EPA-810/B-92-003
                      United State*           Office of Water (WH-550)     EPA 810-8-82-003
                      Envfaomnemal Protection   Office of Peaikhiea and      February 1902
                      Agency               Toxic Subatancea (H-7501C)
                     QUALITY ASSURANCE PROJECT PLAN
                                     FOR THE
          NATIONAL PESTICIDE SURVEY OF DRINKING WATER WELLS
             ANALYTICAL METHOD 2 - CHLORINATED PESTICIDES
                                     Prepared by:

                                  Clean Harbors, Inc.
                                  213 Burlington Road
                              Bedford, Massachusetts 01730
                                    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,  IL  60604-3590

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                                                                      Section No. 1                    ,4
                                                                      Revision No. 3                   ,
                                                                      Date: Februaiy 28, 1990
                                                                      Page 2 of 2
                                     APPROVAL PAGE


Clean Harbors Program Manager 	      Date

Project Coordinator  	      Date

Chemistry Division Manager  	      Date

Clean Harbors QA Officer  	      Date

EPA Project Officer  	      Date

EPA Technical Monitor  	      Date

EPA QA Officer  	      Date

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                                                                           Section No. 2
                                                                           Revision No. 3
                                                                           Date: February 28, 1990
                                                                           Pag* 1 of 3
                                      NATIONAL PESTICIDE SURVEY
                                 QUALITY ASSURANCE PROJECT PLAN FOR
                            ANALYTICAL METHOD 2 - CHLORINATED PESTICIDES
O
         2.   TABLE OF CONTENTS

           Section

                    TITLE AND APPROVAL PAGE

                    TABLE OF CONTENTS

                    PROJECT DESCRIPTION
1.

2.

3.

4.
                    PROJECT ORGANIZATION AND RESPONSIBILITIES
                    4.1    QA Officer's Responsibilities
                    4.2    Analytical QC Coordinator's Responsibilities
                    4.3    Laboratory Staff Responsibilities
              5.     QUALITY ASSURANCE OBJECTIVES FOR
                    MEASUREMENT DATA
                    5.1    Determination of Estimated Detection Limit
                            (EDL)
                    5.2    Determination of GC/MS Detection Limits
                    5.3    Construction of Control Charts
                    5.4    Frequency and Procedure for Matrix Spiking

              6.     SAMPLING PROCEDURES

              7.     SAMPLE CUSTODY
                    7.1    Notification of Laboratory
                    7.2    Holding Time, Storage and Disposal
                            Requirements
                    7.3    Custody Procedures at the Clean Harbors
                            Laboratory

              8.     CALIBRATION PROCEDURES AND FREQUENCY
                    8.1    Preparation of Surrogate and Internal
                            Standards
                    8.2    Preparation of Instrument QC Standard
                    8.3    Preparation of Calibration and LCS/Time
                            Storage
                    8.4    Instrument Calibrations

              9.     ANALYTICAL PROCEDURES

             10.     DATA REDUCTION, VALIDATION AND REPORTING
                    10.1   Data Reduction
                    10.2   Data Validation
                    10.3   Fast Track Reporting
                    10.4   Data Reporting
2

3

1

3
                                                       3

                                                       5
                                                       4

                                                       3
Revisions    Date

   3       2/28/90

   3       2/28/90

   3       2/28/90

   3       2/28/90
          3

          3
          3

          3
                                                                         2/28/90
           2/28/90

           2/28/90
                                                                         2/28/90
           2/28/90

           2/28/90

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                                                                Section No. 2
                                                                Revision No. 3
                                                                Dote:  February 28, 1990
                                                                Page 2 of 3
2.    TABLE OF CONTENTS (continued)

 Section

   11.      INTERNAL QUALITY CONTROL CHECKS
           11.1  Method Blanks
           11.2  Calibration Check Samples
           11.3  Replicate and Spiked Samples
           11.4  Laboratory Control Samples
           11.5  Surrogate Spikes
           11.6  Internal Standard Checks
           11.7  Instrument Quality Control Standards

   12.      PERFORMANCE AND SYSTEM AUDITS
           12.1  Performance Audits
           12.2  System Audits
           12.3  External Audits

   13.      PREVENTIVE MAINTENANCE

   14.      SPECIFIC ROUTINE PROCEDURES USED TO ASSESS
           DATA PRECISION, ACCURACY AND COMPLETENESS

   15.      CORRECTIVE ACTION
           15.1  Immediate Corrective Action
           15.2  Long-Term Corrective Action

   16.      QUALITY ASSURANCE REPORTS TO MANAGEMENT
           16.1  Internal Reports
           16.2  External Reports
                                                1

                                                4
                                                       Revisions    Date

                                                           3      2/28/90
3

3
                                                                  2/28/90
2/28/90


2/28/90

2/28/90




2/28/90
    17.
ARCHIVAL OF RAW DATA
       2/28/90

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Section No. 2
Revision No. 3
Date: February 28, 1990
Page 3 of 3
2. TABLE OF CONTENTS (continued)
Appendices
A.
B.
C.
D.
E.
F.
G.
H.
1.
J.

METHOD 2 (October 27, 1987)
GC/MS SPECTRAL INFORMATION
DIXON'S TEST
STANDARD OPERATING PROCEDURE FOR
MANUAL DATA ENTRY
STANDARD OPERATING PROCEDURE FOR
AUTOMATED DATA ENTRY
NPSIS SAMPLE RECEIPT SOFTWARE FOR
LABORATORIES DATED 4/5/88
NPS RAPID REPORTING SYSTEM 4/12/88
DATA REPORTING FORMAT CHANGES 4/18/88
NPS ANALYTE REPORTING BELOW MRL AND
IDENTIFYING UNKNOWN PEAKS 6/1/88
REVISIONS TO NPS RAPID REPORTING SYSTEM
Pages
32
28
5
19
4
17
3
2
5
4
Revisions
3
3
3
3
3
3
3
3
3
3
Date
2/28/90
2/28/90
2/28/90
2/28/90
2/28/90
2/28/90
2/28/90
2/28/90
2/28/90
2/28/90

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                                   DISTRIBUTION UST


EPA Staff                                                                 No. of Copies

EPA Technical Monitor, EPA/TSD                                               5 copies

Clean Harbors Staff

     Laboratory Manager 	                  1 copy
     Richard Ravenelle

     Program Manager  	                  1 copy
     Louis Macri

     Laboratory Coordinator  	                  1 copy
     John Verban

     Sample Prep. Manager  	                  1 copy
     Doug Buffington

     GC Section Manager  	                  1 copy
     John Verban

     GC Analyst  	                  1 copy
     Kate Duffy

     Laboratory QC Coordinator  	                  1 copy
     Christine Johnson

     Clean Harbors QA Director   	                  1 copy
      Richard Fix, Ph.D.

-------
                                                                       Section No. 3
                                                                       Revtolon No. 3
                                                                       Date: February 28, 1990
                                                                       Pag* 1 of 1
3.0   PROJECT DESCRIPTION
      Clean Harbors, Inc. (Clean Harbors) has been contracted by the USEPA Office of Pesticide
Programs and Technical Support Division to provide analytical services in support of the National
Pesticide Survey (NPS).  The NPS has been designed to meet two major objectives: (1) to determine
the degree to which the drinking water wells of the nation are contaminated by pesticides; and (2) to
better understand how pesticide concentrations in drinking water wells are associated with patterns of
pesticide usage and the vulnerability of ground water to pollution.  Clean Harbors will analyze 750
samples from community water systems and 750 samples from domestic wells for the presence of
chlorinated pesticides using gas chromatography with an electron capture detector by  Method 2
(revised Oct. 27, 1987).
      This Quality Assurance Project Plan  (QAPjP) has been prepared to ensure sample analysis and
reporting in accordance with Method 2 and contractual reports of work.

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                                                                       Section No. 4
                                                                       Revision No. 3
                                                                       Date: February 28, 1990
                                                                       Page 1 of 3
4.    PROJECT ORGANIZATION AND RESPONSIBILITIES
      Figure 4-1  represents Clean Harbors's organization chart for this program.  As program
manager, Mr. Louis Maori will be responsible for technical and administrative direction of the overall
program. Mr. John Verban will coordinate and review all sample preparation and gas
chromatographic work.  He will also be responsible for initiation of bench level corrective actions.
      The key individual responsible for QA is the Director of Quality Assurance, Dr. Richard Fix, who
will serve as Program QA Officer.  Dr. Fix reports directly to the President of Clean Harbors.  The key
individual responsible for Analytical QC activities is Christine Johnson, Analytical QC Coordinator, who
reports directly to the QA Director. Ms. Johnson is thus independent of the technical groups
generating measurement data. The responsibilities of these key QA/QC  individuals on this program
are briefly described below.

4.1   QA OFFICER'S RESPONSIBILITIES
      The Division QA Director, Dr. Richard Fix, is the responsible Quality Assurance Officer for this
project.  He will review and approve the proposed Project Plan for this contract.  He will ensure that
any necessary revisions are made and will check on implementation of the QA Plan during the course
of this project, scheduling performance and/or system audits as necessary.  Dr. Fix will initiate and/or
followup on corrective actions. He will aid in preparation of a section of each Monthly Report
summarizing QA/QC activities which include estimates of precision, accuracy, and completeness of
the required data Audits conducted, quality problems identified, and corrective actions taken will be
described.

4.2   ANALYTICAL QC COORDINATOR'S RESPONSIBILITIES
      Ms. Christine Johnson, the Analytical QC Coordinator, oversees and implements the ongoing
QC program. She will be responsible for the implementation of the analytical QC measures specified
in this Plan.  She will review all QC sample results and  incorporate them  in the appropriate monthly
Analytical Results report.  She will have overall responsibility for preparing the QC section of these
reports.

4.3   LABORATORY STAFF RESPONSIBILITIES
      The Program Manager, Louis Macri,  will have responsibility for meeting budget and schedule
commitments, as well as the technical quality of the work. He will also be the Laboratory contact for
the EPA Technical Monitor, Mikki  Bolyard ((513) 569-7939). Working directly with Mr. Macri will be
John Verban Mr. Verban will be responsible for coordinating sample extraction with Mr. Doug
Buffington and analysis by GC. Mr. Verban will also be responsible for primary data review and

-------
                                                                         Section No. 4
                                                                         FtovMon No. 3
                                                                         D«te:  February 28, 1990
                                                                         Page 2 of 3
initiation of bench level corrective action as well as being backup analyst for Ms. Kate Duffy who will
perform the majority of the analysis and data reduction.
      Ms.  Naomi Beck is responsible for sample receipt. The shipping address for samples is:
           Clean Harbors Analytical Services, Inc.
           213 Burlington Road
           Bedford,  Massachusetts  01730


      Ms.  Beck can be reached at  (617) 275-6111.
      Steve Cappello will be acting project coordinator, assuming the responsibilities previously
assigned to John Verban, from March 3, 1990 until the close of the project.

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                                                           Section No. 4
                                                           Revision No. 3
                                                           Date: February 28, 1990
                                                           Page 3 of 3
                               FIGURE 4-1
                    PROGRAM ORGANIZATIONAL CHART
HARBCFS
  ED FTXARI
  PRESIDENT
                                                       SERVICES
  ^A DIRECTOR
31 RIOSVFD
   C3GRDIA1CR
 Z-3US JCWGCN
                                                DIVISICN
                                     RIOAFD RAVEMEXLE
                                     LABCEVMCFY
                                        PROC7AM MWGER
                                          LOJ1S
                                    SMVUEBMK
                                                                       MOB
                                                                       TECHNZQL
                                                                       GOGRSNPOCR
                                                                       JQRI VEFBAN
        3C SECTTCU
            231
             VBRBM4
       — «ATC DUfTY
       — CGUG BUFTOCICN
                                                                              I
                                    SAMPLE PREP.
                                  'DOUG BUfPINbll
                                   — KZLUf

-------
                                                                      Section No. 5
                                                                      Revision No. 3
                                                                      Date: February 28, 1990
                                                                      Pag* 1 of 2
5.    QA OBJECTIVES FOR MEASUREMENT DATA
5.1   DETERMINATION OF ESTIMATED DETECTION LIMIT (EDL)
      A determination will be made of the standard concentration necessary to produce an ECD
response with a 5/1 signal to noise ratio. Two anatyte mixes will then be prepared and used to spike
eight (8) pairs of reagent water samples. These samples will be prepared and analyzed as a batch.
      The standard deviation (SD) will then be calculated using the following equation.

                SD   - /  —   (   E      x - x) 2
     where:     n = the number of measurements for each anatyte
                X = individual measured value in \igJL, and
                x = average measured value in i*g/L
     The minimum detection level (MDL) will then be computed by the following equation:
                            MDL = SD x 3.500 (Student's t value).
     The estimated detection limit (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. The EDLs,
determined in this manner, must be no greater than two times those determined during methods
development, as listed in Appendix A, Table 2.
     The minimum reportable level,  MRL, will be calculated using the following equation:
                                       MRL = 5 x EDL

5.2  DETERMINATION OF GC/MS DETECTION LIMITS
     Six analyses of each analyte mix will be performed by Multiple-ion detection (MID) GC/MS, using
the three ions specified  by EPA (Appendix B).  The results of these analyses will be used to determine
the concentration at which a 5/1 signal to noise ratio, for the least intense of the ions, is obtained.

5.3  CONSTRUCTION OF CONTROL CHARTS
     Control charts will be used to demonstrate  control of the measurement system. Control charts
will be generated upon completion of the initial determination  of reporting limits. To establish the
control charts, 5 reagent water samples for each  of the two analyte mixes will be spiked at ten times
the MRL and carried through the Method 2 extraction and analysis procedure.  An additional 3 sets of
5 spiked reagent water samples will be similarly generated and analyzed on each of 3 days.  The data
from all 20 samples will  be used to construct the  control chart The mean recovery (R) and standard
deviation (SD) will be calculated as follows:

                SD    = /  —   (   Z      R-R)2

-------
                                                                       Section No. 5
                                                                       Revision No. 3
                                                                       Date:  February 28, 1990
                                                                       Page 2 of 2
     where:     R( = the individual recovery value,
                R = average recovery value, and
                n  = the number of measurements.

     ACCEPTANCE CRITERIA FOR ACCURACY AND PRECISION WILL BE THE FOLLOWING:

     •     The RSD for analytes must be less than or equal to 20%, except where data, listed
           in Appendix A, Table 2,  indicates that poorer precision was obtained by Battelle in
           the method validation. Technical monitors will determine action to be taken if
           criteria are not met.

     •     The mean recovery (R) of each analyte must be within R plus or minus 3x SDs as
           determined by Battelle, but no greater than plus or minus 30 percent.

     •     Initial surrogate recovery control will also be demonstrated on 20 samples.
           Surrogate control charts will be generated to provide control limits for surrogate
           recovery in samples.

     •     Warning limits of 2 standard deviations and control limits of 3 standard deviations
           will be depicted on control  charts for both laboratory control standards and
           surrogates.

     Dixon's test will be used to determine a maximum of three outliers per analyte from the 20

spiked reagent waters.  Appendix C provides a discussion of Dixon's test.

     Established control  charts will be updated with spiked samples prepared with sets of spiked

reagent waters when data from 5 spikes are available. Data from the 5 earliest spiked samples will be

deleted, the precision and accuracy recalculated and the control chart redrawn.


5.4  FREQUENCY AND  PROCEDURE FOR MATRIX SPIKING

     During the survey, EPA will provide field samples from 10% of the sites for the laboratory to
assess the recoveries of spiked analytes from a variety of matrices. These samples are to be spiked
at analyte concentrations  equal to 2, 5  or 10 times the MRL for each analyte. The required spiking

level will be specified on the sample label.

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                                                                        Section No. 6
                                                                        Revision No. 3
                                                                        Dote: February 28, 1990
                                                                        Page 1 of 3
6.    SAMPLING PROCEDURES
      All sampling for the National Pesticide Survey will be performed under the direction of ICF.
Clean Harbors will receive 1-liter water samples, preserved with 10 mg/L of mercuric chloride
preservative.  Sample bottles will be shipped, iced, to the Clean Harbors laboratory in Bedford,
Massachusetts for analysis by Method 2.  Clean Harbors will be responsible for notifying the Technical
Monitor if a sample box arrives without any ice remaining.
      ICF will be responsible for the collection of duplicate samples at 10% of the sites for spiking at
Clean Harbors.  All samples will be clearly labelled to differentiate field samples (FS), backup samples
(BU), lab spikes (LS), and time storage samples (T/S). The field label is reproduced in Figure 6-1.  All
samples will be accompanied by a field sample tracking sheet, depicted  in Figure 6-2.

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                                                      Section No 6
                                                      Revisiion No 3
                                                      Date February 28. 1990
                                                      Page 2 of 3
                              FIGURE 6-1
    TONAL PESTICIDE -JUR'.'E'r

        tt:  PC-2226- 1-9-03
JMM  - METHOD** 9   KIT:  Hi
BACKUP SAMPLE
PRESERVATIVE:  H2S04
 DATE  !    TIME   1  SAMPLER
MATTONAL PESTICIDE SURVEY

SAMPLE **:  PC-^22o-l-9-Ol

JMM  - METHOD** v   i-.'IT:  ill
FIELD SAMPLE
PRESERVATIVE:  H2S04
 DATE  !   TIME   !  SAMPLER

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                                                                             Section No. 6
                                                                             Revision No. 3
                                                                             Date: February 28, 1990
                                                                             Page 3 of 3
                                              FIGURE 6-2
                                NPS FIELD SAMPLE TRACKING SHEET
HELL  I.D. HO.:   0000

FRDS  I.D. No.  (CHS HELL ONLY):

SAMPLE COLLECTION DATE: 	/	/

TRACKING FORM COMPLETES BY:
                                                                                      LAB: SSL
                                                                                  SCENARIO: J_

                                                                                  M7 N5.:  PM-000-6U


: ICF
SAMPLE
N'UMBER
; Sj-OOOO-B-i-01
; FD-wOO-b-3-01
I PD-')uOQ-fc-c-01
! PC-WOO-6-i-v3



BOHLE
SHE
1000
1000
60
1000



SAMPLE
DESCRIPTION
FIELD SAMPLE
FIELD SAMPLE
FIELD SAMPLE
BACKUP SAMPLE

TO BE CuVLETEIi fit:
FIELD TEAM , uj
SAMPLER : TIRE . luMENI! ilj .?.£C£iV£i. CCMMENFS
(INITIAL) ! SAMPLE?
: : : . : »:
: : : . . N:
i ' .1
: : . • N;
CHLORINE  TEST:
SHIPPED BY:
3 ATE TIME
SENT TO:
,

,

LAI ADDRESS:
BAY St. LlI.'IJ est'?«Mf3*":.l«TAL
: *ECE:VE:- AT LAB BY:
: :ATE TI-E
' :2K3ITICH {35
:HEHISTR» JM. :.•.:••. :i.-s :
,
NSTL. « r-srs
1
.1) FOR EXAMPLE: S3TT.E BRQCEH, BOTTLE MiSSIafi, OVERFL.E2 JCTTiE. fj» lAi I-^FEJ
;2) F>;» E1ANPLE: iGTTLE BSOXEK, BOTTLE HISSIN6. S3TrL£ :cu:uiu:r3. TE!ffE*ATUP.E CRITERIA NCT rET
. * •. era ctAHBir. »rr »ct rrr. c,n* !r»viuc

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                                                                     Section No. 7
                                                                     Revision No. 3
                                                                     Dote: February 28, 1990
                                                                     Page 1 of 5
7.   SAMPLE CUSTODY
     This section provides information concerning laboratory notification of sample schedule; EPA
requirements for holding times, storage conditions and disposal; Clean Harbors's system for sample
receipt and tracking, and for monitoring refrigerator temperatures where samples are stored.

7.1   NOTIFICATION OF LABORATORY
     ICF will provide a printout of the sample shipment schedule for each upcoming 2-week period.
ICF will also maintain a sample tracking system into which Clean Harbors will enter data concerning
sample receipt.

7.2  HOLDING TIME, STORAGE AND DISPOSAL REQUIREMENTS
     The maximum extraction holding time for field samples is 14 days from sample collection.
Analysis on primary and confirmatory columns must be completed within 14 days after extraction.  The
maximum  holding time for GC/MS extracts may be extended by the Technical Monitor to 28 days.
Data from samples extracted or analyzed outside the holding times shall not be submitted to the EPA,
nor shall compensation be received by the laboratory.
     Extraction and analysis holding times for time storage samples will differ from holding times
required for field samples. Table 7.1 depicts holding time requirements for time storage samples and
extracts.
     All samples and extracts will be stored in the dark at 4 degrees Centigrade.  Refrigerator
temperatures must be verified and recorded on each working day.
     Water samples will be disposed of after the 14-day holding time has been exceeded.  Sample
extracts will be maintained until disposal is approved by the TSD or OPP Laboratory Coordinator.  All
sample containers and boxes will be returned collect to the EPA or ICF.

7.3  CUSTODY PROCEDURES AT THE CLEAN HARBORS LABORATORY
     Clean Harbors, Inc. maintains a Sample Log-in area to implement custody procedures and to
provide proper storage for all samples collected  by, and/or submitted to Clean Harbors.  The log-in
area is located in the laboratory and is staffed by the Sample Log-in Coordinator who reports to the
Program Manager. The Sample Log-in Coordinator accepts custody of all samples received by Clean
Harbors.
     Upon receipt at Clean Harbors, each sample shipment is inspected to assess the condition of
the shipping container and the individual samples. The enclosed custody records are
cross-referenced with all the samples and sample tags in the shipment; the custody records are
signed by the Sample Log-in Coordinator and placed in the project file. The Sample Log-in

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                                                          Section No. 7
                                                          Revision No 3
                                                          Date February 28. 1990
                                                          Page 2 of 5
               TABLE 7.1  HOLDING TIMES FOR TIME STORAGE SAMPLES
PleanHarbors
                      ipiking      Extraction     Analysis    Re-anaiysis
        Sample I.D.    DATE (A)      Date (B)       Date (C)    Date (D)
                                                              (HTE)
        TSo (DTS)      Day 0 to 13    Day A to     Day B to     Day B + 10  to
        Time Storage                 Day A * 4    Day B+A      Day 3*18
        t»0 days

        TSo (DTS)      Day 0 to 13    Day A to     Day B to     Day B  -10  to
        (Time Storage  Dup;           Day A * 4    Day B * 4    Day B  *  18
         t « 0 days)
        TS.  (HTS)     Day 0 to 13    Day A-10  to  Day B to   No re-analysis
        (Time Storage;               Day A «•  18   Day B * 4
         t = 14 days)
        TS.,  (HTS)     Day 0 to 13    Day A+10 to  Day B to  No re-analysis
        (Time Storage Dup;           Day A -  18   Day B * 4
         t * 14 days)
        Note:  Above dates assume collection is  on Day -1 and receipt  at
               the laboratory on Day 0.

-------
                                                                       Section No. 7
                                                                       Revision No. 3
                                                                       Date: February 28, 1990
                                                                       Page 3 of 5
Coordinator continues the custody by assigning a Clean Harbors Control Number to each sample on
receipt; this number identifies the sample through all further handling.
     The physical appearance of the individual sample containers upon arrival at Clean Harbors is
noted by the Coordinator. A sample is  labeled in 'good* condition when the following criteria are met:
     •     Sample identification tags and seals are securely attached and legible, and agree
           with other custody records; and
     •     Samples are iced.
     Each sample is then recorded in the bound Master Sample Log under its Clean Harbors Control
Number.  Each page of the handwritten Master Log has the following format:
     •     Clean Harbors Control Number;
     •     Sample Description;
     •     Sample Condition;
     •     Signature of person completing sample record; and
     •     Date of Sample Receipt.
     Each analyst working with the sample, records in the Master Sample Log their initials thereby
enabling  the tracking of the samples throughout the lab.  Figure 7-1  shows the organic sample prep
record, which is used to track initial sample volume, final extract volume, sample holding times and
other pertinent sample information as listed on the form. When samples are sent to the client or to
another laboratory for analysis,  the External Transfer of Custody Form (Figure 7-2) is used, and the
recipient  of the samples is requested to return a copy of the signed form for the Sample files.
     Clean Harbors, Inc. maintains large, locked, refrigerated, and nonrefrigerated storage areas with
provision for hazardous material storage.  After logging and necessary preservation or subdivision, the
Sample Coordinator stores each sample in the appropriate area under its Clean Harbors Control
Number.

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                                                            Section No. 7
                                                            Revision No. 3
                                                            Date: February 28. 1990
                                                            Page 3 of 4
                               FIGURE 7-1

      NATIONAL PESTICIDE SURVEY ORGANIC SAMPLE PREP RECORD
       :  3-779-
                                                       Citrcction Holding li


                                                                    (imp:
illitnce | |lniti*t | Firwl
Control | Type/ | SOTDle | Eitrvct
»o. | Site •/ | voluv j voluv
| lottle «|(«() | (.i)
1 1 1
1 1 1
1 1 I
1 1 1
1 1 1
t 1 1
1 1 1
1 II
I 1 1
1 1 1
1 1 1
1 1 1
1 1 1
1 1 1
t II
-— 1 1 1
1
10/vot. Soi*i "9
Solution
natrti | turroqcte
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
| Analyst'*
| netceooc
| l*(crfnce
-------
                                             Section No. 7
                                             Revision No. 3
                                             Date: February 28, 1990
                                             Page 4 o< 4
                      FIGURE 7-2

                CHAIN OF CUSTODY RECORD
fleanHarfaor^
Cloon Mareorj AnaMical 213 Btfkngnn M Bootaro MA 01730
Cllont: Project laa»:
laoort To: AOMreaa:
CHAIN Of CUSTOOV PCCOAO
Sameia Cuanoan (SI71 ?75 6111 Page of
Proiact/P.O. *: n.r..



Phona i:
Invoice To: Addreaa:
Oat* Saeelo* Collected:
bv:
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-------
                                                                     Section No. 8
                                                                     Revision No. 3
                                                                     Date:  February 28, 1990
                                                                     Page 1 of 2
8.   CALIBRATION PROCEDURES AND FREQUENCY
8.1  PREPARATION OF SURROGATE AND INTERNAL STANDARDS
     EPA will provide neat reference materials for 4,4'-Dichlorobiphenyl (DCB) for use as a surrogate
standard and Pentachloronitrobenzene (PCNB) for use as an internal standard. Spiking solutions will
be prepared by accurately (+ 0.01 mg) weighing approximately 0.0050 grams of DCB and 0.001
grams of PCNP into two 10.0 ml volumetric flasks and diluting to volume then serially diluting 1:5 with
MTBE.  Acetone will be used as solvent for DCB and MTBE for PCNB. Aqueous samples will be
spiked with 5.0 ul of the DCB solution, prior to extraction. All standards and blank and sample
extracts will be spiked to contain 0.1 ug/mL of PCNB (5.0 ul added to 1 mL of sample).  All stock
solutions will be entered into the Pesticide Stock Solution Logbook and assigned a unique
identification number traceable to the date of preparation, analyst, lot number of the stock used and
volume taken for dilution.

8.2  PREPARATION OF INSTRUMENT QC STANDARD
     EPA will provide ampuls of reference material diluted in MTBE for QC standard preparation.  The
instrument QC standard will be prepared by diluting the four stocks to the following concentrations:
     •     Heptachlor epoxkje  - 0.0040 ug/mL
           DCPA - 0.050 ug/mL
     •     Chlorothatonil - 0.050 ug/mL
           HCH-detta - 0.040 ug/mL
     All stock solutions will be entered into the Pesticide Stock Solution Logbook and assigned a
unique identification number traceable to the date of preparation, analyst, date of receipt of the stock
used and volume taken for dilution.
     An instrument QC standard will be analyzed daily, or with each sample set, whichever is more
frequent.

8.3  PREPARATION OF CALIBRATION STANDARDS AND LCS/TIME STORAGE SPIKING
     SOLUTIONS
     Calibration standards will be prepared from stock solutions provided by EPA in sealed ampuls.
Two intermediate stock solutions will be prepared containing approximately 15 analytes in  MTBE
which do not co-elute on the primary GC column. Five dilutions will then be prepared from these
independent stocks.  The lowest dilution must be prepared at the minimum reporting level (MRL), as
determined in Section 3.
     LCS spiking solutions will also be prepared from stock solutions provided by EPA, The solution
will be prepared in acetone at a concentration which will generate component concentrations at I0x

-------
                                                                        Section No. 8
                                                                        Revteion No. 3
                                                                        Date:  February 28, 1990
                                                                        Page 2 of 2
the MRL when 0.5 to 1.0 ml is added to 1 liter of reagent water. This solution will also be used to
spike time storage samples at 10x the MRL
      All stock solutions will be entered into the QC Standard Stock Solution Logbook and assigned a
unique identification number traceable to the date of preparation, analyst, date of receipt of the stock
used and volume taken for dilution.

8.4   INSTRUMENT CALIBRATION
      8.4.1 GC/ECD Analysis
      Analysis will be performed on a Hewlett-Packard 5890 gas chromatograph, equipped with dual
electron capture detectors and a 7673 automatic  liquid sampler, capable of simultaneous injection
onto primary and confirmatory columns.
      A primary and  confirmatory calibration curve will be generated at a minimum of three
(suggested five)  concentration levels, including the MRL for each analyte.  Qualitative analyses will be
performed for the following compounds,  Endosulfan I, Endosulfan II, Delta-BHC and Chlorobenzilate.
The relative response of each analyte (RRa) to the internal standard will be tabulated using the
equation:
                                         RRa = A/Ais,
      where:     A = the peak area of the analyte, and
                 Ais = the peak area of the internal standard.
The calibration curve will then be generated by plotting the analyte relative response, RRa, versus
analyte concentration in the sample in ug/L
      The working calibration curve will be verified at alternating concentrations every 24 hours during
analysis of NFS samples; occasionally, that concentration will be the MRL  The response for any
analyte must agree with the predicted response within 25%, or a new calibration curve will be
prepared.  Each time new calibration standard dilutions are prepared, they must be compared to the
existing calibration curve, and the observed concentration must agree within 25% of the expected
concentration.

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                                                                        Section No. 9
                                                                        Revision No. 3
                                                                        Date: February 28, 1990
                                                                        Page 1 of 4
9.    ANALYTICAL PROCEDURES
      Samples submitted to Clean Harbors by U.S. EPA from the National Pesticide Survey will be
prepared and analyzed in accordance with the October 27, 1987 version of Method 2 (Appendix A).
No deviations from this procedure will  be made with respect to the following:  reagents (Section 7)
apparatus and equipment (Section 6),  procedure (Sections 11.2 and 12.3) and data reduction (Section
12).  One deviation occurs in glassware cleaning (Section 4.1.1) with the replacement of heating
glassware at 400oC by a terminal acetone rinse.  This procedure has been demonstrated to provide
glassware of a suitable quality at the Clean Harbors laboratory.  Further precautions include the
segregation of glassware for the NPS analysis. The maximum number of samples (including QC) that
will be extracted and analyzed as a set is fifteen (15).
      All samples submitted to Clean Harbors under this  program for analysis via this method, as well
as method blanks, matrix spikes and laboratory control samples, will be preserved with mercuric
chloride, surrogate-spiked with 4,4'-Dichlorobiphenyl (DCB), buffered to pH 7, mixed with 100 g NaCI
and extracted in a 2-liter separatory funnel with methylene chloride.  The methylene chloride extracts
from each of three extractions will be combined, dried over anhydrous sodium sutfate and
concentrated via Kudema-Danish apparatus to approximately 2  mL The extract will then be solvent
exchanged into methyl-t-butyl ether (MTBE) for gas chromatographic analysis.
      The analysis for the compounds listed in Table 9-1  will be performed using a Hewlett-Packard
5890 gas chromatograph, equipped with dual Ni63 electron capture detectors and dual automatic
liquid samplers.  This GC will be interfaced to a Hewlett-Packard 3359 data acquisition system. As
stated in Method 2, separation will be performed using an SPB-5 capillary column for primary analysis
and a DB-1701 for confirmatory  analysis. Table 9.2 provides chromatographic conditions for this
analysis.
      Prior to the injection of program  samples, each gas chromatograph will be calibrated at three to
five concentration levels with the components of interest.  Calibration solutions will also contain the
internal standard, PCNB. Calibration curves will be generated plotting the analyte concentration
versus relative response to the internal standard.  Each sample  extract will also be spiked with internal
standard solution prior to gas chromatographic analysis.  Concentrations of anarytes in the samples
will be determined from the relative response to the internal standard via the calibration curve.  The
analyst will monitor internal standard (IS) area count responses for all sample injections. A deviation
in a sample of greater than 30 percent of the average IS response of the calibration standards
indicates the possibility from method or matrix interferences with internal standard measurement.
      Appendix A, Section 10.6.2 addresses analysis of QC check standards.  This is not required by
the NPS protocol and therefore  not done. Section 10.7.1, referring to spiking of the target anarytes
into ten percent of the samples  was met by the NPS survey design with the LSS samples.

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                                                                        Section No. 9
                                                                        Revieion No. 3
                                                                        Date: February 28, 1990
                                                                        Page 2 of 4
     The automated data entry system was implemented on November 16, 1989. Its application
began with set 126 and continued until the final set.

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                                                  Section No. 9
                                                  Revision No. 3
                                                  Date: Februwy 28,1990
                                                  Page 3 of 4
                        TABLE 9-1

ANALYTES INCLUDED IN GROUND WATER ANALYSIS METHOD 2,
         MIX A AND MIX B WITH MRL AND MDL DATA
A. Mix A
Chlorneb
Propachlor
Alpha-BHC
Gamma-BHC
Chlorthalonil
Aldrin
Heptachlor epoxide
* Endosulfan I
Dieldrin
Endrin
* Endosulfan II
Endrin Aldehyde
p.p'-DDT
Cis-permethrin
B. MixB
Ethridiazole
Trifluralin
Hexachlorobenzene
Beta-BHC
* Delta-BHC
Heptachlor
DCPA
Qamma-Chlordane
Alpha-Chlordane
p,p'-DDE
* Chlorbenzilate
p,p'-DDD
Endosulfan Sulfate
Methoxychlor
Trans-Permethrin
MRL
1.4
1.3
0.12
0.085
0.12
0.12
0.12
0.12
0.12
0.25
0.25
0.25
0.3
1.8
MRL
0.25
0.25
0.12
0.12
0.12
0.12
0.12
0.12
0.12
0.12
0.68
0.25
0.25
0.6
3.9
MDL
0.276
0.261
0.012
0.107
0.017
0.021
0.022
0.019
0.025
0.033
0.029
0.033
0.06
0.36
MDL
0.002
0.005
0.005
0.009
0.005
0.01
0.016
0.007
0.008
0.007
0.136
0.015
0.013
0.111
0.779
   *  Qualitative analysis only.

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                                                              Section No. 9
                                                              Revteion No. 3
                                                              Deto: February 28, 1990
                                                              Page 4 of 4
                                  TABLE 9-2
   INSTRUMENT CONDITIONS FOR ANALYSIS OF GROUND WATER BY METHOD 2
Primary Conditions
      Column:

      Injection volume:
      Carrier gas:
      Injector temp:
      Oven temp:
Confirmation Conditions
      Column:

      Injection volume:
      Carrier gas:
      Injector temp:
      Oven temp:
30 m x 0.25 mm I.D. SPB-5 bonded fused silica column,
0.25 m film thickness (J&W)
2 uL splitless with 45 second delay
He 30 cm/sec linear velocity
250oC
Program from 60<>C to 300«C at 4<>C/min

30 m x 0.25 mm I.D. DB-1701 bonded fused silica column,
0.25 m film thickness (J&W)
2 uL splitless with 45 second delay
He 30 cm/sec linear velocity
250oC
Program from 60oC to 300°C at 4<>c/min

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                                                                        Section No. 10
                                                                        Revision No. 3
                                                                        Date: February 28, 1990
                                                                        Page 1 of 3
10.   DATA REDUCTION, VALIDATION AND REPORTING
      Proper collection and organization of accurate information followed by clear and concise
reporting of the data is a primary goal in all projects. This section describes the procedures routinely
followed at Clean Harbors for data reduction, validation and reporting. All hard copy data of
chromatograms, prep records, etc. will be stored together in the project file.

10.1  DATA REDUCTION
      Analytical results will be reduced to concentration units specified in Method 2, using the
equations given therein.  Actual blank values will be reported; blank corrections will not be applied.

10.2  DATA VALIDATION
      Data validation is the process of filtering data and accepting or rejecting it on the basis of sound
criteria.  Analytical supervisory and QC personnel will use validation methods and criteria appropriate
to the type of data and the purpose of the measurement. Records of all data will be maintained, even
that judged to be an 'outlying* or spurious value.  The persons validating the data will have sufficient
knowledge of the technical work to identify questionable values. All chromatograms will be reviewed
by Clean Harbors's GC Section Head to ensure proper compound identification and as a general
quantitation check.  Furthermore, approximately 25 percent of calculations and data transfer will be
checked during validation. If any errors are found, all calculations or data transfer of that type will be
checked.
      Analytical data will be validated by the laboratory QC coordinator or supervisory personnel using
criteria specified and in this QA Plan.  Clean Harbors routinely uses results from laboratory reagent
blanks, replicate samples and internal QC samples to validate analytical results. Generic criteria used
to evaluate analytical data are listed below:
      •     Use of approved analytical procedures;
      •     Use of property operating and calibrated instrumentation;
           Acceptable results from analyses of Lab Control samples; and
      •     Precision and accuracy meeting QA objectives as stated in the methods and this
           QA Plan.

10.3  FAST TRACK REPORTING
      Since normal reporting requirements allow sample data to be provided 2 months after sample
collection, a mechanism for fast track reporting is necessary. Reports to the Technical Monitor will be
expedited when the following situations arise:
      •     Confirmed positives for a list of analytes to be specified by EPA.

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                                                                       Section No. 10
                                                                       Revision No. 3
                                                                       Date: February 28, 1990
                                                                       Page 2 of 3
     •     Lack of agreement of + 25 percent between results from primary and confirmatory
           analysis by GC/ECO.
     •     Frequent occurrence of a peak or peaks which are not NFS analytes (excluding
           pnthalates), or which are at levels between the EDL and MRL (no quantitation or
           confirmation is performed).
     •     Refer to Rapid Reporting Memo of June 9, 1989 - Appendix J

10.4 DATA REPORTING
     A flow chart depicting the analytical data validation and reporting scheme, routinely used at
Clean Harbors, is shown in Figure 10-1.  Validation occurs at a minimum of two levels. For this
program, the Technical Coordinator, John Verban, will review all QC data as soon as possible.  He will
initiate sample re-extraction if project QC criteria are not met. A second review by the Project
Manager will take place prior to final reporting of the data
     All  data for a set of samples, including QC and  confirmatory data, will be reported by the
laboratory as a complete set.  Data must be provided within 2 months of sample collection.  Data are
to be provided as an ASCII file in the format specified by EPA on floppy disk. Hard copies of all data
will be kept with the project file by set number.

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                                                       Section No. 10
                                                       Revision No. 3
                                                       Date:  February 28, 1990
                                                       Page 3 of 3
                            FIGURE 10-1

CLEAN HARBORS ANALYTICAL DATA VALIDATION AND REPORTING SCHEME
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                                                    ECISSARY
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              •£Ducr:2s.  REPORT ;
                 ALL VALLTS IN   ;
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             2.

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                                                                       Section No. 11
                                                                       Reviaion No. 3
                                                                       Date: February 28, 1990
                                                                       Page 1 of 3
11.   INTERNAL QUALITY CONTROL CHECKS
      Quality control checks will be performed to ensure the generation of valid analytical results on
these samples.  These checks as listed in Table 11.1 will be performed by appropriate personnel
throughout the program under the guidance of the QA Director and the Laboratory QC Coordinator.  A
brief description of each of these elements is provided below.

11.1  METHOD BLANKS
      Method blanks will be preserved with mercuric chloride and contain all the reagents used in the
preparation and analysis of samples.  Method blanks are processed through the entire analytical
scheme to assess spurious contamination arising from reagents, glassware and other materials used
in the analysis.  A method blank is processed with each set of samples extracted. If the  method blank
exhibits a peak for any analyte (on both columns) which is greater than or equal to one-half the MRL,
the source of contamination must be determined and the sample set re-extracted.

11.2  CALIBRATION CHECK SAMPLES
      A working calibration standard at alternating concentrations (occasionally at MRL) which is
repeated every 24 hours to verify the working calibration curve. If the response for any analyte varies
from the predicted response by more than 25%, a new calibration curve must be prepared for that
analyte.

11.3  REPLICATE AND SPIKED SAMPLES
      Additional samples will be collected at 10% of the sample sites for spiking at the laboratory.
These samples are to be spiked at analyte concentrations equal to 2x, 5x, or 10x the MRL (level
specified on sample label).  Samples for replicate analysis will also  be submitted at the required
frequency.

11.4  LABORATORY CONTROL SAMPLES
      A laboratory control sample must be prepared with preservative and analyzed with each set of
samples extracted. For Method 2, this will consist of two reagent water samples, each spiked with
one of the two calibration mixes, independently prepared in acetone.  The concentration  of these
samples will be 10x the MRL
      An 'out of control" situation exists if more than 15 percent of the  LCS analyte recoveries are
outside the control limit (3 standard deviations), or if the same analyte  is outside the control limit twice
in a row.  All analytical work must be stopped until control is re-established.  Re-extraction of  that
set/batch of samples is required.

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                                                                        Section No. 11
                                                                        Revision No. 3
                                                                        Date: February 28, 1990
                                                                        Page 2 of 3
                                          TABLE 11.1

                                  INTERNAL QC CHECKLIST
Is the instrument control standard's signal to noise ratio greater than the limit the method specifies?

Is the instrument control standard's peak symmetry, resolution and geometry factors within the limit
set by the method?

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

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

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

Is the percent recovery of the surrogate in the LCS within the Control Chart limits?

Is the concentration of a blank above half of the MRL?

Is the concentration of a field sample above 1/2 the minimum 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?

Is the percent recovery of each analyte in the lab control standard within the upper and lower control
limits?

Is the percent recovery of each analyte in the lab spike sample within the upper and lower control
limits?

Is the percent recovery of each analyte in the performance evaluation sample within the limits set by
the survey requirements?

Is the internal standard area within + 30% from the average IS response of the calibration standards?

Does the calibration check standard compare within 25% of the Initial calibration curve?

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                                                                        Section No. 11
                                                                        Revision No. 3
                                                                        Date: February 28, 1990
                                                                        Page 3 of 3
11.5  SURROGATE SPIKES
      All samples, blanks and laboratory control standards will be fortified with DCB before extraction.
A surrogate standard determination must be performed on all samples (including matrix spikes) and
blanks.  The acceptance criteria for surrogate standard recoveries are +. 3 sigma for the lab control
samples and ± 30% from the mean as determined from the current control chart for all other sample
types.  Control charts for surrogate recoveries in the LCS will be prepared and updated as detailed in
Section 3.3 When the surrogate recovery for a sample is outside control limits, the laboratory must
establish that the deviation is not due to laboratory problems. The laboratory shall document
deviations by taking the following actions:
      (1)   Checking calculations to make sure there are no errors.
      (2)   Checking internal standard and surrogate standard spiking solutions for
           degradation, contamination, or other obvious abnormalities.
      (3)   Checking instrument performance.
Recalculation or reanalysis of the sample or extract will be performed 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 the sample data from the analysis with surrogate spike recoveries within the required
limits will be submitted. If reanalysis of the sample extract fails to solve the problem, then both sets of
data for that sample will be reported.
      If the surrogate recovery for an LCS is outside the control limits, then the analyst must evaluate
the sample set for blank surrogate recovery and LCS analyte recovery. The sample set/batch  must be
re-analyzed only if the blank surrogate recovery or the LCS analyte recoveries do not meet
acceptance criteria
      If the surrogate recovery for a method blank is outside the control limits, then the analyst must
check the sample set/batch for a sample free from analyte positives (i.e. a blank).  If the surrogate
recovery from that sample meets criteria, then analysis of the set can proceed.

11.6  INTERNAL STANDARD CHECKS
      Internal standard areas will be evaluated for acceptance by determining whether the measured
peak area or height in any sample deviates by more than 30% from the average for the internal
standard in the calibration standards. Corrective  action for internal standard area count deviations is
detailed in Appendix A, Section 10.5.3.

11.7 INSTRUMENT QUALITY CONTROL STANDARDS
      Instrument QC standards will be evaluated according to Table  10 in  Appendix A for detection,
peak symmetry, resolution and peak Gaussian factor using the calculations provided with the table.
Analysis will not be performed if criteria are not met

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                                                                       Section No. 12
                                                                       RwWonNo. 3
                                                                       Date:  February 28,1990
                                                                       Pago 1 of 1
12.   PERFORMANCE, SYSTEM AND DATA AUDITS
12.1  DATA AUDITS
      Ongoing data audits will be provided by the project coordinator, project manager or Laboratory
QC Coordinator. These audits will consist of a verification of 25% of the calculations generated under
this program and of all positive identifications.

12.2  SYSTEMS AUDITS
      A system audit is a qualitative review to ensure that the quality measures and the analytical
procedures outlined in the QA Project Plan are in place and being followed. Clean Harbors's QA
Director selects projects representing different types of measurement activities for audit by the QA
staff.  System audits of analytical work on this program will be scheduled in accordance with the
volume and diversity of the samples received, and the severity and number of problems uncovered in
early system audits but at a minimum will be held quarterly. Written summary reports for each audit
will be submitted as noted in Section 14.0.

12.3  EXTERNAL AUDITS
      Clean Harbors will cooperate fully in any performance or system audits conducted or arranged
by EPA. The Project Manager, QA Director and QC Coordinator are available to aid in scheduling
such audits.

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                                                                    Section No. 13
                                                                    Revtoion No. 3
                                                                    Date: February 28, 1990
                                                                    Page 1 of 1
13.  PREVENTIVE MAINTENANCE

     Clean Harbors follows an orderly program of positive actions to prevent the failure of equipment

of instruments during use. In the analytical laboratories, preventive maintenance includes attention to

glassware, water supply, reagents and analytical balances as well as more complex instrumentation.

Table 13-1 summarizes the preventive maintenance procedures for the instruments to be used in this

project.  Also listed in the table are the spare parts normally kept in inventory to minimize instrument

down time.

                                       TABLE 13-1

       MAINTENANCE PROCEDURES AND SCHEDULE FOR MAJOR INSTRUMENTATION
  Instrument
Maintenance Procedure/Schedule
Spare Parts
  Gas Chromatograph
  (HP5890)
1.  Change septa daily.
2.  Check syringe for burrs daily.
3.  Change gas line dryers quarterly.
4.  Leak check when  installing new analytical
   column.
5.  Periodically check inlet system for residue build-
   up.
1. Syringes
2. Septa
3. Columns
  Gas Chromatographs/
  Mass Spectrometers
  (Hewlett Packard 5970)
1.  Replace pump oil annually.
2.  Change septa daily.
3.  Change gas line dryers quarterly.
4.  Replace Electron Multiplier as needed.
1. Syringes
2. Septa
3. Column

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                                                                       Section No 14
                                                                       Revision No 3
                                                                       Date  February 28  1990
                                                                       Page 1 of 1
14.   SPECIFIC PROCEDURES FOR ASSESSING MEASUREMENT SYSTEM DATA
      Compare the percent recovery (Ri) for each analyte with established QC acceptance criteria.
QC criteria are established by initially analyzing twenty (20) laboratory control standards and
calculating the average percent recovery (R) and the standard deviation of the percent recovery (SD)
using the following equations:	
                            T—     n
                 SD      /   —    (I,       R, - R )
                            n-1     1 = 1

      where:      n  = the number of measurements for each analyte,
                 R( = individual percent recovery, and
                 R =  average percent recovery.
The QC acceptance criteria is calculated as follows:
      Upper Control Limit (UCL)  = R + 3SD
      Lower Control Limit (LCL) = R - 3SD
      Upper Warning Limit (UWL) = R + 2SD
      Lower Warning Limit (LWL) =  R - 2SD
      The data generated during the initial demonstration of capability (3.3) will be used to set the
initial  upper and lower control and warning limits.
      The performance criteria will be updated on a continuous basis. After each five new recovery
measurements,  R  and RSD will be recalculated using all the data, and new control charts
reconstructed, deleting the five earliest values. Qixon's Test (Appendix C) will be applied where
appropriate. Spiked samples will be corrected for concentrations of analytes native to that sample if
the analyte is present at > 1/2 the MRL
      The instrument QC standard will be assessed using the calculations provided in Table 10
(Appendix A). Accuracy will be estimated from the analysis of laboratory control samples,  and will be
expressed as percent recovery. The formula used to calculate percent recovery is as follows:

                                                 measured value
           Percent Recovery      =    100 x      	
                                                    true value

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                                                                        Section No. 15
                                                                        Revtoion No. 3
                                                                        Date: Februwy 28, 1990
                                                                        Page 1 of 4
15.   CORRECTIVE ACTION
      The acceptance limits for the analyses to be conducted in this program will be generated as
stated in Section 3.  The corrective actions are likely to be immediate in nature and most often will be
implemented by the analyst or technical coordinator. The corrective action will usually involve
recalculation, or reanalyses.  Clean Harbors' ongoing corrective action policy is described here.

15.1  IMMEDIATE CORRECTIVE ACTION
      Specific QC procedures are designed to help analysts detect the need for corrective action.
Often the person's experience will be more valuable in alerting the analyst to suspicious data or
malfunctioning equipment. Instrument and equipment maffunctions  are amenable to immediate
corrective action.  The actions taken should be noted in laboratory notebooks, but no other formal
documentation  is required, unless further corrective action is necessary.  These on-the-spot corrective
actions are an everyday part of the QA/QC system. An example of bench level corrective action is
provided in Figure 13-1. This reextraction request will usually be initiated by the Technical
Coordinator. Additional corrective actions will be noted in instrument maintenance log books and
analysts' notebooks. These data will be filed in the project file to facilitate monthly reports about
bench-level problems to the EPA Technical Monitor that include the date, problem, action taken,
verification that  the problem was solved, and identification of the sample sets analyzed just prior to
and immediately following the corrective action.
      If a corrective action can be taken at this point, as part of normal operating procedures, the
collection of poor quality data can be avoided. If a problem is not solved in this way, more formalized
long-term corrective action may be necessary.

15.2  LONG-TERM  CORRECTIVE ACTION
      The need for this action may be identified by standard QC procedures, control charts,
performance or system audits. Any quality problem which cannot be solved by immediate corrective
action falls into  the long-term category. Appropriate corrective actions may be similar in nature to
immediate corrective action;  i.e., collecting a new set of samples or reanalyzing samples, but the
correction may  proceed more slowly. Clean Harbors uses a system to ensure that the condition is
reported to a person responsible for correcting it who is part of the closed-loop action and follow-up
plan.  The essential steps in the closed-loop corrective action system are:
            Identify and define the problem.
      •      Assign responsibility for investigating the problem.
      •      Investigate and determine the cause  of the problem.
      •      Determine a corrective action to eliminate the problem.

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                                                                      Section No. 15
                                                                      Revision No. 3
                                                                      Date: February 28, 1990
                                                                      Page 2 of 4
                                        FIGURE 15-1

                               NATIONAL PESTICIDE SURVEY

                               Sample Re-extraction Worksheet
Date of Request:  	     Requested by:

Charge Number:  3-729-	
     The following samples require re-extraction and analysis:
Clean Harbor Control Number      Sample Identification   Problem Code   Holding Time Expiration
     A    LC sample recovery outside control limits.
     B    Sample surrogate recovery outside control limits.
     C    Method blank surrogate recovery outside control limit
     0    Method blank contamination at 50% of EDL
     E    Matrix spike recovery outside control limits.

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                                                                         Section No. 15
                                                                         Revision No. 3
                                                                         Date:  February 28, 1990
                                                                         Page 3 of 4
      •     Assign and accept responsibility for implementing the corrective action.
      •     Establish effectiveness of the corrective action and implement it.
      •     Verify that the corrective action has eliminated the problem.
      Documentation of the problem is important to the system. A Corrective Action Request Form
(shown in Figure 15-2) is filled out by the person finding the quality problem.  This form identifies the
problem, possible causes and the person responsible for action on the problem.  The responsible
person may be an analyst, field team leader, QC Coordinator or the QA Director.  If no person is
identified as responsible for action, the QA Director investigates the situation and determines who is
responsible in each case.
      The Corrective Action Request Form includes a description of the corrective action planned and
the date ft was taken, and space for follow-up. The QA Director checks to be sure that initial action
has been taken and appears effective and, at an appropriate later date, checks again to see if the
problem has been fully solved. The QA Director receives a copy of all Corrective Action Forms and
then enters them in the Corrective Action Log. This permanent record aids the QA Director in
follow-up and makes any quality  problems visible to management; the log may also prove valuable in
listing a similar problem and its solution.

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                                                                     Section No. 15
                                                                     Revision No. 3
                                                                     Date:  February 28, 1990
                                                                     Page 4 of 4
                                       FIGURE 15-2
                           CORRECTIVE ACTION REQUEST FORM

                             Corrective Action Request Form No.	
Originator	Date  	
Person Responsible for Replying	     Contract Involved
Description of problem and when identified:
State cause of problem, if known or suspected:
Sequence of Corrective Action:  (If no responsible person is identified, bring this form directly to QA
Director.)
State Date, Person, and Action Planned:
CA Initially Approved By:  	     Date:
Follow-up Dates:

Final CA Approval By:  	     Date:
Information copies to:
RESPONSIBLE PERSON:  	
QA DIRECTOR:	

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                                                                       Section No. 16
                                                                       Revtolon No. 3
                                                                       Date: February 28,1990
                                                                       Page 1 of 1
16.   QA REPORTS
16.1  INTERNAL REPORTS
      The QC Coordinator will prepare written monthly reports on QC activities for the Laboratory
Manager and the QA Director. These reports detail the results of quality control procedures, problems
encountered, and any corrective action which may have been required. As these reports pertain to
this project, they will be made available to the Program Manager and QA Officer.
      All Corrective Action Forms are submitted to the QA Officer for initial approval of the corrective
action planned and a copy is provided to the Program Manager. All system audit reports are provided
to the Program Manager and may be presented to the Clean Harbors President.

16.2  EXTERNAL REPORTS
      Six copies of the monthly report will be provided within 15 (calendar) days after the end of the
period being reported. The copies will be sent to the appropriate EPA Technical Monitor.
      A copy of the cover letter which transmits the monthly report will be forwarded to Mona S.
Snyder, Contract Specialist for the NPS, EPA-CMD, Cincinnati, OH 45268.
      The report format will  contain the following information for the report period:
      •     Summary of progress
                 samples received, analyzed, in progress
           -     status of data processing for analyzed sets of samples
      •     Reports on standards
           -     new dilutions and results of check before using
      •     Summary list of bench-level corrective action
      •     Identification of  problems about any phase of the project
      •     Copies of representative and, if applicable, unusual chromatograms.
      •     Information requested by the Technical Monitor because of specific methodology or
           problems encountered
      •     Changes in personnel
      •     Any other comments.

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                                                                      Section No. 17
                                                                      Ftevtoion No. 3
                                                                      Date: February 28, 1990
                                                                      Pag« 1 of 1
17.  ARCHIVAL OF RAW DATA
NPS ARCHIVAL PROCESS

     1.    The NPS data sets will be stored at the Clean Harbors of Bedford facility at 213
           Burlington Road, Bedford, MA  01730 for a period of one year from the closeout
           audit date of August 30,1990.  After one year the data will be transferred to Clean
           Harbors' warehouse at 10 Mercer Road, Natick, MA 01760. The data will remain at
           this site for a period of seven years from the closeout audit date of August 30,  1990.
           Laurian Carroll, Documents Manager for Clean Harbors, is responsible for all data
           stored in the warehouse. After the seven year period, the data will be disposed of
           unless otherwise requested by the EPA.

     2.    Each data set consists of the following:
           2.1   Copy  of the formattable
           2.2   Copy  of the ICDS
           2.3   Copy  of Clean Harbors' Chain of Custody
           2.4   Copy  of GC injection  log run sheet
           2.5   Copy  of extraction log sheet
           2.6   Copy  of drying and concentrating log sheet
           2.7   Internal Standard summary
           2.8   Continuing Calibration
           2.9   Standard curve data including retention time window data
           2.10 Raw areas, concentrations, and percent recoveries for samples
           2.11  Flag data for determining outliers
           2.12 Internal Quality Control Check
           2.13 GC chromatograms for standards and samples
           2.14 Hand  calculations and notes on set

     3.    The following information is archived in labeled boxes and will follow the same
           storage procedures as the data sets.
           3.1   Initial demonstration of capability
           3.2   Index  for EPA well ID  number versus Clean Harbors' set number
           3.3   Data sets 1 through 153
           3.4   Copies of standard logbook pages
           3.5   Copies of refrigerator logbook pages
           3.6   Sample tracking forms
           3.7   In-house audits
           3.8   Corrective action forms
           3.9   Monthly reports
           3.10 Copies of instrument maintenance logbook pages
           3.11  Standard Operating Procedure for NPS
           3.12 Control Charts for Quality Control Limit
           3.13 Statement of Qualification and copies of resume's for employees involved in NPS
           3.14 Correspondence
           3.15 Standard comparisons
           3.16 NPS check lists for each set
           3.17 NPS sample analysis tracking logbook
           3.18 QA Plan for NPS

     4.    To access data by EPA well number, the Clean Harbors identification number and
           data set that the number is  grouped in must be determined. The index found in first
           data set box can be used to determine the set number for any corresponding EPA
           well number. The appropriate set should be obtained and the necessary
           information for the sample can be acquired.

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                                                                      Appendix A
                                                                      Revteion No. 3
                                                                      Date:  February 28, 1990
                                                                      Page 1 of 32
                                        APPENDIX A

               METHOD 2. DETERMINATION OF CHLORINATED PESTICIDES IN
  GROUND WATER BY GAS CHROMATOGRAPHY WITH AN ELECTRON CAPTURE DETECTOR


1.    SCOPE AND APPLICATION

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

     1.2    This method has been validated in a single  laboratory.  Estimated detection limits (EDL's)
            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.

     1.3    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.

2.    SUMMARY OF METHOD

     2.1    A measured volume of sample of approximately  1L is solvent extracted with methylene
            chloride by mechanical shaking in a separatory funnel or mechanical tumbling in a bottle.
            The methylene chloride extract is isolated, dried and concentrated to a volume of 5 mi-
            after solvent substitution with methyl tertbutyl ether (MTBE). Chromatographic conditions
            are described  which permit the separation and measurement of the analytes in the
            extract by GC  with an electron capture detector  (ECD).

     2.2    An alternative  manual liquid-liquid extraction method using separatory funnels is also
            described.

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.

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

     3.3    Estimated detection limit (EDL) - the minimum concentration of a substance that can be
            measured and reported with confidence that the anaryte concentration is  greater than
            zero as determined from the analysis of a sample in a given matrix containing the
            analyte. The EDL is equal to the level calculated by multiplying the standard deviation of
            replicate measurements times the student's 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 is higher.

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                                                                       Appendix A
                                                                       Revision No. 3
                                                                       Date:  February 28,1990
                                                                       Page 2 of 32
     3.4    Instrument quality control (QC) standard - a MBTE 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.

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

     3.6    Laboratory control (LC) standard - a solution of analytes prepared in the laboratory by
            dissolving known amounts of pure anaiytes 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 - a portion of reagent water analyzed as if it were a sampJe.

     3.8    Performance evaluation sample - a water-soluble solution of method analytes distributed
            by the Quality Assurance Branch, Environmental Monitoring and Support Laboratory,
            USEPA, Cincinnati,  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.  AnaJyte 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 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 - a 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.

     3.11   Surrogate standard - a pure 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 interference may be caused by contaminants in solvents, reagents, glassware
            and other sample processing apparatus that lead to discrete artifacts or elevated
            baselines in gas chromatograms.  All reagents and apparatus must be routinely
            demonstrated to be free from 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 deaned.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 tap and reagent water.
                 Drain, dry, and heat in an oven or muffle furnace at 400oC for 1 hour. Do not heat
                 volumetric ware.  Thermally stable materials such as PCB's might not be eliminated
                 by this treatment  Thorough rinsing with acetone may be substituted for the

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                                                                       Appendix A
                                                                       Revision No. 3
                                                                       Date: February 28,1990
                                                                       Page 3 of 32
                 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    Interference by phthalate esters can pose a major problem in pesticide analysis when
            using the electron capture detector. These compounds generally appear in the
            chromatograms  as large peaks.  Common flexible plastics contain varying amounts of
            phthalates that are easily extracted or leached during laboratory operations. Cross
            contamination of clean glassware routinely occurs when plastics are handled during
            extraction steps, especially when solvent-wetted surfaces are handled.  Interference 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.3,4

     4.3    Interfering contamination may 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 MBTE can minimize sample cross contamination. After
            analysis of a sample containing high concentrations of analytes, one or more injections of
            MBTE should be made to ensure that accurate values are obtained for the next sample.

     4.4    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.  Cleanup of sample extracts may be
            necessary.  Positive identifications must 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 5-7 for
            the information of  the analyst.

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 methanot overnight prior to
                 use.

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                                                                  Appendix A
                                                                  Revision No. 3
                                                                  Data:  February 28, 1990
                                                                  Page 4 of 32
6.2   GLASSWARE

      6.2.1  Separatory funnel - 2000 ml_ with TFE-fluorocarbon stopcock, ground glass or
            TFE-fluorocarbon stopper.

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

      6.2.3  Flask, Erlenmeyer - 500-mL

      6.2.4  Concentrator tube,  Kudema-Danish (K-D) - 10- or 25-mL, graduated (Kontes
            K-570050-1025 or K-570050-2525 or equivalent). Calibration must be checked at
            the volumes  employed in the test. Ground glass stoppers are used to prevent
            evaporation of extracts.

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

      6.2.6  Snyder column, K-D - three ball micro (Kontes K-503000-0121 or equivalent).

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

      6.2.8  Vials - Glass, 5- to 10-mL capacity with TFE-fluorocarbon lined screw cap.

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

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

6.5   Boiling stones - carborandum, #12 granules (Arthur H. Thomas Co.  #1590-033).  Heat
      at 400oC for 30 min prior to use.  Cool and store in a desiccator.

6.6   Water bath - Heated, capable of temperature control (+2<>C).  The bath should be used
      in a hood.

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

6.8   Gas Chromatograph - Analytical system complete with GC suitable for use with capillary
      columns and all required accessories including syringes, analytical columns, gases,
      detector and stripcnart recorder.  A data system is recommended for measuring peak
      areas.

      6.8.1  Primary column - 30 m long x 0.25 mm I.D.  DB-5 bonded fused silica column, 0.25
            um film thickness (available from J&W). Validation data presented in this method
            were obtained using this column.  Alternative columns may be used in accordance
            with the provisions described in Section 10.3.

      6.8.2  Confirmation column - 30 m long x 0.25  mm I.D. DB-1701 bonded fused silica
            column, 0.25 um film thickness (Available from J&W).

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                                                                       Appendix A
                                                                       Revision No. 3
                                                                       Data: February 28, 1990
                                                                       Page 5 of 32
            6.8.3 Detector - Electron capture.  This detector has proven effective in the analysis of
                 spiked reagent and artificial 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, methylene chloride,  MTBE - Distilled-in-glass quality or equivalent.

     7.2    Phosphate buffer, pH7 - Prepare by mixing 29.6  ml 0.1 N HC1 and 50 mL 0.1 M
            dipotassium phosphate.

     7.3    Sodium sulfate, granular, anhydrous, ACS grade  - Heat treat in a shallow tray at 450<>C
            for a minimum of 4  hours to remove interfering organic substances.

     7.4    Sodium chloride, crystal, ACS grade - Heat treat in a shallow tray at 450oC for a
            minimum of 4 hours to remove interfering organic substances.

     7.5    Pentachloronitrobenzene (PCNB) - >98% purity,  for use as internal standard.

     7.6    4,4'-Dichlorobiphenyl (DCB) - 96% purity, for use as surrogate standard (available from
            Chemicals Procurement, Inc.).

     7.7    Reagent Water - Reagent water is defined as water in which an interferant 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.

     7.8    STOCK STANDARD SOLUTIONS (1.00 ug/uL)  - Stock standard solutions may be
            purchased as certified solutions or prepared from pure standards materials using the
            following procedure

            7.8.1 Prepare stock standard solutions by accurately weighing  approximately 0.0100 g of
                 pure material.  Dissolve the material in MTBE and dilute to volume in a 10-mL
                 volume in a 10-mL volumetric flask.  Larger volumes may be used at the
                 convenience 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.

            7.8.2 Transfer the stock standard solutions....

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

      7.9    INTERNAL STANDARD SPIKING SOLUTION - Prepare an internal standard spiking
            solution by accurately weighing approximately 0.0010 g of pure PCNB.  Dissolve the
            PCNB 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 5 uL of the internal spiking solution to 5 mL of sample
            extract results in a final internal standard concentration of 0.1 ug/mL Solution should be
            replaced when ongoing QC (Section 10) indicates a problem.

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                                                                      Appendix A
                                                                      Revision No. 3
                                                                      Date: February 28, 1990
                                                                      Page 6 of 32
     7.10  SURROGATE STANDARD SPIKING SOLUTION - Prepare a surrogate standard spiking
           solution by accurately weighing approximately 0.0050 g of pure DCS. Dissolve the DCB
           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
           25 ug/L and, assuming quantitative recovery of TDBP, a surrogate standard
           concentration in the final extract of 5.0 ug/mL Solution should be replaced when
           ongoing QC (Section 10) indicates a problem.

     7.11  INSTRUMENT QC STANDARD - Prepare instrument QC standard stock solutions by
           accurately weighing 0.0010 g each of chlorothalonil, heptachtor epoxide, DCPA, and
           HCH-delta  Dissolve each analyte in MTBE and dilute to volume in individual 10-mL
           volumetric flasks.  Combine 2 uL of the heptachfor epoxide stock solution, 50 uL of the
           DCPA stock solution, 50 uL of the chlorothalonil stock solution, and 40 uL of the
           HCH-delta stock solution to a 100-mL volumetric flask and dilute to volume with MTBE.
           Transfer the instrument QC standard solution 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. Conventional sampling practices
           should be followed;  however, the bottle must not be prerinsed with sample before
           collection.

     8.2   SAMPLE PRESERVATION

           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 reagent water
                 to the sample bottle at the sampling site or in the laboratory before shipping to the
                 sampling site.  A major disadvantage 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.

           8.2.2 After adding the sample to the bottle containing preservative, seal the sample bottle
                 and shake vigorously for one minute.

           8.2.3 Samples must be iced or refrigerated at 4«C from the time of collection until
                 extraction.  Preservation study results presented in Table 11 indicate that most of
                 the target analytes present in the samples are stable for 14  days when stored
                 under these conditions. However, analyte stability may be affected by the matrix;
                 therefore, the analyst should verify that the preservation technique is applicable to
                 the samples under study.

     8.3   EXTRACT STORAGE

           8.3.1  Sample extracts should be stored at 4oC away from the light  A 14-day maximum
                 extract storage time is recommended. The analyst should verify appropriate extract
                 holding times applicable to the samples under study.

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                                                                       Appendix A
                                                                       Revision No. 3
                                                                       Date: February 28, 1990
                                                                       Page 7 of 32
9.    CALIBRATION

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

      9.2    INTERNAL STANDARD CALIBRATING PROCEDURE - To use this approach, the analyst
            must select one or more internal standards compatible 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 interferences.  PCNB has been
            identified as a suitable internal standard.

            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
                 standards to a volumetric flask.  To each calibration standard, add a know constant
                 amount of one or more internal standard, and dilute to volume with MTBE. 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: RRa = Aa/Ais where:
                 Aa = the peak area of the analyte, and Ais = the peak  area of the internal
                 standard Generate a calibration curve of analyte relative response, RRa, 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 calibration standards. If the response for any analyte
                 varies from the predicted response by more than 25%, the test must be repeated
                 using a fresh calibration standard. Alternatively,  a new calibration curve must be
                 prepared for that analyte.

10.   QUALITY CONTROL

      10.1   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 preparation; 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 EDL) for
                       each of the target anafytes. 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.

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                                                                  Appendix A
                                                                  FtovMon No. 3
                                                                  Date: February 28, 1990
                                                                  Page 8 of 32
      10.2.2     Using a syringe, add 1 mL of the LC sample concentrate to each of a
                 minimum of 4 1-L aliquots of reagent water. A representative groundwater
                 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.

      10.2.3     Calculate the average percent recovery (R) and the standard deviation of
                 percent recovery (RSD), for the  results. Ground water background
                 corrections must be made before R and RSD 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 + 30% whichever  is greater.

10.3  In recognition of the rapid advances occurring in chromatography, the analyst is
      permitted to modify GC columns, GC conditions, or detectors to improve the  separations
      or lower the cost of measurements.  Each time such modifications to the method are
      made, the analyst is required to repeat the procedure in 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 of the mean  from the
                 control charts.

      10.4.3     When the surrogate recovery for a  laboratory method blank is less than 70 or
                 greater than 130 percent of the  mean from the control charts, 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 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 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 from the mean, 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

-------
                                                                    Appendix A
                                                                    Revteion No. 3
                                                                    Date: February 28, 1990
                                                                    Page 9 of 32
                  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
                  recover is 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 that internal standard in
                  any sample deviates by more than 30 percent from average  peak area or
                  height for the internal  standard in the calibration standards.

      10.5.3      When the internal standard peak area or height for any samples 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 insure
                             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 height for the internal
                             standard, assume an error was made during addition of the
                             internal standard to the failed sample extract. Remove an another
                             aliquot of the sample extract  and re-spike internal standard
                             solution. Repeat sample analysis.

                  10.5.3.2   Multiple Occurrence - If the internal standard peak areas or
                             heights for successive samples fail the specified criteria (10.5.2),
                             check the instrument for proper performance.  After optimizing
                             instrument performance, check the calibration curve using a
                             calibration  check standard (Section 9).  If the calibration curve is
                             still applicable and if the calibration check standard internal
                             standard peak area or height is within 25 percent 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) spike a fresh sample aliquot with the internal standard solution
                             for those extracts whose internal standard failed the peak area or
                             height criteria

-------
                                                                   Appendix A
                                                                   Revision No. 3
                                                                   Date:  February 28, 1990
                                                                   Page 10 of 32
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 15 times the EDL

                  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
                            (Ri as (100xA)%/T, where T is the known true concentration of the
                            spike.

                  10.6.1.3   Compare the percent recovery (Ri) for each analyte with
                            established QC criteria  QC criteria are established by initially
                            analyzing five laboratory control standards and calculating the
                            average percent recovery (R) and the standard deviation of the
                            percent recovery (SR) using the following equations:

                                             n
                                 R    =          Ri/n
                            andSR =

                            where:     n = number of measurements for each analyte, and
                                       Ri = individual percent recovery value.

                            Calculate QC acceptance criteria as follows:

                                  Upper Control Limit (UCL) = R + 3SR
                                  Lower Control Limit (LCL) =  R - 3SR

                            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
                            continuous 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 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 must be immediately identified and resolved before
                            continuing the analyses. The analytical 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

-------
                                                                 Appendix A
                                                                 Revision No. 3
                                                                 Dote: February 28, 1990
                                                                 Page 11 of 32
      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
                 Protection Agency (USEPA)  and provided with 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  limits established  by USEPA.

10.7  ASSESSING ANALYTE 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 concentration, or, if it is impractical to
                           determine background levels before spiking, 15 times the EOL

                 10.7.1.2   Analyze one sample aliquot to determine the background
                           concentration (B) of each analyte.  Spike a second sample aliquot
                           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 the
                           determine the concentration after spiking (A) of each analyte.
                           Calculate each percent recovery (Ri) as 100(A-B)%/T, where T is
                           the known true concentration of the spike.

                 10.7.1.3   Compare the percent recovery (Ri) for each analyte with QC
                           acceptance criteria established from the analyses of laboratory
                           control standards.  Monitor all data from closed 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 laboratory performance for that analyte is judged
                           to be in control, the recovery problem encountered 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 \jser 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 a 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 a 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 contamination
      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 the analysis of the instrument QC
      standard. The instrument QC standard contains compounds designed to indicate
      appropriate instrument sensitivity, column performance and chromatographic

-------
                                                                      Appendix A
                                                                      BevWonNo. 3
                                                                      D«te:  February 28, 1990
                                                                      P«g« 12 of 32
            performance.  Instrument QC standard components and performance criteria are listed in
            Table 10. Inability to demonstrate acceptable instrument performance indicates the need
            for re-evaluation of the GC-ECD 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 EDL's published in this method.  If the laboratory
            EDL's differ from those listed in this method, concentrations of the instrument QC
            standard compounds must be adjusted to be compatible with the laboratory EDL's. 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 EXTRACTION METHOD - Validation data  presented in this method were
            generated using the automated extraction procedure with the mechanical separator/
            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 uL of the surrogate
                      standard spiking solution.  If the mechanical separatory funnel shaker is
                      used, pour the entire sample into a 2-L separatory funnel.  If the mechanical
                      tumbler is used, pour the entire sample into a tumbler bottle.

            11.1.2     Adjust the sample to pH 7 by adding 50 mL of phosphate buffer.

            11.1.3     Add 100 g NaCI to the sample, seal, and shake to dissolve salt.

            11.1.4     Add 300 mL methylene chloride to the sample bottle, seal,  and shake 30
                      seconds to rinse the inner walls. Transfer the solvent to the sample
                      contained in the separatory funnel or tumbler bottle, seal, and shake for 10
                      seconds, venting periodically.  Repeat shaking and venting until pressure
                      release is not observed during venting. Reseal and place sample container
                      in appropriate mechanical  mixing device (separatory funnel shaker or
                      tumbler). Shake or tumble the sample for 1 hour. Complete and thorough
                      mixing of the organic and aqueous phases should be observed at least 2
                      minutes 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 minutes.
                      If the emulsion interface between labels layers is more than one third the
                      volume of the solvent layer, the analysts 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. Collect the methylene chloride

-------
                                                                 Appendix A
                                                                 Revision No. 3
                                                                 Date: February 28, 1990
                                                                 Page 13 of 32
                 extract in a 500-mL Ertenmeyer flask containing approximately 5 g anhydrous
                 sodium sulfate.  Swirl flask to dry extract; allow flask to sit for 15 minutes.

      11.1.6     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 5mL

11.2  MANUAL 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. Spike the sample with 50 uL of the
                 surrogate standard spiking solution. Pour the sample the entire sample into
                 a 2-L separator/ funnel.

      11.2.2     Adjust sample to pH 7 by adding 50 mL of phosphate buffer.

      11.2.3     Add 100 g NaCI to the sample, seal, and shake to dissolve salt.

      11.2.4     Add 60 ml methylene chloride to the sample bottle, seal, and  shake 30
                 seconds to rinse the inner walls. Transfer the solvent to the separatory
                 funnel and extract the sample by vigorously shaking the funnel for 2 minutes
                 with periodic venting to release excess pressure.  Allow the organic layer to
                 separate from the water phase for a minimum of 10 minutes.  If the emulsion
                 interface between the 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.  Collect the methylene chloride extract in a 500-mL Erienmeyer
                 flask containing approximately 5 g anhydrous sodium sulfate.

      11.2.5     Add a second 60-mL volume of methylene chloride to the sample bottle and
                 repeat the extraction procedure a second time, combining the extracts in the
                 Erienmeyer flask.  Perform a third extraction in the same manner. Swirl flask
                 to dry extract; allow flask to sit for 15 minutes.

      11.2.6     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-D concentrator by attaching a 25-mL concentrator tube a
                 500-mL evaporative flask. Decant methylene chloride extract into K-D
                 concentrator. Rinse remaining sodium sulfate with two 25-mL portions of
                 methylene chloride and decant rinses  into the K-D concentrator.

      11.3.2     Add 1 to 2 dean boiling  stones to the evaporative flask and attach a macro
                 Snyder column.  Preset the Snyder column by adding about 1 mL methylene
                 chloride to the top. Place the K-D apparatus on a hot water bath, 65 to 70oC,
                 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. Adjust the
                 vertical position of the apparatus and the water temperature as required to
                 complete the concentration in 15 to 20 minutes. At the proper rate of

-------
                                                                      Appendix A
                                                                      Revision No. 3
                                                                      Date: February 28, 1990
                                                                      Page 14 of 32
                       distillation the balls of the column will actively chatter, but the chambers will
                       not flood. When the apparent volume of liquid reaches 2 mL, remove the
                       K-D apparatus and allow it to drain and cool for at least 10 minutes.

           11.3.3      Remove the Snyder column and rinse the flask and its lower joint into the
                       concentrator tube with 1 to 2 mL of MTBE.  Add 10 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 MTBE to the top. Place the
                       micro K-D 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 the concentration in 5 to 10
                       minutes. When the apparent volume of liquid reaches 2 mL, remove the
                       micro K-D from the bath and allow it to drain and cool.  Add 10 mL MTBE
                       and a boiling stone to the micro K-D and reconcentrate to 2mL  Remove the
                       micro K-D from the bath and allow it to drain and cool.  Remove the micro
                       Snyder column, and  rinse the walls of the concentrator tube while adjusting
                       the volume to 5.0 mL with MTBE.

           11.3.4      Transfer extract to an appropriately sized TFE-fluorocarbon-sealed screw-cap
                       vial and store, refrigerated at 4<>C,  until analysis by GC-ECD.

     11.4  GAS CHROMATOGRAPHY

           11.4.1       Table 3 summarizes the recommended operating conditions for the gas
                       chromatograph.  Included in Table 3 are retention times observed using this
                       method. Examples of the separations achieved using these conditions are
                       shown in Figures 1 and 2. Other GC columns, Chromatographic conditions,
                       or detectors may be  used if the requirements of Section 10.3 are met.

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

           11.4.3      Inject 2 uL of the sample extract.  Record the resulting peak sizes in area
                       units.

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

           11.4.5      If the response for a  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 calibration curve described in Section 9.2.2.

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

-------
                                                                        Appendix A
                                                                        Revtoion No. 3
                                                                        Date: February 28, 1990
                                                                        Page IS of 32
13.   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 EDL's and demonstrate
            method range.  AnaJytes were divided into two spiking groups (A and B) for recovery
            studies. EDL 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. Analytes were divided into two spiking
            groups (A and B) for recovery studies.  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.  Results were
            used to predict expected analyte stability in ground water samples.  Analytes were
            divided into two spiking groups (A and B) for recovery studies.  Analyte  recoveries from
            the preserved, spiked ground water samples are  given in Table 11.

-------
                                                                       Appendix A
                                                                       Revision No. 3
                                                                       Date: February 28, 1990
                                                                       Page 16 of 32
REFERENCES
      1.      ASTM Annual Book of Standards, Part 11, Volume 11.02, D3694-82, 'Standard Practice
            for Preparation of Sample Containers and for Preservation', American Society for Testing
            and Materilas, Philadelphia PA p.86, 1986.

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

      3.      Qiam, C.S., and Chan,  H.S.  and Net, Q.S. 'Sensitive Method for the Determination of
            Phthalate Ester Plasticizers in Open-Ocean Biota Samples, "Analytical Chemistry, 47,
            2225 (1975).

      4.      Giam, C.S., and Chan,  H.S.  'Control of Blanks in the Analysis of Phthalates in Air and
            Ocean Biota Samples, 'US National Bureau of Standards, Special Publication 442", pp.
            701-708, 1976.

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

      6.      "OSHA Safety and Health Standards, General Industry,' (29 CFR 110), Occupational
            Safety and Health Administration, OSHA 2206, (Revised, January 1976).

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

      8.      ASTM Annual Book of Standards, Part 11, Volume 11.01, D3370-82, 'Standard Practice
            for Sampling Water, 'American Society for Testing and Materials, Philadelphia, PA, p. 130,
            1986.

-------
                  'iSLE  1.   "E7HOO ANALYTES
- n a '> .• ' 2
Aldrin
Chloraane-a i:na
Chloraane-gamma
Chlorneo
Chlorooenzilate
Chi orotna i om i
DCPA
4, 4 '-COO
4,4'-CCE
4,4' -GOT
2 i e i d n n
Endosui fan ;
Enoosuifan II
Endosui fan suifate
Endnn
Endnn aicenyde
Etndiazoie
HCH-alona
HCH-beta
HCH-delta
HCH-gamma
Heotacnlor
Heptacnlor eooxide
Hexacnlorsoenzene
Metnoxycnlor
cis-Permetnnn
•.rans-rer-etnnn
?ro0acnlor
Tn f 1 urai :n
Chemical Abstracts
Service
Registry Numoer
309-00-2
5103-71-9
5103-74-2
2675-77-5
501-15-6
2921-88-2
1897-45-6
72-54-8
72-55-9
50-29-3
50-57-1
959-98-8
•3213-65-9
1031-07-8
72-20-8
7421-93-4
2593-15-9
319-84-6
319-85-7
319-86-8
58-89-9
76-44-8
1024-57-3
118-74-1
72-43-5
52645-53-1
52645-53-1
1918-16-7
1582-09-8
]:ent .
Ccce( a)
A7
59
38
Al
311
A6
37
312
310
A16
-11
A10
A14
313
A12
A15
Bl
A3
34
35
AS
36
A9
33
314
A17
315
A2
32
;a)   Coce used for identification of oeaks in method f-gures:
     'etter  :naicates wmcn soiling mix (A or 8) contains the
     snaiyte:  IS - internal standard: SUR - surrogate standard.

-------
                    CF :NALYTES  F«GM  REAGENT WATER fSPIKING L£VEL
                                                                AND EDLs (a,
SsiKirg A, lit 'T
.eve 1 , 51 anic .
--a'.. :e jg/L -g/L i(
-'•Grin (h) 0.075
C'-iloraane-alpna C.015
Iniorcane-gamma 0.015
Chiorneo -^ 0.50
Chlorooenzilate (h) 5.0
Chlortnalonil 0.025
XPA 0.025
4,4' -000 0. 025
4. 4'- ODE 0.010
A.4'-ODT 0.060
;;elann C.C20
Eicosulfan I 0.015
Encosuifan sulfate 0.015
Enonn 0.015
Enonn aldehyde 0.025
Endosulfan II 0.015
Etndiazole 0.025
HCH-alpha (h) 0.025
HCH-beta 0.010
NO (g)
•JO
NO
NO
NO
NO
NO
NO
NO
NO
SO
NO
NO
NO
NO
NO
NO
NO
NO
HCH-delta 0.010 0.0036
HCH-gamma 0.015
-ieotacnlor 0.010
^eotacnlor epoxide 0.015
4exacn1orobenzene 0.0050
*etnoxycnlor 0.050
ci s-??rmethrin 0.50
•.rans-?ermethrin 0.50
3"9oacnlor 0.50
Tnfluralin 0.025
(a) Data corrected for amount found
'b) n • numoer of data points.
(c) 3 - average percent recovery.
Id) S - standard deviation.
(2) ^SO » percent relative standard
(f) £DL • estimated detection limit
NO
NO
NO
NO
NO
NO
NO
NO
NO
in blanic.



deviation
in samole
o)
7
7
'
7
3
7
7
T
7
^
*
^
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7
*
7
7
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7
7
7
7
*
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7
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7
7




.
in yq
^(c) si:) Rso(e) E:L;
56
117
109
47
99
119
112
115
127
87
77
78
129
72
95
148
96
94
95
84
80
67
71
115
120
64
122
90
108





/u
0.00456
0.00132
0.000515
0.0794
0.7076
0.00354
0.00102
0.00140
0.000797
0.0123
0.0034
0.00292
0.000779
0.00198
0.00355
0.00778
0.00416
0.00177
0.00113
0.000622
0.00190
0.000484
0.00189
0.00246
0.00685
0.0782
0.0581
0.0798
0.000816





calculated by
9
3
3
c2^~
5
12
4
5
6
CsS^
s22<
Cy^Jf
4
18

^*lf*S.
i/^
8
12
7
16
7
18
^yj^v
11
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18
3





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O.C
O.C
o.c
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5.0
0.0
o.c
0.0
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-------
                            CONFIRMATION CHROMATOGRAPHIC ::NOIT:ONS
ina;
                                        elative Retention 7i.re  -'or
                                                 C;iC''"ors  ';'
                         (b)
lanfimation  (c)
Aldrin
Chlordane-aiona
Chlordane-gamma
Chlorneo
Chlorobenzi late
Chlorotnalom 1
:CPA
4.4'- ODD
- . 4' -ODE
» . 4 ' -ODT
Dieldrin
Endosuifan I
Endosulfan II
Endosuifan sulfate
Enarin
Endrin aldehyde
Etndiazole
HCH-alpha
HCH-beta
HCH-delta
HCH-gamma
Heptachlor
yeotacnlor eooxide
Hexacnlorooenzene
Methoxycftlor
;: s -Permetnrin
trans-Pennetnrin
'rooacnlor
Tn flural in
(a) Retention time relative :o ?CNB --t«r'
approximately 34 mm.
(b) Primary conditions:
Column: 30 m long x 0.25 "« I
1.18
1.31
1.28
0.75
1.41
1.04
.21
.42
.35
.48
.35
.30
.40
.47
.38
1.43
0.69
0.93
0.98
1.03
0.99
1.11
1.24
0.94
.57
.72
.73
0.85
0.93
iai standara *hi


2. 38-5 bonced
1.12
1.31
1.29
0.77
1.42
1.17
1.21
1.38
1.32
1.48
1.35
1.28
1.45
(d)
1.38
1.52
0.67
0.97
1.18
1.22
1.04
1.08
1.24
(d)
1.53
(d)
(d)
0.91
(d)
en eiutes at


fused sil ica
  Injection volume:
       Carrier gas:
     Injector temp:
     Detector temo:
         Oven temp:
          Detector:
column.  0.25  jfl •"•'* t^cfcness (
2 uL soiitless  •
-------
:;   Cannrraf. on conditions:
           .: . -inn
        Oven :emo
         Zetec'.cr
20 ^ 'anq x :.Z5 im 1.3.  33-1'Cl sonaed  f-sea
:::umn.  C.25 -m
: jL cri't'ess *itfi 45 secona ieiay
-e ?30 c^i/sec ', -near velocity
150'C
* ? n * *"
3-ogram from 60*C to 300*C at 4'C/inn
ECD
    Data not available

-------
-ai.1 i
Cr ANAIYTES FROM REAGENT WATER (SPIKING  LEVEL 2'
So i King A, nt ' n
.evei . 51 an*
-nai.:e jg/i -g/L
Aldnn 0.075
Ifiloraane-ai:na 0.075
Ihloraane-gamma 0.075
Chlorneo 2.5
Chlorooenzi! ate 5.0
Chlortnalom 1 0.13
3CPA 0.13
4.4'-000 0.13
4. 4 '-ODE 0.050
-.4 '-DDT 0.20 3,
3i slarin 0.10
•Inaosulfan : 0.075
Enaosulfan suifate 0.075
E.idrin 0.075
Enorin aldehyae 0. 13
Enaosulfan I'. 0.075
Etnduzole 0.13
HCH-alpha 0.025
HCH-beta 0.050
uCH-aelta 0.050
HCH-gamma 0.075
Heotacnlor 0.050
Heotacnlor eooxiae 0.075
Hexacnlorooenzene 4- 0.025
^ethoxycnlor 0.25
ci s-^ermethrrn 2.5
:rans-?ermetnnn 2.5
^opacnlor 2.5 0
"nfluralin 0.13
NO
NO
NO
NO
NO
NO
NO
NO
NO
' X 1
"NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
.524
NO
nib)
(f) 7
3
3
3
3
8
3
3
*
5
3
3
3
3
3
3
7
3
3
3
3
3
3
3
3
3
3
7
7
^(c) i(d) SSO(e)
55
93
92
95
99
100
93
94
96
95
9(5
93
96
96
99
99
92
94
34
100
93
30
37
138
97
98
112
103
37
0.00456
0.0110
0.0103
0.203
0.708
0.00916
0.0190
0.0163
0.00213
0.0445
0.00841
0.00593
0.00945
0.00618
0.0103
0.00658
0.0104
0.00177
0.00709
0.00698
0.00564
0.00716
0.00616
0.00885
0.0344
0.212
0.0985
0.223
0.0138
9
5
5
9
5
T
5
3
4
15
9
3
3
9
8
9
9
8
3
4
3
7
9
(jfo^)
^^T
9
d
9
12
(a) 3ata corrected for amount founa -i sianK.
',5) n » numoer of data points.
vc) R • average percent recovery
'd) S • stanaard deviation.



;e) SSD « percent relative stanoara
;f) NO - interference not detec:
ea •



cevuticn.
i :' an*.
















-------
"ABLE 5.   RECOVERY  CF  ANAUTES  "SOM  REAGENT  WATER  (SPIKING  LEVEL  2]
$0 i < i no imt • n
^svei , 5
-naiyte -g/L
Aldnn 0.15
Chloraane-alona 0.15
Chloroane-gamma 3.15
Chlorned 5.0
Chlorooenzilate 10
Chlorthalonil 0.25
OCPA 0.25
4. 4'- 000 0.25
4. 4'- ODE 3.10
4.4'-OOT 3.50
Dieldrin 3.20
Endosulfan I 3.15
Enaosuifan sulfate 0.15
Endrin 0.15
Endrin aldehyde 0.25
Endosulfan II 0.15
Etridiazole 0.25
HCH-alpha 0.050
HCH-beta 0.10
HCH-delta 0.10
HCH -gamma 0.15
Heptachlor 0.10
Heptacnlor epoxide 0.15
Hexachlorobenzene-^- 0.050
Methoxycnlor 0.50
CTS-Permethrin 5.0
•.rans-Permethrin 5.0
3rooachlor 5.0
Trifluralin 0.25
(a) Oata corrected for amount f
(b) n « nuraoer of data points.
1 an*
.g/L
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
'-0
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
ound


T,(0)
(f) 3
3
3
5
7
3
3
7
3
^
2
a
5
3
3
3
5
3
7
7
3
7
3
5
3
3
6
T
7
•n 2lar.K.


;(cj
86
99
99
97
108
91
103
107
99
112
37
37
102
38
38
92
103
92
95
102
89
98
87
99
105
91
111
103
103



Sf3)
0.0142
0.0183
0.0181
0.601
0.535
0.0210
0.0307
0.0157
0.0118
0.0984
0.0173
0.0131
0.0221
0.0133
0.0191
0.0148
0.0166
0.00490
0.00661
0.0115
0.0150
0.0117
0.0134
0.0110
0.0655
0.473
0.306
0.440
0.0121



RSO(e)
11
12
12
12
5
9
12
6
12
15
10
10
15
10
9
11
6
11
7
11
11
12



10
6
9
5


(c) R • average percent recovery.
(d) S • stanoard deviation.





(e) RSO - percent relative stanoard ctviation.
(f) NO • interference not detec
ted •
i rlan«.




-------
"ABLE  5.   -"ECCVERY  CF  ANALYSES  FROM  REAGENT  WATER  (SPUING -EYEL 4)  (a)
3s i ki rto imt i n
_evei . 31 an*
- n a I y C e
ildrin
Chlordane-aioha
Chloraane-gamma
Chlorneo
Chlorooenzi late
Chlorthaloml
:CPA
4.4'-ODO
A, 4 '-ODE
4. 4 '-GOT
3ieldnn
i.naosuifan !
Endosuifan sulfate
Endnn
Endnn aldehyde
Endosuifan II
Etridiazole
HCH-alpha
HCH-beta
HCH-delta
HCH-gamma
Heptacnlor
Heptacnlor epoxide
Hexacnlorooenzene
Metnoxycnlor
CT s-Permetnnn
:rans-?ermetnrin
3fooachlor
~ri f 1 ural i n
-9/1
0.38
0.38
0.38
13
25
0.63
0.63
0.63
0.25
i C
0.50
0.33
0.33
0.33
0.63
0.38
0.63
0.13
0.25
0.25
0.38
0.25
0.38
0.13
1.3
13
13
13
0.63
(a) Data corrected for amount
(b) n • numoer of
data points
-3/L
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
0.526
NO
found

-;s)
(f) 8
5
6
7
6
3
6
6
5
7
3
3
6
6
7
3
6
7
6
6
3
6
3
6
6
7
6
7
7
in blanic.

R(c)
95
39
38
90
89
94
89
92
S3
99
100
101
93
100
98
101
34
91
96
34
93
37
83
35
96
101
94
S3
90


s ,' a ) R
0.0356
0.0109
0.00920
0.834
0.892
0.0540
0.0140
0.0248
0.00856
3.135
0.0505
0.0391
0.0184
0.0295
0.0547
0.0399
0.0245
0.00865
0.00820
0.0285
0.0335
0.00667
0.0318
0.00335
0.0614
0.986
0.511
0.925
0.0337


S0(e)
10
3
3
7
4
9
3
4
4
9
10
10
5
a
9
10
5
7
3
14
9
3
10
3
5
3
4
3
6


(c) R • average percent recovery.
(d) S - standard
te) RSD « percent
deviation.

relative standard
(f) NO - interference not detected

deviation.
in blanic.










-------
"ABLE ". -"ECCVERY

Cr ANALY'-i ,'
S 3 '.King Amt
•*OM REAGENT
; n
•A i cS

(SPIK

ING .EYEl

:) (a)

,ave i . si ann
~nai/te
Aldnn
Ihlordane-aioha
Chloraane-gamma
Chlorneo
Chlorooenzi 1 ate
Chlorthaloni 1
DCPA
4.4'- 000
4, 4'- DOE
4.4'-ODT
jieidrin
•ndosulfan I
•ndosulfan sulfate
Enorin
Endrin aldehyde
Endosulfan 11
Etridiazole
HCH-alpha
HCH-beta
HCH-delta
HCH -gamma
Heptacnlor
Heptachlor epoxide
Hexacnlorobenzene
Methoxychlor
cis-Permethrin
trans-Permetnrin
=rooacn1or
Triflural in
(a) Data corrected
'b) n - numoer of
-g/L -<
1.5
1.5
1.5
50
100
2.5
2.5
2.5
1.0
5.0 ;.
Z.3
'. . 5
I c
L5
2 5
1.5
2.5
0.50
1.0
1.0
1.5
1.0
1.5
0.50
5.0
50
50
50
2.5
for amount f
data points.
3/1 ^(0
NO (f)
NO
NO
NO
NO
NO
NO
NO
NO
1Z2
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
cunfl -n 3! am

i) -
3
3
3
3
3
3
3
3
3
3
a
3
3
3
3
3
3
3
3
3
3
8
3
3
3
8
a
I
3


(c)
95
90
90
97
93
97
93
91
89
93
95
95
91
96
95
94
39
95
91
91
96
36
96
77
91
93
91
98
38


S.-3)
0.0516
0.0904
0.0855
1.75
8.30
0.0966
0.176
0.189
0.0877
0.362
0.0875
0.0618
0.111
0.0691
0.163
0.0829
0.117
0.0170
0.0673
0.0669
0.0512
0.0474
0.0596
0.0241
0.3S8
3.80
4.72
1.78
0.149


=SO(e)
4
7
7
4
10
4
3
10
10
6
5
i
9
5
7
6
5
4
3
7
4
6
4
6
9
3
10
4
7


(d) R - average percent recovery.
'a) S • standard aeviation.
(e) RSO • percent
relative stancars :ev«t:cn.
;f) NO • interference not aetec
:ea •-• :'an<





-------
"A3LE 3. -"CCVERY OF iNALYTES FROM HARD ARTI
:r.<
-naiyte
ildrin
Chloraane-alpha
Chloraane-gamma
Chlorneo
Chlorooenzi late
Chlorthalonil
DC PA
4,4'-ODD
4,4' -DDE
4. 4 '-DOT
Dieldrtn
Endosulfan 1
Endosulfan II
Endosulfan suifate
Enorin
Endrin aldehyde
Etridiazole
HCH-alpha
HCH-beta
HCH-delta
HCH -gamma
Heptachlor
Heptacnlor epoxiae
Hexacnlorobenzene
Methoxycnlor
cis-Pennethrin
trans-Permethnn
Propachlor
Tri fl ural in
(a) Corrected for
• i"* CVCI " ' ' a 1
. <
f 11 i«L un

-rr,t • -i imt ' i
jg/L -g/L n(b) S(c)
3.15
0.15
0.15
5.0
10
0.25
0.25
0.25
3.10
3.15
3.CSO
0.15
0.15
0.15
0.15
0.25
15
0.050
0.050
0.10
0.15
0.10
0.050
0.050
0.50
5.0
5.0
5.0
0.25
amount found m
Absopure Nature Artesian Spri
Company in ?1
(b) n « number of
ymouth, Michigan
"data points.
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
bl
ng
,

(M 7
7
7
7
6
7
7
5
-
7
^
7
6
6
7
7
6
7
6
7
5
7
7
6
5
7
5
5
5
an*: artifi
100
96
96
95
98
103
100
96
96
98
103
102
94
98
103
98
91
106
92
99
115
85
103
82
101
96
97
116
36
OUND WATER

S(cJ) RSD(
0.0163
0.0189
0.0180
0.339
1.03
0.0262
0.0317
0.0221
0.0125
0.0169
0.00451
0.0124
0.0170
0.0141
0.0166
0.0265
0.992
0.00347
0.00282
0.0124
0.0104
0.0108
0.00382
0.00511
0.0502
0.594
0.487
0.206
0.0257
cial ground water was
water Obtained from




the Absopure




e)
11
13
13
7
11
10
13
9
13
12
9
8
12
10
11
11
7
7
6
12
6
13
7
12
10
12
10
4
12

Water


(c) R • average oercent recovery.
(d) S • standard
(e) RSO » cercent
deviation.

relative standard
(f) NO • interference not detected i

Deviation.
n olantc.










-------
•ABLE  9.   RECOVERY OF ANALYTES  FROM  ORGANIC-CONTAMINATED
          :ROUNO WATER (SPIKING  LEVEL  •;  ;a)
imt in imt 'n
Samole, 31anK.
-nalyte ug/L ug/L
ildrin 0.15
Chlordane-alpha 0.15
Chlordane -gamma 0.15
Chlorneb 5.0
Chlorobenzilate 10
Chlorthaloml 0.25
OCPA 0.25
4. 4 '-ODD 0.25
4.4'-OOE 0.10
4.4'-DDT 0.15
Oieldrin 0.050
Endosulfan I 0.15
Endosulfan II 0.15
Endosulfan sulfate 0.15
Endrin 0.15
Endrin aldehyde 0.25
Etridiazole 15
HCH-alpha 0.050
HCH-beta 0.050
HCH-delta 0.10
HCH- gamma 0.15
Heptachlor 0.10
Heptachlor epoxide 0.050
Hexachlorobenzene 0.050
Methoxychlor 0.50
cis-Permethrin 5.0
trans-Permethrin 5.0
Pnjpachlor 5.0
Tnfluralin 0.25
(a) Corrected for amount found in
water spiked with fulvic acid
well -characterized fulvic acid
Substances Society (associated
in Denver, Colorado), was used
(b) n • number of data points.
(c) R « average percent recovery.
(d) S • standard deviation.
NO (f)
NO
NO
NO
NO
NO
NO
NO
SO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
blanic;
at the
, avai
with
•



(e) RSO « percent relative standard devi
(f) NO • interference not detected
in ol
n ( b ) R ( c )
^
•?
7
7
7
7
7
5
^
/
/
7
7
6
6
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
artificial
59
99
99
75
102
71
101
101
99
34
32
34
72
104
84
76
98
36
100
103
85
35
32
68
104
86
102
95
87
ground
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
S(d) 
-------












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-OL1
STUDY  RESULTS


: " a \ , : 2
-: dr i n
Inloraane-alpha
In 1 ore ane- gamma
Ihlorneo
Chlorobenzilate
Chlortnaloml
:CPA
4.4--OCD
•1.4' -ODE
4.4 '-GOT
:;eldr:n
Ndosulfan I
•ndosulfan II
Endosulfan sulfate
Endrin
Endrin aldehyde
Etndiazole
HCH-aloha
HCH-beta
HCH-delta
HCH-gamma
Heptacnlor
weptacnlor epoxide
uexacnlorobenzene
Methoxycnlor
:i s-?ertnethrin
:rans-Permetnrin
:-ooacnlor
~n fl ural in
Zominq
.sve i .
-g/L
0.15
0.15
0.15
5.0
10
0.25
0.25
0.25
0.10
0.15
0.050
0.15
0.15
0.15
0.25
15
0.050
0.050
0.10
0.15
0.10
0.050
0.050
0.50
5.0
5.0
5.0
0.25
;a) 3 « average oercent recovery
(D) RSO • percent
(c) 2ata not avail
Ta v

;(a>
"3
73
73
39
103
90
95
SO
S3
57
33
39
35
97
91
35
75
37
38
94
90
62
39
67
103
88
111
87
68
from
n

=SO(b)
4
10
10
2
9
2
10
S
10
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9
1
11
3
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9
5
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10
tnol icate
"av '4

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94
102
101
90
108
(c)
103
109
98
33
34
40
35
112
39
85
67
96
(c)
101
102
74
94
30
115
78
109
105
90
analyses.


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able; interferences
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-------
                                     Appendix B
                                     Revision No. 3
                                     Date: February 28, 1990
                                     Page 1 of 28
         APPENDIX B

GC/MS SPECTRAL INFORMATION

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-------
                                Appendix C
                                Revision No. 3
                                Date: February 28, 1990
                                Page 1 of S
 APPENDIX C

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:

              Xi  < X2 < X3 < ... < X^ <  Xa

     2)   Decide whether the smallest, XL or the largest, X,,,  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 5X 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 5Z 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
              ru  -    	   -  	   - 0.454
                       10.58 - 10.47       0.11

     2)   A 52 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 10X 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 X: is
      Ratio            n  is between           suspect             suspect
                                                    V  \            / V
                                                  '  Xn-l)            (X2  '
        :io                 3-7            		
                                                  -  Xa-t)           (X2 -
        rn                 8-10            	          	•
                                                    V N            / V
                                                  " X2^            (Xn-1 •
                                                    Y  \           /V
                                                    •"ri-2/           (.A3 "
        r21                11  -  13           	          -	•
                                                   -  X2)            (X,,-! -
                                                    Y  >           ^Y
                                                    An-2/           VA3
        r22                14  -  25           	          	•
                                                   -  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%          11           5Z           10%
    •10
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  5Z  risk level will be used for  ratio  r22.

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

-------
                                                Appendix D
                                                Revision No. 3
                                                Date: February 28, 1990
                                                Page 1 of 19
                      APPENDIX D

STANDARD OPERATING PROCEDURE FOR MANUAL DATA ENTRY

-------
                          Summary Of NFS Data Package


The information generated by NFS samples is combined into data sets.  A s
defined as a group of samples which have been extracted on the same day.
these samples are spiked with a surrogate (DCS) and an internal standard
"The data from these samples is entered into five seperate spreadsheets in
2020 software package and analyzed according to the following plan.
A)  Calibration Curve

   A three point calibration curve is obtained for each individual set by
   analyzing three different concentrations of a group "A" pesticide stocJ
   solution and three different concentrations of a group "B" pesticide st
   solution.  [The reason for having two stock solutions is that some of t
   pesticides would co-elute if analyzed together.  There are fourteen
   individual pesticides in the group "A" mix and fifteen in the group "B*

   The information generated by these chromatograms (date, time, retention
   of compounds, peak areas, etc...) is entered into a spreadsheet in 2020
   pg 3] named CRVXX-X where XX-X is the month and day the curve was run 4
   From this information, the 2020 software calculates a calibration curve
   each compound along with other statistical data which includes the
   correlation efficient.  The correlation coefficient must be > 0.995 ace
   to the QA plan.  Otherwise, a new calibration curve must be prepared (s
   project manager) .

B) Instrument Quality Control Check (IQCC)

   The IQCC is a standard pesticide solution which mooLtors column perform,
   chromatography  performance and sensitivity.  The0.8 and <1.1!
   satisfy QC requirements.  Chlorothalonil and delta-BHC evaluates the pel
   •resolution and  must be >0.50.  All of above criteria must be satisfied.
   Otherwise, the  analysis  must be  stopped  and the problem rectified  (see
   project manager).

C) Continuing Calibration  (CC)

    The  CC  is  one of the  standard pesticide  solutions used to make the
    calibration curve.  A CC must be  run every  12  hours to verify the calibr
    curve.   If  the  response  for any  analytc  varies  from the predicted  respon
   'more than XTl,  a new  calibration  curve must be  prepared.
             -a 51

-------
   The information from the chromotogram is entered into the 2020 spreadi
   [see pgs 13-14) named CCXX-X.

D)  internal Standard Summary Table

   In order for a sample, IQCC,  CC,  etc.,  to meet QC requirements, the Ii
   Standard (I.S.) area, for that run,  must be within 201 of the average
   area of the standards used to make the  calibration curve for that set.
   data from the chromatogram is entered into the 2020 spreadsheet [see j
   15-16]  named ISXX-X.

E)  Warning and Control Limit Flag Table

   For every spiked sample, the  percent recovery of each analyte must be
   calculated to see if the recovery is between the allowable control lis
   (Control limits are genterated by using data from previous sets and th
   Oixon's Test).  In order to meet QC requirements, each sample may have
   more than 15% of the analytes outside the control limits.

   The 2020 spreadsheet (see pgs 17-18] used to calculate these reeoverie
   named FLAXX-X.  The data entered into this spreadsheet is i~"	*"* fro
   percent recovery portion of the CRVXX-X spreadsheet.

-------
               GENERAL LAYOUT OF CURVE SPREADSHEET
1)  STWBARD CURVE DMA
   REFER TO DIACSAMS LABELED (1) CN RAGES 4 AND 5.          	
   IN IKES SECTION OF THE SPREADSHEET,  DATA FROM THE CHROMAIOGRAMS USED
   TO GENERATE THE CALIBRATION CURVE IS ENURED.
   SEE PAGE 9 FOR INSTBDCITON5 ON INURING DATA. INTO THIS SECTION.

2)  CORRELATION CUUIlClEtas & KETfNTTCN TUB WDBCWB
   REFER TDDIA3WM LABELED (2) ON PAGE 4.
   •mis  SECTION OF THE SPREADSHEET AUTOMATICALLY /^][l^irAfnBB S'lXl'lSTJLCAL
   DMA SUZ AS CORRELATION CZZTFIOENT^RElSiriGN TUB NOUNS AM) SLOPE.

3)  EQUATICNS OF STANDARD CALIBRATION CURVES
   REFER TO DIAGRAM LABELED (3) ON PACK 4.
   IN THIS SECTION, THE DA3& THAT VM ENTERED DUO  THE STANDARD CURVE
   !KX STEP 1 IS USED TO GEMXATE THE STMGARD CALIBRATION CURVES FOR EACH
   ANAUfTE. NO DMA IS ENTERED IN THIS SECTION BY THE USER.

4)  SAMPLE PEAK AREAS
   REFER TO DIAGRAMS LABELED (4) Of PAGES 4 AM) 6.
   THIS PART OF THE SPREADSHEET IS USED TO ENTER THE PEAK AREAS OF THE
   HBBU llfS THAT ARE PRESENT IN EACH SAMPLE.            	
   SEE PAGE 9 FOR  INSTfOCTIONS ON ENTERDC DATA INTO THIS SECTION.

5) CONCENTRATION SHL'l'lCN
   REFER TO DIAGRAMS LABELED (5) ON PAGES 4 AM) 7.
   IN *im& SECTION OF THE SPREADSHEET> ^Vf CONCENTRATION OF EACH
   Ma>'i'l(,LLK THAT VAS ENHMD IN STEP 4 IS CALOJLAT1D AUIONATICALLY
   BY THE SOFTWARE.                                       	
   SEC PAGE 9 FOR  INSTKdlONS CN ENTERQC DAXA INTO THIS SECTION.

6) PERCENT RECOVERY SECTION
   REFER TO DIAGRAMS LABELED (6) ON PAGES 4 AM) 8.
   T^gg Hjfl'UJN OF THE SPREADSHEET TAKES THE ^TT1 _fMimJlQg (FROM STEP 4)
   OF SPTJOD SAMPLES ONLY AM) DIVIDES TREK BY THE THEORETICAL
   CCNQDORMXON TO YIELD A PERCENT RECOVERY OF EACH ANALYS.
   SEE PAGE 9  FOR INSTRUCTIONS CN ENTS01C DAI*. INTO THIS SECTION.

-------
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-------
Curve Spreadsheet - Std Crv,  Areas,  Cone,  Percent recoveries
                    All data  is to be obtained from chromatograms

1 )  Standard Curve
   a)  Bring cursor to AO position by hitting "HOME" key.  Bring cursor
       A-l and replace test with set number being worked on.
   b)  Bring cursor to C3 - replace XX with set number being worked on.
   c)  Analysis date:  enter  range of dates for the standard curve.
   d)  Enter the raw areas and retention times for the corresponding
       concentrations at top of each section.  Only the A spike cone ID
       number is at the top of the columns.  The B spikes are as follows

                                A               B
                                A028            A032
                                A029            A033
                                A030            A034

   e)  Hit space bar to calc


 2) Sample Peak Areas
   a)  Move cursor to  "HONE" then move to  right until at block BCS.
       Edit and enter  set I being worked on.
   b)  Analysis date:  Enter range of dates for samples in set being
       worked on.
   c)  In block BG4  -  enter curve *  ie crv-set t being worked on.
   d)  Analyst:  Hit edit, end and enter JV/EOP
   e)  Page:  XX-  replace XX with logbook  page number for set being
       worked on.
   f)  Go  to block BD13, hit /,W.,T,V this  freezes the compounds so you
       can  tell where  you are  entering areas.
   g)  Go  to BX9.  Enter sample blank.  All  lines across for each  sample
       number gets entered for M/B,  LCSA & B  this is QC tttt, for  all
       other samples  it  will be NAOXXXX.   IQ's and CC's are not entered
       here.
   h)  Cell  BI10 is  for  the sample  type code.  Refer to IS  summary sectic
       for  these codes.
   i)  Enter heading info  for  all  samples
   j)  Enter  raw areas for each sample


 3) Concentration
   a)  Go to B065  -  update set I,  date, CRV,  page t.
   b)  Go to BI9,  hit /,  C,  everything,  .  and highlight  all  the headings
        ie BI9-11 BJ9-11... Target range will be  BI69 enter
   c)  Go to BI69,  hit space\bar.   The  concentrations will  be calculated


 4) Percent Recovery
   a)  The percent recoveries  are only  calced for  spike  samples.   Any  fie
        samples are going to  be ignored.  Go to BI69.   Hit /,  copy,  everyth
        ., highlight BI69..BI71.   Target range BJ123.  enter
   b)   Go to BK69  and repeat above step

-------
c)   Next go down the line.   Copy headings for A spikes next to th« CSA
    and a spikes down the line from LCSB
d)   Once headings are copied - go up to cone section for each spike
    sample - write the column letter the values are in ie LCSA - BJ,
    LCSA - BK NA03714 - 3M

-------
'nstrument  Quality Control Check  -  (IQ)
   All  of  the  followed data  is  obtained  from  the  chromatograms
   a.)   For eacn  IQCC, 6 measurements  must  be taken on the chromatogram:
               1.) Distance  from start  - d BHC peak (nun)
               2.)               base width  d BHC (nun)
               3.) Distance  from start  - chlorthal (mm)
               4.)               base width  - chlorthal (ma)
               5.) width at  1/2  height  - 1/2 width DCPA (ma)
               6.) width at  1/10 height -  1/10 width DCPA (ma)
   b.)   Hit "Home" key to get cursor  located  in cell AO.  Key in set #
        the IQ was run with  by hitting the  edit key and typing set I in
        place  of  the  X's.  If there is more than  one per set letter
        then A,B,C etc.
   c.)   Analysis  date:
               hit  "Edit" then "end"  and enter the date the IQ was run on
   d. )   Time:
               repeat above  step and  enter time  as appears on the chromat
   e.)   Move cursor  down to   "W(l/2)-" line and over to 0.5. Enter 1/2 of
        the 1/2 peak  width of OCPA  (should  always be 0.5)
   f.)   Move cursor  down.  Enter  1/2  peak width of DCPA should be 1.0
   g.)   Hove cursoe  down.  Enter  1/10  peak  width of DCPA
   h.)   Move cursor  down.  Enter  start - chlorthal value
   i.)   Move cursor  down.  Enter  start - dBHC value
   j.)   Move cursor  down.  Enter  base  width chlorthal value
   k.)   Move cursor  down.  Enter  base  width dBHC value
   1.)   Hit space bar to calculate
   m.)   Move cursor  to  "RESULTS"  column.  Compare the results to the
        requirements.  If  any fall  outside  the set limits, make a note
        of IQ-sett,  date,  time, and report  to project manager
   n.)   Hit /, S, W
   o.)   Entr IQ-set  * &  letter if needed
        DU2:[EPA_workarea.users)IQ-sett  &  letter
        hit enter

-------
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-------
'sntinuing  Calibration  (CO
  All  cf the  following data is obtained  from  the  chromtograms
  a.)   Hit "Home"  key  to  get the cursor  located  in  cell   AO.  Key
        in  set  «  CC was run by hitting  the  edit key  and  typing  in the
        set number.   If there are more  than one CC per  set,  label
        then as above with A. B,C, etc.  to  differentiate.
  b.)   Contract  No:  3-729-001 should  be left alone
  c.)   Calibration date:  Find the appropriate concentration  in the std
        curve  data  (ie  same as the CC you are  working  on)  Enter the month
        day and year by moving the cursor to the  begining  of  thi« cell an
        striking  the "edit" key.  Move  th cursor  to  the  right  by hitting
        the "end" key and  type in date.
  d.)   Cont.  cal date:
        Enter  month, day,  and year as above
  e.)   Laboratory:  Clean Harbors
        Leave  as  is
  f.)   Time:   (calibration)
        In  the first time  cell from the top of the spreadsheet, enter the
        time as it appears on the chromatogram for the  std curve cone.
  g.)   Time:
        Enter  as  above
  h.)   Move cursor to  line  "MIX A & B-X" Hit  "edit",  "end"  and replace
        "X" with  code for  concentration (i.e.  lb,3,  4b,  L,M,H...) for botl
        initial and daily  columns
  i.)   Calc the  mean I.S. value for the A  and B  spike   compounds from
        the std curve for  the given concentration.  Then enter  the raw  .
        areas for each  compound.  Use  the calc'd  mean  value  for OCB.
   j.)   repeat above step  for daily cont. cal
  k. )   hit space bar to  calculate % difference
   1.)   move cursor to  percent difference column  if  any are  over
        20%, note sample  t,  compound and percent  difference.   Inform
        project manager
  m.)   hit /,S,W
   n.)   enter cc  -  (set I  &  letter  if  any)  at  end of
        DU2:(EPA_workarea.users|cc-
        the cc-#~entered should  be  the  same as cell  AO

-------
                     MHH2J 2 -  OJODLDG OVLBVOm OBX

              fc:3-729-001  SET 12                IabocBnry*2«

     Cadibcaojon CBte: 8/11/68                    USB: 02:46/04:00

     int. Cal. Oaee: 9-ZS8                      One: 16:08/17:35
                                       ,   i.s.
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                                                                 40248
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24.)
25.)
25.)
27.)
28.)
29.)
30.)
               ii In
     cteita-aC
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                                 2869.8
                                 2342.2
                                 2286.6
                                 2413.5
                                 2278.1
                                 1B75.8
                                 1770.8
                                 1520.2
                                 2660.4
                                 2811.9
                                 2458.1
                                 1758.9
                                 550.55
                                 7314.8
                                   3898
                                 2968.5
                                 9260-2
                                 1213.4
                                 L337.2
                                 2778.7
                                 1644.2
                                 1926.6
                                   1892
                                 10L8.2
                                 1939.4
                                 1216.3
                                 2027.7
                                 4336.5
                                 478.89
                          (0.066817
                          | 0.054533
                          10.053238
                          10.056193
                          10.053040
                          10.043674
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                          10.035394
                          JO.061941
                          (0.065469
                          JO.057231
                          (0.038235
                          (0.013051
                          (0.170309
                          (0.090756
                          (0.069115
                          (0.215604
                          (0.028251
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                          (0.044856
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                          (0.028318
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 2638.80
 2008.60
 1924.40
 2129.00
 1859.90
 1525.30
 1397.90
 1190.30
 2036.80
 2147.90
 1947.90
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  454.68
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 4107.50
 3043.90
 9401.40
 1140.70
 1223.80
 2725.90
 1567.40
 1733.60
 1686.30
  900.35
 1668.20
 1044.40
 1725.00
 3532.00
  369.38
•(O.umw
 (0.065563
 (0.049905
 (0.047813
 (0.052897
 (0.046210
 (0.037673
 (0.034732
 (0.029574
 (0.050606
 (0.053366
 (0.048397
 (0.032123
 (O.QU296
 (0.171153
 (0.102054
 (0.075628
 (0.233586
 (0.028341
 (0.030406
 (0.067727
 (0.038943
 (0.043072
 (0.041897
 (0.022370
 (0.041448
 (0.025949
 (0.042859
 (0.087755
 (0.009177
                                                                               1.91)
                                                                               3.511
                                                                              10.2t|
                                                                               5.9I|
                                                                             15.8t|
                                                                             16.4t|
                                                                             ia.3%!
                                                                             18.S%|
                                                                             15.4%)
                                                                             16.011
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                                                                             12.4*1
                                                                              9.4%)
                                                                              8.3*1
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                                                                              1.7I|
                                                                              4.0I|
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                                                    .ilrutoai  :
-------
Internal Standard Summary - IS
   All  of the following data is obtained from the chroroatogram
   a.)   Hit "Home" key to get cursor located in cell AO.   Key in set # b
        worked on by hitting "Edit" key, "Home" key and replace X's with
   b.)   Laboratory & Contract tt stay the same
   c.)   Enter "set number" by hitting "Edit" "End" and enter set I being
        on
   d.)   The "I.S. X area * 10*3" is obtained from the standard curve in i
        lower right corner.  Enter this number in block F9.
   e.)   Enter date or date range of the set being worked on
   f.)   "Alliance Sample *"
        Enter numbers from the log sheet (either QC, ? or A, NAO t)
        The order should be IQCC, blank, LCSA, LCSB, samples
        including CC's and IQCC's.
        For each sample * the sample type in parenthesis must be entered
        These are:  DTS A or B - TS day 0 1st analysis
                    HTE A or B - TS day 0 2nd analysis
                    HTS A or B - TS day 14 analysis
                    LSSA 0,1, or 2 - Lab spike A with cone level
                    LSSB 0,1, or 2 - Lab spike B with cone level
                    FLS - Field Sample
                    LCSA - Lab control Spike A
                    LCSB • Lab control Spike B
   g.)   Enter the raw areas for the I.S. for each of the samples in the s<
   h.)   Enter the dates each sample was run
   i.)   "EPA sample »"
        For each NAO f there is a corresponding CPA number.   These are fot
        in John Verban's office for each set.  Enter each EPA number.  Foi
        cont calibrations enter "cont. cal." For IQ enter "Inst. check",-
        method blank - "Meth. Blank" LCSA - "LCSA" and LCSB - "LCSB"
   j.)   hit space bar to calculate
   k.)   if any % difference is over 20, note sample number,  and a differer
        Report to project manager
   1. )   hit /, S  , w
   m. )   enter IS - set * in place of ISX-XX
        DU2[EPA workarea.userJlS-sett

-------
                   •S.  SUMMARY     TABLE
  LABORATORY:


  I.S. X AR£A»10~3

        EPA      t
     SAMPLE *
                  :iean Harbors
          44209
IINST. CHECK
ICCNT. CAL.     (P193-2
ICONT. CAL.     |P194-2
1 METHOD BLANK   IQC3692
IPC-2497-2-2-01
                 QC3694
 I COOT. CAL.
 IPC-2002-2-2-01
 IPC-2242-2-2-01
 IPC-2242-2-2-06
 IPC-2164-2-2-01
       CHECK
       CAL.
 I COOT. CAL,
 IPC-2164-2-2-08
 IPC-2164-2-2-13
 IPC-2584-2-2-01
IPC-2584-2-2-05
IPC-2S84-2-2-13

 ID<20%
\ P194-4
INA07013  (
                         F/S)
                (NA07016
                |W7g-i
               |P194-3
               |NW)7017 (
               INA07018
               INA07021
                                         Contracct 3-729-001
                                         Set Number  12

                                         DATE:  9/2-9/6/B8
AREA | QATT |
1 i i r
X10-3 | ANALYZED (DIFFERENCE! OF CRV. |
47066 (9/02/88 1
40388 (9/02/88 (
40107 [9/02/88 (
37369 (9/02/B8 (
40124 (9/02/88 |
37687 (9/02/38 |
37774 (9/02/88 (
38908 (9/02/88 (
40815 (9/03/88 |
44716 (9/03/88 |
37063 (9/D3/88 (
41022 (9/03/88 (
40858 (9/03/88 (
39348 (9/03/88 |
44682 (9/06/88 (
47777 (9/06/88 | '
47625 (9/06/88 (
45984 19/06/88 f
42888 19/06/88 |
42044 (9/06/88 (
39904 (9/06/88 (
40152 19/06/88 (
6-46%! 106%!
8.64%| 91%J
9.28%| 91%!
15.47%! 85%
9.24%| 91%!
14.75%f 85%
14.56%! 85%!
U.99%! 88%!
7.68% 92% 1
™ T *•» f
1.15% 101»l
* • *•*» f JLU4V 1
16.16%l 8411
^w " ^*» » f 9^9 ^
7.21%J 93%!
7.58%! 92%!
11.00%) 89%!
1.07%! ioi%!
8.07%! 108%|
7.73%| 108%f
4.02%! 104%(
2.99%! 97%!
4.90%! 95%J
9.74%| 90%!
9.18%! 91%|

-------
riaa  crooram  •  Fla
   Data  is  obtained from the  curve  program.
   a)   Bring  up  the curve program  for  the set being worked on.   Move  to
       the  percent  recovery  section.
   b!   The  Flag  program can  evaluate  3 A spike samples and 3  B  spike  samp
       per  program.  Therefore,  when  extracting information,  keep in  sets
       three  or  less.   To file  extract hit /, S, C enter name (  NAME  Al),
       supersede enter range- you  should be highlighting LCSA and next tw<
       spikes -  the headings  and values.  Once range is entered,  you  will
       back to ready.   (It may  be  helpful to write down your  file names.
       They will be needed.)
   c)   Continue  until all A  spikes  have a cut file
   d)   Repeat above step for  B  spikes but extract 1st the labels than the
        values seperatly. Name these files  Name Bl, Nan* B2 ect.
   e)   Bring up  flag program.  Bring  cursor to AO.  "Edit" and  replace
        X's with set #.  If  there  are more than one, name set I  A,  B,ete.
   f)   Enter set #  being worked on.
   g)   Enter analysis date for  set being worked on
   h)   Enter sane as in AO
   i)   Enter Troa CRV" enter curve * for set
   j)   Position  cursor in H10 sample
   k)   Hit /, S, L
   1)   Enter consolidate, then  enter  1st A file ie Name Al
   m)   Enter "Replace"
   n)   "Input Range" - hit enter
   o)   "Target Range" - hit  enter
       The headings & values from  the LCSA & 2 A spikes should  be in  the
       flag program
   p)   Repeat above steps for 1st  3 B spikes but position cursor in H30
       for B values H47 for  B labels
   q)   Hit the space bar to  recalc
   c)   Hit /, S  , w -  replace FLAX-XX with Fla - set I
       DU2:  [EPA_Workarea.Users) Fla-s«t* &  letter
   s)   Repeat above steps for each set  of  3 A & 3 B spikes or less than 3

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                                                 Appendix E
                                                 Ftovtoion No. 3
                                                 Date: Februaiy 28, 1990
                                                 Pag« 1 of 4
                       APPENDIX E

STANDARD OPERATING PROCEDURE FOR AUTOMATED DATA ENTRY

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HeanHartors
                   Standard Operating Procedure  for  Transferring
               IPS rata from the Hewlett-Packard  Laboratory Automation
                  System to a 20/20 worksheet on the DEC MicroVax
      1.0 SCOPE AND APPLICATION

          This is a process whereby retention times and area counts froi
          standard runs are put in a file and transferred from the Labo
          Automation System 'LAS)  to an IBM PC and then into a 20/20
          worksheet en the DEC MicroVax.  The IBM PC is physically linkei
          both the LAS and the DEC MicrcVax.


      2.0 SUMMARY OF PROCEDURES

          The LAS command RF (Report to File) is used to put compound n<
          retention times, and area counts from the six standard result
          into a file called CALNPS.RPT.  A command file called FRO«LAS.<
          then invoked from the IBM PC. This command file transfers the
          CALNPS.RPT file from the LAS to the hard disk on the IBM via
          (a common file transfer  protocol). A command file called T020
          then invoked on the IBM. This command file transfers the CALN:
          file into a temporary 20/20 file called TEMP and from this fi
          extracts the area counts and retention times and places them
          the final worksheet.
      3.0 STEP BY STEP PROCEDURES

          3.1 Once the six standard result files exist,  go to the direc
              command line in LAS and type RF (Report to File).  This wi
              bring up the Report to File screen.

          3.2 Hit fl to create a report rased on file names/masks. This
              bring up the File Names *asxs screen.  Enter the name of t
              A standard result file and press the tab key to move the
              to the next line. En'ter INIT 7AL in  the Rep.Format line a
              press the tab key to move tr the next  line. Enter  CALNPS
              Rep.File line and press t*i* tab key  to move the cursor to
              Overwrite option. Type YES and then  hit return, wait unti
              File Names/Masks screen re-appears.  Then type in the name
              High 8 standard result file. Then tab  to the Overwrite op
              and type in NO. Tab to the Append option and type  in YES.
              hit return. Wait until the File Names/Masks screen re-app
              Now enter the name of the MED B standard result file and
              return. Repeat this step until all six of the result file
              been entered. MOTE: It is VERY important that the  result

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fleanHarixjrs
              get entered  in  the  correct  order.  The correct order is:  Hi
              High B;  MED  A;  MED  B;  LOW A;  LOW B.  After all the result f
              nave reen  entered and  the File  Names/Masks screen re-appea
              hit tne  End  Function  softkey  (f8).

          3.3 Go to the  I3M  PC  in the  LABSAM  computer room. If it says "
              USE THIS TERMINAL",  hit  the ALT and  S keys together.  This
              stop the automatic  report generator  program.  If the terrain
              looks busy,  you will  have to  wait until it says "DO NOT  US
              TERMINAL". After  hitting ALT-S  you will get a green comman
              at the bottom  of  the  screen in  which the cursor will  be
              blinking.  Type  INVOKE  FROMLAS.CMD and hit enter. The  PC  wi
              then make  a  few beeps,  transfer the  CALNPS.RPT file to the
              and then log off. Wait  until  it is finished doing this (sh
              only be  about  30  seconds).  Instructions on what to do next
              appear en  the  screen  as  a reminder.  When this happens, it
              it is finished  with this step.

          3.4 Hit fiO, then  hit  f8  twice. A "C>" prompt will appear on tl
              screen.  Flip the  switchbox  to position B and type R3V and I
              enter. This  will  stop  the IBM from emulating an HP termina
              start the  DEC  terminal  emulation.

          3.5 The Basic Configuration  menu  will appear on the screen.  Hi'
              to accept  the  default  configuration.

          3.6 Hit the ALT  and Y keys  together. This will make the green.
              command line appear at  the  bottom of the screen. Type INVOf
              T0202Q.CMD and hit  enter.

          3.7 Enter the name of the  20/20 template worksheet and hit ent<
              NOTE: You DO NOT have to enter the file prefix
              DU2:(EPA_WORKAREA.USERS 1 ; but you must spell the rest of tl
              file  name correctly or the program will bomb.

          3.8 Enter the name you  want  to save the  20/20 worksheet under <
              hit enter. Again,  you DO NOT have to enter the  file prefix
              you must enter a  file name that doesn't already exist or t."
              program will bomb.

          3.9 The program will  then copy the CALNPS.RPT file  from the  PC
              the DEC MicroVax,  import that  file  into a temporary 20/20 f
              import  the  information  from the temporary 20/20 file into t
              blank template file and  save it under the name  you specific
              This  will take about three minutes.  When the program is
              finished, instructions  on what  to do next will  appear on tti
              screen  as a reminder.

          3.10  Hit  fS twice  to stop the  DEC  terminal emulation. Turn  the
              switchbox back to  the A  position. At the "C>" prompt, type

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fleanHaitofs
             and hit enter.  When the screen turns blank,  hit enter to <
             "Login Name?"  prompt. Login as user LABSAM  with password >
             At the "Module  Selection:" prompt hit the ALT and Y keys
             together.  This  will give you the green command line as be
             Type INVOKE AREPT.CMD and hit enter. This will re-start t!
             automatic  report  generator program that was  running befor

          3.11 Go back to your  DEC MicroVax terminal and  call up the ne<
             created worksheet. You will have to CALC the worksheet am
             analysis times, etc. The above process only  enters retent
             times and  area  counts for the six standard  runs.

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                                                     Appendix F
                                                     Revision No. 3
                                                     Date:  February 28, 1990
                                                     Page 1 of 17
                          APPENDIX F

NPSIS SAMPLE RECEIPT SOFTWARE FOR LABORATORIES DATED 4/5/88

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MEMORANDUM                                                   4/5/88



TO:       JOANNA HALL, ALLIANCE TECHNOLOGIES,  INC.

FROM:     CHIP LESTER. ICF ISC.

RE:       NPSIS SAMPLE RECEIPT SOFTWARE FOE LABORATORIES
     ICF's National Pesticide Survey Information  System (NPSIS)  is  ready to
collect information from you regarding the receipt  of  well  water samples and
cheir condition.  Please find enclosed the following items:  1) A users memo
containing all operating instructions, and 2) A copy of Carbon Copy software
which is necessary to establish communications with NPSIS over phone lines.
As mentioned previously, che software allows you  to report  the receipt of a
one or more sample kits.  It also prompts you for details regarding the
condition of che samples.  Additional features include;  a bulletin  board whit
allows you to interactively send messages to ICF  staff via  your  computer
keyboard, file transfer, and access to the ICF computerized mail system for
sending memos.  It is also possible for you to speak over the phone to an 1C.'
staff member during your session.

     It is important that you test the communications  link  between  the NPSIS
computer and yours.  We have experienced trouble  when  using Carbon  Copy
software with a computer which has a Manzana 3.5  inch  disk  drive, and also
with computers which have a non-Hercules or non-EGA compatible graphics card

     For testing purposes, your sample kit identification numbers and FedEx
airbill numbers (respectively) are: PD-0000-241 and 1111111111,  and PD-0000-
242 and 2222222222.  Use these sample kit identification numbers when trying
out che NPSIS Sample Receipts Program.

     We feel chat it would be helpful to both parties  if you could  call us
when you are ready to test the NPSIS system, and  we will assist  you over che
phone during your session.  If you would like to  do this, please call Beth
Estrad* at (703) 934-3431.  NPSIS will be available for access 24-hours a da
seven days a week.  We appreciate hearing any comments you  have  regarding
NPSIS.

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                       THE NPSIS  SAMPLE RECEIPT PROGRAM
     .VPSIS is designed to keep crack of che day co day operacions of  Che
Macional Pescicide Survey.  You play an imporcanc role in NPS and your  ciae
notification of receiving a kit of samples is essencial co che success  of  N!
We have designed che Sample Receipt Program with your busy schedule in  mind
NPSIS will obtain che minimum amount of information necessary while still
maintaining a secure system.  You will be entering data into che NPSIS
personal computer via your own computer, modem, and Carbon Copy software.
I.I  Hardware and Software Requirements,
     The NPSIS Sample Receipt Program has a minimum hardware and software
requirement.  Here is a list of icems you will need:
          Hardware:
                    One (1) IBM PC. XT. AT, or Personal System modal with at
                    least 640K memory.

                    One (1) 2400 or 1200 baud Hayes or Hayes compatible nodei
                    with cables. (See Carbon Copy guide for cabling requir-
                    ements and a description of usable modems)

                    One (1) data transmission phone line.
           Software:
                •    NPSIS Sample Receipt  Program access provided for you by
                    ICF.

                •    One  (1) copy Carbon Copy  software which  is provided co yo
                    by ICF for  che duration of  NPS.
 1.2   Initial  Installation Steos.

      Before you can  access and use  SPSIS.  you must first  load  the  Carbon Copy
 software  onto your PC.  The directions  are provided in che Carbon  Copy  manual
 One  item  you  will want  to include  Is  an entry into the "Call Table".  This
 entry will include a name, telephone  number,  and password for  the  NPSIS
 computer.   To enter  these items  Into  che Call Table,  press "2"  from the Carboi
 Copy Parameters'  Screen.  The  information  you must enter  consists  of the
 following:

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                •    Name:  NFS

                •    Telephone Number:  703-^1-0629

                •    Password:  MPS
1.3  Paraagrgrs for C"lBB1Jn1 cations .


     NFS IS will maintain a sec configuration  throughout operation.  Any
changes due co updates in equipment or the system which will affect your
ability to communicate through Carbon Copy will be  forwarded to you.  The
paraaeters which will be maintained at this time are:

               •    2400 baud modem speed.

               •    Answer ring count equal co one.

               •    Re-boot on exit after 5 minutes.  (If there is a power
                    failure or some other type of interruption, you can log
                    back on to NFSIS and resume your  session.)

               •    five minute inactivity time constraint.

               •    Two password attempts.
2—E&fiBXXEKLA
SAMPIJt RECKTPT TO HPSTS
2 1  Establishing a Communications Link
     Once you have installed Carbon Copy and have all of the necessary
hardware, you are ready to "log on" to the NPSIS computer at ICF.  To do this

          Type: C:> CCHELP UPS    in your directory containing Carbon Copy.

This command will automatically dial the NPSIS computer, send your password
for verification, and establish a data link between the two computers.  You
will be able to discern what is taking place by messages to your screen.

2.2  Entering A Sfljy^t Receipt Into NPSIS.

     Once you have established a data link, ( e.g., are "logged on"), you vil
see on the  screen exactly what is on the screen of the NPSIS computer.  This
screen you  are viewing is the main menu for the Saaple Receipt Program.
Remember that you are controlling the NPSIS computer via a 2400 baud phone
line and your typing will appear on the screen ac a much slower race than yoi
are accustomed to.  A few tips on how to use the system are outlined in the
next section.

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2.2.1   Useful  Tips  on How co Use MPSIS.

     Before  you scare,  a few things Co remember are:

     •     Pressing  che  "Esc" key will cancel all changes  for che screen you
          are  currently in and return you co che previous screen.  Pressing
          "Esc" ac  che  Searching Screen recurns you  co  che main menu.

     •     Pressing  "PgDn" or "PgUp" will save the  items you have entered in
          che  current screen and place you in the  next  or previous screen,
          respectively.  This feature is handy to  use when you only have a 1
          items to  enter in a screen which prompts for  several items.

     •     Pressing  "Enter", "arrow up",  or "arrow  down" will move the cursor
          from field to field in each screen.  Remember chat using the
          sideways  arrows will not work.

     •     Pressing  che  "Alt" and "Right Shift" keys  together will place the
          Carbon Copy Control Screen over che NFSIS  Sample Receipt Program.
          You  can then use che communications features  in Carbon Copy.
          Pressing  "F10* again when you are chrough  will replace the NPSIS
          Sample Receipt Program screen you were currently in back on your
          screen,  and

     •     Because you will are mosc likely co be entering information
          regarding a number of kics ac one time,  after you save or cancel
          your entries for one kit. you will be placed at che initial Sample
          Searching Screen for a new kic.  If you  are finished with your da.t:
          entry, simply press "Esc" co exit che Sample Searching screen and t
          placed in the main menu.


2.3  A  Basic Outline of che S^Uffple Receioc Program.

     The NPSIS Sample Receipt Program has chree basic features:

               •    Initial reporting of a SPS sample kit of sample bottles.

               •    AbiliBy co edic or  re-edic an  existing report of a kic
                    receipt, and

               .•    Access co ICFs computerized mail system which provides ch
                    ability to send memoranda to ICF staff.

     The information obtained in an encry for a kit  of  bottles is:

               •    The kit identification number, the  FedEx airbill number.
                    and the last name of che person  making che entry.

               •    Any damage co  che kic as a whole such as melted ice or an
                    breakage of che cooler.

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                    Verification of which boccles belong  in a kit or cooler,
                    nocificacion of any missing boccles or any  additional
                    boccles, and

                    Any damage co each sample boccle which renders  ic unusab]
                    for analysis and Cescing.
     SPSTS Sanml* Receine Prt
     When you have completed the logon procedure, you will see  che  following
main menu on your computer screen:
                NATIONAL PESTICIDE SURVEY INFORMATION SYSTEM

                SELECTION MENU FOR REPORTING SAMPLE RECEIPTS    04/05/88
                         Report \ Edic a Sample Receipt
                         Send a Memo

                         Press 
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               N'PS  Sample  Receipt Searching Screen
         ** Encer :he  following items co access kit information  **

         To find che Kit  information in NPSIS in the most complete
         and accurate  fashion,  please enter the Kit number and the
                         FedEx airbill number.

          Enter kit number:
         	> PD-0001-151

          Enter FedEx  airbill «:
         	> 1111111111

          Enter your  Last name:
         	> CHIANG
                    Press ESC to exit the searching *
     If the kit number you have entered is incorrect, or if the kit number ai
FedEx airbill number combination is incorrect, NPSIS will prompt you to  try '
enter these number again,  as illustrated on the next page.  It is possible-
that the FedEx airbill number on the kit is not the same as the FedEx airbill
number which was entered into the NPSIS system.  This could happen if the
field team loses or damages the airbill.

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     One* you have correctly identified the sample kit, NPSIS will ask you if
:here is any damage co  che  kit as  a whole:
   Kit  No. :    PD-0001-1S1


     Uas  there any damage to the sample kit?   (Y/N)
               PgDn (Next page),  PgUp (Previous page), Esc (Exit)

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     Next. NPSIS will ask you co survey the concents of the kit and check ch«
which bottles are contained within che kit.  You should then look ac the
bottle labels and determine if any are missing.  Don't forget to check and
determine if any bottles have been included in the kit which do not appear  01
the list provided by NPSIS on this screen:
   Kit No.:    PD-0001-151
      Please compare the following bottle numbers
            with those in the sample kit.
             Bottle No:
             Bottle No:
             Bottle No:
             Bottle No:
             Bottle No:
             Bottle No:
PD-0001-1-1-01
PD-0001-1-1-03
PD-0001-1-3-01
PD-0001-1-3-03
PD-0001-1-9-01
PD-0001-1-9-03
      Did you receive exactly these bottles  in  the  sample kit? (Y/N) H
                PgDn  (Next page), PgUp  (Previous page),  Esc  (Exit)

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       ERROR!!   The  kit you entered cannot be found.  .

                 Kit number:   PD-0001-151
                                    AND
       FedEx airbill number:   1111111111

            Please check these numbers and try again!

        NPSIS  is  designed to track Kits and FedEx airbill numbers.
        The  Kit and FedEx airbill number combination you have entered
        does not  match what is currently in the system.  Please enter
        the  correct combination.   If you still have problems, try
        Leaving the FedEx airbill * BLANK.   Only enter the Kit number.
Press any key to continue...
     Then,  you will encounter this screen insuring that you have entered the
FedEx airbill number:
    Kit No.:    PD-0001-151
        Did you encer the correct Kit numoer and FedEx airbill number?
        SPSIS is designed to store and rrack all FedEx airbill numbers.
        This Kit may have a different FedEx airbill number than the
        system,  please enter the new FedEx airbill number:
     Note:  if the correct airbill number was entered before, hit ENTER.
            PgDn (Next page), PgUp (Previous page). Esc (Exit)

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     Next,  NPSIS prompts you Co indicate if any of the individual bottles ha-
been damaged and rendered unusable for analysis:
   Kit No.:    PD-0001-151


      Was there any damage to the sample Bottles?  (Y/N) Y
               PgDn (Next page), PgUp (Previous page), Esc (Exit)

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     If you press "Y" , .VPSIS will then prompt you  for  the apparent cause of
damage:
   Kit No.:    PD-0001-151


      Was chere any damage to the sample kit?   (Y/N)


      Please indicate the cause for damage:

           Kit is broken  (Y/N)  Y

           Ice is melted  (Y/N)

           Other Reason   (Y/N)

       Please enter any comments about the sample kit.

     Comments:  Broken upon arrival.
     Comments:
     PgDn (Next page), PgUp (Previous page), use f ^ or  *-* to select field.

     There may already be comments regarding the kit  in the comment field
shown in the above screen.  In this case, please enter your comments after an
which already appear.  This insures that no information is destroyed.

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     Sow you have completed all of the necessary information needed to verify
chac che proper samples have reached their final destination in usable
condition.   You may save your kit entry by pressing  "Enter".  If you wish to
cancel your kic entry and cry again, press "N" and "Enter".  If you wish  co
view or edic :he current kit entry,  press "R" and "Enter"  and NPSIS will  plact
you back ac che beginning of your entry.
     You have completed all of the data entry screens for this Kit.

     You may save your entry by pressing 'Enter' .

     You may cancel your entry by pressing 'N' and  'Enter'.

     You may verify or edit chis entry by pressing  'R' and  'Enter'.


                    * * *  Accept entries?  * * *
                * Press    ^-      co Save           *
                * Press N and  ^—* co Cancel         *
                * Press R and  -**-1 to Verify or Edit * Y
     By pressing "Enter" ,  you have saved ail of the  information necessary for
a particular sample kit.  NPSIS assumes chat you will encer more Chan one kit
entry per session.  Therefore, you will be placed at  the  initial "Searching
Screen".  If you are finished, press "Esc" and you will be returned to che
main menu.  You can then log off of NPS IS by pressing "Alt" and "Right shift"
at the same time.  You may also send a memo through the ICF computerized mail
system.  To do chis, cursor down co che second menu choice and press "Enter".

     Th« next cwo pages of chis meao describe how to  use  the  ICF electronic
mail system.  Note that the password for you is NPS.  The mail system software
program will prompt you for this password before it will  allow access to the
system.  Also, when you are selecting che recipients  of your  memo, please
press che space bar beside che initials "NPS".  This  will send your memo to
all ICF staff involved in the NPS project.  If you wish to send memos to a
particular  ICF staff member, please call 3eth Estrada for the identification
number of che desired ICF employee.

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     If you have pressed "N",  indicating chac you did noc receive exactly wha
NPSIS assumes you have received,  you will be prompted to encer the appropriat
information.  This information includes pressing a "Y" or a  "N" beside each
bottle, and entering the bottle number found on the labels of any additional
bottles vou have received:
Kit







1.
3.
5.
7.
No.: PD-0001-151
Please indicate which
Bottle No:
PD-0001-1-1-01
PD-0001-1-1-03
PD-0001-1-3-01
PD-0001-1-3-03
PD-0001-L-9-01
PD-0001-1-9-03

bottles you received:
Received (Y/N)
N
H
Y
Y
Y
Y
Please indicate any additional bottles you received:
Bottle No.: PD-0002- 1- 1-05 2. Bottle No. PD- 0002- 2- 2- 01
Bottle No.: PD-OO04-4-4-01 4. Bottle No. - - - -
Bottle No.: - ... 6. Bottle No. - ...
Boctle No. : - - -
8. Bottle No. - .--
     PgDn (Next page).  PgUp (Previous page), use f |or •*—'co select field.

     Notice chat the user has indicated that he did not receive the first rvo
bottles on the list.  Also note that the user has indicated additional bottle
which have come in the sample kit, but which were not on  the list.

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     In order to complete the appropriate information on damaged samples, yoi
muse first press a. "Y" or a "N" in the field Labeled "Damaged Y/N".   If you
have entered a "Y" in this field, you must then identify whac che cause of t!
damage is, to che best of your abilities.  As noted on  the  computer  screen
below,  che "Other" category should be used if the sample is unusable but is
not broken.  Please try to comment whenever possible.
   Kit No.:    PD-0001-151

           Please indicate which bottles are damaged  by  entering Y or N,
           and for those which are damaged, indicate  the  cause  of daaage.
                                   ---CAUSE  ---
    Bottle No:   Damaged           Broken      Other          Comment
    	    (Y/N)              (Y/N)      (Y/N)

   PD-0001-1-3-01   H
   PD-0001-1-3-03   H
   PD-0001-1-9-01   H
   PD-0001-1-9-03   H
   PD-0002-1-1-05   H
   PD-0002-2-2-01   Y                Y
   PD-0004-4-4-01   N
   The  'Other' cause category is for reporting contamination of a. sample,
   e.g. contamination noted on the Sample Tracking Form,  air bubbles,
   or other reasons a sample is unusable.
PgDn (Next page),  PgUp (Previous page), use 4 I or
                                                            to  select  field.

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                                  ELECTRONIC MAIL
Function
Augment   office   communications
electronic transfer of notes and files.
with
        Reading Mail
Summary
Electronic Mail (E-Mail) allows you to send,
receive,  read,  and  subsequently  save  or
discard notes and attached files.

When you  power  up your  workstation  you
will  automatically enter E-Mail if  you  have
received  any mail.  Enter your password to
check your  mail,  or press   twice to
avoid  E-Mail and  continue  to the  Assist
main menu.
Instructions
Operation  of  E-Mail  is  similar  to  Lotus
1-2-3.  Press the Fl  key to receive help  at
any  time during  operation.   If any  more
help is  needed  contact  workstation support
to receive a manual.

For  more  information  on any feature  of
electronic  mail, use  Network  Courier's on*
line help or refer to the User's Manual.
Passwords

Your password will be 'password' until you
change  it  yourself.  Once you  have givea
your  password and entered E-Mail, you can
change  your password  by selecting Options,
then Password.
                                            met
                                            pr<
Select   "Read*  from   your
Highlight    read,then
.
Select the note to read:
a.    Highlight the note (using
     the arrow keys); and press
     .
B.    To save the note, select
     "Storage", then "Save". Enter
     the name of the file to which
     the note should be saved.
Press <£SC> to select another note.
        Writing Mail

          1.   Select "Compose", then "edit".
          2.   Press  when the  highlig
              moves to "TO".
          3.   Select the recipients(s):
              a.    Move the highlight to the
                    first recipient's initials.
              b.    Press the space bar.  A
                    small mark will appear.
              c.    Repeat steps a and b for all
                    recipients. Press the space b;
                    twice to "de-select" recipients
                    The small mark will disappej
              d.    Press  to cancel the
                    entire list.
          4.   Select the initials of those who wi
              receive copies:
              a.    Press the down arrow  to  m
                    to "CCT.
              b.    Select recipients as instruct*
                    above (step 3, a-d)

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Writing Mail, continued

  5.    Eater a. subject and  priority.
       (optional)
  6.    Select attachments (optional):
       a.    Press  and type the
            path  for the document(s).
       b.    Press  and select the
            document(s) to be attached.
       c.    Repeat steps a  and b for
            documents in another directory.
  7.    Enter the text  of your message.
  8.    Press  when finished.
  9.    Select "Transmit" to  post the note
       and attachments.

Quitting tht Mail Program

  1.    Press  from the menu.
  2.    Select "YES".

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                                            App*ndbcG
                                            Revision No. 3
                                            D«to:  February 28, 1990
                                            Pafl*1 of 3
                APPENDIX G

NFS RAPID REPORTING SYSTEM DATED 4/12/88

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   pl- ••    UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
v    '*                         CINCINNATI OHIO *S268
   MEMORANDUM

   DATE:    April 12, 1988

   SUBJECT: KPS Rapid Reporting System
   FROM:    David J. Munch, Chemist
            Drinking Water Quality Assessment Branch

   TO:      MPS Technical Monitors
       Jerry Kotas has requested that any confirmed results  of  health
   significance be reported as quickly as possible.  Therefore,  if  an analy
   listed in the attached tables is observed in the primary  analyses, at or
   above the rapid reporting limit, the following actions  should be
   instituted.  For any listed aoalyte where the rapid  reporting level  is
   less than or equal to 1/2 the minimum reporting level  (MRL),  any
   occurrence at or above 1/2 the MRL should also be processed  as below.
   (Note:  The procedures for determining th* occurrence of  X?S analytes thi
   may occur below the MRL, and are not listed on the attached  tables,  have
   not yet been finalized.)

       1.   The appropriate confirmational analyses  (GC/MS for  methods  1-3,
            6-1, second column for Method 5) should be  performed as soon as
            practical.

       2.   The laboratory should telephone their Technical  Monitor, the sai
            day the confirmation is completed.                             .

       3.   The laboratory should immediately document  the observed result  i
            a letter to their Technical Monitor.

       4.   As quickly as possible on the day the above telephone call  is
            received from the laboratory, the Technical Monitor should  infer
            their Laboratory Analytical Coordinator of  the finding. The
            Technical Monitor should forward on to the  Laboratory Analytical
            Coordinator the above documentation, with any  comments  he/she  ma
            have concerning the validity of the result.

       5.   The Laboratory Analytical Coordinator should inform Jerry Kotas
            and the second Analytical Coordinator of the finding by telepbon
            the same day if possible, and in writing after the  documentation
            is received from the Technical Monitor.

       6.   The Analytical Coordinators are to request, through the
            appropriate Technical Monitors, that all analyses  for this  sampl
            site be conducted, and reported in writing, am soon am  practical

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                 NZTBOD 12
   AMALYTE                    JAPID REPOKTIlfG  LXVIL

tlpht-Chlordtne                     0.5 ug/L
gaaaa-Chlordtae                     0.5 uff/L
Cblorotbtlonil                      150 ug/L
Daethal (DCPA)                     5,000 ug/L
Dieldrin                            0.5 ug/L
Propacblor                          130 ug/L
Triflurtlin                           25 ug/L

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                                             Appendix H
                                             Revision No. 3
                                             Date: February 28, 1990
                                             Page 1 of 2
                  APPENDIX H

DATA REPORTING FORMAT CHANGES DATED 4/18/88

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DAT*:    iprii is. 19M

SUBJECT: Oat* Rtporting Format Changes

mOB:    David J. Hunch, Chemist
         Drinking Rater Quality assessment Branch

TO:      IPS Technical Monitors (See below)


    The purpose of this Memorandum is to consolidate  the  changes  to  the
I?S data reporting format, which have occurred since  it vas  originally
constructed. Tou have preTiously been supplied vith most  of  these changes,
but please check to b« sure that they have all been relayed  to  your
contract and referee laboratories.

    1.   Line 2. columns 1-6 are to be used to record the pi measured  in
         the field. This data will b* found on the field  sample tracking
         sheet.

    2.   Line 2. columns 67-70 are to be used to record the  pi  measured
         upon sample receipt at the laboratory. This  oaly applies  to
         methods 5 and 9.

    3.   Line I, columns 1-13. Sample Identification  lumber, have  been
         expanded to columns 1-14.

    4.   The data entered on line 10, columns 52-60,  concerning the
         internal standard, it should be entered mot  as the  peak  area  but
         as the "percent recovery" as compared to the mean observed  for
         the calibration curve.

    In order to simplify the "Sample Type" cod* (lime 11, columns  1-5).
the following codes should be used to designate the various  types  of
spiked samples.
    LCSt
    LSStff
    OTS0
    rrst
Laboratory Control Sample
Laboratory Spiked Sample
Day 0 Tim* Storage Sample
Extract Tim* Storage Sample
Sample Time Storage Sample
    In addition,  two clarification* have b*«m mad* to  the codes  for
analyt* concentration entries.

    •9ft • lot Detected  « 1/3 liaimum Importing Limit)
    -111 • Below  Minimum It porting Limit but greater than or *
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                                                            Appendix I
                                                            Revtelon No. 3
                                                            Date: February 28, 1990
                                                            Page 1 of 5
                                  APPENDIX I

NPS ANALYTE REPORTING BELOW MRL AND IDENTIFYING UNKNOWN PEAKS DATED 6/1/88

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          I    UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
          w

          '            CMvnioNMi«rrAi CHIMICTIV LASOHATOHY. MASA/NCT.
    '•< ««J>»*                  SmUMMQ «•. MSTl. MB
                               June  1,  1988
MEMORANDUM

SUBJECT:  NPS Anaiyte Reporting Below  MRL and Identifying  Unknown  Peaks

FRCM:     Bod Maxey, Analytical Coordinator
          Environmental Chemistry Laboratory     /^  I \juy4J*

TO:       Dave Munch, Analytical Coordinator
          TSD-Ci nci nnat i

          Aubry E. Dupuy, Jr., Tecnnical  Monitor
          Environmental Chemistry laboratory

     Attached are the procedures that  NPS analytical contractors and  referee
laboratories must adhere to in complying  with the OPP request to report the
presence of analytes below the Minimal Reporting Liroits and to  attempt  ident
fication of unknown peaks.  Please  see that your contractors and Technical
Monitors get this information and that applicable parts are incorporated int<
their respective QAPPs.

     If you have any questions, give me a call.

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        Determining and Reporting the Presence of NPS Analytes Below The
             ".inimal Reporting Levels and Identifying Unknown Peaks


Background Information

     The Office of Pesticide Programs (OPP) has requested that the NPS analyti-
cal contractors and referee laboratories make an effort to  report the presence
of NPS analytes below the Minimal Reporting Levels (MRL).   Me have also been re-
quested to attempt to identify unknown peaks or responses.  To assure chat spur-
ious or ambiguous data is not reported and that a uniform system or analytical
routine is used at all laboratories to accomplish these requests* criteria have
been developed for handling both situations.

Procedure for Determining and Reoomng the Presence of NPS Analytes Below the
1.   For methods 1-7, only peaks with responses of between one-half the establis
     ed MRL and the MRL V on the primary column will be investigated.  A respon
     on the "secondary" GC column, indicating the presence of the analyte, is al
     required for additional work.

2.a  The first occurrence of a peak meeting the requirements of  (1) is noted and
     reported to the Technical Monitor, but no action is taken B/.  Upon a secon
     occurrence of the same suspect analyte, additional work is  required as fol-
     lows.  After five successive failures to "confirm* on the secondary column
     the response on the primary column, discussions with OPP personnel will tak
     place before continuing low-level analytical work on the analyta(s).

  b  With methods 1,2,3, 6 and 7, for responses meeting the requirements of (1)»
     and  (2), the laboratory will attempt LR GC/MS c/ confirmation if the GC/MS
     analyst  feels  it  is within the capability of his instrument.  If the confir
     mation  is not within the capability of the laboratory, such extracts are
     sent weekly, under iced conditions by next-day air, to the  appropriate re-
     feree  Laboratory  having HR GC/MS c/ capabilities.  Copies of chronatograms
     and all  pertinent sample information must be sent along with the extracts
     including extracts of the related Method Blank.   (NPS will  absorb the cost
     of these shipments.)  It is preferred that extracts be in sealed glass
     ampules, but other vials and teflon-faced closures are acceptable if they
     provide a  tight seal and do not  contribute  interferences  to th« extracts.
     Volume level must be marked on the outside of  the vial or ampule.


 A/  * NPS  method 1 MRL  « 4  x  EDL     NPS method 5 MRL  -  3  x EDL
     NPS  method 2 MRL  - 5  x  EDL     NPS method 6 MRL  » 3 x EDL
     NPS  method 3 MRL  « 5  x  EDL     NPS method 7 MRL  «  3  x EDL
     NPS  method 4 MRL  « 5  x  EDL

 B/ * Method 6 has an MRL  >  the Health Advisory Laval.  All  suspect BID
     responses of 1/2  MRL  -  MRL require additional  work for  this method.

 C/ - LR « GC/MS « Low Resolution  mass spectromatry.
     HR GC/MS - High Resolution mass  spactronacry.

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  c.  For Metnods 4 and 5, HPLC Methods, there ia no provision for GC/MS
      confirmation.  Suspect analytes between 1/2 MRL - MRL will be subject
      "- (1)  and (2a) above.

      'revisions of (2b) also apply except references to GC/ns requirements.

3.    Whether the identification of the analyte is attemoted at the contractoi
      Laboratory or at the referee laboratory, only analytes positively con-
      firmed by GC/MS will be reported beyond the Technical Monitor for the
      Method and the Analytical Coordinators.  No unconfirmed data will be
      reported outside the NFS analytical system.  Unsuccessful attempts at
      confirmation will also be reported to the Technical Monitor.

4.    Following either the successful GC/MS confirmation of two such response;
      for the same analyte or two successive failures to confirm the analyte
      by GC/MS without any prior successful GC/MS confirmation on any samples
      discussions with OPP personnel will cake place before continuing low
      level analytical work on that analyte.

Procedure for Determining the Identity of Non-NPS Analytes

      It is expected that, over the course of the NFS Program, numerous
extraneous  responses will be evident on chromatograms from the various methoc
The contractor or referee laboratories will be required to attempt identifi-
cation of peaks or responses on the primary column exhibiting the minimal cm
below.

      1.  For Methods 1, 2, 3, 6, and 7, if, upon initial analyses, the respoi
          of an extraneous peak on the primary column is equal to or greater
          the response of the nearest NFS analyte on that column at 10 x MRL
          (Minimal Reporting Level), an attenpt must be made to identify that
          known peak or response by GC/MS.  Pull scan spectra and subsequent
          library search are expected and must be followed by comparison of t
          spectra of the unknown compound with those of an authentic standard
          the suspected compound.

      2.  The work in (1) must be attempted by the contractor and/or referee
          oratories on the  first occurrence of such a peak and the results of
          attempt  reported  to the Technical Monitor for the Method.  If the
          analytical contractor feels his system or instrument is not capable
          the confirmatory work, he oust send both that extract and that of t
          related Method Blank t? the appropriate referee lab under iced
          conditions by next-day air.

          It is preferred that extracts be  in sealed glass ampules, but other
          vials and teflon-faced closures are acceptable if they provide a ti
          seal and do not contribute interferences to the extracts.  Volume 1
          must be marked on the outside of  the vial or ampule.  (IPS will aba
          costs of these shipments.)

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      Specific sample and analytical  information  must accompany each such
      extract.

        o  Sample i.d. number/  weiqht of sample matrix contained in the
           ampule, copies of chroma tog rams from the primary GC col mm,
           identification of the retention window for the unknown response!a]
           as defined by the last NFS analyte to elute before the unknown
           peak or response and the first NFS analyte to elute following the
           unknown response.

3.    Whether the identification of the unknown compound is attempted at the
      Contractor Laboratory or at the referee laboratory/ only the compounds
      positively confirmed by GC/MS will be reported beyond the Technical
      Monitor for the Method and the Analytical Coordinators.  No unconfirmed
      data will be reported outside the NFS analytical system.  Unsuccessful
      attempts at identification will also be reported to the Technical
      Monitor.

4.    Following either the successful confirmation of two such extraneous peal
      proving to be the same compound or two failures to identify a response
      with the same retention time without a prior successful GC/MS confirmat:
      on a sample/ discussions with OPP personnel will take place before cont:
      with identification work on that particular compound.

      THE QUALITY ASSURANCE PROJECT PLANS FDR BOTH  THE ANALYTICAL CONTRACTORS
      AND REFEREE LABORATORIES TOR METHODS 1, 2,  3, 6, AND 7 MUST REFLECT THE1
      COMMITMaJTS TO THESE TWO REQOIREMHTTS.

      THE QUALITY ASSURANCE PROJECT PLANS FOR BOTH THE ANALYTICAL CONTRACTORS
      AND REFEREE LABORATORIES FOR METHODS 4 AND 5 MUST REFLECT THEIR COMMIT-
      MENTS TO THE REQUIREMENT FOR DETERMINING AND REPORTING NPS ANALYTES BELC
      THE MRL.

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                                                  Appendix J
                                                  Revision No. 3
                                                  Date: February 28, 1990
                                                  Page 1 of 4
                      APPENDIX J

REVISIONS TO NPS RAPID REPORTING SYSTEM DATED 6/9/89

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             \ 5J8R'    UNITED STATES ENVIRONMENTAL PROTECTION AGENCY

                                             -            -
               KIMORANDUM

               DATS:    June 9, 1989

               SUBJECT:  Revisions to HPS Rapid Reporting  System

               rtOM:    David J. Hunch. TSD Project Manager
                        National Pesticide Survey

               TO:      NPS Technical Monitors
                   Recently the health  adTitory documents  for  priority UPS analytes  were
               finalized (at least as finalized as  they  ever get).   In many cases,  the
               health effect value used to deteraioe  the concentration of  each  analyta
               that "tri90tred" the  rapid reporting systea. has  changed.   The purpose of
               this •••ora.advia is to transmit  to  you  the final rapid reporting
               concentration*, and to remind everyone of the provisions of the  rapid
               reporting system.

                   le you remember,  if  an aaalyte luted in the  attached tables is
               observed 10 the primary  analyses,  at or above the rapid reporting limit.
               the following actions should be instituted, for thy  listed  antlyte where
               the rapid reporting level is less  than or equal to 1/2 the  einiaui
               reportiof level  (KRU. aay occurrence  at  or above 1/2 the HXL should  alto
               be processed as belo*.

                   I.   The appropriate confirmational analyses  (CC/HS for methods
                        1-3,i-7.  second eoluma for method  b) should b* performed as  soon
                        as practical.

                   :.   The laboratory  should  telephone their  Technical Monitor, the same
                        day the confirmation is completed.

                   J.   The laboratory  should  immediately  document  the observed result in
                        a letter  to  their Technical Hoaitor.

                   4.   &• quickly as possible oa the day  the  above telephone call  IS
                        received  from the  laboratory, the  Technical Monitor should  inform
                        their  laboratory Amelytieal Coordinator  of  the finding. The
                        Technical Monitor  should  forvard on  to the Laboratory Analytical
                        Coordinator  the above  documentation,  with aay comments  he/she nay
                        have  coaceraiaf the validity  of the  result.

                   5.   Tae Laboratory  Analytical Coordinator  should inform the Surtey
                        Director  and the second Analytical Coordinator of the finding by
                        telephone the sene day if possible,  and  in writing after the
                        docuaemtetiom ie received frost the Technical Monitor.
U.S. Environmental Protection Agency
Region 5, Library (PL-12J)
77 West Jackson Boulevard, 12th Floor
Chicago,  IL  60604-3590

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                 HETBOD 12
   JUULYTE                    RAPID REPORTIUC LTYIL

tlpbt-Chlordtne                     0.5 ug/L
guaa-Chlordane                     0.5 u0/L
CblorotbAloail                      150 ug/L
Dtcthtl (DCPA)                    5,000 ug/L
DicldriD                            0.5 ug/L
Propacblor                          130 ug/L
Triflurtlin                          25 ug/L

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                                   - 2 -
    6.   The Analytic*! Coordinators are  to  requeit,throuoh  the
         appropriite Technical Monitors,  that  all analy***  for  this  saaple
         •it« b« conducted,  and reported  in  writing.  «*  «oon a*  practical.

    II you ha»* any qutation* conc«rnmo  th»t« proc«dur««,  pl*a*e l«t  lob
H«x»y or •• knot*.  Xl«o,  pl«a«» pass on thif information to  your contract
and referte laboratories.

Attachjient
Addressees:

    M. Bolyard
    A. Dupuy
    R. Haxey
    I. Sorrell
    M. Zuiker
cc:
    J. Bolted
    H- Brass
    L. Jobnson
    A. Kroner
    C. Lester
    L. Vac Den Berg

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