5550              '                                                    905R80110
                       METHOD  645:  ANALYSIS OF CERTAIN AMINE PESTICIDES AND
                             LETHANE IN WASTEWATER BY GAS  CHROMATOGRAPHY
            1.  SCOPE AND APPLICATION

               1.1  This method covers the determination of certain amine pesticides
                    and lethane in municipal and industrial wastewater.  The following
                    parameters may be determined by this method.

                    Parameter                                            CAS No.
                    Alachlor                                           15972-60-8
                    Butachlor                                          23184-66-9
                    Diphenamid                                           957-51-7
                    Fluridone                                          59756-60-4
                    Lethane                                              112-56-1
                    Norflurazon                                        27314-13-2
               1.2  The estimated detection limit (EDL) for each parameter is listed in
                    Table 1.  The EDL was calculated from the minimum detectable
                    response of the nitrogen/phosphorous detector equal to 5 times the
                    gas chromatographic (GC) background noise assuming a 10 mL final
                    extract volume of a 1 liter reagent water sample and a GC injection
                    of 5 pL.  The EDL for a specific wastewater may be-different
                    depending on the nature of interferences in the sample matrix.

               1.3  This is a gas chromatographic (GC) method applicable to the
                    determination of the compounds listed above in municipal and
                    industrial discharges.  When this method is used to analyze
                    unfamiliar samples for any or all of the compounds listed above,
                    compound identifications should be supported by at least one
                    additional qualitative technique.  Section 13 provides gas
                    chromatograph/mass spectrometer (GC/MS) conditions appropriate for
                    the qualitative confirmation of compound identifications.

               1.4  This method is restricted to use by or under the supervision of
                    analysts experienced in the operation of gas chromatographs and in
                    the interpretation of chromatograms.

           2.  SUMMARY OF METHOD

               2.1  The amine pesticides and lethane are removed from the sample matrix
                    by extraction with methylene chloride.  The extract is dried,
                    exchanged into hexane, and analyzed by gas chromatography.  Column
                    chromatography is used as necessary to eliminate interferences
                    which may be encountered.  Measurement of the pesticides is
                    accomplished with a nitrogen/phosphorous specific'.detector.
                                  U.S. Environmental Protection Agency
                                  Region  V, Library
                                  230 South Dearborn Street
                                           lllfnnk

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US. Environmental Protection Agency-

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    2.2  Confirmatory analysis by gas chromatography/mass spectrometry is
         recommended (Section 13) when a new or undefined sample type is
         being analyzed if the concentration is adequate for such
         determination.

3.  INTERFERENCES

    3.1  Solvent, reagents, glassware, and other sample processing hardware
         may yield discrete artifacts and/or elevated baselines causing
         misinterpretation of gas chromatograms.  All of these materials
         must be demonstrated to be free from interferences under the
         conditions of the analysis by running laboratory reagent blanks as
         described in Section 9.1

         3.1.1  The use of high-purity reagents and solvents helps to
                minimize interference problems.  Purification of solvents by
                distillation in all-glass systems may be required.

         3.1.2  Glassware must be scrupulously cleaned (1).  Clean all
                glassware as soon as possible after use by rinsing with the
                last solvent used in it.  This should be followed by
                detergent washing with hot water and rinses with tap water
                and reagent water.  It should then be drained dry and heated
                in a muffle furnace at 400°C for 15 to 30 minutes.  Solvent
                rinses with acetone and pesticide-quality hexane may be
                substituted for the muffle furnace heating.  Volumetric ware
                should not be heated in a muffle furnace.  After drying and
                cooling, glassware should be sealed and stored in a clean
                environment to prevent any accumulation of dust or other
                contaminants.  Store the glassware inverted or capped with
                aluminum foil.

    3.2  Interferences co-extracted from the samples will vary considerably
         from source to source, depending on the diversity of the industrial
         complex or municipality being sampled.  While general cleanup
         procedures are provided as part of this method, unique samples may
         require additional cleanup approaches to achieve the detection
         limits listed in Table 1.

4.  SAFETY

    4.1  The toxicity or careinogenicity of each reagent used in this method
         has not been precisely defined; however, each chemical compound
         should be treated as a potential health hazard.  From this
         viewpoint, exposure to these chemicals must be reduced to the
         lowest possible level by whatever means available.  The laboratory
         is responsible for maintaining a current awareness file of OSHA
         regulations regarding the safe handling of the chemicals specified
         in this method.  A reference file of material data handling sheets
         should also be made available to all personnel involved in the
         chemical analysis.  Additional references to laboratory safety are
         available and have been identified (2-4) for the information'of the
         analyst.

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5.  APPARATUS AND EQUIPMENT

    5.1  SAMPLE CONTAINERS - Narrow-mouth glass bottles, 1-liter or 1-quart
         volume, equipped with polytetrafluoroethylene (PTFE)-lined screw
         caps.  Wide-mouth glass bottles, 1-quart volume, equipped with
         PTFE-lined screw caps may also be used.  Prior to use,  wash bottles
         and cap liners with detergent and rinse with tap and distilled
         water.  Allow the bottles and cap liners to air dry, then muffle at
         400°C for 1 hour.  After cooling, rinse the cap liners  with hexane,
         seal the bottles, and store in a dust-free environment.

         5.1.1  Automatic sampler (optional)—Must incorporate glass sample
                containers for the collection of a minimum of 250 mL.
                Sample containers must be kept refrigerated at 4°C and
                protected from light during compositing.  If the sampler
                uses a peristaltic pump, a minimum length of compressible
                silicone rubber tubing may be used.  Before use, however,
                the compressible tubing should be thoroughly rinsed with
                methanol, followed by repeated rinsings with reagent water
                to minimize the potential for contamination of the sample.
                An integrating flow meter is  required to collect
                flow-proportional composites.

    5.2  KUDERNA-DANISH (K-D)  GLASSWARE

         5.2.1  Synder column—Three-ball macro (Kontes K-503000-0121 or
                equivalent).

         5.2.2  Concentrator tube—10-mL, graduated (Kontes K-570050-1025 or
                equivalent) with ground glass stopper.

         5.2.3  Evaporative flask—500-mL (Kontes K-570001-0500  or
                equivalent).  Attach to concentrator tube with springs.

    5.3  GAS CHROMATOGRAPHY SYSTEM

         5.3.1  The gas chromatograph must be equipped with a glass-lined
                injection port compatible with the detector to be used.  A
                data system is recommended for measuring peak areas.

                5.3.1.1 Column 1—180 cm long by 2 mm ID, glass, packed with
                        10 percent OV-11 on Gas Chrom W-HP (100/120 mesh) or
                        equivalent.

                5.3.1.2 Column 2—180 cm long by 2 mm ID, PyrexR glass,
                        packed with 3 percent Dexsil  300 on Chromasorb W-HP
                        (80/100 mesh) or equivalent.

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            5.3.1.3 Column 3—180 cm long by 2mm ID Glass, packed with 3
                    percent SP-2100 on Supelcoport (100/120 mesh) or
                    equivalent.

            5.3.1.4 Column 1 was used to develop the accuracy and
                    precision statements in Section 12.  Guidelines for
                    the use of alternate column packings are provided in
                    Section 10.3.1.

            5.3.1.5 Detector—Nitrogen/phosphorous.  This detector has
                    proven effective in the analysis of wastewaters for
                    the parameters listed in the scope and was used to
                    develop the method performance statements in Section
                    12.  Guidelines for the use of alternate detectors
                    are provided in Section 10.3.

5.4  CHROMATOGRAPHIC COLUMN—300 mm long x 10 mm ID Chromaflex, equipped
     with coarse fritted bottom plate and PTFE stopcock.  (Kontes
     K-420540-0213 or equivalent).

5.5  DRYING COLUMN—Approximately 400 mm long x 20 mm ID borosilicate
     glass, equipped with coarse fritted bottom plate.

5.6  MISCELLANEOUS

     5.6.1  Balance—analytical, capable of accurately weighing to the
            nearest 0.0001 g.

     5.6.2  Separatory funnel—two-liter, equipped with PTFE stopcock.

     5.6.3  Water bath—heated witheconcentric ring cover, capable of
            temperature control (±2eC).  The bath should be used in a
            hood.

     5.6.4  Standard solution storage containers—15-mL bottles with
            PTFE-lined screw caps.

     5.6.5  Boiling chips—Approximately 10/40 mesh.  Heat to 400°C for
            30 minutes or Soxhlet extract with methylene chloride.

REAGENTS AND CONSUMABLE MATERIALS

6.1  REAGENTS

     6.1.1  Acetone, hexane, and methylene chloride—demonstrated to be
            free of analytes.

     6.1.2  Florisil—PR grade (60/100 mesh).  Purchase activated at
            1250°F and store in glass containers with glass stoppers or
            foil-lined screw caps.  Before use, activate each batch over-
            night at 200°C in foil-covered glass containers.  To prepare
            for use, place the amount necessary for the number of
            columns to be run in a 500-mL reagent bottle and add 2

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                percent by weight of reagent water.  Seal and mix thoroughly
                by shaking or rolling for 10 minutes.  Allow to stand for at
                least 2 hours prior to use.  The mixture must be
                homogeneous.  Keep the bottle tightly sealed to ensure
                proper activity.

         6.1.3  Reagent water—reagent water is defined as a water in which
                an interferent is not observed at the method detection limit
                of each parameter of interest.

         6.1.4  Sodium hydroxide (NaOH) solution (ION)—dissolve 40 g NaOH
                in reagent water and dilute to 100 ml.

         6.1.5  Sodium sulfate—granular, anydrous.  Condition by heating at
                400°C for 4 hours in a shallow tray.

         6.1.6  Sulfuric acid (HgSO/j) solution (1+1)—add measured
                volume of concentrated H2$04 to equal volume of reagent
                water.

         6.1.7  Sodium thiosulfate—(ACS) Granular.


    6.2  STANDARD STOCK SOLUTIONS (1.00 ug/uL)—These solutions may be
         purchased as certified solutions or prepared from pure standard
         materials using the following procedures.

         6.2.1  Prepare standard stock solutions by accurately weighing
                about 0.0100 grams of pure material.  Dissolve the material
                in hexane or other suitable solvent and dilute to volume in
                a 10-mL volumetric flask.  Larger volumes can be used at the
                convenience of the analyst.  If compound purity is certified
                at 96% or greater, the weight can be used without correction
                to calculate the concentration of the standard stock.

         6,2.2  Store standard stock solutions at 4°C in 15-mL bottles
                equipped with PTFE-lined screw-caps.  Standard stock
                solutions should be checked frequently for signs of
                degradation or evaporation, especially just prior to
                preparing calibration standards from them.

         6.2.3  Standard stock solutions must be replaced after 6 months or
                sooner, if comparison with check standards indicates a
                problem.

7.  SAMPLE COLLECTION, PRESERVATION, AND STORAGE

    7.1  Collect all  samples in duplicate.  Grab samples must be collected
         in glass containers.  Conventional sampling practices (5) should be
         followed, except that the bottle must not be prewashed with sample
         before col lection.

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    7.2  The samples must be iced or refrigerated at 4°C from the time of
         collection until extraction.

    7.3  Chemical preservatives should not be used in the field unless more
         than 24 hours will elapse before delivery to the laboratory.  If
         the samples will not be extracted within 48 hours of collection,
         the sample should be adjusted to a pH range of 6.0 to 8.0 with
         sodium hydroxide or sulfuric acid.

    7.4  All samples must be extracted within 7 days and completely analyzed
         within 40 days of extraction (6).

8.  CALIBRATION AND STANDARDIZATION

    8.1  CALIBRATION

         8.1.1  A set of at least three calibration solutions containing the
                method analytes is needed.  One calibration solution should
                contain each analyte at a concentration approaching but
                greater than the estimated detection limit (Table 1) for
                that compound; the other two solutions should contain
                analytes at concentrations that bracket the range expected
                in samples.  For example, if the detection limit for a
                particular analyte is 0.2 ug/L, and a sample expected to
                contain approximately 5 yg/l is analyzed, solutions of
                standards should be prepared at concentrations representing
                0.3 ug/L, 5pg/l, and 10 pg/L for the particular analyte.

         8.1.2  To prepare a calibration solution, add an appropriate volume
                of a standard stock solution to a volumetric flask and
                dilute to volume with hexane.

         8.1.3  Starting with the standard of lowest concentration, analyze
                each calibration standard according to Section 10.3 and
                tabulate peak height or area responses versus the mass of
                analyte injected.  The results can be used to prepare a
                calibration curve for each compound.  Alternatively, if the
                ratio of response to concentration (calibration factor) is a
                constant over the working range (<10% relative standard
                deviation), linearity through the origin can be assumed and
                the average ratio or calibration factor can be used in place
                of a calibration curve.

         8.1.4  The working calibration curve or calibration factor must be
                verified on each working day by the measurement of one or
                more calibration standards.  If the response for any analyte
                varies from the predicted response by more than ±10%, the
                test must be repeated using a fresh calibration standard.
                If the results still do not agree, generate a new
                calibration curve.

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9.  QUALITY CONTROL

    9.1  MONITORING FOR INTERFERENCES

         Analyze a laboratory reagent blank each time a set of samples is
         extracted.  A laboratory reagent blank is a one-liter aliquot of
         reagent water.  If the reagent blank contains a reportable level of
         any analyte, immediately check the entire analytical system to
         locate and correct for possible interferences and repeat the test.

    9.2  ASSESSING ACCURACY

         9.2.1  After every 10 samples, and preferably in the middle of each
                day, analyze a laboratory control standard.  Calibration
                standards may not be used for accuracy assessments and the
                laboratory control standard may not be used for calibration
                of the analytical system.

                9.2.1.1 Laboratory Control  Standard Concentrate - from stock
                        standards prepared as described in Section 6.3,
                        prepare a laboratory control standard concentrate
                        that contains each analyte of interest at a
                        concentration of 2 ug/mL in acetone or other
                        suitable solvent.

                9.2.1.2 Laboratory Control  Standard - using a pipet, add
                        1.00 mL of the laboratory control standard
                        concentrate to a one-liter aliquot of reagent water.

                9.2.1.3 Analyze the laboratory control standard as described
                        in Section 10.  For each analyte in the laboratory
                        control standard, calculate the percent recovery
                        (P-j) with the equation:


                                    loo si
                        where S-j = the analytical results from the
                                   laboratory control standard, in pg/L; and
                              T-j = the known concentration of the spike,
                                   in ug/L.

         9.2.2  At least annually, the laboratory should participate in
                formal performance evaluation studies, where solutions of
                unknown concentrations are analyzed and the performance of
                all  participants is compared.

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    9.3  ASSESSING PRECISION

         9.3.1  Precision assessments for this method are based upon the
                analysis of field duplicates (Sect. 7.1).  Analyze both
                sample bottles for at least 10% of all samples.  To the
                extent practical, the samples for duplication should contain
                reportable levels of most of the analytes.

         9.3.2  For each analyte in each duplicate pair, calculate the
                relative range (7) (RRi) with the equation:
                              100 R,
                     RRi
                where   Rj =    the absolute difference between the
                                duplicate measurements Xj and Xg, in
                                ug/L; and
                        X-j =    the average concentration found ([Xj +
                                X2]/2), in wg/L.

         9.3.3  Individual relative range measurements are pooled to
                determine average relative range or to develop an expression
                of relative range as a function of concentration.

10. PROCEDURE

    10.1 SAMPLE EXTRACTION

         10.1.1 Mark the water meniscus on the side of the sample bottle for
                later determination of sample volume.  Pour the entire
                sample into a 2-liter separatory funnel.  Check the pH of
                the sample with wide-range pH paper and adjust to within the
                range of 5 to 9 with sodium hydroxide or sulfuric acid.

         10.1.2 Add 60 ml of methylene chloride to the sample bottle and
                shake for 30 seconds to rinse the walls.  Transfer the
                solvent to the separatory funnel and extract the sample by
                shaking the funnel for 2 minutes with periodic venting to
                release vapor pressure.  Allow the organic layer to separate
                from the water phase for a minimum of 10 minutes.  If the
                emulsion interface between layers is more than one-third the
                volume of the solvent layer, the analyst must employ
                mechanical techniques to complete the phase separation.  The
                optimum technique depends on the sample, but may include
                stirring, filtration of the emulsion through glass wool, or
                centrifugation.  Collect the extract in a 250-mL Erlenmeyer
                flask.

         10.1.3 Add an additional 60-mL volume of methylene chloride to the
                sample bottle and complete the extraction procedure a second
                time, combining the extracts in the Erlenmeyer flask.

         10.1.4 Perform a third extraction in the same manner.  Pour the
                combined extract through a drying column containing about

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       10 cm of anhydrous sodium sulfate, and collect it in a
       500-mL K-D flask equipped with a 10 ml concentrator tube.
       Rinse the Erlenmeyer flask and column with 20 to 30 ml of
       methylene chloride to complete the quantitative transfer.

10.1.5 Add one or two clean boiling chips to the flask and attach a
       three-ball Snyder column.  Prewet the Snyder column by
       adding about 1 ml of methylene chloride to the top.  Place
       the K-D apparatus on a hot water bath (80 to 85°C) so that
       the concentrator tube is partially immersed in the hot water
       and the entire lower rounded surface of the flask is bathed
       in steam.  Adjust the vertical position of the apparatus and
       the water temperature as required to complete the
       concentration in 15 to 20 minutes.  At the proper rate of
       distillation, the balls of the column will actively chatter
       but the chambers will not flood.  When the apparent volume
       of liquid reaches 1 ml_, remove the K-D apparatus and allow
       it to drain and cool for at least 10 minutes.  Remove the
       Snyder column and rinse the flask and its lower joint into
       the concentrator tube with 1 to 2 ml of methylene chloride.

10.1.6 For FlorisilR column cleanup or gas chromatography, the
       extract must be in hexane solution.  To exchange the solvent
       to hexane, add one or two fresh boiling chips to the flask
       and ampul containing the extract, add 50 ml of hexane, and
       reattach the Snyder column.  Pour about 1 mL of hexane into
       the top of the Snyder column, and concentrate the extract at
       85 to 95°C in the hot-water bath as above.  When the
       apparent volume of liquid reaches 1 mL, remove the K-D
       apparatus from the water bath and allow it to drain and cool
       for at least 10 minutes.

10.1.7 Remove the Snyder column, rinse the flask and its lower
       joint into the concentrator tube with 1 to 2 ml of hexane.
       A 5-mL syringe is recommended for this operation.  Dilute to
       10 mL with hexane for analysis by gas chromatography
       (Section 10.3) if cleanup is not required. If the extract
       requires cleanup, proceed to Section 10.2.  If the extracts
       will be stored longer than 2 days, they should be
       transferred to Teflon-sealed screw-cap bottles.  Proceed
       with gas chromatographic analysis.

10.1.8 Determine the original sample volume by refilling the sample
       bottle to the mark and transferring the liquid to a 1,000 mL
       graduated cylinder.  Record the sample volume to the nearest
       5 mL.

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10.2 CLEANUP AND SEPARATION

     10.2.1 Cleanup procedures may not be necessary for a relatively
            clean sample matrix.  The cleanup procedures recommended in
            this method have been used for the analysis of alachlor,
            butachlor, diphenamid and lethane in various clean waters
            and municipal effluents.  The use of Florisil^ as the
            cleanup material for fluridone and norflurazon has been
            demonstrated to yield recoveries of less than 50 percent,
            and is not recommended as a cleanup material for these
            compounds.  Use of specific detectors may obviate the
            necessity for cleanup of relatively clean sample matrices.
            If particular circumstances demand the use of an alternative
            cleanup procedure, the analyst must determine the elution
            profile and demonstrate that the recovery of each compound
            of interest is no less than 85 percent.

     10.2.2 Place the necessary amount of deactivated Florisil^ into a
            20-mm-IO chromatographic column and tap the column to settle
            the FlorisilR.  Add 1 to 2 cm of anhydrous sodium sulfate
            to the top of the Florisil^.

     10.2.3 Pre-elute the column with 50 to 60 ml of hexane.  Discard
            the eluate and, just prior to exposure of the sodium sulfate
            layer to the air, transfer the sample extract onto the
            column by decantation.  Complete the transfer by rinsing
            with two additional 2-mL volumes of hexane.  Alternatively,
            a measured aliquot of the extract may be taken for cleanup.

     10.2.4 Just prior to exposure of the sodium sulfate layer to the
            air, elute the column with 100 ml hexane.  Discard the
            eluate and repeat the elution with 200 mL of 6-percent
            acetone in hexane (volume/volume).  Collect the eluate in a
            500-mL K-D flask equipped with a 10-mL concentrator tube
            (Fraction 1).  All elutions should be carried out using a
            flowrate of about 5 mL/minute.

     10.2.5 Perform a second elution with 200 mL of 15-percent acetone
            in hexane (Fraction 2).  Collect each fraction in a separate
            K-D apparatus.  The elution pattern for these compounds is
            shown in Table 3.

     10.2.6 Determine, from Table 3, the fractions of interest and
            concentrate by standard K-D technique, as indicated in
            Paragraph 10.1.5, using hexane in place of methylene
            chloride, to a volume of 10 mL.

     10.2.7 Analyze the fractions by gas chromatography.

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10.3 GAS CHROMATOGRAPHY ANALYSIS

     10.3.1 Recommended columns and detectors, and operating conditions
            for the gas chromatography system are described in Section
            5.3.  Table 1 summarizes the recommended operating
            conditions for the gas chromatograph.  Included in this
            table are estimated retention times and detection limits
            that can be achieved by this method.  Examples of the
            separations achieved are shown in Figures 1-3.  Other packed
            columns, chromatographic conditions, or detectors may be
            used if data quality comparable to Table 2 is achieved.
            Capillary (open-tubular) columns may also be used if the
            relative standard deviations of responses for replicate
            injections are demonstrated to be less than 6 percent and
            data quality comparable to Table 2 is achieved.

     10.3.2 Inject 2 to 5 uL of the sample extract using the
            solvent-flush technique (8).  Record the volume injected to
            the nearest 0.05 pL, the total extract volume, and the
            resulting peak size in area or peak height units.

     10.3.3 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
            the day.  Three times the standard deviation of a retention
            time for a compound can be used to calculate a suggested
            window size; however, the experience of the analyst should
            weigh heavily in the interpretation of chromatograms.

     10.3.4 If the response for the peak exceeds the working range of
            the system, dilute the extract and reanalyze.

     10.3.5 If the measurement of the peak response is prevented by the
            presence of interferences, further cleanup is required.

11.  CALCULATIONS

     11.1   Determine the concentration (C) of individual compounds in
            the sample in ug/L with the equation:

                               (A) (Vt)

                             ~
            where  A = amount of material injected, in nanograms;
                  V-j = volume of extract injected, pL;
                  Vt = volume of total extract, uL; and
                  Vs = volume of water extracted, mL.

     11.2   Report the results for the unknown samples in pg/L.  Round
            off the results to the nearest 0.1 ug/L or two significant
            figures.

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12.  METHOD PERFORMANCE

     12.1 Estimated detection limits (EDL) and associated
          chromatographic conditions are listed in Table l.(9)  The
          detection limits were calculated from the minimum detectable
          response of the EC detector equal to 5 times the GC background
          noise, assuming a 10-mL final extract volume of a 1-liter
          sample and a GC injection of 5 pL.

     12.2 Single laboratory accuracy and precision studies were
          conducted by Environmental Science and Engineering (6), using
          spiked samples.  The results of these studies are presented in
          Table 2.

13.  GC/MS CONFIRMATION

     13.1 It is recommended that GC/MS techniques be judiciously
          employed to support qualitative identifications made with this
          method.  The mass spectrometer should be capable of scanning
          the mass range from 35 AMU to a mass 50 AMU above the
          molecular weight of the compounds of interest.  The instrument
          must be capable of scanning the mass range at a rate to
          produce at least 5 scans per peak, but not to exceed 7 scans
          per peak utilizing a 70-V (nominal) electron energy in the
          electron impact ionization mode.  A GC to MS interface
          constructed of all-glass or glass-lined materials is
          recommended.  A computer system should be interfaced to the
          mass spectrometer that allows the continuous acquisition and
          storage on machine-readable media of all mass spectra obtained
          throughout the duration of the chromatographic program.

     13.2 Gas chromatographic columns and conditions should be selected
          for optimum separation and performance.  The conditions
          selected must be compatible with standard GC/MS operating
          practices.  Chromatographic tailing factors of less than 5.0
          must be achieved.  The calculation of tailing factors is
          illustrated in Method 625 (10).

     13.3 At the beginning of each day that confirmatory analyses are to
          be performed, the GC/MS system must be checked to see that all
          DFTPP performance criteria are achieved (11).

     13.4 To confirm an identification of a compound, the background
          corrected mass spectrum of the compound must be obtained from
          the sample extract and compared with a mass spectrum from a
          stock or calibration standard analyzed under the same
          chromatographic conditions.  It is recommended that at least
          25 nanograms of material be injected into the GC/MS.  The
          criteria below must be met for qualitative confirmation.

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     13.4.1    The molecular ion and other ions that are present
               above 10-percent relative abundance in the mass
               spectrum of the standard must be present in the mass
               spectrum of the sample with agreement to plus or
               minus 10 percent.  For example, if the relative
               abundance of an ion is 30 percent in the mass
               spectrum of the standard, the allowable limits for
               the relative abundance of that ion in the mass
               spectrum for the sample would be 20 to 40 percent.

     13.4.2    The retention time of the compound in the sample
               must be within 6 seconds of the same compound in the
               standard solution.

     13.4.3    Compounds that have similar mass spectra can be
               explicitly identified by GC/MS only on the basis of
               retention time data.

13.5 Where available, chemical ionization mass spectra may be
     employed to aid in the qualitative identification process.

13.6 Should these MS procedures fail to provide satisfactory
     results, additional steps may be taken before reanalysis.
     These may include the use of alternate packed or capillary GC
     columns or additional cleanup.

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REFERENCES

    1.   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.

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

    3.   "OSHA Safety and Health Standards, General  Industry" (29 CFR 1910),
         Occupational Safety and Health Administration, OSHA 2206 (Revised,
         January 1976).

    4.   "Safety in Academic Chemistry Laboratories," American Chemical
         Society Publication, Committee on Chemical  Safety, 3rd Edition,
         1979.

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

    6.   Test procedures for Pesticides in Wastewaters, EPA Contract Report
         #68-03-2897.  Unpublished report available  from U.S. Environmental
         Protection Agncy, Environmental Monitoring  and Support Laboratory,
         Cincinnati, Ohio 45268.

    7.   "Handbook for Analytical Quality Control in Water and Wastewater
         Laboratories," EPA-600/4-79-019, U.S. Environmental Protection
         Agency, Environmental Monitoring and Support Laboratory -
         Cincinnati, Ohio 45268, March 1979.

    8.   Burke, J.A., "Gas Chromatography for Pesticide Residue Analysis;
         Some Practical Aspects," Journal of the Association of Official
         Analytical Chemists, 48, 103/ (1965).

    9.   "Evaluation of Ten Pesticide Methods," U.S. Environmental
         Protection Agency, Contract No. 68-03-1760, Task No. 11, U.S.
         Environmental Monitoring and Support Laboratory, Cincinnati, Ohio
         45268 (In Preparation).

   10.   "Methods for Organic Chemical Analysis of Municipal and Industrial
         Wastewater" EPA-600/4-82-057, U.S. Environmental Protection Agency,
         Environmental Monitoring and Support Laboratory - Cincinnati, Ohio
         45268.

    11.  Eichelberger, J.W., Harris, L.E., and Budde, W.L., Anal. Chem., 46,
         1912 (1975).

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                                    Table 1
              Gas  Chromatography and Detection  Limits of Certain
                              Amines and Lethane
Parameter
           Retention Time (minutes)
        Column 1Column 2Column 3
  Estimated
Detection Limit
      (ug/L)
Alachlor
Butachlor
Diphenamide
Fluridone
Lethane
Norflurazon
6.9 —
10.5
10.8 —
2.2 2.45 2.1
2.0 —
18.4 —
0.2
0.3
0.2
0.5
0.1
0.02
Column 1:
180 cm long by 2 mm ID glass, packed with 10-percent OV-11 on Gas
Chrom W-HP, 100/120 mesh; nitrogen carrier gas at a flow rate of
30 mL/min.  Column temperature is held at 225°C for 4 min. after
injection and then programmed to 275°C at 4°/min and held for 8
min.
Column 2:
Column 3:
180 cm long by 2 mm ID glass, packed with 3-percent Dexsil 300 on
Chromasorb W-HP, 80/100 mesh; nitrogen carrier gas at a flow rate
of 30 mL/min.  Column temperature at 300°C isothermal.

180 cm long by 2 mm ID glass, packed wtih 3-percent SP-2100 on
Supelcoport, 100/120 mesh; nitrogen carrier gas at a flow rate of
40 mL/min.  Column temperature at 275'C isothermal.

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                                    Table  2
                   Single Laboratory Accuracy and Precision
Relative
Parameter
Alachlorn


Butachlor


Diphenamid
Fluridone**


Lethane


Norf lurazon**

* 1
2
3

Spike Average Standard
Matrix Range Number of Percent Deviation
Type* (ug/L) Replicates Recovery (%)
1
1
1
1
2
3
1
1
1
1
1
3
= Manufacturing
= Manufacturing
= Manufacturing
255
996
286
1,420
9.3
740
20.8
998
167
576
243
1,048
effluent wastewaters.
effluent wastewater +
effluent wastewater +
7
7
7
7
7
7
7
7
7
7
7
7
POTW
POTW
113
104
93
92
100
98
92
88
93
97
89
102
effluent at
effluent at


.1
.8
.8
.0
.4
.3
.6
.5

a
a
9.
13.
8.
4.
14.
7.
11.
11.
19.
29.
7.
- 6.
ratio of 1
ratio of 1
0
3
2
3
2
0
5
4
9
4
4
1
:200.
:1.
**    Florisil cleanup not employed.

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                                    Table  3
                         Florisil* Cleanup Recoveries
Solvent
Fraction**
1
2
Average Percent Recoveries
Alachlor Butachlor Diphenamid
103 95
ND ND 96
Lethane
106
ND
*  Two-percent deactivated.
** 1 = 6-percent acetone/hexane.
   2 = 15-percent acetone/hexane.

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u

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                                  r»VTF
U.S.  Environmental Protection Agency
Region V, Library
230  South Dearborn Street
Chicago,  Illinois  60604

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                024
                 Retention Time (H1n.)
FIGURE 3.  GAS CHROMATOGRAH OF FLURIOOME,' COLUMN 3.

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