&EPA
United States            Office of Water (WH-550)     EPA 810-B-92-011
Environmental Protection    Office of Pesticides and      February 1992
Agency                Toxic Substances (H-7501C)
                 QUALITY ASSURANCE PROJECT PLAN
                                FOR THE
      NATIONAL PESTICIDE SURVEY OF DRINKING WATER WELLS
                         ANALYTICAL METHOD 3
                                Prepared by:

                         Environmental Chemistry Section
                           Office of Pesticide Programs
                       U.S. Environmental Protection Agency
                             NASA/SSC Bldg. 1105
                      Stennis Space Center, MS 39529-6000
                                Prepared for:

                       U.S. Environmental Protection Agency
                           Technical Support Division
                            Office of Drinking Water
                          26 W. Martin Luther King Drive
                            Cincinnati, Ohio 45268
                          U.S. Environmental Protection Agency
                          Region 5, Library (PL-12J)
                          77 West Jackson Boulevard, 12th Floor
                          Chicago, II  60604-3590

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                                                                        Section No 1
                                                                        Revision No 4
                                                                        Date- December 1989
                                                                        Page 2 of 2
                                    APPROVAL PAGE
4
           Robert Maxey
                            _,  ECS Project Leader
                            _,  EPA Technical Monitor
           Aubry E. Dupuy, Jr.    Section Chief, ECS
                            _,  Acting ECS QAC
           Danny McDaniel
           Lora Johnson
           Elizabeth Leovey
                             ,  NPS QAO
                             ,  OPP QA Officer
 List for Distribution:

      R. Maxey, OPP/ECS
      A. Dupuy, OPP/ECS
      D. McDanie! OPP/ECS
      L Johnson, NPS QAO
      E. Leovey, OPP/QAO
      G. Gardner, OPP/ECS
      S. Mecomber, OPP/ECS
      E. Flynt, OPP/ECS
      J. Watkins, STI

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                                                                       Section No 2
                                                                       Revision No 4
                                                                       Date  December 1989
                                                                       Page 1 of 6
                             NATIONAL PESTICIDE SURVEY
                        QUALITY ASSURANCE PROJECT PLAN FOR
                                ANALYTICAL METHOD 3
2.    TABLE OF CONTENTS

 Section                                                   Pages     Revisions     Date

    1.   TITLE AND APPROVAL PAGE                          2          4        12/89

    2.   TABLE OF CONTENTS                                6          4        12/89

    3.   PROJECT DESCRIPTION                              1       ;-  4        12/89

    4.   PROJECT ORGANIZATION AND RESPONSIBILITIES        2          4        12/89

    5.   QUALITY ASSURANCE OBJECTIVES FOR
         MEASUREMENT DATA                                5          4        12/89
         5.1   Initial Determination of Capabilities;
                Determination of EDLs; Determination
                of Reporting Levels
         5.2   Determining and Reporting the Presence
                of NPS Analytes Below the Minimal
                Reporting Levels (MRL) and Identifying
                Unknown Peaks
              5.2.1  Procedure for Determining and
                       Reporting the Presence of
                       NPS Analytes Below the MRL
              5.2.2  Procedure for Determining the
                       Identity of and Reporting
                       the Presence of Non-NPS
                       Analytes
         5.3   Laboratory QC Requirements for Primary
                Analysis
         5.4   Laboratory QC Requirements for Secondary
                Column Analysis
         5.5   Laboratory QC and Extract Handling Related
                to GC/MS Confirmation
         5.6   Sample Management

    6.   SAMPLING PROCEDURES                             4          4        12/89
         6.1   Sample Requirements
         6.2   Labelling of Sample Bottles
         6.3   Field Sample Tracking Form

    7.   SAMPLE CUSTODY                                   6          4        12/89
         7.1   Tracking and Notification of Sample
                Shipments
         7.2   Sample Requirements Following Receipt at
                Laboratory
              7.2.1  Storage Conditions
              7.2.2  Holding Times
              7.2.3  Disposal

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                                                                          Section No 2
                                                                          Revision No 4
                                                                          Date- December 1989
                                                                          Page 2 of 6
2.    TABLE OF CONTENTS (continued)

 Section            ,                                         Pages     Revisions     Date

         7.3   Return of Sample Kits to EPA Contractor
                 (ICF)
         7.4   Receipt of Extracts from Analytical Contractors
                 for GC/MS Confirmation at ECL
         7.5   Internal Practices Concerning Sample Storage

     8.   CALIBRATION PROCEDURES AND FREQUENCY           7          4        12/89
         8.1    Method 3 Standards
               8.1.1   Calibration Solutions
               8.1.2   Standards Prepared at ECL
               8.1.3   QA for Diluting  and Checking the
                        Standards
               8.1.4   Calibration Solutions and ECL
                        Standards Verification
               8.1.5   Frequency of Calibration Standards
                        Checks
               8.1.6   Association of Calibration Standards
                        to Survey Sample Analysis
         8.2   Instrumentation Checks and Quantitation Procedure
               8.2.1   Calibration of HR GC/MS
               8.2.2   Calibration of Low Resolution GC/MS

     9.   ANALYTICAL PROCEDURE                               4          4        12/89
         9.1    Summary of Method
         9.2   Major Equipment/Instrumentation to Be Used With
                 Method 3
         9.3   Analytical Method
               9.3.1   Method as Developed by Battelle
               9.3.2   Differences from Battelle Method
               9.3.3   Requirement for Authorization to Deviate
                        from Battelle's Method
         9.4   Sample Sets

   10.   DATA REDUCTION, VALIDATION AND REPORTING          6          4        12/89
         10.1   Data Reduction
         10.2   Data Validation
         10.3   Data Reporting
         10.4   Storage of Lab. Data
         10.5   Fast-Track Reporting   •
         10.6   GC/MS-Data Reduction, Validation, and Reporting
               10.6.1  Data Reduction
               10.6.2  Data Validation
               10.6.3  Data Reporting
               10.6.4  Filing and Storage of GC/MS Data

   11.   INTERNAL QUALITY CONTROL CHECKS                  11          4        12/89
         11.1   Primary Analyses
         11.2   Confirmational (Secondary-Column) GC Analyses
         11.3   GC/MS Confirmation

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                                                                        Section No 2
                                                                        Revision No 4
                                                                        Date  December 1989
                                                                        Page 3 of 6
2.   TABLE OF CONTENTS (continued)

 Section
         11.4 Control Charts
              11.4.1  Establishing Control Charts
              11.4.2  Outliers
              11.4.3  Plotting Data on Control Charts
              11.4.4  Out-of-Control Situations
              11.4.5  Updating Control Charts
         11.5 Other QC Checks Performed at ECL
              11.5.1  Diazomethane QC Check
              11.5.2  Florisil Elution Check
              11.5.3  QC Datasheet
              11.5.4  QA Data Form
         11.6 Exceptions to the QAPjP
              11.6.1  Request for Approval
              11.6.2  Documentation and Following
                       Requirements

         AUDITS
         12.1 Requirements
         12.2 Frequency
         12.3 Nature of Audits
              12.3.1 Tech. Systems to be Addressed
              12.3.2  Data Quality Audits
              12.3.3  Performance Evaluation Audits
         12.4 Standard
         12.5 Reporting and use of Audit Results
                                                                 Revisions
Date
12.
   13.
   14.
12/89
      PREVENTATIVE MAINTENANCE
      13.1  Gas Chromatographs
      13.2  GC/MS

      SPECIFIC PROCEDURES FOR ASSESSING
      MEASUREMENT SYSTEM DATA
      14.1  Formulas Related to Instrument Control
             Standards and Determination of
             Chromatographic and Column
             Performance
      14.2  Formulas for Calculating Statistics
      14.3  Formulas for Defining Control Limits
   15.    CORRECTIVE ACTION

   16.    QUALITY ASSURANCE REPORTS TO
         MANAGEMENT
12/89
                                                                                 12/89
                                                                              12/89

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                                                                      Section No 2
                                                                      Revision No 4
                                                                      Date  December 1989
                                                                      Page 4 of 6
2. TABLE OF CONTENTS (continued)
Appendices Pages
A.
B.
C.
D.
E.
F.
G.
H.
1.
J.
*K.
*L
SAMPLE CUSTODY
BATTELLE'S VERSION OF NPS METHOD 3
DIAZOMETHANE PREPARATION AND SAFETY
DATA FLOW (REDUCTION, VALIDATION, AND
REPORTING)
SIGNIFICANT FIGURES AND ROUNDING OF NUMBERS
STORAGE OF NPS HARDCOPY DATA FILES AT ECL
DIXON'S TEST
ADDITIONAL QUALITY CONTROL CHECKS
ECL COMPUTER PROGRAMS
RAPID REPORTING NOTIFICATION
GC/MS CHARACTERISTIC IONS FOR METHOD 3
ADDENDA TO METHOD 1 :
6
50
6
12
4
3
3
13
3
6
2

Revisions
4
4
4
4
4
4
4
4
4
4
4

Date
12/89
12/89
12/89
12/89
12/89
12/89
12/89
12/89
12/89
12/89
12/89

      JUNE 1988 TO DECEMBER 1989
12/89
In this QAPJP Rev. 4, an asterisk in the left hand margin of the text indicates an addition or
revision to the ECS NPS QAPJP Rev. 3 of June 15, 1988.  The edited text will be followed by an
effective date in parenthesis and, when applicable, a reference to the addendum in Appendix L
which addressed the change.

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Section No  2
Revision No. 4
Date'  December 1989
Page 5 of 6
2. LIST OF FIGURES
Figure
ECL ANALYTICAL TEAM - METHOD 3
LABEL OF SAMPLE BOTTLES
FIELD SAMPLE TRACKING FORM
SAMPLE RECEIPT SCREENS FOR NPS LABORATORIES
TEMPERATURE MONITORING CHART EPA/ECL
NPS EXTRACT SHIPMENT
STANDARD SOLUTION DATA FORM
CALIBRATION SOLUTION RECEIVING FORM
STANDARD DILUTION FORM
FLOW CHART FOR DATA REDUCTION, VALIDATION,
AND REPORTING
MASS SPEC CONFIRMATION SHEET
DIAZOMETHANE QC FORM
ADSORBENT CHECK FORM
EXCEPTIONS TO NPS QAPjP
EQUATION USED TO CALCULATE PEAK SYMMETRY
FACTOR (PSF) AND PEAK GAUSSIAN FACTOR (PGF)
EPA REFEREE LABORATORY PROGRESS - QA REPORT
TECHNICAL MONITOR PROGRESS - QA REPORT
ANALYTICAL COORDINATOR STATUS REPORT

Figure No.
4-1
6-1
6-2
7-1
7-2
7-3
8-1
8-2
8-3
10-1
10-2
11-1
11-2
11-3
14-1
16-1
16-2
16-3

Section
4
6
6
7
7
7
8
8
8
10
10
11
11
11
14
16
16
16

Page
2 of 2
3 of 4
4 of 4
4 of 6
5 of 6
6 of 6
5 of 7
6 of 7
7 of 7
5 of 6
6 of 6
7 of 11
9 of 11
11 of 1 1
3 of 3
2 of 4
3 of 4
4 of 4

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                                                                      Section No 2
                                                                      Revision No. 4
                                                                      Date December 1989
                                                                      Page 6 of 6
2.   LIST OF TABLES

Title

ENVIRONMENTAL CHEMISTRY LABORATORY SAMPLE
REQUIREMENTS
Table No.
   6-1
Section
           2 of 4

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                                                                             Section No 3
                                                                             Revision No 4
                                                                             Date: December 1989
                                                                             Page 1 of 1
3.   PROJECT DESCRIPTION

     The National Pesticide Survey (NPS) of drinking water wells is a joint project between the EPA
Office of Pesticide Programs (OPP) and Office of Drinking Water (ODW). Expectations for the full

Survey are that well-water samples will be analyzed for over 100 pesticides or degradation products
from approximately 1500 domestic and community water system wells. Seventeen of these analytes

are included in NPS Method 3 with which phenoxy and phenol compounds will be determined.

     There is a referee laboratory for each method; the OPP Environmental  Chemistry Laboratory at

Bay St. Louis, MS  will serve this function for NPS Method 3. The roles of the  referee laboratory in this

Survey are:
     •     to analyze duplicates of samples sent to the analytical contractor (primary lab.)
           limited to 20% or a maximum of 5 samples per week from those  taken the first 6
           months;

           to perform High Resolution GC/MS Confirmation of low concentration suspected
           residues not amenable to analysis by Low Resolution GC/MS;

     •     to provide a Technical Monitor and/or EPA Project Officer to oversee analytical
           and/or contractual aspects of work done by the analytical contractor;

           to evaluate any QC activities required of the analytical contractors, including
           conducting and participating in NPS audits;

     •     to provide verification analyses of blind samples;

     •     and to verify prior to use all analytical standards prepared for use with this method
           by EPA/Technical Support Division - Cincinnati or their contractor.
     The phenoxy - phenol pesticides and/or degradation products  included as analytes for this

method are:
     1/    Acifluoffen
           Bentazon
     1/    Chloramben (Amiben)
           2,4-D
           Dalapon
           2,4-DB
           DCPA acid metabolites
           Dicamba
           3,5-Dichlorobenzoic acid
           Dichlorprop (2,4-DP)
           Dinoseb
     1/    5-Hydroxy dicamba
     1/    4-Nitrophenol
           PCP
           Picloram
           2,4,5-T
           2,4,5-TP (Silvex)
     1/    Qualitative Analyte

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                                                                           Section No 4
                                                                           Revision No. 4
                                                                           Date.  December 1989
                                                                           Page 1 of 2
4.    PROJECT ORGANIZATION AND RESPONSIBILITIES
      Referee laboratory responsibilities for NPS Method 3 will be carried out by OPP's Environmental
Chemistry Lab. (ECS) which is managed by Dr. Aubry E. Dupuy, Jr., Section Chief. Mr. Robert Maxey,
chemist at ECS, will serve as both EPA Technical Monitor and Project Officer for the Method.  Mr.
Maxey, as ECS Project Leader, will also be responsible for day-to-day management of NPS analytical
activities.  Mr. Danny McDaniel, Acting ECS-QAO, will provide QA oversight (effective 050189; see
Appendix L; Addendum of 050189).  The Sample Custodian for ECS and for the NPS Project is Gerald
Gardner.
      Mr. Stanley Mecomber and Ms. Elizabeth Flynt will handle sample preparation. Analytical work
will be handled by Ms. Jan Watkins backed up by Ms. Elizabeth Flynt.  Data review has been
assigned to Mr.  William Mitchell and  Mr. Joe Ferrario. Data handling and reporting will be handled by
Ms. Watkins backed up by Ms. Flynt. Mr. Joe Ferrario will  provide Low Resolution GC/MS confirmation
while Mr. Danny McDaniel will handle High Resolution GC/MS work (effective 050189; see Appendix L;
Addendum of 050189). Refer to the  Method 3 Organization Chart, Figure 4-1, at the end of
this Section.
      Federal Express shipments of  samples and of extracts for GC/MS analysis to ECS-Bay St. Louis,
MS should be addressed to ECL's Sample Custodian:
*         U.S. EPA
          Environmental Chemistry Section
          NASA/SSC Bldg. 1105
          STENNIS  SPACE CENTER, MS 39529-6000
          ATTN: Gerald Gardner
          (601) 688-3170 (or 3217)
*    The Assistant Sample Custodians for NPS are:
          Mr. John Cuevas
          (601) 688-3170 (or 3217)
          Mr. Stanley Mecomber
          (601) 688-3170 (or 3217)
          (effective 081288; see Appendix L; Addendum of 081288)
     The telephone number for the  EPA Technical Monitor and Project Officer for NPS Method 3 is:
          Mr. Robert Maxey
          (601) 688-1225 (or 3217)
     In Mr. Maxey's absence, Dr. Aubry Dupuy will serve as the appropriate EPA contact for
Technical Monitor and Project Officer responsibilities for Method 3.
          Dr. Aubry E. Dupuy
          (601) 688-3212

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                                              Section No 4
                                              Revision No 4
                                              Date  December 1989
                                              Page 2 of 2
            FIGURE 4-1

ECS ANALYTICAL TEAM - METHOD 3

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                                                                            Section No 5
                                                                            Revision No 4
                                                                            Date' December 1989
                                                                            Page 1 of 5
5.    QA OBJECTIVES FOR MEASUREMENT DATA

      5.1   Initial Determination Of Capabilities; Determination Of EDLs; Determination Of
           Reporting Levels

      1.    Determine concentration of standard necessary to produce an instrument detector
           response with a 5/1 signal to noise ratio.

      2.    Spike eight reagent water samples at the concentration determined above, and analyze in
           a single day analyte run.

      3.    Compute Minimum Detectable  Level (MDL) by multiplying the standard deviation by the
           Student's t value, appropriate for a 99% confidence level, and a standard deviation
           estimate with n-1 degrees of freedom.

      4.    The EDL equals either the concentration of analyte yielding a detector response with a 5/1
           signal to noise ratio, or the  calculated MDL, whichever is greater.

      5.    Determined EDLs must be no greater than twice those determined during methods
           development.

      6.    The acceptability of EDLs exceeding the above  limits will be determined by the Technical
           Monitor, based on health effect values.

      7.    These eight EDL extracts will also be analyzed using the confirmation column. EDLs
           determined on the confirmational column must equal those determined on the primary
           column; if  not, the higher of the two EDLs will prevail to assure that there is a minimal
           response on both columns.  Again, EDLs exceeding this requirement will be approved on
           a case-by-case basis, by the Technical Monitors.

*     8.    The laboratories will be required to perform up to six analyses per analyte mix by GC/MS,
           for the appropriate Methods. These analyses will be performed by MID, using the three
           ions specified by EPA. The  purpose of these analyses are to determine the concentration
           at which a 5/1 signal to noise ratio, for the least intense of the three ions, is obtained. See
           Appendix K for a Table of the three ions for each analyte (effective 06/15/88; see
           Appendix L; Addendum Of 07/12/88).

      9.    The Minimum  Reportable Level (MRL) for Method 3 is 5 X EDL.

      10.   The lower  concentration calibration standard must be prepared at a concentration equal
           to the minimum reportable level.

      5.2   Determining and Reporting the Presence of NPS Analytes Below the Minimal
           Reporting Levels and Identifying Unknown Peaks

Background Information

      The Office of Pesticide Programs  (OPP)  has requested that the NPS analytical contractors and

referee laboratories make an effort to report the presence of NPS analytes below the Minimal

Reporting Levels (MRL). We have also  been requested to attempt to identify  unknown peaks or

responses.  To assure that spurious or  ambiguous data is not reported and that a uniform system or

analytical routine is used at all laboratories to accomplish these requests, the following procedures will
be used.

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                                                                            Section No. 5
                                                                            Revision No 4
                                                                            Date:  December 1989
                                                                            Page 2 of 5
           5.2.1   Procedure for Determinining and Reporting the Presence of NPS Analytes
                  Below the Minimal Reporting Level

      1.    For Method 3, only peaks with responses of between one-half the established MRL and
           the MRL A/ on the primary column will be investigated.  The first time such a response is
           noted on the primary column, no further analytical work is underdertaken; the second time
           such a response is noted, analysis on the confirmatory GC column is required.

      2. (a)  For Method 3, if the response on the second column is positive, further analytical work
           under (3) below is required.

        (b) For Method 3, if the response on the second column is negative, that fact is noted. After
           five attempts at second column confirmation have failed for the same analyte, the ECL
           Project Leader is informed, and discussions with OPP personnel will take place before
           continuation of analytical work on that analyte.

      3.    For responses meeting the requirements of (1) and 2(a), the laboratory will attempt LR
           GC/MS B/ confirmation if the GC/MS analyst feels it is within the capability of his
           instrument. If the confirmation is not within the capability of the LR GC/MS, the extracts
           will be run on HR GC/MS.  Copies of chromatograms the related Method Blank, and all
           pertinent sample information must accompany the extracts.  Correct volume level should
           be clearly marked on the outsid^ of the extract tube.
           A/    =    NPS Method 3   MRL = 5 X EDL

           B/    =    LR GC/MS = Low resolution mass spectrometry
                      HR GC/MS = High resolution mass spectrometry

           Only analytes positively confirmed by GC/MS will be reported beyond the ECL Project
           Leader for Method 3 and the Analytical Coordinators.  No unconfirmed data will be
           reported outside the NPS analytical system. Unsuccessful attempts at confirmation will
           also be reported to the ECL Project Leader.

      5.    Following either the successful GC/MS confirmation of two such responses for the same
           analyte or two successive failures to confirm the analyte without any prior successful
           GC/MS confirmation on any samples, discussions with OPP personnel will take place
           before continuing low-level analytical work on that particular analyte.

      6.    As a referee laboratory, ECL will also be receiving sample extracts from the contractor
           when HR GC/MS work is required.  These extract shipments will be received and logged
           in by the ECL Sample Custodian or his Representative, and the ECL Project  Leader will be
           notified.

           5.2.2   Procedure for Determining The Identity of and Reporting the Presence of
                  NonNPS Analytes

      It is expected that, over the course of the NPS Program, numerous extraneous responses will be

evident on chromatograms from the various methods. The referee laboratories will be required to

attempt identification of peaks or responses exhibiting the minimal criteria below.

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                                                                       Section No  5
                                                                       Revision No 4
                                                                       Date-  December 1989
                                                                       Page 3 of 5
 1.    For Method 3, if the response of an extraneous peak upon initial injection and
      exclusive of the Method Blank, on the primary column is equal to or greater than the
      response of the nearest NPS analyte on that column at 10X MRL (Minimal Reporting
      Level), an attempt must be made to identify that peak by GC/MS. Full scan spectra
      and subsequent library search is expected and must be followed by comparison of
      the spectra of the unknown compound with that of an authentic  standard of the
      suspected  compound.

 2.    The work in (1) must be attempted on the first  occurrence of such a peak and the
      results of the attempt at confirmation reported to the ECL Project Leader for Method
      3.  If the LR GC/MS analyst feels  his instrument is not capable of the confirmatory
      work, the extract is submitted to the HR GC/MS analyst. Volume level of extract
      should be marked on the outside of the extract vial.

      Specific sample and analytical information must accompany each such extract.

           Sample i.d. number, weight of sample matrix contained in the vial,
           copies of chromatograms from the primary GC column, identification of
           the retention window for the unknown peaks as defined by the last NPS
           analyte to elute before the unknown peak and the first NPS analyte to
           elute following the unknown peak. The related Method Blank extract
           must also be included.

 3.    Only those compounds positively confirmed by GC/MS  will be reported beyond the
      ECL Project Leader for Method 3 and the Analytical Coordinators. No unconfirmed
      data will  be reported outside the NPS analytical system. Unsuccessful attempts at
      identification will also be reported to the ECL Project Leader.

 4.    Following either the successful confirmation of  two such extraneous peaks proving
      to be the same compound or two failures to identify the same unknown peak,
      discussions with OPP personnel will take place before continuation with
      identification work on that particular compound.

 5.3   Laboratory QC Requirements For Primary Analyses

 1.    Laboratory control standard mixes, which together contain all method analytes and the
      surrogate, will be analyzed with each set of samples.

2.    A set of samples is defined as all samples, blanks, spiked samples, etc., on which similar
      analytical operations are performed at the same time and which  are analyzed in a single
      run.

3.    The internal standard area checks detailed in Method 3, will be used but may not deviate
      by  more  than +_ 20% of the average peak height or area of the internal standard in the
      calibration standards. The control limits will be reassessed following completion of the
      initial demonstration of  capabilities.

4.    The calibration curves,  as defined in Section 8.12, are not used for quantitation, but for a
      check of linearity. For quantitation, procedural standards (calibration standards prepared
      by  methylation of weighed acids or phenols) containing the  method analytes and the
      surrogate will be prepared for each set of samples.  The concentration of each analyte in
      each procedural mix will be 10xMRL These will be used as the  "single point quantitation"
      standards for the LCS's which have been spiked at 10xMRL Positives, analyte amounts
      at 1/2 MRL or above, are analyzed by use of these procedural standards that are within.
      +/- 20%  of the .response of the suspect residue. The column check must be quantitated

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                                                                        Section No  5
                                                                        Revision No 4
                                                                        Date.  December 1989
                                                                        Page 4 of 5
      against the weighed ester standard at 10xMRL  Refer to Section 8.20 for detailed
      procedure (effective 06/88).

5.    The measurement system is to be evaluated whenever any analyte is observed in a
      Method Blank, at a concentration greater than or equal to  1/2 the Minimum Reportable
      Level. Method Blanks are to be analyzed with each set of samples.

      A sample set in which the surrogate compound recovery of the Method Blank has failed to
      meet the  +. 30% criteria can be validated by use instead of a Field Sample, from that
      same sample set, which meets all of the quality control requirements for a Method Blank.

      Note: This is not a procedure to validate the surrogate or the Method Blank; rather,  it is a
           procedure to validate the sample set by use of a Field Sample as a Method Blank.

6.    The criteria for monitoring instrument control standards will be utilized as stated in the
      method.

7.    The requirement for surrogate recoveries from Field Samples and Method Blanks is the
      Mean Recovery, R,  on the applicable_~Control Chart H^ 30 percentage points (i.e.  R ±
      30%). It is not R ± .30 R. (effective 0~81888).

8.    The requirements for monitoring  calibration  standard responses will be followed as written
      in the method.

9.    Samples failing any QC criteria must be reanalyzed.

10.   Only qualitative analysis will  be required for  chloramben, 4-nitrophenol, 5-OH dicamba and
      acifluorten. While these analytes are to be analyzed in at least one of the concentration
      levels of the calibration standards, they are  not subject to any of the QC requirements.

11.   Each time that a new calibration  standard dilution is prepared, it must be compared to the
      existing calibration curve, and the observed concentration  must agree within  +/- 20% of
      the expected concentration.

12.   Any deviation from the analytical  procedures or QC requirements, must be approved by
      the appropriate ECS-NPS Project Leader and documented in writing.

5.4   Laboratory QC Requirements For Second  Column Analyses
1.    Quantitate by comparison to a calibration standard, which  is within +/- 20% of the
      concentration  of the analyte(s) determined using the primary column.

2.    The concentration(s) for the  analyte(s) on the secondary column should quantitate within
      +/- 25% of the result determined on the primary column (effective 03/20/89).

3.    If the concentration determined on the secondary column does not agree within the limits
      stated above, the analyst must confer with the ECS-NPS Project Leader concerning
      resolution of the discrepancy prior to submitting the extract for GC/MS analysis (effective
      06/88).

4.    If the concentration determined on  the secondary GC  column meets the criteria in 2 above
      and GCMS is positive, report the concentration of the  analyte found on the primary
      column (effective 06/88).

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                                                                      Section No 5
                                                                      Revision No 4
                                                                      Date  December 1989
                                                                      Page 5 of 5
5.5   Laboratory QC And Extract Handling Related To GC/MS Confirmation

1.     The sample extract is to be compared to a standard prepared at the concentration
      determined for the analyte on either the primary or secondary column, whichever
      concentration is the lower.

2.     If additional sample extract treatment is performed for GC/MS analysis (blowdown, etc.),
      the standard and sample  extract must both undergo the same treatment.

3.     Results of the GC/MS analysis are simply reported as the presence or absence of the
      analyte.

4.     If low concentrations of the analyte(s) preclude confirmation using Low Resolution GC/MS,
      High Resolution GC/MS Confirmation must be attempted. HRGC/MS may also be
      required if the analyte concentration is greater than or equal to 1/2 the lowest adverse
      health effect for that analyte or if requested by the ECS-NPS  Project Leader.

5.6   Sample Management

1.     Samples must arrive at the laboratory with ice still remaining in the shipping box.  If a
      sample box arrives at the  laboratory without any ice remaining, the Sample Custodian
      should adhere to the following instructions (effective 11/06/89).

      a.    Analyze the affected samples - you will receive payment for samples that arrive with
           melted ice.

      b.    Take the temperature of the standing water in the bottom of the sample kit, record
           the temperature in degrees Centigrade on the sample tracking form and input the
           value into NPSIS. DO NOT TAKE THE TEMPERATURE OF THE SAMPLE IN THE
           BOTTLE.

      c.    Record any subjective observations you have about the samples and/or sample kit
           (i.e. the bottle was warm to the touch).

      d.    Contact the ECS-NPS Project Leader if you  have any further questions.

2.     Strict adherence to sample and extract maximum  holding times (14 days)  is required for
      both primary and secondary column analyses. All analyses should be  completed as soon
      as possible, but under extenuating circumstances, the maximum extract holding time may
      be extended to 28 days for GC/MS analyses only, if approved by the ECS-NPS  Project
      Leader.

3.     Water samples are to be disposed of after the 14  day sample holding  time has been
      exceeded. Sample extracts  must be maintained until disposal is approved by the ECS-
      NPS Project Leader.

-------
                                                                            Section No. 6
                                                                            Revision No. 4
                                                                            Date. December 1989
                                                                            Page 1 of 4
6.    SAMPLING PROCEDURES
      6.1   Sample Requirements
      For this method, ECL will be provided one 1-Liter sample preserved with mercuric chloride at 10
mg/liter. This sample is to be shipped iced along with those needed for Methods 1 and 6, by
overnight air and is to arrive iced at  ECL.  This sample is for duplicate analysis of the field sample sent
to the primary analytical contractor.  No "backup" or reserve sample will be shipped.
      ECL, as a referee laboratory, is envisioned to receive no more than 10% of the total 1500
samples now expected to be taken in the Survey.  Table 6-1, found at the end of Section 6.0,
summarizes these sample requirements.
      6.2   Labelling Of Sample Bottles
      The Implementation Contractor, ICF, will supply information on the labels, sample numbering
system, and  explanations for field coding  or decoding at the laboratory. This label is shown in
Figure 6-1.
      6.3   Field Sample Tracking Form
      ICF will supply a copy of this form along with explanations for field coding or decoding at the
laboratory. This form is shown in Figure 6-2.

-------
                                                            Section No 6
                                                            Revision No. 4
                                                            Date: December 1989
                                                            Page 2 of 4
                           TABLE 6-1

ENVIRONMENTAL CHEMISTRY LABORATORY SAMPLE REQUIREMENTS
                LAB NAME
RCT TYPE
Saaple Types
BQTHETYPE
ANAL. HETBX
PriBary
Referee
Shipping Blank
Backup Saaple
Lab Spites
Tine/Storage
«»
Totals
ft>. of Sites
TOTAL RBQ'D
BSL I
Referee
ICOOoL lOOCtL 6QOL
1 3 6

111




111
ISO ISO ISO
ISO ISO ISO
Total Bottles:

       lOOCttU-
        2SOdL»
         6CnL«
                                300
                                N.A.
                                150

-------
                                 Section No. 6
                                 Revision No. 4
                                 Date. December 1989
                                 Page 3 of 4
      FIGURE 6-1
LABEL OF SAMPLE BOTTLES


  SAMPLE *: PD-OOOO-6-i-Oi

  BSL - METHOD*  1   KIT:  611
'  FIELD SAMPLE
•  PRESERVATIVE:   HgC12
   DATE   1  TIME  '- SAMPLER
   NATIONAL PESTICIDE  SURVEY

   SAMPLE #: PD-OOGO-6-3-OL- —
   BSL - METHOD* 3 - KIT:
   FIELD SAMPLE
   PRESERVATIVE:  Had 2
    DATE   ',   TIME  i  SAMPLER
    NATIONAL PESTICIDE SURVEY

    SAMPLE *: PD-OOOO-6-6-O1

    BSL - METHOD* 6  KIT: 611
    FIELD SAMPLE
    PRESERVATIVE:  HqC12
     DATE   ',   TIME   ', SAMPLER
     ' J «J. lL PE5TTCI SS SURVEY
     BSL - METHOD* 1  KIT: 611
     BACKUP  SAMPLE
     PRESERVATIVE:  HgC12
      DATE   ',   TIME   ! SAMPLER

-------
                                                                                     Section No 6
                                                                                     Revision No. 4
                                                                                     Date- December 1989
                                                                                     Page 4 of 4
                                              FIGURE 6-2
                                  FIELD SAMPLE TRACKING FORM
HELL I.D. WJ.:   0000

FRDS I.D. Mo.  (US HELL ONLY):

SAMPLE COLLECTIH  DATE: 	/	/.

TRACKING FORM COMPLETED BY:  	
    LftB: BSL
SCENARIO: J_

KIT  NO.:  PS-t-000-611
BQI   I ot A
                                                   TO SE COMPLETED Bf:
Iff
SAMPLE
KUMBER
FIHWOO-6-1-01
PD-OOOO-b-3-01
PD-OOOO-6-e-Ol
PD-0000-t-i-')3

BOTTLE
SIZE
1000
1000
60
1060

SAMPLE
DESCRIPTION
FIELD SAMPLE
FIELD SAMPLE
FIELD SAMPLE
BACKUP SAMPLE
FIELS TEAR i LAB
sAHPLER : TIftE i UJIWENTS 11) iftEL-iVti CCMKEKIi ;
ilKITIALl : SAMPLED .
: : : : it
1
: : : • N
; : : : ><
: : : ! N:
  CHLORINE  TEST:

SHIPPED BY: i
OATE TIME
SEKT TO:
t

.


: F.ECElVEi- AT LAB BY:
.
: :ATE T:»E
LAB ADSRtSs: . ISttlTiai (l\
&AY St. LUIS EPA'EMV1PONȣHTAL ;
^EHISTF.- .At. •'.;£. 1105 :

NSTL. »S 3V.:*
1 '
i
     il) FOP. EXAMPLE:  E3TTLE BRWB, BOTTLE fCs-iiiS, QVERFU.Ev ?TtU£. CAf KA^ I-?.u?FE£
     u) FQfi EUU9LE:  BOTTLE BSOtH, BOTTLE MISSING. S3TTlE,:CftTM|tt7Cg. TEHPEF.ATURE CRITERIA KCT *£T
     1:1 FM EXAflPLE:  1C£ RELTE9, £01 LEAklNS
        ( ub coMMti should concur Kith NFSIS SAKPLE RECEIPT  )

-------
                                                                          Section No 7
                                                                          Revision No 4
                                                                          Date: December 1989
                                                                          Page 1 of 6
7.    SAMPLE CUSTODY
      7.1   Tracking And Notification Of Sample Shipments
      The proposed EPA system for notification of the laboratory of sample shipments and for
notification of the Implementation Contractor (ICF) of receipt of the samples is delineated on the flow
chart  and diagram, Labelled Figure 7-1, "SAMPLE RECEIPT SCREENS FOR NPS LABORATORIES" at
the end of Section 7.0. This system will be computerized.
      7.2   Sample Requirements Following Receipt At Laboratory
      Tracking of all samples arriving at the laboratory will begin upon receipt of any sample and will
continue through each phase of the analysis.
           Upon receipt of samples, each is identified according to its "Field Sample Number",
           logged in and stored at 4oC. This information is documented on a "NPS LOGGING
           FORM".
           The Sample Custodian or his/her Representative will compile "sets" of samples for
           Method 3 comprised of 8 samples and appropriate controls as covered in Section
           9.4 of this QAPjP. The composition of each set is documented on a "NPS SET
           COMPOSITION FORM'.
      •     Transfer of samples into and out of storage will be documented on an internal
           chain-of-custody record. Only those  samples in the "set" on which analytical work
           will be done will be removed. This information is documented on a "SAMPLE
           CONTROL RECORD FORM".  The analyst will sign and date this Record when
           removing or returning samples to storage.
           After removal from storage, samples are tracked through extraction and G.C.
           Analysis via an "ECL/NPS SAMPLE TRACKING FORM".
           Following extraction, sample  extracts are stored in a refrigerator at 4oC until
           analyses are complete. Following analysis, they are transferred to screw-cap tubes
           (teflon liners), the extract level marked, and stored by set in a freezer at 0' to -20'C.
           An "EXTRACT STORAGE DATA SHEET" records chain-of-custody of extracts from
           GC Analysis to GC/MS Confirmation,  if required, and to disposal.
           Copies of all the above mentioned Forms and Records can be found in
           Appendix A .
           7.2.1  Storage Conditions
      Upon receipt at the laboratory, samples will be stored under refrigeration at 4oC and protected
from light.
           7.2.2  Holding Times
      Samples have a maximum holding  time of 14 days from time of collection until the start of
extraction.
      Extracts have a maximum holding time of 14 days from date of extraction to GC Analysis and
GC/MS Confirmation, if required.  The holding time for GC/MS Analysis may be extended an additional
14 days upon approval of the ECL Project Leader.

-------
                                                                           Section No 7
                                                                           Revision No 4
                                                                           Date  December 1989
                                                                           Page 2 of 6
           7.2.3  Disposal

     Samples held longer than 14 days without being extracted are to be disposed of after approval

is given by the ECL Project Leader.
     The samples arrive with a 10 mg/liter concentration of mercuric chloride which is added as a

preservative.  Disposal of these samples will be to an EPA-approved water treatment system capable

of handling these concentrations of mercuric chloride and which is connected to the ECL facility.

     7.3   Return Of Sample Kits To EPA Contractor (ICF)

     ICF is to provide information on this.

*    7.4   Receipt and Tracking of Extracts from Analytical Contractors for GC/MS Confirmations
           at ECS (effective 06/05/89)

     To carry out its  responsibilities as a referee lab. (see Section 3), ECS will  be receiving from

Analytical Contractors sample extracts meeting the requirements of Section 5.2.  For all such extracts

arriving at ECS, tracking will begin upon receipt and continue through final disposition according to

the following procedure.

           Upon receipt at ECS, the Sample Custodian or his representative will check extracts
           against the NFS EXTRACT SHIPMENT form, filling in the Date Received at ECS,
           Conditions of Shipment, Number of Refrigerator where strored, the Container
           Number and signing where appropriate.  (A copy of this form is attached at the end
           of this Section and is labelled Figure 7-2.) He should then place the extracts in
           containers labelled by date and store in a refrigerator at 4<>c.

          The Sample Custodian will make necessary copies  of paperwork received with the
           extract shipment, giving all the original paperwork to the NPS Technical Monitor for
          the Analytical Contractor and a copy of the original  paperwork to the GCMS analyst.
          The Sample Custodian should keep on file, in the receiving room, a copy of the
           NPS EXTRACT SHIPMENT form.

          The GCMS analyst should remove extracts from the designated refrigerator, analyze
          the extracts by GCMS, then complete the remainder of the NPS Extract Shipment
          form and the GCMS Data Sheets.  The analyst should give all completed forms and
          GCMS spectra to the NPS Technical Monitor.

          The Technical Monitor will use the information from  the NPS EXTRACT SHIPMENT
          form to complete an overall tracking form, the NPS GCMS EXTRACT TRACKING
          FORM. He will send a copy of the GCMS Data Sheet to the NPS Data Manager and
          to the Analytical Contractor. He will also send the Analytical Contractor a copy of
          the GCMS spectra.  ECS will maintain the original paperwork on file.

          GC/MS results will be reported as in Sections 10.5 and/or 10.63.

          The Technical Monitor for the appropriate Method will receive all results and reports
          of GC/MS confirmation analyses and a monthly report from the ECS Sample
          Custodian on the total number of extracts received for each Method.

          The Technical Monitor will inform the Analytical Contractor, in writing,  of the results
          of each GC/MS confirmation attempt.

-------
                                                                             Section No 7
                                                                             Revision No 4
                                                                             Date. December 1989
                                                                             Page 3 of 6
      •     Disposal of extracts will be according to Section 7.23 and will be authorized by the
           Technical Monitor.
      7.5   Internal Practices  Concerning Sample Storage
      The temperatures of coolers, refrigerators, and freezers where samples and/or extracts are
stored are monitored each working day and this activity and the temperature are recorded in a log
book  maintained for this purpose.  A copy of this record is included as Figure 7-3 at the end of this
Section.
      The ECS Sample Custodian, Gerald Gardner, or the Assistant Sample Custodians are
responsible for monitoring these storage areas (effective 081288; see Appendix L; Addendum of
081288). ECS has an agreement with the facility contractor to provide weekly preventive maintenance
and emergency repair services on large coolers where samples will be stored.

-------
                                                     Section No. 7
                                                     Revision No. 4
                                                     Date-  December 1989
                                                     Page 4 of 6
                    FIGURE 7-1
SAMPLE RECEIPT SCREENS FOR NPS LABORATORIES

-------
                                                                     Section No 7

                                                                     Revision No 4

                                                                     Date  December 1989

                                                                     Page 5 of 6
                                   FIGURE 7-2


                             NPS EXTRACT SHIPMENT
(a
JJ   TJ
3   
eg jj —< 4)
% u Q,*>


alS§
   3
              —* "x
              en to

              2£
          81
   — « ffi
   o   c

                 831
           «,
           £1


           8
VJ
a.
                  (0
                    2
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-------
                                                         Section Mo. 7
                                                         Revision No 4
                                                         Date December 1989
                                                         Page 6 of 6
                               FIGURE 7-3
                   TEMPERATURE MONITOR CHART EPA/ECL
* WALK-IN
COOLERS/BLDG.  1105
DATE
TEMP.
PERSON CHECKING
                           * WALK-IN/UPRIGHT
                           FREEZERS/BLDG. 2204/1105
                                                    REMARKS
DATE    TEMP
PERSON  CHED'
•CING  I
                                 -t
                                                  T
                                                  	L

-------
                                                                             Section No 8
                                                                             Revision No 4
                                                                             Date  December 1989
                                                                             Page 1 of 7
8.    CALIBRATION PROCEDURES AND FREQUENCY
      8.1   Method 3 Standards
           8.1.1   Calibration Solutions
      Calibration solutions will be provided and sent to both the referee lab (ECL) and primary
analytical contractor by EPA/TSD-Cincinnati through their contractor Bionetics.  The solutions are to
be in flamesealed glass ampules. These solutions will be sent iced by next-day air to ECL and will be
accompanied by a "STANDARD SOLUTION  DATA FORM".  The ECL Sample Custodian or other
Designated Representative will receive these standards shipments, note whether or  not they were iced
and  date of receipt, and relinquish custody of the standards to a member of the Method 3 analytical
team. A sample copy of this form is attached at the end of this Section and is labeled Figure 8-1.
      A "CALIBRATION SOLUTION RECEIVING FORM" will be initiated to record the date  solutions are
received, number of sets,  condition, and place of storage at ECL.  These forms will be kept in a
designated folder.  A copy is found at the end of this Section and labeled Figure 8-2.
           8.1.2  Standards Prepared at ECL
      ECL will prepare and maintain separately weighed stock standards of each analyte.  These
stock standard materials should be from the same lot numbers as those used to prepare  the
EPA/Bionetics-supplied calibration solutions.  These ECL-prepared standards will be used to verify the
concentrations of the calibration solutions and resolve problems or questions that may arise
concerning any of the standards.
      A standards log book  is maintained to record name of person  weighing the standard, chemical
identifier of standard, date of preparation, purity lot  no., source, balance calibration data, and standard
weighing data.
           8.1.3  QA for Diluting and Checking the Standards
      Prior to dilution, calibration solutions and/or EPA/ECL stock  standards are removed from freezer
storage and allowed to reach room temperature.
      Calibration solutions and all subsequent dilutions are labeled with the standard  identifier, Batch
No,' solvent, preparer, date and concentration. The Batch Nos. provide a means of tracking them to
origin.
      The EPA/ECL prepared standards are labeled with standard identifier, date standard was
weighed, solvent, preparer, and concentration. These standards can be tracked to origin  by the date
the standard was weighed which will lead to a specific entry in the ECL standards log book as
covered in 8.12.
      A "STANDARD DILUTION FORM" (Figure 8-3)  at the end of this Section is used to record all
information on dilutions and  to facilitate the tracking of standards.

-------
                                                                             Section No 8
                                                                             Revision No 4
                                                                             Date- December 1989
                                                                             Page 2 of 7
           8.1.4  Calibration Solutions and ECL Standards Verification
      Calibration solutions will be the stock material for all standards used in the NFS at both the
referee and analytical contractor laboratories.  To verify their concentrations, they must by analyzed
against the ECL prepared standards before use. The calibration solutions and ECL prepared
standards must differ by no more than +. 15%. Following the comparison, all values must be reported
to the ECS Project Leader.  Standards with differences  >±  15% require resolution at this point before
work with the standard can proceed.
           8.1.5  Frequency of Calibration Standards Checks
      Calibration standards must be checked against ECS prepared standards each time a new
calibration standard is prepared from a calibration solution.  Criteria in 8.14 apply.
      Concentrations of calibration solutions must be verified at  ECS each time new Batch Nos. are
prepared at EPA/TSD-Cincinnati or Bionetics and before shipment to the analytical contractor.  Criteria
in 8.14 apply.
           8.1.6  Association of Calibration Standards to Survey Sample Analyses
      Each calibration (bench) standard used in analytical determinations must be able to be traced
to its origin and every field sample or control  sample analyzed must be associated with the  specific
calibration standard(s) used.
      To facilitate these requirements, each standard mix  with different components or different
concentrations of these components must have a uniquely different name and a  date of preparation.
This standard  identifier and date must appear on each chromatogram of the standard.  It may also
appear on the computerized data printout.
*     8.2  Instrument Calibration and Quantitation (effective  06/88)
      A Hewlett-Packard 5890 A dual capillary GC with electron-capture detectors is used to analyze
Method 3 samples. The internal standard (ISTD)  selected  for use with Method 3 is 4,4-
dibromooctafluorobiphenyl (DBOB) and is compatible with the GC columns and chromatographic
conditions for this Method.
      Weighed methyl ester standards are used for the calibration/ linearity check of the gas
chromatograph.  A minimum of three  standards will be diluted from an ECS-prepared standards mix,
and the lowest concentration of each must be at the Minimum Reporting Level (MRL). The  higher
concentrations -will span the range of concentrations expected in the sample extracts and in the
Laboratory  Control Spikes (LCS). Thus, the standards for instrument calibration should range from
MRL to 10xMRL
      Following injection of the ECS-prepared standards, the relative response (RRa) of each analyte
to the ISTD is calculated with the following equation:

-------
                                                                             Section No 8
                                                                             Revision No 4
                                                                             Date: December 1989
                                                                             Page 3 of 7
                 RRa = Aa / A,s ' Where
                      Aa = Area of the analyte
                      Ats = Area of the internal standard
The calibration curve is generated by plotting RRa versus analyte concentration in ug/liter.
      Although a calibration curve is drawn for each analyte, it is not used for quantitation but only for
QC purposes. The working calibration curve must be verified previous to sample analysis and every
eight  hours during an analysis sequence.  If the response for any analyte varies from the predicted
response by more than +/- 20%, the GC injection should be repeated and/or a new calibration curve
prepared for that analyte. If the predicted response for an analyte continues to vary by more than +/-
20%,  a new calibration standard mix should be prepared. If a new calibration standard is prepared,
the ECS Project Leader must be informed.
      Initially, the  current requirements of the Instrument Quality Control Standard must be met.
      Procedural Standards are prepared at 10xMRL by methylating weighed acids or phenols.  The
surrogate must be incorporated into  one of the mixes. These analyte mixes are used as "single  point
quantitation" standards.  (See Section 5.3.)
      Following injection of a standard, the relative response (RRstd) of each analyte to the internal
standard is calculated with the following equation:
                 RRstd = (Aa/Ais) /C, where
                 Aa = Area of the analyte
                 Ais = Area of the internal standard
                 C = Concentration of analyte at 10xMRL.
      In a similar manner, a response factor (RRsamp) of each analyte to the internal standard of
each sample  is calculated with the following equation:
                 RRsamp = (Aa/Ais), where
                 Aa = Area of the analyte
                 Ais = Area of the internal standard
      The ratio of  the RRsamp to the RRstd of a given analyte in a sample will result in the
determination of the concentration of the analyte.
      If a new calibration curve must be prepared, the ECS Project  Leader must be informed.
           8.2.1  Calibration of HR GC/MS
      Scanning Mode  -     The instrument is calibrated by the MCAL and CALIB routines in the
                           MAT 312 operations manual
      MID Mode        -     The instrument must be further calibrated by using the ESCAN and
                           ECAL routines in the manual

-------
                                                                            Section No 8
                                                                            Revision No 4
                                                                            Date  December 1989
                                                                            Page 4 of 7
     The instrument will be tuned for proper relative ion intensities by using DFTPP-7 (if possible)
when library searches are indicated.
*          8.2.2  Calibration of Low Resolution GC/MS (effective 06/88)
     The instrument is calibrated according to the manufacturer's recommendations using the
CALIBRATION (CAL) routines specified in the manual.
     The mass spectrometer will be tuned to EPA's specifications using DFTPP (effective 06/88).
   -' Eichelburger, J.W.; Harris, L.E.; Budde, W.L "Reference Compound to Calibrate Ion Abundance
Measurements in Gas Chromatography - Mass Spectrometry Systems" Anal. Chem. 1975,47(7), 995-1000.

-------
          FIGURE 8-1
  STANDARD SOLUTION DATA FORM
                                   Section No 8
                                   Revision No 4
                                   Date: December 1989
                                   Page 5 of 7
I I—
! lui
     I I  i  M I  I I  I i  i  I I  < 1  l i
 -12:  j i I  i i  !  i i  j j  i  | i  i I  i i
 o:3l  I—.oninir^tfoi—oicr>l—•.&s;sig
  10!
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            oio;o:o:o
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     ;o:oioioio'o:oioiototO'Oio:o:oioio:
     !OIOiC:OlOiOiO: O>OiO:O|OlO:O
-------
                                                         Section No 8
                                                         Revision No 4
                                                         Date Decemoer 1989
                                                         Daae 6 of 7
                           FIGURE 8-2

              CALIBRATION SOLUTION RECEIVING FORM
Date Received:      	      Date Checked:
Person Receiving:	Person Checking:
Ware Samples Iced?J _ - _ Relinquished Custody; (Yes/No)

Method No:  (If3 ror 6)
            (circle one)
Comments:
 Person Assuming Custody:	Date^

 Number of Sets:	
 Date Calibration Solutions  arrived at EPA/ECL written
 on individual standard cartons:  (Yes/No)	
 Date Stored:	Freezer No:	Boon No:

 Ccmrents on condition of Calibration Solutions:

-------
                                                                                       Section No  8

                                                                                       Revision No 4

                                                                                       Date  Decemoer 1989

                                                                                       Page 7 of 7
                                              FIGURE 8-3


                                    STANDARD DILUTION FORM
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-------
                                                                            Section No 9
                                                                            Revision No a
                                                                            Date  December 198
                                                                            Page 1  of 4
9.   ANALYTICAL PROCEDURE
     9.1   Summary Of Method
     This Method  is applicable to the determination in ground water of the phenoxy acid and phenol
analytes listed in Section 3 and their salts and esters.
     A measured volume of sample (approximately 1-Liter) is adjusted to pH 12 or greater with 6N
sodium hydroxide and allowed to sit, with periodic shaking, for 1 hour to  hydrolyze salts and esters of
the phenoxy/phenol analytes.  Extraneous organic material  is removed by dichloromethane solvent
washes. The sample is acidified, and the chlorinated acids are then extracted with diethyl ether by
shaking in a separatory funnel.  Using diazomethane as a derivatizing agent, the acids are converted
to their methyl derivatives.  Excess derivatizing reagent is removed, and the esters are determined by
electroncapture gas-chromatography (ECD).
     A Florisif cleanup procedure is included to aid in the elimination of interferences that may be
encountered.
     Capillary gas-chromatography with ECDs is used for both primary and secondary analyses of
the sample extracts.
     For sample extracts with suspect-positive analytes, (i.e.-those with positive responses on both
the primary and secondary GC columns), such extracts will be analyzed by either Low Resolution
GC/MS (LRGC/MS) or High Resolution GC/MS (HRGC/MS)  to confirm the presence or absence of the
analyte.
     9.2   Major Equipment/Instrumentation To Be Used With Method 3
           Hewlett-Packard 5890A dual capillary gas-chromatograph with dual  ECD.  Identical
           instrument for backup.
     •     Hewlett-Packard 7673A autosampler. Identical  unit for backup.
           Hewlett-Packard 3359A Lab Automation System
           Finnigan MAT 312 High  Resolution GC/MS
           Finnigan Mat 5100 Low Resolution GC/MS
     9.3   Analytical Method
           9.3.1   Method As Developed By Battelle
     This Method  is presented in Appendix B.

-------
                                                                         Section No. 9
                                                                         Revision No 4
                                                                         Date:  December 1989
                                                                         Page 2 of 4
      9.3.2  Differences From Battelle Method

3.5        Instrument Quality Control (QC) Standard - use isooctane instead of methyl tert-
           butyl ether (MTBE)

4.1.1       Glassware Cleaning and Preparation

           1.     All new glassware should be pre-soaked in Chromic-Sulfuric acid cleaning
                 solution.

           2.     Wash glassware with 2-5% Chem-solv, Micro*, or similar cleaning solution.
                 Pre-soak heavily soiled glassware.

           3.     Rinse will with tap water.

           4.     Rinse glassware with acetone, methylene chloride and hexane respectively.
                 (Safety note: wear rubber gloves not permeable to or attacked by solvents
                 and wear safety glasses.)

           5.     Bake glassware in oven overnight (approx. 12 hours) at 400'C. For this
                 purpose, glassware is stacked on aluminum or stainless steel trays and
                 loaded into the oven.

           6.     Upon cooling, rinse glassware with acetone, methylene chloride and  hexane.

4.2        All clean baked glassware will be rinsed with acetone, methylene chloride, and
           hexane prior to use.  No acid-rinsing of glassware.

6.2.7       Flask - flat bottom - 250 ml with 24/40 ground glass joint.  Fisher (or equiv.) cat no.
           10-101B

6.9        See Appendix No. C for Diazald Kit for diazomethane generator apparatus and
           procedure.

7.3        Acidified sodium sulfate - Acidify by slurrying lOOg of sodium sulfate (heated at
           400oC overnight and stored in a desiccator) with enough acetone to just cover the
           solid. Add 1 ml Ultrex concentrated sulfuric acid to slurry and mix thoroughly.
           Remove the acetone under vacuum using a rotary evaporator. Bake dried acidified
           sodium sulfate at 400'C overnight then store in desiccator until needed.  Mix 1 g of
           the resulting solid with 5 ml of reagent water and measure the pH of the  mixture
           with pH paper. The pH must be below pH 4.

7.1.6       Stock Standard Solutions are prepared in acetone.

7.1.7       Internal Standard Solutions are prepared in isooctane. Final internal standard
           concentration should read 0.25 ug/ml.

7.1.8       Surrogate Standard Spiking Solutions are prepared in acetone; concentration will
           differ.
Denotes reference to Battelle's Method and is not part of the ECL numbering system.

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                                                                        Section No. 9
                                                                        Revision No. 4
                                                                        Date:  December 1989
                                                                        Page 3 of 4
7.1.9       Instrument QC Standards are prepared in isooctane from known amounts of methyl
           derivatives, not acids; concentrations will differ.

10.6.1      The laboratory must, on an ongoing basis, analyze at least two laboratory controls
           (all analytes) per sample set.

10.6.1.1    The spiking concentrations in the laboratory control standard should be 10 times
           the MRL

10.6.1.2    Add mercuric chloride to the laboratory control sample in amounts to produce a
           concentration of 10 mg/L See 8.21 Sample Preservation.

10.7       Will not be done at Referee Laboratory.

10.8       Add mercuric chloride to the Method Blank in amounts to produce a concentration
           of 10 mg/L See 8.21 Sample preservation.  Change EDL to MRL

10.10      Refer to Section 5.4 and 5.5.

11.1       Automated Hydrolysis, cleanup, and extraction Method is not used (11.2 Manual
           Method used)

11.2.1      Spiking volume of the Surrogate Standard Solution may vary, but will not exceed
           200 ul.

11.2.3      Let the sample sit at room temperature for 1 hour, shaking the separatory funnel
           and contents periodically (every 15 min.).

11.2.7      Drain lower aqueous layer into a 2 Liter Ertenmeyer flask and combine ether extracts
           in a 250 ml Erienmeyer flask over approximately 1 g of acidified sodium  sulfate
           (avoid getting water into the ether extract).

11.2.8      Periodically (every 15 min.) vigorously shake the sample and drying agent.

11.2.9      Record weight of filled water sample bottle.  Pour contents into a 2 Liter separatory
           funnel. Record weight of empty bottle and subtract difference to determine weight
           of sample.

11.3       Extract Concentration -  Using a warm (35o-40o) water bath and a stream of dry
           filtered nitrogen, concentrate the ether extract to about 8 ml.  Do not let  ether
           approach dryness. Quantitatively, transfer contents to a centrifuge tube with ethyl
           ether and using a warm water bath (35o^40oQ and a stream of dry filtered nitrogen,
           further concentrate extract to 0.5 ml. Add 2ml of MTBE and reconcentrate to 2 ml.
           Add 250 ul of methanol and adjust volume to 4.5 ml with MTBE.

           Note: Centrifuge tubes must be used instead of concentrator tubes.  Avoid use of
                ground-glass joints with diazomethane. (See  11.51  - Preparation of
                diazomethane)
Denotes reference to Battelle's Method and is not part of the ECL numbering system.

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                                                                             Section No 9
                                                                             Revision No 4
                                                                             Date  December 1989
                                                                             Page 4 of 4
      11.4        The gaseous diazomethane method is not used.

      11 5.1
      and
      11.5.2      Use Method, Appendix # C, for preparing diazomethane (alcoholfree ethereal
                 solutions).  Diazomethane solution should remain tightly capped, have a yellow
                 color, and may be stored at 0'-5'C for a period of up to 6 months.

      11.5.3      Add 1  ml of diazomethane solution to each centrifuge tube.  Samples should turn
                 yellow after addition of the diazomethane solution and remain yellow for at least 2
                 mm.  Repeat methylation procedure if necessary.

      11.5.5      Do not use silicic acid. Use dry filtered nitrogen, and warm water bath to remove
                 any diazomethane that may remain. Adjust the volume to 5.0 ml with MTBE.

      11.6        Preparation of Column Check - Prepare a Column Check by pipetting, onto a
                 Florisil® column, 1  ml of a standard containing the methyl derivatives of  the analytes
                 of interest at 10 times the concentration of the bench or calibration standards.  This
                 control is carried through the normal Florisil® cleanup.
      9.3.3  Requirement For Authorization To Deviate From Battelle's Method
      Any differences from the Method in Section 9.31 must be discussed with and approved by the
ECL Project Leader for this Survey. The ECL Project Leader may require that such requests be in
writing and be supported by a rationale, facts, or laboratory data.
      9.4   Sample Sets
      Samples will be carried through the analytical work in discrete groups or "sets". A set is a
collection of field samples and QC checks or  controls sufficient to assess the quality and validity of
any data generated from the set independently of any other set. Specific controls included in sets with
this Method are a Florisil® Cleanup Control, Method Blank, and 2 Laboratory Control Spikes which
together comprise all analytes. At a maximum, 8 Field Samples may be run in a set.
     Denotes reference to Battelle's Method and is not part of the ECL numbering system.

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                                                                          Section No 10
                                                                          Revision No -l
                                                                          Date  December 1989
                                                                          Page 1 of 6
10.  DATA REDUCTION, VALIDATION, AND REPORTING
     10.1  Data Reduction
     ECL will use an H-P 3354 Data System to acquire, store, and analyze raw data from the
instrument and to generate data reports associated with each analysis. Information generated are
compound retention times, peak areas, relative response factors, and analyte concentrations. These
values  plus sample i.d. and instrument parameters will comprise a DATA REPORT. Concurrent with
sample analyses,  hardcopy chromatograms will be generated and along with the DATA REPORTS will
form a HARDCOPY DATA FILE.  (Refer to Figure 10-1 at the end of this Section.)
     Each sample chromatogram will be labelled with the Field Sample Number, final volume of
extract, ul injected, dilution information if applicable, mg-eq. of sample, date, and initials of analyst.
     Each chromatogram of a standard must be labelled with the unique identifier of the bench or
calibration standard,  amount injected, date of preparation of the standard, date of analysis, and  initials
of the analyst.
     10.2  Data Validation
     Information from each DATA REPORT will be evaluated and verified by an analyst experienced
in chromatography and with this Method.  Evaluation will include all QC CHECKS against
ACCEPTANCE CRITERIA as specified in Section 11.0 and the DATA MEASUREMENT requirements for
analyses  as specified in Section  5.0.
     Additionally,  the following sampling and tracking data will be evaluated:
           Is the date from sampling to receipt at ECL within the NPS requirements? (1 day)
           Is the date from sampling to extraction within the NPS requirements? (14 days)
           Is the date from extraction to analysis, including GC/MS confirmation, within NPS
           requirements? (14 days)
     SAMPLE DATA REPORTS  on all samples and controls within the set will be prepared along with
QC SUMMARIES of all QC DATA from the set. For these sample extracts that must be referred to
GC/MS confirmation,  the GC analyst will prepare the "GC/MS CONFIRMATION SHEET" which conveys
to the GC/MS operator information on the extract necessary for the confirmation work. See Figure
10.2 at the end of this Section.
     All data generated under 10.1  and 10.2 will be PEER REVIEWED by an analyst under the
direction of the ECL Quality Assurance Coordinator (QAC) or his Designated Representative. This
review will include review of the HARDCOPY DATA FILE for the sample set and validation of all sample
data and  QC checks  from which SAMPLE DATA  REPORTS and QC SUMMARIES are derived.
Discrepancies will be resolved by the ECL QAC,  Project  Leader, and the analyst. Upon completion of
all reviews, the PEER REVIEWER will sign and date all forms  and records indicating validation of the
data.

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                                                                            Section No 10
                                                                            Revision No 4
                                                                            Date  December 1989
                                                                            Page 2 of 6
      10.3  Data Reporting
      Analytical sample data and QC data from the Instrument Control Standard (see Section 11.1)
will be reported via an ASCII text file on a floppy diskette. See Appendix C for instructions on the data
format and  specific data to be keyed into the ASCII files.  The data in the SAMPLE DATA REPORTS
and QC SUMMARIES will contain any data to be entered into the ASCII file.
      A d-Base III program has been written to generate and manage these ASCII files.
      Sampling data and tracking data will be entered into the files by the ECL Sample Custodian
and/or analytical team members who are completing analytical work with time limits (i.e. sample or
extract holding times).
      The floppy diskettes containing these files will be sent each month to EPA/Cincinnati, Ohio to:
                      Christopher Frebis
                      EPA/Technical Support Division
                      26 W. Martin Luther King Drive
                      Cincinnati, Ohio 45268
      Data  for a set of samples are to be reported  no later than 2 months from the earliest sample
collection date within that set.
      Where rounding of numbers or determination of significant digits is required, ECL will adhere to
the procedures and criteria in Appendix E.
      10.4  Storage of Lab. Data
      The HARDCOPY DATA FILE (chromatograms of samples, controls, associated standards and
the related  DATA REPORTS or computerized printouts) will be maintained and filed  by Method and
set. The data file on a set will also contain all forms used in evaluating samples and and QC
SUMMARIES. Sampling and tracking data will also be filed.
      It is the responsibility of the analyst to assure that all elements of the HARDCOPY DATA FILE
are in the file.  It is the responsibility of the PEER REVIEWER to see that these same elements remain
intact following review, and that they are stored by Method and Set in the RECORDS ROOM.
      These files will be retained in storage until ECL is notified by NPS Management of further
disposition.
      Raw data is acquired and stored on hard-disk and can be retrieved if necessary. There is no
provision for back-up  magnetic tape storage. The HARDCOPY DATA FILE will contain all elements
needed to support a sample analysis.  The Procedure for storage of NPS files is attached as
Appendix F.
      10.5  Fast-Track Reporting
      The NPS has determined that two situations  will require "FastTrack Reporting" of data.
           Confirmed positive residues for certain analytes to be specified by EPA.  This data
           will also be reported routinely with the  appropriate set data.

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                                                                             Section No 10
                                                                             Revision No 4
                                                                             Date1 December 1989
                                                                             Page 3 of 6
           A situation when results from the secondary GC column do not agree with results
           from the primary column within criteria set forth in Section 5.4.  This situation is to
           be discussed with the ECL Project Leader prior to reporting the data.
      A protocol has been provided by NPS on reporting the "confirmed positives" mentioned above.
See Appendix_J_ for the NPS protocol and the list of analytes and their rapid reporting levels. The ECL
Project Leader will assume the duties and responsibilities assigned  to the Technical Monitor in the
memo.
      Also included in the Appendix are forms to be used at ECS in reporting analytes subject to
rapid  reporting requirements.  Forms for all three Methods  being run at ECS are included with this
QAPJP since an action level in one Method triggers rapid reporting for all Methods.
      It is the responsibility of the GC analyst for this Method to be  aware of these rapid reporting
levels, to assure that the ECS report forms are initiated upon determining that a particular residue
associated with his/her Method is subject to rapid reporting, and to inform the ECS Project Leader
immediately.
      10.6  GC/MS
           10.6.1  Data Reduction
      All HR GC/MS data are acquired by a Digital POP II/34 computer and stored on a CDC-CMD
disc drive. The LR GC/MS data are acquired by a Finnigan 5100 data system based on Superlncos
software. Identification is based on selected ion monitoring of EPA-designated ions and the retention
time of the analyte of interest. The GC/MS analyst will search for the analyte of interest at the proper
retention time of the standard and also look for characteristic ions.  The peak areas of the selected
ions for the analyte of interest in the sample being confirmed are then compared to the same ions
generated from a standard of the analyte of interest at about the same concentration level.  If marked
differences in relative abundance are observed, the analyst and Technical Monitor should account for
the discrepancy before a  positive identification is established (effective 06/88).  Hard copies of data
are made and kept on file. After all the results have been reviewed, the raw data is transferred to a
magnetic tape.
           10.6.2 Data Validation
      The hard copies of  the MS data are reviewed by the  mass spectrometrist for accuracy and
completeness. The data must also meet the other QA requirements in this QAPJP [See Section 5.1(8),
5.21, 5.22, 5.5, 5.6(2)], that apply.  Then the Section Chief  or the ECS Project Leader reviews the data,
and a decision is made as to whether or not the presence  of a compound can be confirmed.
           10.6.3 Data Reporting
      The results of the GC/MS confirmatory analyses will be reported to the ECS Project Leader if the
sample(s) were extracted  at ECS and to the appropriate Technical Monitor for the analytical contractor
if the extractions were done by the contractor.  (See Figure 10-2 at  the end of this Section.) One set
of hardcopy data supporting each confirmation should be attached to the form.

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                                                                         Section No 10
                                                                         Revision No ~
                                                                         Date  December 198S
                                                                         Pane 4 of 6
           10.6.4  Filing and Storage of GC/MS Data

     The NPS Project Officer will be responsible for the initial filing and storage of GC/MS results and
data as described in Sections  10.4.

     Raw data will  be stored on magnetic tape by the GC/MS analyst as described in Section 10.61.
Any GC/MS analysis or confirmation can be reconstructed from this raw data.

                     STORAGE OF NPS HARDCOPY DATA FILES AT ECL

           The HARDCOPY DATA FILES and all related reports will be filed according to NPS
     Method No., and then by Sample Set.

           ECL has a RECORDS ROOM available for this purpose.  It is equipped with shelving
     for storage, a  smoke alarm, and a sprinkler system.  Activation of the smoke alarm is
     monitored 24  hours a  day by the NSTL fire department which can respond within 2
     minutes to an alarm.  ECL will take precautions to protect from sprinkler syystem water
     damage all files stored in this room.

           The RECORDS  ROOM is also the office of the ECL QAC and is locked when the
     room is unoccupied. Access is limited to the ECL Laboratory Manager, the ECL QAC,
     and Project/Team Leaders.

           The STORED RECORDS LOG is used to log files into the RECORDS ROOM and to
     record removal and subsequent return of these files.

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                                                           Section No 1C
                                                           Revision No 4
                                                           Date  Decemoerl989
                                                           paae 5 of 6
                             FIGURE 10-1

     FLOW CHART FOR DATA REDUCTION, VALIDATION, AND REPORTING
    (7)
  Sampling/
Tracking  Data
                        (1)
       Instrument
        Response
  Chromatogram
   (Hardcopy)
 (2)
                         (3)
      Disk Storage
                           Analysis of Raw Data
                              By Data System
                   (5)
  Data  Report (Printout)
    Hard Copy
    Data File
(6)
Evaluation of Sample  Data;
  Evaluation of QC  Checks
Against Acceptance  Criteria
(8)
                            Sample Data Reports
                           QC Su«nmaries (by Set)
                           (9)
                               I Peer Review  \  (10)


Data Packets
(ASCII Cards)
                                                 (11)
                              Monthly Reports    (12)

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                                                       Section No ' C
                                                       Revision No 4
                                                       2ate  Cecemoer 1989
                                                       Paae 6 or 6
                              FIGURE 10-2

                      MASS SPEC CONFIRMATION SHEET
 Major project n*a«
 Person requesting
 Confirmation
 Date submitted"
                                        Sub-project name__
                                        Person  preforming
                                        Confirmation _
                                        Date completed" -
 Sample No.
                    Specific  details of sample  extracts

                                        Sample  Cone g/ml
4
2
3
4
    Compound  Cone   Mass Spec  Mass Spec   Mass Spec
              Kg/ml  Number     Confirms-   est Cone.
                               tion
                                                       Mass  Spec
                                                       Confirmation
                                                       Code
 Sample No.
                                        Sample Cone g/ml
Compound  Cone   Haas Spec  Mass Spec
          Ng/al  Number     Confirtaa-
                            tion
                                            Mass Spec
                                            est. Cone
                                                        Mass  Spec
                                                        Confirmation
                                                        Code
2.
3.
Sample No
                                        Sample  Cone  g/ml
   Compound  Cone   Mass Spec  Mass Spec    Mass Spec
             Ng/ml  Number     Confirtaa-    est. Cone
                               tion
                                                        Mass Spec
                                                        Confirmation
                                                        Code
Sample No.
                                        Sample Cone g/«l_
  Compound  Cone   Mass  Spec   Mass Spec   Macs Spec   Mass Spec
             Kg/ml  Number      Confirms-   est. Cone   Confirmation
                               tion                     Code

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                                                                               Section No ' 1
                                                                               Revision No 4
                                                                               Date  December 1989
                                                                               Page 1 of 11
11.   INTERNAL QUALITY CONTROL CHECKS
      Summarized in this Section are all the QC checks and controls required for analysis of NPS
samples.  These QC checks are classified according to the analysis type (i.e.- primary column,
secondary column, GC/MS Confirmation).
      11.1 Primary Analyses
Type of QC Check
• Instrument Control-7
Standard
PSF
PGF
Resolution
Sensitivity
• Method Blank
• Lab Control Standard
• Calibration Standards
- Field Samples
- Internal Standard
- Surrogate Spike
- Performance Eval
Samples
• Shipping Blank
• Spiked Sample
• Time Storage Samples
Frequency
1 day (or I set if
uninterrupted
analysis of the set
extends to 2 days)
1 set
1 std mix
Mm 1 day or each
working shift
Maximum 5 set
Each sample
Each sample
As needed
Criteria for Acceptance
0 70 < PSF < 1 05
0 70 < PGF < 1 05
> 040
_> EDL for dmoseb
No peaks within the retention window
of any analyte > Vi MRL for that
analyte
Refer to Section 1143
All analyte repsonses within jf 20% of
that predicted by current calibration
curve
See individual QC checks
Response must be wrthin + 20% of
average response of internal standard
in calibration stds.
Recovery must fall within window of R
(recovery of surrogate from applicable
control chart) + 30 percentage points
(effective 08/18/89)
To be determined
Corrective Action
Reevaluation of GC System
Reevaluation of GC System
Reevaluation of GC System
Reevaluation of GC System
Out-of-control situation, Method Blank must be brought in
control before proceeding
Out-of-control situation, work must be stopped until
control is establihsed Refer to Section 1143
1 Prepare a fresh calibration standard, or
2 Prepare a new calibration curve
See individual QC checks
Refr to Appendix C , Section 105, in the written method
1. Check calculations
2 Check mternal.and surrogate std spiking solutions
3 Reanalyze the sample extract
4 If reanalysrs of extract results tn surrogate being *in-
control," submit only data from 'm-control' analysis
5. If reanalysis fails to put surrogate in control,
reevaluate analytical method and measurement
system Reextract failed sample when system is
again in control
Out-of-control situation, problem must be corrected and
analytical system put back in control as evrdneced by
successfully analyzing a second P-E Sample
NOT APPLICABLE TO ECL REFEREE RESPONSIBILITIES
NOT APPLICABLE TO ECL REFEREE RESPONSIBILITIES
NOT APPLICABLE TO ECL REFEREE RESPONSIBILITIES
     V  Refer to Section 14 1 and to Appendix C . Table 10 on page 35 of the written Method

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                                                                          Section No 11
                                                                          Revision No 4
                                                                          Date  December 1989
                                                                          Page 2 of 11
    11.2  Confirmational (Secondary-Column) GC Analyses
Type of QC Check
• Calibration Standards
« Instrument Control^'
Standard
Sensitivity
• Method Blank
• Shipping Blank
• Quantitation
- Calibration Std.
- Analyte Concentration
Value
Frequency
mm 1 day or
each working
shift
1 day
1 set
Criteria for Acceptance
All analyte responses within 20%
of that predicted by current
calibration curve
> EDL for dinoseb
No peak within retention window
of any analyte >_ 'h MRL for that
analyte
Corrective Action
1 Prepare a fresh calibration
standard, or
2. Establish a new calibration
curve
Reevaluation of GC System
Out-of-control situation; Method
Blank must be brought back in
control before proceeding
NOT APPLICABLE TO ECL REFEREE RESPONSIBILITIES
As required by
suspect
positives from
primary column
Per analyte
+_ 20% of cone, of the analyte
determined on the primary
column
+_ 25% of the cone, determined
on the primary column
Use proper std. cone.
Confer with ECL Project Leader.
I/ Refer to Section 14.1 and to Appendix C , Table 10 on page 35 of the written Method.
    11.3 GC/MS Confirmation

    •    GC/MS Confirmation will be required for all compounds confirmed by second
         column GC analysis.

    •    The sample is to be compared to a standard prepared at the concentration
         determined for the sample, on either the primary or secondary  column, whichever
         concentration is lower.

         If an analyte is confirmed by second column GC analysis but is not present when
         analyzed by GC/MS, the analyst must demonstrate that the analyte was not lost
         while concentrating  the extract.  A standard of the analyte should be prepared at
         the concentration determined by GC analysis, and then concentrated and analyzed
         in the same manner as the sample extract.

         The Method Blank should be prepared and analyzed using the same procedures as
         those used for the sample.

         Confirmation is accomplished by comparison to the mass spectra of the authentic
         standard and is based on characteristic EPA-designated ions and on the retention
         time.

         In the event that interferences preclude the use of the designated EPA ions, other
         characteristic ions may be substituted on approval by the ECS-NPS Project Leader.

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                                                                       Section No 11
                                                                       Revision No 4
                                                                       Date: December 1989
                                                                       Page 3 of 11
      Results of the GC/MS analysis are simply reported as the presence or absence of
      the analyte.

      Mass Spectral Confirmation Codes

           MIS - Three individual ions are scanned
           SPECTRA - All or a significant portion of the spectra is scanned
11.4  Control Charts

      11.4.1  Establishing Control Charts

A.    ECL,  as a referee lab for Method 3, will be required to demonstrate control of the
      measurement system via use of control charts.  Control must be demonstrated for each
      analyte for which quantitation is required and for the surrogate at a concentration equal to
      that spiked into samples.

B.    To establish the control charts, following initial  demonstration of capability, 5 reagent
      water samples will be spiked at 10 times the Minimal Reporting Level (MRL) for the
      method and carried through extraction and analysis. Only results of analyses on the
      primary column are  used in establishing the control charts. An additional 15  samples will
      be spiked and analyzed, 5 on each of 3 days.  The data from these 20 spiked samples
      will be used to construct control charts.

C.    Criteria for Accuracy and Precision

      1.    The RSDs for  any analyte must be <_ 20%, except where data, generated by Battelle
           at the corresponding level, indicated poorer precision.  The RSDs exceeding 20%
           will be evaluated on a case-by-case basis by Technical Monitors for each method.

      2.    The mean recovery (x) of each analyte must lie between Battelles' mean recovery
           for each analyte (at the corresponding level) +. 3  times the RSD for that analyte as
           determined by Battelle during methods development, but no greater than Battelle's
           mean recovery +_ 30%.

           Example:

           For an  analyte "A"

                Battelle  demonstrated  recovery (x)  of 80% for Analyte "A" with RSD of 5%.
                Acceptable recoveries will be 80%  +_ 3 (5%) = 80% ± 15%  = 65% - 95%;

                or, Battelle demonstrated recovery (x) of 80% with RSD of 15% for analyte "A".
                The acceptable recovery would be limited to 80% +_ 30%  =  50% - 110%.

      3.    Surrogate

           In establishing the control chart for the surrogate, criteria in C(1) and (2) above,
           apply; it follows that one of the spike  mixes must  contain the surrogate at the
           concentration  as spiked into actual samples.

           Surrogate recoveries from samples will be required to be within +_ 30% of the mean
           recovery determined for that surrogate during the initial demonstration of capabil-
           ities.

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                                                                               Section No 11
                                                                               Revision No 4
                                                                               Date  December 1989
                                                                               Page 4 of 11
                 An LCS in which the surrogate compound recovery has failed to meet the quality
                 control limits can  be validated if the following conditions are met.
                 a.     The LCS meets all other quality control criteria; and
                 b.     the surrogate compound recovery observed for the Method Blank, associated
                       with the same sample set,  meets the quality control limits determined using
                       the control chart for that surrogate.
           4.    Warning Limits/Control Limits
                 The control charts will be drawn  up so as to depict both warning limits (±20) and
                 control limits (± 3  o) about the mean.
           11.4.2  Outliers
      Dixon's test will be used to determine outliers.  There can be no more than 3 outliers per analyte
from the 20 spiked controls.  The Dixon test for outliers can be found in Appendix G.
           11.4.3  Plotting Data on Control Charts
      Data (analyte recoveries in percent) from the LCS on the primary column will be plotted on the
control chart for each analyte.
           11.4.4  Out-of-Control Situations
      1.    In the following instances, analytical work must be stopped until an "in-control" situation is
           established.
           a.     More than 15% of the analytes of a particular method are outside ± 3 a
           b.    The same analyte is outside +. 3 a twice in a row, even though >85% of the total
                 analytes are in control.
      2.    An "alert" situation arises when one of the following occurs:
           a.     Three or more consecutive points for an analyte are outside -h 2 o  but inside the +_
                 3 a
           b.    A run of 7 consecutive points for an analyte above or below the mean.
           c.     A run of 7 points for an analyte in increasing or decreasing order.
                 The "alert" situation implies a trend toward an "out-ofcontrol" situation. The analyst
                 is required to evaluate  his analytical system before proceeding.  If "alert" or "out-of-
                 control" situations occur frequently, re-establishing control charts may be required
                 by the ECL Project Leader before analytical work can proceed.
           11.4.5  Up-dating Control Charts
      Following establishment  of the control  chart,  a  spiked control(s) is part of each  analytical or
sample "set".  When 5 such controls have been run, the recoveries of these analytes will be
incorporated into the control chart by adding these 5 most recent recoveries to the 20 original points
and then deleting the first 5 of the original points.  Accuracy and precision are re-calculated and the

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                                                                           Section No 11
                                                                           Revision No 4
                                                                           Date December 1989
                                                                           Page 5 of 11
chart re-drawn.  The newly drawn chart will then apply to all data in sample sets subsequent to the
last one used to update the chart.
     In the event there were 1-3 outliers when establishing the control chart, add the 5 most recent
points and delete only the first 2-4 points so that a total of 20 points are used in the up-dated control
chart.
     11.5  Other QC Checks Performed at ECL
           11.5.1  Diazomethane QC Check
     See "DIAZOMETHANE QC CHECK FORM" and Instructions at the end of this Section,
Figure 11-1.
           11.5.2  Florisil® Elution Check
     See the "ADSORBENT CHECK FORM" and Instructions at the end of this Section, Figure 11 -2.
           11.5.3  Quality Control Data Sheet
     Information on all solvents, reagents, and solutions used during each NFS set extraction and
cleanup, must be kept on a "QUALITY CONTROL DATA SHEET".  This information sheet would also
record storage conditions and disposal.  See Appendix H.
           11.5.4  NFS Groundwater Quality Assurance Data Form
     Before any work begins on samples  or controls, a "NFS GROUNDWATER QUALITY
ASSURANCE  DATA FORM", is initiated by the processing laboratory.  After extraction, concentration,
and cleanup, all pertinent set information is recorded on this form. This form and information for
completing it are in  Appendix H.
     11.6  Exceptions to the QAPjP
           11.6.1  Request for Approval
     Occasionally,  it may become necessary for personnel assigned  to the NFS to request approval
for exceptions or deviations from this QAPjP. This approval must come from the ECL Project  Leader
and may be initially  requested either verbally or in writing,  but in either case, the request must be
supported by  a clear rationale,  laboratory data, and documentation. When approval is requested, the
particular issue or exception will be assigned a reference number consisting of the laboratory name,
NFS Method No., date, and a number to differentiate among the several discussions that may take
place on that day.
           EXAMPLE:  ECL 3-040888-1  indicates that an exception to the QAPjP for Method 3
                     was requested on  April 8, and it was the first  one that day.
           11.6.2  Documentation and Following Requirements
     The ECL Project Leader will enter into a log book the reference  number, the exception
requested, and the information and documentation required to support approval of the exception to
the QAPJP.

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                                                                            Section No 11
                                                                            Revision No 4
                                                                            Date  December 1989
                                                                            Page 6 of 11
     The person requesting the exception to the QAPJP must prepare a folder labelled with the
reference number and his/her name, and within a time frame specified by the ECL Project Leader
have in the folder documentation of the problem/exception and all supporting information and data.  A
form "EXCEPTIONS TO NPS QAPJP" is included at the end of this Section as Figure 11-3.  A
completed version must be included with each request for an exception to the QAPjP.

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                                                                         Section Nc  11
                                                                         Revision No 4
                                                                         Date  December 1989
                                                                         Page 7 of 11
                                       FIGURE 11-1
                                DIAZOMETHANE QC FORM

PREPARATION:
Date Prepared: 	      Analyst Preparing  	
Diazald Lot No. 	     Date:
KOH Lot No.           	                          Date:
PROCESSING:
Date Methylated 	      Analyst Methylating
 ' Standard Used  	     Date:
  1.   Reagent Blank -
  2.   Spike A -
  3.   Spike B -
  4.   Spike C -
G.C. ANALYSIS:
Date Analyzed  	     Analyst
Diazomethane Satisfactory? Yes	   No	
G.C. Bench Standard 	     Date:
COMMENTS:
     Standard must have been prepared no longer than 30 days before Diazomethane check.

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                                                                     Section No 11
                                                                     Revision No 4
                                                                     Date: December 1989
                                                                     Page 8 of 11
                            FIGURE 11-1 (continued)

                    DIAZOMETHANE QC FORM/INSTRUCTION


                INSTRUCTIONS FOR HE DIAZOMETHANE QC CHECK

     For each batch of diazomethane prepared for use with NPS Method 3, complete
Part A of the "DIAZOMETHANE CHECK FORM".

     To check the quality of the batch, prepare a BLANK (1 ml diazomethane w/no spike)
and 3 replicate SPIKES at the Method 3 Control Spike Level.  Bring final volumes to 10.0
ml in isooctane following derivatization procedure. Analyze the BLANK and 3 replicate
SPIKES by GC. Mean recoveries of the analytes and  the surrogate must be within the
control limits (except for chloramben) as reflected by the control chart in current use with
Method 3. There  must also  be no interfering peaks in the BLANK (for ANY Method  3
analytes) j> V* MRL If the diazomethane meets the above criteria, it can be used for NPS
analytical work.

     For any exceptions to  the above criteria, check  with the ECL Project Leader before
using diazomethane.

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                                                                           Section No 11
                                                                           Revision No 4
                                                                           Date  December 1989
                                                                           Page 9 of 11
                                        FIGURE 11-2
                                ADSORBENT CHECK FORM
PROCESSING date:
Adsorbent checked: Silica-gel 	     Florisil
                   Bottle date  	     Jar letter 	
                   Lot No. 	     Lot No.  	
                   Cat. No. 	
 * Adsorbent Batch # 	     Prepared by
** Standard Used              	     Date: 	
G.C. ANALYSIS date:
G.C. Analyst 	     G.C. Column
Adsorbent Satisfactory?  Yes	   No	
Bench Standard  	     Date: 	
RESULTS/COMMENTS:
 * Adsorbent Batch # - Silica-gel: The date deactivated.
                       Florisil: The date removed from oven and placed in desiccated
'* Florisil/lntermediate Standard used must match Bench Standard.

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                                                                     Section No 11
                                                                     Revision No 4
                                                                     Date  December 1989
                                                                     Page 10 of 11
                            FIGURE 11-2 (continued)

                   ADSORBENT CHECK FORM/INSTRUCTIONS


                INSTRUCTIONS FOR THE ADSORBENT CHECK FORM

     A Florisil® QC check must be run each time new batches of Florisil® have been
activated  (see Battelle Method, Section 7.1.5) and before use with NPS Method 3 work.  A
Florisil* QC check is also run with each sample set.

     To check a newly activated batch of Florisil® prior to use, pipette 2 ml of a recent
NPS3-7 procedural standard onto a column prepared according to Battelle Method 11.6,
and elute as per instructions in 11.6.2 - 11.6.6.  Final volume is 10 ml. Compare to the
same procedural  standard, and be aware that the concentration of the analytes in the
Florisil® eluate are now at half-concentration of the procedural standard. (5 ml ->  10 ml
final volume.)

     Determine recoveries (%) and enter them on the "ADSORBENT CHECK FORM".
Recoveries must be 80% - 120% for all analytes EXCEPT chloramben, and there must be
no interfering peaks j>  Vfe MRL for any Method 3 analyte.

     For any exception to the above criteria, check with the ECL Project Leader before
using the Florisil®.

     For the Florisil® QC check run with each set, the procedural standard from that set
must be used.

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                                                                           Section No 11
                                                                           Revision No 4
                                                                           Date December 1989
                                                                           Page 11 of 11
                                       FIGURE 11-3

                                EXCEPTIONS TO NPS QAPjP


Date                                            Method
Reference No.
Suggested Exception(s):
                                                Signature of Person Seeking Exception
Approved	   Disapproved

Comments:
                                                  Bob Maxey, Technical Monitor

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                                                                             Section No  12
                                                                             Revision No 4
                                                                             Date.  December 1989
                                                                             Page 1 of 2
12.  AUDITS (Technical Systems/Data Quality/Performance Evaluation)
     12.1  Requirements
     Technical Systems and Data Quality Audits shall be conducted by the ECL QAC on NPS
Method 1 analytical work to assess the adherence to the QA Project Plan and to assess the quality of
data generated  by the analytical systems.  Performance Evaluation Audits will be initiated by ECL's
QAC to evaluate the technical personnel and the analytical system.
     12.2  Frequency
           12.2.1   Technical Systems and Data Quality
     These audits shall be conducted at the beginning of the survey after 30 samples have been
analyzed and at least once every six months thereafter, exclusive of external audits.
           12.2.2   Performance
     At least one audit every six months.
     12.3  Nature of Audits
           12.3.1   Technical Systems Audits shall include the following:
                12.3.1.1  Project Management System
                      12.3.1.1.1   Personnel - Qualifications
                      12.3.1.1.2   Documentation - QAPjP and  SOPs
                      12.3.1.1.3   Communications about changes in requirements
                      12.3.1.1.4   Analyst feedback
                12.3.1.2  Sample Tracking System - receipt through disposal or storage
                12.3.1.3  Systems for Sample Preparations, e.g. extractions, clean up, etc.
                12.3.1.4  Systems for Analytical Operations
                      12.3.1.4.1   Standards
                      12.3.1.4.2   Calibrations
                      12.3.1.4.3   Documentation of Analytical Operations
                      12.3.1.4.4   Corrective Action Loop
                      12.3.1.4.5   Instrument  Maintenance
                12.3.1.5  Data Management  Systems
                      12.3.1.5.1  Collections
                      12.3.1.5.2   Reduction
                      12.3.1.5.3  Verification
                      12.3.1.5.4  Internal Review
                      12.3.1.5.5   Reporting
                      12.3.1.5.6   Use of QC  Data at Bench Level
                      12.3.1.5.7   Data Storage and Retrieval

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                                                                              Section No 12
                                                                              Revision No. 4
                                                                              Date:  December 1989
                                                                              Page 2 of 2
                 12.3.1.6  Laboratory Management Systems
                      12.3.1.6.1   Major Equipment Purchases
                      12.3.1.6.2   Services and Supplies (solvents, etc.)
                      12.3.1.6.3   Maintenance of Ancillary Equipment
                      12.3.1.6.4   General Physical Set Up - space, cross contamination, etc.
                      12.3.1.6.5   Cold Storage Facilities
           12.3.2  Data Quality Audits
      Shall include tracking 3 samples from Method 1 from  log-in through preparation, primary and
confirmatory analyses (including related set QC checks and other information), data handling and
disposal.
           12.3.3  Performance  Evaluation Audits
      Shall consist of providing a P-E sample every six months. The audit will consist of a P.E.
solution to be spiked into a water matrix and analyzed as a routine NPS sample.  The concentration of
the analytes in the P.E. solution will be unknown to the analysts involved in the method.
      12.4  Standard
      ECL's Quality Assurance Project Plan for Method 1; Printed Analytical Procedure for Method  1
and ECL's Quality Assurance Facilities Plan.
      12.5  Reporting and Use of Audit Results
      Following any of the above audits, the ECL QAC shall report the results in writing to both the
Lab Section Chief and NPS Project Leader. If deficiencies are found, each shall be specifically
identified along with the cause, if known. The QAC  will provide a written plan or suggestion for
corrective action to the NPS Project Leader with  a copy to ECL's Section Chief.  The QAC shall also
follow up with a limited audit to verify that deficiencies were resolved by the proposed corrective
action.

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                                                                           Section No 1 3
                                                                           Revision No 4
                                                                           Date  December 1989
                                                                           Page 1 of 2
13.   PREVENTIVE MAINTENANCE
      13.1  Gas Chromatographs
      Two Hewlett Packard 5890A dual EC/capillary Gas Chromatographs are used with Method 3
related analyses. An  HP7673A autosampler is also used. Routine maintenance for these instruments
is described below.                                              »
      Maintenance Item                           Schedule
           change injection port septa             •     following 2 days analytical work or as
           change compressed gas traps and filter         required
              dryers                             •     every 6 months or as required
      •     service or change injection port liner     •     as required by instrument performance
      •     bake-out  or replacement of GC column   •     as required by instrument performance
           replacement of EC detector             •     as required by lack of sensitivity or noise
      Spare parts are maintained at ECL to accommodate the above maintenance requirements, and
at least one spare GC column of each required type is on hand. ECL has a blanket purchase-order
with Hewlett-Packard. Through it, parts and service can  be accessed by telephone and usually are
provided in 2-5 working days, if needed.
      A log book will  be maintained for each instrument.  In  it will be kept records of all daily or
routine maintenance,  problems and their resolution, and  major repairs.  It  is the responsibility of the
analyst to make the above entries, and sign and date them.
      13.2  GC/MS
      The following schedule of maintenance tasks and spare parts applies to the Varian Mat 312 and
the Finnigan 5100.
      Routine maintenance will be performed on the GC/MS and purge and trap units in accordance
with the following schedule:
      Tasks                           Frequency
      Clean source                     Monthly or as  required by performance
      Bake out magnetic and            Monthly or as  required by performance
        electric sectors
      Bake out GC column              Daily or as required
      Change pump oil                 Every 6 months or as required by use
      Change GC column               As required by performance
      Change injection port septa        Weekly or as required
      Clean injection  port liner           Monthly or as  required by performance
      Most  maintenance is done inhouse. When a problem  is encountered which cannot be resolved
here, Finnigan  MAT is contacted and service is arranged. Critical spare parts are also available to
minimize  downtime and the following list of replacement parts and consumable spares is maintained
within the laboratory at all times.
      1)    Columns  (at least one of each type used)
      2)    Ferrules for columns
      3)    Syringes

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                                                                           Section No 13
                                                                           Revision No 4
                                                                           Date  December 1989
                                                                           Page 2 of 2
4)    Filaments (at least two of each)
5)    Gold gaskets
6)    Injection port septa
7)    Vacuum pump oil

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                                                                           Revision No •!
                                                                           Date  December 1989
                                                                           Page 1 of 3
14.  SPECIFIC PROCEDURES FOR ASSESSING MEASUREMENT SYSTEM DATA

     The formulas in this section are those used to calculate internal QC checks and statistics related
to QC checks.
     14.1  Formulas Related to Instrument Control Standards and Determination of
           Chromatographic and Column Performance

     •     Peak Symmetry Factor (PSF). See Figure 14-1 at the end of this section.

           PSF =       W(1/2)
                     0.5 X W(1/2)

           , where W(1/2)    =    the width of the front of the Chromatographic peak at half-height,
                                assuming the peak is split at the highest point and W(1/2) is the
                                peak width at half height.

           Peak Gaussian Factor (PGF). See Figure 14-1 at the end of this section.

           PGF =  1.83X W(1/2) , where
           W(1/2) = peak width at half-height

           W(1/10) =  peak width at tenth-height.

           Resolution  (R)

           R = t/W , where

           t = the difference in elution times between two peaks, and

           W = the average  peak width, at the baseline, of the two peaks.

     14.2  Formulas For Calculating  Statistics

           Standard Deviation(s)
           s =
                 r        * i   '
                          	  .where
                          n-1

           xr..xn  = individual sample values

             x  = sample mean
             n   = sample size or no. of sample values

           Coefficient of Variation (CV)

           CV =  s

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                                                                       Section \c  ' 4
                                                                       Revision No 4
                                                                       Date  December 1989
                                                                       Page 2 of 3
      Relative Standard Deviation (RSD)

      RSD = CVX 100

•     Mean Recovery (R)

                n                                        r
      R =       2 R/n
                i=1

      Percent Recovery (%R)

      %R = (net value of spike) X 100
              True value of spike     .where

      (net value of spike) =  (gross value) - (value attributed to background or Blank)

      Minimum Detection Limit (MDL)

      MDL = s X t (.99) („_.,)         , where

      t(.99) = "Student's t-value appropriate for a one tailed test at 99% confidence level and a

      standard deviation estimate with (n-1) degrees of freedom.

14.3  Formulas Defining Control Limits

      Upper Control Limit (UCL) = R + 3s

      Upper Warning Limit (UWL) = R + 2s

      Lower Warning Limit (LWL) = R - 2s

      Lower Control Limit (LCL) = R - 3s    .where

      R = Mean Recovery

      S = Standard Deviation

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                                                      Section No 14
                                                      Revision No. 4
                                                      Dale  December 1989
                                                      Page 3 of 3
                       FIGURE 14-1

EQUATION USED TO CALCULATE PEAK SYMMETRY FACTOR (PSF)
            AND PEAK GAUSSIAN FACTOR (PGF)
            o
            a.
                                                 r 8
                                                 : *

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                                                                            Section \c  1 5
                                                                            Revision No 4
                                                                            Date  December 1989
                                                                            Page 1 of 1
15.   CORRECTIVE ACTION
      Corrective action is required when out-of-control situations develop regarding QC criteria,
procedures, or specific Survey requirements. Sections 5 and 11 contain specific QC objectives and
criteria for this Method, and Section 7 contains specific sampling and tracking requirements. All of
these elements are evaluated as required by established NPS guidelines, and log books are
maintained as documentation.
      An analyst, team member, or Sample Custodian experienced with this Method and involved  in
day-to-day activities with it will be the first to be aware of a problem, inconsistency, or QC parameter
outside acceptance limits.  It is  his/her responsibility to note the nature and significance of the
problem and to bring it to the attention of the ECL Project Leader.  Such problems shall be properly
documented through use of the 'SAMPLE RECEIPT SCREENS FOR NPS LABORATORIES"  (refer to
end of Section 7) and a related log book in Sample Receiving or by means of the "QUALITY
ASSURANCE DATA FORM" (see Appendix H).
      The following areas will be addressed:
           specific exception to the QC requirement
           when the problem was first noted and by whom
           who was notified
           corrective or remedial action required
           action taken
      •     verification that a QC exception or problem was resolved and the date
           sample "set" numbers and specific samples involved
      If the ECL Project Leader  cannot readily resolve the problem or provide guidance for  corrective
action, the ECL Quality Assurance Coordinator (ECL QAC) must be notified. The QAC will take a lead
role in developing a strategy to  resolve the problem.  Verification that the problem has been resolved
must also be provided before analytical work continues.
      Al| QC exceptions, problems, corrective actions, and verification documentation  must  be
reported monthly to the ECL Project Leader for this Method. For any problems requiring involvement
of the ECL QAC, the ECL Project Leader must be immediately informed.

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                                                                             Revision Nc 4
                                                                             Date December 1989
                                                                             Page 1 of 4
16.   QA REPORTS TO MANAGEMENT
Internal Referee Laboratory QA Reporting System
      The ECL NPS Project Leader will interact daily with the analyst performing the bench work and
data generation for Method 3. The analyst will inform the Project Leader immediately when any QA
problem or unusual  situation develops. The analyst will follow the verbal notification with a written note
explaining the problem. The ECL Project Leader will keep ECL's QA Coordinator informed and will
discuss unresolved problems with  him. The Project Leader will inform the ECL Section Chief of major
problems.
      The analyst for Method 3 will complete an "EPA Referee-Laboratories Progress QA Report". A
copy of this form, Figure 16-1, is included in this section. Copies of this form will be submitted monthly
to the Project Leader, who will in turn provide copies to the Section Chief and ECL QA Coordinator.
The  ECL QA Coordinator will submit on a quarterly basis copies of these forms to OPP's Quality
Assurance  Officer and to the NPS Quality Assurance Officer.  Copies of the ECL internal audit reports
(refer to Section 12.5) will be sent to OPP's  Quality Assurance Officer.
Referee Laboratory Responsibilities for External Contract Monitoring - QA Monitoring - QA
Reporting System
      Six copies of the Primary Analytical Contractor Laboratory's report are to be provided monthly to
the ECL Technical Monitor for Method 3.  These reports are to be provided within 15 calendar days
after the end of the month being reported. The format of this report is covered in the contractor's
QAPjP for Method 3.
      The Technical Monitor for Method 3 will provide the ECL Analytical Coordinator with a quarterly
"Technical Monitor Progress - QA Report", Figure 16-2, a copy  of which appears in this section.
Copies of the "Monthly Contract Monitoring QA Report" for that quarter will be attached to the
Technical Monitor Report.  A copy  of these reports will also be provided quarterly by the ECL
Analytical Coordinator to ECL's Quality Assurance Coordinator, to OPP's QAO and to the NPS QAO.
      The ECL Analytical Coordinator will submit an "Analytical Coordinator Status Report" through the
ECL  Section Chief to the Director of the NPS. Copies of the quarterly reports from the  Technical
Monitor will be attached to the Analytical Coordinator Status Report. A copy of the latter report, Figure
16-3, is included in this section.

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                                                                Section No 15
                                                                Revision No 4
                                                                Date. December 1989
                                                                Page 2 of 4
                                  FIGURE 16-1

                 EPA REFEREE LABORATORY PROGRESS - QA REPORT

Method 0 	

Report Period 	                          »

Analyst 	
                                   \
Date
 I.   Progress:

     9 samples  received

     # samples  analyzed
       samples invalidated
     No. of data sets  sent  to  EPA  Data Manager

  2.  Standards:   8  stock standards diluted
                  Results of check befo.re using dilution

  3.   Bench Level Corrective Actions (s)

      Date
      Problem
      Action Taken
      Verification  of  Correction
       Sample sec  analyzed prior to problem ______________________________
       (Use back of page and same for mac to report additional  corrective
       actions.)

   4.   Problems (Project-Related):


   5.   Information requested by Technical Monitor -  (control charts, etc.)

   6.   Changes  in  Personnel:


   7.  Comments:

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                                                                Section No l 6
                                                                Revision No 4
                                                                Date December 1989
                                                                Page 3 of 4
                                 FIGURE 16-2
                  TECHNICAL MONITOR PROGRESS - QA REPORT
Method S
Laboratory
Report  Period

 Date  	
 1.  Progress:

     f samples received

     9 samples analyzed
      9  samples  invalidated
      No.  for data sets sent to EPA  Data Manager

  2.  Major Problems and  Status

      a.  Technical:
       b.  Contractural:
    3.  Comments

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                                                                Section No 16
                                                                Revision No. 4
                                                                Date.  December 1989
                                                                Page 4 of 4
                                 FIGURE 16-3
                   ANALYTICAL COORDINATOR STATUS REPORT
                                                      Report  rerioo_
                                                      Prepared  By  _
                                                      Date
Monthly - Financial  States
        - Contract Administrative  Needs
   Quarterly - Data Summary
             - Copies  of quarterly reports  from Technical Monitors

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                                      Appendix A
                                      Revision No 4
                                      Date-  December 1989
                                      Page 1 of 6
   APPENDIX A
SAMPLE CUSTODY

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                                ENVIRONMENTAL CHEMISTRY LABORATORY
                                        NPS SAMPLE LOGGING
METHOD
PREPARED BY:
(1,3,6)
LAB. I.D.
(FIELD SAMPLE I)









i












DATE:
DATE SAMPLBD





1




'





DATE SHIPPED















I
1
1
1
1
1
1


1

DATE RECEIVED
»-



















•

TIME SAMPLED
%





















CONDr























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                           NPS SET COMPOSITION FORM
                                   METHOD 3
APPROVED BY PROJECT OFFICER
SIGNATURE
DATE
                                 Set  No.
                           SET CONTROLS
1. Florisil elution check

2. Method  Blank

3. Lab  Control Spike A

4. Lab  Control Spike B
       Field Sample  No.
NPS FIELD SAMPLES

     Date Sampled
Date Arrived at ECL
 9.

 10.

 11.

 12.

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SAMPLE CONTROL RECORD
       EPA/ECL
LABORATORY "
SAMPLE NO.

(REMOVED
BY

^DATE AND TIME
REMOVED

REASON

DATE AND TIME
RETURNED


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           ECL NFS SAMPLE TRACKING FORM
                             METHOD 3
Date
Sample
Taken
Date
Rec'd
at ECL
Date
Extracted
Date
Analysis
Completed
Date Removed
for QC/MS
Confirmation
GC/MS
Confirmation
Completed

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                            NFS Method 0 3.Extract Storage Data Sheet

 ctracts Relinquished  By	Date:	Received By
                                                                 Set:
                                                                     Date:
••iisple Code
Who Stored
Date
Stored
Refrig. or
Freezer No.
Room No.
Removed
By
Purpose
Date
Removed
Returned
by
Date
Return'
             Date Disposed:
                                       Authorized by:

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                                        Acpendix E
                                        Revision No  4
                                        Date  December 1989
                                        Page 1 of 50
     APPENDIX B
BATTELLE'S VERSION

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         Method 3.  Determination of Chlorinated Acids in Ground
      Water by Gas Chromatography with an Electron Capture Detector


1.    SCOPE AMD APPLICATION

     1.1   This  is  a gas  chromatographic  (GC) method applicable  to the
          determination  of certain  chlorinated  acids  in ground  water.
          Analytes that  can be determined by this method  are  listed  in
          Table 1.

     1.2   This  method may be applicable  to "the  determination  of salts  and
           esters of analyte acids.   The  form of each  acid is  not distin-
           guished by this method.  Results  are  calculated and reported for
           each listed analyte as the total  free acid.

     i.3   This method has been validated in a single laboratory.  Esti-
           mated detection  limits (EOLs) have been determined and are
           listed  in  Table  2.  Observed detection limits may vary between
           ground  waters,  depending upon the nature of interferences in  the
           sample  matrix and  the  specific instrumentation used.

      1.4   This  method is  restricted  to  use  by  or under the supervision  of
           analysts experienced  in  the use of GC and  in the interpretation
           of gas  chromatograms.   Each  analyst  must demonstrate the  ability
           to generate acceptable results with  this method  using the
           procedure  described in Section  10.2.

      1.5   When this  method is used to analyze  unfamiliar samples for any
            or,all  of the analytes above, analyte identifications must be
            confirmed by at least one additional qualitative technique.

  2.   SUMMARY OF METHOD

      2.1   A measured volume  of  sample of approximately  1 L  is  adjusted  to
            pH  12  with 6 N  sodium hydroxide  and  shaken for 1 hour to
            hydrolyze derivatives.  Extraneous  organic material  is removed
            by  a solvent wash.  The sample is acidified,  and  the chlorinated
            acids  are extracted with  ethyl ether by mechanical  shaking  in a
            separatory funnel  or  mechanical  tumbling  in a bottle.  The  acids
            are  converted  to their  methyl esters using diazomethane  as  the
            derivatizing agent.   Excess  derivatizing  reagent  is removed, and
            the esters are determined by GC  using an  electron capture
            detector  (ECO).1

       2.2   The method provides a Florisil  cleanup procedure  to aid  in the
             elimination of interferences that may be encountered.

  3.   DEFINITIONS

       3.1   Artificial  ground water  -- an aqueous matrix designed to mimic a
             real ground water sample.  The artificial ground water  should be
            •reproducible  for  use by  others.

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3.2   Calibration standard  -- a known amount or"  a  pure  anaiyte,
      dissolved  in an organic solvent, analyzed  under the same
      procedures and conditions used  to analyze  sample  extracts
      containing that anaiyte.

3.3   Estimated  detection  limit (EDL)  --  the minimum concentration of
      * <-i'h«T?nco  th«t  ran be rr»??sured and  reported with confidence
      ...„> cue anaiyie  concentration  is greater than zero as deter-
      mined from the  analysis of  a  sample in  a given matrix containing
      the anaiyte.  The EDL is  equal  to  the Teuel  calculated by
      multiplying  the  standard  deviation  of replicate measurements
      times the students'  t value appropriate  for a 99 percent
      confidence level  and a standard deviation estimate with n-1
      degrees of freedom or the level of the compound  in a  sample
      yielding a peak in the final  extract with signal-to-noise  ratio
      of  approximately five, whichever value is higher.

 3.4   Internal standard --a pure compound added  to  a  sample  extract
       in  a known amount and used to calibrate concentration measure-
       ments  of other analytes that are sample components.   The
       internal  standard must be  a compound that is not a sample
       component.

 3.5   Instrument quality  control (QC) standard  -- a methyl  tert-butyl
       ether  (KTBE) solution containing  specified  concentrations of
       specified analytes.  The instrument  QC  standard is analyzed each
       working day  prior to the analysis  of sample extracts and
       calibration  standards.   The  performing  laboratory uses this
       solution to demonstrate  acceptable instrument performance  in the
       areas  of sensitivity, column performance,  and chromatographic
       performance.

  3.6   Laboratory control  (LC)  standard  -- a solution  of analytes
       prepared in the laboratory by dissolving known  amounts of pure
       analytes in a known  amount of reagent water.   In  this  method,
       the LC standard  is  prepared by adding  appropriate volumes of the
       appropriate standard solution to  reagent water.

  3.7   Laboratory method  blank --  an  aliquot  of reagent water analyzed
       as if it were a  sample.

  3.8  Performance evaluation  sample --  A water-soluble solution of
       method analytes distributed by the Quality Assurance Branch,
        Environmental Monitoring  and  Support Laboratory, USEPA,  Cincin-
        nati, Ohio.   A  small measured volume of the  solution  is  added  to
        a known volume  of reagent water and analyzed using  procedures
        identical  to  those used for samples.  Anaiyte  true  values  are
        unknown to the  analyst.

   3.9   Quality control check sample --a water soluble  solution
        containing known concentrations  of analytes  prepared  by a
        laboratory other  than the laboratory performing  the analysis.
        The performing.laboratory uses this solution to  demonstrate that
        it can obtain acceptable identifications  and measurements with a

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          method.  A small  measured  volume  of the solution  is  added to a
          known volume of reagent water  and  analyzed with procedures
          identical to those used  for  samples.  True values  of analytes
          are known by the analyst.

    3.10  Stock  standard solution  -- <. concentrated  solution containing  a
          certified standard that  is a method  analyte,  or  a concentrated
          solution of  an analyte prepared in the  laboratory with an
          assayed  reference compound.

                  ..  .'.:.•.;;:>: -- i ^jre compound added  to a sample  in  a
           known  amount and  used to detect gross abnormalities during
           sample preparation.  The  surrogate standard  must be a compound
           that is not a sample component.

4.   INTERFERENCES

     4.1   Method interferences  may  be caused by contaminants  in  solvents,
           reagents, glassware  and other sample processing  apparatus that
           lead  to discrete artifacts  or elevated baselines  in gas chroma-
           togratns.  All reagents  and  apparatus must be routinely demon-
           strated to  be free from interferences  under  the  conditions  of
           the analysis by  running laboratory  method blanks as described in
           Section  10.8.

           4.1.1   Glassware must be  scrupulously cleaned.2  Clean  all
                    glassware as soon  as possible after use by thoroughly
                    rinsing  with the last solvent used   in it.  Follow  by
                    washing  with hot water and detergent and thorough
                    rinsing  with dilute  acid, tap and reagent  water.   Drain
                    dry,  and heat  in an  oven or muffle  furnace at  400"C for
                    1  hour.   Do  not  heat volumetric ware.  Thermally stable
                    materials such as  PCBs  might not be eliminated by  this
                    treatment.   Thorough rinsing with acetone  may  be substi-
                    tuted for the  heating.   After drying and cooling,   seal
                    and store glassware in  a clean environment to  prevent
                    any accumulation of dust or other contaminants.  Store
                    inverted or capped with aluminum foil.

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

       4.2   The  acid  forms  of the analytes are strong  organic acids which
             react readily with alkaline substances and can be lost  during
             sample preparation.  Glassware and glass wool  must be  acid-
             rinsed with (U9) hydrochloric  acid and the sodium sulfate must
             be acidified with sulfuric  acid prior to use to avoid analyte
             losses due to adsorption.

       4.3   Organic acids and  phenols,  especially chlorinated compounds,
             cause the most direct, interference with-the determination.
             Alkaline hydrolysis and subsequent extraction  of the  basic

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         sample remove many chlorinated hydrocarbons and phthalate  esters
         that might otherwise interfere with the electron capture
         analysis.

   4.£   Interferences by phthalate  esters  can  pose  a  major  problem in
         pesticide  analysis when using  the  ECO.  These compounds general-
         ly  appear  in the chromatogram  as  large peaks.  Common flexible
         plastics contai.n varying amounts  of phthalates.,  that are easily
         ^•'erected  c - " :;.ched curing laboratory operations.   Cross
         contamination of clean glassware  routinely  occurs  when plastics
         are handled during extraction  steps,  especially when sol-
         vent-wetted  surfaces are handled.   Interferences from phthalates
         can best be minimized by avoiding the use of plastics in the
          laboratory.   Exhaustive cleanup of reagents and glassware may  be
          required to eliminate background phthalate contamination.^'^

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

     4.6   Matrix  interferences may be caused  by contaminants that are
          coextracted  from  the sample.   The extent of matrix interferences
          will  vary considerably from source to source, depending upon  the
          ground  water  sampled.  The cleanup procedures in Section  11  can
           be used to overcome many of these interferences.   Positive
           identifications-should be  confirmed using the confirmation
           column specified in  Table  3.

5.    SAFETY

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

      5.2  Diazomethane is a toxic  carcinogen  and can explode  under certain
           conditions.   The following precautions must be followed:

            5.2.1   Use only a  well  ventilated  hood  -- do not breath vapors.

             5.2.2   Use a safety screen.
                                        II

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5.2.3   Use mechanical pipetting aides.

5. 2.4   Do not heat above 9CTC -- EXPLOSION may result.

5.2.5   Avoid grinding surfaces, ground glass joints, sleeve
        bearings, glass          --
5.2.6   Store away from
                  Avoid  grinding  surfaces, ground glass joints, sleeve
                  bearings,  glass stirrers --  EXPLOSION may  result.
                  Store  away from alkali  metals  --  EXPLOSION may  result.
          5.2.7   Solutions of diazomethane decompofe  rapidly in  the
                  presence of solid materials such as  copper powder,
                  calcium chloride, and boiling chips.

    5.3   Ethyl ether is an extremely flammable solvent.   If a mechanical
          device is used for sample extraction, the device should be
          equipped with an explosion-proof motor and placed in a hood to
          avoid possible damage and injury due to an explosion.

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

     6.1   SAMPLING  EQUIPMENT

          6.1.1   Grab  sample  bottle  --  Borosilicate,  1-L  volume with
                  graduations  (Wheaton Media/Lab  bottle  219820),  fitted
                  with  screw caps lined with TFE-fluorocarbon.   Protect
                   samples from light.  The  container must be washed  and
                  dried as described in Section 4.1.1  before use  to
                   minimize contamination.   Cap liners  are cut to  fit from
                   sheets (Pierce Catalog No. 012736)  and extracted  with
                   methane! overnight prior to use.

     6.2   GLASSWARE

           6.2.1   Separatory  funnel --  2000-mL, with TFE-fluorocarbon
                    stopcocks,  ground glass or TFE-fluorocarbon stoppers.

           6.2.2    Tumbler bottle --  1.7-L (Wheaton Roller  Culture  Vessel),
                    with TFE-fluorocarbon lined  screw cap.   Cap liners are
                    cut  to fit  from sheets  (Pierce  Catalog  No. 012736) and
                    extracted with methanol overnight prior to use.

            6.2.3    Concentrator tube,  Kuderna -Danish  (K-0)  -- 10- or 25-mL,
                    graduated (Kontes K-570050-2525 or Kontes K-S700SO-102S
                    or equivalent).  Calibration must  be checked at  the
                    volumes employed in the test.   Ground glass stoppers are
                    used to prevent evaporation of extracts.

            6.2.4   Evaporative flask, K-0 -- 500-mL (Kontes K-570001-0500
                    or  equivalent).  Attach  to concentrator tube with
                    springs.

          .  6.2.5 - Snyder column,  K-0 --  three-ball macro  (Konles  K-503000-
                    0121  or equivalent).

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     6.2.6   Snyder column, K-0 --  two-ball  micro (Kontes K-569001-
             0219 or equivalent).

     6.2.7   Flask, round-bottom -- SOO-ml with 24/40 ground glass
             joint.

     6.2.8   Vials  -- glass, 5- to 10-mL capacity with TFE-fluoro-
             carboa lined  screw cap.

     6.2.9   Disposable  pipets  --  sterile plugged borosilicate glass,
             5-ml  capacity (Corning 70.78-5N or equivalent).

6.3  Separatory  funnel  shaker  -- Capable  of holding  eight  2-L  separa-
      tory funnels  and  shaking  them with rocking  motion  to  achieve
      thorough  mixing  of separatory funnel  contents  (available  from
      Eberbach  Co.  in  Ann Arbor, MI).

6.4   Tumbler --  Capable of holding 4  to 6 tumbler bottles  and
      tumbling  them end-over-end at 30 turns/min (Associated Design
      ana Mfg.  Co., Alexandria, VA).

6.5   Boiling stones --  Teflon, CHEKVARE (Norton Performance Plastics
      No. 015021).

6.6   Water  bath -- Heated, capable of temperature control  (i2"C).
      The bath should  be used  in a hood.

€.7   Balance  -- Analytical, capable  of accurately weighing to  the
      nearest  0.0001 g.

 6.8   Gaseous  diazomethane generator  -- Diazomethane generator
       assembly as  shown in Figure  1 (available from Aldrich Chemical
       Co.).

 6.9   Diazomethane solution generator --  Assemble from two 20 x  150 mm
       test tubes,  two Meoprene rubber stoppers, and a source of
       nitrogen.   The diazomethane collector is cooled  in an approx-
       imately 2-L  thermos  for  ice bath or a cryogenically  cooled
       vessel  (Thermoelectrics Unlimited Model SK-12 or equivalent).
       The generation/collection assembly is shown in Figure 2.

  6.10  Glass wool  -- Acid  washed (Supelco 2-0383 or  equivalent)  and
       heated  at <50*C  for 4 hours.

  6.11  GAS CHROMATOGRAPH -- Analytical system  complete  with GC  suitable
       for use with capillary  columns and all  required  accessories
       including  syringes, analytical columns,  gases, detector and
       stripchart  recorder.  A data system is  recommended  for  measuring
       peak  areas.

       6.11.1   Primary column -- 30 m long x  0.25 mm 1.0.  DB-5 bonded
                fused  silica column, 0.25  urn film thickness (available
                from JiW).  Validation data"presented in this method-
                                    /3

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                  were  obtained  using  this  column.   Alternative  columns
                  may be  used  in accordance with  the provisions  described
                  in Section  10.3.

          6.11.2  Confirmation column  --  30 m long x 0.25 mm 1.0. 08-1701
                  bonded  fused silica  column, 0.25 urn film thickness
                  (available  from JiW).

          6.11.3  Detector -- Electron capture.  This detector has proven
                  effective in the analysis of spiked reagent and arti-
                  ficial  ground waters.   An ECO was used to generate  the
                  validation data presented  in this method.  Alternative
                  detectors,   including a mass  spectrometer, may  be used  in
                  accordance with the provisions described  in
                  Section  10.3.

7.    REAGENTS  AND CONSUMABLE MATERIALS

     7.1   Acetone,  methanol,  methylene chloride,  KTBE  --  Pesticide  quality
           or  equivalent.

     7.2   Ethyl ether, unpreserved  -- Nanograde,  redistilled in glass if
           necessary.  Must be free  of peroxides  as indicated by EH Quant
           test strips (available from Scientific Products Co.,  Cat.  No.
           PI 126-8,  and other suppliers).  Procedures recommended for
           removal of peroxides are  provided with the test strips.

     7.3   Sodium sulfate, granular,  anhydrous, ACS grade --  Heat treat  in
           a shallow tray  at 4SO*C for a minimum of 4 hours to remove
           interfering organic  substances.   Acidify by slurrying 100  g
           sodium sulfate  with  enough ethyl  ether  to just cover  the  solid.
           Add  0.1  ml  concentrated sulfuric  acid  and mix  thoroughly.
           Remove the  ether under vacuum.   Mix 1  g of  the resulting  solid
           with 5 ml of  reagent water and  measure the  pH of the mixture.
           The  pH must be  below pH 4.  Store at  130*C.

      7.4   Sodium hydroxide  (HaOH), pellets -- ACS grade.

            7.4.1   NaOH,  6 N -- Dissolve 216 g NaOH in 900 ml reagent
                    water.

      7.5   Sulfuric acid  (l^SO^). concentrated,  ACS grade -- sp. gr.  1.84.

            7.S.I   H?S04, 12 N  -- Slowly  add  335 ml concentrated H2S04  to
                     665 ml of reagent water.

       7.6   Potassium  hydroxide  (KOH), pellets --  ACS grade.

            7.6.1    KOH, 37%  (w/v) -- Dissolve 37 g KOH  pellets in  reagent
                     water  and dilute  to  100 ml.

       7.7   Carbitol  (diethylene glycol  monoethyl ether), ACS grade --
            available  from Aldr.ich Chemical Co.

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7.8   Oiazald,  ACS  grade  --  available  from  Aldrich  Chemical  Co.

7.9   Chazald solution  --  Prepare  a  solution  containing 10 g Oiazald
      in 100 ml of  a 50:50 by  volume mixture  of ethyl  ether and
      carbitol.  This solution is  stable for  one month or longer when
      stored at 4*C in  an amber bottle with a Teflon-lined screw cap.

7.10  Sodium chlorid.e (NaCl),  crystal, ACS grade -- Heat, treat  in a
      shallow tray at 450"C for a  minimum of 4 hours to remove
      interfering organic substances.

"   '   '  '-'-Oibromooctafluorobiphenyl  (OBOB)  --  >997. purity,  for use  as
             -   ........  ,.  .......  ........ /..v.Vv.i, fr-  •-•'••  '• ~ .

7.12  2,4-Oichlorophenylacetic  acid (OCAA) --  >99% purity,  for use  as
       surrogate standard  (available from Aldrich Chemical  Co).

 7.13  Reagent  water -- Reagent  water  is defined as water in which an
       interferent  is not observed at  or above  the  EDL of any analyte.
       Reagent  water used to generate  the  validation  data in this
       method was distilled water  obtained  from the Magnetic.Springs
       Water Co., Columbus, Ohio.

 7.14  Silicic  acid, ACS  grade

 7.15  Florisil  -- 60-100/PR mesh  (Sigma No.  F-9127).  Activate  by
       heating  in a shallow container at 150'C  for at  least  24  and  not
       more  than 48 hours.

 7.!6  STOCK STANDARD SOLUTIONS (1.00 ug/pL) -- Stock  standard  solu-
       tions may be purchased as  certified solutions  or  prepared from
       pure  standard materials  using  the following procedure:

        7.16.1   Prepare stock  standard solutions by accurately weighing
                approximately  0.0100 g of pure  material.   Dissolve the
                material  in HTBE and dilute to  volume in a 10-mL volu-
                metric  flask.   Larger  volumes may be  used at the conven-
                ience of  the analyst.   If  compound purity is certified
                at  96%  or greater, the weight may be used without
                correction to  calculate the concentration of the stock
                standard.  Commercially prepared stock standards may  be
                used at any concentration  if they are certified  by  the
                manufacturer or by an independent  source.

         7.16.2  Transfer the  stock standard  solutions  into  TFE-fluoro-
                carbon-sealed screw cap vials.  Store  at  room tempera-
                 ture and protect  from light.

         7.16.3   Stock standard  solutions should be replaced after two
                 months or  sooner  if comparison with  laboratory control
                 standards  indicates a problem.

   7.-17   INTERNAL STANDARD SPIKING SOLUTION — Prepare an internal
         standard spiking solution by  accurately weighing approximately

                                      8

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         0.0010 g of pure OBOB.   Dissolve the D80B in MTBE and dilute  to
         volume in a 10-ml_ volumetric flask.  Transfer the internal
         standard spiking solution  to a TFE-fluorocarbon-sealed  screw  cap
         bottle and store at room temperature.  Addition of  25 ul  of the
         internal standard spiking  solution to  10 ml of sample extract
         results  in a final internal  standard concentration  of 0.25
         Solution should be replaced  when ongoing QC (Section  10)
         indicates a problem.

   7.18  SURROGATE STANDARD SPIKING SOLUTION  -- Prepare a  surrogate
         standard spiking  solution  by accurately weighing  approximately
         0.0010  g of pure  DCAA.  Dissolve the DCAA  in  MTBE and dilute to
         volume  in  a 10-mL volumetric flask.  Transfer the surrogate
         standard spiking  solution to a TFE-fluorocarbon-sealed screw cap
         bottle  and  store  at  room temperature.   Addition of 50 uL of  the
         surrogate  standard  spiking solution to a 1-L sample prior  to
         extraction results  in  a surrogate  standard concentration  in  the
         sample of  5 ug/L and,  assuming quantitative recovery of OCAA, a
          surrogate  standard concentration  in the final extract  of
          0.5 pg/mL.  Solution should be replaced when ongoing QC  (Section
          10) indicates a problem.

    7.19  INSTRUMENT QC STANDARD --  Prepare a diluted  dinoseb  solution by
          adding  10 pi of  the 1.0 uc/uL dinoseb stock  solution to  MTBE and
          diluting to volume  in a 10-rcL volumetric  flask.   To  prepare the
          instrument QC standard, add <0 uL of  the  diluted dinoseb
          solution,  16 ul  of  the 4-nitrophenol  stock solution, 6 ul of the
          3,5-dichlorobenzoic acid stock solution,  50  ul  of the surrogate
          standard  spiking solution,  25 ul  of the internal standard
          spiking solution,  and  250 ul of methanol  to a 5-mL volumetric
          flask and  diluting  to  volume with MTBE.  Methylate sample as
          described  in Section  11.<.  Dilute the sample to  10 ml  in MTBE.
          Transfer  the instrument QC standard to a TFE-fluorocarbon-
           sealed screw cap bottle  and  store at room temperature.   Solution
           should be replaced when  ongoing  QC (Section 10) indicates a
           problem.

8.   SAMPLE  COLLECTION. PRESERVATION.  AND STORAGE

     8.1   Grab  samples must be collected in  glass  containers.   Conven-
           tional sampling practices8 should  be followed;  however, the
           bottle must not be prerinsed with  sample before collection.

     8.2   SAMPLE PRESERVATION AND STORAGE

           8.2.1  Add mercuric  chloride to the sample bottle in amounts  to
                    produce a  concentration  of 10 mg/L.  Add 1 ml of a
                    10  mg/mL  solution of mercuric chloride in water  to the
                    sample  bottle at the sampling site or  in the laboratory
                    before  shipping to  the  sampling site,  A major  dis-
                    advantage of mercuric chloride is that it  is a  highly
                    toxic chemical; mercuric chloride must be  handled  with
                    caution,  and samples containing mercuric chloride  must
                    be  disposed of  properly.

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     8.2.2   After the sample is collected  in the  bottle containing
             preservative, seal the bottle  and  shake  vigorously for
             1  mm.

     8.2.3   The samples must be iced or refrigerated at 4"C awav
             from light  from the time of collection until extraction.
             Preservation  study results given  in Table  11 indicate
             that most  analytes present in samples stored under these
             conditions  are  stable for at least^S days  after
             collection.   However, analyte stability may be affected
             by  the  matrix;  therefore, the analyst should verify that
             the preseraation  technique is applicable to the samples
             under  study.
8.3   EXTRACT STORAGE

      8.3.1   Extracts should be stored  at  A'C away  from light.
              Preservation study results given in  Table 11  indicate
              that that most analytes are stable  for 28 days;  however,
              the analyst should verify  appropriate  extract holding
              times  applicable  to the samples  under  study.

CALIBRATION

9.1    Establish  GC operating  parameters equivalent  to  those indicated
       in Table 3.  The  GC system must be calibrated using  the internal
       standard technique  (Section  9.2).

 9.2    INTERNAL STANDARD CALIBRATION  PROCEDURE --  To use this  approach,
       the  analyst must  select one  or more  internal  standards  compat-
       ible in analytical  behavior  to the compounds  of interest.   The
       analyst must further demonstrate  that the measurement of  the
       internal  standard  is not affected by method or  matrix  interfer-
       ences.
       9.2.1   Prepare calibration standards at  a  minimum of  three
               (suggested five) concentration  levels for each  analyte
               of interest by adding volumes of  one  or more stock stan-
               dards  to a volumetric flask.  To  each calibration
               standard,  add  a  known constant  amount of one or more
               internal standards  and 250 uL methanol,  and dilute  to
               volume with MTBE.   Esterify acids with  diazomethane as
               described  in  Section  11.3.  One of the  calibration
               standards  should be representative of  an analyte
               concentration near, but  above,  the EDL.   The other
               concentrations should correspond to  the range  of
               concentrations expected  in  the sample  concentrates,  or
               should define the working range of the detector.

        9.2.2   Inject 2 uL of each calibration standard'and tabulate
               the relative response for each analyte (RRa) to  the
                internal standard using  the equation:
                                     10

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                    a ~    a/  i s

                  where:   Aa   =  the peak area  of  the analyte, and
                          A,s =  the peak area  of  the internal standard.

                  Generate a  calibration curve  of  RR, versus  analyte
                  concentration in the sample in ug/L.

          9.2.3   The working  calibration curve must^be verified  on each
                  working shift by the measurement of one or  more calibra-
                  tion standards.   If the response for  any analyte varies
                  from the predicted response by more than ±20%,  the test
                  must be repeated  using a fresh calibration  standard.
                  Alternatively,  a  new  calibration curve must be prepared
                  for that analyte.

10.   QUALITY  CONTROL

     iO.l   Each laboratory using this  method  is  required  to operate a
           quality control  (QC) program. The  minimum requirements of  this
           program consist of the following:  an  initial  demonstration  of
           laboratory capability; the analysis  of  surrogate standards  in
           each and every sample as a continuing check  on sample  prepara-
           tion; the monitoring of internal  standard  area counts  or peak.
           heights  in each and every sample as  a continuing check on  system
           performance; the analysis of laboratory control standards,  QC
           samples,  and performance evaluation (PE) samples  as continuing
           checks on  laboratory performance; the analysis of  spiked samples
           as  a continuing check  on recovery performance; the analysis of
           method blanks  as  a  continuing check on contamination;  and
           frequent analysis of  the  instrument QC standard to assure
           acceptable instrument  performance.

      10.2  INITIAL  DEMONSTRATION OF CAPABILITY  -- To establish the ability
            to perform this method,  the analyst  must perform  the  following
            operations.

            10.2.1  Select a  representative spike  concentration  (suggest
                    15 times  the EOL) for each  of the target  analytes.
                    Using a stock standard that differs from  calibration
                    standard,  prepare a laboratory control (LC)  check sample
                    concentrate in methanol 1000 times  more concentrated
                     than the selected spike concentration.

             10.2.2   Using a  syringe,  add 1 ml of the LC sample concentrate
                     to each  of a  minimum of four 1-L aliquots of reagent
                     water.   A  representative ground water may be used  in
                     place of the reagent water, but one  or more  unspiked
                     aliquots must be  analyzed  to determine background
                     levels,  and the spike  level must,  at a minimum,  exceed
                     twice the  background level  for the test  to be  valid.
                     Analyze  the aliquots according to  the method beginning
                     in Section 11.                      -     •
                                          11.


                                          I*

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     10.2.3   Calculate the average percent  recovery  (R)  and  the
             standard deviation of the  percent  recovery  (Sp),  for  the
             results.  Ground water background  corrections must  be
             made before  R and SR calculations  are performed.

     10.2.4   Table 2 and  Tables 4-9 provide single laboratory
             recovery and precision data obtained for the method
             analytes from reagent  and  artificial ground waters,
             respectively.   Similar results from dosed reagent and
             artificial  ground  waters should be expected by any
             experienced laboratory.   Compare results obtained in
             Section 10.2.3 to the  single laboratory recovery and
             precision data.  If  the results are not comparable,
             review potential problem areas and  repeat the test.
             Results are comparable  if  the calculated percent
             relative standard deviation (RSD) does  not exceed  2.6
             times  the single laboratory RSD or  20  percent, whichever
              is  greater, and your mean  recovery  lies within the
              interval R+3S  or R+30'/.  whichever  is greater.

10.3   In recognition of  the  rapid advances  occurring in  chromato-
      graphy, the analyst is permitted  to modify  GC  columns, GC
      conditions, or detectors  to improve the  separations or lower the
      cost  of measurements.   Each tme  such modifications to the
      method are made,  the  analyst  is required to repeat the procedure
      in Section 10.2.

10.4   ASSESSING SURROGATE RECOVERY

      10.4.1  All samples and blanks must be fortified with the
              surrogate spiking compound before  extraction.  A
              surrogate standard determination must  be performed  on
              all samples (including matrix spikes)  and blanks.

      10.4.2 Determine whether the  measured surrogate concentration
               (expressed as percent  recovery)  falls  between 70  and  130
               percent.

       10.4.3  When  the  surrogate recovery  for  a  laboratory  method
               blank is  less than 70  or greater than 130 percent,  the
               laboratory must  take  the following actions:

               (1)  Check calculations  to make sure  there are no
                    errors.

               (2)  Check internal  standard and  surrogate standard
                    spiking solutions for degradation, contamination,
                    or other obvious abnormalities.

               (3)  Check instrument performance.

               Reinject the laboratory  method  blank extract.   If  the
               reanalysis fails-the  70  to  130  percent recovery
               criteria, the analytical system must be  considered "out

                                    12

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            of  control."   The problem must be  identified and
            corrected  before continuing.

    10.4.4  When the surrogate  recovery  for  a  sample is less  than 70
            percent or greater  than  130  percent,  the laboratory must
            establish  that the  deviation is  not due to laboratory
            problems.   The laboratory  shall  document deviations by
            taking the following actions:
                                              »-
            (1)  Check calculations  to make sure there are no
                 errors.

            (2)  Check internal standard and surrogate  standard
                 spiking  solutions for degradation, contamination,
                 or other obvious abnormalities.

             (3)  Check  instrument performance.

             Recalculate  or  reanalyze  the extract if the above steps
             fail  to reveal  the cause  of the noncompliant surrogate
             recoveries.   If reanalysis  of  the sample or extract
             solves the problem,  only  submit the sample data from the
             analysis with surrogate spike  recoveries within the
             required limits.   If reanalysis of the sample or extract
             fails  to solve the problem, then report all data for
            • that  sample  as suspect.

10.5   ASSESSING  THE  INTERNAL STANDARD

      10-.5.1  An internal  standard peak  area or  peak height check must
             be performed on all samples.   All  sample  extracts  must
             be fortified with the  internal  standard.

      10.5.2  Internal standard recovery must  be evaluated for
              acceptance by  determining  whether the measured peak area
              or peak height for the internal  standard in any sample
              deviates by more  than  30 percent from the average peak
              area or height for the internal  standard  in the calibra-
              tion  standards.

      10.5.3  When  the internal standard peak area  or height  for  any
              sample  is outside the limit specified in  10.5.2,  the
              laboratory  must  investigate.

               10.5.3.1  Single occurrence •- Reinject  an  aliquot of
                        ^the extract to  ensure  proper  sample  injection.
                         If  the reinjected sample extract aliquot
                        displays an internal  standard  peak  area or
                        height within specified limits, quantify and
                         report results.  If the reinjected  sample
                        extract aliquot displays an internal standard
                         peak area or  height outside the specified
                         limits, but-extract aliquots from other  .
                         samples continue to give the proper area or

                                    13

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                      height for the internal  standard, assume  an
                      erro<- was made during addition of the  internal
                      standard to the failed sample extract.   Repeat
                      the  analysis of that sample.

            10.5.2.2  Multiple Occurrence -- If the internal
                      standard peak areas or heights for  successive
                      samples  fail the specified criteria (JO.5.2),
                      check*the  instrument for proper  performance.
                      After optimizing instrument performance,  check
                      the calibration curve using a calibration
                      check standard  (Section 9).   If  the calibra-
                      tion curve is  still  applicable and  if the
                      calibration check  standard internal standard
                      peak area  or height  is within ±30% of the
                      average internal  standard  peak  area or height
                      for the calibration  standards,  reanalyze those
                      sample extracts whose internal  standard  failed
                      the specified criteria.   If  the  internal
                      standard peak areas or heights  now fall  within
                      the  specified limits, report the results.   If
                      the  internal standard peak areas or  heights
                      still  fail  to fall within the specified  limits
                      or if  the  calibration curve is  no  longer
                       applicable, then generate a new calibration
                       curve  (Section 9) and reanalyze those sample
                       extracts  whose  internal standard  failed the
                       peak area or  height  criteria.

10.6  ASSESSING  LABORATORY PERFORMANCE

      10.6.1   The  laboratory must, on an  ongoing  basis, analyze at
              least  one  laboratory control  standard  per sample  set (a
              sample set  is all those samples extracted within  a
              24-hour period).

              10.6.1.1  The spiking concentration in the  laboratory
                        control  standard should be IS  times the EDI.

              10.6.1.2  Spike  a  1-L aliquot of reagent water with a
                        laboratory control  (LC) sample concentrate
                        (the  volume of the  spike should  be kept to a
                        minimum  so the solubility of the  analytes of
                        interest in  water  will not  be  affected) and
                        analyze  it to  determine  the concentration
                        after spiking  (A)  of each  analyte.  Calculate
                        each percent recovery  (Rj)  as  (100xA)%/T,
                        where T is the known true  concentration of the
                        spike.

               10.6.1.3  Compare the percent recovery  (R^J  for  each
                         analyte with established QC acceptance
                         criteria.  QC criteria are established by
                         initially analyzing five laboratory control

                                   U

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standards and calculating the averaae percent
recovery  (P) ind the standard deviation of the
percent recovery (SpJ using the following
equations:
       R,/n

                    \     / n   \ 2 j
        -iii  ^-ii^i
          ii*i     .    *. •  i      i
      I n-l ! -
 where:   n   = number of measurements for each
             analyte, and
         Rj  = individual percent recovery
             value.

 Calculate  OC acceptance criteria  as follows:

      Upper Control Limit  (UCL)  -  R *  3Sp
      Lower Control Limit  (LCL)  -  R -
  Alternatively,  the -data generated during the
  initial demonstration of capability (Section
  10.2)  can be used to set the initial  upper and
  lower  control limits.

  Update the performance criteria on a con-
  tinuous basis.   After each five to ten new
  recovery measurements (RiS), recalculate R and
  SR using all the data, and construct new
  control limits.  When the total number of data
  points reach twenty, update  the control limits
  by calculating R and SR  using  only the most
  recent twenty data points.

  Monitor all  data from  laboratory control
  standards.   Analyte recoveries must  fall
  within the established control limits.

   If the recovery of any such analyte falls
  outside the designated range, the laboratory
   performance for that analyte  is judged to be
   out of control, and the source of the problem
   roust  be immediately identified and resolved
   before continuing  the analyses.   The analyti-

             15

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                       cal  result,  for  that  analyte  in samples  is
                       suspect  and  must  be  so  labeled.  All results
                       for  that analyte  in  that  sample  set must  also
                       be  labeled  suspect.

     10.6.2  Each Quarter,  it is essential  that  the laboratory
             analyze (if available) QC check standards.   If  the
             criteria established by the U.S.  Environmental  Protec-
             tion Agency (USEPA) and provided wvth the  QC standards
             are not met,  corrective action needs to be taken and
             documented.

     10.6.3  The laboratory must analyze an unknown performance
             evaluation sample  (when available) at least once a year.
             Results for each  of the target analytes need to be
             within acceptable limits established  by USEPA.

10.7  ASSESSING AMAIYTE RECOVERY

      10.7.1   The laboratory  must,  on  an ongoing basis,  spike  each of
              the target analytes  into ten  percent of the samples.

              10.7.1.1   The spiking concentration in the sample  should
                        be one to five times the background  concentra-
                        tion, or,  if it is'impractical  to determine
                        background levels before spiking, 15 times the
                        EDL.

               10.7.1.2  Analyze one sample aliquot to determine the
                        background concentration  (B) of each analyte.
                        Spike  a second  sample aliquot with a  labora-
                        tory control  (LC)  sample  concentrate  (the
                        volume of  the spike should be kept to a
                        minimum so the  solubility of the  analytes of
                        interest  in water  will  not be affected)  and
                        analyze it to determine the concentration
                        after  spiking  (A)  of  each analyte.   Calculate
                        each percent  recovery (R^) as  100(A-B)%/T,
                        where  T is the  known  true concentration of  the
                         spike.

               10.7.1.3  Compare the percent recovery (R,) for each
                         analyte with QC acceptance criteria esta-
                         blished from the analyses of laboratory
                         control standards.

                         Monitor all data  from  dosed samples.  Analyte
                         recoveries must fall within the established
                         control limits.

                10.7.1.4  If  the recovery of any such analyte  falls
                         outside  the designated range,  and the  labora-
                         tory  performance  for that analyte  is judged, to
                         be  in control, the  recovery problem encoun-

                                   . 16

                                  -Q

-------
                         tered with the  dosed sample is judged to be
                         matrix-related,  not system-related^  The
                         result for that analyte in the unspiked sample
                         is labeled suspect/matrix to  inform the user
                         that the results are suspect  due to matrix
                         effects.

  10.8  ASSESSING LABORATORY CONTAMINATION (METHOD BLANKS) --  Before
        processing any samples,  the analyst must demonstrate  that  all
        glassware and reagent  interferences are under control.   This  is
        accomplished by the analysis of 2 laboratory method  blank.   A
        laboratory method blank  is  a 1-L  aliquot of  reagent  water
        analyzed as if it was  a  sample.   Each time  a  set of  samples is
        extracted or there is  a  change  in reagents,  a  laboratory method
        blank must be processed  to  assess laboratory contamination.  If
        the method blank exhibits z peak within the retention time
        window of any analyte which is  greater than or equal to one-
        half the  EDL  for that analyte,  determine the source of contam-
         ination  before processing samples and eliminate the  interference
        problem.

   10.9  ASSESSING INSTRUMENT  PERFORMANCE (INSTRUMENT QC STANDARD)  --
         Instrument  performance  should be monitored on  a daily basis  by
         analysis of the  instrument QC standard.  The instrument QC
         standard contains  compounds designed  to indicate  appropriate
         instrument sensitivity,  column performance and chromatographic
         performance.  Instrument QC standard  components and performance
         criteria are. listed in  Table 10.  Inability  to demonstrate
         acceptable instrument performance indicates  the need for
         revaluation of the GC-ECO system.   A GC-ECD chromatogram
         generated from the analysis of  the  instrument  QC standard is
         shown in Figure 3.  The sensitivity requirements are set based
         on the EDLs published in this  method.  If laboratory EDLs differ
         from those listed in this  method,  concentrations of the instru-
         ment QC  standard compounds must be  adjusted to be compatible
         with the laboratory EDLs.   An  instrument QC standard should be
         analyzed with each sample set.

    10.10 ANALYTE  CONFIRMATION - When doubt exists over the  identification
         of a peak  on the chromatogram, confirmatory techniques such  as
         mass spectrometry or a second gas chromatography column must be
         used.   A suggested confirmation column is described in Table 3.

    10.11 ADDITIONAL QC -  It  is  recommended that the  laboratory  adopt
          additional quality  assurance practices for  use with this
         method.  The specific  practices that are most productive depend
          upon the needs  of the  laboratory and the  nature of the samples.


11.  PROCEDURE

    11.1  AUTOMATED HYDROLYSIS* CLEANUP,. AKO EXTRACTION METHOD --  Valida-
          tion data presented in this method were generated using  the


                                       17

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automated extraction  procedure with the mechanical  separatory
funnel  shaker.

11.1.1   Add preservative to any  samples not  previously  preserved
         (Section 8.2).   Mark the water meniscus  on the  side of
         the sample bottle for later determination of sample
         volume.  Spike sample with 50  pi  of  the  surrogate
         standard spiking solution.  If the mechanical separatory
         funnel shaker is used,  pour the entire sample into a 2-1
         separatory funnel.  If the mechanical tumbler is used,
         pour the entire sample into a  tumbler bottle.

 11.1.2   Add 250 g NaCl  to  the sample,  .seal,  and shake to
         dissolve  salt.

 11.1.3   Add 17 ml of 6  N  NaOH to  the sample,  seal,  and  shake.
         Check  the pH of the  sample with pH paper;  if the  sample
         does  not  have  a pH greater than or equal  to 12,  adjust
         the pH by adding  more 6  N NaOH.   Shake  sample  for 1  hour
         using  the appropriate mechanical  mixing device.

 11.1.4  .Add 300 ml  methylene chloride  to  the sample bottle to
         rinse the bottle, transfer the methylene chloride to the
         separatory  funnel or tumbler  bottle, seal, and shake for
         10 s, venting periodically.   Repeat shaking and venting
         until pressure release is not observed during venting.
         Reseal and place  sample container in appropriate
         mechanical  mixing device.  Shake or  tumble  the sample
         for 1 hour.  Complete and thorough mixing  of the  organic
         and aqueous phases  should be observed  at  least 2  min
         after starting the mixing device.

  11.1.5 Remove  the  sample container from the mixing device.  If
          the  tumbler is used, pour contents  of  tumbler  bottle
          into a  2-L  separatory  funnel. • Allow the organic layer
          to separate from the water phase for a minimum of 10
          min.   If the emulsion  interface  between layers is more
          than one third the volume of the solvent layer,  the
          analyst must employ mechanical  techniques to complete
          the phase  separation.   The optimum technique depends
          upon the sample, but may include stirring, filtration
          through glass wool, centrifugation, or other physical
          methods.  Drain  and discard  the organic phase.   If the
          tumbler is used, return the  aqueous phase  to  the tumbler
          bottle.

   11.1.6 Add  17 ml  of  12 N ^504 to the  sample,  seal,  and shake
          to mix.  Check  the pH of the sample with  pH paper; if
          the  sample does not have a pH less  than or equal to 2,
          adjust  the pH by adding more 12 N  ^$04..

   11.1.-7 Add  300 ml ethyl ether to the sample, seal,  and shake
           for 10 s,  venting periodically.  Repeat shaking and
           venting until pressure release  is  not observed during

                               18

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            venting.   Reseal  and place sample  container  in  approp-
            riate mechanical  mixing device.  Shake  or  tumble  sample
            for 1 hour.  Complete and thorough mixing  of  the  organic
            and aqueous phases should be observed  at  least  2  mm
            after starting the mixing device.

     11.1.8  Remove the sample container from the mixing  device.  If
            the tumbler is used, pour contents of tumbler bottle
            into  a-2-L separatory  funnel.  Allow the organic layer
            ;•„  -.:, .-.:'.. from the water  phase for a minimum of  10
            min.   If  the  emulsion  interface between layers is  more
            than  one  third  the  volume of  the  solvent layer,  the
            analyst must  employ mechanical techniques to complete
            the phase separation.   The  optimum technique depends
            upon the  sample, but may include  stirring, filtration
             through glass wool, centrifugation, or other physical
            methods.   Drain and discard the aqueous phase.   Collect
             the extract in a 500-ml round-bottom  flask  containing
             about 10  g of acidified anhydrous sodium  sulfate.
             Periodically vigorously  shake the sample  and drying
             agent.  Allow the extract  to remain in contact with the
             sodium sulfate  for approximately  2 hours.

      11.1.9  Determine the original  sample volume by refilling the
             sample bottle to the  mark  and transferring the water  to
             a  1000-mL graduated  cylinder.  Record the sample  volume
             to  the nearest  5 mL.

11.2  MANUAL HYDROLYSIS, CLEANUP,  AND EXTRACTION METHOD  -- Alternative
      procedure.

      11.2.1   Add preservative to any samples  not  previously  preserved
              (Section 8.2).   Mark the water meniscus  on  the  side  of
              the sample bottle for later determination  of  sample
              volume.   Pour the entire  sample  into a  2-L separatory
              funnel.   Spike  sample with 50 uL of  the  surrogate
              standard spiking solution.

      11.2.2  Add 250 g NaCl  to the  sample, seal,  and shake to
              dissolve salt.

      11.2.3  Add 17 mL of 6 N  NaOH  to  the sample, seal, and shake.
              Check the pH of the  sample  with  pH paper;  if the sample
              does not have  a pH  greater  than  or equal to 12,  adjust
              the pH  by adding  more  6 N NaOH.   Let the sample  sit  at
              room temperature  for 1 hour, shaking the  separatory
              funnel  and  contents periodically.

       11.2.4  Add 60  mL methylene chloride to the sample bottle to
              rinse the bottle, transfer the  methylene  chloride to the
               separatory  funnel and extract the sample-by vigorously
               shaking the funnel  for 2 min with periodic venting to
               release excess pressure.  Allow the organic layer to
               separate from the water  phase for a minimum of  10 min.

                                    19

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           If  the emulsion  interface  between  layers  is more  than
           one third  the  volume of  the  solvent  layer,  the  analyst
           must employ mechanical techniques  to complete  the  phase
           separation.  The optimum technique depends  upon the
           sample,  but may  include  stirring,  filtration  through
           glass wool, centrifugation,  cr other physical  methocs.
           Discard  the methylene  chloride phase.

   11.2.5  Add a second  60-mL volume of methylene chlori-^ 1.c  : .
           .c.«v^ uOtllc  ^ad iepcat the extraction procedure o
           second time,  discarding  the methylene chloride layer.
           Perform a third extraction  in the same manner.
    11.2.6  Add 17 mL of 12 N ^50$ to the  sample, seal, and «_: '•••••
           to mix.  Check the pH of the  sample with pH paper;  iv
           the sample does not have a pH less than or equal to 2,
           adjust the pH by adding more  12 N
    11.2.7  Add  120 mL ethyl ether  to  the  sample,  seal,  and  extract
            the  sample by  vigorously  shaking the  funnel  for  2  min
            with periodic  venting to  release excess  pressure.   Allow
            the  organic  layer  to  separate  from the water phase for a
            minimum of  10  min.   If  the emulsion interface between
            layers  is more than one third the volume of the  solvent
            layer,  the  analyst must employ mechanical techniques to
            complete  the phase separation.  The optimum technique
            depends  upon the sample,  but tr,ay include stirring,
            filtration  through glass wool,  centrifugation, or other
            physical  methods.   Remove the aqueous phase to a  2-L
            Erlenmeyer flask and collect the ethyl ether phase  in a
            500-mL round-bottom flask containing  approximately  10 c
            of  acidified  anhydrous sodium  sulfate.

     11.2.8 Return the  aqueous phase  to  the separatory funnel,  add  a
            60-mL volume  of ethyl  ether  to the sample,  and  repeat
            the extraction  procedure a  second time,  conbining the
            extracts in the 500-mL erlenmeyer flask.  Perform a
            third extraction  with  60 mL of ethyl  ether in the same
            manner.  Periodically  vigorously shake  the sample and
            drying agent.  Allow the extract to remain in contact
            with the sodium sulfate for approximately 2 hours.

     11.2.9  Determine  the original sample  volume by refilling  the
             sample  bottle to the mark and  transferring the water to
             a  1000-mL  graduated cylinder.  Record the  sample volume
             to the nearest 5 mL.

11.3  EXTRACT CONCENTRATION

     11.3.1  Assemble a K-0 concentrator  by attaching  a concentrator
             tube to a  500-mL  evaporative flask.

     11.3.2 Pour the dried extract  thrpugh a funnel plugged with
             acid washed  glass wool,  and collect the extract in the

                                  20


                                 2.7

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           K-D in concentrator.   Use  a  glass rod to crush any caked
           sodium sulfate during  the  transfer.   Rinse the round-
           bottom flask and funnel  with 20 to 30 mL of ethyl ether
           to complete the quantitative transfer.

    11.3.3  Add 1 to 2 clean boiling stones to the evaporative flask
           and attach a macro Snyder column.  Prewet  the Snyder
           column by adding about 1 mL ethyl ether  to the  top.
           . Uce the K-0 apparatus on a hot water bath,  60  to 65*C,
           so  that  the concentrator tube  is partially immersed  in
           the hot  water,  and the entire  lower  rounded  surface  of
            the flask  is  bathed with hot vapor.   At  the  proper  rate
            of distillation the balls of the column  will  actively
            chatter  but the chambers will  not  flood.  When  the
            apparent volume of liquid reaches  1  mL,  remove  the  K-0
            apparatus  and allow  it  to drain and  cool for at least 10
            min.

     11.3.4  Remove the Snyder column  and rinse the  flask and its
            lower joint into the concentrator tube with  1 to 2 mL of
            ethyl ether.   Add 2  mL of MTBE and a fresh boiling
            stone.  Attach a micro-Snyder column to the  concentrator
            tube and prewet the  column by adding about 0.5  mL of
            ethyl ether to the top.  Place  the micro  K-0 apparatus
            on the water bath so that the concentrator tube is
             partially immersed in the hot water.  Adjust the
             vertical position of the apparatus  and  the water
             temperature  as  required to complete  concentration  in 5
             to 10-min.  When the apparent  volume of liquid reaches
             O.S  mL, remove  the micro K-0  from the  bath and allow it
             to drain  and cool.   Remove  the micro Snyder column and
             add,250 uL of  methanol.   If the gaseous diazomethane
             procedure  (Section  11.4)  is used  for esterification of
             pesticides,  rinse the  walls of the  concentrator tube
             while adjusting the  volume to 5.0 mL with MTBE.  If the
             pesticides will  be  esterified using the diazomethane
             solution (Section 11.5),  rinse the walls of the concen-
             trator tube  while adjusting the volume to 4.5  mL with
             MTBE.

11.4  ESTERIFICATION OF ACIDS USING GASEOUS OIA20METHANE  --  Validation
      results presented in this method were generated  using  the
      gaseous diazomethane derivatization procedure.

      11.4.1  Assemble the diazomethane generator (Figure 1) in a
              hood.

      11.4.2   Add 5  mL of ethyl ether to Tube  1.   Add 1 mL of ethyl
              ether,  1 ml of carbitol,  1.5 ml of 37% aqueous KOH, and
              0.2 grams Oiazald  to  Tube 2.  Immediately place the exit
              tube into the concentrator tube containing the sample
              extract.  Apply nitrogen  flow (10 ml/rain)  to  bubble
              diazomethane  through the  extract for  1 min.   Remove
              first sample.  Rinse the  tip of the diaromethane

                                  21

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            generator with ethyl ether after methylation of each
            sample.  Bubble diazomethane through the second sample
            extract for 1 min.  Diazomethane reaction mixture  should
            be used to esterify only two samples; prepare new
            reaction mixture  in Tube 2 to esterify each  two addi-
            tional  samples.   Samples should turn yellow  after
            addition of diazomethane and remain yellow for  at  least
            7  rain..  Repeat methylation procedure if  necessary,.
                                             »--
     11.4.3 Seal  concentrator tubes with stoppers.   Store  at  room
                     ure  in  ?.  hood  for 30 min.
     !..-.-  ..."  • any unreacted  diazomethane  by adding 0.1 -to
             «..;. ^.iins silicic acid to  the  concentrator tubes.  Allow
             to stand until the evolution of  nitrogen gas has stopped
             (approximately 20 min).  Adjust  the sample volume to
             5.0 ml with HTBE.

11.5  ESTERIFICATION OF ACIDS USING DIAZOMETHANE SOLUTION  --  Alterna-
     tive  procedure.

      11.5.1  Assemble  the  diazomethane generator  (Figure  2)  in  a
             hood.   The  collection  vessel  is a  10- or  15-ml  vial,
             equipped  with a  Teflon-lined  screw cap  and  maintained at
             0-5'C.

      11.5.2 Add a sufficient amount of ethyl ether  to tube  1 to
              cover the first  impinger.  Add  5 mL  of  HTBE to  the
              collection vial.  Set the nitrogen flow at 5-10 mL/min.
              Add 2 ml Diazald solution  (Section 7.9) and 1.5 ml of
              37% KOH solution to the  second  impinger.   Connect the
              tubing as shown and allow the nitrogen flow to purge the
              diazomethane from the reaction  vessel  into  the collec-
              tion vial for 30 min.  Cap  the  vial when collection  is
              complete and maintain at 0-5'C.  When  stored at 0-5*C
              this diazomethane solution may be used over a  period of
              48 h.

       11.5.3  To each  concentrator  tube containing sample or standard,
              add  0.5  ml diazomethane solution.   Samples  should turn
              yellow after addition of the diazomethane  solution and
              remain yellow for at  least 2 min.   Repeat  methylation
              procedure  if necessary.

       11.5.4  Seal  concentrator  tubes with stoppers.  Store  at room
               temperature  in  a hood for 30 min.

       11.5.5   Destroy any  unreacted diazomethane by adding 0.1 to
               0.2 grams silicic acid  to  the  concentrator tubes.  Allow
               to stand until  the evolution of  nitrogen gas has stopped
               (approximately 20 min).  Adjust  the sample volume to
               S.O ml with HTBE.
                                   22

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11.6  FLOR1SIL CLEANUP

      11.6.1  Place a small  plug of glass wool  into a 5-ml  disposable
              glass pipet.  Tare the pipe!,  and measure  1 g of
              activated Florisil into the pipet.

      11.6.2  Apply 5 ml of 5 percent methanol  in  HTBE  to  the
              Florisil.  Allow the liquid to just  reach the top of the
              Florisil.   In this and subsequent steps,  allow the
              liquid  level to just reach the top^of the Florisil
              before  applying the  next rinse, however,  do not allow
              the  Florisil to go dry.  Discard eluate.

       11.6.3  Apply  5 ml  methylated  sample to the Florisil leaving
               silicic acid  in the  tube.  Collect eluate in K-D  tube.

       11.6.4   Add  1  ml of 5  percent  methanol in HTBE to the  sample
               container,  rinsing  walls.   Transfer the rinse  to  the
               Florisil column  leaving  silicic acid in the  tube.
               Collect eluate in a K-D  tube.  Repeat with  1-ml and 3-ml
               aliquots of 5 percent methanol  in MTBE,  collecting
               eluates in K-0 tube.

       11.6.5  If necessary, dilute eluate to 10 mL with 5 percent
               methanol in HTBE.   Spike with 25 ul of  internal standard
               solution.  Thoroughly mix sample and place aliquot in a
               GC vial for subsequent analysis.

       11.6.6  Seal  the vial and  store in a refrigerator if  further
               processing will  not be performed immediately.  Analyze
               by  GC-ECD.

  11.7 GAS  CHROHATOGRAPHY

        11.7.1  Table 3 summarizes the  recommended operating  conditions
                for the GC.   Included in  Table  3 are retention times
                observed using this method.   Examples of the separations
                achieved using these conditions  are  shown in Figures £
                and 5.  Other GC columns, chromatographic conditions, or
                detectors may be used if the requirements of Section
                10.3  ere met.

        11.7.2  Calibrate the system daily as described in Section 9.
                The  standards and  extracts must be in MTBE.

        11.7.3  Inject 2  uL  of  the sample extract.  Record the  resulting
                peak size in area units.

        11.7.4  The  width of the  retention  time window  used  to  make
                identifications should be based upon measurements of
                actual retention  time  variations  of standards over the
              -  course of a day.   Three  times  the  standard deviation of
                a  retention time can be  used to calculate a. suggested
                window size for a compound.  However,  the experience of

                                     23

-------
                  the analyst should weigh  heavily in the interpretation
                  of chromatograms.

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

12.   CALCULATIONS

     12.1   Calculate analyte concentrations in the  sample  from the relative
           response  for  the analyte to  the internal  standard (RRa) using
           the equation  for the  calibration curve described in Section
           9.2.2.

     12.2  For samples  processed as part of a set where  the laboratory
           control standard recovery falls  outside of the control  limits in
           Section 10,  results for the affected analytes must  be  labeled as
           suspect.

 12.  PRECISION AND ACCURACY

     13.1  In  a single  laboratory,  analyte recoveries from reagent water
           were determined at five concentration  levels.  Results were used
           to  determine analyte  EDLs and demonstrate method range.  In
           cases  where  analytes  coeluted using  primary  analytical condi-
           tions, results from  confirmatory GC  conditions were used.   EDI
           results  are  given in Table  2.  Method range  results are given  in
           Tables 4-7.

      13.2  In a single  laboratory, analyte recoveries  from two artificial
            ground waters were determined  at  one concentration level .
            Results were used to demonstrate  applicability of  the method to
            different ground water matrices.  Analyte recoveries  from the
            two artificial matrices are  given in Tables 8 and  9.

      13.3  In a  single laboratory, analyte recoveries from a ground water
            preserved with mercuric chloride were determined 0,  14, and 28
            days  after  sample preparation.  Analyte recoveries were also
            determined  from sample extracts stored  at 4*C for 14  and 28
            days.   Results were  used to predict expected  analyte  stability
            in ground water samples and sample  extracts.  Analyte recoveries
            from  the preserved,  spiked ground water samples and  stored
            sample  extracts are given  in Table 11.
                                          24


                                          3\

-------
REFERENCES
    "Pesticide  Methods Evaluation," Letter Report £33 for EPA Contract NO.
    68-03-2697.  Available from U.S. Environmental Protection Agency,
    Environmental Monitoring and Support Laboratory, Cincinnati, Ohio
    '5268.

    "T".  .'-u-: P-;'-. ,• f :ttcrieri:,  Pert, n, Volume  n.02, 03694-82,
    ••• •-r.-iTr,J  ;-,-ri irr ^or Pren?.r?t ion cf Sample  Containers  ?n
-------
               TABLE 1.   METHOD ANALYTES
Analyte
CAS Ho.
U)
Ident.
Code (b)
  . t.i.0;.
U. lC.lt;..-....
2,4-D
Dal apon
2,4-OB
DCPA acid metabolites (c)
Dicamba
3,5-Dichlorobenzoic acid
Dichlorprop
Dinoseb
5-Hydroxyd i carcca
4-Nitrophenol
PC?
Picloran
2,4,5-T
2,4.5-7?
(a) CAS No. - Chenucal Abs
(b) Code used for Identi
I-i-j-bO-^
94-75-7
75-99-0
94-82-6
--
1918-00-9
51-36-5
120-36-5
88-85-7
7600-50-2
100-02-7
87-86-5
1918-02-1
93-76-5
93-72-1
tracts Service -Reg is try
fication of peaks in
9
' 6
1
12
16
4
2
5
13
10
3
7
15
11
8
Number.
figures;
                                                             IS
    4,<'-d1brorr,ooctafluorobiphenyl   internal   standard;   SUR
    2,4-dichloropheoylacetic  acid  surrogate  standard.
(c)  DCPA monoacid  and  diacid  metabolites  included 1n method
    scope; DC?A  diacid metabolite  used  for validation
    studies.
                                    26

-------
TABLE 2.  RECOVERY OF ANALY'ES FROM REAGENT WATER (SPIKING LEVEL 1) AND  EDLs  (a)


Analyte
Spiking
Level ,
yg/L
Arr.t i n
Blank,
pg/L n(b) R(c) S(d) RSD(e) EDL(
-------
  TABLE:  3.   PRIMARY AND CONFIRMATION  CHROKATOGRAPHIC  CONDITIONS
                           Relative Retention Time for Given Conditions
                           Priri?r
                                                  Confirmation (b)(c!)


-.ViK W«.4.U1>
Chloramben
2,4-D
Oalapon
2,4-DB
DCPA acid metabolites (c)
Dicamba
3,5-Oichlorobenzoic acid
Dichlorprop
Oinoseb
5-Hydroxydicamba
4-Nitrophenol
PCP
Picloran
2,4.5-T
2,4,5-TP
Surrogate
(a) Retention time relative
approximately 27.5 rnin.
(b) Retention time relative
approximately 27.6 min.
(c) Primary conditions:
i ri


l.Ofa
0.927
0.126
1.17
1.30
0.815
0.662
0.923
1.17
1.09
0.667
1.03
1.25
1.10
1.07
0.799
to OS03 internal

to DBOS internal

«
1C T
.53
1.27
1.19
1.02
0.171
1.19
1.37
0.876
0.705
0.971
1.25
1.14
0.805
1.02
1.36
1.15
1.10
0.540
standard which elutes «t

standard which elutes at


       Column:   30 ra  long  x 0.25 isn I.D.  08-5  bonded  fused  silica
                column,
                0.25  ten film thickness (JiW)
                2 uL splitless with 45 second  delay
                He 630 on/sec linear velocity
                250-C
                320 "C
                Program from 60*C to 300'C at  4*C/min
                ECO
Confirmation conditions:
       Column:  30 m long x 0.25 ntn  I.D. 08-1701 bonded fused  silica
                column, 0.25  um film thickness (JiW)
                2  uL splitless  with  45 second delay
                He S30 cm/sec  linear velocity
                250*C
                320-C
                 Program from 60'C  to 300'C at 4'C/rain
                 ECO
Injection volume:
     Carrier 'gas:
   Injector temp
   Detector temp
       Oven temp
        Detector
 Injection  volume:
      Carrier gas:
    Injector temp:
    Detector temp:
        Oven temp:
         Detector:

-------
TABLE 4.   RECOVERY  Of  ANALYTES FROM REAGENT WATER (SPIKING LEVEL ?)  U)
Spiking Amt in
Level, Blank,
Analyte ug/L ug/L n(b)
Acifluorfen 0.040 N0(f) 7
Bentazon 0.20 NO 7
Chlorair-bcr, ( , 0.080 NO 7
2,4-0 " 0.20 NO 7
Dalapon " 2.0 NO 6
2,4-OB (g) 0.80 NO 7
DCPA di acid metabolite 0.040 NO 7
Oicamba 0.080 • NO - 7
3,5-Dichlorobenzoic acid 0.12 NO 7
Dichlorprop O.<0 NO 7
Dinoseb (g) 0.080 NO 7
5-Hydroxydicamba 0.040 NO 7
4-Nitrophenol 0.20 NO 7
PCP (h) 0.0080 NO
Picloram 0.12 NO 7
2,4,5-T 0.080 NO 7
2,4,S-7P (g) . - 0.040 NO 7
U) Data corrected for amount detected in blank.
(b) n • number of recovery data points.
(c) R • average percent recovery.
(d) S - standard deviation.
(e) RSD - percent relative standard deviation.
(f) NO - interference not detected in blank.
(c) Results from confirmatory analysis conditions
(h) Analyte not detected at this spiking level.


R(c)
88
92
118
90
107
37 '
89
155
85
no
118
49
148
-
166
87
140






.



S(d)
0.00826
0.03A6
0.0310
0.0248
0.457
0.229
0.0318
0.0269
0.0117
0.0689
0.0623
0.00547
0.0450
-
0.0468
0.0144
0.0249










RSO(e)
23
19
33
14
21
78
89
22
11
16
66
28
15
-
24
21
44








                                       29

-------
TABLE 5.   RECOVERY  Or  AMALYTES FP.OK REAGENT WATER (SPIKING  LEVEL  3)  (c)
Spiking Amt in
LeveK Blank,
Analyte ug/L ug/L n(b) R(c)
Acifluorfen 0.20
Bentazon 1.0
Chloic... --) 0.40
2,4-0 1.0
Oalapon 10
2,4-08 (a) 4.0
DCPA diacid metabolite 0.20
Dicamba 0.40
3,5-Dichlorobenzoic acid 0.60
Dichlorprop 2.0
Oinoseb (g) 0.40
5-Kydroxvoicamba 0.20
4-Nitrophenol 1.0
PCP 0.040 x
Picloram 0.60 0.
2,4,5-T 0.40
2,4,5-TP (g) 0.20
(a) Data corrected for amount detected
(b) n - number of recovery data points
(c) R - average percen.t recovery.
(d) S - standard deviation.
N0(f)
'HO
NO
HO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
,308
NO
NO
in bl
•


*-
6
4
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
ank.



121
120
111
131
100
87
74
135
102
107
42
103
131
130
91
117
134




- S(d) RSD(e)
0.0318
0.163
0.0615
0.274
2.24
0.518
0.0200
0.129
0.098
0.418
0.0971
0.0325
0.234
0.0242
0.149
0.0639
0.0631




13
14
13
21
20
15
13
24
16
19
34
16
18
47
17
14
23




(e) RSO - percent relative standard deviation.
(f) HO - interference not detected in
(c) Results from confirmatory analysis
blank.
condi

tions.






                                       30





                                       37.

-------
TABLE 6.   RECOVERY OF AHALYTES  FROM  REAGENT WATER  (SPIKING  LEVEL 4) (a)
Spiking Ant in
LeveK Blank,
Analyte ug/L ug/L n(b) R(c)
Acifluorfen 0.50
Bentazon 2.5
Chloramnen (Q) 1.0
2,4-0 '" 2.5
Dalapon 25 1
2,4-DB (g) 10
DCPA dlacid metabolite 0.50
Dicamba 1.0
3,5-Dichlorobenzoic acid 1.5
Dichlorprop 5.0
Oinoseb (g) 1.0
5-Hydroxydicamba 0.50
4-Nitrophenol 2.5
PC? 0.10
Picloram 1.5
2,4,5-T 1.0
2,4,5-TP (g) 0.50
(a) Data corrected for amount detected
(b) n - number of recovery data points
(c) R • average percent recovery.
(d) S - standard deviation.
H0(f)
NO
NO
NO
.33
NO
NO
HO
NO
NO
NO
NO
NO
NO
NO
NO
NO
6
6
6
6
6
6
6
6
6
6
5
6
6
6
6
6
6
89
90
89
94
82
55
50
87
101
90
31
85
93
82
82
90
90
S(d) RSO(e)
0.0525
0.500
0.137
0.307
2.69
0.657
0.0652
0.0683
0.139
0.525
0.123
0.0567
0.267
0.00950
0.200
0.0948
0.0587
12
22
15
13
12
12
26
8
9
12
40
13
11
9
16
10
13
in blank.
•














(e) RSO - percent relative standard deviation.
(f) NO - interference not detected in
(g) Results frora confirmatory analysis
blank.
condi

tions.






                                       31

-------
TABLE 7.  RECOVERY Of AHALYTES FROM REAGENT WATER  (SPIKING  LEVEL  5)  (a)
Analyte
Spiking   Ant in
 Level,   Blank,
   ug/L     ug/L   n(b)   R(c)
S(d)  RSD(e)
Acifluorfen 2.0 N0(f)
Bentazon 10 NO.
Chloramben (g) 4.0 NO
2,4-0 10 NO
Dalapon 100 NO
2,4-08 (a) <0 NO
OCPA diacid metabolite 2.0 NO
Oicamba 4.0 NO
3,5-Dichlorobenzoic acid 6.0 NO
Oichlorprop 20 NO
Dinoseb (a) 4.0 NO
S-Hydroxydicamba 2.0 NO
4-Nitrophenol 10 NO
PCP 0.40 NO
Picloram 6.0 NO
2,4,5-7 4.0 NO
2,4,S-7P (a) 2.0 NO
*-
6
6
6
6
6
6
6
6
6
6
6
6
6
6
5
6
6
90
80
55
74
81
59
23
79
88
78
74
67
73
73
73
77
84
0.0676
1.02
0.0888
0.481
4.28
1.30
0.-338
0.126
0.340
0.623
0.267
0.170
0.387
0.0208
0.518
0.181
0.0861
4
13
4
6
5
5
74
4
6
4
Q
13
5
6
12
6
-
(a) Data corrected for amount detected in blank.
(b) n • number of recovery data points.
(c) R - average percent recovery.
(d) S - standard deviation.
(e) RSO - percent relative standard deviation.
(f) NO • interference not detected in blank.




















(g) Results from confirmatory analysis conditions.
                                         32

-------
  TABLE  8.   RECOVERY OF  AHALYTES  FROM HARD ARTIFICIAL GROUND WATER
            (SPIKING LEVEL 3)  (a)
Analyte
« .L t i 1 Uci i C «•
Bentazon
Chloraraben (g)
2,4-0
Dalapon
2,4-DB (g)
DCPA dUcid metabolite
Dicaraba
3,5-Dichlorobenzoic acid
Oichlorprop
Dinoseb (g)
5-HydroxydiCcmba
4-Nitrophenol
PCP
Picloram
2,4,5-T
2,4,5-TP (g)
Spiking Amt in
Level, Blank,
ug/L ug/L n(b)
»--
0.20
1.0
0.40
1.0
10
4.0
0.20
0.40
0.60
2.0
0.40
0.20
1.0
0.040
0.60
0.40
0.20
..HD(f)
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
5
5
7
5
5
7
5
6
6
5
5
2
7
7
c
5
6
R(c)
103
82
112
no
128
(h)
81
92
82
106
89
88
127
84
97
96
105
S(d) RSD(e)
0.040
0.378
0.043
0.051
3.027
-
0.048
0.068
0.049
0.099
0.054
0.012
0.374
0.006
0.139
0.017
0.014
20
46
O
5
24
-
27
19
Q
^
15
5
27
11
24
4
6
(a)   Data corrected  for amount detected in blank; hard  artificial  ground water
     used to  generate  these  results was Absopure Natural  Artesian spring v«ier
     obtained from the Absopure Water Company  in Plymouth,  Michigan.
(b)   n -  number of recovery  data points.
(c)   R -  average percent  recovery.
(d)   S -  standard deviation.
(e)   RSO  •  percent relative  standard deviation.
(f)   HO - interference not detected  in  blank.
(g)   Results  from confirmatory analysis conditions.
(h)   Analyte  not recovered from hard  artificial  ground water.
                                       33

-------
 TABLE 9.  RECOVERY OF ANALYTES FROM ORGANIC-CONTAMINATED  ARTIFICIAL
          GROUND WATER  (SPIKING LEVEL 3)  (a)
Spiking

• ••"• • j - -
Acifluorfen
Bentaion
Chloranben (gj
2,4-0
Dalapon
2,4-DB (g)
OCPA diacid metabolite
Oicamba
3,5-Dichlorobenioic acid
Dichlorprop
Dinoseb (g)
5-Hydroxydicamba
4-Nitrophenol
PCP
Picloram
2,4,5-7
2,4,5-TP (g)
Level ,
ug/L
0.20
1.0
0.40
1.0
10
4.0
0.20
0.40
0.60
2.0
0.40
0.20
1.0
0.040
0.60
0.40
0.20
Air.t in
Blank,
ug/L
..H0(f)
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
0.197
NO
NO


n(b)
7
7
7
7
7
7
7
7
7
7
5
7
7
5
7
7
c
(a) Data corrected for amount detected in bl
artificial ground water
spiked with humic' acid
used to
at the
generate
these
1 mg/L concent


RU)
110
111
104
112
109
79
78
107
96
106
71
102
118
133
86
108
108


S(d)
0.024
0.089
0.049
0.093
1.140
0.583
0.018
0.026
0.029
0.105
0.035
0.013
0.102
0.004
0.044
0.027


RSO(e)
11
8
12
8
11
19
11
5
5
5
13
5
c
5
£
6



















0.028 13
ank; organic-contaninated
result
ration
s was reagent water
level .
Humic
acid
     (sodiun salt) obtained  fros  Aldrich  (HI,675-2)  wes  used.
(b)   n - number of recovery  data  points.
(c)   R - average percent  recovery.  '
(d)   S • standard deviation.
(e)   RSD - percent relative  standard  deviation.
(f)   HO •  interference not detected in blank.
(g)   Results from confirmatory analysis conditions.
                                       34

-------
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-------
Nitrogen
      Tube 1
     FIGURE 1.  GASEOUS DIAZOnETHAtlE GENERATOR
                              a?

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-------
                                               Appendix C
                                               Revision No 4
                                               Date  December 1989
                                               Page 1 of 6
              APPENDIX C
DIAZOMETHANE PREPARATION AND SAFETY

-------
ppendix:   SAFETY;
               All chemical compounds used  in  this  method  should be treated as
          potential hazards unless known  to be otherwise.  Analysts should become
          familiar with  all the safety  information  provided here before attempting
          the analysis.  Material Safety  Data  Sheets  and gather pertinent information
          have been supplied  for the more hazardous substances used in this method
          (diazomethane, mercuric chloride, benzene,  and  ether). The individual labo-
          ratories are responsible for  maintaining  a  file of  Material Safety Data
          Sheets on all  hazardous substances in use by that  laboratory.  All personnel
          should be made aware of the existence of  the file  and  it should be readily
          available to  them.
          Precautions to be followed when handling or preparing diazomethane.

               1.  Use an efficient high draft hood - do not breath fumes.

               2.  Avoid use of ground-glass joints or any glassware which is
                   chipped, cracked or has not beer, carefully firepolished.  Failure
                   to do so may result in an EXPLOSION. The DIA2ALD kit supplies such
                   glassware.

               3.  Use a sturdy explosion proof  safety shield.

               4.  Use disposable PVC gloves.


           Preparation of diazomethane (alcohol  - free  ethereal solutions)

               Add 2-(2-Ethoxyethoxy)-ethanol  (35 ml)  and ether  (20 ml) to a
           solution of potassium hydroxide (6 g) in water  (10  ml).  This solution
           is  placed  in  a 500 ml round bottom distilling  flask fitted with  dropping
           funnel and efficient condenser in a water bath  at 65*C.  As the distil-
           lation of  the ether starts* a solution of 21.5 g of Diazald  in about
           200 ml of  ether  is added  through the dropping  funnel over  20 min.   During
           the distillation,  the solution is mixed continuously by  a small  magnetic
           stir bar.   The rate of  distillation should approximately equal  the  rate of
           addition.   When  the dropping  funnel is empty,  another 40 ml  of  ether is
           added slowly  and the distillation is continued until the distilling ether
           is colorless. The combined ethereal distillate contains about  3 g  of
           diazomethane. A diagram of the diazomethane apparatus has been provided.

                Before attempting  this procedure read all safety information  con-
           cerning diazomethane preparation.
                Diazomethane solution should remain tightly capped, and may be stored
           at 0*-5*C for a period of up to 6 months.  The intensity of the yellow
           color is an indicator of the strength of the diazomethane / ether solution.

-------
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    lo 1894, von Peehman esublished the
  ctruoureCHtNi for the ydlow gas liberated
  from nitrosomethylurcthane upon treat-
  meat with alkali.' During the subsequent 90
  yean, diazomethanc (less commonly re-
  ferred to as azimcthylenc or diaiiranc) has
  proven to be one of the most valuable and
  versatile reagents available to the synthetic
  chemist. It is easily the most common mcth-
  jlating reagent for carboxyiic acids, and has
 S'oUnfl wide* application in the methyUUon
  of phenols, elcohols. cnols, and hetero-
  atoms such as nitrogen and sulfur. Diazo-
  methane effects the ring expansion (or chain
  homologation) of ketones or. under suitable
  conditions, forms cpoxides from the same
  ketones in the manner of sulfur ylids. Acid
  chlorides are converted to or-diazokctones
  which are valuable synthetic intermediates
  in their own right. In addition. CHiNt acts
  as a powerful dipole in many cydoaddition'
  reactions with unsaturated systems, and of-
  ten the resulting nitrogen-containing hcterc-
  cydic ring can be decomposed (either ther-
  mally or pnotochcmically) to afford cyclo-
  propane (or other) derivatives. Each of (he
  above rcaoJon categories will be treated sep-
  arately in the REACTIONS section.

             STRUCTURE
     The structure of diazomethane can be
  represented by the valence uutomcrs 1
  through S (Scheme I). Although the true
  eketrank distribution over the the molecule
  can be represented as a weighted sura of Ihe
  five structures shown, the majority of di-
 of the isomers of diazomethane were calcul-
 ated.'
   A gas at room temperature, diazometh-
 ane liquifies at -23 «C (density MS) and
 freezes at -1X5 "C. It can be protonatcd in
 fluorosulfonic acid at very low tempera-
 tures' and possesses an ionization potential
 of 9.03cV.-
   The most recent comprehensive-review of  ,
.•diazomethane- chemistry  appearccT.fiin'c
 yean ago:1 the reader is directed to this work
 for references to earlier reviews. Recently,
 two reviews concerning diazoalkanes have
 appeared; one involves organomctallic syn-
 thesis4 and the other the synthesis of "un-
 usual organic molecules".1
   SAFETY CONSIDERATIONS
    Although quite safe when handled as a
 dilute solution in an inert solvent, diazo-
  methane presents several safety hazards of
  which all users of the reagent should be
  aware. It is both extremely toxic* and highly
  irritating.' causing pulmonary edema when
  inhaled in high concentrations. Long-term.
  tow-tod exposure may lead to sensnization,
  resulting in asthma-like symptoms.'* Also.
  diazomethane and Kveral of its chemical
  precursors have been died as carcinogens."
     Diazomethane has been known to ex-
  plode quite unaccountably, both as a gas
  and a liquid, although rough surfaces are
  proven initiators of detonations." Thus.
  ground-class joints and any glassware which
  have not been carefully firepoUshed must
       roe allowed to come in contact with di-
                                                                                                       T. Ki
                                                                                        Aldrich Chemical Cospatty, «n<
 azomethane or its solutions. In bdditioi
 contact with alkali metals or drying agen
 such as calcium sulfatc can result in an e:
 plosion. If moisture must be removed fro
 a solution containing diazomcthane, the re
 ommcnded drying agent is potassium h
 droxide pellets. Finally, solutions should n
 be exposed to strong light, which has be
 reported" to initiate detonations.
,'".  Fortunately. if the reagent is generated i
 ing the proper equipment and is handled c
 ly as a dilute solution ai low temperature (<
 0*O, the risks cited above are minimize
 Of course, *ll reactions  involving dia.
 methane should be carried out in an ef fid
 fume hood and  behind  a sturdy  uf
 chidd. Finally, it is recommended that sc
 lions of diazomethane be used immedii
 ly and not stored, even at low icmperatv
            PREPARATION
    By far, the most common and convcn
  method for generating diazomcthane i:
  the  base-catalyzed decomposition of
  mcthyl-N-nitroso  amines of the gen
  structure 6. where R represents a sulfo
  carbonyl. or similar electron -withdraw
  group. The mechanism  of diazomett
  generation is outlined in Scheme II. For i
  ity.  a specific chemical presunor is
  ployed: A/-methyl-/V-nitrc-A/-nitn>»oj
  idine (MNNG. 7). In the first step, t- <
   aiomethane reactions are best conceptual-
   (zed and explained by structure 1. Recently
   the Urtalekoroi&cncrxics and energies of
   Isooerization for the optimized geometries
•1983 by Aldrich ChcBk
                                                   *«fa» Aaa.  yet. 16. Ho. 1.

-------
  PO Bai 355 (U./wi


SAhcfr jiK

    I AL  U-t
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         A  i
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                        Mb  3'v


                       K  l A L
                                 SAFETY    DATA

                                   COST  «  <^CO4« MLOU: -

     WAIEK  SPKAY.
     CARBJN OiOAiUC. DRY  CHEMICAL  PGWOER,  ALCOHCL OR POLYMER FOAM.

     SPECIAL FlkE FlbHTING  PROCEDURES:

     HEAR  iELF-CUNIAlNED  BREATHING  APPARAlUS AND PROTtCTIVE CLOTHING  10
     PREVENT CUNTAcT WITH SKIN AND  tYES.

     ONUSOAL FlKt Mi«J  EXPLOSION HAZARDS:

     EMlTi lOXlc hOMfeS UNOEK FIRE  CCNUITICNS.
                           SECTION V    HEALTH HAZARD DATA

      MAY bE HAKMI-UL  dY  INHALATION.  INGEST ION* OR SKIN  ABSORPTION.
      CAUSED SfcVEKc  IRRITATION.
      MAY CAJSL ALLtKolC  SKIN REACTION.
      TU Tht o£SI U  uUR  KNOWLEDGE.  THE  CHEMICAL, PHYSICAL. AND
      TOXICULuGICAL  PROPERTIES HAVE  NOT  BEEN THOROUGHLY INVESTIGATED.
      FIRST AIU:
      IN CAiE Of CONTACT.  IMMEDIATELY FLUSH EYES OR SKIN HiTH COPIOUS
      AMOUNIi Ut- «A(tK FOR AT LEAST  15 MINUTES WHILE  REMOVING CONTAMINATED
      CLCTHlNi ANJ  SHOES.
      IF l.NHALtU. KertuVE  TO FRESH  AIR. IF NOT BREATHING GIVE ARTIFICIAL
      RESPIRATION;  PkEFERAdLY MCUTH-TO-MOUTH. IF BREATHING is DIFFICULT.
      GIVE OXYGEN.
      CALL A PHYSICIAN.
      .
  «« !'J 1MO
  •?»*••.««•««•
                             :«Ce
                                                                  C*.LM.

-------
                                   HHH7338SO


              ,M A  I  b  R I  A L   S A r T.  I Y    DATA   ShfcET


DATE:  OL/^O/bo CATALOG * 02000-0  GUST  #  S40048  P.O. *                   PAGf


      DISCARD  v.u NT AM la ATEO CLUThlNG AND  SHOES.
                           SECTION  VI    REACTIVITY DATA
      INCUMPAIIdlLIIY:
      STRONv, AclDS
      STRONo 6AStS
      STRONo uXlLUZlNu AGENTS
      STRONG REJUClNu AGENTS

      MAZAKUUUS DECOMPOSITION  PRODUCTS:

      TOXIC FUMES UFi
      CARBbN MUNOXiOE, CARBON  DIOXIDE
      NlTRuGEN UXIuES
      SULFUR JXIDES
                       SECTION  VII   _SPILL CR LEAK  PKCCECURES


      SPILLS OK LEAKS:

      EVACUATE AREA.
      WEAR RESPIRATOR.  CHEMICAL SAFETY GOGGLES,  RUBBER 600TS AND  HEAVY
      RUBfabR GLOVES.
      SwEEP UP, PLACE  IN A BAG AND HOLD FOR  WASTE  DISPCSAL.
      VENTILATE AKfcA AND *ASH SPILL SITE  AFTER  MATERIAL PICKUP  IS COMPLETE.

      WASTE DISPOSAL:

      PLEASE LUNTALT  THE TECHNICAL SERVICES  OEPAR1MENT. BE  SURE TO MENTluN
      THE NAME, CATALOG NUMBER. AND THE QUANTITY OF THE MATERIAL.

      OBSERVE ALL  FEDERAL. STATE C LOCAL  LAWS  CONCERNING HEALTH C POLLUTION


          SECTION  VIU   PRECAUTIONS TO BE  TAKEN IN HANDLING  AND STORAGE

      CHEMICAL SAFETY  GOGGLES.
      RUBBER GLOVES
      OSHA/MSHA-APPRUVED RESPIRATOR.
      USE JNLY  IN  A CHEMICAL FUME HOOD.
      DO NUT BREATHE UUST.
      00 NUT GET  IN EYES. ON SKIN, CN  CLOTHING.
      WASH  THUkUUGMLY AFTER HANDLING.
       SEVERE  ikRHANC.
      AVOIU  ALL  CONTACT.
      KEEP  TIGHTLY CLOSED.
       STORE  IN  A  COOL DRY PLACE.


                   SECTION IX    SPECIAL_PR.ECAUTIONS_AND COMMENTS

                                    NOT APPLICABLE

       THE ABOVE INFORMATION  IS BELIEVED TO BE CORRECT BUT DOES NOT  PURPORT
       TO Bt ALL INCLUSIVE AND SHALL  BE OSED ONLY  AS  A GUIDE. ALDRtCH  SHALL
       NOT BE HELD LlAbLE  FOR  ANY  DAMAGE RESULTING FROM HANDLING  OR  FROM
       CONTACT «1TH THE  ABOVE  PRODUCT. SEE REVERSE SIDE OF  INVOICE OR  PACKl
       SLIP FOR ADDITIONAL TERMS AND  CONDITIONS  OF SALE.
   »ULA       Mtto*         CM*«           f,
   •<• W»M SL fMI AM. IMOCH Oww* CAJM.V  imcri fTmi«M C*     IM»HII rtmim
   "•* • • — — -—-  - - - -   —     ICinMH LM.       tl

-------
                                                      Appendix H)
                                                      Revision No 4
                                                      Date. December 1989
                                                      Page 1 of 12
                     APPENDIX D
DATA FLOW (REDUCTION, VALIDATION, AND REPORTING)

-------
                     OSJDE RETRESENTATION OF DATA FLOW



1.  Samples are taken in the field.

2.  Samples are iced and shipped to the laboratory.

        	 ._.! ^.v-^™,^ ;,... ,. :'.•_-.  : • field samples along with QC samples.

4.  Laboratory-enters field and QC data on a computer in "sets" and it
    enters instrument control standard data in a seperate file.

5.  Laboratory creates an ASCII file of the data using the specified formats
    on an ISA PC compatible floppy disk.

6.  Laboratory sends the floppy disk to Christopher Frebis at the EPA in
    Cincinnati,  Ohio.

                     26 W. Martin  Luther King Drive
                     Cincinnati, OH 45268

NOTE:   The maximum time from item 1 to  item  6 is two  (2) months.

 7.  Computer Sciences  Corporation (CSC)  personnel transfer the data from PC
     to TBA 3090 mainframe in North Carolina (or possibly to IEM Logical
     Mainframe in Cincinnati).
 8.  The data is ^i**** on the mainframe and then checked for compliance
     with QC requirements using SAS, a statistical programming language.

 9.  A hard copy of the edited data, with "suspect" data highlighted,  is
     sent to the technical monitor for their review.

 10.  The technical monitor returns the data to C. Frebis with comments,
     deletions, etc. — this is the final data.

 11.  The data is re edited per the technical monitor's review and a SAS data
     set is created for the data.

 12.  The "approved" field samples are sent to ICF for their analyses.

 13.  All QC data is retained by C. Frebis to generate a QC report at the end
     of the survey and to write monthly reports to  Dave Munch.

-------
                        NOTES ON NFS DATA FORMATS



1. The format for any date is mm/dd/yy

      A missing date should be entered 01/01/60

2. The format for any time is hh:mm in military time

      A missing time should be entered 00:00      *

3. Any other data that is missing should be entered with a period  (.)

4. The number of decimal places  should be as follows:

      Concentration          3   (significant  digits)
      Percent Recovery       1
      Internal Standard      0
      Instrument Controls    2
      pH                     1
      Temperatures          0
      Volumes                0

 5. The  codes for Column are as follows:

      Primary         PRIM
      Confirmatory    CONF
      Third           GCMS

 6. The codes for I*h are as follows:

       TSD              .                         TSD
       OPP                                       OPP
       WERL                                      WER
       Radian                                    RAD
       Battelle                                  BCD
       James M. Montgomery                       JMM
       Alliance                                  ALL
       Environmental Sciences and Engineering    ESE


  7. The codes -for Type are as follows:

        Field Sample                 SAMP
        Shipping Blank              SBLK
        Method Blank                 MBLK
        Lab Control Standard        I£S@
        Lab Spike Sample             LSS@*
        Time  Storage  for Extract     HTE@
        Time  Storage  for Sample      HTS@

    where @  is the mix letter (A,B,C or D)
      and £ is the spiking level  (1,2 or 3)

-------
                     NOTES ON NFS DATA POF3-RIS (cont.)
8. There should be at least one blank line between samples  in the NPS  data
   file.

9. The codes for Concentrations and Percent Recoveries  are  as follows:
      Not Analyzed --
      Not Detected (< Minimum Reporting Level)     ^         -999
      Saturated                                   *'         -777
      Other                                                 -333
      Below Report Limit,  but Distinct Peak                 -111

      Above Reporting Limit,  but not ^lantified             +888

10. If a reported value is greater than (>)  sane number in the NPS instrument
    control data, then use a minus sign (-)  instead of >

-------
               REVISIONS TO FORMAT FOR  NFS DATA FILES
Format for National Pesticide Survey (NFS)  Data
                               \
  Line     Column          Revision

   11       52-62    «      Revised "Enter Internal Standard" to "PERCENT
                           RECOVERY OF INTERNAL STANDARD AS COMPARED
                           AGAINST THE CALIBRATION STANDARD".

Notes on NPS Format

   4)  Revised   "Internal Standard 0 (area count)" to
       	    Internal Standard 1 (percent recovery)

   9)  - 999 -  revised to denote "Not Detected  (<  1/2 MRL)"

       - Ill -  revised to denote ">  1/2  MRL but <  MRL"

-------
                      TABLE 1: USES OF DATA CODES IN NFS

                                 SAMPLE TYPE
                                                                    LSS,DIS
      SAMP           MBLK            SELK           LCS           HIE,HIS
         (a)             .(a)             .(a)_
                                                      ****            ****
                                                      ****            -333 (d)
      -444(6)         ****            -444(6)         ****            -444(6)
      -555 (f)         -555 (f)         -555(f)         ****            ****
      -666 fa)         ****            -666 ^)         ****            ****
      -777ft)         -777ft)         -777ft)         -777 W         -777 (h>
       888 d)          888 d)          888 d)         ****            ****
      -999(J)         -999(j)         -999(j)         ****            ****
                      «W         =nc
-------
             -333
                           NFS DATA REPORTING CODES  (cont.)



                                          rm^y
-999
                                              888
                                      -333    -999    888
                                                                           INN



                                                                        HUM





                                                                        OGHF
                                            -333   -555   -999    888     GOTS
                                                                         GCMS

                                                                      (at referee)
              -333   -999    888
                 -333
                                                    failure)
     -444
                                                  -6.66
                                           -333    -666    -999
                                          -333  -555 •  -999  888
                                           -333  -999    888
                                            HUM
                                            CCNF
                                            GCMS
                                             OOS

                                         (at referee)
                                             vit^t TO nc ^fli
                -111
                         -333
    -777a    -999
                                                      catx:
                                                                            PRIM
       -111   -333   -999	              X-7W


-333^55 -999^888  -333^5-99^888   -SSS^SS -999 888  -SS'S -S^S -999 888  QCMS

    /N          /I\          XN           /K
  /
-333 -999  888
                  -333-999  888
       -333-999  888
                                                         -333-999  888
      a. - Dilute and reanalyze

-------
                      CHECKS PERFOrfrED ON NFS DATA BY CSC
1.  Is the instrument control standards's signal to noise ratio greater than
    the limit the method specifies?

2.  Is the instrument control standard's peak symmetry factor within the
    lijnits set by the method?

3-.  Is the instrument control standard's peak geometry factor within the
    limits set by the methods?

4.  Is the instrument control standard's resolution within the limits set by
    the method?

5.  Is the date from sampling to receipt within the limits set by the survey
    requirements?

6.  Is the date from sampling to extract within the limits set by the survey
    requirements?

7.  Is the date  from  extract to analysis within the limits set by the survey
    requirements?

 8.   Is the percent recovery of the  surrogate within the limits set  by the
     survey requirements?

 9.   Is the concentration of a blank above  the reporting limit?

10.   Is the concentration of a field sample above the reporting limit?

        A. If so, is there a confirmation analysis for the analyte?

        B. Is the concentration of the confirmatory column within the limits
           set by survey requirements?
 11.   Is the internal standard within the limits set by the method requirements?

 i2.   Is the percent recovery of each analyte  in the lab control standard within
      the  limits set by the survey requirements?

 13.   Is the percent recovery of each analyte  in the lab. spike sample within
      the  limits set by the survey requirements?

-------
               FOFMftT FOR NATIONAL PESTICIDE SURVEY (NFS)  DATA
LINE   OOIIJKNS     DESCRIPTION

 1       1-9       Well I.D.
        13-20      Date_Sam
        23-30      Date_Shp
        33-40      Date.Rec
        43-50      Tine Sam
        53-60      Timelloe
           [FOR METHODS 5 AND 9 ONLY]
         1-10      enter VEIL IDEOTIFICATION NUMBER
        13-20      enter DATE SAMPLED
        23-30      enter DATE SHIPPED
        33-40      enter DATE RECEIVED
        43-50      enter TIME SAMPLED.
        53-60      enter TIME ICED
            [FOR METHODS 5 AND 9 ONLY]
        63-66      enter pH

        BIANK

          1-8      Ini_Tenp
        11-18      Stbjremp
        21-29      Condition

          1-8      enter INITIAL TEMPERATURE OF WATER
        11-18      enter STABILIZED TEMPERATURE OF WATER
        21-80      enter CONDITION OF SAMPLE UPON RECEIPT AT LABORATORY

        BLANK

          1-6      Sairp S
          9-11     Lab
         14-18     Set S
         21-28     Date_Spk
         31-38     Date_Ext
         41-48     Date Ana
         51-56     Site *
         59-64     Column

          1-6       enter SAMPLE IDENTIFICATION NUMBER
          9-11      enter LAB ABBREVIATION
         14-18      enter SET NUMBER
         21-28      enter DATE SPIKED
         31-38      enter DATE EXTRACTED
         41-48      enter DATE ANALYZED
         51-56      enter SITE NUMBER
         59-64      enter ANALYSIS  COLUMN

-------
           FOPtfAT FOR NATIONAL PESTICIDE SURVEY  (NFS) DATA  (cent.)
T.TNE   COLUMNS

  9     BLANK
 - r.
  11
   12

   13

   14

   15

   16
   17-?
 8-13
16-22
25-31
34-40
43-49
52-60
65-70

  1-5
  0-13
 16-22
 25-31
 34-40
 43-49
 52-62
 65-70

 BLANK

  1-8

  1-80

  BLANK

   1-7
  29-33
  39-45
  67-71

   1-25
  28-34
  39-63
  66-72
DESCRrPripN
Spiker
Extract
Analyst
Sam Vol
Ext Vol
Int.  Std.
% Surr

enter SAMPLE TYPE
 enter SPIKER1 S INITIALS
 enter EXTRACTOR'S INITIALS
 enter ANALYST'S INITIALS
 enter VOLUME OF SAMPLE
 enter VOLUME OF EXTRACT
 enter INTERNAL STANDARD
 enter PERCENT RECOVERY OF SURROGATE
  Comments

  enter ANY PERTINENT COMMENTS ON SAMPLE AND ANALYSIS
  Analyte
  Cone.
  Analyte
  Cone.

  enter ANALYTE'S NAME
  enter CONCENTRATION OR PERCENT
  enter ANALYTE'S NAME
                                                    _
                      enter CONCENTRATION OR PERCENT RECOVERY

-------
             FOR NATIONAL PESTICIDE SURVEY (NPS)  INSTRUMENT CONTROL DATA
LINE   COLUMNS     DESCRIPTION

 1       1-3       Lab
         6-11      Method
        14-21      Date_Ana
        24-30      Analyst
        35-37      S/N   '
        42-44      PSF
        49-51      PGF
        55-58      Res.

 2      BLANK

 3-?      1-3       enter LAB ABBREVIATION
         6-11      enter METHOD NUMBER
        14-21      enter DATE ANALYZED
        24-30      enter ANALYST'S INITIALS
        33-37      enter SIGNAL TO NOISE RATIO
        40-44      enter PEAK SYMMETRY FACTOR
        47-51      enter PEAK GEOMETRY FACTOR
        54-58      enter RESOLUTION

-------
   •* TSO FOREGROUND HAROCOPY  ****
OSNAME=CPSFSOO.NPS.FORHAT.QATA
                                                 CMETHOD3 )
I_Terap  S_Tenp  Dato_Saa  Date_Shp  Datc_Rec  Tiue_Sa«   Ti«ne_Ice
                01/01/60  01/01/60  01/01/60

Receipt Condition
TSO
                   01
                           ui-\(._-uU  Date_Ext   Oat«_-Ana  Column
                           01/01/60  04/30/87   05/03/87   PRIM
Type    Spiker  Extract  Analyst  Sae_Vol   £xt_Yol»  Int. Std.    X Surr
..;_..      -        .        ...      1000        5         35        101.3
Coeaents
NONE.

Analyte                      Cone.

Acifluorfen                   -999
2*4-06                        -999
Bentazon                       -999
Chlorauben                    -999
 2*4-0                         -999
 Oslapon                       -999
 DCPA acid metabolites         -999
 Oicamba                       -999
 3*5-Dichlorbenzoic acid       -999
                                    Analyte

                                    Dichloroprop
                                    Oinoseb
                                    5-Hydroxy Oicamba
                                    4-Nitrophenol
                                    PCP
                                    Pichoram
                                    2*4,5-T
                                                    Cone .

                                                      -999
                                                      -999
                                                      -090
                                                      -999
                                                      -999
                                                      -999
                                                      -999
                                                      -999
-Tenp  S«-Temp  Oate_Sa«  Oate_Shp
              01/01/60  01/01/60  01/01/60
                                               Time_Sam   Time_Ice
 Receipt Condition
 Samp #
              Lab   Set  tt   Oate.Spk   Date.Ext  Date_Ana  Coluon
              TSD    01     04/30/87   04/30/87  05/03/87   PRIM
 Type    Spiker  Extract  Analyst  Sa« Vol   Ext.Vol   Int. Std.
 LCSA     CM      CM       CM      1000        5         31

 Consents
 NONE.
  Analyte

  Acifluorfen
  2*4-08
  Bentazon
  Chloramben
  2*4-0
  Oalapon
  DCPA acid aetabolites
  Dicaaba  •
  3*5-Oichlorbenzoic acid
                           Cone.

                            100.6
                             94.7
                               •

                             97l 5
                        Analyte

                        OichloroproD
                        Dinoseb
                        5-Hydroxy Oicamba
                        4-Nitrophenol
                        PCP
                        Pichoraa
                        2*4*5-T
                        2*4*5-TP
                                                                2  Surr
                                                                99.4
Cone.

  98.9
  94.5
  89.9
    •
  91.1
  93.3
    9
  85.5
          S_Te»p
                             »-* M c K»

-------
                                                    Appena;x -
                                                    Revision No 4
                                                    Date  December 1989
                                                    Page 1 of 4
                   APPENDIX E
SIGNIFICANT FIGURES AND ROUNDING OF NUMBERS

-------
            SIGNIFICANT  FIGURES AND  ROUNDING  OF  NUMBERS
1  Introduction

To  obtain  meaningful  data  on  water quality,  the  sample  collector  must  obtain a
representative sample and then deliver U unchanged for analysis. The analyst must perform
the proper analysis in the prescribed fashion, complete calculations, and convert results to
final form for permanent recording of the analytical data in meaningful, exact terms. These
results are transferred to a storage facility'for future interpretation and use.

The following sections discuss processing of actual values, recording and reporting of data in
 the proper way, some means of quality control of data, and the storage and retrieval of data.

 2  The Analytical Value

 3    Significant Figures

 The term "significant  figure" is used, sometimes rather loosely, to describe a judgment of
 the reportable digits in a result. When  the judgment  is not soundly based, meaningful digits
 are lost  or  meaningless digits are reported. On the  other hand, proper  use of significant
  figures gives an indication of the reliability of the analytical method used.

  Tne following discussion describes the process of retention of significant figures.

  A number is an expression of quantity. A figure or digit is any of the characters 0, 1, 2, 3, ^,
  5,  6, 7, 8,  9, which, alone or in combination, serve to express a number. A significant figure
  is a digit that denotes the amount of the quantity in the particular decimal place in which it
  stands.  Reported analytical values should contain only significant figures. A value is made
  up of significant figures when it contains all digits known to be true and one last digit in
  doubt.  For example,  if a value is reported as 18.8 mg/1, the 18 must be firm while the 0.8  is
  somewhat  uncertain, but presumably better than one of the values 0.7 or 0.9 would be.

   The number zero may or may not be a significant figure depending on the situation.

   Final zeros after a decimal point arc always meant  to be significant figures. For example,  to
   The nearest milligram, 9.8 g is reported as 9.800 g.

   Zeros  before a decimal point with nonzero  digits preceding them are significant. With  no
   preceding nonzero digit, a zero before the decimal point is not significant.

   If there arc no nonzero digits preceding a decimal point, the zeros after the decimal point
   but preceding other nonzero digits are not significant. These zeros only indicate the position
   of the decimal point.

    Final  zeros in  a  whole number  may or  may not be significant. In  a conductivity
    measurement of 1,000 ^mho/cm, there is no implication by convention that the conductiv-
    ity is  1,000 ± 1 pmho. Rather, the zeros only indicate the magnitude of the number.

-------
A  good measure of the significance of one  or  more zeros  interspersed in a number is to
determine whether the zeros can be dropped by expressing the number in exponential form.
If  they can, the zeros may not  be significant. For example, no zeros can be dropped when
expressing  a weight of 100.08  g in exponential form; therefore the zeros are significant.
However, a weight of 0.0008 g can be expressed in exponential form as 8 X \Q~4 g, so the
zeros are not  significant. Significant figures  reflect the limits in accuracy  of the particular
method of analysis. It must be decided whether the number of significant digits obtained for
resulting values is sufficient for interpretation  purposes. If not, there is  little that can be
done within the limits of the given laboratory operations to improve these values. If more
significant  figures are needed,  a'further improvement in method «or selection of another
method will be required.

Once the number of significant figures obtainable from a type of analysis is established, data
resulting from such analyses are reduced according to set rules for rounding off.

 4    Rounding Off Numbers

 Rounding off of numbers is a  necessary operation in  all analytical areas. It is automatically
 applied  by the limits of measurement of every instrument and all glassware. However, when
 it is applied in chemical calculations incorrectly or prematurely, it can adversely affect the
 final results. Rounding off should be applied only as described in the following sections.

 5     Rounding-Off Rules

  If  the figure following those  to be retained is less  than 5, the figure is dropped, and the
  retained figures are kept unchanged. As an example, 11.443 is rounded off to 11.44.

  If  the figure following those to be retained is  greater than 5, the figure is dropped, and the
  last retained figure is raised by 1. As an example, 11.446 is rounded off to 11.45.

  If  the figure following those to be retained is 5, and if there are no figures other than zeros
  beyond the  five,  the figure 5 is dropped, and the last-place figure retained is increased by
  one if it is an odd number or it is kept unchanged if an even number. As an example, 11.435
  is rounded off to 11.44, while 11.425 is rounded off to 11.42.

  6      Rounding Off Arithmetic Operations

   When a series of numbers  is added, the sum should  be rounded off to the same number of
   decimal places as the addend with the smallest number of places. However, the operation is
   completed with  all decimal places  intact, and  rounding off is done afterward.  As an
   example.
   The sum must be rounded off to 33.4.
                                                        7*0

-------
When one number is subtracted from another, rounding off should be completed after the
subtraction operation, to avoid possible invalidation of the'operation.

When tv/o numbers  are to be multiplied, all digits are carried through the operation, then
the product is rounded off to the number of significant digits of the multiplier with the
fewer significant digits.

When two numbers are to be divided, the division is carried out on the two numbers using
  .. uigio. "t'nen the  quotient is rounded off to the number of significant digits of the divisor _
or dividend, whichever has the fewer.                        »

When a  number contains n significant digits, its  root can be relied on for n digits, but its
 power can rarely be relied on for n digits.

 7     Rounding Off the Results of a Series of Arithmetic Operations

 The preceding rules for rounding off are reasonable for most calculations; however, when
 dealing  with two nearly equal numbers,  there is a danger of loss of all significance when
 applied  to a series  of computations that rely on  a relatively small difference in two values.
 Examples are calculation of variance and standard deviation. The recommended procedure is
 to carry several extra figures through the calculations and then to round off the final answer
  to the proper number of significant figures.
                                   1 I

-------
                                                Revision No 4
                                                Date  December 1989
                                                Page 1 of 3
                APPENDIX F
STORAGE OF NPS HARDCOPY DATA FILES AT ECL

-------
                STORAGE OF NFS HARDCOPY DATA FILES AT ECL

     The HARDCOPY DATA FILES and all related reports will be filed according
to NPS Method No., and then by Sample Set.

     ECL has a RECORDS ROOM available for this purpose.  It is equipped with
shelving for storage, a  smoke alarm, and a  sprinkler system.  Activation of
the snoke alarm is monitored 24 hours a day by the NSTL fire department which
can respond within 2 minutes to an alarm.   ECL will take precautions to
protect from sprinkler system water damage  all files stored in this  room.

     The RECORDS ROOM is also the  office of the  ECL QAC and is locked when
the room is unoccupied.   Access  is limited  to the ECL  Laboratory Manager,  the
ECL QAC and Project/Team Leaders.

     The STORED RECORDS LOG is used to log  files into  the  RECORDS ROOM
and to record removal and subsequent return of these files.

-------
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-------
                                     Appendix G
                                     Revision No  4
                                     Date  December 1989
                                     Page 1 of 3
 APPENDIX G
DIXON'S TEST

-------
DIXON'S TEST

Dixon's test is used to confirm the suspicion of outliers of a set of data
(for example, control chart data points).  It is based on ranking the data
points and testing the extreme values for credibility.  Dixon's test is based
on the ratios of differences between observations and does not involve the
calculation of standard deviations.                  *

The procedure for Dixon's test is as follows (from Taylor, 1987):

     1)   The data is ranked in order of increasing numerical value.  For
         example:

              Xx  < X2 <: X3 < ...  < X,,.! < X,,

     2)   Decide whether the smallest, X^  or the largest,  Xn,  is
         suspected to be an outlier.

     3)   Select  the risk you are willing to take for false rejection.
         For use in this QAPP we will be using a 5% risk of false
         rejection.

     4)   Compute one of the ratios in Table 1.  For use in this QAPP we
         will be using ratio r22,  since we will  be  using between  20  and
         17 points for the control charts.

     5)   Compare the ratio calculated in Step 4 with the appropriate
         values  in Table 2.  If the calculated ratio is greater than the
         tabulated value, rejection may be made with the tbulated risk.
         Fort his QAPP we will be using the 5% risk values (bolded).

Example (from Taylor)

     Given  the  following  set of ranked data:

         10.45, 10.47, 10.47,  10.48, 10.49,  10.50,  10.50,  10.53,  10.58

     The value  10.58  is suspected  of  being an  outlier.

     1)   Calculate ru

                       10.58 - 10.53       0.05
              rn  -    	   -   	   - 0.454
                       10.58 - 10.47       0.11

     2)   A 5% risk of false rejection (Table 2), ru - 0.477

     3)   Therefore there is no reason to reject the value 10.58.

     4)   Note that at a 10% risk of false rejection ru -  0.409,  and the  value
         10.58 would be rejected.

-------
                                    TABLE 1




                             CALCULATION OF RATIOS
                         For use if           if X,, is             if Xj is

      Ratio            n is between           suspect             suspect
                                                  V   \            / V

                                                 ' *n-l)            (X-2  ~


        ru                 3-7
        :n                8 - 10
        '21                11 *
       r22                14 -  25
  v  '\           fv
~  *K-l)           ^A2 "




-  x2)           (Vi  -






  Y  ^           fv
-  J^a-2J           <-A3 ~




-  X2)
  V  N           / V
"  Ao-2/           VA3





-  X3)           (X.,.2
Note that  for  use in this QAPjP ratio r22 will be used.

-------
                                   TABLE 2




              VALUES  FOR USE WITH THE DIXON TEST FOR OUTLIERS








                                        Risk of False, Rejection



   Ratio          n           0.5%          1%           5%           10%
     -10
     -ii
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
0.994
0.926
0.821
0.740
0.080
0.725
0.677
0.639
0.713
0.675
0.649
0.674
0.647
0.624
0.605
0.589
0.575
0.562





0.988
0.889
0.780
0.698
0.637
0.683
0.635
0.597
0.679
0.642
0.615
0.641
0.616
0.595
0.577
0.561
0.547
0.535
0.524
0.514
0.505
0.497
0.489
0.941
0.765
0.642
0.560
0.507
0.554
0.512
0.477
0.576
0.546
0.521
0.546
0.525
0.507
0.490
0.475
0.462
0.450
0.440
0.430
0.421
0.413
0.406
0.806
0.679
0.557
0.482
0.434
0.479
0.441
0.409
0.517
0.490
0.467
0.492
0.472
0.454
0.438
0.424
0.412
0.401
0.391
0.382
0.374
0.367
0.360
Note that for this QAPjP  the  5%  risk level will be used for ratio r
                                                                    22-

-------
Reference:
     John K.  Taylor,  Quality Assurance of Chemical Measurements. Lewis
     Publishers,  Chelsea, MI,  1987.

-------
                                               Appendix H
                                               Revision No 4
                                               Date- December 1989
                                               Page 1 of 13
             APPENDIX H
ADDITIONAL QUALITY CONTROL CHECKS

-------
                                 QUALITY ASSURANCE DATA FORM
                                     NFS GROUND V«TER
  Sampling Date(s)_
                                                                  Method
  Arrival Date(s)  at ECL
                                                                  Set No.
                                       Set Composition

                     sample wt. (gins)    pH
                                                               sample wt.  (gms)   pH
1.
2.
3.
4.
5.
6.

7.

8.
1

1
1



1
1

9- 1 1
10. |
11.
12.
13.
14.




1
15.

16.



   Method Blank
                               Standards and Set Controls Data

                                    Name / Date of Std. Used   Mt. Spiked   Initials
   Shipping Blank
   Shipping  Blank
    LCS
    LCS
    LCS
    LSS
    LSS
    LSS
    LSS
    LSS
    LSS
    Surrogate
    Column Check
    Column Check
***
**•*
STOP! l . Has Sample Control Record been completed for both distribution and
         return of samples?
       . Has Set Composition Form been attached?                           "
       . Has ECL/NPS Sample Tracking Form been attached?                   ~
     Signature:
                                              Date:

-------
Procedure

Hydrolysis
pH Adjustment
Extraction
Derivatization
Cleanup:
      -Florisil
                 Accomplished
                                 Sample Preparation

                                 Initials of Employee(s)
                                 Doing Work	
Comments
Extracts Relinquished By:

Extracts Received By: 	
                                                                  Date:
                                                                  Date:
                                     GC Analysis
Date  Begun:
                          Analyst(s):
Internal Std.  Spike Data:
     Spiked By:
                                     Date:
     Name / Date of Std. Used:
I.D.  of Instrument Used for Analysis:
1.

2.

3.
               4.

               5.

               6.
                                                            Date Completed:
                                                            Arat.  Used:

7.
8.
9.
Analysis Dates
10.
11.
12.

13. 16.
14.
15.
 STOP!!   .  Is GC work complete?
         .  Have NFS Data Report Forms on each sample been  completed for each
           GC column?
         .  Has remedial QC work been carried out with  results attached?
         .  If any sample in this set will be reextracted,  list  the/^tiigit -
           code no. of the sample.                                 ^-4
         .  IB any sample in this set a reextracted sample?
 Signature:
                                Date:
                                                     Disposition of Extracts:
 Data Reviewed By:
                                                     Date:
'Final Disposition of Extracts:

 Date of Final Disposition:	
                                                          Signature:

-------
                            EXCEPTIONS TO QC REQUIREMENTS

NFS Method	     Set	

State exception, when noticed,  who notified, remedial  actib*h required, action taken;
sign and date for each separate incident. Attach to this QUALITY ASSURANCE DATA FORM
verification that the QC problem was resolved  and the  date  it was resolved.

-------
QUALITY ASSURANCE DATA FORM INSTRUCTIONS

     To fill out the QA Data Form, refer to the Assigmerit Sheet and Sample
Tracking Form for the set.

Sampling Date(s):                               »

     This information is on the Sample Tracking  Form.

Arrival Date(s) at ECL;

     This information is on the bottom of  the Sample Tracking Form under
Date Received.

Set No.:

     This information is in the title of the Assignment Sheet.

 Set Composition:

     The correct order of the controls and samples  is copied  from the As-
 signment Sheet onto the Set Composition portion of  the Quality  Assurance
 Data Form.   For each sample, write both the  sample  name and 9 digit sample-
 code number.  The number to the left of each control name or  sample name in
 this section is the Set Composition Number.  It,  in conjunction with the
 Set Number, will be used to identify  the controls and samples throughout
 the extraction and G.C. Analysis.  Set Composition  Numbers are  initially
 assigned on the Assignment Sheet for  each set.   After determination, the
 weight in grams and pH is  recorded for each  water sample. The  weight  for
 all controls is 1000 gms.  No  pH is recorded for controls.  Column Checks
 are simply listed next to  their Set Composition Numbers,  pH  and weight
 data being inapplicable.

      In the event that a Ground Vbter Sample is a reextraction, place an R
 before the 9 digit sample  - code number and follow it with the Set Number
 and Set Composition Number,  in parenthesis,  of  the original Ground Vbter
 Sample.

 Standards and Set Controls Data;

      The purpose of this section is to provide information about the spik-
  ing standards used in the set.  Copy this information from the Assignment
 Sheet.  In the  empty brackets to the right of the Method Blank, Laboratory
 Control Spikes, Surrogate and Column Checks, write the date  the control was
 originated.   This is the date of extraction for  all but  the  Column Checks.
 The Column Checks are originated on the date the florisil columns  are begun.
  For the Shipping Blanks and Laboratory Sample Spikes, t"he 9  digit  sample -
  code  numbers are placed in the empty brackets.

-------
     The information for  the Name / Date of Std. Used and Amt. Spiked
action can be copied from the Assignment Sheet.  The date in parenthesis
following the standard name indicates the date the standard was prepared.

     The person who spikes a  standard should  writ* his  initials behind it
in the Initials section.

Questions:

     Has Sample Control Record been completed for both  distribution
     and return of samples?

     The Sample Control Record is kept  in the Receiving Room.   Vfoen NFS
     water samples are removed from the cooler for extraction,  they are
     signed out on the Sample Control Record.  The empty sample bottles
     are  later returned to the Receiving Room and signed in on the Sample
     Control Record.

     Has  Set Composition Form been attached?

     The  Assignment  Sheet  is prepared at EPA/ECL by the Project Manager
     and  sent  to  the Processing Laboratory at the start of each set
     extraction.

     Has ECL/NPS  Tracking  Form been  attached?

     The ECL/NPS  Sample  Tracking Form  tracks the samples from storage
      through extraction, and G.C.  Analysis.

 Signature:

      The person completing this page of  the  form  should sign and date the
 form here.

 Sample Preparation:

      The NFS Method * O Extraction Procedure is broken down into six parts
 in this  section.  The Date Accomplished and Initials of Bnployee(s) Doing
 Vbrk should be provided for each.  There is a section provided for comments
 (exceptions to routine) if applicable.

 Signatures;

      Vhen sample extracts are delivered for GC analysis, the employee re-
 linquishing the  extracts and the employee receiving the extracts should
 sign and date the QA Data Form.

-------
G.C. Analysis

Date tiequn:

     Vfite the date the extracts are spiked with the Internal Standard.

Analyst (s);                                     »

     Write the name of the person(s) who analyzed the samples on the ins-
trument(s) and performed the calculations on the set.

Date Completed;

     Write the date all calculations and data forms for the G.C. analysis
are completed and submitted for review.

 Internal Std. Spike Data:

     This  section provides information concerning the Internal Std., the
 date the set was spiked, amount used and the name and date of standard used.
 This date  is the date  the Internal  Std. was prepared.

 I.D. of  Instrument Used for Analysis:

     Write in  the  serial no(s). of  the G.C.(s)  used.

 Analysis Dates:

      In this section,  the controls  and  samples are  referred to  by  their
 Set Composition numbers as written  on the first page of this form.  Beside
 each set composition number,  record the date of the last injection on a
 Gas Chromatograph for each  control  or sample.

 Questions:

      Is G.C. work complete?

      Is all analysis on the instrument completed?

      Have NFS Data Report Forms on samples been completed for each G.C. column'

      This includes the primary and confirmatory G.C. columns.

      Has remedial QC work been carried out with results attached?

      The  analyst is responsible for conducting QC checks.   If any portion
      of the data falls out of the  acceptable QC limits,.remedial  QC work
      must be done.  All QC checks  and QC  remedial work is outlined in the
      QC Requirements  and Criteria  Attachment.

-------
    If any sample in this set will be reextracted, list the 9 digit - code
    no. of the sample.

    Refer to the Set Composition section of this form to find the 9 digit -
    code no. of the sample.
                                               »-

    Is any sample in this set a reextracted sample?

    If the answer is Yes and additional information on the original sample
    is needed, refer to the Set Composition section of this form.  Any
    reextracted sample will have an R preceding the 9 digit sample- code
    number and be followed by the bracketed Set Number and Set Composition
    Number of the original sample.

Signature;

    The  person completing  this  page of  the form  should sign and  date  the
form here.

Disposition of Extracts:

     Following reviev  of  the  G.C.  Analysis Data,  sample tubes are quanti-
tatively  transferred to culture  tubes and volumes marked. All information
on concentrator  tubes  is  transferred to the culture tubes, which are then
stored in a cooler.  At this tijne,  the "EXTRACT STORAGE DATA SHEET",(See
Appendix A),  is completed by  recording all pertinent extract information.

Data Reviewed By:

     Signature of person who reviewed completed data set.  This must be
someone other than the person who analyzed the set.

Date:

     Write the date the review was completed.

Final Disposition of Extracts:

     Sample extracts will be held until the Technical Monitor approves of
their disposal (See 7.23 of the QAPP).

-------










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-------
               INTERNAL QUALITY CONTROL CHECKLIST

               Method 03/  Extraction Set  *	
CRITERIA FOR RESULTS
SURROGATE RECOVERY:

DCAA recovery must be within
+ 30% of mean recovery determined
during the initial demonstration
of capabilities.
ACCEPTABLE LIMITS*
PASS
    FAIL
Mean:   84.6%
Range:  54.6 to 114.6%
 INTERNAL STANDARD AREA:

 Peak area for internal standard
 in any sample must  not deviate
 by more than 20% from the mean
 peak area for the calibration
 standards it was analyzed
 against.
 PASS
     FAIL
 Mean:_

 Mean:
 LABORATORY CONTAMINATION:

 Method blank should not contain
 a peak greater than or equal to
 one-half MRL for each analyte.
 PASS
      FAIL
 Blank date_

 Analyte	
                                              Amount found
 INSTRUMENT PERFORMANCE:

 See Section 11.1  of Method 3.
  PASS_

  R:
  S/N:
  PSF:
  PGF:
      FAIL
>0.4
>3.0
0.70 to 1.05
0.70 to 1.05
  CALIBRATION STANDARD INTEGRITY:

  A calibration curve based on newly
  prepared standards must give
  results which are within 20% of
  the expected value for the most
  recently prepared calibration
  solutions.
  PASS
      FAIL
  Calib. Curve
     (date)
  Calib. Level
  *Note any exceptions to the Acceptable Limits.
  Prepared by
   Date

-------
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-------
                                           Appendix I
                                           Revision No 4
                                           Date: December 1989
                                           Page 1 of 3
        APPENDIX I
ECL COMPUTER PROGRAMS

-------
BASIC F-P'OCRftM: REGVAP

MAR 23, 1988   15:43:27

5REM***REGVAR, WRITTEN FOR ECL BY UUD,  OCT l,19So
10LETN = T = C1=C2 = H 1=1)2 = 0
28PRIHT"ENTER COMPOUND NAME";
3GDIMASC403
SSDIMUt 1C-<0>3
36DIMPC1G03
37DIMXC16G3
38DIMBC1GG3
39DIMGC1GG3
48INPUTA*
50PRINT"ENTER -1  AFTER YOUR  LAST DATA POINT"
 70PRINTI
 86PR1 NT "ENTER YOUR  VALUE FOR X";
 96INPUTUCI3
 ieeiFUCI3=-lTHEN150
 12ePRINT"EHTER YOUR  VALUE  FOR Y  " ;
 I30INPUTP[ I 3
 146NEXTI
 156PRINT
 166PRIHT-ARE ALL VALUES CORRECT? ";
 17eiNPUTEt
 18GIFB*="Y"THEN26G
 !9ePRINT"EHTER THE NUMBER  OF THE FAIR  IN  ERROR":
 288 INPUT I
 216PR1NT"ENTER THE CORRECT X";
 228INPUTUCI3
 238PRINT-ENTER THE CORRECT Y";
 240INPUTPCI3
 256GOTOieG
 260FORI=1TON
 278LETC1=C1*UCI3
 280LETC2=C2*|XCI3;TRBC33>;DCI3;
 S18PRINTTRB(48>;CCn
 S28LETT-T+GCI3
 S38NEXTI
 548PRINT"THE-SUM
 358PRINT

-------
StOFF I NT
57GPRINT
5SeLETZ=Z+l
6iePRIHT"IUPUT M V VftLUE. USE ft -1 TO END THE OPERftTI OH. "
62idINPUTT
630IFT=-1THEN720
64eLETV='. VftLUE  IS  "V
eeepRiNT-vouR v VRLUE  is  -T
6700UTDVC"L1",E
686PRIHT
696PRIHT-YOUR X VALUE  IS  "V
780PRINT"YOUR Y VftLUE  IS  "T
710GOT0606
726PRINT
73eOUTDVC"Tl-,E
74eiFLS*MnftHY"THEMlCi
750PR1HT-IF  YOU HftVE SEVERftL  GROUPS  AND  WOULD  LIKE TO OMIT";
760PRIHT-THE NEXT  QUESTION,  ENTER MANY  INSTEAD  OF Y OR H. "
770PRINT
78©PRIHT"LO  YOU WftUT TO ENTER ANOTHER GROUP'' "
7961HPUTL*
800 1 FL* = "MANY "THEN 10
8ieiFLf*MY"THEHlO
826ENH

END  OF FILE

-------
                                             Appendix „
                                             Revision No 4
                                             Date  December 1989
                                             Page 1 of 6
          APPENDIX J
RAPID REPORTING NOTIFICATION

-------
      \
      I    UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
*/,t (	,t
-------
                                    -2-
    If you hive any questions concerning these procedures,  please let Bob
Haxey or me knov.   Also,  please pass on this information  to your contract
and referee laboratories.  They will need to have this  information in hand
prior to their conducting the dry run.

Attachment          «.     .                         ^

Addressees:

    A. Dupuy
    L. Kamphake
    C. Madding
    R. Maxey
    R. Sorrell
    R. Thomas
 cc:
    J. Kotas
    H. Brass
    A. Kroner
    J. Orme

-------
                 METHOD  13
   AKALYTE                RAPID REPORTING LEVEL
       i .
                                    V
Acifluorfen                      130 ug/L
Bentazcm                        87.5 ug/L
2,4-D                            100 ug/L
Dalapon                          800 ug/L
Dicamba                           13 ug/L
Dinoseb                          3.5 ug/L
Pentachlorophenol                300 ug/L
Picloram                         700 ug/L
2.4,5-T                     *     105 ug/L
2,4,5-TP                          70 ug/L

-------
                                       METHOD  6
ANALXTE





Rapid
Reporting
Level (ppb)





Analytical Results
Primary GC Column
«- (ppb)





Secondary GC Column
(ppb)




*
GC/MS
(pos. or neq. or N/R*

.



    NOT ANALYZED
QA Assessment:

     Is there any QC problem(s)  with the set or the sample for either Method that may
     adversely impact the identification or quantitation of the above analytes?  If yes,
     describe.
                                                              R. Maxey, Project Leader

-------
                                                                                          BSL
                                    NPS RAPID REPORTING NOTIFICATION
                                          NPS METHODS 1,3 AND 6
       Date:
       Set No.:
       NPS Field Sample No.:.

       BSL Lab. I.D. No.:
                                             METHOD 1
ANALYTE





Rapid
Reporting
Level (ppb)





Analytical Results
Primary GC Column
(PCb)




•
Secondary GC Column
(PPb)





GC/MS
(pos. or neg. or N/R





•
                                             METHOD 3
,
ANALXTE





Rapid
Reporting
Level (ppb)





Analytical Results
Primary GC Column
(PCb)





Secondary GC Column
(PCb)





GC/MS
(pos., neg., or N/R'





          NOT ANALYZED

-------
                                                  Appendix K
                                                  Revision No 4
                                                  Date December 1989
                                                  Page 1 of 2
                APPENDIX K
GC/MS CHARACTERISTIC IONS FOR METHOD 3

-------
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-------
                                                    Appendix L
                                                    Revision No 4
                                                    Date  December 1989
                                                    Page 1 of 9
                    APPENDIX L
ADDENDA TO METHOD 3 - JUNE 1988 TO DECEMBER 1989

-------
                                                                           05/01/89
                           Environmental Chemistry Section
                                 Addendum  - Method 3
Revision to Section 4, page'l/ paragraph 1,  sentence 4*

  - Change "Dr. Y. A. Yonan• ECL-QAO . . .•  to "Mr. Danny McDaniel/
    Acting ECS-QAC. . ."

Revision to Section 4, page I/ paragraph 2,  sentence 2

  - Change "..handled by Ms. Jan Watkins."  to  "...handled by Ms. Jan Watkins
    backed up by Ms.  Elizabeth Flynt."

 Revision to Section 4; page 1, paragraph 2, sentence 3

   - Change ". . .  M.  George Sand."  to ".  .  .Mr. William Mitchell and
     Mr. Joe  Ferrario."

 Revision to Section 4/  page 1« paragraph 2/ sentence 4

   - Change "Data handling and reporting will  be handled  by Ms. Watkins backed up by
     Mr. Mecomber and Ms. Flynt."  to  "Data handling and reporting will be handled by
     Ms. Watkins backed up by Ms. Flynt."

 Revision to Section 4, Figure 4-1 - ECS ANALYTICAL TEAM - Method 3

   - Delete  ECS ANALYTICAL TEAM diagram from Figure 4-1.

   - Replace with  revised diagram on following page.


                                       Approved
                                                EPA/ECS-NPS  Project Deader/
                                                F.CS Analytical Coordinator
                                       Approved
                                                           QAO-NPS^
                                       Approved  Tn^a^^      /rfrd*
                                                           QAO-ODIQ

                                       Approved
I
                                                          MPS Director

-------
                                                        Project:  NFS
                                                        Section No:  4
                                                        Revision No: 4
                                                        May 1989
                                                        Page  of
        Sample Custodian

        G. Gardner (EPA)
       Assistant Sample
       Custodians

       J.  Cuevas  (EPA)
       S.  Mecomber  (EPA)
Sample Prep./Ext.

E. Flynt (EPA)
S. Mecomber (EPA)
                                 ECS ANALYTICAL TRAM

                                     METHOD 3
                                  NPS Project Leader

                                    Bob Maxey (EPA)
      GC

J. Watkins (STI)*
E. Flynt (EPA)
                                        ECS-QAC (Acting)

                                        D. McDaniel
                                      Data Review

                                    W. Mitchell  (AARP)
                                    J. Ferrario  (EPA)
    GC/MS
J. Ferrario (EPA)
 Data Handling/
 Reporting

J. WatJcina (STI
E. Flynt (EPA)
   *  = Sverdrup Technology Inc. (In-house Contractor for ECS)
       ECS provides overall technical direction  to Sverdrup Technology,  Inc.
       FIGURE 4-1:  ECS ANALYTICAL TEAM - METHOD 3

-------
                                                            8/12/83
                   ENVIRONMENTAL CHEMISTRY LABORATORY
                          ADDENDUM - METHOD 3
Addition to Section 4, page 1, paragraph  2,  sentence 3
                                         »^ _
  -Add "Data review has been assigned to  Mr,  George Sand.

Addition to Section 4, page 1, paragraph  3

  -Change "NASA/NSTL Bldg. 1105
           NSTL,MS  39529"

               to

           "NASA/SSC Bldg.  1105
           STENNIS SPACE CENTER.  MS 39529-6OOO"

 Addition to  Section 4,  page  1, paragraph 4

   -Change "The Assistant Sample Custodian for NPS  is:

                  Mr.  John Cuevas
                  (601)688-3170 (or 3217)*

                       to

           "The Assistant Sample Custodians  -for  NPS are:
             Mr. John Cuevas
              (601)688-3170  (or 3217)
Mr. Stanley Mecomber
(601)688-3170  (or  3217)
 Figure 4-1: ECL ANALYTICAL TEAM was revised. The new chart  is
             enclosed.
                                     Approved
                                     Approved
                                      Approved
                                           ' EPA/ECS-NPS Project leader/
                                            ECS Analytical Coordinator

-------
                                                          Project: NFS
                                                          Section No: 4
                                                          Revision No: 3
                                                          June 1988
                                                          Page  of
                                   ECL ANALYTICAL TEAM

                                       METHOD 3

                                   I                    I
                                   | NPS Project Leader |
                                   I                    I
                                   I   Bob Haxev (EPA)  1


Sample Custodian
G. Gardner (EPA)
J. Cuevas (EPA)
1
I
1
1
1


1 1
1 1
I Y.Yonan (EPA) |

1 1
| Data Review |
1 I
                                                  I George Sand (EPA)
I
|  Sample  Prep./Ext.
I
I
|  S. Hecomber (EPA)
       GC
J. Watkins (STI)*
         I
     GC/MS
| D. McDaniel  (HR)(EPA)|
I J. Ferrario   (LR)EPA)I
|   |    Data Handling/
|   |    Reporting
   I
   I  J. Watkins (STI)
 I                    I
 |  Sample Prep./Ext.  |
 j  Elizabeth Flynt,   |
 I  (STI) *	|
         STI = Sverdrup Technology Inc. (In-house Contractor for ECL)
         Sverdrup is providing the ECL several person years of support.
         ECL provides overall technical direction to Sverdrup Technology,
       FIGURE 4-1:  ECL ANALYTICAL TEAM - METHOD 3
                                                Inc.

-------
                                                            7/21/88
                   Environmental Chemistry Laboratory
                          Addendum - Method 3
Addition to Section 2,  page 1,  Appendix H

  -Add "Internal Quality Control Checklist" below "QC Data Sheet"

  -Add an Appendix "K:   QC/MS CHARACTERISTIC IONS FOR METHOD 3"

Addition to Section 5,  page 1, number 8, end of paragraph

  -Add "See Appendix K  for a Table of the three ions for each analyte"

Addition to Appendices

  -Add Internal Quality Control Checklist  (enclosed) to end of Appendix G

  -Add a cover sheet for Appendix K: GC/MS CARACTERISTIC IONS FOR METHOD 3.
    (For the appendix contents/ see the enclosed GC/MS Characteristic Ions
    Table.)
                              Approved
                                                N^TDirector

-------
             INTERNAL QUALITY CONTROL CHECKLIST

             Method 03/  Extraction  Set f
CRITERIA FOR RESULTS
                                           ACCEPTABLE LIMITS
SURROGATE RECOVERY:

DCAA recovery must be within
+ 30% of mean recovery determined
Airing the initial demonstration
of capabilities.
                                             PASS
                                                        FAIL
                                           Mean:  84.6%
                                           Range: 54.6 to 114.6%
INTERNAL STANDARD AREA:

Peak area  for internal standard
in any sample must not deviate
by more than 20% from the mean
peak area  for the calibration
standards  it was analyzed
against.
                                              PASS
                                                         FAIL
                                           Mean:_

                                           Mean:_

                                           Mean:
 LABORATORY CONTAMINATION:

 Method blank should not contain
 a peak greater than or equal to
 one- half MRL for each analyte.
                                              PASS
                                                          FAIL
                                            Blank date

                                            Analyte
                                            Amount found
 INSTRUMENT PERFORMANCE:

 See Section 11.1 of Method 3.
                                              PASS
                                                          FAIL
R:
S/N:
PSF:
PGF:
>0.4
>3.0
0.70 to 1.05
0.70 to 1.05
  CALIBRATION STANDARD INTEGRITY:

  A calibration curve based on newly
  prepared standards oust give
  results which are within 20% of
  the expected value for the most
  recently prepared calibration
  solutions.
                                               PASS
                                                          FAIL
                                             Calib. Curve
                                                (date)
                                             Calib. Level
*Note any exceptions to the Acceptable Limits.
  Prepared by
                                             Date
                                1C?

-------
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