EPA Document #: 815-R-05-005
METHOD 527     DETERMINATION OF SELECTED PESTICIDES AND FLAME
                 RETARD ANTS IN DRINKING WATER BY SOLID PHASE
                 EXTRACTION AND CAPILLARY COLUMN GAS
                 CHROMATOGRAPHY/ MASS SPECTROMETRY (GC/MS)
                                  Revision 1.0
                                  April 2005
Ed K. Price, Brahm Prakash, Mark M. Domino, and Barry V. Pepich (Shaw Environmental, Inc.)
David J. Munch (U.S. EPA, Office of Ground Water and Drinking Water)
                         TECHNICAL SUPPORT CENTER
               OFFICE OF GROUND WATER AND DRINKING WATER
                  U. S. ENVIRONMENTAL PROTECTION AGENCY
                            CINCINNATI, OHIO 45268
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                                    METHOD 527.0

     DETERMINATION OF SELECTED PESTICIDES AND FLAME RETARDANTS IN
 DRINKING WATER BY SOLID PHASE EXTRACTION AND CAPILLARY COLUMN GAS
                CHROMATOGRAPHY/ MASS SPECTROMETRY (GC/MS)
1.  SCOPE AND APPLICATION

   1.1   This is a gas chromatography/mass spectrometry (GC/MS) method for the determination of
        selected semivolatile organic compounds in drinking waters. Accuracy and precision data
        have been generated in reagent water, finished ground and surface water for the compounds
        listed in the table below.  The single laboratory Lowest Concentration Minimum Reporting
        Level (LCMRL) has also been determined in reagent water.(1)
Analyte
Atrazine
Bifenthrin
Bromacil
Chlorpyrifos
Dimethoate
Esbiol
Esfenvalerate*
Fenvalerate*
Hexabromobiphenyl
2,2',4,4',5,5'-Hexabromodiphenyl ether (BDE-153)
Hexazinone
Kepone*
Malathion
Mirex
Norflurazon*
Nitrofen*
Oxychlordane
Parathion*
2,2',4,4',5-Pentabromodiphenyl ether (BDE-99)
2,2',4,4',6-Pentabromodiphenyl ether (BDE-100)
Prometryne
Propazine
Terbufos-sulfone
Chemical Abstract Services
Registry Number (CASRN)
1912-24-9
82657-04-3
314-40-9
2921-88-2
60-51-5
28434-00-6
66230-04-4
51630-58-1
59080-40-9
68631-49-2
51235-04-2
143-50-0
121-75-5
2385-85-5
27314-13-2
1836-75-5
27304-13-8
56-38-2
60348-60-9
189084-64-8
7287-19-6
139-40-2
56070-16-7
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Analyte
2,2',4,4'-Tetrabromodiphenyl ether (BDE-47)
Thiobencarb
Vinclozolin
Chemical Abstract Services
Registry Number (CASRN)
5436-43-1
28249-77-6
50471-44-8
         *These are potential problem compounds (Sect. 13.2).

    1.2   The Minimum Reporting Level (MRL) is the lowest analyte concentration that meets Data
         Quality Objectives (DQOs) that are developed based on the intended use of this method.  The
         single laboratory lowest concentration MRL (LCMRL) is the lowest true concentration for
         which the future recovery is predicted to fall, with high confidence (99 percent), between 50
         and 150 percent recovery. The procedure used to determine the LCMRL is described
         elsewhere.1

    1.3   Laboratories using this method will not be required to determine the LCMRL for this method,
         but will need to demonstrate that their laboratory MRL for this method meets the require-
         ments described in Section 9.2.4.

    1.4   Determining the Detection Limit (DL) for analytes in this method is optional (Sect. 9.2.6).
         Detection limit is defined as the statistically calculated minimum concentration that can be
         measured with  99% confidence that the reported value is greater than zero.2 The DL is
         compound dependent and is dependent on extraction efficiency, sample matrix, fortification
         concentration, and instrument performance.

    1.5   This method is intended for use by analysts skilled in solid phase extractions, the operation  of
         GC/MS instruments, and the interpretation of the associated data.

2.  SUMMARY OF METHOD

    2.1   A 1-liter water sample is fortified with surrogates and passed through a solid phase extraction
         (SPE) disk containing polystyrenedivinylbenzene (SDVB) to extract the target analytes and
         surrogates.  The compounds are eluted from the solid phase with a small amount of ethyl
         acetate (EtOAc) and methylene chloride  (MeCb). The extract is dried by passing it through a
         column of anhydrous sodium sulfate, concentrated with nitrogen, and then adjusted to a 1-mL
         volume with ethyl acetate after adding the internal standard. A l-|iL, splitless injection is
         made into a GC equipped with a high-resolution fused silica capillary column that is
         interfaced to a MS.  The analytes are separated and identified by comparing the acquired  mass
         spectra and retention times to reference spectra and retention times for calibration standards
         acquired under identical GC/MS  conditions.  The concentration of each analyte is determined
         by using  the internal standard technique.  Surrogate analytes are added to all Field and Quality
         Control (QC) Samples to monitor the extraction efficiency of the target analytes.
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3.  DEFINITIONS

   3.1   ANALYSIS BATCH - A set of samples that is analyzed on the same instrument during a
         24-hour period that begins and ends with the analysis of the appropriate Continuing Calibra-
         tion Check (CCC) Standards. Additional CCCs may be required depending on the length of
         the analysis batch and/or the number of Field Samples.

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

   3.3   CONTINUING CALIBRATION CHECK (CCC) STANDARD - A calibration standard
         containing one or more method analytes, which is analyzed periodically to verify the accuracy
         of the existing calibration for those analytes.

   3.4   DETECTION LIMIT (DL)  The minimum concentration of an analyte that can be identified,
         measured and reported with 99% confidence that the analyte concentration is greater than
         zero.  This is a statistical determination (Sect. 9.2.5), and accurate quantitation is not expected
         at this level.2

   3.5   EXTRACTION BATCH - A set of up to 20 Field Samples (not including QC samples)
         extracted together by the same person(s) during a work day using the same lot of solid phase
         extraction devices, solvents, surrogate solution, and fortifying solutions. Required QC
         samples include Laboratory Reagent Blank, Laboratory Fortified Blank, Laboratory Fortified
         Matrix, and either a Field Duplicate or Laboratory Fortified Matrix Duplicate.

   3.6   FIELD DUPLICATES (FD1 and FD2) - Two separate samples collected at the same time
         and placed 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.

   3.7   INTERNAL STANDARD (IS) - A pure analyte added to an extract or standard solution in a
         known amount and used to measure the relative responses of other method analytes and
         surrogates. The internal standard must be an analyte that is not a sample component.
   3.8   LABORATORY FORTIFIED BLANK (LFB) - An aliquot of reagent water or other blank
         matrix to which known quantities of the method analytes and all the preservation compounds
         are added. The LFB is processed and 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.

   3.9   LABORATORY FORTIFIED SAMPLE MATRIX (LFSM)  - An aliquot of a Field Sample to
         which known quantities of the method analytes and all the preservation compounds are added.
         The LFSM is processed and analyzed exactly like a sample, and its purpose is to determine
         whether the sample matrix contributes bias to the analytical results.  The background
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      concentrations of the analytes in the sample matrix must be determined in a separate aliquot
      and the measured values in the LFSM corrected for background concentrations.

3.10  LABORATORY FORTIFIED SAMPLE MATRIX DUPLICATE (LFSMD) - A second
      aliquot of the Field Sample used to prepare the LFSM, which is fortified, extracted and
      analyzed identically to the LFSM.  The LFSMD is used instead of the Field Duplicate to
      access method precision and accuracy when the occurrence of a target analyte is infrequent.

3.11  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, sample preservatives, internal standards, and surrogates that are used in the
      extraction batch. The LRB is used to determine if method analytes or other interferences are
      present in the laboratory environment, the reagents, or the apparatus.

3.12  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.

3.13  LOWEST CONCENTRATION MINIMUM REPORTING LEVEL (LCMRL) - The single-
      laboratory LCMRL is the lowest true concentration for which the future recovery is predicted
      to fall, with high confidence (99 percent), between 50 and 150 percent recovery/1-*

3.14  MINIMUM REPORTING LEVEL (MRL) - The minimum concentration that  can be reported
      by a laboratory as a quantitated value for a target analyte in a sample following analysis.  This
      defined concentration must meet the criteria defined in Section 9.2.2 and must  not be any
      lower than the concentration of the lowest continuing calibration check standard for that
      analyte.

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

3.16  QUALITY CONTROL SAMPLE (QCS) -A sample prepared using a PDS of method analytes
      that is obtained from a source external to the laboratory and different from the  source of
      calibration standards. The second source PDS and the surrogate PDS are used  to fortify the
      QCS at a known concentration. The QCS is used to check calibration standard integrity.

3.17  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.

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

   4.1   All glassware must be meticulously cleaned.  Wash glassware with detergent and tap water,
         rinse with tap water, followed by reagent water.  Non-volumetric glassware can be heated in a
         muffle furnace at 400 C for 2 hours as a substitute for a solvent rinse. Volumetric glassware
         should not be heated in an oven above 120 C.

   4.2   Method interferences may be caused by contaminants in solvents, reagents (including reagent
         water), sample bottles and caps, and other sample processing hardware that lead to discrete
         artifacts and/or elevated baselines in the chromatograms.  All items such as these must be
         routinely demonstrated to be free from interferences (less than l/j the MRL for each target
         analyte) under the conditions of the analysis by analyzing laboratory reagent blanks as
         described in Section 9.3.1.  Subtracting blank values from sample results is not permitted.

   4.3   Matrix interferences may be caused by contaminants that are co-extracted from the sample.
         The extent of matrix interferences will vary considerably from source to source, depending
         upon the nature of the water. Water samples high in total organic carbon (TOC) may have
         elevated baseline or interfering peaks.

   4.4   Relatively large quantities of the buffer and preservatives (Sect. 8.1.1) are added to sample
         bottles.  The potential exists for trace-level organic contaminants in these reagents. Interfer-
         ences from these sources should be monitored by analysis of laboratory reagent blanks, par-
         ticularly when new lots of reagents are acquired.

   4.5   Solid phase extraction disks have been observed to be a source of interferences.  The analysis
         of field and laboratory reagent blanks can provide important information regarding the
         presence or absence of such interferences. Brands and lots of solid phase extraction devices
         should be tested to ensure that contamination does not preclude analyte  identification and
         quantitation.

   4.6   Analyte carryover may occur when a relatively "clean" sample is analyzed immediately after
         a sample containing relatively high concentrations of compounds. Syringes and splitless
         injection port liners must be cleaned carefully or replaced as needed.  After analysis of a
         sample containing high concentrations of compounds, a laboratory reagent blank should be
         analyzed to ensure that accurate values are obtained for the next sample.

   4.7   Silicone compounds may be leached from punctured autosampler vial septa, particularly when
         particles of the septa sit in the vial.  This can occur after repeated injections of the same
         autosampler vial. These silicone compounds, which appear as regularly spaced
         chromatographic peaks with similar fragmentation patterns, can unnecessarily complicate the
         total ion chromatograms and may cause interferences at high levels.

   4.8   Quantitation of bromacil should be reviewed for potential common interferences. The
         quantitation ion suggested in Table 2 (205 m/z) can be found in the SDVB solid phase, and so
         method blanks should be carefully examined for this potential interference. The ion at 207
         m/z may be used as an alternate quantitation ion; however, this ion is associated with column
         bleed.

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5.  SAFETY

   5.1   The toxicity or carcinogen!city of each reagent used in this method has 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 an awareness
         of OSHA regulations regarding safe handling of chemicals used in this method. A reference
         file of MSDSs should be made available to all personnel involved in the chemical analysis.
         Additional references to laboratory safety are available.3"5

   5.2   Pure standard materials and stock standard solutions of these compounds should be handled
         with suitable protection to skin and eyes, and care should be taken not to breathe the vapors or
         ingest the materials.

6.  EQUIPMENT AND SUPPLIES (All specifications are suggested. Catalog numbers are included
   for illustration only.)

   6.1   SAMPLE CONTAINERS - 1-liter amber glass bottles fitted with polytetrafluoroethylene
         (PTFE) lined screw caps.

   6.2   VIALS - Various sizes of amber glass vials with PTFE-lined screw caps for storing standard
         solutions and extracts. Amber glass 2-mL autosampler vials with PTFE faced septa.

   6.3   VOLUMETRIC FLASKS - Class A, suggested sizes include 1, 5, and 10 mL for preparation
         of standards and dilution of extract to final volume.

   6.4   GRADUATED CYLINDERS - Suggested sizes include 5, 10,  and 250 mL.

   6.5   MICRO SYRINGES - Suggested sizes include 10, 25, 50, 100, 250, 500, and 1000 |iL.

   6.6   DRYING COLUMN - The drying column must be able to contain 5 to 7 g of anhydrous
         sodium sulfate  (Na2SO4).  The drying  column should not leach  interfering compounds or
         irreversibly adsorb target analytes. Any small glass column may be used, such as a glass
         pipette with glass wool plug (Chase Scientific Glass, Inc. PI005, 4.5 mL Monstr-Pette or
         equivalent).

   6.7   CONICAL COLLECTION TUBES - 50 mL,  or other glassware (Fisher Cat. No.:  05-569-
         6C) suitable for collection of the eluent from the solid phase  disk after extraction and for
         collecting extract from drying tube.

   6.8   ANALYTICAL BALANCE - Capable of weighing to the nearest 0.0001 g.

   6.9   SOLID PHASE EXTRACTION (SPE) APPARATUS USING DISKS

      6.9.1  SPE DISKS - 47-mm diameter and 0.5-mm thick, manufactured with a
             polystyrenedivinylbenzene (SDVB) sorbent phase (Varian Cat. No.: 1214-5010 or
             equivalent).
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   6.9.2   SPE DISK EXTRACTION GLASSWARE - funnel, PTFE-coated support screen, PTFE
          gasket, base, and clamp used to support SPE disks and contain samples during extraction.
          May be purchased as a set (Fisher Cat. No.:  K971100-0047 or equivalent) or separately.

   6.9.3   VACUUM EXTRACTION MANIFOLD - Designed to accommodate extraction
          glassware and disks (Varian Cat. No.: 1214-6001 or equivalent).

   6.9.4   An automatic or robotic system designed for use with SPE cartridges may be used if all
          quality control requirements discussed in Section 9 are met.  Automated systems may use
          either vacuum or positive pressure to process samples and solvents through the cartridge.
          All extraction and elution steps must be the same as in the manual procedure.  Extraction
          and/or elution  steps may not be changed or omitted to accommodate the use of an
          automated system.

6.10   EXTRACT CONCENTRATION SYSTEM - Extracts are concentrated by blowdown with
      nitrogen using water bath set at 40 C (Meyer N-Evap, Model 111, Organomation Associates,
      Inc., or equivalent).

6.11   LABORATORY OR ASPIRATOR VACUUM SYSTEM - Sufficient capacity to maintain a
      vacuum of approximately 15 to 25 inches of mercury for extraction disks.

6.12   GAS CHROMATOGRAPH/MASS SPECTROMETER (GC/MS) SYSTEM

   6.12.1  FUSED SILICA CAPILLARY GC COLUMN - 30 m x 0.25-mm inside diameter (i.d.)
          fused silica capillary column coated with a 0.25um bonded film of poly (dimethylsiloxy)
          poly(l,4-bis(dimethylsiloxy)phenylene)siloxane (J&W DB-5MS or equivalent).  Any
          capillary column that provides adequate  capacity, resolution, accuracy, and precision as
          summarized in Section 17 may be used.  A nonpolar, low-bleed column is recommended
          for use with this method to provide adequate chromatography and minimize column
          bleed.

   6.12.2  GC INJECTOR AND OVEN - Equipped for split/splitless injection. Some of the target
          compounds included in this method like  the brominated diphenyl ethers (BDEs) are
          subject to thermal breakdown in the injector port. This increases when the injector is not
          properly deactivated or at excessive temperatures. The injection system must not allow
          analytes to contact hot stainless steel or other metal surfaces that promote decomposition.
          The performance data in Section 17 was obtained using hot, splitless injection using a 2-
          mm i.d. glass deactivated liner (HP Cat. No.:  5181-8818).  Other injection techniques
          such as temperature programmed injections, cold on-column injections and large volume
          injections may be used if the QC criteria in Section 9 are met. Equipment designed
          appropriately for these alternate types of injections must be used if these options are
          selected.

   6.12.3  GC/MS INTERFACE - Interface should allow the capillary column or transfer line exit
          to be placed within a few millimeters of the ion source. Other interfaces, like jet separa-
          tors, are acceptable as long as the system has adequate sensitivity and QC performance
          criteria are met.

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       6.12.4 MASS SPECTROMETER - The MS must be capable of electron ionization at a nominal
             electron energy (e.g., 70 eV is recommended) to produce positive ions. The spectrometer
             must be capable of scanning at a minimum from 45 to 650 m/z with a complete scan
             cycle time (including scan overhead) of 1.0 second or less. (Scan cycle time = total MS
             data acquisition time in seconds divided by number of scans in the chromatogram).  The
             spectrometer should produce a mass spectrum that meets all criteria in Table 1 when a
             solution containing approximately 5 ng of decafluorotriphenyl phosphine (DFTPP) is
             injected into the GC/MS. Use a single spectrum at the apex of the DFTPP peak, an
             average spectrum of the three highest points of the peak, or an average spectrum across
             the entire peak to evaluate the performance of the system. The scan time should be set so
             that all analytes have a minimum of at least five scans across the chromatographic peak.
             Ten to 15 scans across chromatographic peaks are recommended.

       6.12.5 DATA SYSTEM - An interfaced data system is required to acquire, store, and output MS
             data. The computer software should have the capability of processing stored GC/MS data
             by recognizing a GC peak within a given  retention time window.  The software must
             allow integration of the ion abundance of any specific ion between specified time or scan
             number limits. The software must be able to calculate relative response factors (RRFs),
             construct linear regressions or quadratic calibration curves, and calculate analyte
             concentrations.

7.  REAGENTS AND STANDARDS

   7.1   REAGENTS AND SOLVENTS - Reagent grade or better chemicals should be used in all
         tests. Unless otherwise indicated, it is intended that all reagents will conform to the
         specifications of the Committee on Analytical Reagents of the American Chemical Society
         (ACS), where such specifications are available. Other grades may be used, provided it is first
         determined that the reagent is of sufficiently high purity to permit its use without lessening the
         quality of the determination.

       7.1.1  HELIUM - 99.999 percent or better, GC carrier gas.

       7.1.2  REAGENT WATER - Purified water which does not contain any measurable quantities
             of any target analytes or interfering compounds at or above l/j the MRL  for each
             compound of interest.

       7.1.3  METHANOL (MeOH) (CASRN 67-56-1) - High purity, demonstrated to be free of
             analytes and interferences (Fisher, GC Resolve Grade or equivalent).

       7.1.4  ETHYL ACETATE (EtOAc) (CASRN 141-78-6) - High purity, demonstrated to be free
             of analytes and interferences (B& J Brand, High Purity Solvent Grade or equivalent).

       7.1.5  METHYLENE CHLORIDE (MeCl2) (CASRN 75-09-02) - High purity, demonstrated to
             be free of analytes and interferences (B& J Brand GC2, Capillary GC/GC-MS Grade or
             equivalent).

       7.1.6  SODIUM SULFATE (Na2SO4), ANHYDROUS (CASRN 7757-82-6) - Soxhlet
             extracted with methylene chloride for a minimum of four hours or heated to 400 C for
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          two hours in a muffle furnace. An "ACS grade, suitable for pesticide residue analysis,"
          or equivalent, of anhydrous sodium sulfate is recommended.

   7.1.7   SAMPLE PRESERVATION REAGENTS - These preservatives are solids at room
          temperature and may be added to the sample bottle before shipment to the field.

      7.1.7.1   POTASSIUM DfflYDROGEN CITRATE (CASRN 866-83-1) - The sample must
               be buffered to pH 3.8 to inhibit microbial growth and analyte degradation.

      7.1.7.2   L-ASCORBIC ACID (CASRN 50-81-7) - Ascorbic acid reduces "free chlorine" at
               the time of sample collection (ACS Reagent Grade or equivalent).

      7.1.7.3   ETHYLENEDIAMINETETRAACETIC ACID (EDTA), TRISODIUM SALT
               (CASRN 10378-22-0) - Trisodium EDTA is added to inhibit metal-catalyzed
               hydrolysis of analytes.

7.2   STANDARD SOLUTIONS - When a compound purity is assayed to be 96 percent or greater,
      the weight can be used without correction to calculate the concentration of the stock standard.
      Solution concentrations listed in this section were used to develop this method and are
      included as an example.  Standards for sample fortification generally should be prepared in
      the smallest volume that can be accurately measured to minimize the addition of excess
      organic solvent to aqueous samples. Even though stability times for standard solutions
      are suggested in the following sections, laboratories should use standard QC practices to
      determine when their standards need to be replaced.

   7.2.1   INTERNAL STANDARD (IS) SOLUTIONS - This method uses three internal standard
          compounds listed in the table below.
Internal Standards
acenaphthene-t/io
phenanthrene-t/io
chrysene-t/i2
CASRN
15067-26-2
1517-22-2
1719-03-5
      7.2.1.1
INTERNAL STANDARD PRIMARY DILUTION (ISTD PDS) STANDARD
(500 jig/ mL) - Prepare, or purchase commercially, the Internal Standard Primary
Dilution Standard at a concentration of 500 |ig/mL.  If prepared from neat or solid
standards, this solution requires the preparation of a more concentrated stock
standard similar to the procedure followed for the analyte stock (Sect. 7.2.3.1). The
Internal Standard PDS used in these studies was purchased in acetone.  The Internal
Standard PDS has been shown to be stable for 1 year in amber glass screw cap vials
when stored at -10 C  or less.  Use 10 jiL of this 500-|ig/mL solution to fortify the
final 1-mL extracts (Sect. 11.3.7). This will yield a concentration of 5 |ig/mL of
each internal standard.
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7.2.2   SURROGATE (SUR) ANALYTE STANDARD SOLUTIONS  - The three surrogates
       for this method are listed in the table below.
Surrogates
l,3-dimethyl-2-nitrobenzene
triphenylphosphate
perylene-t/i2
CASRN
81-20-9
115-86-6
1520-96-3
   7.2.2.1
7.2.3
     SURROGATE PRIMARY DILUTION STANDARD (SUR PDS) (500 |ig/mL) -
     Either purchase a SUR PDS from a commercial source or prepare one from a neat
     material at a concentration of 500 jig/mL. The Surrogate PDS used in these studies
     was purchased in acetone. This solution will be used to fortify all QC and Field
     Samples. The PDS has been shown to be stable for 1 year when stored in amber
     glass screw cap vials at -10 C or less.
ANALYTE STANDARD SOLUTIONS - Obtain the analytes listed in the table in
Section 1.1 as neat or solid standards or as commercially prepared ampulized solutions
from a reputable standard manufacturer. Two separate analyte stock solutions will need
to be prepared, one to fortify LFBs, LFSMs, and LFMSDs (Analyte Fortification
Solution), and one to prepare the calibration standards (Analyte Primary Dilution
Standard). The Analyte Fortification Standard is diluted in methanol prior to spiking
water samples. This avoids potential bias in the fortified samples as noted in Section
7.2.3.3.  The Analyte Primary Dilution Standard is diluted in ethyl acetate to be
consistent with the sample extract composition. Prepare the Analyte Stock and Primary
Dilution Standards as described below.
   7.2.3.1  ANALYTE STOCK STANDARD SOLUTIONS (0.25 to 1.0 mg/mL) - Analyte
           standards may be purchased commercially as ampulized solutions (Accustandard
           Mix 1, Cat. No.: S-10617A-R1; Mix 2, S-1617B-R1; and Mix 3, S-10617C-R1 or
           equivalent), or prepared from neat materials. Mix 1 and 2 were prepared in
           methanol.  Mix 3, which contains the BDEs and hexabromobiphenyl, was prepared
           in isooctane/ethyl acetate (4/1). Stock standards have been shown to be stable for 6
           months when stored in amber glass screw cap vials at -10 C or less.

   7.2.3.2  ANALYTE PRIMARY DILUTION STANDARD (50 |ig/mL) - Prepare the
           50-|ig/mL Analyte PDS by volumetric dilution of the Analyte Stock Standard
           Solution (Sect. 7.2.3.1) in ethyl acetate to make a 50-|ig/mL solution. The Analyte
           PDS is used to prepare calibration solutions. Care should be taken during storage to
           prevent evaporation. The Analyte PDS has been shown to be stable for 6 months
           when stored in an amber glass  screw cap vial at -10 C or less.

   7.2.3.3  ANALYTE FORTIFICATION SOLUTION (5.0 to 50 |ig/mL) - The Analyte
           Fortification Solution contains all method analytes of interest in  methanol.  It is
           prepared by dilution of the Analyte Stock Standard Solutions and is used to fortify
           the LFBs, the LFSMs and the LFSMDs with method analytes. It is recommended
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7.2.4
     that three concentrations be prepared so that the fortification levels can be rotated.
     The Analyte Fortification Solutions have been shown to be stable for 6 months
     when stored in an amber glass screw cap vial at -10 C or less.

     Note: The Analyte Stock Standard Solution must be diluted with methanol to create
     the Analyte Fortification Solution.  Decreased recoveries of Dimethoate were
     observed when the LFB, LFSM, and the LFSMD were fortified with a solution that
     was diluted in ethyl acetate.  Recoveries as low as 35% were observed for
     Dimethoate when as little as 200 uL of ethyl acetate was used to fortify the target
     analytes in the 1-L water samples.

CALIBRATION SOLUTIONS - Prepare a calibration curve of at least five Calibration
  Solutions over the concentration range of interest from dilutions of the Analyte PDS in
  ethyl acetate.  All calibration solutions should contain at least 80 percent ethyl acetate
  so that gas chromatographic performance is not compromised. The lowest
  concentration  of calibration standard must be at or below the MRL.  A constant
  concentration  of each internal standard and surrogate (in the range of 2 to 5 ng/|iL) is
  added to each  Calibration Solution. For instance, for method development work, 10 jiL
  of the 500-|ig/mL Internal Standard PDS and 10 |iL  of the 500-|ig/mL SUR PDS were
  added to each  Calibration Solution to yield a final concentration of 5 |ig/mL for each.
  The calibration solutions have been shown to be stable for 6 months when stored in an
  amber glass screw cap vial at -10 C  or less.
Cal
Level
1
2
O
4
5
6
Vol. of
50ug/ml
Analyte PDS
(uL)
5.0
10.0
20.0
40.0
100.0
200.0
Vol. of
500ug/ml
ISTD PDS
(uL)
10.0
10.0
10.0
10.0
10.0
10.0
Vol. of
500ug/ml
SUR PDS
(uL)
10.0
10.0
10.0
10.0
10.0
10.0
Final
Vol. of
CAL Std.
(uL)
1000
1000
1000
1000
1000
1000
Final Cone.
of Analytes
(ug/mL)**
0.25
0.50
1.00
2.00
5.00
10.00
        "Concentration of SUR is 5ug/mL and concentration of ISTD is 5 ug/mL.
          Concentrations are calculated in final volume.

7.2.5   GC/MS TUNE CHECK SOLUTION (5 |ig/mL) (CASRN 5074-71-5) - Prepare a
       decafluorotriphenylphosphine solution in MeCb. DFTPP is more stable in methylene
       chloride than in acetone or ethyl acetate. Store this solution in an amber glass screw cap
       vial at -10 C or less.
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8.  SAMPLE COLLECTION, PRESERVATION, AND STORAGE

   8.1   SAMPLE BOTTLE PREPARATION

       8.1.1  Grab samples must be collected in accordance with conventional sampling practices using
             a 1-liter or 1-quart amber bottle fitted with a PTFE-lined screw-cap.6 Some of the
             pyrethroid compounds photodegrade.

       8.1.2  Preservation reagents, listed in the table below, are added to each sample bottle prior to
             shipment to the field (or prior to sample collection).
Compound
L-Ascorbic acid
Ethylenediaminetetraacetic acid,
trisodium salt
Potassium dihydrogen citrate
Amount
O.lOg/L
0.35 g/L
9.4 g/L
Purpose
Dechlorination
Inhibit metal-catalyzed
hydrolysis of targets
pH 3.8 buffer mixture,
microbial inhibitor
          8.1.2.1
          8.1.2.2
Residual chlorine must be reduced at the time of sample collection with 100 mg of
ascorbic acid per liter. Sodium thiosulfate and sodium sulfite cannot be used
because they were found to degrade target analytes.  Sodium thiosulfate produced
an extraneous sulfur peak and required more frequent instrument maintenance.

Trisodium EDTA (0.35 g/L) must be added to inhibit metal-catalyzed hydrolysis of
the target analytes, principally,  esbiol, thiazopyr, malathion, chlorpyrifos,
thiobencarb, parathion, terbufos-sulfone, vinclozolin, atrazine, and propazine.
          8.1.2.3   The sample must be buffered to pH 3.8 using Potassium dihydrogen citrate (9.4
                   g/L). This is added to inhibit microbial degradation of analytes, and to reduce base
                   catalyzed hydrolysis of some of the target analytes.

   8.2   SAMPLE COLLECTION

       8.2.1  Open the tap and allow the system to flush until the water temperature has stabilized
             (usually approximately 3 to 5 minutes). Collect samples from the flowing system.

       8.2.2  When sampling from an open body of water, fill a 1-L (or 1-quart) wide-mouth bottle or
             1-L beaker with water sampled from a representative area, and carefully fill sample
             bottles from the container. Sampling equipment, including automatic samplers, must be
             free of plastic tubing, gaskets, and other parts that may leach interfering analytes into the
             water sample.

       8.2.3  Fill sample bottles, taking care not to flush out the sample preservation reagents.
             Samples do not need to be collected headspace free.
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       8.2.4  After collecting the sample, cap the bottle and agitate by hand until preservatives are
             dissolved. Keep the sample sealed from time of collection until extraction.

   8.3   SAMPLE SHIPMENT AND STORAGE - Samples must be chilled during shipment and
         must not exceed 10 C during the first 48 hours after collection.  Sample temperature must be
         confirmed to be at or below 10 C when they are received at the laboratory. Samples stored in
         the lab must be held at or below 6 C until extraction, but should not be frozen.

   8.4   SAMPLE AND EXTRACT HOLDING TIMES - Results of the sample storage stability
         study (Sect. 17, Table 7) indicated that most compounds listed in this method have adequate
         stability for 14 days when collected, dechlorinated, preserved, shipped and stored as described
         in Sections 8.1, 8.2, and 8.3. Water samples should be extracted as soon as possible but must
         be extracted within 14 days. Extracts must be stored at 0 C or less and analyzed within 28
         days after extraction. The extract storage stability study data are presented in Section 17,
         Table 8.

9.  QUALITY CONTROL

   9.1   QC requirements include the Initial Demonstration of Capability (IDC) and ongoing QC
         requirements that must be met when preparing and analyzing Field Samples. This section
         describes each QC parameter, their required frequency, and the performance criteria that must
         be met in order to meet EPA quality objectives. The QC criteria discussed in the following
         sections are summarized in Section 17, Tables 9 and 10. These QC requirements are
         considered the minimum acceptable QC criteria. Laboratories are encouraged to institute
         additional QC practices to meet their specific needs.

       9.1.1  METHOD MODIFICATIONS - The analyst is permitted to modify GC columns, GC
             conditions, evaporation techniques, internal standards  or surrogate standards, and MS
             conditions.  However, each time such method modifications are made, the analyst must
             repeat the procedures of the IDC.

   9.2   INITIAL DEMONSTRATION OF CAPABILITY - The IDC must be successfully performed
         prior to analyzing any Field Samples. Prior to conducting the IDC, the analyst must first
         generate an acceptable Initial Calibration following the procedure outlined in Section  10.2.

       9.2.1  INITIAL DEMONSTRATION OF LOW SYSTEM BACKGROUND - Any time a new
             lot of SPE cartridges or disks is used, it must be demonstrated that a Laboratory Reagent
             Blank is reasonably free of contamination and that the criteria in Section 9.3.1 are met.

       9.2.2  INITIAL DEMONSTRATION OF PRECISION (IDP) - Prepare, extract, and analyze 4
             to 7 replicate LFBs fortified near the midrange of the initial calibration curve according
             to the procedure described  in  Section 11.  Sample preservatives as described in Section
             8.1 must be added to these  samples. The relative standard deviation (RSD) of the results
             of the replicate analyses must be less than 20 percent.

       9.2.3  INITIAL DEMONSTRATION OF ACCURACY - Using the same set of replicate data
             generated for Section 9.2.2, calculate average recovery. The average recovery of the
             replicate values must be within 30 percent of the true value.
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9.2.4   MINIMUM REPORTING LEVEL (MRL) CONFIRMATION - Establish a target
       concentration for the MRL based on the intended use of the method. Establish an Initial
       Calibration following the procedure outlined in Section 10.2. The lowest calibration
       standard used to establish the Initial Calibration (as well as the low-level Continuing
       Calibration Check standard) must be at or below the concentration of the MRL.
       Establishing the MRL concentration too low may cause repeated failure of ongoing QC
       requirements. Confirm or validate the MRL following the procedure outlined below.

   9.2.4.1   Fortify, extract, and analyze seven replicate Laboratory Fortified Blanks (LFBs) at
            the proposed MRL concentration.  These LFBs must contain all method
            preservatives described in Section 8. Calculate the mean (Mean) and standard
            deviation for these replicates. Determine the Half Range for the prediction interval
            of results (HRpiR) using the  equation below

                                      HRPIR = 3.963S

            where S is the standard deviation, and 3.963 is a constant value for seven
            replicates.(1)

  9.2.4.2    Confirm that the upper and  lower limits for the Prediction Interval of Result (PIR =
            Mean +_ HRPIR) meet the upper and lower recovery limits as shown below

       The Upper PIR Limit must be <150 percent recovery.

                                 Mean + HRP1R
                             FortifiedConcentration

       The Lower PIR Limit must be > 50 percent recovery.
                                 Mean - HRPIR
                             FortifiedConcentration

  9.2.4.3    The MRL is validated if both the Upper and Lower PIR Limits meet the criteria
            described above (Sects. 9.2.4.2). If these criteria are not met, the MRL has been set
            too low and must be determined again at a higher concentration.

9.2.5   CALIBRATION CONFIRMATION - Analyze a Quality Control Sample as described in
       Section 9.3.9 to confirm the accuracy of the standards/calibration curve.

9.2.6   DETECTION LIMIT DETERMINATION (optional) - While DL determination is not a
       specific requirement of this method, it may be required by various regulatory bodies
       associated with compliance monitoring. It is the responsibility of the laboratory to
       determine ifDL determination is required based upon the intended use of the data.

       Replicate analyses for this procedure should be done over at least 3 days (both the sample
       extraction and the GC analyses should be done over at least 3 days). Prepare at least 7
                                     527-15

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          replicate LFBs at a concentration estimated to be near the DL. This concentration may
          be estimated by selecting a concentration at 2-5 times the noise level. The DLs in Table
          1 were calculated from LFBs fortified at various concentrations as indicated in the table.
          The appropriate fortification concentrations will be dependent upon the the sensitivity of
          the GC/MS system used. All preservation reagents listed in Section 8. 1 .2 must also be
          added to these samples. Analyze the seven replicates through all steps of Section 11.

          NOTE: If an MRL confirmation data set meets these requirements, a DL may be
          calculated from the MRL confirmation data, and no additional analyses are necessary.

          Calculate the DL using the following equation:

                            J X, t /
                                t /   i i     c\ c\c\\
                                (n-l, l-or=0.99)

          where:
                 t (n-i, i-a=o.99) = Student's t value for the 99% confidence level with n-l degrees of
                 freedom
                 n = number of replicates
                 5 = standard deviation of replicate analyses.

          NOTE: Do not subtract blank values when performing DL calculations.
9.3    ONGOING QC REQUIREMENTS - This section summarizes the ongoing QC criteria that
      must be followed when processing and analyzing Field Samples.

   9.3.1   LABORATORY REAGENT BLANK (LRB) - An LRB is required with each extraction
          batch to confirm that potential background contaminants are not interfering with the
          identification or quantitation of target analytes. If the LRB produces a peak within the
          retention time window of any analyte that would prevent the determination of that
          analyte, determine the source of contamination and eliminate the interference before
          processing samples.  Background contamination must be reduced to an acceptable level
          before proceeding. Background from method analytes or other contaminants that inter-
          fere with the measurement of method analytes must be below  Vs of the MRL. Blank
          contamination may be estimated by extrapolation, if the concentration is below the lowest
          calibration standard. This procedure is not allowed for sample results as it may  not meet
          data quality objectives.  If the target analytes are detected in the LRB at concentrations
          equal to or greater than this level, then all data for the problem analyte(s) must be
          considered invalid for all samples in the extraction batch.

   9.3.2   CONTINUING CALIBRATION CHECK (CCC) - CCC  Standards are analyzed at the
          beginning of each analysis batch, after every ten Field Samples, and at the end of the
          analysis batch. See Section 10.3  for concentration requirements and acceptance criteria.

   9.3.3   LABORATORY FORTIFIED BLANK (LFB) - An LFB is required with each extraction
          batch.  The fortified  concentration of the LFB must be rotated between low, medium, and
          high concentrations from batch to batch.  The low concentration LFB must be as near as
                                         527-16

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       practical to, but no more than two times the MRL. Similarly, the high concentration LFB
       should be near the high end of the calibration range established during the initial cal-
       ibration (Sect.  10.2).  Results of the low-level LFB analyses must be 50 to 150 percent of
       the true value.  Results of the medium and high-level LFB analyses must be 70 to
       130 percent of the true value. If the LFB results do not meet these criteria for target
       analytes, then all data for the problem analyte(s) must be considered invalid for all sam-
       ples in the extraction  batch.

9.3.4   MS TUNE CHECK - A complete description of the MS Tune Check is found in Section
       10.2.1. Acceptance criteria for the MS Tune Check is summarized in Section 17, Table
       1. The MS Tune Check must be performed each time a major change is made to the mass
       spectrometer, and prior to establishing and/or re-establishing an initial calibration
       (Sect. 10.2).  In this method daily DFTPP analysis is not required.

9.3.5   INTERNAL STANDARDS (IS) -The analyst must monitor the peak area of the IS in all
       injections during each analysis day. The  IS response (peak area) in any chromatographic
       run must not deviate from the response in the most recent CCC by more than 30%, and
       must not deviate by more than 50% from the area measured during initial analyte
       calibration. If the IS  area in a chromatographic run does not meet these criteria, inject a
       second aliquot of that extract.

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

   9.3.5.2    If the reinjected extract fails again, the analyst should check the calibration by
            reanalyzing the  most recently acceptable calibration standard. If the calibration
            standard fails the criteria of Section 10.3, recalibration is in order per SectionlO.2.
            If the calibration standard is acceptable, extraction of the sample may need to be
            repeated provided the sample is still within the holding time.  Otherwise, report
            results obtained from the reinjected extract, but annotate as suspect. Alternatively,
            collect a new sample and re-analyze.

9.3.6   SURROGATE RECOVERY - The surrogate standard is fortified into the aqueous
       portion of all samples, LRBs, CCCs, LFSMs, and LFSMDs prior to extraction. It is also
       added to the calibration standards.  The surrogate is a means of assessing method
       performance from extraction to final chromatographic measurement. Calculate the
       recovery (%R) for the surrogate using the equation

                                           (  A\
                                     %R=   xlOO
                                           UJ

       where A = calculated  surrogate concentration for the QC or Field Sample, and B =
       fortified concentration of the surrogate.

   9.3.6.1    Surrogate recovery must be in the range of 70 - 130%. When surrogate recovery
            from a sample, blank, or CCC is less than 70 percent or greater than 130 percent,
            check 1) calculations to locate possible errors, 2) standard solutions for degradation,

                                      527-17

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            3) contamination, and 4) instrument performance.  Correct the problem and
            reanalyze the extract.

   9.3.6.2   If the extract reanalysis meets the surrogate recovery criterion, report only data for
            the reanalyzed extract.

   9.3.6.3   If the extract reanalysis fails the 70 to 130 percent recovery criterion, the analyst
            should check the calibration by injecting the last calibration standard that passed. If
            the calibration standard fails the criteria of Section 9.3.6.1., recalibration is in order
            per Section 10.2.  If the calibration standard is acceptable, extraction of the sample
            should be repeated provided the sample is still within the holding time. If the re-
            extracted sample also  fails the recovery criterion, report all data for that sample as
            suspect/surrogate recovery to inform the data user that the results are suspect due to
            surrogate recovery.

9.3.7   LABORATORY FORTIFIED SAMPLE MATRIX (LFSM) - Analysis of an LFSM is
       required in each extraction batch and is used to determine that the sample matrix does not
       adversely affect method accuracy. If the occurrence of target analytes in the samples is
       infrequent, or if historical trends are unavailable, a second LFSM or LFSMD must be
       prepared, extracted, and analyzed from a duplicate Field Sample used to prepare the
       LFSM to assess method precision. Extraction batches that contain LFSMDs do not
       require the analysis of a Field Duplicate (Sect. 9.3.8).  If a variety of different sample
       matrices are analyzed regularly, for example, drinking water from groundwater and
       surface water sources, method performance should be established for each.  Over time,
       LFSM data should be documented for  all routine sample sources for the  laboratory.

   9.3.7.1   Within each extraction batch, a minimum of one Field Sample is fortified as an
            LFSM for every 20 samples extracted. The LFSM is prepared by spiking a sample
            with an appropriate amount of the Analyte Fortification Solution (Sect. 7.2.3.3).
            Select a spiking concentration that is greater than or equal to the matrix background
            concentration, if known. Use historical data and rotate through the designated
            concentrations when selecting a fortifying concentration.

   9.3.7.2   Calculate the percent recovery (%R) for each analyte using the equation
            where A = measured concentration in the fortified sample, B = measured
            concentration in the unfortified sample, and C = fortification concentration.
                                                 C

   9.3.7.3   Analyte recoveries may exhibit matrix bias. For samples fortified at or above their
            native concentration, recoveries should range between 70 and 130 percent, except
            for low-level fortification near or at the MRL (within a factor of 2-times the MRL
            concentration) where 50 to 150 percent recoveries are acceptable. If the accuracy
            of any analyte falls outside the designated range, and the laboratory performance for
            that analyte is  shown to be in control in the CCCs, the recovery is judged to be ma-
            trix biased. 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.
                                       527-18

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9.3.8   FIELD DUPLICATE OR LABORATORY FORTIFIED SAMPLE MATRIX
       DUPLICATE (FD or LFSMD) - Within each extraction batch, a minimum of one Field
       Duplicate (FD) or Laboratory Fortified Sample Matrix Duplicate (LFSMD) must be
       analyzed. Duplicates check the precision associated with sample collection, preservation,
       storage, and laboratory procedures. If target analytes are not routinely observed in Field
       Samples, an LFSMD should be analyzed rather than an FD.

  9.3.8.1    Calculate the relative percent difference (RPD) for duplicate measurements (FD1
            and FD2) using the equation

                                    FDl-FD2
                                                xlOO
                                  (FDl + FD2)/2

  9.3.8.2    RPDs for Field Duplicates should be < 30 percent. Greater variability may be
            observed when Field Duplicates have analyte concentrations that are within a factor
            of 2 of the MRL.  At these concentrations Field Duplicates should have RPDs that
            are < 50 percent.  If the RPD of any analyte falls outside the designated range, and
            the laboratory performance for that analyte is shown to be in control in the CCC,
            the recovery is judged to be matrix biased. 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.

  9.3.8.3    If an LFSMD is analyzed instead of a Field Duplicate, calculate the relative percent
            difference (RPD) for duplicate LFSMs (LFSM and LFSMD) using the equation


                         RPD =
                               (LFSM+LFSMD)/2

  9.3.8.4    RPDs for duplicate LFSMs should be < 30 percent for samples fortified at or above
            their native concentration. Greater variability may be observed when LFSMs are
            fortified at analyte concentrations that are within a factor of 2 of the MRL.  LFSMs
            fortified at these concentrations should have RPDs that are < 50 percent for samples
            fortified at or above their native concentration. If the RPD of any analyte falls
            outside the designated range, and the laboratory performance for that analyte is
            shown to be in control in the CCC, the  recovery is judged to be matrix biased.  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.

9.3.9   QUALITY CONTROL SAMPLES (QCS) - As part of the IDC (Sect.  9.2), each time a
       new Analyte PDS (Sect. 7.2.3.2) is prepared, and at least quarterly,  analyze a QCS
       sample from a source different from the source of the calibration standards. If a second
       vendor is not available then a different lot of the standard should be used. The QCS
       should be prepared and analyzed just like a CCC. Acceptance criteria  for the QCS is
       identical to the CCCs; the calculated amount for each analyte must be  30 percent of the
       expected value.  If measured analyte concentrations are not of acceptable accuracy, check
       the entire analytical procedure to locate and correct the problem.
                                     527-19

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10.  CALIBRATION AND STANDARDIZATION

    10.1  Demonstration and documentation of acceptable mass spectrometer tune and initial calibration
         is required before any samples are analyzed. After the initial calibration is successful, a con-
         tinuing calibration check is required at the beginning and end of each period in which analyses
         are performed, and after every tenth sample. Verification of mass spectrometer tune must be
         repeated each time a major instrument modification is made or maintenance is performed, and
         prior to analyte calibration.

    10.2  INITIAL CALIBRATION

       10.2.1 MS TUNE/MS TUNE CHECK- Calibrate the mass and abundance scales of the MS with
             calibration compounds and procedures prescribed by the manufacturer with any modifi-
             cations necessary to meet tuning requirements. Inject 5 ng or less of the DFTPP solution
             (Sect. 7.2.5) into the GC/MS system.  Acquire a mass spectrum that includes data for m/z
             45 to 450. Use a single spectrum of the DFTPP peak, an average spectrum of the three
             highest points of the peak, or an average spectrum across the entire peak to evaluate the
             performance of the system.  If the DFTPP mass spectrum does not meet all criteria in
             Table 1, the MS must be retuned and adjusted to meet all criteria before proceeding with
             the initial calibration.

       10.2.2 INSTRUMENT CONDITIONS - Operating conditions are described below. Conditions
             different from those described may be used if QC criteria in Section 9 are met. Different
             conditions include alternate GC columns, temperature programs, MS conditions, and
             injection techniques and volume, such as cold on-column and direct injection port liners
             and/or large volume injection techniques. Equipment designed for alternate types of
             injections must be used if these options are selected.

         10.2.2.1  Inject a l-|iL aliquot into a hot, splitless injection port held at 250 C with a split
                   delay of 1 minute. The temperature program is as follows: initial oven temperature
                   of 55 C, hold for 0 minutes, ramp at 20 C/min to 200 C, hold for 2 minutes,
                  ramp at 4 C/min to a final temperature of 300 C and hold for 0.75 minute.  Total
                  run time is approximately 35 minutes.  Begin data acquisition at 4.4 minutes.

                  Note: The GC was operated in a constant flow rate mode at a rate of 1.4 mL per
                  minute and an initial head-pressure of 12.0 psi.

         10.2.2.2   Target compounds can exhibit decreased sensitivity for low-level injections due to
                   degradation or irreversible adsorption in the injector port. Deactivated glass or
                   quartz inlet liners are recommended. A loss in response for BDE-47, BDE-99,
                  BDE-100, BDE-153, fenvalerate, esfenvalerate, hexazinone, nitrophen, norflurazon,
                   and parathion are generally a result of degradation or adsorption occurring in the
                  inlet liner or on the inlet seal.  A loss in response for the lower molecular weight
                  target analytes such as vinclozolin, prometryn, bromacil and chlorpyrifos can
                  usually be attributed to degradation of the first meter of the GC column.
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   10.2.2.3   MS Detection and Sensitivity -Adjust the cycle time to measure at least five or
            more spectra during the elution of each GC peak. Ten to 15 scans across each GC
            peak are recommended. The scan range can be set from m/z 45-670 for the entire
            chromatographic run provided that there are enough scans across each GC peak at
            the method reporting limit.

      10.2.2.3.1 An alternate approach that was used during method development is to establish
               two scan ranges.  Acquire data from a suggested range of m/z 45 - 450 with a
               total cycle time (including scan overhead time) of 1.0 second or less for the
               first 19 minutes of the run. Adjust the scan range to m/z 45 - 670 for the final
                16 minutes of the run. If this approach is taken, the analyst must ensure that the
               scan range is changed just prior to the elution of the third internal standard peak
               (chrysene-d!2).  The time at which the increased scan range  occurs will be
               dependent on chromatographic parameters.

10.2.3  CALIBRATION SOLUTIONS - Prepare a set of at least five calibration standards as
       described in Section 7.2.4. The lowest concentration of the calibration  standard must be
       at or below the MRL,  which will depend on system  sensitivity.  The MRL must be
       confirmed using the procedure outlined in Section 9.2.4 after establishing the initial
       calibration.  Acceptable calibration over a large dynamic range, greater than about 40-
       fold, may require more than one calibration curve.  If this approach is taken, each curve
       must contain at least 5 calibration  standards.  In addition, Field Samples must be
       quantitated using the same number of curves over the same concentration range used to
       collect the IDC data (Sect. 9.2).

10.2.4  CALIBRATION - The GC/MS system is calibrated using the internal  standard tech-
       nique. Concentrations may be calculated through the use of an average relative response
       factor (RRF) or through the use of a calibration curve. Calculate the RRFs using the
       equation
      where
             Ax = integrated peak area of the analyte,
             Ais = integrated peak area of the internal standard,
             Qx = quantity of analyte injected in ng or concentration units,
             Qts = quantity of internal standard injected in ng or concentration units, and
             RRF = relative response factor.

      Average RRF calibrations may only be used if the RRF values over the calibration range
      are relatively constant.

   10.2.4. 1  Suggested quantitation ions are designated in Table 2.  Some of the polybrominated
           diphenyl ethers have ions at higher mass that may offer better selectivity.
           Quantitation at high m/z values, however, can suffer from imprecision due to mass
           defect associated with halogenated compounds on some mass spectrometers. This is
           observed as irregular, jagged extracted ion peak shapes.
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   10.2.5 As an alternative to calculating average RRFs and applying the RSD test, use the GC/MS
          data system software to generate a linear regression or quadratic calibration curve.  Forc-
          ing the calibration curve through the origin is not recommended. Examples of common
          GC/MS system calibration curve options are: \)Ax/Ais vs. Qx/QjS, and 2) RRF vs. Ax/Ais.

   10.2.6 CALIBRATION ACCEPTANCE CRITERIA- Acceptance criteria for the calibration of
          each analyte is determined by calculating the concentration of each analyte and surrogate
          in each of the analyses used to generate the calibration curve or average RRF. Each
          calibration point, except the lowest point, for each analyte should calculate to be 70 to
          130 percent of its true value. The lowest point should calculate to be 50 to 150 percent of
          its true value. If these criteria cannot be met, the analyst will have difficulty meeting
          ongoing QC criteria. It is recommended that corrective action is taken to reanalyze the
          calibration standards, restrict the range of calibration, or select an alternate method of
          calibration. The data presented in this method were obtained using quadratic fits.
          Quadratic fit calibrations should be used with caution, because the non-linear area of the
          curve may not be reproducible.

10.3   CONTINUING CALIBRATION CHECK (CCC) - The CCC verifies the initial calibration at
      the beginning and end of each group of analyses,  and after every tenth sample during
      analyses. In this context, a "sample" is considered to be a Field Sample.  The LRBs, LFBs,
      LFMs, LFMDs and CCCs are not counted as samples.  The beginning CCC for each analysis
      batch must be at or below the MRL in order to verify instrument sensitivity prior to any
      analyses. If standards have been prepared such that all analytes are not in the same calibration
      standard (or all low CAL points are not in the same CAL standard), it may be necessary to
      analyze more than one CCC to meet this requirement. Alternatively, it may be cost effective
      to prepare or obtain a customized standard to meet this criteria. Subsequent CCCs should
      alternate between a medium and high concentration.

   10.3.1 Inject an aliquot of the appropriate concentration calibration solution and analyze with
          the same conditions used during the initial calibration.

   10.3.2 Determine that the absolute areas of the quantitation ions of the internal standards have
          not changed by more than 30 percent from the average area measured during initial
          calibration. If any IS area has changed by more this amount, remedial action must be
          taken (Sect. 10.3.4). Control charts are useful aids in documenting system sensitivity
          changes.

   10.3.3 Calculate the concentration of each analyte and surrogate in the check standard. The
          calculated amount for each analyte for medium and high level CCCs must be 
          30 percent of the true value.  The calculated amount for the lowest calibration level for
          each analyte, which must be at a concentration less than or equal to the MRL, must be
          within  50 percent of the true value. If these criteria are not met, then all data for the
          problem analyte must be considered invalid,  and remedial action (Sect. 10.3.4) should be
          taken which may require recalibration.  Any  Field Sample extracts that have been
          analyzed since the last acceptable calibration verification should be reanalyzed after
          adequate calibration has been restored, with the following exception. If the continuing
          calibration fails because the calculated  concentration is greater than 130 percent (150
                                         527-22

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             percent for the low-level CCC) for a particular target compound, and Field Sample
             extracts show no detection for that target compound, non-detects may be reported without
             re-analysis.

       10.3.4 REMEDIAL ACTION - Failure to meet CCC QC performance criteria may require
             remedial action.  Major maintenance such as cleaning an ion source, cleaning the mass
             analyzer, replacing filament assemblies, replacing or shortening GC columns, etc.,
             require returning to the initial calibration step (Sect. 10.2).

11. PROCEDURE

   11.1  Important aspects of this analytical procedure include proper preparation of laboratory
         glassware, sample containers (Sect. 4.1), and sample collection and storage (Sect. 8). This
         section describes the procedures for sample preparation,  solid phase extraction (SPE) using
         disks, and extract analysis.

   11.2  SAMPLE BOTTLE PREPARATION

       11.2.1 Samples are preserved, collected and stored as presented in Section 8. All field and QC
             samples must contain the preservatives listed in Section 8.1.2, including the LRB and
             LFB. Before  extraction, mark the level of the sample on the outside of the sample bottle
             for later sample volume determination. If using weight to determine volume (Sect.
             11.3.8), weigh the bottle with collected sample before extraction.

       11.2.2 Add an aliquot of the SURPDS (Sect. 7.2.2.1) to each sample to be extracted. For
             method development work, a 10-jiL aliquot of the 500-|ig/mL SUR PDS was added to 1
             L for a final concentration of 5.0 |ig/L.

       11.2.3 If the sample is an LFB, LFSM, or LFSMD, add the necessary amount of Analyte Fortifi-
             cation Solution (Sect. 7.2.3.3). Swirl each sample to ensure all components are mixed.
             The analyte fortification solution should be prepared in methanol for reasons stated in
             Section 7.2.3.3.

       11.2.4 Proceed with sample extraction using SPE disks (Sect. 11.3).

   11.3  DISK SPE PROCEDURE - The disk extraction procedure may be carried out in a manual
         mode or by using a robotic or automatic sample preparation device. This section describes the
         disk SPE procedure using the equipment outlined in Section 6.9 in its simplest, least
         expensive mode without the use of a robotics system. The manual mode described below was
         used to collect data presented in Section 17. The use of a robotics system is allowed; however,
         extraction and/or elution steps may not be changed or omitted to accommodate the use of an
         automated system.

       11.3.1 SAMPLE PREPARATION - Prepare the samples as described in Section 11.2.

       11.3.2 DISK CLEANUP - Assemble the extraction glassware onto the vacuum manifold,
             placing disks on a support screen between the funnel and base. Add a 5-mL aliquot of a
             1:1 mixture of EtOAc and MeCb, drawing about half through the disk, and allowing the
                                            527-23

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       solvent to soak the disk for about a minute. Draw the remaining solvent through the disk
       to waste until the disk is dry of solvent.

11.3.3  DISK CONDITIONING - The conditioning step is critical for recovery of analytes and
       can have a marked effect on method precision and accuracy. Once the conditioning has
       begun, the disk must not go dry until the last portion of the sample passes, because ana-
       lyte and surrogate recoveries may be affected. If the disk goes dry during  the condition-
       ing phase, the conditioning must be started over. The analyst should note  premature
       drying of the solid phase, because the sample may require re-extraction due to low surro-
       gate (and analyte) recoveries.  During conditioning, it is not unusual for the middle of the
       solid phase disk to form a wrinkle.  This typically does not adversely affect extraction.

  11.3.3.1   CONDITIONING WITH METHANOL - Add approximately  lOmLofMeOHto
            each disk.  Pull about 1 mL of MeOH through the disk and turn off the vacuum
            temporarily to let the disk soak for about one minute. Draw most of the remaining
            MeOH through the disk, but leave a layer of MeOH on the surface of the disk. The
            disk must not be allowed to go dry from this point until the end of the sample
            extraction.

  11.3.3.2   CONDITIONING WITH WATER - Follow the MeOH rinse with two  10-mL
            aliquots of reagent water, being careful to keep the water level above the disk
            surface.  Turn off the vacuum.

11.3.4  DISK EXTRACTION - Add the sample to the extraction funnel containing the
       conditioned disk and turn on the vacuum.  Adjust the flow rate to 10 - 15  mL/min.  Do
       not let the disk go dry before all of the sample has been extracted. Drain as much water
       from the sample container as possible.  After  all the sample has passed, pull air through
       the disk by maintaining full vacuum (minus 10 to  15 in. Hg) for 10 minutes.  If the disk is
       dried for a period much longer than 10 minutes, there will be a loss of recovery for the
       surrogate l,3-dimethyl-2-nitrobenzene. After drying, turn off and release the vacuum.

11.3.5  DISK ELUTION - Detach the glassware base from the manifold without disassembling
       the funnel from the base. Dry the underside of the base.  Insert collection tubes into the
       manifold to catch the extracts as they are eluted from the disk. The collection tube must
       fit around the drip tip of the base to ensure collection of all the eluent. Reattach the base
       to the manifold.  Add 5 mL of EtOAc to the empty sample bottle and thoroughly rinse the
       inside of the bottle. Transfer the EtOAc to the disk and, with vacuum, pull enough
       EtOAc into the disk to soak the sorbent. Allow the solvent to soak the disk for about one
       minute. Using a vacuum, pull the remaining solvent slowly (dropwise) through the disk
       into the collection tube.  Next, add 5 mL of MeCb to the empty sample bottle and
       thoroughly rinse the inside of the bottle. Transfer the MeC^ to the disk and, with
       vacuum, pull enough methylene chloride into the disk to soak the sorbent. Allow the
       solvent to soak the disk for about one minute. Pull the remaining solvent  slowly through
       the disk into the collection tube. Rinse the SPE funnel surface with a 5-mL aliquot of 1:1
       EtOAc/MeCb and pull the solvent slowly through the disk into the collection tube.
       Repeat this last rinse of the SPE funnel.  Detach glassware from manifold and remove
       collection tube from the manifold.

                                     527-24

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   11.3.6  DRYING OF THE EXTRACT - Small amounts of residual water from the sample
          container and solid phase may form an immiscible layer with the solvent in the extract.
          Set up a drying column (Sect. 6.6) packed with about 5-7 grams of anhydrous sodium
          sulfate. Pre-rinse the sodium sulfate column with about 2 mL of 1:1 EtOAc/MeCb.
          Place a clean collection tube that can hold at least 30 mL beneath the drying column.
          Add the entire extract to the column  and follow with two 3-mL aliquots of 1:1
          EtOAc/MeCl2.

      11.3.6.1 Extracts should be examined visually  for water droplets after drying. Extracts that
              contain water have been noted to rapidly degrade the inertness of the GC inlet and
              the head of the GC column requiring much more frequent maintenance.

   11.3.7  EXTRACT CONCENTRATION - Concentrate the extract to about 0.7 mL under a
          gentle stream of nitrogen in a warm water bath (at ~ 40 C). Do not blow down samples
          to less than 0.5  mL, because the most volatile compounds (dimethoate, and 1,3-dimethyl-
          2-nitrobenzene) will exhibit diminished recovery.  Transfer the extract to a 1-mL
          volumetric flask and add the internal standard (method development used 10 jiL of
          500-|ig/mL IS PDS for an extract concentration of 5 |ig/mL). Rinse the collection tube
          that held the dried extract with small amounts of EtOAc and add to the volumetric flask
          to bring the volume up to the 1-mL mark. Transfer to an autosampler vial.

   11.3.8  SAMPLE VOLUME OR WEIGHT DETERMINATION - Use a graduated cylinder to
          measure the volume of water required to fill the original sample bottle to the mark made
          prior to extraction (Sect. 11.2.1). Determine volume to the nearest 10 mL for use in the
          final calculations of analyte concentration (Sect. 12.2). If using weight to determine
          volume, reweigh empty sample bottle.  From the weight of the original sample bottle
          measured in Section 11.2.1, subtract the empty bottle weight. Use this value for analyte
          concentration calculations in Section 12.2.

11.4   ANALYSIS OF SAMPLE EXTRACTS

   11.4.1  Establish operating conditions as described in Section 10.2.2. Confirm that compound
          separation  and resolution are similar to those summarized in Table 2 and Figure 1 (Sect.
          17).

   11.4.2  Establish a valid initial calibration following the procedures outlined in Section 10.2 or
          confirm that the calibration is still valid by running a CCC as described in Section 10.3.
          If establishing an initial calibration for the first time, complete the IDC as described in
          Section 9.2.

   11.4.3  Analyze aliquots of Field and QC Samples at appropriate frequencies (Sect. 9) with the
          GC/MS conditions used to acquire the initial calibration and/or the CCC.  At the conclu-
          sion of data acquisition, use the  same software that was used in the calibration procedure
          to tentatively identify peaks in predetermined retention time windows of interest. Use the
          data system software to examine the ion abundances of components of the chromato-
          gram.
                                        527-25

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       11.4.4 COMPOUND IDENTIFICATION - Identify a sample component by comparison of its
             mass spectrum (after background subtraction if necessary) to a reference spectrum in the
             user-created database.

         11.4.4.1   Establish an appropriate retention time window for each target analyte, internal
                   standard and surrogate standard to identify them in QC and Field Sample chromat-
                   ograms.  Ideally, the retention time window should be based on measurements of
                   actual retention time variation for each compound in standard solutions collected on
                   each GC/MS over the course of time. The suggested variation is plus or minus
                   three times the standard deviation of the retention time for each compound for a
                   series of injections. The injections from the initial calibration and from the IDC
                   (Sect. 9.2) may be used to calculate a suggested window size. However, the
                   experience of the analyst should weigh heavily on the determination of an
                   appropriate retention window size.

         11.4.4.2   In general, all ions that are present above 30 percent relative abundance in the mass
                   spectrum of the standard should be present in the mass spectrum of the sample
                   component and should agree within an absolute 20 percent. For example, if an ion
                   has a relative abundance of 30 percent in the standard spectrum, its abundance in
                   the sample spectrum should be in the range of 10 to 50 percent. Some ions,
                   particularly the molecular ion,  are of special importance, and should be evaluated
                   even if they are below 30 percent relative abundance.

         11.4.4.3   Identification is hampered when sample components are not resolved
                   chromatographically and produce mass spectra containing ions contributed by more
                   than one analyte.  When GC peaks  obviously represent more than one sample
                   component (i.e., broadened peak with shoulder(s) or valley between two or more
                   maxima), appropriate analyte spectra and background spectra can be selected by
                   examining plots of characteristic ions. When analytes coelute (i.e., only one GC
                   peak is apparent), the identification criteria can be met but each analyte spectrum
                   will contain extraneous ions contributed by the coeluting compound

12. DATA ANALYSIS AND CALCULATIONS

   12.1  Identify method analytes present in the Field and QC Samples as described in Section 11.4.4.
         Complete chromatographic resolution is not necessary for accurate and precise measurements
         of analyte concentrations if unique ions with adequate intensities are available for
         quantitation.

       12.1.1 In validating this method, concentrations were calculated by measuring the characteristic
             ions listed in Table 2 (Sect. 17). Other ions may be selected at the discretion of the
             analyst.

   12.2  Calculate analyte and surrogate concentrations, using the multipoint calibration established in
         Section 10.2. Do not use daily continuing calibration check data to quantitate analytes in
         samples. Adjust the final analyte concentrations to reflect the actual sample volume or weight
         determined in Section 11.3.8.  Field Sample extracts that require dilution should be treated as
         described in Section 12.3.
                                            527-26

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   12.3  EXCEEDING CALIBRATION RANGE - An analyst must not extrapolate beyond the
         established calibration range. If an analyte result exceeds the range of the initial calibration
         curve, the extract may be diluted with EtOAc, with the appropriate amount of internal
         standard added to match the original level, and the diluted extract injected. Acceptable
         surrogate performance (Sect. 9.3.6) should be determined from the undiluted sample extract.
         Incorporate the dilution factor into final concentration calculations. The resulting sample
         should be documented as a dilution, and MRLs should be adjusted  accordingly.

   12.4  Calculations must utilize all available digits of precision, but final reported concentrations
         should be rounded to an appropriate number of significant figures (one digit of uncertainty),
         typically two, and not more than three significant figures.

         NOTE: Some data in Section 17 of this method are reported with more than 2 significant
         figures. This is done to better illustrate the method performance data.

13. METHOD PERFORMANCE

   13.1  PRECISION, ACCURACY, AND MINIMUM REPORTING LEVELS - Tables for these
             data are presented in Section 17.  Lowest Concentration MRLs for each target analyte are
             presented in Table 3. This involved preparing, extracting, and analyzing seven replicates
             at five concentrations (0.1, 0.2, 0.35, 0.5, and 1.0 |ig/L) and then calculating the LCMRL
             following the procedure described in reference 1. Detection Limits (DLs) were
             determined following the procedure outlined in Section 9.2.6.  The DLs are included in
             Table 3 for comparison. Single laboratory precision and accuracy data are presented in
             Tables 4-6.

   13.2  POTENTIAL PROBLEM COMPOUNDS

      13.2.1  MATRIX ENHANCED SENSITIVITY - Fenvalerate, Esfenvalerate, Nitrophen,
             Parathion and to a lesser extent, Norflurazon can exhibit "matrix-induced
             chromatographic response enhancement."7"11 Compounds that exhibit this phenomenon
             often give analytical results that exceed 100%  recovery in fortified extracts at low
             concentrations and in continuing calibration checks. If this is observed, more frequent
             recalibration will be required. It has been proposed that these  compounds are susceptible
             to GC inlet absorption or thermal degradation so that analytes  degrade more when
             injected in a "cleaner" matrix. The injection of a "dirty"  sample extract coats surfaces
             with matrix components and "protects" the problem compounds from decomposition or
             adsorption.  As a result, a relatively greater response is observed for analytes in sample
             extracts than in calibration solutions.  This effect is minimized by using deactivated
             injection liners, and by minimizing the liner volume as much as is practical (Sect. 6.12.2).
             The analyst may also choose to condition the injection port after maintenance by
             injecting a few aliquots of a field sample extract prior to establishing an initial
             calibration.  Preparation of calibration standards in clean sample extracts is not allowed.

      13.2.2  As the injector becomes dirty, the analyst may note a fall-off in response for the later
             eluting compounds. During method development, some of the analytes lost as much as
             50% of their response over the course of 150 - 200 injections.  This required recalibration
                                            527-27

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             and/or routine maintenance.  If routine maintenance is put off too long, the analyst may
             experience difficulty meeting the low-level CCC recovery criteria (at the MRL
             concentration).

      13.2.3  Kepone can be problematic.  It occasionally exhibited recoveries below 70%.
             Dimethoate exhibited unacceptable recoveries in the LFSMs if it was fortified in EtOAc.
             This was the reason that the Analyte Fortification Solution is prepared in methanol (Sect.
             7.2.3.3).

   13.3  SAMPLE STORAGE STABILITY STUDIES - An analyte storage stability study was
         conducted by fortifying the analytes (5.0 //g/L of each analyte) into chlorinated surface water
         samples that were collected, preserved, and stored as described in Section 8. The precision
         and average recovery of triplicate analyses, conducted on Days 0, 3, 7, and 14, are presented
         in Table 7.

   13.4  EXTRACT STORAGE STABILITY STUDIES - Extract storage stability studies were
         conducted on EtOAc extracts obtained from a chlorinated surface water fortified at 5.0 //g/L.
         The precision and average recovery of triplicate injections are reported in Table 8.

14. POLLUTION PREVENTION

   14.1  This method utilizes solid phase extraction to extract analytes from water. It requires the use
         of very small volumes of organic solvent and very small quantities of pure analytes, thereby
         minimizing the potential hazards to both the analyst and the environment as compared to the
         use of large volumes of organic solvents in 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 or on-line at
         http://membership.acs.org/c/ccs/pub_9.htm.

15. WASTE MANAGEMENT

   15.1  The analytical procedures described in this method generate relatively small amounts of waste
         since only small amounts of reagents and solvents 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.
                                            527-28

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16. REFERENCES

1.   Statistical Protocol for the Determination of the Single-Laboratory Lowest Concentration Minimum
   Reporting Level (LCMRL) and Validation of the Minimum Reporting Level (MRL), available at
   www.epa.gov/OGWDW/methods/sourcalt.html

2.  Glaser, J.A., D.L. Foerst, G.D. McKee, S.A. Quave, and W.L. Budde, "Trace Analyses for
   Wastewaters", Environ. Sci. Technol.. 15 (1981) 1426_1435.

3.  "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.

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

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

6.  ASTM Annual Book of Standards, Part II, Volume 11.01, D3370-82,  "Standard Practice for
   Sampling Water," American Society for Testing and Materials, Philadelphia, PA, 1986.

7.  Erney, D.R., Gillespie, A.M., Gilvydis, D.M., and Poole, C.F., "Explanation of the Matrix-Induced
   Chromatographic Response Enhancement of Organophosphorous Pesticides During Open Tubular
   Column Gas Chromatography with Splitless or Hot On-Column Injection and Flame Photometric
   Detection." J. Chromatogr.. 638 (1993) 57-63.

8.  Mol, H.G.J., Althuizen, M., Janssen, H., and Cramers, C.A., Brinkman, U.A.Th., "Environmental
   Applications of Large Volume Injection in Capillary GC Using PTV Injectors," J. HighResol.
   Chromatogr.. 19 (1996) 69-79.

9.  Erney, D.R., Pawlowski, T.M., Poole, C.F., "Matrix Induced Peak Enhancement of Pesticides in Gas
   Chromatography," J. High Resol. Chromatogr.. 20 (1997) 375-378.

10. Hajslova, J., Holadova, K. , Kocourek, V., Poustka, J., Godula, M., Cuhra, P., Kempny, M., "Matrix
   Induced Effects: A Critical Point in the Gas Chromatographic Analysis of Pesticide Residues," _L
   Chromatogr.. 800  (1998) 283-295.

11. Wylie, P., Uchiyama, M., "Improved Gas Chromatographic Analysis of Organophosphorous
   Pesticides with Pulsed Splitless Injection," J. AOAC International 79, 2, (1996) 571-577.
                                           527-29

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17. TABLES, DIAGRAMS, FLOWCHARTS AND VALIDATION DATA

TABLE 1. ION ABUNDANCE CRITERIA FOR BIS(PERFLUOROPHENYL)PHENYL
PHOSPHINE,(DECAFLUOROTRIPHENYL PHOSPHINE, DFTPP)
Mass
(M/z)
51
68
70
127
197
198
199
275
365
441
442
443
Relative Abundance Criteria
10-85% of base peak
<2%ofm/z69
< 2% of m/z 69
10-80% of base peak
<2%ofm/zl98
Base peak or >50% ofm/z 442
5-9% ofm/z 198
10-60% of base peak
> 0.5 ofm/z 198
< 150% ofm/z 443
Base peak or >30% ofm/z 198
15-24% of m/z 442
Purpose of Checkpoint1
Low-mass sensitivity
Low-mass resolution
Low-mass resolution
Low- to mid-mass resolution
Mid-mass resolution
Mid-mass resolution and sensitivity
Mid-mass resolution and isotope ratio
Mid- to high-mass sensitivity
Baseline threshold
High-mass resolution
High-mass resolution and sensitivity
High-mass resolution and isotope ratio
*A11 ions are used primarily to check the mass measuring accuracy of the mass spectrometer and data
system, and this is the most important part of the performance test. The three resolution checks, which
include natural abundance isotope ratios, constitute the next most important part of the performance test.
The correct setting of the baseline threshold, as indicated by the presence of low intensity ions, is the
next most important part of the test. Finally, the ion abundance ranges are designed to encourage some
standardization to fragmentation patterns.
                                           527-30

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TABLE 2. RETENTION TIMES (RTs), SUGGESTED QUANTITATION IONS (QIs), AND
SUGGESTED INTERNAL STANDARD REFERENCE
Analyte
l,3-Dimethyl-2-Nitrobenzene (SUR)
Acenaphthene-dlO (IS#1)
Dimethoate
Atrazine
Propazine
Phenanthrene-dlO (IS#2)
Vinclozolin
Prometryn
Bromacil
Malathion
Chlorpyrifos
Thiobencarb
Parathion
Terbufos-Sulfone
Oxychlordane
Esbiol
Nitrophen
Kepone
Norflurazon
Hexazinone
Triphenylphosphate (SUR)
Chrysene-dl2 (IS#3)
Bifenthrin
2,2',4,4'-Tetrabromodiphenyl Ether (BDE-47)*
Mirex
2,2',4,4',6-Pentabromodiphenyl Ether (BDE-100)*
2,2',4,4',5-Pentabromodiphenyl Ether (BDE-99)*
Perylene-dl2 (SUR)
Fenvalerate
Hexabromobiphenyl
Esfenvalerate
2,2',4,4',5,5'-Hexabromodiphenyl Ether (BDE-153)*
Peak#
(Fig. 1)
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
29
30
31
32
RT
(min)
4.86
6.99
8.64
8.81
8.87
9.33
10.30
10.63
11.08
11.21
11.40
11.46
11.63
12.53
12.64
12.78
15.37
16.71
17.05
17.59
18.16
19.26
19.48
20.24
21.40
23.64
24.77
26.27
27.56
27.58
28.07
29.07
Quan.
Ion
134
164
87
200
229
188
212
241
205
173
197
100
291
153
185
123
283
272
145
171
326
240
181
326
272
403.8
403.8
264
167
308
167
643.5
IS#
Ref
1
-
1
1
1
-
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
-
3
3
3
3
O
3
3
O
3
3
*The degree of bromination of these molecules and the relative abundance of the bromine isotopes can
yield m/z values for parent and/or daughter ions that require setting fractional m/z values for ion
extraction routines. Failure to account for this can lead to poor precision.
                                          527-31

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TABLE 3. LCMRLs AND DLs IN REAGENT WATER FOR SDVB DISK PROCEDURES
Analyte
Dimethoate
Atrazine
Propazine
Vinclozolin
Prometryn
Bromacil
Malathion
Chlorpyrifos
Thiobencarb
Parathion
Terbufos-Sulfone
Oxychlordane
Esbiol
Nitrophen
Kepone
Norflurazon
Hexazinone
Bifenthrin
2,2',4,4'-Tetrabromodiphenyl Ether (BDE-47)
Mirex
2,2',4,4',6-Pentabromodiphenyl Ether (BDE-100)
2,2',4,4',5-Pentabromodiphenyl Ether (BDE-99)
Hexabromobiphenyl
Fenvalerate
Esfenvalerate
2,2',4,4',5,5'-Hexabromodiphenyl Ether (BDE-153)
Spiking
Cone.
(ug/L)1
0.10
0.10
0.10
0.20
0.10
0.20
0.20
0.10
0.20
0.20
0.10
0.35
0.10
0.20
0.20
0.20
0.10
0.20
0.10
0.10
0.35
0.20
0.37
0.35
0.20
0.20
DL
(ug/L)
0.025
0.036
0.039
0.084
0.028
0.093
0.057
0.026
0.038
0.062
0.041
0.110
0.041
0.071
0.076
0.076
0.046
0.040
0.028
0.022
0.051
0.097
0.110
0.079
0.062
0.140
LCMRL
(ug/L)
0.36
0.16
0.18
0.29
0.20
0.45
0.51
0.12
0.13
0.29
0.27
0.27
0.31
0.51
0.35
0.53
0.41
0.21
0.18
0.31
0.29
0.39
0.44
0.67
0.48
0.40
S/N@
LCMRL
7
12
15
15
17
9
12
11
10
5
18
9
15
13
5
14
22
21
6
13
6
6
10
16
12
11
Spiking concentration used to determine DL.
                                      527-32

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TABLE 4. PRECISION AND ACCURACY DATA FOR METHOD ANALYTES FORTIFIED
         AT 1.0 AND 5.0 //g/L IN REAGENT WATER EXTRACTED WITH SDVB DISKS
Analyte
Dimethoate
Atrazine
Propazine
Vinclozolin
Prometryn
Bromacil
Malathion
Chlorpyrifos
Thiobencarb
Parathion
Terbufos-Sulfone
Oxychlordane
Esbiol
Nitrophen
Kepone
Norflurazon
Hexazinone
Bifenthrin
2,2',4,4'-Tetrabromodiphenyl Ether (BDE-47)
Mirex
2,2',4,4',6-Pentabromodiphenyl Ether (BDE-100)
2,2',4,4',5-Pentabromodiphenyl Ether (BDE-99)
Hexabromobiphenyl l
Fenvalerate
Esfenvalerate
2,2',4,4',5,5'-Hexabromodiphenyl Ether (BDE-153)
l,3-Dimethyl-2-Nitrobenzene (SUR)
Triphenylphosphate (SUR)
Perylene-dl2 (SUR)
Concentration = 1.0
ug/L,
n=5
Mean %
Recovery
114
109
94.6
116
106
127
107
98.0
102
107
111
106
119
116
103
134
120
102
93.0
93.0
93.4
98.4
102
120
111
96.4
92.6
88.0
84.4
%RSD
5.3
13
9.1
5.0
4.1
5.1
2.1
3.3
1.8
4.1
4.2
3.9
4.1
3.5
4.3
1.9
7.0
1.8
5.0
3.4
8.1
8.6
5.8
3.6
3.4
10
3.2
2.0
4.8
Concentration = 5.0
ug/L,
n=5
Mean %
Recovery
85.8
85.8
82.3
93.8
85.6
103
86.4
84.6
87.0
87.4
93.2
84.0
97.2
100
82.8
106
94.1
78.7
81.3
75.4
83.6
86.8
82.0
95.6
86.3
85.4
87.7
88.4
78.5
%RSD
4.5
8.7
9.1
6.0
5.6
5.7
4.5
5.4
4.7
5.1
4.3
6.0
5.2
4.6
4.3
5.8
6.8
4.3
4.1
4.7
3.9
5.4
3.6
4.4
4.8
9.3
9.1
4.8
5.6
Precision and accuracy determinations were obtained by using a technical mixture of
Hexabromobiphenyl (Firemaster BP-6). Actual spiked concentrations for the isomer 2,2',4,4',5,5'-
Hexabromobiphenyl are 0.74 //g/L and 3.70 //g/L, respectively.
                                          527-33

-------
TABLE 5. PRECISION AND ACCURACY DATA FOR METHOD ANALYTES FORTIFIED
         AT 1.0 AND 5.0 ^g/L IN SURFACE WATER EXTRACTED WITH SDVB DISKS
Analyte
Dimethoate
Atrazine
Propazine
Vinclozolin
Prometryn
Bromacil
Malathion
Chlorpyrifos
Thiobencarb
Parathion
Terbufos-Sulfone
Oxychlordane
Esbiol
Nitrophen
Kepone
Norflurazon
Hexazinone
Bifenthrin
2,2',4,4'-Tetrabromodiphenyl Ether (BDE-47)
Mirex
2,2',4,4',6-Pentabromodiphenyl Ether (BDE-100)
2,2',4,4',5-Pentabromodiphenyl Ether (BDE-99)
Hexabromobiphenyl J
Fenvalerate
Esfenvalerate
2,2',4,4',5,5'-Hexabromodiphenyl Ether (BDE-153)
l,3-Dimethyl-2-Nitrobenzene (SUR)
Triphenylphosphate (SUR)
Perylene-dl2 (SUR)
Concentration = 1.0
ug/L,
n=5
Mean %
Recovery
112
106
92.4
115
101
119
106
94.6
96.0
105
107
94.4
114
111
91.4
122
120
96.8
92.6
79.6
95.8
108
102
124
113
108
79.8
82.8
83.2
%RSD
2.7
4.5
6.3
4.7
2.9
2.1
2.5
2.4
2.7
2.1
1.6
4.9
2.6
2.7
5.0
4.8
2.2
2.4
6.3
5.4
5.1
4.6
9.2
3.4
2.9
6.7
5.2
3.6
3.0
Concentration = 5.0
ug/L,
n=5
Mean %
Recovery
89.3
102
89.8
103
91.0
104
95.4
91.1
95.0
93.8
97.3
90.6
104
98.8
88.1
105
101
89.8
88.8
86.6
91.0
93.4
95.2
105
97.3
91.3
96.5
97.7
92.6
%RSD
2.6
2.9
4.1
6.0
4.9
3.2
4.0
4.8
4.5
4.7
4.6
3.4
4.8
3.7
4.0
3.2
3.1
5.1
2.9
5.6
1.8
2.7
2.5
3.9
3.3
5.3
14
4.2
4.2
Precision and accuracy determinations were obtained by using a technical mixture of
Hexabromobiphenyl (Firemaster BP-6). Actual spiked concentrations for the isomer 2,2',4,4',5,5'-
Hexabromobiphenyl are 0.74 //g/L and 3.70 //g/L, respectively.
                                          527-34

-------
TABLE 6. PRECISION AND ACCURACY DATA FOR METHOD ANALYTES FORTIFIED
          AT 1.0 AND 5.0 nfL IN GROUND WATER EXTRACTED WITH SDVB DISKS
Analyte
Dimethoate
Atrazine
Propazine
Vinclozolin
Prometryn
Bromacil
Malathion
Chlorpyrifos
Thiobencarb
Parathion
Terbufos-Sulfone
Oxychlordane
Esbiol
Nitrophen
Kepone
Norflurazon
Hexazinone
Bifenthrin
2,2',4,4'-Tetrabromodiphenyl Ether (BDE-47)
Mirex
2,2',4,4',6-Pentabromodiphenyl Ether (BDE-100)
2,2',4,4',5-Pentabromodiphenyl Ether (BDE-99)
Hexabromobiphenyl J
Fenvalerate
Esfenvalerate
2,2',4,4',5,5'-Hexabromodiphenyl Ether (BDE-153)
l,3-Dimethyl-2-Nitrobenzene (SUR)
Triphenylphosphate (SUR)
Perylene-dl2 (SUR)
Concentration = 1.0
ug/L,
n=5
Mean %
Recovery
114
120
97.8
116
102
128
106
100
100
103
110
102
109
109
84.4
116
114
98.2
86.6
90.4
86.4
86.8
87.8
116
111
99.8
95.4
89.8
85.8
%RSD
7.1
7.2
9.8
6.0
8.2
7.3
6.1
3.5
6.4
4.2
8.1
12
8.3
6.3
6.7
6.4
7.7
6.0
6.8
8.0
5.8
8.9
5.1
8.4
8.2
9.8
5.8
4.6
3.3
Concentration = 5.0
ug/L,
n=4
Mean %
Recovery
78.0
89.7
82.5
95.8
84.5
93.3
85.3
84.8
85.8
86.6
87.3
85.8
94.8
89.2
75.0
94.5
92.9
76.7
78.0
72.7
79.8
82.7
79.5
93.7
87.7
82.7
85.5
86.1
82.9
%RSD
4.3
9.6
9.5
8.9
9.7
9.5
10
10
9.6
9.8
11
10
8.6
8.4
7.4
7.8
7.5
11
5.6
12
3.8
4.2
6.1
7.2
9.4
4.6
12
9.6
8.5
Precision and accuracy determinations were obtained by using a technical mixture of
Hexabromobiphenyl (Firemaster BP-6). Actual spiked concentrations for the isomer 2,2',4,4',5,5'-
Hexabromobiphenyl are 0.74 //g/L and 3.70 //g/L, respectively.
                                          527-35

-------
TABLE 7. AQUEOUS SAMPLE HOLDING TIME DATA FOR SAMPLES FROM CHLORINATED SURFACE WATER, FORTIFIED
        WITH METHOD ANALYTES AT 5 /zg/L, AND PRESERVED ACCORDING TO SECTION 8
Analyte
Dimethoate
Atrazine
Propazine
Vinclozolin
Prometryn
Bromacil
Malathion
Chlorpyrifos
Thiobencarb
Parathion
Terbufos-Sulfone
Oxychlordane
Esbiol
Nitrophen
Kepone
Norflurazon
Hexazinone
Bifenthrin
2,2',4,4'-Tetrabromodiphenyl Ether
(BDE-47)
Mirex
2,2',4,4',6-Pentabromodiphenyl
Ether (BDE- 100)
2,2',4,4',5-Pentabromodiphenyl
Ether (BDE-99)
DayO
% Rec.
82.5
78.6
79.1
86.3
84.7
96.8
86.3
84.9
87.1
89.6
86.9
80.7
92.7
97.7
68.4
103
98.5
89.5
87.2
83.8
87.3
92.6
DayO
% RSD.
6.4
10
11
12
11
14
12
8.9
11
9.8
12
9.0
9.6
8.5
10
11
5.8
2.5
1.1
2.5
4.4
3.1
Day 7
% Rec.
95.8
78.9
78.7
83.1
85.5
98.5
86.1
81.8
90.4
87.3
89.5
78.9
93.1
94.8
70.8
102
92.8
80.9
75.6
75.7
83.5
77.7
Day 7
% RSD.
2.3
0.1
1.2
2.8
2.4
2.0
3.7
1.4
3.8
1.3
2.5
5.4
3.8
4.0
2.8
2.6
2.1
8.1
9.0
9.7
11
8.2
Day 14
% Rec.
88.0
72.7
74.3
81.7
84.7
101
85.2
83.5
86.9
88.1
88.7
77.6
91.3
96.4
71.7
101
116
87.6
87.2
84.3
88.9
94.1
Day 14
% RSD.
6.7
14
14
16
10
8.6
10
10
13
12
14
12
14
9.0
15
12
7.9
4.8
6.4
5.5
4.2
6.1
Day 21
% Rec.
80.9
72.6
72.1
80.6
82.9
95.4
79.6
74.9
85.1
85.4
84.3
75.7
89.8
90.8
74.9
99.4
110
78.7
76.5
71.8
78.6
84.5
Day 21
% RSD.
6.2
5.9
6.7
5.9
4.8
5.5
4.9
4.8
4.9
3.7
5.1
5.6
4.1
8.0
1.9
4.2
4.0
5.8
4.2
6.2
2.9
6.9
Day 28
% Rec.
87.1
75.5
72.1
78.9
85.3
109
85.5
75.3
86.5
92.7
86.8
68.8
88.9
96.3
75.7
114
130
72.7
71.0
64.5
74.5
78.9
Day 28
% RSD.
9.6
9.5
9.9
7.2
7.5
7.3
7.8
6.8
6.9
6.4
7.1
7.0
7.3
6.2
9.6
7.0
3.7
5.2
6.8
6.7
2.6
4.8
                                                 527-36

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TABLE 7. AQUEOUS SAMPLE HOLDING TIME DATA FOR SAMPLES FROM CHLORINATED SURFACE WATER, FORTIFIED
          WITH METHOD ANALYTES AT 5 //g/L, AND PRESERVED ACCORDING TO SECTION 8 (CONTINUED)
Analyte
Hexabromobiphenyl
Fenvalerate
Esfenvalerate
2,2 ' ,4,4 ' , 5 , 5 ' -Hexabromodiphenyl
Ether (BDE- 153)
l,3-Dimethyl-2-Nitrobenzene (SUR)
Triphenylphosphate (SUR)
Perylene-dl2 (SUR)
DayO
% Rec.
92.5
116
103
89.8
74.9
79.9
96.9
DayO
% RSD.
4.4
2.9
3.3
4.6
7.7
9.8
8.3
Day 7
% Rec.
76.9
97.7
84.6
79.2
81.9
84.2
89.5
Day 7
% RSD.
11
18
12
28
5.1
2.4
3.9
Day 14
% Rec.
92.4
104
102
93.3
80.3
87.7
92.1
Day 14
% RSD.
5.2
5.1
5.1
6.1
12
16
5.2
Day 21
% Rec.
80.5
106
96.9
84.9
79.3
90.8
99.1
Day 21
% RSD.
10.6
14
12
5.1
8.1
4.8
4.5
Day 28
% Rec.
74.9
97.3
92.4
87.5
82.4
96.6
104
Day 28
% RSD.
3.7
6.9
2.5
10
9.7
7.5
4.3
Average recovery and precision are based on five samples.
                                                     527-37

-------
TABLE 8. EXTRACT HOLDING TIME DATA FOR SAMPLES FROM CHLORINATED SURFACE WATER, FORTIFIED WITH
        METHOD ANALYTES AT 5 ^g/L, AND PRESERVED ACCORDING TO SECTION 8
Analyte
Dimethoate
Atrazine
Propazine
Vinclozolin
Prometryn
Bromacil
Malathion
Chlorpyrifos
Thiobencarb
Parathion
Terbufos-Sulfone
Oxychlordane
Esbiol
Nitrophen
Kepone
Norflurazon
Hexazinone
Bifenthrin
2,2',4,4'-Tetrabromodiphenyl Ether
(BDE-47)
Mirex
2,2',4,4',6-Pentabromodiphenyl
Ether (BDE- 100
2,2',4,4',5-Pentabromodiphenyl
Ether (BDE-99)
DayO
% Rec.
82.5
78.6
79.1
86.3
84.7
96.8
86.3
84.9
87.1
89.6
86.9
80.7
92.7
97.7
68.4
103
98.5
89.5
87.2
83.8
87.3
92.6
DayO
% RSD.
6.4
10
11
12
11
14
12
8.9
11
9.8
12
9.0
9.6
8.5
10
11
5.8
2.5
1.1
2.5
4.4
3.1
Day 7
% Rec.
87.5
78.1
76.0
85.3
89.6
104
89.7
87.0
92.2
90.4
94.4
81.8
94.2
95.8
73.7
105
98.9
88.9
84.2
86.1
92.2
90.0
Day 7
% RSD.
8.8
13
11
13
0.0
0.7
3.3
3.3
2.5
0.3
2.1
4.1
2.7
5.3
0.2
1.8
2.1
2.1
2.3
3.0
5.2
6.4
Day 14
% Rec.
84.1
76.3
77.1
88.8
86.1
98.6
87.5
87.4
88.7
89.7
90.9
83.7
92.8
98.2
75.3
106
122
84.5
86.7
81.3
87.5
88.2
Day 14
% RSD.
11
14
15
14
12
12
14
12
12
12
14
3.9
12
10
11
10
8.4
2.8
3.2
2.2
1.0
0.8
Day 21
% Rec.
86.9
78.9
78.7
90.3
87.1
102
84.4
83.7
90.4
90.7
90.1
82.3
96.0
97.9
74.9
117
123
86.3
81.1
80.5
85.1
95.2
Day 21
% RSD.
9.4
14
14
12
13
13
12
11
10
14
13
4.3
11
13
12
19
11
2.2
1.4
5.2
2.4
3.1
Day 28
% Rec.
94.2
86.1
83.3
87.5
87.0
112
89.4
84.4
88.6
96.2
90.5
87.6
92.9
100
75.5
115
135
87.6
85.7
82.5
87.0
95.1
Day 28
% RSD.
4.9
12
13
11
12
13
11
7.4
10
12
12
5.4
9.0
8.8
11
12
13
5.2
1.6
6.9
1.7
3.9
                                                 527-38

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TABLE 8. EXTRACT HOLDING TIME DATA FOR SAMPLES FROM CHLORINATED SURFACE WATER, FORTIFIED WITH
          METHOD ANALYTES AT 5 ^g/L, AND PRESERVED ACCORDING TO SECTION 8. (CONTINUED)
Analyte
Hexabromobiphenyl
Fenvalerate
Esfenvalerate
2,2 ' ,4,4 ' , 5 , 5 ' -Hexabromodiphenyl
Ether (BDE- 153)
l,3-Dimethyl-2-Nitrobenzene (SUR)
Triphenylphosphate (SUR)
Perylene-dl2 (SUR)
DayO
% Rec.
92.5
116
103
89.8
74.9
79.9
96.9
DayO
% RSD.
4.4
2.9
3.3
4.6
7.7
9.8
8.3
Day 7
% Rec.
85.1
107
94.7
90.5
75.1
90.1
92.9
Day 7
% RSD.
8.7
2.4
4.4
9.1
10
3.9
3.4
Day 14
% Rec.
89.0
101
102
84.9
76.1
88.5
89.0
Day 14
% RSD.
0.4
3.9
1.9
5.4
9.3
12
3.7
Day 21
% Rec.
89.7
120
110
92.3
77.6
92.9
98.5
Day 21
% RSD.
1.2
8.4
5.4
3.3
13
11
12
Day 28
% Rec.
94.5
119
110
104
79.9
94.4
107
Day 28
% RSD.
4.2
8.5
5.9
6.0
11
13
7.4
%Recovery and %RSD calculated based on triplicate injections of a single sample extract that was split into enough vials to permit a new vial to be
used on each day of the holding time study.
                                                          527-39

-------
TABLE 9.  INITIAL DEMONSTRATION OF CAPABILITY QUALITY CONTROL
REQUIREMENTS
  Method
  Reference
Requirement
Specification and
Frequency	
Acceptance Criteria
  Section
  9.2.1
Initial
Demonstration of
Low System
Background
Analyze LRB prior to any
other IDC steps
Demonstrate that all target
analytes are below 1/3 the
reporting limit or lowest
calibration standard, and that
possible interferences from
extraction media do not prevent
the identification and
quantification of method analytes.
  Section
  9.2.4
Minimum
Reporting Limit
(MRL)
Confirmation
Fortify, extract and analyze
7 replicates at the proposed
MRL concentration.
Calculate the mean and the
Half Range (HR).  Confirm
that the upper and lower
limits for the Prediction
Interval of Result (Upper
PIR, and Lower PIR, Sect.
9.2.4.2) meet the recovery
criteria.
                                                           Upper PIR < 150%

                                                           Lower PIR > 50%
  Section
  9.2.2
Initial
Demonstration of
Precision (IDP)
Analyze 4-7 replicate LFBs
fortified near the midrange
concentration
%RSDmustbe  < 20%
  Section
  9.2.3
Initial
Demonstration of
Accuracy
Calculate average recovery
for replicates used in IDP
Mean recovery + 30% of true
value
                                           527-40

-------
TABLE 10.   ONGOING QUALITY CONTROL REQUIREMENTS (SUMMARY)
  Method
  Reference
Requirement
Specification and
Frequency	
Acceptance Criteria
  Section
  10.2.1
MS Tune Check
Analyze DFTPP to verify
MS tune each time the
instrument is calibrated.
Criteria are given in Table 1, or
the system
meets the manufacturer's
recommended criteria
  Section
  10.2
Initial Calibration
Use internal standard
calibration technique to
generate an average RRF or
first or second order
calibration curve.  Use at
least 5 standard
concentrations.  Check the
calibration curve as
described in Sect. 10.2.6.
When each calibration standard
is calculated as an unknown
using the calibration curve, the
result should be 70-130% of the
true value for all except the
lowest standard, which should
be 50-150% of the true value.
Recalibration is recommended
if these criteria are not met.
  Section
  9.3.1
Laboratory Reagent
Blank (LRB)
Daily, or with each
extraction batch of up to 20
samples, whichever is more
frequent.
Demonstrate that all target
analytes are below l/j the MRL,
and confirm that possible
interferences do not prevent
quantification of method
analytes. If targets exceed l/j
the MRL, results for these
subject analytes in the
extraction batch are invalid.
  Section
  10.3
Continuing
Calibration Check
(CCC)
Verify initial calibration by
analyzing a calibration
standard at the beginning of
each analysis batch prior to
analyzing samples, after
every 10 samples, and after
the last sample.

Low CCC - at or below the
MRL concentration
Mid CCC - near midpoint in
initial calibration curve
High CCC - near the highest
calibration standard.
                                            527-41
                                                               50% of true value
                                                              30% of true value
                                                              30% of true value

-------
Method
Reference
Requirement
Specification and
Frequency	
Acceptance Criteria
Section
9.3.3
Laboratory
Fortified Blank
(LFB)
One LFB is required daily or
for each extraction batch of
up to 20 field samples.
Rotate the fortified
concentrations between low,
medium, and high amounts.
Results of LFB analyses at
medium and high fortifications
must be 70-130% of the true
value for each analyte and
surrogate. Results of the low-
level LFB must be 50-150% of
the true value.
Section     Internal Standard
9.3.5        (IS)
                    Acenaphthene-6?7o
                    phenanthrene-6?7o (IS#2), and
                    chrysene-t/72 (IS#3), are
                    added to all standards and
                    sample extracts.  Compare IS
                    areas to the average IS area
                    in the initial calibration.
                             Peak area counts for all ISs in
                             LFBs, LRBs, and sample
                             extracts must be within + 50%
                             of the average peak area
                             calculated during the initial
                             calibration and + 30% from the
                             most recent CCC.  If ISs do not
                             meet this criterion,
                             corresponding target results are
                             invalid.
Section
9.3.6
Surrogate Standards
Surrogate standards, 1,3-
dimethyl-2-nitrobenzene,
triphenylphosphate, and
perylene-6?72 are added to all
calibration standards and
samples, including QC
samples. Calculate surrogate
recoveries.
Surrogate recovery must be 70-
13 0% of the true value. If a
surrogate fails this criteria,
report all results for sample as
suspect/surrogate recovery.
Section     Laboratory
9.3.7        Fortified Sample
            Matrix (LFSM)
                    Analyze one LFSM per
                    analysis batch (20 samples or
                    less) fortified with method
                    analytes at a concentration
                    close to but greater than the
                    native concentration.
                    Calculate LFSM recoveries.
                             Recoveries at mid and high
                             levels not within 70-130% or
                             low-level recoveries not within
                             50-150% of the fortified
                             amount may indicate a matrix
                             effect.
Section     Laboratory
9.3.8        Fortified Sample
            Matrix Duplicate
            (LFSMD)  or
            Field Duplicates
            (FD)
                    Extract and analyze at least
                    one FD or LFSMD with each
                    extraction batch (20 samples
                    or less). A LFSMD may be
                    substituted for a FD when
                    the frequency of detects are
                    low. Calculate RPDs.
                             Target analyte RPDs for the
                             LFMD or FD should be
                             <30% at mid and high levels of
                             fortification and < 50% near the
                             MRL.
                                           527-42

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Method
Reference
Requirement
Specification and
Frequency	
Acceptance Criteria
Section
9.3.9
Quality Control
Sample (QCS)
Analyze QCS during the IDC
and at least quarterly.
Results must be 70-130% of
the expected value.
Section
8.4
Sample Holding
Time
14 days with appropriate
preservation and storage
Sample results are valid only
if samples are extracted
within sample hold time.
Section
8.4
Extract Holding
Time
28 days with appropriate
preservation and storage
Sample results are valid only
if extracts are analyzed within
extract hold time.
                                          527-43

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FIGURE 1. EXAMPLE CHROMATOGRAM FOR A REAGENT WATER FORTIFIED WITH METHOD 527 ANALYTES AT 5 (iG/L.
NUMBERED PEAKS ARE IDENTIFIED IN TABLE 2.


















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1






































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3






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a
6


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7 10
8










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9



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12 15

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13







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21


20
17












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19



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1
ll
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24
26 28
27
32
1

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18 20 22 24 26 28 30 32
                                                        Time (Minutes)
                                                     527-44

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