Monobromoacetic Acid
Dichloroacetic Acid
Dalapon
Trichloroacetic Acid
Bromochloroacetic Acid
Dibromoacetic Acid
Bromodichloroacetic Acid
Chlorodibromoacetic Acid
Tribromoacetic Acid
1.50
1.00
1.50
1.00
0.500
1.00
0.500
1.00
2.50
5.00
Mean
Meas.
Cone.
w/L
1.42
1.02
1.27
0.935
0.465
0.869
0.477
1.07
2.62
5.19
Std.
Dev.
W/L
0.103
0.051
0.122
0.087
0.048
0.049
0.044
0.098
0.150
0.587
Rel.
Std.
Dev., %
7.3
5.0
9.6
9.3
10
5.6
9.2
9.2
5.7
11
Mean
Recovery
%
94.7
102
84.7
93.5
93.0
86.9
95.4
107
105
104
8 Produced by the analysis of seven aliquots of fortified reagent water.
                                       552.2-28

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                    TABLE 4.   ANALYTE ACCURACY AND PRECISION DATA9
                               LEVEL 4  IN REAGENT WATER
Fortified
Cone.
Analyte /jg/L
Monochloroacetic Acid
Monobromoacetic Acid
Dichloroacetic Acid
Dalapon
THchloroacetic Acid
Bromochloroacetic Acid
Dibromoacetic Acid
Bromodichloroacetic Acid
Chlorodibromoacetic Acid
Tribromoacetic Acid
6.00
4.00
6.00
4.00
2.00
4.00
2.00
4.00
10.0
20.0
Mean
Meas.
Cone.
W/L
5.24
4.36
6.89
3.87
1.74
4.33
1.87
3.93
11.4
24.0
Std.
Dev.
M9/L
0.664
0.475
0.782
0.147
0.144
0.402
0.113
0.377
0.866
1.82
Rel.
Std.
Dev., %
13
11
11
3.8
8.3
9.3
6.0
9.6
7.6
7.6
Mean
Recovery
%
87.3
109
115
96.8
87.0
108
93.5
98.2
114
120
8 Produced by the analysis of seven aliquots of fortified reagent water.
                                       552.2-29

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                    TABLE 5.   AHALYTE ACCURACY AND PRECISION DATA*'"
                            LEVEL 3  IN OECHLORINATED TAP WATER6
Background
Cone.
Analyte /ig/L
Monochloroacetic Acid
Monobromoacetic Acid
Dichloroacetic Acid
Dal apon
Trichloroacetic Acid
Bromochloroacetic Acid
Dibromoacetic Acid
Bromodichloroacetic Acid
Chlorodibromoacetic Acid
Tribromoacetic Acid
<0.6
0.420
0.625
<0.4
0.300
1.23
1.27
0.588
1.23
<2.0
Forti-
fied
Cone.
W/L
3.00
2.00
3.00
2.00
1.00
2.00
1.00
2.00
5.00
10.0
Mean
Meas.
Cone.
/ig/L
2.53
2.20
3.77
1.96
1.12
2.91
2.35
2.52
6.36
11.8
Std.
Dev.
M/L
0.090
0.034
0.096
0.157
0.167
0.062
0.110
0.388
0.502
1.65
Rel.
Std.
Dev.
%
3.6
1.5
2.5
8.0
15
2.1
4.7
15
7.9
14
Mean
Rec.
%
84.3
89.0
105
98.0
82.0
84.0
108
96.6
103
118
3 Produced  by  analysis  of seven aliquots  of fortified  dechlorinated  tap water.
b Background level  subtracted.
c Chlorinated  surface water from a local  utility to  which  ammonium chloride was added
  as the dechlorinating agent.
                                       552.2-30

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                    TABLE 6.  ANALYTE ACCURACY AND PRECISION DATA*'"
                            LEVEL 3  IN  HIGH  IONIC STRENGTH WATERC
Background
Cone.
Analyte /tg/L
Monochloroacetic Acid
Monobromoacetic Acid
Dlchloroacetic Acid
Dalapon
Trichloroacetic Acid
Bromochloroacetic Acid
Dibromoacetic Acid
Bromodichloroacetic Acid
Chlorodibromoacetic Acid
Tribromoacetic Acid
0.761
1.47
1.50
0.675
1.01
2.06
4.36
1.07
2.48
4.63
Forti-
fied
Cone.
M9/L
3.00
2,00
3.00
2.00
1.00
2.00
1.00
2.00
5.00
10.0
Mean
Meas.
Cone.
W/L
3.32
3.19
4.44
2.39
1.75
3.71
5.48
3.37
7.94
17.2
Std.
Dev.
W/L
0.429
0.099
0:264
0.259
0.110
0.269
0.255
0.308
1.00
1.55
Rel.
Std. Mean
Dev. Rec
% %
13
3.1
5.9
11
6.3
7.3
4.7
9.1
13
9.0
85.3
86.0
98.0
85.8
74.0
82.5
112
115
109
126
* Produced  by  analysis  of seven aliquots of fortified  high  ionic  strength  water.

b Background level subtracted.

0 Chlorinated  ground water from a water source displaying a hardness of 460 mg/L as
  CaC03
                                       552.2-31

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                     TABLE  7.   ANALYTE ACCURACY AND PRECISION DATA3
                            LEVEL 3  IN HIGH HUHIC CONTENT GROUND WATER"
Background
Cone.
Analyte M9/L
Monochloroacetic Acid
Monobromoacetic Acid
Dichloroacetic Acid
Oalapon
Trichloroacetic Acid
Bromochloroacetic Acid
Dibromoacetic Acid
Bromodichloroacetic Acid
Chlorodibromoacetic Acid
Tribromoacetic Acid
<0.6
<0.4
<0.6
<0.4
<0.2
<0.4
<0.2
<0.4

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                    TABLE 8.  LABORATORY PERFORMANCE CHECK SOLUTION
PARAMETER
INSTRUMENT
SENSITIVITY
CHROMATOGRAPHIC
PERFORMANCE
COLUMN
PERFORMANCE
ANALYTE
MCAA
BCAA
CDBAA
SURROGATE. (2,3-DBPA)
CONC., tig/ml
IN MTBE
0.006
0.004
0.010
0.010
ACCEPTANCE
CRITERIA
DETECTION OF
ANALYTE;
S/Na > 3
PGFb BETWEEN
0.80 AND 1.15
RESOLUTION0
> 0.50
   S/N,  a  ratio of peak signal to baseline noise.

   peak  signal  -  measured as height of peak.
   baseline  noise -  measured as maximum deviation in baseline  (in  units  of height)
                     over a width equal to the width of the base of the peak.
   PGF = Peak Gaussian  Factor
           1.83  x  W
                   1/2
   PGF =
   where W1/2  =  the peak width at half height (in sees).
         W1/10 = the  peak width at one-tenth height (in sees)

   This is a measure of the symmetry of the peak.
c  Resolution between two  peaks  is  defined by the equation:

         t
         ave
   where t = the difference in elution times between the two peaks.
        Wave  =  the  average peak width of the two peaks  (measurements  taken at
                baseline).

This a measure  of  the  degree of separation of two peaks under specific  chromatographic
conditions.
                                        552.2-33
*U.S. GOVERNMENT PRINTING OFFICE: 1996 - 750-001/< 1001

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-------
U.S. EPA Headquarters Library
      Mail code 3201
1200 Pennsylvania Avenue NW
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