&EPA
United States           Office of Water (WH-550)     EPA 810-B-92-012
Environmental Protection   Office of Pesticides and     February 1992
Agency               Toxic Substances (H-7501C)
                QUALITY ASSURANCE PROJECT PLAN
                              FOR THE
     NATIONAL PESTICIDE SURVEY OF DRINKING WATER WELLS
           ANALYTICAL METHOD 6  - ETHYLENE TH1OUREA
                              Prepared by:

                               BATTELLE
                            Columbus Division
                             505 King Avenue
                        Columbus, Ohio 43201-2693
                              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
                                                                            Revision No. 3
                                                                            Date: April 29, 1988
                                                                            Page 2 of 2
                                      APPROVAL PAGE
o-
r-
                                                                            Date
<>BCD Project Manager

 	           Date
 BCD QAU Manager

 	           Date
 EPA Contract Technical Officer

 	           Date
 EPA Contract Project Officer

 	           Date
 EPA QA Officer

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                                                                        Section No 2
                                                                        Revision No 3
                                                                        Date: April 29, 1988
                                                                        Page 1 of 3
                              NATIONAL PESTICIDE SURVEY
                        QUALITY ASSURANCE PROJECT PLAN FOR
                      ANALYTICAL METHOD 6 - ETHYLENE THIOUREA
2.    TABLE OF CONTENTS

 Section                                                    Pages     Revisions     Date

     1.     TITLE AND APPROVAL PAGE                         2          3       4/29/88

     2.     TABLE OF CONTENTS                               3          3       4/29/88

     3.     PROJECT DESCRIPTION                             2          3       4/29/88

     4.     PROJECT ORGANIZATION AND RESPONSIBILITY        6          3       4/29/88
           4.1     Project Organization
           4.2     Authority, Responsibilities, and
                     Communication
                  4.2.a    NPS Contract Technical Monitor
                  4.2.b    NPS Contract Project Officer
                  4.2.c    Battelle Project Manager
                  4.2.d    CSC
                  4.2.e    Battelle Sample Receipt
                             Personnel
           4.3     Position of the QA Function within the
                     Project Organization

     5.     QA OBJECTIVES FOR MEASUREMENT DATA           6          3       4/29/88
           5.1     Initial Demonstration of Capabilities --
                     Determining Reporting Limits
           5.2     Initial Demonstration of Capabilities --
                     Determining MS Detection Limits
           5.3     Assessing  Laboratory Performance
                  5.3.a    Control Charts
                  5.3.b    Laboratory Control Standards
           5.4     Assessing  Surrogate Recovery
           5.5     Assessing  the Internal Standard
           5.6     Assessing  Analyte Recovery
           5.7     Assessing  Laboratory Contamination
           5.8     Assessing  Instrument Performance
           5.9     Analyte Confirmation
           5.10    Treatment  of Unidentified Peaks
           5.11    Performance Evaluation Samples

     6.     SAMPLING PROCEDURES                            4          3       4/29/88

     7.     SAMPLE CUSTODY                                 6          3       4/29/88

     8.     CALIBRATION PROCEDURES AND FREQUENCY        3          3       4/29/88
           8.1     Instrumentation
           8.2     Calibration Procedures

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                                                                        Section No 2
                                                                        Revision No. 3
                                                                        Date: April 29, 1988
                                                                        Page 2 of 3
2.    TABLE OF CONTENTS (continued)

 Section                                                    Pages     Revisions     Date

    9.      ANALYTICAL PROCEDURES                          2          3       4/29/88

   10.      DATA REDUCTION, VALIDATION AND REPORTING       7          3       4/29/88
           10.1    Data Reduction and Storage
                  10.1.a   Primary and Confirmatory
                             GC-NPD Analyses
                  10.1.b   GC-MS Identification or
                             Confirmation
                  10.1.C   Datastorage
           10.2    Data Validation
           10.3    Data Reporting
                  10.3.a   ASCII Data Packets
                  10.3.b   Monthly Reports

   11.      INTERNAL QUALITY CONTROL CHECKS                2          3       4/29/88

   12.      PERFORMANCE AND SYSTEM AUDITS                 4          3       4/29/88
           12.1    System Audits
                  12.1.a   Sample Receiving/Storage
                  12.1.b   Labwsre
                  12.1.C   Materials, Reagents, Solvents,
                             and Gases
                  12.1.d   Chemical Solutions/Performance
                             Standards
                  12.1.e   Analytical Methods
                  12.1 .f    Analyst Training
                  12.1.g   Equipment Calibration/
                             Maintenance
                  12.1.h   Facilities
                  12.1.i    Standard Operating Procedures
                  12.1.J    Data Records/Reports
           12.2    Performance Audits
           12.3    Audits Conducted by the USEPA

   13.      PREVENTIVE MAINTENANCE                         4          3       4/29/88

   14.      SPECIFIC ROUTINE PROCEDURES USED TO
           ASSESS DATA PRECISION, ACCURACY AND
           COMPLETENESS                                    2          3       4/29/88
           14.1    Standsrd Devistion
           14.2    Percent Recovery
           14.3    Relstive Standard Deviation
           14.4    Peak Symmetry snd Peak Gaussian
                    Factors
           14.5    Minimum Detectsble Level
           14.6    Estimated Detection Limit
           14.7    Minimum Reporting Level
           14.8    Control Limits

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2.   TABLE OF CONTENTS (continued)

 Section

          14.9    Dixon's Test
          14.10   Rounding Numbers and Significant
                  Figures

   15.     CORRECTIVE ACTION

   16.     QUALITY ASSURANCE REPORTS TO
          MANAGEMENT
                                                               Section No 2
                                                               Revision No 3
                                                               Date- April 29, 1988
                                                               Page 3 of 3
Pages   Revisions     Date
                  4/29/88
                  4/29/88
Appendices

    A.    METHOD 6.  DETERMINATION OF ETHYLENE
         THIOUREA (ETU) IN GROUND WATER BY GAS
         CHROMATOGRAPHY WITH A NITROGEN-
         PHOSPHORUS DETECTOR

    B.    DIXON'S TEST FOR OUTLIERS

    C.    ETU CONFIRMATION BY LOW-RESOLUTION
         GC-MS

    D.    STANDARD OPERATING PROCEDURE FOR USE
         OF ADMIRAL FREEZERS

    E.    STANDARD OPERATING PROCEDURE FOR USE
         OF HOTPOINT REFRIGERATORS

    F.    STANDARD OPERATING PROCEDURE FOR
         WEIGHT DETERMINATIONS USING AN
         ELECTRONIC ANALYTICAL BALANCE

    G.    STANDARD OPERATING PROCEDURE FOR
         THE USE OF TOP LOADING BALANCES

    H.    DATA ENTRY FORMATS FOR ASCII REPORTS

    I.    STANDARD OPERATING PROCEDURE FOR
         QUALITY ASSURANCE UNIT PERFORMANCE
         AND SYSTEM AUDITS FOR NPS SURVEY

    J.    STANDARD OPERATING PROCEDURE FOR
         PROPER USE OF SIGNIFICANT FIGURES
         AND ROUNDING
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                                                                              Section No 3
                                                                              Revision No 3
                                                                              Date: April 29, 1988
                                                                              Page 1 of 2
3.    PROJECT DESCRIPTION
      The U.S. Environmental Protection Agency will conduct a National Pesticide Survey to locate
and define the type and extent of pesticide contamination of national ground water and to aid in
predicting causes and trends in ground water contamination. There will be eight methods used for
the Survey, seven for the determination of pesticides and pesticide degradates and one for nitrate, for
determination of trace levels of over 120 analytes of interest in ground water samples collected for the
NPS.  Approximately 1500 domestic and community water system wells will be sampled.
      During implementation of Contract No. 68-03-3525, Battelle will conduct National  Pesticide
Survey (NPS) Method  6 to detect, quantify, and confirm the presence or absence of ethylene thiourea
(ETU) in ground water by gas chromatography using a nitrogen-phosphorus  detector (GC-NPD).
Commitment to quality is an integral part of every staff member's job at Battelle. The Project Team
recognizes the formal functions necessary to assure clients that the work meets their needs and to
define and control the quality of data and products. These functions are quality assurance (QA) and
quality control (QC). Quality assurance functions are a management tool independent  of the technical
organization of projects, including all systems designed to assure both Battelle's administrative and
project management and the client of the quality of our research and products.  Quality control
functions are integral activities within technical support projects that are designed to assess or control
data precision and accuracy. These functions deal with establishing procedures for attaining
prescribed standards of performance  in the monitoring and measurement processes.  Specific QA
goals for Contract No. 68-03-3525 include:
           Fulfillment of every commitment to quality, integrity, and propriety,
      •     Identification, anticipation, and avoidance of potential risks,
           Assurance of credentials of technical personnel,
      •     Quality assurance training,
      •     Inspections and audits for adherence to the QA Project Plan and completeness and
           accuracy of reporting, and
           Assurance that any problems are promptly assessed and appropriate corrective
           actions are implemented.
Specific QC goals include:
           Assurance that all data are scientifically valid, defensible, and of known and
           acceptable precision and  accuracy, and
           Maintenance of the QA Project Plan after consultation with EPA to reflect all
           available information for NPS Method 6.

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                                                                              Section No  3
                                                                              Revision No. 3
                                                                              Date: April 29, 1988
                                                                              Page 2 of 2
This document describes quality assurance and quality control procedures to be enacted during the
project. Each of the components listed below is considered an integral part of the entire Quality
Assurance Project Plan, and each component is necessary to assure defendable analytical results:
      Both data and product quality are vitally important.  Data quality includes all features  and
characteristics that bear on given objectives, particularly accuracy, precision, completeness,
representativeness,  and comparability. Product quality encompasses the means of ensuring the
quality of the data and the ability to respond to EPA needs in an efficient and responsive manner.
These goals of data and product quality are reflected in this QA Project Plan.

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                                                                             Section No 4
                                                                             Revision No 3
                                                                             Date:  April 29, 1988
                                                                             Page 1 of 6
4.    PROJECT ORGANIZATION AND RESPONSIBILITY
      Three major activities are key to efficient, high-quality projects: planning, performance, and
assurance. High-quality products are realized through Battelle's project management system.
High-quality performance is achieved through the skills and competence of Battelle's technical staff
following carefully designed QC  procedures.  QA is the responsibility of the technical staff with
assistance from Battelle's independent QA organization that verifies compliance with regulations and
project plans.

4.1   Project Organization
      The organization of this project, shown in Figure 1, has been structured to provide the planning,
control, accountability, technical quality, responsiveness and flexibility needed to achieve EPA's
objectives for the NPS.  This  organization will also ensure that the project will have the attention and
commitment of Battelle management to provide responsiveness and quick resolution of any conflicts.
      Ms. Tina Engel will serve as Project Manager on Contract No. 68-03-3525 because of her direct
involvement with the development of NPS Method 6.  Ms. Engel has been Battelle's focal point for
interaction with EPA personnel during the development and validation of NPS Method 6. Her
management of this project will assure a smooth transition into the NPS analytical contract.
      Ms. Engel  reports directly  to Dr. Judith Gebhart, the Manager of the Analytical Chemistry
Section.  Dr. Gebhart will review the progress of the project and, as needed, provide management
guidance and assistance to Ms.  Engel.  Dr. Gebhart reports to Dr. Ronald L Joiner, the Vice President
of the Chemistry and Biomedical Sciences Department; Dr. Joiner is also available to provide
additional management assistance. The relationship of the project to the overall Battelle organization
is shown in Figure 2.
      Also key to the project  are the following personnel:
      •     Ms. Ramona Mayer, Manager of the Quality Assurance Unit (QAU) -Ms. Mayer
           directed QAU activities during the NPS Pilot Study.  Ms. Mayer will coordinate QA
           activities and report  directly to Battelle senior management.
           Ms. Sandy Anderson -- Ms. Anderson is the QA Specialist assigned to conduct
           audits and review data for this project.  Ms. Anderson has chemistry training and
           years of experience  auditing data generated by the Analytical Chemistry
           Department.
           Mr. David Zimmerman, Method  Leader - Mr. Zimmerman performed all aspects of
           Method 6 during  the NPS Pilot Survey. He will be responsible for overseeing daily
           laboratory activities,  reviewing results, and performing all GC analyses.
           Mr. Thomas Danison, Sample/Data Manager - Mr. Danison developed and will
           maintain the Method 6 database during the NPS Pilot Study. Mr.  Danison will
           oversee sample receipt and generation of analysis results.

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       FIGURE 1

PROJECT ORGANIZATION
                                     Section No. 4
                                     Revision No. 3
                                     Date: April 29, 1988
                                     Page 2 of 6
   Vice Presiaen-
   -. D.Barker
h
                   •iirtU  P"!«.
                     R . A . M<
     ..s
         Enaei
  fietnod Leaner
  I . - . I: .•nffi&r.T.sn

   E. A. •- ircher

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                                             Section No. 4
                                             Revision No. 3
                                             Date: April 29, 1988
                                             Page 3 of 6
                    FIGURE 2


RELATIONSHIP OF PROJECT TO OVERALL BATTELLE ORGANIZATION
             Battelle
         Columbus Division
        W.J.Madia,President
                      Manufac & Adv  Materials
                      Elect & Defense Systems
                      Inform & Engin Systems
      Biological and Chemical
     Sciences Technical Center
     A.D.Barker, Sr. Vice Pres
                       Ocean Sciences & Tech
                            Toxicology
                      Environmental  Sciences
     Chemistry and Biomedical
        Sciences Department
       R.L.Joiner, Vice Pres
                      Medical  &  Chem Sciences
                 —  Chemistry & Spectroscopy
                      Hazardous  Materials Lab
       Analytical Chemistry
              Section
        J.E.Gebhart,Manager
           Project Team
        T.M.Engel, Manager

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                                                                             Section No 4
                                                                             Revision No 3
                                                                             Date: April 29, 1988
                                                                             Page 4 of 6
      •     Mr. Bruce Hidy, MS Confirmation Coordinator -- Mr. Hiay will provide mass
           spectrometry (MS) support.
      •     Ms. Elizabeth Kircher -- Ms. Kircher will be trained by Mr. Zimmerman and
           subsequently perform laboratory functions required by Method 6.

4.2   Authority, Responsibilities, and Communication
      Final responsibility for QA/QC for this project rests with the Project Manager, Ms. Tina M. Engel.
Ms. Engel will communicate results, progress, and other pertinent information to the NPS Contract
Technical Monitor. Ms. Engel will be the primary contact at Battelle for the NPS Contract Technical
Monitor.
      Mr. David Zimmerman, the Method Leader, will have  primary responsibility for quality.  Mr.
Zimmerman will direct all daily laboratory activities and perform required GC analyses. Mr.
Zimmerman will also be responsible for training laboratory  personnel (Ms.  Kircher) in the use of
Method 6.  Mr. Zimmerman will evaluate Method 6 analytical and  QC results, initiate corrective actions
when necessary, and report corrective actions to Ms. Engel. Mr.  Zimmerman will be responsible to
Ms. Engel for completing all work in accordance with the defined QA requirements of the project and
the specific QA requirements for NPS Method 6. Mr. Zimmerman will eventually be responsible for
sample receipt and generation of results from the Method 6 database.
      Mr. Thomas Danison, the Sample/Data Manager, will be responsible for receipt of samples and
for other computerized sample tracking and data reporting functions.  Mr.  Danison will continue to
maintain the Method 6 database, but will train Mr. Zimmerman to take over sample receipt and results
generation duties.  Mr. Danison will report directly to Ms. Engel.
      Mr. Bruce Hidy will be responsible for conducting MS confirmations  of ETU when required.  Mr.
Hidy will report progress and results directly to Ms. Engel.
      The QA program, designed to assure Ms. Engel, her line management, and EPA that data are
complete,  defensible, and traceable, will function in parallel to the technical leadership.  The Project
Team and the QA team will have comparable authority and responsibility to the Project Manager for
final approval of work and resolution of conflicts.
      Responsibilities of the QA Manager and the QA team include:
           Coordination of QA/QC matters with EPA to ensure that all policies and procedures
           are in accordance with EPA guidelines,
      •     Overseeing all QA procedures for the project,
           Identifying and responding to quality needs and problems, answering questions for
           guidance and assistance, and training project staff in QA/QC requirements and
           procedures,
      •     Ensuring that the QA Project Plan includes sufficient and appropriate specifications
           for QA/QC,

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                                                                            Section No 4
                                                                            Revision No 3
                                                                            Date:  April 29, 1988
                                                                            Page 5 of 6
     •     Interacting with the Project Manager to ensure that QA/QC procedures are
           understood by technical personnel,

     •     Developing SOPs or protocols for performing system inspections and audits,

           Auditing all data before release to EPA,

     •     Performing system and performance audits as required, and

           Preparing periodic reports of progress and QA inspection/audit findings to Battelle
           management and the Project Manager.


     4.2.a  NPS Contract Technical Monitor
     All analytical results and relevant technical information will be communicated to the NPS Method

6 Contract Technical Monitor:
           Dr. Aubry Dupuy, Jr. [Telephone # (601) 688-3212]
           U.S. EPA
           Environmental Chemistry Laboratory
           NASA/NSTL
           Building 1105
           NSTL, MS  39529


     4.2.b  NPS Contract Project Officer

     All contractual information will be communicated to the NPS Method 6 Contract Project Officer:
           Mr. Robert A. Maxey [Telephone # (601) 688-1225]
           U.S. EPA
           Environmental Chemistry Laboratory
           NASA/NSTL
           Building 1105
           NSTL, MS  39529


     4.2.c  Battelle Project Manager
     Inquiries from EPA personnel regarding this project should be directed to the Battelle Project
Manager:

           Ms. Tina M. Engel [Telephone # (614) 424-4149]
           Battelle Columbus Division
           505 King Avenue
           Columbus, OH  43201


     4.2.d  CSC

     Analytical results will be submitted to Mr. Chris Frebis at CSC:

           Mr. Chris Frebis
           USEPA/CSC
           26 West Martin Luther King Dr.
           Cincinnati,  OH 45268

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                                                                            Section No 4
                                                                            Revision No 3
                                                                            Date: April 29, 1988
                                                                            Page 6 of 6
      4.2.e   Battelle Sample Receipt Personnel
      Federal Express shipments of samples should be addressed to the Battelle Sample/Data
Manager:
           Mr. Thomas Danison [Telephone # (614) 424-5599]
           Battelle Columbus Division
           505 King Avenue
           Columbus, OH 43201
The Battelle Receiving Department will be provided with a list of alternate personnel in the event that
Mr. Danison is not available to take possession of samples.

4.3   Position of the QA Function within the Project Organization
      In accordance with EPA guidelines, QA personnel for this project will function independently of
the technical groups that generate, process, interpret, and report data. Implementation of the QA
program relies on strong management and well-defined organization.  Overall management
responsibility for  the QA program rests with Ms. Ramona Mayer, Manager of the QAU. Ms. Mayer
reports directly to Dr. Ann D. Barker, Senior Vice President of Biological and Chemical Sciences. An
organizational chart showing the position of the QA function within Battelle Columbus Division and its
relationship to the project is shown in Figure 1. The QA Manager and her staff will interact with
project management throughout the project by conducting audits and inspections and working with
the Project Team to implement and/or correct required QA procedures. The QAU will assure the
Battelle project management that QC procedures outlined in this QA Project Plan are  properly
implemented and documented.

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                                                                              Section No 5
                                                                              Revision No 3
                                                                              Date: April 29, 1988
                                                                              Page 1 of 6
5.    QA OBJECTIVES FOR MEASUREMENT DATA

      The purpose of this project is to provide EPA with analytical support necessary to implement the

National Pesticide Survey.  Battelle will perform the organic analysis procedure defined in NPS

Methods 6.  Battelle's objective is to perform Method 6 as written, incorporating any modifications

specified by EPA, and to yield results fully acceptable to both EPA and Battelle.  NPS Method 6 is

included for reference as Appendix A.

      The following capability demonstration procedures and QC requirements will be followed.

Samples failing any QC criteria will be reanalyzed at Battelle's expense. Deviations from analytical

procedures and/or QC requirements must be approved by the EPA Technical Monitor and

subsequently documented in writing.


5.1   Initial Demonstration of Capabilities •- Determining Reporting  Limits

      Prior to analysis of NPS samples,  Battelle will determine the ETU minimum reporting level  (MRL)

using the following procedure:

      (1)   After optimization of primary analytical instrumentation, the concentration of ETU in
           the final extract, in ^g/mL, necessary to produce an instrument detector response
           with a 5:1  signal-to-noise ratio (S/N) will be determined. The equivalent ETU
           concentration in the original water sample, assuming quantitative recoveries and a
           1 0-fold concentration factor, will be calculated.

      (2)   Eight reagent water samples will be spiked at the concentration level determined in
           Step (1); the eight spiked water samples will be processed and analyzed in a single
           day using the primary column.

      (3)   The Minimum Detectable Level (MDL) will be calculated using the equation given in
           Section 14.5.

      (4)   The estimated detection limit (EDL) will be calculated as described in Section 14.6.
      (5)   If the calculated EDL is greater than 10 ng/L (two times the value given in NPS
           Method 6), the results will be reported to the NPS Contract Technical Monitor for
           resolution.

      (6)   The eight extracts generated in step (2) will be analyzed using the confirmation
           column, and the EDL will be recalculated as described in steps (3) and (4).  If the
           calculated EDL determined using the confirmation column is greater than the EDL
           determined using the primary column, the higher EDL will prevail to assure that
           minimal criteria are met on both columns.

      (7)   The ETU MRL is defined as three times the EDL calculated using primary analytical
           conditions (Section 14.7).

      Results from the initial determination of MRLs will be reported to the NPS Contract Technical

Monitor for approval prior to analysis of NPS samples.

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                                                                             Section No. 5
                                                                             Revision No. 3
                                                                             Date: April 29, 1988
                                                                             Page 2 of 6
5.2   Initial Demonstration of Capabilities - Determining MS Detection Limits
      Battelle performed analyses by low-resolution gas chromatography-mass spectrometry (GC-MS)
to determine the estimated MS detection limit for ETU. Battelle obtained a mass spectrum for ETU
and selected three characteristic ions for subsequent use during selected ion monitoring analyses.
Solutions containing low levels of ETU were analyzed with and without preconcentration to determine
the concentration at which a 5:1  S/N for the least intense characteristic ion is obtained.
      Results from initial MS detection limit studies were reported to the NFS Contract Technical
Monitor for approval; MS confirmation procedures to be used in the NPS project are given in
Appendix C.

5.3   Assessing Laboratory Performance
      5.3.a  Control Charts
      Control of the measurement system will be accomplished via use of control charts.  Control
must be demonstrated for ETU and the surrogate, propylene thiourea (PTU).  Prior to analysis of NPS
samples, Battelle will generate control charts.  These control charts will be continuously updated and
used to determine when the analyses being performed using Method 6 are "in control." Samples or
sample sets will be reanalyzed at Battelle's expense if judged out of control.
      Five reagent water samples will be spiked at 10 times the MRL for the  method and carried
through extraction and analysis using primary conditions.  An additional 15 samples will be spiked and
analyzed, five on each of three different days. The results from these 20 spiked samples will be used
to construct control charts using the following criteria for accuracy and precision:
      (1)    The relative standard deviations (RSDs) for ETU and PTU must be <20 percent.
      (2)    The mean  recoveries for ETU and PTU (x) must lie between the  mean recovery ±3
           times the RSD listed in Method 6  (at the corresponding concentration level), but  no
           greater than Battelle's mean recovery ±30 percent.
Failure to meet the above criteria will be reported to the NPS Contract Technical Monitor.
      Control charts will be  generated containing both warning limits (±2RSD) and control limits
(±3RSD) about the mean. Dixon's test (see Appendix B) will be used to determine outliers using a
one percent risk of false  rejection.  Up to three outliers can be removed from the data set generated
from the 20 spiked samples prior to compiling the control charts.  During analysis of NPS samples,  a
spiked control is included in each sample set.  When five spiked controls have been analyzed, the
results from these controls will be incorporated into the control charts, and up to five of the earliest
plotted points will be dropped from the control chart; a total of 20 points will  be  included on each
control chart at all times after initial generation of the control chart. Accuracy and precision will be
recalculated and the chart will be redrawn. The updated control chart will be applied to all data in
sample sets subsequent to the last one used  to update the chart.

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                                                                              Section No 5
                                                                              Revision No. 3
                                                                              Date: April 29, 1988
                                                                              Page 3 of 6
      The original control charts will be submitted to the NPS Contract Technical Monitor for approval
and inclusion in the EPA Project Plan prior to analysis of NPS samples; updated control charts will be
provided to the NPS Contract Technical Monitor upon request.

      5.3.b Laboratory Control Standards
      A laboratory control standard (LCS) will be processed and analyzed with each set of samples.
A sample set is defined as all samples extracted by the same analyst on the same day within 12
hours. The laboratory control standard is prepared by spiking reagent water containing 10 mg/L
mercuric chloride with surrogate and ETU at 10 times the MRL  The recoveries of ETU and PTU must
be within the control limits (±3RSD) of the current control chart. If the recovery of ETU or PTU is not
within the control chart control limits, the measurement system is "out of control",  all samples
associated with the  laboratory control standard are invalidated, and work will be stopped until the
problem is  resolved. However, a laboratory control standard in which the PTU surrogate compound
recovery has failed to meet the quality control limits is validated if the laboratory control standard
meets all other required quality control elements, and the PTU recovery observed for the method
blank associated with that same sample set meets the control limits determined using the current PTU
control chart.  Sample sets will be reanalyzed at Battelle's expense if deemed "out of control." Out of
control situations will be reported to the NPS Contract Technical Monitor. The following observations
indicate an "alert" situation:
           Three or more consecutive ETU or PTU recoveries outside the warning limits
           (±2RSD) but  within the control limits (±3RSD),
           A run of seven consecutive points for ETU or PTU above or below the mean, or
           A run of seven consecutive points for ETU or PTU in increasing  or decreasing order.
An alert situation will warrant close evaluation to avoid deterioration to an out of control situation.

5.4   Assessing Surrogate Recovery
      All samples and blanks will be fortified with the surrogate standard, PTU, prior to extraction. The
PTU recovery must be within ±30 percent of the mean recovery indicated on the  current control chart
for PTU.  Samples in which PTU recoveries do not meet these requirements will be reanalyzed at
Battelle's expense.

5.5   Assessing the Internal  Standard
      The internal standard, 3,4,5,6-tetrahydro-2-pyrimidinethiol (THP), is added to every sample
extract before analysis.  The internal standard peak area for any sample must not deviate by more
than ±20 percent from the mean peak area for the calibration standards. A sample set for this
purpose is  defined as all sample extracts and calibration samples  analyzed using the same instrument

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                                                                            Section No. 5
                                                                            Revision No 3
                                                                            Date: April 29, 1988
                                                                            Page 4 of 6
in a continuous period.  If an internal standard deviates from the mean by more than 20 percent, the
analysis is out of control, and actions as described in Section 10.4 of Method 6 will be taken.

5.6  Assessing Analyte Recovery
     EPA will provide a duplicate ground water sample for use  as a Laboratory Sample Spike (LSS)
for 10 percent of all samples collected.  Battelle will spike the duplicate water sample with ETU at 2, 10
or 20 times the ETU  MRL, as specified by EPA, prior  to sample preparation and analysis.

5.7  Assessing Laboratory Contamination
     A laboratory method blank, consisting of 50 mL of reagent water containing 10 mg/L of mercuric
chloride preservative and spiked with the surrogate, will be analyzed with each set of samples.  If the
method blank exhibits a peak within the retention window of ETU and is greater than or equal to
one-half the MRL for that analyte, an out of control situation has developed and will be reported to  the
NPS Contract Technical Monitor. If the method blank exhibits a  PTU surrogate recovery that is not
within the PTU control chart, that sample is invalidated unless a  field sample in the same sample set
meets all of the quality control  requirements for a method blank.

5.8  Assessing Instrument Performance
     Instrument performance will be monitored daily by analysis of the Method 6 instrument QC
standard as described in Section 10.9 of Method 6.  The instrument QC standard contains
compounds designed to  indicate appropriate instrument sensitivity, column performance, and
chromatographic performance.  The instrument QC standard described in Section 10.9  of Method 6
may be modified to reflect MRL requirements as described in that section.

5.9  Analyte Confirmation
     If ETU is observed at a concentration greater than or equal to half the MRL using primary
GC-NPD analytical conditions, the sample will be reanalyzed using confirmatory GC-NPD conditions
and compared to a standard containing ETU at a concentration  within ±20 percent of that expected
from primary analysis results. If primary and confirmatory calculated ETU concentrations vary by more
than 25 percent, the NPS Contract Technical Monitor will be informed for resolution of the
discrepancy.  If the presence of ETU is confirmed  using the second set of GC-NPD conditions, Battelle
will inform the EPA Contract Technical Monitor by  phone and followup letter, and the presence of ETU
in the sample will be confirmed by GC-MS.
     Confirmation by GC-MS will be done by comparison to a standard containing ETU at a
concentration near that expected in the sample extract. If additional sample treatment is performed to
allow GC-MS confirmation, the  standard and sample  must both undergo the same treatment. GC-MS

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                                                                             Section No 5
                                                                             Revision No 3
                                                                             Date: April 29, 1988
                                                                             Page 5 of 6
results will be reported as qualitative (presence or absence), not quantitative, and the ETU
concentration determined using primary GC-NPD conditions will be reported to the EPA Contract
Technical Monitor.  Low-resolution GC-MS calibration procedures and operating conditions are given
in Appendix C.
      If confirmation can not be performed by low-resolution GC-MS, the sample extract or extracts will
be sent weekly, at EPA's expense under iced conditions by next-day air, to the Environmental
Chemistry Laboratory, NASA/NSTL for confirmation by high-resolution GC-MS.  Sample extracts will be
sealed in glass ampules or vials with Teflon-faced closures such that a tight seal and
noncontaminating conditions are  provided.  The volume level of the sample extracts will be marked on
the outside of the containers.  Copies of chromatograms and all  pertinent sample information will be
sent along with the extracts.
      Following either two successful or two unsuccessful  GC-MS confirmation attempts, discussions
with the EPA Contract Technical Monitor will be initiated before continuation of low-level GC-MS
confirmation work.  Only ETU concentrations positively confirmed by GC-MS will be reported by the
EPA Contract Technical Monitor to the Method and Analytical Coordinators.  Unconfirmed results will
not be reported outside the NPS analytical system.

5.10  Treatment of Unidentified Peaks
      During the course of the ETU  analyses, unidentified  peaks may be detected using the primary
GC-NPD  analytical conditions.  If the response of an extraneous peak on the primary column is  equal
to or greater than the response of the ETU at ten times the MRL, Battelle will attempt to identify  that
unknown peak by low-resolution GC-MS.  If possible, a full scan spectra will be generated for the
unknown component, and the spectra will be evaluated  by comparison to available library spectra. If
possible, the spectra will be compared to a spectra generated at Battelle from an authentic standard
of the suspected compound. Successful as well as unsuccessful identification attempts will be
reported to the EPA Contract Technical Monitor.
      Battelle will attempt to identify unknowns as soon as they are detected in an extract.  If
identification of the unknown is not possible by low-resolution GC-MS, Battelle will package and send
the  extracts from the sample in question and its method blank to EPA as described in Section 5.9. for
identification by high-resolution GC-MS.  Sample and analytical information will be sent with the
extracts, including the sample ID No., weight of the sample matrix contained in the ampule  or vial, and
copies of chromatograms from the primary GC column with the unknown(s)  clearly marked.
      If an unidentified compound displaying the same retention  time is successfully or unsuccessfully
identified twice, the situation will be  discussed with EPA Contract Technical Monitor before
continuation of identification work  with that peak.  Only compounds positively confirmed by GC-MS will

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                                                                             Section No 5
                                                                             Revision No 3
                                                                             Date. April 29, 1988
                                                                             Page 6 of 6
be reported by the EPA Contract Technical Monitor to the Method and Analytical Coordinators.  No
unconfirmed results will be reported outside the NFS analytical system.

5.11  Performance Evaluation Samples
      EPA may provide Battelle with blind performance evaluation samples. Performance evaluation
samples will be analyzed with NPS samples and the results will be reported to the  NPS Contract
Technical Monitor.

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                                                                             Section No 6
                                                                             Revision No 3
                                                                             Date: April 29, 1988
                                                                             Page 1 of 4
6.    SAMPLING PROCEDURES
      Battelle will conduct NPS Method 6 on ground water samples submitted by EPA.  Sample bottle
preparation, sample collection, and sample shipping will be performed by EPA's implementation
contractor (ICF).  NPS Method 6 involves the extraction and analysis of a 50-mL water sample.
Samples will be collected in 60-mL bottles each containing 0.6 ml_ of 1 g/L mercuric chloride
(preservative) in deionized water.  Samples from a site will be shipped as a kit.  The composition of a
kit is demonstrated in Figure 3. Samples will be iced immediately after collection and shipped iced for
overnight delivery.  Samples that are not iced at receipt will not be analyzed and the problem will be
reported to the EPA Contract Technical Monitor. Samples will be stored at 4±2°C away from light
until processed.
      Sample bottles will be labeled by field collection personnel.  Labels will include the following
information:
           National Pesticide Survey - NPS,
      •     Sample number,
           Sampling date,
      •     Sample description, and
      •     Sampler.
An example of the label used by ICF  is given as Figure 4.
      Field personnel will also record pertinent  information such as sampling date and time and
sample temperature at collection onto field sample tracking sheets. These sheets will be transferred
to the analytical laboratories with the samples.  An example of a field sample tracking sheet
used by ICF is included as Figure 5.

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                                                        Section No 6
                                                        Revision No 3
                                                        Date.  April 29, 1988
                                                        Page 2 of 4
                       FIGURE 3

       COMPOSITION OF METHOD 6 SAMPLE KIT
    LAB NAME
BCD
KIT TYPE
Sample Types
BOTTLE TYPE
ANAL METHOD
Primary
Referee
Shipping Blank
Backup Sample
Lab Spikes
Time Storage
T/S Dups @ 30
Totals
No. of Sites
TOTAL REQ'D
BCD #1
Regular
60 mL
6
1


1



2
1,275
2.550
BCD #2
Reg. + LS
60 mL
6
1


1
1


3
150
450
BCD #3
Reg. + LS+T/S
60 mL
6
1


1
1
2
2
7
75
525
Total Bottles:

   1,OOOmL=    0
    250 mL =    0
     60 mL = 3,525

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                                                                       Section No 6
                                                                       Revision No. 3
                                                                       Date:  April 29, 1988
                                                                       Page 3 of 4
                                       FIGURE 4

                                  SAMPLE NPS LABEL
     NATIONAL PESTICIDE SURVEY

     SAMPLE #: PD-0005-5-6-01

     BCD - METHOD* 6 KIT: 521
     FIELD SAMPLE
     PRESERVATIVE: HgCI2
     DATE I  TIME  I SAMPLER
Legend:  - R = resample
          B = performance evaluation
Well type - D = domestic
          C = commercial
Sample type identifier -
          01 = field sample
          03 = backup sample
          04 = lab spike (A1)
          06 = lab spike (A3)
Sample Number Explanation:
PD-0005-5-6-01
         | Sample Type Identifier
     i    Method # (6)
  |   [  Lab # (5)
  !  Site #
 Well Type
NPS Designation

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                                                    FIGURE 5

                                    NPS FIELD SAMPLE TRACKING SHEET
HELL. i.O. NO.:   0000

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

SAMPLE COLLECTION DATE: 	/

TRACKING FORM  COMPLETED BY:
                                                                                            Section No. 6
                                                                                            Revision No. 3
                                                                                            Date:  April 29, 1988
                                                                                            Page 4 of 4
                                                                         LAB:  BSL.
                                                                    SCENARIO:  _l_

                                                                    HT !£.:   PM-000-6U
                                                                    £01  1 o:   1
                                                     TO  3£ COMPLETED BY:
ICF
SAMPLE
NUMBER
f 5-0000-6- 1-01
FD-(JUOO-6-3-01
PD-OOOO-fc-e-01
PI-vOOO-6-1-03
i

BOTTLE
SIZE
1000
1000
t>0
1000

SAMPLE
DESCRIPTION
FIELD SAMPLE
FIELD SAMPLE
FIELD SAMPLE
BACKUP SAMPLE
FIELD TEAM , L«3
SAMPLER 1 TIRE : COMMENTS til '.RECEIVE; ; COHHENIS sli
(INITIAL) i SAMPLED , ;
: : ; : : u;
: : : HI
; : . : : *:
: : ; : • N;
 LHLQRiNE  TEST:
 !   SHIPPED BY:
                                                                        : RECEIVE; AT LAB sv:
 1   DATE 	
 !   SENT TO:
TIME
LAB ADDRESS:
BAY St. u;j-3
CHEMIST*' .Ai.

NSTL. C.S -3'5:s


t'+'.s. 11. •*



;  :-ATE
 .   -li  For.  ciAHPLE:  B3TT.E BROKEN, BOTTLE MsSSi.15,  OVERFL.Ei ?CTTi£. CAP »»i  :?.uFF£S
 :   ii)  F3R  EXAMPLE:  3QTTLE BROKEX, BOTTLE HISSING.  S3TTLE  ICkTWlMTES. TE«£t.AT'jF.E CRITERIA KCT -£T
 :    -"  FLR  EiAMPLE:  SC£ MELTED,  SOI LEAKING
 :       i  Lib  comnts should concur nth NPS 13 SAMPLE  RECEIPT  i

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                                                                             Section No 7
                                                                             Revision No. 3
                                                                             Date: April 29, 1988
                                                                             Page 1 of 6
7.    SAMPLE CUSTODY
      The EPA implementation contractor, ICF, will notify Battelle about sample shipments using a
computerized bulletin board system. Battelle will access this bulletin board system via phone lines
using an IBM-compatible computer equipped with a modem. Battelle will check the bulletin board
weekly to obtained updated information regarding on-going  and projected sampling efforts being
coordinated by ICF. Battelle will check the bulletin board daily if sampling efforts are underway or
imminent. Battelle will report routine sample receipt information such as time of receipt and
temperature of samples at receipt to ICF using the same bulletin board system.
      Samples should be sent to the attention  of Mr. Thomas Danison at the address listed in Section
4.2.d. The Battelle Receiving department will be supplied with names of two alternative staff members
to be called in the event that Mr. Danison is not available to  take immediate receipt of the samples.
      Mr. Danison will check the samples for general condition (temperature and breakage)
immediately upon receipt.  Samples that are not iced at receipt will not be analyzed, and the problem
will be reported to the EPA Contract Technical  Monitor for subsequent resolution of the situation with
ICF. Samples will be immediately stored at 4±2°C away from light until they are processed.
      All information on the ICF field sample tracking sheets (Figure 5) and a description of the
general  condition of the samples upon receipt will be entered into a computer database (Beckman
LABManager®) using a terminal.  An example of the sample  login screen is given in Figure 6.  At this
time, a nine-digit Battelle identification number  (BCD ID) and two-digit Sample Type code will be
assigned using the system described in Figure 7. Samples  can subsequently be tracked using either
the EPA identification code or the BCD ID. Photocopies of the ICF field sample tracking sheets,
Federal  Express  shipping lists, and a hardcopy log of samples in the database will be filed. An
example of the hardcopy log of samples contained in the database is shown in Figure 8.
      Samples will be processed within 14 days of collection. Sample extracts will be immediately
analyzed or stored at -70±2°C and protected from light.  Stored sample  extracts will be allowed to
warm to room temperature before analyses.  Sample extracts will be analyzed  and, if necessary,
confirmed by the alternative GC-NPD conditions and by low-resolution GC-MS within  14  days of
extraction.  The holding time for GC-MS analysis may be extended an additional 14 days upon
approval of the EPA Contract Technical Monitor.
      Time storage samples will be extracted within ±4 days of the proper date and analyzed within
four days of extraction.  Day 0 time storage samples will be spiked and immediately extracted within
the 14-day holding time for samples and will be analyzed within four days of extraction.  Day 14 time
storage  samples will be spiked at the same time as the corresponding Day 0 time storage samples
and stored at 4±2°C until extraction. Day  14 time storage samples will be extracted no sooner than
10 days and no later than 18 days after spiking and will be analyzed within four days of  extraction.

-------
                                    FIGURE 6

                            SAMPLE LOGG1N SCREEN
                                                                       Section No. 7
                                                                       Revision No. 3
                                                                       Date: April 29, 1988
                                                                       Page 2 of 6
                                        > — — — •— •
^ - a  - s «* •

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                                                                           Section No 7
                                                                           Revision No. 3
                                                                           Date: April 29, 1988
                                                                           Page 3 of 6
                                         FIGURE 7

                              BCD LAB IDs AND BCD NOT IDs
Sample Code
XX    =    Sample code (SA = sample, BS = backup sample, LS = laboratory spike, TS = time
           storage, LC = laboratory control, BL = laboratory method blank, PE = performance
           evaluation sample, 1C = instrument control standard, ST = stock/reagent, and CS =
           calibration standard)

Battelle Laboratory Identification Number (BCD ID)
YY    =    year (88, 89,...)
B     =    fixed; indicates an NPS sample
X     =    incremented letter
xxxxx =    incremented number (0001, 0002,...)

Battelle Notebook Identification Number (BCD Not ID)
xxxxx  =    Battelle laboratory notebook number
yy    =    Notebook page number containing description of sample
zz    =    Notebook page line number containing description of sample

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Section No 7
Revision No 3
Date:  April 29, 1988
Page 4 of 6


FIGURE 8



HARDCOPY OF NFS DATABASE SAMPLE LOG

BCD ID
88BA00014
88BA00015
88BA00016
88BA0001 7
88BA00018
88BA00019
88BA00020
88BA00021
88BA00022
88BA00023
88BA00024
88BA00025
88BA00026
88BA00027
88BA00028
88BA00029
88BA00030
88BA00031
88BA00032
88BA00033
88BA00034
88BA00035
88BA00036
88BA00037
88BA00038
88BA00039
88BA00040
88BA00041
88BA00042
88BA00043
88BA00044
88BA00045
88BA00046
88BA00047
88BA00048
88BA00049
88BA00050
88BA00051
88BA00052
88BA00053
88BA00054
88BA00055
88BA00056

SAMPLE ID
PD-0004-5-6-01
PD-0004-5-6-03
PD-0008-5-6-01
PD-0008-5-6-03
PD-0007-5-6-01
PD-0007-5-6-03
PD-0007-5-6-06
PD-0005-5-6-01
PD-0005-5-6-03
PD-0005-5-6-04
PD-0003-5-6-01
PD-0003-5-6-03
PD-0003-5-6-06
PD-0006-5-6-01
PD-0006-5-6-03
PD-0001 -5-6-01
PD-0001 -5-6-03
PD-0001 -5-6-04
PD-001 3-5-6-01
PD-001 3-5-6-03
PD-001 3-5-6-06
•
•
•
PD-001 0-5-6-01
PD-001 0-5-6-03
PD-0009-5-6-01
PD-0009-5-6-03
PD-0009-5-6-04
PD-0002-5-6-01
PD-0002-5-6-03
PD-001 1-5-6-01
PD-001 1-5-6-03
PD-001 1-5-6-06
PD-001 2-5-6-01
PD-001 2-5-6-03
PD-001 2-5-6-04
•
•
•
•
*
•
BCD
NOT ID
43307-04-04
- -
43307-05-05
- -
43307-06-06
- -
43307-07-07
43307-08-08
- -
43307-09-09
43307-10-10
- -
43307-11-11
43307-12-12
- -
43307-04-04
- -
43307-05-05
43307-06-06
- -
43307-07-07
43307-23-23
43307-13-13
43307-14-14
43307-08-08
- -
43307-09-09
- -
43307-10-10
43307-04-04
- -
43307-05-05
- -
43307-06-06
43307-07-07
- -
43307-08-08
43307-12-12
43307-11-11
43307-23-23
43307-23-23
43307-09-09
43307-10-10
Date
Rec'd
04/19/88
04/19/88
04/20/88
04/20/88
04/21/88
04/21/88
04/21/88
04/21/88
04/21/88
04/21/88
04/22/88
04/22/88
04/22/88
04/22/88
04/22/88
04/26/88
04/26/88
04/26/88
04/26/88
04/26/88
04/26/88
01/01/60
01/01/60
01/01/60
04/27/88
04/27/88
04/27/88
04/27/88
04/27/88
04/28/88
04/28/88
04/29/88
04/29/88
04/29/88
04/29/88
04/29/88
04/29/88
01/01/60
01/01/60
01/01/60
01/01/60
01/01/60
01/01/60
Sample
Code
SA
BS
SA
BS
SA
BS
LS
SA
BS
LS
SA
BS
LS
SA
BS
SA
BS
LS
SA
BS
LS
1C
LC
BL
SA
BS
SA
BS
LS
SA
BS
SA
BS
LS
SA
BS
LS
BL
LC
1C
1C
LC
BL
Set
#
07

07

07

07
07

07
07

07
07

08

08
08

08
07
07
07
08

08

08
09

09

09
09

09
08
08
08
09
09
09

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                                                                             Section No 7
                                                                             Revision No 3
                                                                             Date- April 29, 1988
                                                                             Page 5 of 6
      A laboratory control standard (Section 5.3.b) and a laboratory method blank (Section 5.7) will be
prepared and analyzed with each sample set.  BCD IDs will be assigned to the laboratory control
standard and the laboratory method blank using the sample login form  (Figure 6) following  the criteria
outlined in Figure 7. The laboratory control standard and laboratory method blank can be traced
using the BCD ID.
      Samples will be grouped into sets as defined  in Section 5.3.b.  When samples are processed
using Method 6, all laboratory activities will be described in a Battelle laboratory notebook.  When
sample extracts are generated, these extracts will be assigned a Battelle laboratory notebook
identification number (BCD Not ID) following the criteria given in Figure 7.  In addition, all stock
solutions, spiking solutions, and calibration solutions generated with the sample set or intended for
use with the sample set will also be assigned BCD Not  IDs.  BCD Not IDs will be entered into the
database using a Beckman-LABManager® data entry screen (Figure 9) following the criteria outlined in
Figure 7. All sample extracts can be traced  using the BCD Not ID.
      Unused samples  or samples not extracted before the 14-day maximum holding time will be
disposed or returned to EPA  or ICF at EPA's expense.  The EPA Contract Technical Monitor will be
consulted to determine  final disposition of unused samples.  Sampling kits will be returned to ICF at
EPA's expense.  After analyses, sample extracts will be stored at -20±2°C or lower until disposal is
approved by the EPA Contract Technical Monitor.
      The water samples, which contain mercuric chloride, will be solidified with Fixsorb-1000 (sodium
silicate-type clay); solidified water samples and extracts will be buried in a secure chemical
management facility. Sample extracts will be disposed  of as hazardous waste.
      A refrigerator adjusted to 4±2°C has been designated for storage of samples and a freezer
capable of maintaining temperatures at or below -20±2°C has been designated for storage of sample
extracts.  The refrigerator and freezer temperatures are  monitored daily and the temperatures are
recorded ^n log sheets displayed on the front of the units.  The SOP describing use of the freezer is
included as Appendix D of this QA Project Plan, "Standard Operating Procedure for Use of Admiral
Freezers."  The SOP describing use of the refrigerator is included as Appendix E of this QA Project
Plan, "Standard Operating Procedure for Use of Hotpoint Refrigerators." Examples of the
refrigerator/freezer log sheets are included in these two SOPs.

-------
                          FIGURE 9

                    DATA ENTRY SCREEN
                                                              Section No. 7
                                                              Revision No. 3
                                                              Date: April 29, 1988
                                                              Page 6 of 6
i M C 1 I C  P T I I T C * " M
     : s c
        : j. .-•' c
                            — »- s   e •

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                                                                            Section No 8
                                                                            Revision No 3
                                                                            Date: April 29, 1988
                                                                            Page 1 of 3
8.    CALIBRATION PROCEDURES AND FREQUENCY

8.1   Instrumentation
     Instrumentation that will be used for this project includes but is not limited to the following:

           GC-NPD analyses will be performed using an HP5890 dual capillary gas
           chromatograph equipped with an autosampler, a split/splitless injection assembly,
           and two NPD assemblies.  Each detector will be connected to a chromatography
           data system via a Beckman digimetry to allow computerized acquisition of raw
           GC-NPD data. The gas chromatograph will be operated as described in Section
           11.3 and Table 1 of Method 6.  A second dual NPD HP5890 gas chromatograph is
           available as backup.

     •     GC-MS confirmation will be conducted  using a low-resolution Finnigan 4500 mass
           spectrometer. A Finnigan INCOS® data system equipped  with Finnegan software
           Revision 5.5 will be used for MS data collection and processing. Other mass
           spectrometers are  also available for ETU confirmations;  detection limit studies will be
           conducted with any mass spectrometer used for this study to determine the
           minimum level of ETU that can be confirmed with each instrument.  Results of the
           detection limit studies will be communicated to the EPA Contract Technical Monitor
           prior to confirmation of ETU presence in sample extracts.  Specific GC-MS
           calibration  procedures and operating conditions are given in Appendix C.

           An HP1000 Series  A computer will be used for collection and processing of all
           chromatographic data. This computer will also be used for maintaining the Method
           6 database. Two Beckman software products will be  used.  Beckman PeakPro® will
           be used for chromatographic data acquisition and processing.  Beckman
           LABManager® will be used for maintaining the Method 6 database and generating
           hardcopy and ASCII reports.

           The HP1000 Series A  computer will be  accessed with IBM XT or IBM  PS/2  Model 50
           or 60 computers each equipped with Reflections-3+® terminal emulation software.
           These IBM  computers will also be equipped with a modem to allow access of the
           ICF bulletin board system via phone lines. These IBM computers will also be used
           for generation of control charts (Section 5.3.a) using Lotus Symphony® software.1

           A Mettler AE 240 balance will be used for preparing the ETU stock standard
           solution, internal standard spiking solution, and surrogate  standard spiking solution
           as described in Sections 7.11, 7.12, and 7.13 in Method 6. The calibration and
           operation of this balance is described in Appendix F,  "Standard Operating
           Procedure  for Weight  Determinations Using an Electronic Analytical Balance."

           A Mettler P1200N balance will be used  for weighing larger amounts of materials
           such as the salts described in Section 11.1.1 of Method 6.  The calibration and
           operation of this balance is described in Appendix G, "Standard Operating
           Procedure  for the Use of Top Loading Balances."
   1  Ouchi, G. I., "Control Charting with Lotus 1-2-3", American Laboratory, Feb. 1987, 82-95.

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                                                                              Section No 8
                                                                              Revision No 3
                                                                              Date: April 29, 1988
                                                                              Page 2 of 3
8.2   Calibration Procedures

      Calibration procedures and frequency are defined in Section 9.2 of Method 6 and can be

summarized as follows:

      •    ETU stock solutions, prepared as specified in Section 7.11 of Method 6 will be
           provided to Mr. Zimmerman monthly by EPA.  Mr. Zimmerman will store the ETU
           stock solutions at -20±2°C or lower and protected from light and describe the
           receipt of the samples in a Battelle laboratory notebook.

      •    Ms. Kircher will use in-house supplies of the surrogate standard, PTU (prepared at
           Battelle), and the internal standard, THP (obtained from Aldrich), to  prepare
           surrogate and internal standard spiking solutions as described in Sections  7.12 and
           7.13 of Method 6.  Ms.  Kircher will store the surrogate and internal standard spiking
           solutions at 4±2°C protected from light as specified in Method 6. Ms. Kircher will
           describe preparation of surrogate and internal standard solutions, including
           information such as the source of the neat materials, in a  Battelle laboratory
           notebook and assign the solutions BCD  Not IDs as described in Section 7.   All stock
           solutions can be traced by their BCD Not ID.

           Ms. Kircher will prepare calibration solutions using stock ETU solutions obtained
           from EPA and surrogate and internal standard stock solutions prepared as
           described above; calibration solutions will contain ETU at  or slightly below the MRL
           specified by EPA and at four additional higher calibration  levels spanning the
           working range of the detector.  One of the calibration standards will contain ETU at
           or close to the spiking level of  the laboratory control standard.  Ms.  Kircher will
           describe preparation of calibration solutions in a Battelle laboratory  notebook and
           assign these solutions BCD Not  ID  as described in Section 7.  Since the laboratory
           notebook description will contain the date that these calibration solutions were
           prepared as well as the source of the materials used to prepare the solution and
           preparation procedures, the BCD Not ID will be used to identify which calibration
           standards belong to specific sample sets.

      •    Mr. Zimmerman  will optimize the  GC-NPD instrumentation  and demonstrate
           acceptable instrument performance  by analysis of instrument QA standards
           specified in Method 6; he will analyze the five calibration solutions and generate a
           calibration curve as described  in Section 9.2 of Method 6  (Appendix A).

           Mr. Zimmerman  will analyze a minimum of one calibration  solution each working
           day; the resultant data  will be treated as a sample and ETU concentrations will  be
           calculated. Variation of the calculated ETU concentration  from the expected ETU
           concentration of more than 20 percent will result in  evaluation of the calibration
           standard and/or chromatographic system.  After identification and correction of  the
           problem, Mr. Zimmerman will recalibrate the GC-NPD with the five calibration
           standards as described earlier. Alternatively, GC-NPD instrumentation will be
           recalibrated on each working day.

      ETU solutions are known to be relatively unstable at room temperature even in organic solvents

containing dithiothreitol (DTT).  Therefore, the integrity of calibration solutions left at room temperature

for analysis more than one time is questionable. In addition, the stability of the NPD is  not normally

sufficient to compare detector response from one day to the next.  As an alternate approach, new

ETU calibration solutions will be prepared with each set of samples and compared to one of the most

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                                                                                 Section No 8
                                                                                 Revision No 3
                                                                                 Date-  April 29, 1988
                                                                                 Page 3 of 3
recently prepared calibration solutions as a check on calibration solution integrity.  If the two
calibration solutions do not compare within ±20 percent, the new calibration solutions are considered
suspect and calibration solutions will be reprepared and analyzed with the previous calibration
solutions to determine the source of the deviation.  If the new calibration solutions are not acceptable,
other possible sources of the problem will be evaluated, such as decomposition of stock solutions or
decomposition of the original calibration solution.

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                                                                            Section No. 9
                                                                            Revision No. 3
                                                                            Date: April 29, 1988
                                                                            Page 1 of 2
9.   ANALYTICAL PROCEDURES
     Analyses for ETU will be conducted following the procedure outlined in Method 6. Determination
of Ethylene Thiourea in Ground Water by Gas Chromatography with a Nitrogen-Phosphorus Detector.
Equipment that will be used at Battelle to perform Method 6 is described in detail in Section 8. The
ionic strength and pH of a measured 50-mL volume of sample are adjusted by addition of ammonium
chloride and potassium fluoride.  The sample is poured onto an Extrelut column.  ETU is eluted from
the column in 400 mL of methylene chloride.  The extract is solvent exchanged to ethyl acetate and
concentrated to a volume of 5 ml.  Primary and confirmatory GC-NPD analytical conditions are
described which permit the separation  and measurement of ETU in the extract. The retention times
for ETU, PTU, and the internal standards specified in the method were accurate at the time Method 6
was developed, but are representative  of the specific GC columns used during that time.  For this
reason, the absolute retention times specified in the method may not always be followed, but it is not
possible to provide alternative retention times in this Quality Assurance Project Plan. Method 6 is
included on this QA Project Plan  as Appendix A.
     A set of samples is defined by EPA as the number of samples processed by an analyst in one
day within 12 hours.  Battelle  will  use sample  sets containing up to 12 samples, including one process
blank, one laboratory control standard, and up to 10 field samples.
     Problems encountered and observations made during processing of sample sets that do not
compromise the QC for the entire sample set will be recorded in the Battelle laboratory notebook by
the person performing the task, specifically Ms. Kircher (sample processing) or Mr. Zimmerman
(GC-NPD analyses).  Problems requiring corrective action will be documented using a Report of
Deviation form as described in Section 15.
     The following variations from Method 6  (Appendix A)  are noted:
           Change Section 10.7.1.1 to read "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, 10 times the MRL."
           Change Section 10.8 to  read "...If the method blank exhibits a peak within the
           retention time window of ETU which is greater than or equal to  one-half the MRL for
           ETU, determine the source of contamination before processing  samples and
           eliminate the interference problem."
     •     Change Table 1, primary conditions to read:
           Column:               5 m long x 0.25 mm I.D. DB-Wax bonded fused silica
                                column (J&W), 0.25 jim film thickness
           Carrier gas:            He @ 8.5 mL/min  (room temperature)
           Detector:              Nitrogen-phosphorus
           Detector temperature:  250°C
           Makeup gas:          He @ 30 mL/min
           Detector gases:        Air @ 70 mL/min;  H2 @ 3.5 mL/min
           Oven temperature:     205°C

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                                                                             Section No. 9
                                                                             Revision No. 3
                                                                             Date:  April 29, 1988
                                                                             Page 2 of 2
           Sample:               2 ^L splitless; 0.10 min split delay
           Injector temperature:    275°C
           Split flow:              60 mL/min
           Septum purge:         9 mL/min

           Change Table 1, confirmation conditions to read:

           Column:               5 m long x 0.25 mm  I.D. SPB-35 bonded fused silica column
                                 (Supelco),  0.25 urn film thickness
           Carrier gas:            He @ 8.5 mL/min (room temperature)
           Detector:              Nitrogen-phosphorus
           Makeup gas:           He @ 30 mL/min
           Detector gases:        Air @ 70 mL/min; H2 @ 3.5 mL/min
           Oven temperature:     130°C
           Sample:               2 ^L splitless; 0.10 min split delay
           Injector temperature:    275°C
           Split flow:              60 mL/min
           Septum purge:         9 mL/min

           Change Section 10.2.1 to read "...prepare a laboratory control (LC) check sample
           concentrate in 1000 ng/mL DTT  in  ethyl acetate approximately 1000 times..."

           Change Section 8.3.1 to read "...Extracts should be stored at -70±2°C away from
           light."

           Change Section 7.11.2 to read "...Store at -70±2°C and  protect from light."

Any future method  mo'difications in Method 6 will be communicated to the EPA Contract Technical
Monitor and confirmed in writing.

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                                                                            Section No. 10
                                                                            Revision No. 3
                                                                            Date. April 29, 1988
                                                                            Page 1 of 7
10.   DATA REDUCTION, VALIDATION, AND REPORTING
      Data reduction, validation and reporting schemes have been developed to assure traceability
and easy evaluation and validation of all results. The complete data flow and reporting scheme is
depicted in Figure 10.

10.1   Data Reduction and Storage
      10.1.a  Primary and Confirmatory GC-NPD Analyses
      Raw or  initial GC-NPD data are in the form of the voltage readings generated by the detector.
These voltage readings will be collected via a Beckman digimetry and stored initially on the permanent
disk of the HP1000 computer and finally on magnetic tape.  The raw data is processed using
Beckman PeakPro® chromatography software.  PeakPro® routines use operator designated guidelines
for identification of compounds on the basis of peak retention times and integration of the compound
peaks to provide peak area data. PeakPro® will integrate the ETU, surrogate, and internal standard
peaks and determine peak areas for each compound and peak area ratios for ETU and PTU relative to
the internal standard. PeakPro® will then generate calibration curves for ETU and PTU by plotting
ETU concentration or PTU percent recovery versus the appropriate peak area ratios.  PeakPro® uses
the generated calibration curve to calculate ETU concentration or PTU recovery in the sample  extracts.
      After results are evaluated  by an experienced analyst (Mr. Zimmerman), the computerized
results are automatically entered into a computerized database created  by  Beckman LabManager®
software; this  NPS Method 6 database will also contain hand-entered information such as sample
identification,  date of receipt, sample  condition at receipt, date of extraction, and other relevant
information. The LabManager® program will generate ASCII text reports as described in Section
10.3.a as well as other information such as lists allowing easy comparison of EPA-assigned Sample ID,
the BCD ID, and the BCD Not ID (extract).

      10.1.b  GC-MS Identification or Confirmation
      In the case of mass spectrometry, identification is also made on the basis of the mass spectra
and retention  time of the peak.  Finnigan INCOS® software will be used to search for ETU on the
basis  of expected retention time  and characteristic ions. When ETU  confirmation is required, the  ETU
peak area, relative to the internal standard, will be compared to the area generated from a standard
containing ETU  at approximately the level expected in the sample being confirmed. Specific GC-MS
calibration procedures, operating conditions,  and confirmation requirements are given in  Appendix C.
When identification of an unknown is  desired, a full scan spectra will be generated for the unknown
component, and the spectra will  be evaluated by comparison to available library spectra.  If possible,

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                                                        Section No. 10
                                                        Revision No. 3
                                                        Date: April 29, 1988
                                                        Page 2 of 7
                              FIGURE 10

                    DATA FLOW AND REPORTING SCHEME
Detector Reading
<
1
r
Permanent Disk Storage |
                                              Magnetic .Tape Storage  J
                             Computer  Data Analysis  |
Sampling Data  (manual)   \—*  NFS Method 6 Database  j
                                              Magnetic  Tape Storage  \
                                          —* Magnetic Tape Storage  \
                                QAU  Audit of Data    |
                              Data Packets (ASCII)  |
                                 Monthly Reports    |
                              Yearly  Final Reports  |

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                                                                             Section No  10
                                                                             Revision No 3
                                                                             Date:  April 29, 1988
                                                                             Page 3 of 7
the spectra will be compared to a spectra generated at Battelle from an authentic standard of the
suspected compound.  Procedures used for identification of unknowns are described in Section 5.10.


      10.1 .c   Data Storage
      Raw and finished results are archived in hardcopy and electronic (magnetic tape) forms.  The

following information will be filed as hardcopy:
           Photocopies of the ICF field sample tracking sheets, Federal Express shipping lists,
           and a hardcopy log of samples in the database (see example in Figure 8),

           Chromatograms showing computer integration for calibration samples and sample
           extracts (GC-NPD and GC-MS),

           Printouts showing analysis results for sample extracts (GC-NPD and GC-MS),

           Mass spectra generated during GC-MS confirmation, if applicable,

           A copy of the PeakPro® analysis method used to analyze the sample extracts; the
           method printout includes a description of the calibration curve generated and the
           calibration procedure,

           Copies of the calibration curves for ETU and PTU,

      •     A PeakPro® summary report listing peak areas and calculated ETU concentrations
           and PTU  percent recoveries; the summary report is valuable for evaluating several
           QC features such as variability of the internal standard peak area and recovery of
           the PTU surrogate standard,

           ETU  and  PTU control charts generated using Lotus Symphony®,

           Copies of the ASCII text files generated as described in Section 10.3.a,

           A listing of EPA-assigned Sample ID, the BCD ID, and the BCD Not ID (extract) for
           each sample, and

      •     Report of Deviation forms, if any, as described in Section 15.
Hardcopy data will be stored in a locked office and filed by sample set. People with access to these
data include Ms.  Engel, Mr. Zimmerman,  and the QAU.  Mr. Zimmerman will be responsible for
maintaining the project file.
      The following information will be stored  on magnetic tape.

           All raw and processed GC-NPD and GC-MS  results, specifically all voltage readings
           from  the specified detector as well as peak integration information determined by
           the relevant software package, and

      •     The Method  6 database.

Magnetic tapes are stored in  locked temperature/humidity controlled facility; only Battelle analytical
laboratory personnel have access to this facility.  Specific data files are subject to a security system
which will only allow access to Ms. Engel, Mr. Zimmerman, and Mr. Danison. The QAU will be allowed

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                                                                              Section No 10
                                                                              Revision No. 3
                                                                              Date:  April 29, 1988
                                                                              Page 4 of 7
access for auditing purposes.  Mr. Danison and Mr. Zimmerman will be responsible for maintaining the
magnetic media used for this project.
      All data reduction and storage procedures will be cross checked by the QAU during data audits
and inspections.

10.2  Data Validation
      Prior to submission of results to EPA, all results will be validated initially by Mr. Zimmerman and
the Project Manager, and finally by the QAU.
      Results submitted to EPA fall into two categories: results generated by computerized routines
and results entered or calculated by hand. The computerized routines that will be used for Method 6
data reductions are well-characterized.  QAU will evaluate these routines during system audits and
establish the validity of these routines.  The QAU will perform the same calculations by hand and
establish that the  computerized routine is functioning as expected and provides the correct results.
The routines will be rechecked periodically as prompted by a change in computer hardware or
software or other  relevant conditions such as a loss of power to the computer prior to analysis of more
NPS ground water samples.
      The QAU will be provided with all  hardcopy data listed in Section 10.1.C. The QAU will check
any hand-entered information appearing in the ASCII text reports (sample identification, date of
receipt,  sample condition at receipt, date of extraction, and other relevant information) against  the
original  NPS field  sample tracking sheet and the Battelle laboratory notebook, prior to submission of
results to EPA.  As mentioned earlier, compound quantification calculations are rarely made by hand.
However, any calculations made other than by validated computer routines will be checked and
validated by the QAU prior to release of the results to EPA. All results will be audited by the QAU
prior to submission to EPA.

10.3  Data Reporting
      10.3.a  ASCII Data Packets
      Analytical results and  results from the instrument  QC standard described in Section 5.7 of this
QA Project Plan will be submitted in the form of an ASCII text file on a floppy disk.  The ASCII text file
will contain all information required by EPA in a specified format;  the specified report formats for
analytical results and instrument QC standard results for Method 6 are shown in Figures 11 and 12,
respectively. Specific data format requirements are summarized in Appendix H.
      The ASCII text file reports will be generated directly from the NPS Method 6 database described
in Section 10.1. Analytical results and related instrument QC standard results from each sample set
will be reported together as a packet in a single ASCII file.  Analytical results  will be submitted  to Mr.
Chris  Frebis, CSC (Section 4.2.d) within 57 days of sample receipt.   Mr. Frebis will prescreen the

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                                                      Section No. 10
                                                      Revision No. 3
                                                      Date: April 29, 1968
                                                      Page 5 of 7
                             FIGURE 11

         ASCII REPORT FORMAT FOR NPS METHOD 6 ANALYTICAL RESULTS
Fld-pH  SJTemp  Date Sam   Date_Shp  Date_Rec  Time_Sam  Time_Ice
                04/11/88   04/11/88  04/12/88  00:00     00:00

Receipt Condition
BOTTLES LOOSE IN BOX

Samp #         Lab  Set #   Date Spk  Date_Ext   Date_Ana  Column
PD-9001-5-6-01 BCD  03      04/13/88  04/13/88   04/14/88  PRIM

Type   Spiker  Extract  Analyst  Sam_Vol  Ext_Vol  Int. Std.    % Su
SAMP   EAK     EAK      DPZ      50       5          81.0         90.

Comments


Analyte                      Cone.

ETU                         -999.0
Fld-pH  SJTemp  Date_Sam  Date_Shp  Date_Rec   Time_Sam  Time_Ice
                04/11/88  04/11/88  04/12/88   05:30     00:00

Receipt Condition
ICE OK SAMPLES LOOSE  IN  BOX   FORM FOR PD-9002-5-6-01

Samp #         Lab  Set  #   Date_Spk  Date_Ext  Date_Ana  Column
PD-9005-5-6-01 BCD  03      04/13/88  04/13/88  04/14/88  PRIM

Type   Spiker  Extract   Analyst  Sam_Vol  Ext_Vol  Int. Std.    %  Si
SAMP   EAK     EAK       DPZ      50       5         100.1         85

Comments
Analyte                      Cone.

ETU                           15.3

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                                                         Section No. 10
                                                         Revision No. 3
                                                         Date: April 29. 1988
                                                         Page 6 of 7
                        FIGURE 12

ASCII FORMAT FOR NPS METHOD 6 INSTRUMENT QC RESULTS

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                                                                             Section No 10
                                                                             Revision No 3
                                                                             Date: April 29, 1988
                                                                             Page 7 of 7
results for QA/QC criteria and completeness and send the results to the EPA Contract Technical
Monitor.
      The EPA Contract Technical Monitor will be immediately verbally informed of analytical results
under the following conditions:
      •     ETU is detected in a sample at or above half the MRL and is subsequently
           confirmed using confirmatory GC-NPD conditions, or
           ETU is detected in a sample above the reporting level using both primary and
           confirmatory GC-NPD conditions, but the quantification results from primary and
           confirmation analyses do not agree within 25 percent.
These contacts and actions taken as a result of these contacts will be subsequently confirmed in
writing.

      10.3.b  Monthly Reports
      Six copies of a monthly report will be provided within 15 calendar days after the end of the
period being reported.  The monthly reports will  be sent to the EPA Contract Technical Monitor, and a
copy of the cover letter will be forwarded to Mona S. Snyder, Contract Specialist for the NPS,
EPA-CMD, Cincinnati, OH 45268.
      Monthly reports will contain the following information for the subject reporting period:
      •     Summary of progress, including samples received, analyzed, and in progress, and
           status of data processing for analyzed sets of samples,
           Reports on standards, including new dilutions and results of checks before using,
           Identification of problems encountered during the subject reporting period,
           Summary list of bench-level corrective actions,
           Copies of representative and, if applicable, unusual chromatograms,
           Information request by the EPA Contract Technical Monitor because of specific
           methodology or problems encountered,
      •     Changes in operational personnel, and
           Comments.

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                                                                              Section No  11
                                                                              Revision No. 3
                                                                              Date:  April 29, 1988
                                                                              Page 1 of 2
11.   INTERNAL QUALITY CONTROL CHECKS
      Battelle will institute internal QC checks as a means of providing a quality product.  Specific
criteria for acceptable results and corrective action to be  undertaken for unacceptable results are
given in Section 5.0.  The QC checks that will be conducted during this project are summarized in
Table 1.

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                                                                                                                          Section No. 11
                                                                                                                          Revision No. 3
                                                                                                                          Date:  April 29,  1988
                                                                                                                          Page 2 of 2
                                                                      TABLE  1

                                               INTERNAL QUALITY CONTROL CHECKS
                                                          TABLE 1   INTERNAL QUALITY CONTROL  CHECKS
(uility Control Chock
Frequency of Iho
                                                                                Criteria for Acceptable ROM It*
                                                                                                                        Correct!TO Action
Control chortt
ETU ind PTU control  chirtt iro updated
by including roiulto fro*  ono labora-
tor;   control  atandard  run with  otch
Mt.
                                        ETU  and  PTU  recoverio* fro*  laboratory   Stop  work  and  raaolvo  probloe   b
                                        control   »tandarda   oust   bo  vithin   evaluating  ayatee.     An  in-contro
                                        control  I into.                          oi tuition  ouot  bo  dooonotrotod   t
                                                                                continue cork.
Aooooo eurrogate  recovery
Aeeeee internal *tanderd iroo
Aooooo MO If to recovery
ith  blind
porforoanco   eta tuition   stop loo;   the
ochodulo io net  provided.
                                        The ourrogato recovery ouot be vlthin
                                         21  percent  of  the  eean  recovery
                                        detoreinod   for   PTU   fro*   current
                                        control chart.

                                        The  internal  atandard peek  area for
                                        any aaeplo  euot  not doviote  by  core
                                        than   21  percent  fro* the eeo*  peak
                                        area  for  the calibration  aooploo  in
                                        that aaople aot.

                                        The ETU recovery   io  eipected to  bo
                                        oithin lint* opocified  in  updated ETU
                                        control   chart;   noncoopliance   eoy
                                        indicate eatrii effecte.

                                        Tho eothod blank  ohould not contain o
                                        peak greater than  or eijjel  to one half
                                        the M. for ETU.
                                        Acceptance  criteria
                                        Table i of khthod t.
                                                                                                      are   given
                                        fill be eotabliahod by EPA.
Outlined in Sectiono  114.1 and 1» 4
of Uothod I.
                                                                                Outlined   in   Section   II.i.I   ei
                                                                                Method «.
                                                                                                                        Outlined in Section II.? of Method •.
                                                                                                                        Outlined in  Section II I of Method *.
Inotrueont  ouet   be   eaintainod   o
repaired; apocified criteria ouat  a
eot before analyaie of aaoplo*.

lilI be o*tabli*hed by EPA.

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                                                                             Section No. 12
                                                                             Revision No. 3
                                                                             Date: April 29, 1988
                                                                             Page 1 of 4
12.   PERFORMANCE AND SYSTEM AUDITS
      The QAU Manager will be responsible for assuring systematic checks to determine the quality of
operation of all functions and activities associated with this project.  Checks will consist of system
audits and performance audits.  A project-specific SOP entitled "Standard Operating Procedure for
Quality Assurance Unit Performance and System Audits for NPS Survey" contains specific instructions
for performance and system audits and is included as Appendix I of this Quality Assurance Project
Plan.

12.1  System  Audits
      A system audit will be conducted shortly after laboratory operations are functional and
subsequently half way through the contract or more frequently at the discretion of management.
System audits are on-site inspections and reviews of the QC system.  System audits will be repeated
when significant changes are made in procedures due to equipment updates or replacement, software
changes and other variables as they arise. Results of system audits will be reported to the Project
Manager as described in Section 16.  The following is a noninclusive list of items to be evaluated and
validated during the system audit:

      12.1.a   Sample Receiving/Storage
      The systematic procedure for receiving samples will be reviewed to ensure the integrity of
samples. This will include noting the time of arrival, the number and condition of samples received
and an examination of the accompanying paper work. Storage facilities will be examined to assure
that appropriate conditions are provided and that samples are properly stored to protect the sample
integrity.

      12.1.b   Labware
      Cleaning, storage and use of labware will be examined to assure that procedures and
equipment  are appropriate for the intended use and to determine that no contamination has occurred
that could affect the interpretation of analytical results.

      12.1.C   Materials, Reagents, Solvents, and Gases
      Materials, reagents, solvents, and gases will be checked to assure that they conform to the
specifications defined in the method of analysis.  Only those materials with  appropriate performance
capabilities and freedom from impurities will  be used. Attention will be given to assure that these
items  are properly stored to protect them from degradation and contamination.  Expiration  dates will
be noted so that only viable materials are used in preparations and analysis.  If stability is suspect,
retesting will be required.   Documentation of lot/batch numbers will be  required to provide traceability

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                                                                             Section No 12
                                                                             Revision No. 3
                                                                             Date: April 29, 1988
                                                                             Page 2 of 4
should questions arise regarding any results where they were used. Method blanks will be used to
determine what bias, if any, these materials might have on the analytical results.  These blanks will be
run as frequently as is necessary to reliably establish the bias.

      12.1.d  Chemical Solutions/Performance Standards
      All measuring devices such as volumetric glassware, syringes, analytical balances, meters, etc.,
will be appropriately calibrated and in good working order to capably conduct measurements with the
degree of accuracy required by the analytical method to be followed. Concentrations of prepared
standard solutions will be verified against primary analytical reference standards, if available, or by the
most direct, reliable, approved method of measurement when such standards are not available.
Aliquots will be taken in the largest practical volumes to minimize error associated with  such
measurements.  All preparations will be labeled to identify solutes and solvents used, concentration,
date of preparation and expiration date (if applicable), and the name of the preparer.  The source of
materials will be identified in the laboratory record book.  Stored solutions and standards will be
rechecked periodically to assure that their stability isn't suspect and that no contamination has
occurred.

      12.1.e  Analytical Methods
      Only approved, validated methods which meet the requirements for selectivity, accuracy,
precision and range as specified for this program will be used.

      12.1.1   Analyst Training
      Analysts assigned to work on this program will be selected on the basis of their formal
education and experience to conduct the kinds of analyses required. Special on-the-job training is
done to emphasize the importance of technique and adherence to SOPs.  All training is documented
and will be checked to assure that it meets program requirements for the work to be done.

      12.1.g  Equipment Calibration/Maintenance
      Documented procedures are available for care and maintenance of equipment. These
procedures will be reviewed and equipment logs will be checked  to assure that operations are
conducted as stated to ensure the performance of equipment.  This includes the primary analytical
equipment as well as auxiliary equipment, such as pH meters, balances, gauges, thermometers, etc.
      Internal instrument calibration checks will be performed as required and these operations will be
documented.  Performance during analysis will be documented by use of performance  standards.
Performance criteria will be predetermined and stated in the analytical method.  Routine preventative
maintenance will be conducted according to a written schedule.  Should problems occur, trouble

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                                                                              Section No  12
                                                                              Revision No. 3
                                                                              Date. April 29, 1988
                                                                              Page 3 of 4
shooting will be conducted to identify problems and their cause so that appropriate corrective action
can be taken quickly and accurately to avoid more complicated failures.

      12.1.h   Facilities
      Facilities will be inspected periodically, on a monthly basis, to maintain control of the laboratory
environment to eliminate contaminating influences, optimize instrument operating conditions  and
maintain good housekeeping and safe working conditions.

      12.1.1  Standard Operating Procedures
      Written standard operating procedures are available to cover equipment and operations done in
the laboratory. These, along with the Statement of Work and approved Quality Assurance Project
Plan, will be used as the basis for performance review.

      12.1.J  Data Records/Reports
      Documentation and reports generated in connection with this program will be audited
periodically to assure that records and results meet program requirements.  This audit will include the
master sample log which shows what samples have been received from and by whom, the date of
receipt,  and sample description; any required custody records; analytical instrument and auxiliary
equipment activity logs; laboratory record books that document all operations that have occurred
including sample identification and preparations, transfer of samples, details concerned with  analysis,
and deviations from  procedure that might have occurred,  controls that were run, instrument
identification, and analysts signatures along with the dates of the work, any associated raw data
resulting from the preparation and analysis, all observations, and discussions and conclusions
throughout the progress of the work.  In addition, computer printouts and charts will be reviewed, as
necessary to determine that all required work was done and is properly labeled, that results  meet
requirements, and that reported  observations are in agreement with data that were generated.
Special  attention will be given to sample identification, analytical parameters and their limits of
detection, final results, estimation of precision and accuracy, types of corrections applied to the raw
data, references to approved analytical methods, reliability of the data and its interpretation.

12.2  Performance Audits
      Scheduled performance audits will be conducted by the QAU. A performance audit is an
independent check by the QAU to evaluate the data produced by the laboratory's analytical  system.
Performance audits include:
           An on-site analyst work review conducted at a frequency no less than once per
           quarter.  The on-site audit is a means of evaluating performance that can not be
           assessed by evaluation of data. The analyst's techniques, observance of

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                                                                            Section No 12
                                                                            Revision No  3
                                                                            Date: April 29, 1988
                                                                            Page 4 of 4
           procedures as defined by written methods this QA Project Plan, and general
           knowledge of the project objectives will be assessed.  On-site work review results
           will be reported to the Project Manager.

           An audit of all data produced during the NPS analytical effort.  QAU will audit all
           data for adherence to QA objectives and specified reporting formats prior to release
           of the data to EPA.
12.3 Audits Conducted by the USEPA

     The USEPA will perform periodic systems and data audits using USEPA-assigned staff. These

audits will be preannounced to BCD; at minimum, the Battelle QAU Manager and the BCD Project

Manager will be present during these audits. Results of USEPA systems and data audits will be

supplied to BCD in writing; BCD will respond to all USEPA systems and data audit results and

describe the responses to USEPA in writing.

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                                                                            Section No 13
                                                                            Revision No 3
                                                                            Date- April 29, 1988
                                                                            Page 1 of 4
13.   PREVENTATIVE MAINTENANCE
      Preventative maintenance will be conducted to minimize occurrences of unpredicted instrument
failure. Necessary spare parts will be kept on hand so that any necessary repairs can be made
quickly.  Preventative maintenance steps that will be taken to minimize instrumentation downtime are
summarized in Table 2. Spare parts  necessary for routine instrument maintenance are listed in Table
3.
      All maintenance performed is recorded in record log books for each instrument. If necessary,
the instrument will be recalibrated after any maintenance operation as described in Section 8.0 of this
QA Project Plan.  Whenever instruments are serviced, the record log book will show the part number,
the date, the person doing the maintenance, and the reason for the maintenance work. An example
of  a record  log book page is shown in Figure 13.
      In general,  Battelle performs instrument maintenance using in-house personnel.  However, if
outside maintenance is required, sufficient additional instrumentation (GC, MS) is available for use to
eliminate downtime.

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                                                                  Section No 13
                                                                  Revision No 3
                                                                  Date: April 29, 1988
                                                                  Page 2 of 4
                                FIGURE 13

                    INSTRUMENT RECORD LOG BOOK


                       Routine Maintenance Record
Date
1/29
2/10
2/12
2/14
ID
D7
D7
D7
D7
Work Performed and Comments
Changed system
Changed system
Changed system
Installed pressure



regulator on a
                   eliminate pulsing

3/18       D7      Installed Dual Column system, graphite seal at injection part
                   Changed bead on Det B
                   Replaced system

3/22       D7      Installed SPB-5, new system

3/22       D7      Reinstalled dual column

3/23       D7      Installed SPB-5
                   Replaced system

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                                                                      Section No 13
                                                                      Revision No. 3
                                                                      Date: April 29, 1988
                                                                      Page 3 of 4
                                      TABLE 2

                      PREVENTATIVE MAINTENANCE SCHEDULE
Maintenance Operation
Frequency
GC-NPD Primary and Confirmatory

   Clean or replace rhubidium bead in NPD

   Replace septa

   Break off ends of GC column or replace column

   Clean injection port liner

MS Confirmation

   Replace mechanical pump oil

   Replace filament

   Replace electron multiplier

   Clean ion source
When poor response is observed

Every day

When poor chromatography is observed

When poor chromatography is observed


Every 3 months

When old filment burns out

When multiplier gain is <1x104

When poor tuning is observed

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                                                                Section No 13
                                                                Revision No 3
                                                                Date: April 29, 1988
                                                                Page 4 of 4
                                TABLE 3

                      SPARE INSTRUMENT PARTS
Gas Chromatography           Mass Spectrometry
Fused silica capillary columns     Mechanical pump oil

Syringes                       Filaments

Rhubidium bead assemblies      Electron multiplier
                              Replaceable source components (ceramics)

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                                                                            Section No  14
                                                                            Revision No. 3
                                                                            Date: April 29, 1988
                                                                            Page 1 of 2
14.   SPECIFIC ROUTINE PROCEDURES USED TO ASSESS MEASUREMENT SYSTEM DATA
14.1  Standard Deviation
      NPS data precision will be expressed in terms of standard deviation (s) with n-1 degrees of
freedom. The standard deviation is the square root of the variance of a set of values and is calculated
using the equation:
                s =
                        I  (Xrx)2
                           n-1
      where:     n  = the number of data points;
                X| = the recovery for sample i in ng/L; and
                x  = the average recovery for all samples in
14.2  Percent Recovery
      Data accuracy is expressed in terms of percent recovery (R) calculated using the equation:
                                        R = (100C)/S
      where:     C = the calculated level of analyte in the sample, and
                S = the level of the analyte spiked into the sample.

14.3  Relative Standard Deviation
      The relative standard deviation (RSD) is calculated using the equation:
                                       RSD = (100s)/x

14.4  Peak Symmetry and Peak Gaussian Factors
      Acceptable instrument performance is expressed in terms of the peak symmetry factor (PSF)
and peak Gaussian factor (PGF).  These calculations are demonstrated in Table 5 and Figure 2 of
Method 6 (Appendix A).

14.5  Minimum Detectable Level
      The MDL (Section 5.1) is expressed in ^g/L and is calculated using the equation:
                                        MDL  = ((s) t)
           where:      t = the student's t value appropriate for a 99 percent confidence
                      level (t = 3.500 for eight measurements and seven degrees of
                      freedom).

14.6  Estimated Detection Limit
      The EDL (Section 5.1) is expressed in ^g/L  and equals either the concentration of analyte
yielding a detector response with a 5:1 S/N or the calculated MDL, whichever is greater.

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                                                                              Section No. 14
                                                                              Revision No. 3
                                                                              Date: April 29, 1988
                                                                              Page 2 of 2
14.7  Minimum Reporting Level
      The MRL (Section 5.1) is expressed in ^g/L and is defined as three times the EDL calculated
using primary analytical conditions.

14.8  Control Limits
      To construct a control chart (Section 5.3.a), the standard deviation (s) is calculated as described
in Section 14.1 for the measurements (usually 20 total). Warning limits (±2RSD) are calculated using
the equation:
                                     ±2RSD = ±2(100s)/x
Control limits (±3RSD) are calculated using the equation:
                                     ±3RSD = ±3(100s)/x

14.9  Dixon's Test
      Dixon's Test is a criterion used for detecting outliers.  Dixon's test is explained in Section
17-3.1.1 and Table A-14 of Appendix B.2 The following assumptions will be made in applying Dixon's
Text:
           The probability or risk acceptable for rejecting an observation will be 1% (a = .01),
      •     The test will be used to reject "extreme observations" in either direction  as opposed
           to  rejecting extreme observations in only one direction  (high or low), and
           The number of observations (n) will be 20, 19, or 18 since the test will be used to
           reject a maximum of three observations.

14.10   Rounding Numbers and Significant Figures
      Procedures for rounding numbers and determination of significant figures is described in
Appendix J, "Standard Operating Procedure for Proper Use of Significant Figures and Rounding."
   2 Natrella, M. G., Chapter 17. Treatment of Outliers, Experimental Statistics. NBS Handbook 91,
August 1, 1963.

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                                                                              Section No 15
                                                                              Revision No. 3
                                                                              Date: April 29, 1988
                                                                              Page 1 of 3
15.   CORRECTIVE ACTION
      The need for correction action occurs when a circumstance arises which threatens the quality of
analytical results.  In order for corrective action to be initiated, awareness of a problem must exist.  In
this project, the vanguard for early recognition of problems which will affect data quality is the
personnel conducting the laboratory analysis.  Each Project Team member is aware of QC procedures
and subtleties associated with each analytical  method. These experienced personnel quickly detect
minor instrument changes, changes in method performance, and drifts or malfunctions which can be
corrected, thus preventing major interruptions  of method performance.  A primary  method of detection
of instrumentation problems will arise from analysis of calibration standards periodically during use  of
the instruments and by use of internal standard control charts to quickly indicate changes in
instrument performance.  A primary method of monitoring method performance is  the use of surrogate
standard control charts to quickly indicate changes in analyte recoveries.  If major problems arise, the
Project Team will decide upon the proper corrective action  and initiate it immediately, thus minimizing
data loss. Therefore, the Project Team, and more specifically Mr. Zimmerman, will have a prime
responsibility for recognizing the need for and initiating corrective action.  Decisions on whether to
take corrective action and what  action(s) to take will be made in consultation with  the Method Leader
(Mr. Zimmerman) and the Project Manager (Mrs. Engel). Such decisions will be based on action  limits
discussed in other sections.  The Method Leader or Project Manager will apprise the EPA Contract
Technical Monitor of corrective action situations and discuss potential actions with the Technical
Monitor.  When a corrective action is taken, the Project Manager will be responsible for notifying the
QAU Manager so that she can, if deemed necessary, intensify the audits of the effected measurement
system. The Method Leader or  Project  Manager will follow  up on corrective action situations to assure
resolution of the situation.
      The second level of recognition of the need for corrective action will  be the QAU Manager and
the Project Manager. The QAU  Manager will determine the need for corrective action from the results
of the system and performance  audits described in Section 12.0 and during routine validation of all
Method 6 results.  Data inconsistencies  and/or invalid data  will alert the QAU Manager, Project
Manager and Method  Leader to the necessity  of corrective  action. These individuals will be
responsible for initiating appropriate corrective action.
      Each Project Team  member will be briefed on the project objectives  and data quality required to
meet those objectives.  Data quality objectives for this project are listed in  Section 5.0.  Each individual
will be informed of these objectives and will have responsibility to notify the Method  Leader  or Project
Manager whenever a measurement system is not yielding data within these objectives.
      Situations requiring corrective action will be reported  using the Report of Deviation form shown
in Figure 14.  The Method Leader and Project  Manager are responsible for following up all situations
requiring corrective action. These individuals are responsible for informing the EPA Contract

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                                                                                  Section No. 15
                                                                                  Revision No. 3
                                                                                  Date:  April 29, 1988
                                                                                  Page 2 of 3
Technical Monitor of the situation and will assure adequate resolution of such situations.  All relevant
information regarding the situation initiating the corrective action and the resolution of the situation are
included on this form.  The Report of Deviation form will be included in the project files.  Descriptions
of deviations will be included in the Monthly Reports to the EPA Contract Technical Monitor.

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                                                                              Section No  15
                                                                              Revision No. 3
                                                                              Date: April 29, 1988
                                                                              Page 3 of 3
                                          FIGURE 14
                                   REPORT OF DEVIATION
Project Number:
Title:
Date of Deviation:
Description of Deviation:
Persons Notified:
Samples Involved (include set number):
Description of Remedial Action:
Person Completing Remedial Action:
Description of Resolution of Deviation:
Date of Resolution of Deviation:
Report Prepared by:  	           Date:
Reviewed by:  	           Date:
              Study Manager

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                                                                            Section No 16
                                                                            Revision No 3
                                                                            Date- April 29, 1988
                                                                            Page 1 of 1
16.  QUALITY ASSURANCE REPORTS TO MANAGEMENT
     The results of periodic activities to assess the quality of the data generated during the project
will be reported to the Project Manager by the QAU Manager. The QAU Manager is responsible for
submission of monthly QA reports in the form of memoranda listing all QAU activities for that month.
Activities include dates of and a summary of results from system or performance audits conducted
during that month, a list of all analysis data approved by the QAU for submission to EPA, periodic
assessment of measurement data accuracy, precision, and completeness, and significant QA
problems and recommended solutions.  Results of system audits will be reported to the Project
Manager in memoranda form within one week of the audit.  Results of performance audits will be
supplied to the Project Manager within one week of the audit using Battelle's Critical Phase Inspection
Check Sheet shown in Appendix I.  The Method Leader or the Project Manager will be responsible for
responding to all issues/concerns referenced in monthly QA reports and results of performance audits.
However, these documents are considered internal Battelle documents and will not be provided to
EPA. EPA will  be apprised  of QA/QC deviations and issues via phone conversations initiated by the
Project Manager and in Reports of Deviation (Figure 14), which will be summarized in the monthly
progress reports to the EPA Contract Technical Monitor described in Section 10.3.b.

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                                                Appendix A
                                                Revision No 3
                                                Date: April 29, 1988
                                                Page 1 of 27
                  APPENDIX A

METHOD 6. DETERMINATION OF ETHYLENE THIOUREA
   IN GROUND WATER BY GAS CHROMATOGRAPHY
    WITH A NITROGEN-PHOSPHORUS DETECTOR

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       Method 6.   Determination of Ethylene Thiourea (ETU) in Ground
      Water by Gas Chromatography with a  Nitrogen-Phosphorus Detector


1.    SCOPE AND APPLICATION

     1.1   This is a gas chromatographic  (GC)  method applicable to the
           determination of ethylene thiourea  (ETU,  Chemical  Abstracts
           Registry No.  96-45-7)  in ground water.

     1.2   This method has been validated in a single laboratory.   The
           estimated detection limit (EDL) has been  determined and is
           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.

     1.4   When this method is used to analyze unfamiliar samples for ETU,
           identification must be confirmed by at  least one additional
           qualitative technique.

2.    SUMMARY OF METHOD

     2.1   The ionic strength and pH of a measured 50-mL volume of sample
           are adjusted by addition of ammonium chloride and potassium
           fluoride.  The sample is poured onto an Extrelut column.  ETU is
           eluted from the column in 400  mL of methylene chloride.  The
           extract is solvent exchanged to ethyl acetate and concentrated
           to a volume of 5 ml. Chromatographic conditions are described
           which permit the separation and measurement of ETU in the
           extract by GC with a nitrogen-phosphorus  detector (NPD).

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 analyte,
           dissolved in an organic solvent, analyzed under the same
           procedures and conditions used to analyze sample extracts
           containing that analyte.

     3.3   Estimated detection limit (EDL) --  The  minimum concentration of
           a substance that can be measured and  reported with confidence
           that the analyte concentration is greater than zero as
           determined from the analysis of a sample  in a given matrix

                                       72

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      containing the analyte.   The EDL is equal to the level
      calculated by multiplying the standard deviation of replicate
      measurements times  the  students' t value appropriate for a 99
      percent confidence  level  and a standard deviation estimate with
      n-1 degrees of freedom  or the level of the compound in a sample
      yielding a peak in  the  final extract with signal-to-noise ratio
      of approximately five,  whichever value is higher.

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

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

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

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

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

                                   73

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

           4.1.1   Glassware must be scrupulously cleaned.1  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 400*C for 1 hour.  Do
                   not heat volumetric  ware.   Thermally stable materials
                   might not be eliminated by this treatment.  Thorough
                   rinsing with acetone and methylene chloride may be
                   substituted  for the  heating.  After drying and cooling,
                   seal and store glassware in a clean environment to
                   prevent any  accumulation of dust or other contaminants.
                   Store inverted or capped with aluminum foil.

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

     4.2   Interfering contamination may occur when a sample containing a
           low concentration of ETU is  analyzed immediately following a
           sample containing a  relatively high concentration of ETU.
           Between-sample rinsing of the sample syringe and associated
           equipment with ethyl acetate can minimize sample cross contamin-
           ation.  After analysis of a  sample containing high concentra-
           tions of ETU, one or more injections of ethyl acetate should be
           made to ensure that  accurate values are obtained for the next
           sample.

     4.3   Matrix interferences may be  caused by contaminants that are
           coextracted from the sample.  The extent of matrix interferences
           will vary considerably from  source to source, depending upon the
           ground water sampled.  Positive identifications must be confirm-
           ed using the confirmation column specified in Table 1.

                                         74

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5.    SAFETY

     5.1   ETU is a cancer suspect agent and teratogen.  Primary standards
           of ETU should be prepared in a hood.   A NIOSH/MESA approved
           toxic gas respirator should be worn when the analyst handles
           high concentrations of ETU.  Each laboratory is responsible for
           maintaining a current awareness file of OSHA regulations
           regarding the safe handling of the chemicals specified in this
           method.  A reference file of material  safety data sheets should
           also be made available to all personnel involved in the chemical
           analysis.  Additional references to laboratory safety are
           available and have been identified2"4 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 -- 60-mL screw cap vials (Pierce No.
                   13075 or equivalent) and caps equipped with a PTFE-faced
                   silicone septa (Pierce No. 12722 or equivalent).  Prior
                   to use, wash and heat vials and septa as described in
                   Section 4.1.1.

     6.2   GLASSWARE

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

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

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

           6.2.4   Vials -- Glass, 5- to 10-mL capacity with TFE-fluoro-
                   carbon lined screw cap.

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

     6.4   Water bath -- Heated, capable of temperature control (±2*C).
           The bath should be used in a hood.
                                        75

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

     6.6    Tube  heater --  Capable  of  holding  eight K-D concentrator tubes
           and heating the mid-section  of  the tubes to 35-40*C while
           applying a  nitrogen  stream.

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

           6.7.1    Primary column  --  10 m  long x 0.25 mm I.D. DB-Wax bonded
                   fused silica column, 0.25  pm 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.

           6.7.2    Confirmation column  --5m long x 0.25  mm I.D. DB-1701
                   bonded  fused silica  column, 0.25 urn film thickness
                   (available  from J&W).

           6.7.3    Detector --  Nitrogen-phosphorus detector (NPD).  This
                   detector has proven  effective in the analysis of spiked
                   reagent and  artificial  ground waters.  A NPD 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    Reagent  water -- Reagent water  is  defined as water in which  an
           interferent is  not  observed  at  or  above the EDL of any analyte.
           Reagent  water used  to generate  the validation data in this
           method was  distilled water obtained from the Magnetic Springs
           Water  Co.,  Columbus, Ohio.

     7.2    Acetone, methylene  chloride, ethyl acetate -- Distilled-in-glass
           quality  or  equivalent.

     7.3    Nitrogen gas -- high purity.

     7.4    Extraction  column,  Extrelut  QE  --  Obtained from EM Science
           (Catalog No. 902050-1).

     7.5    Ammonium chloride,  granular, ACS grade -- for pH and ionic
           strength adjustment  of  samples  (available from Baker Chemical
           Co.).


                                       76

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               7.6   Potassium fluoride,  anhydrous,  ACS grade -- for ionic strength
                     adjustment of sample (available from Baker Chemical Co.).

               7.7   Mercuric chloride,  granular,  ACS grade -- used as sample preser-
                     vative (available from Mallinckrodt).

               7.8   Dithiothreitol  (DTT) -- for use as a free-radical scavanger
                     (available from Aldrich Chemical Co.)*

                     7.8.1   DTT in ethyl acetate, 1000 ug/mL -- Prepare by adding
                             1 g DTT to a 1-L volumetric flask and diluting to volume
                             with ethyl  acetate.   Store at room temperature.

               7.9   Propylene thiourea (PTU) --  for use as a surrogate standard.
                     Prepared from carbon disulfide and 1,2-d.iaminopropane using the
                     procedure published by Hardtmann, et.  al. (Journal of Medicinal
                     Chemistry, lfi(5), 447-453,  1975).

               7.10  3,4,5,6-Tetrahydro-2-pyrimidinethiol (THP) -- >98% purity, for
                     use as an internal  standard (available from Aldrich Chemical
                     Co.).

               7.11  STOCK STANDARD SOLUTION (0.10 ug/uL) - The stock standard
                     solution may be purchased as  a certified solution or prepared
                     from pure standard material  using the following procedure:

                     7.11.1  Prepare stock standard solution by accurately weighing
                             approximately 0.0010  g of pure ETU.  Dissolve the ETU in
                             ethyl acetate containing 1000 M9/mL of DTT and dilute to
                             volume in a 10-mL volumetric flask.  Larger volumes may
                             be used at the convenience of the analyst.  If ETU
                             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.

                     7.11.2  Transfer the stock standard solution into a TFE-fluoro-
                             carbon-sealed screw cap vial.   Store at 4'C and protect
                             from light.

                     7.11.3  The stock standard solution should be replaced after two
                             weeks or sooner if comparison with laboratory control
                             standards indicates a problem.

               7.12  INTERNAL STANDARD SPIKING SOLUTION -- Prepare an internal
                     standard spiking solution by  accurately weighing approximately
                     0.0010 g of pure THP.  Dissolve the THP in ethyl acetate
                     containing 1000 ug/mL of DTT  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

                                                  77

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\

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           at 4'C and protect  from light.   Addition of 50 ML of the
           internal  standard spiking  solution  to 5  ml of sample extract
           results in a final  internal  standard  concentration of 1.0
           Solution  should be  replaced  when ongoing QC (Section 10)
           indicates a problem.

     7.13  SURROGATE STANDARD  SPIKING SOLUTION -- Prepare a surrogate
           standard  spiking solution  by accurately  weighing approximately
           0.0010 g  of pure PTU.   Dissolve  the PTU  in ethyl acetate
           containing 1000 ug/mL  of DTT 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 4*C and protect  from light.   Addition of 5 Ml of the
           surrogate standard  spiking solution to a 50-mL sample prior to
           extraction results  in  a surrogate standard concentration in the
           sample of 10 yg/L and,  assuming  quantitative recovery of PTU, a
           surrogate standard  concentration in the  final extract of
           0.10 Mg/mL.

     7.14  INSTRUMENT QC STANDARD -•  Prepare the instrument QC standard by
           adding 10 uL of the ETU stock standard solution, 1.0 mL of the
           internal  standard spiking  solution, and  100 ML of the surrogate
           standard  spiking solution  to a  100-mL volumetric flask and
           diluting  to volume  with ethyl  acetate containing 1000 M9/mL °f
           DTT.  Transfer the  instrument QC standard to a TFE-fluorocarbon-
           sealed screw cap bottle and  store at  room temperature.
           Solution  should be  replaced  when ongoing QC (Section 10)
           indicates a problem.

8.   SAMPLE COLLECTION. PRESERVATION. AND  STORAGE

     8.1   Grab samples must be collected  in 60-mL  screw cap glass vials
           (Section  6.1.1).  Conventional  sampling  practices5 should be
           followed; however,  the bottle must not be prerinsed with sample
           before collection.

     8.2   SAMPLE PRESERVATION AND STORAGE

           8.2.1   Add mercuric chloride to the sample bottle in amounts to
                   produce a concentration  of 10 mg/L.  Add 60 \ii of a
                   solution containing  10  mg/mL of mercuric chloride in
                   water to the sample  bottle at the sampling site or in
                   the laboratory before shipping to the sampling site.
                   Mercuric chloride  is a  highly toxic chemical.  Mercuric
                   chloride must  be handled with caution, and samples
                   containing  mercuric  chloride must be properly disposed.

           8.2.2   After the sample is  collected in the bot+le containing
                   preservative,  seal the  sample bottle and shake vigor-
                   ously for 1 min.
                                       70

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           8.2.3   ETU can degrade quickly in water even when the sample is
                   refrigerated.   Samples should be extracted as soon as
                   possible and must be extracted within 14 days of
                   collection.  The samples must be iced or refrigerated at
                   4*C and protected from light from the time of collection
                   until  extraction.   Preservation study results given in
                   Table  4 indicate that 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   Extracts should be stored at 70*C away  from light.
                   Preservation study results given in  Table 4 indicate
                   that extracts  are stable for at least 28 days when
                   stored under these conditions.  The  analyst should
                   verify appropriate extract holding times applicable to
                   the samples  under study.

9.    CALIBRATION

     9.1   Establish GC operating parameters equivalent to those indicated
           in Table 1.  The GC  system must be calibrated using the internal
           standard technique (Section 9.2).

     9.2   INTERNAL STANDARD CALIBRATION PROCEDURE.  To use this approach,
           the analyst must select one or more internal standards compat-
           ible in analytical behavior to the compound  of  interest.   The
           analyst must further demonstrate that the measurement of the
           internal standard is not affected by method  or  matrix interfer-
           ences.   THP has been identified as a suitable internal -standard.

           9.2.1   Prepare ETU  calibration standards at a  minimum of three
                   (suggested five) concentration levels by adding volumes
                   of the ETU stock standard to a volumetric flask.   To
                   each calibration standard, add a known  constant amount
                   of one or more internal standards, and  dilute to volume
                   with ethyl acetate containing 1000 pg/mL of DTT.   One of
                   the calibration standards should be  representative of an
                   ETU concentration near, but above, the  EDL.  The other
                   concentrations should correspond to  the range of concen-
                   trations expected in the sample concentrates, or should
                   define the working range of the detector.

           9.2.2   Inject 2 \ii  of each calibration standard and tabulate
                   the relative response for ETU to the internal standard
                   (RRa)  using  the equation:
                                        79

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                   where:   Aa  -  the  peak area of ETU,  and
                           A-js -  the  peak area of the internal  standard.

                   Generate a calibration curve of RRa versus ETU concen-
                   tration in the sample in M9/L.

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

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 prepara-
           tion; the monitoring  of internal  standard area counts or peak
           heights in each and every sample as a continuing check on system
           performance; the analysis of  QC samples,  laboratory control
           standards, 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 ETU.   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 concen-
                   tration.

           10.2.2  Using a syringe, add  50 uL of the LC sample concentrate
                   to each of a  minimum of four 50-mL aliquots of reagent
                   water.   A representative ground water may be  used in
                   place of the  reagent  water, but one or more unspiked
                   aliquots must be analyzed to determine background
                   levels, and the spike level must, at a minimum, exceed
                   twice the background  level  for  the test, to be valid.
                   Analyze the aliquots  according  to the method  beginning
                   in Section 11.
                                        80

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

      10.2.4   Tables  2-3 provide  single  laboratory recovery and
              precision  data obtained for ETU 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 calcu-
              lated percent  relative standard deviation (RSD) does not
              exceed  2.6 times  the single laboratory RSD  or
              20  percent,  whichever  is greater, and your  mean recovery
              lies  within  the interval R+3S  or R+30% whichever  is
              greater.

10.3  In recognition  of  the  rapid advances occurring in chromato-
      graphy,  the analyst  is permitted to modify GC columns, GC
      conditions, or  detectors  to improve the separations or lower the
      cost of measurements.   Each 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.

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

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

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

              (3)  Check instrument  performance.
                                   81

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              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,  the laboratory must
              establish that the deviation is not due to laboratory
              problems.   The laboratory shall  document deviations by
              taking the  following  actions:

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

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

              (3)  Check  instrument performance.

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

10.5  ASSESSING THE INTERNAL STANDARD

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

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

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

              10.5.3.1  Single  occurrence --  Reinject an aliquot of
                       the extract to ensure proper  sample injection.
                       If  the  reinjected sample extract aliquot
                       displays an internal  standard peak  area or
                       height  within  specified  limits, quantify and

                                   82

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                        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.   Repeat
                        the analysis  of  that sample.

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

10.6  ASSESSING LABORATORY PERFORMANCE

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

              10.6.1.1  The spiking concentration in the laboratory
                        control standard should be 15 times the EDL.

              10.6.1.2  Spike a reagent  water aliquot with a labora-
                        tory  control  (1C)  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 parameter.   Calcu-
                        late  each percent recovery (Ri) as (lOOxA)VT,

                                  83

-------
where T
spike.
                  is the known true concentration of the
10.6.1.3  Compare the percent recovery (Rj) for each
          parameter with established QC acceptance
          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:
             1-1
          and
        where:     n  - number of measurements for each
                       analyte,  and
                  R.J  « individual percent recovery
                       value.

          Calculate QC acceptance criteria as follows:

               Upper Control  Limit (UCL) • R + 3Sp
               Lower Control  Limit (LCL) - R - 3Sp

          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 contin-
          uous  basis.  After  each five to ten new
          recovery measurements  (RiS), recalculate R and
          SR using all the data, and construct new
          control  limits.   When  the total number of data
          points reach twenty, update the control limits
          by calculating  R and SR using only the most
          recent twenty data  points.
                     84

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

                        If the recovery of ETU falls outside the
                        designated  range, the  laboratory performance
                        for ETU 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 ETU in
                        samples is  suspect and must be so labeled.
                        All results for ETU  for that sample set  must
                        also be labeled suspect.

      10.6.2   Each  quarter, it is essential  that  the laboratory
              analyze (if available)  QC check  standards.  If the
              criteria established  by the U.S.  Environmental  Protec-
              tion  Agency (USEPA) and provided 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  acceptable 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 concentra-
                        tion,  or, if it is impractical to determine
                        background  levels before  spiking, 15  times  the
                        EDL.

              10.7.1.2  Analyze one sample aliquot to determine  the
                        background  concentration  (B) of each  para-
                        meter.  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  to determine the concentration
                        after spiking (A) of each  parameter.   Calcu-
                        late each percent recovery (R-j)  as
                        100(A-B)%/T,  where T is  the known true
                        concentration of  the spike.

              10.7.1.3  Compare the percent  recovery (R-j) for each
                        parameter with QC acceptance criteria deter-

                                   85

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                       mined  by  the  analysis  of laboratory control
                       standards.

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

              10.7.1.4  If  the recovery of ETU falls outside the
                       designated range,  and  the laboratory perfor-
                       mance  for ETU 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 ETU in  the
                       unspiked  sample is labeled suspect/matrix  to
                       inform the user that the results are suspect
                       due to matrix effects.

10.8  ASSESSING LABORATORY  CONTAMINATION  (METHOD BLANKS) --  Before
      processing any samples,  the analyst must demonstrate that all
      glassware and  reagent interferences are  under control.   This is
      accomplished by the analysis of a laboratory method blank.  A
      laboratory method blank  is  a 50-mL  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 ETU  which is greater  than or equal to one-half  the EDL
      for ETU, 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
      analysis of the instrument  QC standard.   The instrument QC
      standard contains compounds designed to  indicate appropriate
      instrument sensitivity,  column  performance and chromatographic
      performance.  Instrument QC standard components and performance
      criteria are listed in Table 5.   Inability to demonstrate
      acceptable instrument performance indicates the need for
      reevaluation of the GC-NPD  system.   A GC-NPD chromatogram
      generated from the analysis of  the  instrument QC standard is
      shown in Figure 1.  The  sensitivity requirements are set  based
      on the EDL published  in  this method.  If the laboratory EDL
      differs from that listed in this method, concentrations of the
      instrument QC  standard compounds must be adjusted to be com-
      patible with the laboratory EDL. 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 1.
                                   86

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     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  SAMPLE EXTRACTION

           11.1.1  Add preservative to any samples not previously preserved
                   (Section 8.2).  Pipet 50 mL of water sample into a 60-mL
                   bottle containing 1.5 g of ammonium chloride and 25 g of
                   potassium fluoride.  Close bottle and shake vigorously
                   until salts are dissolved.  Spike sample with 5 uL of
                   the surrogate standard spiking .solution.

           11.1.2  Pour contents of bottle onto Extrelut column.  Allow the
                   column to stand undisturbed for 15 min.

           11.1.3  Add 5 mL of 1000 ug/mL DTT in ethyl acetate to a K-D
                   concentrator tube equipped with a 500-mL flask.

           11.1.4  Add 400 mL of methylene chloride in 50-75 mL portions to
                   the Extrelut column and collect the eluant in the K-D
                   apparatus (Section 11.1.3).  The water, ammonium
                   chloride and potassium fluoride remain on the Extrelut
                   column while the ETU is removed from the column in the
                   methylene chloride eluate.  Discard the Extrelut column.

     11.2  EXTRACT CONCENTRATION

           11.2.1  Add 1 or 2 clean boiling stones to the K-D apparatus and
                   attach a macro Snyder column.  Prewet the Snyder column
                   by adding about 1 mL of methylene chloride to the top.
                   Place the K-D apparatus in a 65-70'C water bath so that
                   the K-D tube is partially immersed in the hot water, and
                   the entire lower rounded surface of the flask is bathed
                   with hot vapor.  When the apparent volume of liquid
                   reaches 5 mL, remove the K-D apparatus and allow it to
                   drain and cool for at least 10 min.

           11.2.2  Reduce the liquid volume in the K-D tube to approximat-
                   ely 1 mL by placing the sample extract in a tube heater
                   at 35-40*C under a stream of nitrogen.  The tube heater
                   heats the solvent in the K-D tube at volume markings
                   between 1 and 10 mL.

           11.2.3  Dilute sample extract to 5 mL with ethyl acetate; rinse
                   walls of K-D tube while adding ethyl acetate.  Immed-
                   iately spike sample extract with 50 uL of internal
                   standard spiking solution.  Agitate sample extract to
                   disperse internal standard.  Transfer sample extract to

                                        37

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                   a GC vial  and  determine  ETU  by  GC-NPD as described in
                   Section 11.3.   Sample  extracts  should be protected from
                   light and  analyzed within  24 hours of extraction.
                   Sample extracts can  be stored for up to 28 days,  frozen
                   at -10*C and protected from  light.

     11.3   GAS CHROMATOGRAPHY

           11.3.1   Table 1 summarizes the recommended GC operating condi-
                   tions.  Included in  Table  1  are retention times observed
                   using this method.   An example  of the separations
                   achieved using these conditions are shown in Figure 1.
                   Other GC columns, chromatographic conditions,  or
                   detectors  may  be used  if the requirements of
                   Section 10.1 are met.

           11.3.2   Calibrate  the  system daily as described in Section 9.
                   The standards  and extracts must be in ethyl acetate
                   containing 1000 (jg/mL  DTT.

           11.3.3   Inject 2 ML of the sample  extract.  Record the resulting
                   peak size  in area units.

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

           11.3.5   If the response for  the  peak exceeds the working range
                   of the system, dilute  the  extract with ethyl acetate
                   containing 1000 \ig/ml  DTT  and reanalyze.

12.   CALCULATIONS  -- Calculate the ETU  concentration in the sample from the
     ETU relative  response (RRa)  to the internal standard using the
     calibration curve described  in Section 9.2.2.

13.   PRECISION AND ACCURACY

     13.1   In a single laboratory, ETU  recoveries  from reagent water  were
           determined at five concentration levels.  Results were used to
           determine the ETU  EOL  and demonstrate method range.  EDL and
           method  range data  are  given  in Table 2.

     13.2   In a single laboratory, ETU  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.  ETU recoveries from the  two
           artificial matrices are given  in Table  3.

                                       38

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13.3  In a single laboratory,  ETU recoveries from a ground water
      preserved with  mercuric  chloride were determined 0, 14, and 28
      days after spiking  the sample  with ETU.   Sample extracts were
      also reanalyzed after they were stored for 28 days at -10*C and
      protected from  light.  Results were used to predict expected ETU
      stability in ground water  samples and sample extracts.  ETU
      recoveries from the preserved, spiked ground water samples and
      stored extracts are given  in Table 4.

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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 Materials, Philadel-
    phia, PA, p. 86, 1986.

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

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

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

5.  ASTM Annual Book of Standards, Part 11, Volume 11.01, 03370-82, "Stan-
    dard Practice for Sampling Water,"  American Society for Testing and
    Materials, Philadelphia, PA, p. 130, 1986.

6.  Nitz, S., Moz, P. and F. Korte, "A Capillary Gas-Liquid Chromatographic
    Method for Determination of Ethylenethiourea and Propylenethiourea  in
    Hops, Beer, and Grapes," J. Agric. Food Chem., 1982, 3JJ, 593-596.
                                        90

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      TABLE  1.  PRIMARY AND CONFIRMATION CHROMATOGRAPHIC  CONDITIONS
                                    Retention Time, min
Analyte Primary column
ETU
THP (internal standard)
PTU (surrogate standard)
3.5
5.1
2.7
Confirmation column
4.5
5.0
2.2
Primary conditions:

                Column:

           Carrier gas:
            Makeup gas:
        Detector gases:
  Injector temperature:
  Detector temperature:
      Oven temperature:
                Sample:
              Detector:

Confirmation conditions;

                Column:

           Carrier gas:
            Makeup gas:
        Detector gases:
  Injector temperature:
  Detector temperature:
      Oven temperature:
                Sample:
              Detector:
10 m long x 0.25 mm I.D. DB-Wax bonded fused
silica column (J&W), 0.25  m film thickness
He 9 30 cm/sec linear velocity
He (? 30 mL/min flow
Air 9 100 mL/min flow; H2 I? 3 mL/min flow
220'C
230'C
220'C isothermal
2 uL splitless;  9 sec split delay
Ni trogen-phosphorus
5 m long x 0.25 mm I.D. DB-1701 bonded fused
silica column (J&W), 0.25  m film thickness
He 9 30 cm/sec linear velocity
He 9 30 mL/min flow
Air 9 100 mL/min flow; H2 9 3 mL/min flow
150'C
270'C
150'C isothermal
2 uL splitless; 9 sec split delay
Nitrogen-phosphorus
                                   91

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        TABLE  2.   RESULTS  FROM  EDL AND METHOD  RANGE STUDIES (a)
Spiking
Level ,
ug/L
5.0
10
25
100
Amt in
Blank,
M9/L
0.492
ND (b)
NO
NO


n(d)
7
7
7
7


R(e)
97 (c)
102
94
97


S(f)
0.845
0.886
1.31
5.96


RSD(g)
17
9
6
6


EDL(h)
5.0
-
-
•
(a)   Studies  conducted  in  reagent  water;  average recovery of PTU
     surrogate  from seven  spiked reagent  water samples was 100%
     (RSD was 8.5%).
(b)   ND  - not detected.
(c)   Data corrected for  amount  detected  in  blank.
(d)   n » number of  recovery data points.
(e)   R - average percent recovery.
(f)   S » standard deviation.
(g)   RSD -  percent  relative standard  deviation.
(h)   EDL -  estimated  detection  limit  in  sample in   ug/L;  calculated by
     multiplying standard  deviation  (S)  times  the  students'  t value
     appropriate for  a 99% confidence level  and  a  standard deviation
     estimate with  n-1 degrees  of  freedom,  or  level  of compound in
     sample yielding  a peak in  the final  extract with signal-to-noise
     ratio  of approximately 5,  whichever  value is  higher.
                                   92

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          TABLE 3.  RESULTS  FROM MATRIX EVALUATION  STUDIES  (a)


Matrix
Amt in
Blank,
H9/L


n(e) R(f)


S(9)


RSD(h)
Hard (b)                       ND (d)         7     93    0.372        4

Organic-contaminated (c)      ND             7     93    0.253        3
(a)  Samples were spiked with at the 10  ug/L level with ETU.
(b)  Absopure Natural Artesian Spring Water obtained from the Absopure
     Water Company in Plymouth Michigan.
(c)  Reagent water spiked with fulvic acid at the 1 mg/L concentration
     level.  A well-characterized fulvic  acid,  available from the
     International Humic Substances Society (associated with the United
     States Geological Survey in Denver,  Colorado), was used.
(d)  ND - not detected.
(e)  n - number of recovery data points.
(f)  R « Average percent recovery.
(g)  S - standard deviation.
(h)  RSD - percent relative standard deviation.
                                   93

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          TABLE  4.   RESULTS  FROM  PRESERVATION STUDY
Extraction Date
Day 0
Day 0
Day 14
Day 28
Analysis Date
Day 0
Day 28 (c)
Day 14
Day 28
R(a)
86
87
80
45
RSD(b)
2
3
6
10
(a)   R « percent  recovery;  average  of triplicate analyses.
(b)   RSD - percent  relative standard  deviation of triplicate
     analyses.
(c)   Sample extract stored  for  28 days at 4"C and protected
     from light.
                              94

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-------
                                            Appendix B
                                            Revision No. 3
                                            Date: April 29, 1988
                                            Page 1 of 3
        APPENDIX B

DIXON'S TEST FOR OUTLIERS

-------
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 < ...  < Vl < Xn

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

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

Example (from Taylor)

     Given  the  following  set of ranked data:

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

     The value  10.58  is suspected  of being an outlier.

     1)   Calculate rn

                       10.58 -  10.53       0.05
              ru  -    	   -   	   - 0.454
                       10.58 -  10.47       0.11

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

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

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

-------
                                     TABLE  1

                             CALCULATION OF  RATIOS
                         For  use if           if Xj, is             if X: is
      Ratio            n is between          suspect             suspect
                                                                    
-------
                                   TABLE 2




              VALUES  FOR USE WITH THE DIXON TEST FOR OUTLIERS








                                        Risk of False Rejection



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





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

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

-------
                                                    Appendix C
                                                    Revision No. 3
                                                    Date: April 29, 1988
                                                    Page 1 of 5
                  APPENDIX C

ETU CONFIRMATION BY LOW-RESOLUTION GC-MS

-------
                 ETU CONFIRMATION BY LOW-RESOLUTION GC-MS
1.   SCOPE

    1.1
         Confirmation  by  gas  chromatography-mass  spectrometry (GC-MS)  will
         be conducted  on  all  samples  exhibiting  a peak with intensity
         greater than  or  equal  to half the minimum reporting level (MRL)
         occurring at  a retention time corresponding to ethylene thiourea
         (ETU)  under both primary and secondary  NPS Method 6 conditions.

    1.2  If the ETU concentration is  sufficient,  this confirmation will  be
         carried out by low-resolution GC-MS  according to the procedure
         outlined.

    1.3  The detection limit  for ETU  by low-resolution GC-MS is 0.5 pg/ml in
         the analyzed  extract,  corresponding  to  a detection limit of 5 ftg/L
         in the original  water  sample.  An additional 10:1 concentration  of
         the extract is required to achieve this  detection limit.

2.  SUMMARY

    2.1  ETU confirmation is  performed by low-resolution GC-MS, and results
         are compared  to  analysis of  a standared  containing ETU at a con-
         centration near  that expected in the sample extract.

    2.2  If required,  the sample and  standard are further concentrated prior
         to analysis by nitrogen blowdown.

    2.3  Results of the analysis are  reported as  the presence or absence  of
         the analyte.

3.  APPARATUS

    3.1  Nitrogen Evaporator  — Organomation  N-Evap Analytical Evaporator
         Model  111 or  equivalent, capable of  maintaining concentrator tubes
         at 35-40°C while applying a  nitrogen stream over the sample extract

    3.2  Low-resolution GC-MS analytical system  -- recommended instrumenta-
         tion and conditions  for low-resolution  GC-MS confirmation of ETU
         are:
                Instrumentation:

                  MS conditions:


                MID description:



                         Column:
                                   Finnigan 4500 mass spectrometer with a
                                   Finnigan 9610 gas chromatograph
                                   Multiple ion detection (MID),  ionizing
                                   energy 70 eV, electron multiplier voltage
                                   2400 V,  preamp 10-7 volts/amp
                                   Total  scan time 0.6 sec;  integration time
                                   0.2 msec; ETU masses monitored 72,  73,
                                   104,  and 102 (molecular ion);  internal
                                   standard mass monitored 116
                                   5  m long x 0.25 mm I.D. DB-Wax bonded
                                   fused  silica capillary column, 0.25 /*m
                                   film thickness
                                       102

-------
                        Carrier:   He @ 80 cm/sec linear flow
                  Injector temp:   280°C
                      Injection:   2.0 nL splitless
               Oven temperature:   180°C isothermal for 0.5 min; programmed
                                   from 180°C to 250°C at 25°C/min; iso-
                                   thermal at 250°C for 3 min

4.  PROCEDURE

    4.1  Sample Prepartion

         4.1.1  If GC-NPD analyses indicate that the concentration of ETU in
                the sample is greater than 50 pg/L (representing an extract
                concentration of 0.50 pg/mL), the sample extract should be
                analyzed by low resolution GC-MS without any further sample
                concentration using the conditions specified in Section 3.2.


         4.1.2  If GC-NPD analyses indicate that the concentration of ETU in
                the sample is between 5 and 50 /tg/L (representing an extract
                concentration of between 0.05 and 0.50 ng/ml),  concentrate
                the extract by a factor of 10 under a stream of nitrogen
                while heating at 35-40°C.  Analyze the resulting concentrate
                by GC-MS using the conditions specified in Section 3.2.

         4.1.3  If GC-NPD analyses indicate that the concentration of ETU in
                the sample is less than 5 pg/L, the extract should be
                shipped to the EPA referee laboratory for high resolution
                GC-MS analysis as described in Section 5.9 of the Quality
                Assurance Project Plan.

    4.2  Calibration

         4.2.1  Prepare a standard containing approximately the concentra-
                tion of ETU expected in the sample extract after primary or
                secondary GC analysis, whichever determined concentration is
                lower.

         4.2.2  If additional sample concentration is required for GC-MS
                analysis (Section 4.1), concentrate the standard as des-
                cribed in Section 4.1.2.

         4.2.3  Analyze the standard by GC-MS, using the conditions speci-
                fied in Section 3.2, and compare the results to those
                obtained for the sample.  Representative selective ion
                profiles for a 0.5 /tg/mL standard are given in Figure 1.

    4.3  Identification and Reporting

         4.3.1  ETU identification in the sample is to made on the basis of
                mass spectra and retention time after comparison to the GC-
                MS results obtained from analysis of the standard.
                                            103

-------
4.3.2  If the sample exhibits  a peak at the appropriate retention
       time and of similar area (relative to the internal standard)
       to the ETU standard for the molecular ion (m/z 102) and two
       of the confimation ions (m/z 72,73 or 104) monitored, the
       presence of ETU is confirmed.

4.3.3  Report the results of the GC-MS analysis as the presence or
       absence of ETU.
                               104

-------
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                                                                         Is* 
-------
                                           Appendix D
                                           Revision No. 3
                                           Date: April 29, 1988
                                           Page 1 of 5
           APPENDIX D

STANDARD OPERATING PROCEDURE
  FOR USE OF ADMIRAL FREEZERS

-------
Page 1 of 4
                            Analytical  and Structural Chemistry Center
                            SOP ASCC-20-002-01
                            September 19,  1986
                                  Kev Words:   Refrigeration
                                              Storage
Title:
                 STANDARD OPERATING PROCEDURE
                  FOR USE  OF  ADMIRAL FREEZERS
Originated by:
        Approved by:
                                       s<^
                      Charles  V.  Sueper
                 Date:
                                                  Date:
                      Johnl R.  Nixon,  Manager
                      Aira/ytical  and  Structural  Chemistry Center
        Approved by:  //
                                                   Date:
  Approved by: l
                      )uane E.  Hilmas, "Manager
                      Chemistry and Biomedical Sciences Department
                                                        Date:
                      Ramona A.  Mayer,
                      Quality Assurance Unit
        Approved by:
&*
                                    L
                      AnnJ I.  BarTcer,  Director
                      Biological  and  Chemical  Sciences
                                                  Date:
Circulation List:

      QAU

      QCWG

Record of Reviews:

      Date:         Reviewed  by:
                                     Date
                 Reviewed by:
     &PPROVED
                                            107

-------
Page 2 of 4                       Analytical  and Structural Chemistry Center
                                  SOP ASCC-20-002-01
                                  September 19,  1986


                       STANDARD OPERATING PROCEDURE
                        FOR USE OF ADMIRAL FREEZERS


1.  EQUIPMENT DESCRIPTION

    1.1.  Admiral  Freezer or equivalent.

    1.2.  Manufactured by Rockwell International's Admiral Group.


2.  OPERATING PROCEDURE

    2.1.  Plug the unit into an appropriate electrical outlet.

    2.2.  Place a thermometer on a shelf near the center of the unit.

    2.3.  Turn the temperature  control  to the "C"  setting  and  let  the  unit
          run for 2 hours.

    2.4.  Turn the  temperature  control   to  the  "D"  setting for  operation
          below 12 C.

          2.4.1.   The  freezer may  be  operated in the range  of  -20  C to  0  C
                  with the  temperature being  selected using the temperature
                  control gauge.  A setting of  "A"  gives  a temperature  near
                  0 C  while a setting of "E"  gives a temperature near -20 C.

    2.5.  Allow  24  hours  for  the  temperature  to  stabilize.     If   the
          temperature   is  not  in  the  desired  range,  reset  the  gauges  as
          stated   in Section 2.4  and  allow temperature to  stabilize before
          rechecking.

    2.6.  Temperatures should be recorded on  a  log  sheet,  to be kept on  the
          door of the unit,  by  the  individuals using  the freezer.   [See
          attachment.]

3.  MAINTENANCE AND CLEANING

    3.1.  The unit  should be cleaned  as needed,  using  warm,   soapy water.
          Take care to prevent  contamination  from hazardous materials which
          may be  present  (i.e.,  wear rubber gloves).

    3.2.  Defrosting  the  unit  should  be done  when  frost  has  built up  to
          approximately 1/4" thickness in the  freezer compartment.

          3.2.1.   Remove   any  temperature  sensitive  contents   to   another
                  freezer/refrigerator.


APPROVED                                108

-------
Page 3 of 4                        Analytical and  Structural  Chemistry Center
                                  SOP  ASCC-20-002-01
                                  September  19, 1986

                       STANDARD OPERATING PROCEDURE
                        FOR USE  OF ADMIRAL FREEZERS

          3.2.2.   Turn  off the power to the  unit.
          3.2.3.   Open  the door  and allow ambient air  to melt  the  frost.
          3.2.4.   Dry the  moisture from the  unit.
          3.2.5.   Turn  the unit's  power back on.
          3.2.6.   Check the temperature after a stabilization  period.
          3.2.7.   Replace  contents when temperature is  satisfactory.
    3.3.   Maintenance  should be  performed only by a qualified  refrigeration
          specialist.
    APPROVED
             ^^
                                        109

-------
Page 4 of 4
                Analytical and Structural Chemistry Center
                SOP ASCC-20-002-01
                September 19, 1986
                       STANDARD OPERATING PROCEDURE
                        FOR USE OF ADMIRAL  FREEZERS
                                ATTACHMENT

                          Freezer Temperature  Log
Location of Freezer:
  Temperature
Date
Initials
Temperature
Date
                                         110
Initials

-------
                                           Appendix E
                                           Revision No. 3
                                           Date: April 29, 1988
                                           Page 1 of 4
            APPENDIX E

  STANDARD OPERATING PROCEDURE
FOR USE OF HOTPOINT REFRIGERATORS

-------
Page 1 of 3                       Analytical and Structural Chemistry Center
                                  SOP ASCC-20-003-01
                                  September 22, 1986


                                  Kev Words:  Refrigeration
                                              Storage
Title:                  STANDARD OPERATING  PROCEDURE
                     FOR USE OF HOTPOINT REFRIGERATORS
      Originated by:       ^>ji   ~/...~^ _  Date:
                      Charles V.  Sueper '
        Approved by:    SW\*~l/f  ~ A^t2u>^	  Date:
                      John R. Nixon,  Manager
                      Analytical  and  Structural Chemistry Center


        Approved by:   /S\ ,!/,i*~~ J' rtL^-1^,^ „  , ^     Date:   £/ /£*r/J''
                      Duane E. Hilmas,  Manager                    '
                      Chemistry and  Biomedical Sciences Department

                      _^-               *-< ,
                    s^\/—          / / . ~\
        Approved by:  ^".--^^t-.^-   /'  '?_'<'•«	  Date:  	•'_
        Approved by:    7(^7^^f^\   ^^     Date:   ////7/&
                      Anna UT Barker,  Director                  // /
                      Biological  and Chemical  Sciences


Circulation List:
      QAU
      QCWG

Record of Reviews:

      Date:        Reviewed by:             Date         Reviewed by:
                                        112

-------
Page 2 of 3                       Analytical and  Structural  Chemistry Center
                                  SOP ASCC-20-003-01
                                  September 22,  1986


                        STANDARD OPERATING PROCEDURE
                     FOR USE OF HOTPOINT  REFRIGERATORS
 1.  EQUIPMENT DESCRIPTION

    1.1.  Hotpoint Refrigerator.

    1.2.  Manufactured by General Electric Company

 2.  OPERATING PROCEDURE

    2.1.  Plug the unit into an appropriate electrical outlet.

    2.2.  Place a thermometer on a shelf near the center of the unit.

    2.3.  Set  the dual  temperature  gauges  to  "5"  and  "C"  to  achieve  a
          temperature near the middle of the 0 C to 10 C operating range.

          2.3.1.  The  refrigerator  may  be  set  to  the  wanner  end of  the
                  range, ca. 10 C, or  the  colder range,  ca.  0 C, by setting
                  the gauges to "1"  and "A", or "10" and "E", respectively.

          2.3.2.  An intermediate temperature may be achieved by varying the
                  settings on the gauges to give the desired temperature.

    2.4.  Allow  24  hours  for  the  temperature  to  stabilize.    If  the
          temperature  is  not  in the  desired  range,  reset  the  gauges  as
          stated  in  Section 2.3  and  allow temperature  to stabilize before
          rechecking.

    2.5.  Temperatures should be recorded  on  a  log  sheet,  to be kept on the
          door of the unit,  by the individuals using the refrigerator.   [See
          attachment.]

3.  MAINTENANCE AND CLEANING

    3.1.  The unit  should be  cleaned  as  needed,  using  warm,  soapy water.
          Take care  to  prevent  contamination from hazardous  materials  which
          may be present (i.e., wear rubber gloves).

    3.2.  Maintenance should be performed  only  by a qualified refrigeration
          specialist.

4.  SAFETY PRECAUSTIONS

    4.1.  If the unit is used for storage of hazardous/toxic materials, this
          information should be clearly posted.

                                       113

-------
                                                            (<••'«•     '1
                                                            •** t  4 ^o.i ,i,
                                                                             ., 1-
Page 3 of 3
Analytical and Structural Chemistry  Center
SOP ASCC-20-003-01
September 22, 1986
                       STANDARD  OPERATING PROCEDURE
                     FOR USE OF HOTPOINT REFRIGERATORS
                                 ATTACHMENT

                       Refrigerator Temperature Log
Location of Refrigerator:

Temperature
















Date
















Initials
















Temperature
















Date














•

Initials
















                                       114

-------
                                                     Appendix F
                                                     Revision No 3
                                                     Date: April 29, 1988
                                                     Page 1 of 5
                      APPENDIX F

      STANDARD OPERATING PROCEDURE FOR WEIGHT
DETERMINATIONS USING AN ELECTRONIC ANALYTICAL BALANCE

-------
                                                                - <-    Date:
                      Ramona A. Mayer, Manager
                      Quality Assurance Unit
        Approved by:          ^^      ^      ^~-  Date:
                     ATfha'D. Barker, Senior V^ce^President      '   '
                     Biological and Chemical /sciences


Circulation  List:                                              APPROVED
      QAU
      QCWG
Record of Reviews;
      D?te:         Reviewed by:            Date         Reviewed by:
                                     116

-------
Page 2 of 4                       Analytical  and Structural Chemistry Center
                                  SOP ASCC-20-010-02
                                  (Revised)
                                  September  11,  1987


                       STANDARD OPERATING PROCEDURE
                      FOR WEIGHT DETERMINATIONS  USING
                     AN  ELECTRONIC ANALYTICAL BALANCE
1.  SCOPE

    1.1.  This procedure  is  applicable for  accurate weighing of  solid  and
          liquid  materials   on   self  calibrating   electronic   analytical
          balances.

    1.2.  This procedure may not be applicable  for  volatile liquids  weighed
          in open containers  or for hot and  cold materials.

2.  SUMMARY

    2.1.  Milligram  to gram  weight determinations  are  accurately  performed
          on a properly maintained  electronic analytical balance.

3.  APPARATUS

    3.1.  Electronic analytical  balance (Mettler Models  SAE50,  AE100,  AE1SO,
          AE200,  AE240,  or equivalent).

4.  PROCEDURE

    4.1.  If the balance  is  dual range,  select the  range  desired  following
          instructions in  the manual.

    4.2.  Ensure  that  the analytical  balance  calibration  check  has  been
          updated as discussed in Section  5.2.

    4.3.  Select   appropriate  integration  time  (compensates  for  external
          vibrations)  and  stability detection  (ensures only  stable  values
          are shown) as  instructed  in  the  manual.

    4.4.  Ensure  that the balance pan is clean  and  empty;  also,  ensure  that
          all  weight adjustment controls are  set to  zero.

    4.3.  With  all   sliding   doors on the   instrument  closed,   zero   the
          instrument.

    4.4.  Place the  object to  be weighed on  the pan and  close all  sliding
          doors.   Allow the balance to achieve  equilibrium.



                                                         APPROVED

                                        117

-------
Page 3 of 4                       Analytical  and Structural Chemistry Center
                                  SOP ASCC-20-010-02
                                  (Revised)
                                  September  11,  1987


                       STANDARD OPERATING PROCEDURE
                      FOR WEIGHT DETERMINATIONS  USING
                     AN ELECTRONIC ANALYTICAL BALANCE
    4.5.   Record the weight determined  or  tare the weight of  the  object  on
          the balance  as  appropriate.   Careful  addition of material  to  tared
          containers is permitted without  first  removing  the container from
          the balance  pan.

    4.6.   For a tared  container with added  contents,  allow the balance  to
          achieve  equilibrium  and record the  weight determined.

    4.7.   After each weight  determination  is  completed,  remove the object
          which has  been  weighed; ensure that the balance  pan and housing
          are clean and  dry,  then re-zero the instrument with  all  sliding
          doors closed.

5.   QUALITY  CONTROL

    5.1.   Annual  calibration  and  service  is  performed  by  a  manufacturer
          service  representative or  by  the Battelle  Instrument  Laboratory.
          The dates  of service  are  recorded  in the Balance  Maintenance and
          Calibration  Log  Book   and  a  report  is  submitted  to the  Quality
          Assurance  Office.

    5.2.   Calibration  Check and  Cleaning

          5.2.1.   Schedule

                  5.2.1.1.   The   calibration   of   each  balance  should   be
                            checked  prior  to  using the balance.   Should  a
                            particular   study  require   a   more   stringent
                            calibration  schedule,  such  information will  be
                            contained in  the  pertinent  study  specific SOP  or
                            QA plan.

          5.2.2.   Since  the balance is  self-calibrating,  only  a  small  brush
                  and   an   absorbent    material   (kleenex,   kimwipe,   or
                  equivalent)  is needed.

          5.2.3.   Method

                  5.2.3.1.   Ensure  that  the  balance  pan and  housing are
                            clean and dry.  Brush any  loose material  off the
                            pan  and  out  of  the  housing  with a dusting brush.
                            Wipe up any liquids with an absorbent material.


                                     118                    APPROVED

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                                                               f •"•*--
                                                               L- ' -  * ' ' ;   -
                                                                  •   t    '
                                                                     •'• -L  ' /

Page 4 of 4                       Analytical and Structural Chemistry Center
                                  SOP ASCC-20-010-02
                                  (Revised)
                                  September 11, 1987


                        STANDARD  OPERATING  PROCEDURE
                      FOR WEIGHT DETERMINATIONS USING
                     AN ELECTRONIC  ANALYTICAL  BALANCE
                            The balance  pan  may be removed  and  cleaned,  as
                            necessary, with an appropriate cleaning solution
                            (e.g., Alconox in water).

                  5.2.3.2.   Check the  balance level  indicator  to  determine
                            that the  balance  is level.   If necessary,  level
                            the balance using the  leveling feet.

                  5.2.3.3.   Calibrate the balance with  internal  calibration
                            weights  as described in  the  appropriate manual.

                  5.2.3.4.   Record the date and your  initials in the Balance
                            Maintenance and Calibration  Log Book.

6.  TROUBLE SHOOTING

    Refer to the appropriate balance manual  for troubleshooting.
                                                          APPROVED

                                    119

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                                             Appendix G
                                             Revision No. 3
                                             Date: April 29, 1986
                                             Page 1 of 4
             APPENDIX G

   STANDARD OPERATING  PROCEDURE
FOR THE USE OF TOP LOADING BALANCES

-------
Page 1 of 3                       Analytical  and Structural  Chemistry
                                  SOP ASCC 20-028-01
                                  June 22, 1987
                                Kev  Words:
Title:                 STANDARD OPERATING PROCEDURE
                    FOR THE USE  OF  TOP LOADING BALANCES
-^  ^
      Originated by:      j -f^    &T _  Date:
                      Su/arTS.  Hetzel                                (
        Approved by:      \^^ fJu^            Date:   £/ZQ/3O
                      Johyft.  Nixon,  Manager                      '
                      Chemistry  and  Spectroscopy Section
        Approved by:     ^sj*.*^**-^ y~ >. . .  -         Date:
                      Ronald  L.  Joine-r',  Vice  President
                      Chemistry  and  Biomedical  Sciences  Department
        Approved by:       t^^f^ ^ J//L^C        Date:
                      Raniona  A.  Mayer,  Manager7
                      Quality Assurance Unit
        Approved by:                '^i ^ —           Date:
                                rker,  Senior Vice President
                      Biogical  and  Chemical  Sciences
Circulation List:

      QAU

      QCWG

Record of Reviews:

      Date:        Reviewed  by:             Date          Reviewed  by:
                                                                    APPROVED

                                    121

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 Page  2  of  3                        Analytical and Structural  Chemistry  Center
                                   SOP ASCC 20-028-01
                                   June  22, 1987


                        STANDARD OPERATING PROCEDURE
                     FOR THE USE OF TOP  LOADING BALANCES


 1.    EQUIPMENT DESCRIPTION

      1.1.  Equipment type - top loading balance

      1.2.  Manufacturer  and  Model   Number  -  Mettler  P1200N,   PC4400,  or
            equivalent

 2.    SUMMARY

      2.1.  The top  loading  balance  can be used to  weigh materials up to a
            total  of 1099 +/-  0-03  grams.   The balance  calibration  check
            schedule is defined by study-specific requirements.

 3.    OPERATING PROCEDURE

      3.1.  Check  to make sure that  the balance is  level,  using the bubble
            level  located on  the  front.    Adjust  the   legs  to  level  the'
            balance, if necessary.

      3.2.  Make sure that the balance  pan is clean.

      3.3.  Look in  the  balance log  to ensure that  the  balance calibration
            check  has  been  performed.    If  not,  do  so  following  the
            directions in section 4.

      3.4.  Place  a  weighing  vessel  on the balance  pan  and tare the vessel
            with the tare knob and/or weight control knobs-.  Record the tare
            weight, if the balance does not have tare capability.

      3.5.  Place  the  material  to be weighed  in the tared  vessel.  Adjust
            the weight  control  knobs until one  of the  moving  weight  lines
            aligns  with  the   stationary  weight  marker.    If  this  is  an
            electronic  balance,   wait  for   the   readout   to   stabilize.
            Determine the  weight  of  the material directly  from  the readout
            or by difference.

      3.6.   Clean the balance pan when finished.

4.    CALIBRATION

      4.1.   Annual   calibration  and   service   is  performed  by  a  service
            representative.    The  dates  of  service  are  recorded in  the
            Balance Maintenance and Calibration Log Book.
                                                                   APPROVES
                                       122

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Page 3 of 3                        Analytical and Structural Chemistry Center
                                  SOP ASCC 20-028-01
                                  June 22, 1987


                       STANDARD OPERATING PROCEDURE
                    FOR THE USE OF TOP LOADING BALANCES


      4.2.   Calibration checks  are  performed  as  required for  a  particular
            project.    Calibration  schedules  should  be  contained  in  the
            pertinent  study-specific  SOP.

            4.2.1.  Set the tare knob  to  "0"  and  zero the balance with  the
                   zero adjust  knob.   Check  the  calibration with  standard
                   weights  which bracket  the  weight range of the  materials
                   to  be measured.  The  range  must  be within  the capacity of
                   the balance.   If any measured mass  is  different from  the
                   known mass  by more  than 2.0 percent where


                   Percent  Difference  »   (known mass  - mass measured)   X  100
                                                  known mass


                   notify  the  manufacturer and  stop  using  the balance  until
                   the problem is  corrected.

            4.2.2.  Record  the  weights determined  for  the calibrated  test
                   weights  in  the  Balance  Maintenance and  Calibration Log Book.
                                      123

-------
                                                 Appendix H
                                                 Revision No. 3
                                                 Date: April 29, 1988
                                                 Page 1 of 6
               APPENDIX H

DATA ENTRY FORMATS FOR ASCII REPORTS

-------
               PCRAT FOR NATICtftL PESTICIDE SURVEY (NFS) DATA
T.TW   OCTI3MMS     '»•
 1       1-6       FldjH
         9-14      S_Tenp
        17-24      Date_Sam
        27-34      Date_Shp
        37-44      Datejtec
        47-54      Time_Sam
        57-64      Time_Ice
           [TOR METHODS 5 AND 9 ONLY]
        68-69      F«

 2       1-6       enter pH OF FIELD SAMPLE
         9-14      enter SIMILIZED TEMPERAIURE OF WAIER
        17-24      enter EPJE SAMPLED
        27-34      enter EME SHIPPED
        37-44      enter EPJE REEETVED
        47-54      enter TIME SAMPLED
        57-64      enter TIME ICED
           [FCR METHODS 5 AND 9 CULY]
        67-70      enter pH OF LAB SAMPLE

 3      BLANK

 4       1-17      Receipt Condition

 5       1-80      enter COOITTON OF SAMPLE UPCN RZEZIPT AT LABORATORY

 6      BLANK

 7       1-6       Sanp t
        16-18      Lab
        21-25      Set f
        28-35      Date_Spk
        38-45      Date.Ext
        48-55      Date. Ana
        58-63      Column
                   enter SAMPLE H3ENTIFICATICN NUMBER
        16-18      enter LAB ABBREVIATION
        21-25      enter SET NUMBER
        28-35      enter DATE SPIKED
        38-45      enter DATE EXTRACTED
        48-55      enter DATE ANALYZED
        58-63      enter AlttLYSIS COLUMM

        BLANK
                                      125

-------
           POBMftT FOR rWnOWL PFSTICIHR SURVEY (NFS)  IMA (cent.)
T.TMF   COLIMB     nF.qrRTPTI(3J

 10      1-4       Type
         8-13      SpUcer
        16-22      Detract
        25-31      Analyst
        34-40      Sam_Vbl
        43-49      Ext.Vol
        52-60      Int. Std.
        65-70      % Surr

 11      1-5       enter SAMPLE TYPE
         8-13      enter SFIKER'S INITIALS
        16-22      enter EXTRACTOR'S INITIALS
        25-31      enter ANALYST'S INITIALS
        34-40      enter VOLUME OF SAMPLE
        43-49      enter VOLUME OF EXTRACT
        52-62      enter INTETOP^L STAICftRD (as % of calibration standard)
        65-70      enter PERCENT RECOVERY OF SURROGATE

 12     BLANK

 13      1-8       Cements

 14      1-80      enter ANY PEKmETT Cd-METTTS ON SAMPLE AND ANALYSIS

 15     BLANK

 16      1-7       Analyte
        29-33      Cone.
        39-45      Analyte
        67-71      Cone.

         1-25      enter ANALYTE'S NAME
        28-34      anter CONCENTRATION OR PERCENT RECOVERY
        39-63      enter ANALYTE'S NAME
        66-72      enter CCTONERATICN CR PERCENT RECOVERY
                                  126

-------
             FCR twnaM, PJXL'K• 11IK SURVEY (NFS) QGTRUMENT CCNUCL
T.TMF   QOLLM35
 1       1-3      Lab
         6-11     Mettol
        14-21     Date_Ana
        24-30     Analyst
        35-37     S/N
        42-44     PSF
        49-51     PGF
        55-58     Res.

 2      BLANK

3-?      1-3      enter LAB ABBREVI&TICU
         6-11     enter MEIHCD NUMBER
        14-21     enter EPJE AM^LYZED
        24-30     enter ATP^LYST'S INITIALS
        33-37     enter SIO^L TO NOISE HATIO
        40-44     enter PEAK SYMMETRY FACTOR
        47-51     enter PEAK GEOMETRY FACTOR
        54-58     enter RESOLOTICN
                                   127

-------
                         NOTES ON NFS DA3A FCE&KTS


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

      A missing date should be entered 01/01/60

2. "me format for any time is hh:mn in military time

      A missing time should tie entered 00:00

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

4. The number of decimal places should be as follows:
      Concentration
      Percent Recovery       1
      Internal Standard     ^ '/
      Instrument Controls    2
      PH                     1
      Temperatures           0
      Volumes                0

5.  The codes for Column are as follows:

      Primary          PRIM
      Confirmatory     CCNF
      Tnird            GCMS

6.  The codes for Lab are as follows:

      TSD                                        TSD
      OPP                                        OPP
      WE3L                                       WER
      Radian                                     RAD
      Battelle                                   BCD
      James M. MontgomerY                        JI-M
      Alliance                                   ALL
                    Sciences and Engineering     ESE
7. "Die codes for lype are as follows:

      Field Sample                 SAMP
      Shipping Blank               SBLK
      Method Blank                 MBLK
      Lab Control Standard         LCS@
      Lab Spike Sample             LSS@#
      Day 0 Time Storage           DTS@
      Time Storage for D-xract     HTE§
      Time Storage for Cample  ,    HTS@
      ?evib''>M*AACe. c»;o.lwe.Ti «« St-^»K   P5V1-
   where (§ is the mix letter (A,B or C)
    and # is the spiking level (1,2 or 3)
                                    128

-------
                      NOUS CM NFS EMA FORTIES (cant.)
 8. itere should be at least one blank line between samples in the NFS data
    file.

 9. Hie codes for Concentrations and Percent Recoveries are as follows:

       Not Analyzed
       Not Detected « 1/2 Reporting Limit)                    -999
       Saturated                                               -777
       Other                                                   -333
       Below Reporting Limit, but above 1/2 Reporting Limit    -ill

       Above Reporting Limit, but not Quantified                 888

10. If a reported value is greater than (» some number in the NFS instrumer
    control data, then use a minus sign (-) instead of  >
                                129

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                                              Appendix i
                                              Revision No. 3
                                              Date: April 29, 1988
                                              Page 1 ol 19
                APPENDIX I

STANDARD OPERATING PROCEDURE FOR QUALITY
 ASSURANCE UNIT PERFORMANCE AND SYSTEM
          AUDITS FOR NPS SURVEY

-------
 Paae  1 of 7                       Analytical and  Structural Chemistry Center
                                  SOP ASCC 50-083-01
                                  April 29, 1988

                                                                       >*7
                                  Kev Words:                              "
Title:                  STANDARD  OPERATING  PROCEDURE
                         FOR  QUALITY ASSURANCE UNIT
                       PERFORMANCE AND SYSTEM AUDITS
                               FOR NPS SURVEY
      Originated by:  Jv^ ^ f- C*>s.>j  2* _  Date:
                      Tina M. Engel
        Approved by:   ^  £. cs*-  _  Date:
                      Jutfith E.  Gebhart,  Manager
                      Analytical  Chemistry Section  '
                         s*-.

        Approved by:   r^-~-'    *^ /-<- - _  Date:
                      Ronald L.  Joirter,  Vice President
                      Chemistry  and Biomedical  Sciences Department


        Approved by:   /^v-._^^-r^_x   •' / J^t^f^A^    Date:     ^
                     n^amona A.  Mayer, Manag.er
                      Quality Assurance Unit
        Approved by: /  n>U t/l /ArUX/^^A^C-^        Date:
                       \nna D." Barker,  Senior Vice President
                      Biological  and Chemical  Sciences


Circulation List:

      QAU                  .                                APPROVED
      QCWG
Record of Reviews:
       ate:        Reviewed by:             Date         Reviewed by:
                                      131

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Page 2 of 7                       Analytical  and Structural Chemistry Center
                                  SOP ASCC 50-083-01
                                  April  29,  1988
                                                                   ->

                                                                 w-'>  \.
                       STANDARD OPERATING PROCEDURE                   '~.f >
                         FOR QUALITY ASSURANCE UNIT
                       PERFORMANCE AND SYSTEM AUDITS
                              FOR NPS SURVEY
1.  SUPPORT AREA

    1.1.  Quality Assurance Unit

2.  SUBJECT

    2.1.  Performance and System Audits

3.  DESIGNATED CONTACT

    3.1.  Manager,  Quality Assurance  Unit

4.  BACKGROUND

    4.1.  Requirements

          4.1.1.   A   number   of  regulatory   agencies,   including   the
                  Environmental  Protection Agency  (EPA),  require a  Quality
                  Assurance  (QA)  Program  to  assure  the  reliability  and
                  quality of monitoring and measurement  data.   EPA specifies
                  that an  independent Quality  Assurance Unit  (QAU)  conduct
                  audits   to  monitor  the  capability  and performance  of  a
                  regulated activity.   The audits are of  three  basic types:
                  (1)  System  Audits,  that are  overall   evaluations  of  the
                  effectiveness   of   an  activity's   QA   system  in   meeting
                  intended  objectives,  (2)  Performance  Audits,  that  are
                  determinations of  the  accuracy of  the total  measurement
                  system  or a component part  thereof,  and  (3)  Data  Audits,
                  that are  determinations of  the  quality  of  the  results
                  submitted to EPA.

    4.2.  Purpose

          4.2.1.   This Standard Operating  Procedure  (SOP)  describes  the
                  procedures that will be  followed by the QAU  in  conducting
                  Performance,   System,   and  Data   Audits   on   the  above
                  referenced  program.   This  SOP  describes the  EPA  audit
                  requirements for this  program along with  current  Battelle
                  QA policy enacted to meet the needs  of clients.
                                      132

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Page 3 of 7                       Analytical and Structural Chemistry Center
                                  SOP ASCC 50-083-01
                                  April 29, 1988

                                                                  u* - •
                       STANDARD  OPERATING  PROCEDURE
                         FOR  QUALITY ASSURANCE  UNIT
                       PERFORMANCE AND SYSTEM AUDITS
                               FOR NPS  SURVEY
5.  PERSONNEL REQUIREMENTS

    5.1.  QA  Performance,  System,  and  Data  Audits  will  be  performed  by
          trained QA Specialists.   As the need  arises,  technical  personnel
          will  also  participate  in  audits.     In  all   instances,  the  QA
          Specialists will  organize, direct,  and lead the audits.

    5.2.  QA Specialists

          5.2.1.   QA  Specialists have, as a minimum, a college degree in one
                  of  the sciences  and/or a minimum of five years' experience
                  in  the field or laboratory and/or in  work associated  with
                  QA  operations.   QA Specialists are assigned to the QAU ana
                  are supervised by the Manager  of  the  QAU.   QA Specialists
                  report administratively to  the Manager of Support Services
                  and directly to  the Senior Vice  President for Biological
                  and Chemical  Sciences on technical and quality issues.  QA
                  Specialists operate  independently  of  organizational  units
                  and personnel engaged  in conducting the  activities to  be
                  audited.

    5.3.  Technical  Personnel

          5.3.1.   In   the  event   that  specialized  technical   expertise  is
                  needed to  adequately assess   the  quality  of  an  activity,
                  technical  personnel  may  be   asked   to  participate  in
                  Performance,  System, or  Data  Audits.   Technical  personnel
                  may assist  the QA Specialists  in any or all aspects of the
                  audit  process as needed.

6.  PROCEDURE

    6.1.  Audit  Schedule -- Specific  audit dates  will be established by QAU
          personnel  and  project technical  team members.   System and Perfor-
          mance  Audits can  be conducted separately or simultaneously.

          6.1.1.   A  System Audit will  be  conducted  shortly after laboratory
                  operations   are  functional   and   subsequently  half   way
                  through the contract or  more  frequently at the discretion
                  of  management.
                                       133                     APPROVED

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Page 4 of 7                       Analytical  and Structural  Chemistry Center
                                  SOP ASCC 50-083-01
                                  April  29,  1988


                       STANDARD OPERATING PROCEDURE
                        FOR QUALITY ASSURANCE UNIT                      "'*•
                       PERFORMANCE AND SYSTEM AUDITS
                              FOR NPS SURVEY


          6.1.2.   Performance  Audits  will be  conducted  quarterly or  more
                  frequently at  the discretion  of  management once  systems
                  are operational  and generating data.

          6.1.3.   Data Audits will  be  conducted each  time a  data  set  is
                  generated for  submission to EPA.

    6.2.   System  and  Performance  Audits  --  System Audits will evaluate  all
          components  of   the  sample  tracking,  analytical,  and  reporting
          activities  to  determine  the  system's overall  effectiveness  in
          addressing control measures.   Implementation  and  effectiveness  of
          the requirements contained in  the documents  listed in  Section  VI.C
          of this SOP will  be  examined.   The  System Audit will provide  an,
          objective  means  of  ensuring  that:  the necessary procedures  for
          each element of the project activity are  established;  records  are
          being   adequately  generated  and  maintained   to   assure   proper
          documentation,  retrievability,  and traceability  of  information;
          the established  controls  are   effective  in  producing  quality,
          results;   and   formal   QA/QC  measures  are   being  used  by   all
          applicable components  of the project.   Performance Audits will  be
          conducted  during laboratory activities.   Performance  Audits will
          verify  that actual practice  is in  accordance with  preestablished
          procedures and other guidelines.

          6.2.1.   The  Audit Team  will  be composed  of  a  combination  of  QA
                  Specialists, technical  personnel,  and  other  individuals  as
                  appropriate.   The  Audit Team  will  range  from upwards  of
                  one  individual.    The  QA Specialist  will direct  the  audit
                  and  be the Audit Team  Leader.

          6.2.2.   The  Audit  Team   will   review  the   following  applicable
                  documents  in   preparation  for  the  audit:   the  QA  project
                  plan, project  contractual documents,  SOPs  (included  in  the
                  QA project plan),  NPS  Method 6  (included in  the QA  project
                  plan), previously  generated data and  reports,  and Battelle
                  general  policies.

          6.2.3.   The  Critical  Phase Inspection Check Sheet  (Figure  1) will
                  be used  for System and  Performance Audits.   The Audit Team
                  will  use  the  Critical  Phase  Inspection  Check  Sheet  to
                  guide  the audit and  document  objective evidence reviewed
                  during the process.  Additional issues can be addressed  at
                  the  discretion of  the  QA Specialist  or Audit Team members.

                                       134                       APPROVED

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Page 5 of 7                       Analytical  and Structural  Chemistry Center
                                  SOP ASCC 50-083-01
                                  April  29,  1988

                                                               >•» »
                       STANDARD OPERATING PROCEDURE            V/'Mr/ i.
                        FOR QUALITY ASSURANCE UNIT                '  '  'it-,:  ;
                       PERFORMANCE AND SYSTEM AUDITS
                              FOR NPS SURVEY


                  The  Audit   Team  will   have  the   latitude  to   pursue   a
                  questionable condition or  practice even if the  discovered
                  condition was  not specified on the original check sheet.

          6.2.4.   The results  of the evaluation  of each  check sheet question
                  will   be   documented.      Documents,   files,   personnel
                  qualifications,   and   other  records   reviewed  and
                  observations made during the  course  of the  audit  will  be
                  listed  or attached to  the check sheets.

          6.2.5.   Any  significant   problems   noted  that  could  affect the
                  integrity  of  an  activity will  immediately be brought  to
                  the attention  of  the  person performing the  operation and
                  the Project  Manager.  A verbal report will  be followed  by
                  issuance  of  an Audit Comment  Sheet  (Figure 2) at  the end
                  of the audit.   At  the  end of each  audit day,  the  Audit
                  Team will  verbally brief  the  Project Manager  on  audit
                  progress,  problems,  and subsequent   plans  to  facilitate
                  prevention  of  recurrence  of  any  problems  that  may have
                  been noted.

          6.2.6.   At the end  of  the audit,  the Audit Team  will  meet   in
                  private to  review the  audit results;  review and  document
                  all   significant  problems  on  Audit  Comment Sheet; and
                  review the check  sheets  for completeness.

          6.2.7.   After the Audit  Team's private meeting,   the  Audit Team
                  Leader will  conduct  a post  audit briefing  with appropriate
                  personnel and  management of the activity being audited to:
                  present positive  aspects of the activity  being audited  if
                  applicable  and  any  other  positive  comments  that  may   be
                  appropriate  to  the  situation; discuss  any significant
                  problems  identified on  the Audit  Comment Sheet or  other
                  concerns  found during  the   audit;   assure  the appropriate
                  personnel  fully  understand  and acknowledge  the  reported
                  problems; and  document  the  names,  titles,  and  positions  of
                  those in attendance  at  the  post audit  briefing.

          6.2.8.   Following  the  audit,   Audit  Comments   Sheets   will   be
                  finalized  and  approved  by the  QAU  Manager.    An  Audit
                  •Report  briefly describing the  following essentials  of the
                  audit will be  prepared by the Audit Team  Leader:  activity
                  audited,  dates  of  audit,  audit  team members,  type and


                                        135                  APPROVED

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Page 6 of 7                       Analytical  and Structural  Chemistry Center
                                  SOP  ASCC 50-083-01
                                  April  29,  1988

                                                               '^ •>
                       STANDARD OPERATING PROCEDURE            '  •-*'••-
                        FOR QUALITY ASSURANCE UNIT
                       PERFORMANCE AND SYSTEM AUDITS
                              FOR NPS SURVEY


                  scope of  audit,  personnel  contacted,  summary  of  audit
                  results  including positive points,  problematic areas,  and
                  references   to   Audit   Comment  Sheets,   any   additional
                  comments  or   recommendations,  and  a  statement  on  the
                  effectiveness  of the QA elements audited.   The  QAU Manager
                  will  also approve the  Audit Report.

          6.2.9.   The completed  Audit Comment  Sheets and Audit  Report will
                  then   be   routed  to  the  Project  Manager  and  persons
                  responsible  for  the specific  tasks via the  QA Inspection
                  Routing Sheet  (Figure  3).   The Project Manager  and project
                  personnel will  fill  out the Corrective  Action  sections  of
                  the  Audit   Comment   Sheets   and  forward   them   to  the
                  management  listed in  Figure  3.   A  period of  seven  days
                  will  be requested for the return of  the forms  to the QAU.
                  All  Audit Comment Sheets and  Audit Reports will  be copied
                  and  filed   within  the  QAU   before   the  originals  are
                  circulated to  appropriate  personnel.   These copies will  be
                  destroyed  once   the  original  documents  with   Corrective
                  Action  Descriptions   appropriately  addressed   have  been
                  returned.

          6.2.10.  The Corrective Action  Descriptions  will  be  reviewed by  the
                  QA  Specialist who led  the  audit and the  Manager of the  QAU
                  to  assure that appropriate  measures have been initiated  to
                  resolve noted  problems.    If  the  corrective actions  are
                  adequate,  the  forms will  be  signed  by  the  QA Specialist
                  and Manager of the QAU.

          6.2.11.  If  the  corrective  action  responses  are unacceptable  (do
                  not   meet   Battelle   Policy   or   EPA-specified   project
                  requirements)  or  do   not  fully  address   the   reported
                  problems,  the  QA  Specialist  and  the Manager  of the  QAU
                  will  fill in the appropriate  information at  the  bottom  of
                  the Audit Comment Sheet.  Verbal discussions will  then  be
                  held  with the  Project  Manager to  come  to  agreement on  a
                  resolution.   If  a resolution  cannot be reached,  the  issue
                  will   be   taken   up  with   appropriate  management   for
                  settlement.     The corrective  action  finally agreed  upon
                  will  be documented and  retained in  the QAU  file.


                                                             •V-PROYED
                                         136

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Page 7 of 7                       Analytical  and Structural  Chemistry Center
                                  SOP ASCC 50-083-01
                                  April  29,  1988


                       STANDARD OPERATING PROCEDURE
                        FOR QUALITY ASSURANCE UNIT
                       PERFORMANCE AND SYSTEM AUDITS
                              FOR NPS SURVEY


    6.3.   Data Audits  --  Data  Audits will  be  performed on  all data  sets
          submitted to EPA.   Prior to  submission  to EPA, all  finished  and
          raw data  associated  with the  data set will  be submitted to  the
          QAU.   The  QAU  will  audit  data  to   establish that  project  QA
          requirements were  met  during  generation  of  the  data  and  to
          establish the  completeness,  traceability,  accuracy  of  reported
          data.   All  reported data are reviewed  for  agreement  with  raw  data.

          6.3.1.   Data sets submitted to  QAU for audit  will  be  accompanied
                  by a completed  Data  Package  Checklist form   (Figure  4).
                  All  materials necessary to complete  the Data Audit  are
                  listed  in the Data  Package Checklist  along with  comments
                  designed  to  aid  the QAU in the audit.    Each data  set  will
                  also be   accompanied  by  an  Internal  Quality   Control
                  Checklist  (Figure 5)  listing  project  QA requirements  and
                  documentation  that  these  QA   requirements  were  met  for
                  submitted data sets.

          6.3.2.   Data Audit results  are  reported  to  the  Project  Manager
                  using a  Audit Comment  Form (Figure 2) which  specifies  if
                  the  data  is   approved as  submitted  or  if discrepancies
                  exist that must  be  addressed.   Discrepancies are  addressed
                  by the  Project  Manager or  project  personnel   involved  in
                  the  specified tasks and  the  form  is  routed to management
                  and  the  QAU  for  approvals as described  in Sections 6.2.9.
                  and  6.2.10.  of  this  SOP.    If  the  corrective action
                  responses   are  unacceptable,   issues  are   resolved   as
                  described  in  Section 6.2.11. of this SOP.
                                                                 APPROVES-
                                                               *

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                     CRITICAL PHASE INSPECTION CHECK SHEET
TEST ARTICLE
STUDY TITLE
       PROJECT NUMBER
CRITICAL PHASE(S)
QA AUDITOR
AUDIT TYPE:  o SYSTEM  a PERFORMANCE
              DATE              	
Sample Receipt and Storage
ITEM
Who is responsible for sample receipt
and storage?
Is portion of QA Project Plan describing
sample receipt procedure available?
Is above sample receipt procedure followed?
Is ICF informed when samples are received?
Is information on ICF Sample Tracking form
transferred to Method 6 database?
What is disposition of ICF Sample Tracking form?
Where are samples stored?
Where are standards and sample extracts stored?
Is the temperature of the cold storage
recorded daily in a permanent record?
Are temperature excursions noted and
appropriate actions taken when required?
YES










NO










COMMENT (S)










Additional Comments:
                 FIGURE 1.  CRITICAL PHASE INSPECTION CHECK SHEET

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Sample Preparation
ITEM
Who is responsible for sample preparation?
Are NPS Method 6 and modifications outlined in
the QA Project Plan describing sample prepar-
ation available?
Is above sample preparation procedure followed?
Are SOPs for operation of laboratory equipment
such as balances available?
Are Method 6 and SOPs followed?
Are analytical balances routinely checked before
use? Is documentation available?
Is the laboratory maintained in a clean and
organized manner?
Are safety practices (lab coats, lab glasses,
etc.) consistently used in the laboratory?
Are the hoods in good conditions and functional?
Are chemical waste disposal policies/procedures
well-defined and followed?
Are laboratory reagents and chemicals dated
upon receipt? Are expired reagents present?
Are solutions and reference materials properly
labeled with concentrations, date of
preparation, and identity of person preparing
the sample?
Is a laboratory notebook containing descriptions
of solution preparation and sample preparation
properly maintained (GLP guidelines)?
Are primary standards traceable to neat
materials?
YES














NO














COMMENT (S)














Additional  Comments:
                              FIGURE 1.  (Continued)
                                       139

-------
GC-NPD Sample Analysis
ITEM
Who is responsible for GC-NPD analyses?
What instrument is used for 6C-NPO analyses?
Are NPS Method 6 and modifications outlined in
the QA Project Plan describing primary and
confirmatory GC-NPD conditions available?
Are Method 6 and modifications followed?
Is the instrument manual available in the work
area?
Is a permanent instrument service record
maintained in a log book?
Is the Instrument Quality Assurance Standard
analyzed prior to samples?
What data system is used for GC-NPD data
collection?
Are adequate backup supplies available (beads,
injection port liners, columns, etc) for
preventative maintenance?
YES









NO









COMMENT (S)









Additional  Comments:
                               FIGURE  1.   (Continued)

-------
GC-MS Sample Analysis
ITEM
Who is responsible for GC-MS analyses?
What instrument is used for GC-MS analyses?
Are NPS Method 6 and modifications outlined in
the QA Project Plan describing GC-MS confirm-
ation conditions available?
Are Method 6 and modifications followed?
Is the MS tuned with DFTPP prior to analyses of
samples?
Is a permanent instrument service record
maintained in a log book?
What data system is used for GC-MS data
collection?
Are adequate backup supplies available for
preventative maintenance?
YES








NO








COMMENT (S)








Additional  Comments:
                            FIGURE 1.  (Continued)
                                             141

-------
Data Handling and Review
ITEM
Who is responsible for data handling?
Who is responsible for data review?
What data system is used for calculations, data
compilation, and generation of reports?
Is the operation of the data system validated
with a test set of data?
Are results spot-checked by a second person or
the QAU?
Do records ind-'cate that corrective action is
taken when analytical results fail to meet QC
requirements?
Are all data maintained in a paper file for
on-site inspection?
Chromatograms of raw data?
Calibration curves?
Control charts?
Analysis reports?
Copies of text file reports?
Are raw and finished data stored on magnetic
tape?
YES








NO








COMMENT(S)








Additional Comments:
                             FIGURE  1.   (Continued)

-------
Quality Control
                                                    OffJCMLCOl
ITEM
Does this program have a current QA Project
Plan? What revision?

Do project personnel have a copy of the QA
Project Plan?
Are project personnel aware of the contents of
the QA Project Plan?
Does the QA Project Plan adequately address the
Personnel?
Facilities and equipment?
Operation of instruments?
Documentation of procedures?
Preventative maintenance?
EPA's data QC requirements?
Data validation?
Data reporting requirements?
Feedback and corrective action?
YES




NO




COMMENT (S)




Additional Comments:
                       FIGURE 1.  (Continued)

-------
Summary Checksheet
ITEM
Do responses to the evaluation indicate that
project and supervisory personnel are aware
of QA/QC and its application to the project?
Have responses with respect to QA/QC aspects of
the project been open and direct?
Has a cooperative attitude been displayed by all
project and supervisory personnel?
Have any QA/QC deficiencies been discussed?
Is the overall quality assurance adequate to
accomplish the objectives of the project?
Have corrective actions recommended during
previous audits been implemented?
YES






NO






COMMENT (S)






Additional  Comments:
                             FIGURE 1.  (Continued)

-------
                              UJ
                              tn


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                              o.
                              o
                              UJ
                              oi
                              a:
                              o
                              LJ
                o
                H—

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OS
Q.
O OE
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t— *—
U> UJ
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                                                                        145

-------
                                    rce SESST
T2ST A2TICLZ	?EASS_
STUDY TTTLS	
SPONSOR        	PROJECT SO.
Q.A. AUDITOR	DAIS
 ?^
 ^
sigz &&d dace this Rjsuzlrg Sheec iz  rhe  scace prsvidcd. beside your &aset a-d
rercrz Che entire set vhes css?ieted  tc  the Qualir/ Assurance Ccit 20 latir tha:
     ROUTS TO                               SXCXATTRS                     DATS
   Dave  Zimmerman
   Tom Dam'son
   Elizabeth Kircher
   Tina Enael
   Judy Gebhart
   Ron Joiner
  Georoe Rogers
  Anna Barker
  Ramona
                 FIGURE 3.   DUALITY  ASSURANCE INSPECTION ROUTING SHEET

                                        146

-------
Name:
DATA PACKAGE CHECKLIST

             Date:
QA Reference:

Data Sets:
             Project  No:
MATERIAL

n ASCII Text Data
n Field Sample Tracking Sheet
D Lab Notebooks
D Calibration Data  (Analysis
  Method, Calibration Curves,
  Raw Calibration Data)
                 COffOT
n Sample Data (Chromatograms,
  Printouts, Summary Report)
D Control Charts
D Internal QC Checklist
                   FIGURE 4.  DATA PACKAGE CHECKLIST

                                     147
                                                                     4/29/88

-------
Ext net ion Set
Extracted
  IKTBWAL QUALITY OJKTROL CHECKLIST




/    /         Analyzed      /     /
Files

Criteria for Aecootaoie Results Acceetaole LIB its
CONTROL CHARTS Control Chart
ETU recovery fro* the LCS and PTU
recovery froe the LCS or Wth Blk PTU liiiU to
aust be within the 3 Std lie it*
of the current control chart. ETU liait* to
Alert conditions occur when:
-Three or sore ETU or PTU recoveries fall outside the 2 Std warning
lieits, but within the 3 Std control liaits.
-Seven consecutive point* for ETU or PTU fall above or below the seen.
-Seven consecutive points for ETU or PTU are in increasing or
decreasing order.
SURROGATE RECOVERY
PTU recovery aust be within 31 Control Chart
percent of the aean recovery
of PTU froe the current control PTU aean
chart. (Uth Blk excluded if a field
saepl* oeets Uth Blk criteria.) PTU lieits U
INTERNAL STANDARD AREA
IS peak area for any saeple aust MS U 1211
not deviate by eore than 21 percent (Expressed as recovery relative
free the eean peak area for the to the aean area of the
calibration standards. calibration standards.)
LABORATORY CONTAMINATION
The eethod blank should not contain < 4.5 ug/L
a peak grater than or equal to
one-half the URL for ETU.
INSTRUMENT PERFORMANCE
Froe Table 6 of Method 8.
S/N: > 3
PSF: I.9C to 1.IC
POP: 1.93 to 1.17
CALIBRATION STANDARD INTEGRITY
If the ayatee is not recalibrated, Level of Ck Std
or ia recalibrated using new Acceptable range
standards, at least one previously
prepared atandard lust be run and to
Actua i Resu i ts Cseeenxs
LCS file Ho.
PTU ( LCS / BUC ) J pass fail
ETU I1M/9M » pass fail
See Control Chart. pas* alert
See Control Chart. pass alert
See Control Chart. pass alert
Fi les: pass
Range: fail
Files: pass
Range: fail
Uth Blk file No.
Aet of ETU found pass fail
Inst QC file No.
S/N pass fail
PSF pass fail
PGF P»»« f*'l
Ck std file No.
Result P*» '»''
analyzed as i saeple, giving a result
within 211 of the expected value.
Prepared by Date / / */2Bj
                          FIGURE 5.   INTERNAL  DUALITY CONTROL CHECKLIST

-------
                                                 Appendix J
                                                 Revision No. 3
                                                 Date: April 29, 1988
                                                 Page 1  of 5
                 APPENDIX J

STANDARD OPERATING PROCEDURE FOR PROPER
  USE OF SIGNIFICANT FIGURES AND ROUNDING

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Page 1 of 4                       Analytical  and Structural Chemistry Center
                                  SOP ASCC-30-001-01
                                  September 19,  1986


                                  Kev Words;   Calculations
                                              Data
                                              Reporting of Results


Title:                 STANDARD OPERATING PROCEDURE
            FOR PROPER USE OF SIGNIFICANT FIGURES AND ROUNDING
      Originated by:    'l/VUL{JM\.  1UWJ?L*^-r-     Date:
                      Merl
in K.  L.  Bicking      J'


         / L
        Approved by:       V*w    ,       , — • _  Date:
                      John R.  Nixon,  Manager
                      Analytical  and  Structural  Chemistry Center
        Approved by:      \_u~*~~ f ^jr^L. __       Date:
                      Duane E.  Hilmas,  Manager                  '
                      Chemistry and Biomedical  Sciences  Department
        Approved bv :  _  ZZi-^,^ -^L^    /^^£\^/ _  Date:
                      Ramona A.  Mayer,  Manager
                      Qua! itv. Assurap«-TUnit
        Approved by:      /ȣj          >v"        Date:
                      Anna LT.  Barker,  Director
                      Biological  and Chemical Sciences
Circulation  List:

      QAU

      QCWG

Record of Reviews:

      Date:         Reviewed by:             Date          Reviewed by:
                                       150

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                                                         OFFICIAL COPY


Page 2 of 4                       Analytical  and Structural  Chemistry Center
                                  SOP  ASCC-30-001-01
                                  September  19, 1986


                       STANDARD OPERATING PROCEDURE
             FOR PROPER USE OF SIGNIFICANT FIGURES  AND ROUNDING


1.  SCOPE

    1.1.  This  Standard  Operating  Procedure  (SOP)  is  applicable  to  all
          projects which  require manipulation of numerical data.

2.  SUMMARY

    2.1.  The number  of  significant  figures  reported  is dependent  on  the
          number of significant figures in each individual quantity  used to
          compute  the reported  number.   The number  of significant  figures
          reported cannot  be more  than  the  smallest  number used  in  any
          related  calculations.

          Rules  are provided  for proper  rounding of the final  answer.

3.  PROCEDURE

    3.1.  Number of Significant Figures

          3.1.1.   An   experimental   result  should   be  reported  so that  it
                  contains  only the digits  known  with certainty,  plus  the
                  first  uncertain  digit.    For example,   the  number   "61.6"
                  implies  that there  is  uncertainty  in   the  first  decimal
                  place (±0.05).

          3.1.2.   The  number  of  significant  figures  will   depend  on  the
                  particular  activity/piece  of equipment  being  used.  Most
                  activities  will  generate between two  and four significant
                  figures.    The   analyst  must  be  aware   of the  number  of
                  significant  figures  provided by a particular activity.

          3.1.3.   Zeros  to  the right  of  significant  digits  are  used  to
                  indicate  the order  of magnitude  and  are not significant.
                  When necessary,  employ  scientific   notation  to  avoid
                  ambiguities.   For  example, 2000  ml  implies from one to as
                  many as  four significant  figures.  However,  2.0 X  103 ml
                  or 2.0  L  imply only  two  significant figures.

    3.2.  Number of Significant Figures  in Calculations

          3.2.1.   Addition  and Subtraction

                  The  number  of significant  figures in the final answer will
                  be  determined by  the  number with  the fewest  number of
                  decimal places.  For example,


                                         151

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                                                                            OFFICIAL 001


              Page  3  of  4                       Analytical and. Structural Chemistry Center
                                               SOP ASCC-30-001-01
                                               September 19, 1986

I
                                     STANDARD OPERATING PROCEDURE
,                          FOR PROPER USE OF SIGNIFICANT FIGURES  AND ROUNDING


                                         3.4 + 0.02 +  1.31 - 4.7.
i
i                                The  final  answer is limited to  one decimal  place because
                                of the uncertainty introduced in  the  first  decimal  place
j                                by the "3.4".

                        3.2.2.   Multiplication and Division

1                                The  number  of figures  in  the  result  is  equal  to that of
                                the  quantity with the least number  of  significant figures.
                                For  example,
                                The  answer  is limited to  two  significant  figures  because
                                of the  ":4".

                  3.3.   Number  of Significant Figures in a Final Reported Result

                        3.3.1.   The  number  of significant  figures in the  final  reported
                                result  will be determined  by  the needs of  each individual
                                project.    However,   the  number  of   significant  figures
                                reported can  never be greater  than the smallest number  of
                                significant figures in the data.

                        3.3.2.   In  performing calculations, carry one  extra  significant
                                figure  through  all calculations.   Round  to  the  correct
                                number  of significant figures in the last step.

                  3.4.   Rounding of Numbers

                        3.4.1.   When the first digit discarded  is  less than  "5",  the  last
                                digit   retained   is   not  changed   ("round-down").     For
                                example,

                                         3.46325 rounded to 4 digits  - 3.463,  and

                                         3.46325 rounded to 3 digits  - 3.46.

                        3.4.2.   When the first digit discarded  is  greater  than "5", or  if
                                it is  a "5"  followed  by at least  one  non-zero digit,  the
                                last  digit   retained   should   be  increased  by  one  unit
                                ("round-up").   For example,

                                         8.37652 rounded to 4 digits  - 8.377,  and

                                         8.37652 rounded to 3 digits  - 8.38.
                                                         152

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                                                                         CO
Page 4 of 4                      Analytical  and  Structural  Chemistry Center
                                 SOP ASCC-30-001-01
                                 September  19, 1986


                       STANDARD OPERATING PROCEDURE
            FOR PROPER USE OF SIGNIFICANT FIGURES AND ROUNDING


          3.4.3.   When  the first digit  discarded is  exactly  "5",  the last
                  digit  retained should be  rounded  upward  if  it  is  an odd
                  number,  but  not adjusted if it  is an even  number  (i.e. the
                  last  digit  retained  will  always be  an  even  number).   For
                  example,

                           4.355 rounded to  3 digits  - 4.36,  but

                           4.365 rounded to  3 digits  - 4.36.

4.  REFERENCES  •

    "Fundamentals  of Analytical  Chemistry", D.  A.   Skoog  and D.  M.  West;
    Saunders,  Philadelphia, 1982; Chapter 3.
                                                                  APPROVED

                                      153

-------