Interim Guidance for the
      Preparation of Quality Assurance
      Project Plans for Chemical Tests
in the Underground Injection Control Program

         Prepared by the EPA
                 Workgroup
                 July 1985

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S
'fffi
 \       UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
 ,3
                        WASHINGTON,. D.C.  20460


                                 2 (985
                                                           OFFICE OF
                                                            WATER
     MEMORANDUM

     SUBJECT:  Outdance fop—^he  Preparation of  Quality Assurance
                                       Chemical  Tests (UICB #35)
     FROM:     Victor J .^-Kimm,/Director
               Office of Drinking Water

     TO:       Water Management  Division  Directors
               Regions  I-X
     The attached document provides  guidance  on the preparation
     of quality assurance- project plans  for chemical tests and
     instructs the Regions to  include  in the  grant agreement or
     workplan a statement by the States  that?,  they  will  submit a
     QA project plan within 120 days after  receiving this guidance i/
     from EPA.  This document  is the product  of months  of meetings
     of the UIC-QA workgroup which is  composed  of  representatives
     from EPA (RO, HQ, EMSL) and the States  (TX, MS, NM).

     The guidance document'consists  of a short  guidance (5 pages) and
     attachments which are intended  as technical assistance to the
     States.  It should be introduced  to the  States ASAP  in order
     for them to begin the preparation of QA  project plans for all
     chemical tests done in support  of the  UIC  program.

     If you need additional information,  feel free to call me on
     382-5508 or Mario Salazar  (Project  Manager) on 382-5561.


     Attachment

     cc:  Nancy Wentworth, QAMS
          UIC Representatives,. Regions I-X
          Water Supply Branch Chiefs
                                                     [J
                                                    ^ ••:....>;...:i vV.li-:, ::::•.I'A!
                                                    'r>fER ;v^hAiidv;ij-iT GiViSIP

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          Interim  Guidance  for  the
      Preparation  of  Quality  Assurance
      Project  Plans  for  Chemical  Tests
in the Underground Injection  Control  Program
         Prepared by the EPA UIC-QA
                 Workgroup

                 July 1985

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    TABLE OF CONTENTS
Title
Acknowledgements
Glossary
Abbreviations
Guidance





Attachment A












Section



I
II
III
IV
V
VI
I
II
III
IV

V

VI
VII
VIII
IX
X
XI
Subiect



Background
Purpose
Guidance
Implementation
Filing
Responsibility
Plan Overview
Organization and Responsi-
bility v
Sampling Procedures
Sample Preservation Stabiliza-
tion and Chain of Custody
Laboratory and Field Equipment'
Operation and Calibration
Procedures
Analytical Procedures
OoC'jiTientat i on , Data Reduction,
Validat ior% -a-.nd Reporting
Internal Quality Control Checks
Performance and Systems Audits
Preventive Maintenance
Precision and Accuracy
Paae
i
i i
vi i
1
2
3,
4
5
5
A.I
A. 3
2^.4
A. 7

A. 10

A. 12
2^.15
A. 16
A. 19
A. 21

XII
Protocols/Limits                  Ai.22

Data Representativeness,          A.23
       bil i ty and Completeness

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                     .TABLE  OF  CONTENTS  (cont.)
Title
Section
   Subject
Page
Attachment B
Attachment C
Attachment D
 XIII

  XIV

   XV

    I


   II
                   III



                    IV

                     V
                    II
Attachment E
   II

    I
Corrective Action                 A.24

Quality Assurance Reports         A.25

Standard Operating Procedures     A.27

Examples of Completed Sample      B.I
Labels

Standard Procedures for the       B.3
Collection of Ground-Water
Samples from Residential and
Municipal Wells

Containers, Preservation          B.18
Techniques and Holding Times
(with summarized page)

Chain of Custody form             B.25

Sampling, Preservation and        B.26
Storage Considerations for
Trace Organic Materials
(including Volatile Organics)

Compatibility in the Hydro-
geological Environment            C.I

Compatibility test for ease of    C.6
injection

Quality Control Sample Request    D.I
Form

Example of an SOP                 D.2

Example of a QA project plan      E.I

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                       ACKNOWLEDGMENTS


This document was orepared by the Underground Injection Control

Quality Assurance (UIC-QA) workgroup.  Members of this workgroup

are: .
 Mario Salazar (Chairman)
 Paul Osborne (Co-Chairman)
 Juanita Hillman
 Bernie Orenstein
 Gene Coker
 Linda Kirkland
 Ron Van Wyck
 Irwin Pomerantz
 Joe Roesler
 Jeff Van Ee
 Fred Hille
 Phil Baca

 Richard Ginn
EPA,ODW Headquarters
EPA,UIC Section,  Region VTII
EPA,RQAO*,  Region VTII
EPA,UIC Section,  Region V
EPA,UIC Section,  Region IV
EPA,RQAO Staff,  Region VI
EPA,UIC Section,  Region VI
EPA,ODW QAO,Headquarters
EPA,EMSL Cincinnati
EPA,EMSL Las  Vegas
Mississippi DNR,UIC program
New Mexico Oil Conservation Division,
UIC program
Texas Railroad Commission, UIC program
   See list  of abbreviations and glossary

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                         GLOSSARY OF TERMS

AUDIT;

     a systematic check to determine the quality of operation

     of some function or activity.   Audits may be of two basic

     types:   (1)  performance audits  in which quantitative data

     are independently obtained  for  comparison with routinely

     obtained data in a measurement  system, or (2)  system

     audits  of a  qualitative nature  that consist of an on-site

     review  of a  laboratory's quality assurance system and

     physical facilities for sampling, calibration, and

     measurement.


DATA QUALITY:

     The totality of features and characteristics of data that

     bears on its ability to satisfy a given purpose.    The

     characteristics of major importance are accuracy, precision,

     completeness, representativeness, and comparability.

     These characteristics are defined as follows:

     0    Accuracy - the degree  of agreement of a measurement
          (or an  average of measurements of the same thing),  X,
          with an accepted reference or true value, T, usually
          expressed as the difference between the two  values,
          X-T, or the difference as  a percentage of the reference
          or true value, 100 (X-T)/T, and sometimes expressed as
          a  ratio, X/T.  Accuracy is a measure of the  bias in a
          s y s t em.

     0    Precision - a measure  of mutual ageeement among
          individual measurements of the same property, usually
          under prescribed similar conditions.  Precision is
          best expressed in terms of the standard deviation.
                                    11

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          Various measures of precision exist depending upon
          the "prescribed similar conditions."

     0    Completeness - a measure-of the amount of valid data
          obtained from a measurement system compared to the
          amount that was expected to be obtained under correct
          normal conditions.

     0    Representativeness - expresses the degree to which
          data accurately and precisely represent a character-
          istic of a population, parameter variations at a
          sampling point, a process  condition, or an
          environmental condition.

          Comparability - expresses  the confidence with which
          one data set can be compared to another.


DATA VALIDATION   ,  '

     A system process for reviewing  a body of data against a

     set of criteria to provide assurance tha "the data are

     adequate for their intended use.  Data validation consists

     of data editing, screening, checking,' auditing, verification,

     certification,  and review.
                              111

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ENVIRONMENTALLY RELATED MEASUREMENTS




     A term used to describe  essentially  all  field and labora-




     tory investigations that generate data involving (1) the



     measurment of chemical,  physical, or biological parameters




     in the environment, (2)  the determination of the presence




     or absence of criteria or priority pollutants in waste




     streams,  (3)  assessment  of health and ecological effect




     studies,  (4)  conduct  of  clinical  and epidemiological




     investigation, (5)  performance of engineering and process




     evaluations,  (6)  study of laboratory simulation of



     environmental events, and (7)  study  or measurement




     on pollutant  transport and fate,  including diffusion models






PERFORMANCE AUDITS;



     Procedures used to determine quantitatively the accuracy




     of the total  measurement system or component parts thereofw






QUALITY ASSURANCE;




     The total integrated  program for  assuring the reliability




     of monitoring measurement data. "  A system for integrating




     the quality planning, quality assessment, and quality




     improvement efforts to meet user  requirements.






QUALITY ASSURANCE  PROGRAM  PLAN:



     An orderly assembly of detailed and  specific procedures



     which delineates  how  data of known and acceped  quality data
                               IV

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     is produced for a specific project.   (A given agency or




     laboratory would have only one quality assurance program



     but would have a quality assurance project plan for each




     of its projects.)






QUALITY CONTROL;



     The routine application of procedures for obtaining



     prescribed standards of performance  in the monitoring and




     measurement process.
                               v

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STANDARD OPERATING PROCEDURE  (SOP):  .



     A written document which  details  an  operation,  analysis or




     action whose mechanisms  are thoroughly  prescribed and




     which is commonly accepted  as  the method  for performaing



     certain routine or repetitive  tasks.
                               VI

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                         A33REVIATIONS   '


API    - African Petroleum Institute

CERCLA - Comprehensive Emergency Response Compensation and
         Liability Act (Superfund)

CFR    - Code of Federal Regulations

DI     - Direct Implementation (States in which EPA has implemented
         a UIC Program).

FR     - Federal Register

Lab    - Laboratory

NPDES  - National Pollutant Discharge Elimination System

0 & G  - Oil and Gas

PWSS   - Public Water System Supervision

QA     - Quality Assurance

QAMS   - Quality Assurance Management Sfaff

QAO    - Quality Assurance Officer

QC    •- Quality Control

RCRA   - Resource Conservation and Recovery Act

RO     - Regional Office

RQAO   - Regional (Office) Quality Assurance Officer

SDWA   - Safe Drinking Water Act of 1974 as amended

SOP    - Standard Operating Procedure

SQAO   - State Quality Assurance Officer

TDS    - Total Dissolved Solids

UIC    - Underground Injection Control

UIC-QA - Underground Injection Control Quality Assurance

USDW   - Underground Source of Drinking Water

1425   - Oil and Gas programs.  From §1425 of the SDWA which
         makes special provisions for delegation of the UIC
         program for Oil and Gas related injection wells.
                              VII

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  \      UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
  *                     WASHINGTON. D.C.  20460
                    AUG  -21985
                                                       OFFICE OF
                                                        WATER
 MEMORANDUM

 SUBJECT:   Inter^artSuidance for the Preparation of QA Project
           Plarfs* for Chemical -Tests,  in the UIC** Program -
            fTCP.G #3:

 FROM:     "Victor J.
           Office of Drinking Water
 TO:        Water Supply Branch Chiefs/ Underground Injection
           Control Section Chiefs/QAOs - Regions I-X

 Background

 On September 30, 1983, the final version of the general grant
 regulations was published under 40 CFR Part 30.  In §30.503(e)
 the regulations require that States and local governments
 receiving assistance from EPA implement a Quality Assurance  .
 (QA)  program.   The QA program must have: 1) a management plan
 identifying the State agency and/or office responsible, resources
 available and  the person in charge of the program; and 2) a
 commitment on  the part of the State to develop and implement
 QA project plans for environmental measurements, in accordance
 with  scientific methods approved by EPA.  This latter requirement
 would mean, among other things, that each entity administering
 a  UIC program  must structure all the components of its sampling
 and testing program, including^ s^amp_lj.ng and^^testjjii.g_by . the.       <^-
 operators^ to  insure that data fs of~"k~n"owrHqua 1 i t y and to
"conform with EPA accepted procedures and State requirements.

 In the case of Direct Implementation (DI) programs, the Director
 (RA)  establishes criteria for QA of all environmentally related
 measurements submitted in support of UIC activities.  The autho-
 rity  for QA in the UIC program is based on 40 CFR §144.28(g),
 §144.51 (e) and §144.52(a)(5), which require adequate QA to be
 used  when submitting data mandated by the program.  Data submitted
 by well operators also need to include QA elements.

 * See glossary of terms (p.ii)
 ** See list of abbreviations (p.vii)

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   Due  to  the newness of some of the testing procedures  used in the
   UIC  program and the program itself, implementation  will  take
   place in  three sequential phases.  The first phase  will  address
   traditional chemical tests*.  The second will address  widely
   used physical tests, and the third, less well known geophysical
   tests.

   Purpose

   The  purpose of a Quality _As.surance_ jprogram^ _is to help  assure
 S that methods to obtain environmental measurement datajare
 V technically" valid, scientifically defensible and of known quality.
   For  this  reason, EPA is requiring States to assess  the adequ'acy—:
   of their  present data gathering-activities and  is offering
   technical help where needed to assist States in upgrading
   their programs to meet Federal QA standards.  If a  State already
   has  a comprehensive, coordinated and effective QA program for
   which a QA project plan(s) have been prepared,  it should submit
   the  plan  to the Regional Office (RO) for evaluation.   The RO ^may
/  _£e^omi^jT^_£Oj^^evi_sions to assure that the QA project plans'   "^
   "a*re~Tn~"^co'n forma nee with scientific methods approved by 'EPA.

   This guidance will help recognized UIC agencies (i.e., State
   agencies, ROs) in the preparation of a^ QA project plan for
   chemical  tests in the UIC program.  It is not the intention  of
 ^EPA  to modify the existing UIC delegated program in any  manner.
   This guidance does not change the parameters which  are being
   tested  for and does not change the frequency of these  tests.

   Specific  QA project plans may deviate from this guidance with
   proper  justification which is acceptable to the ROs.   The
   EPA  will  evaluate those project plans in light of the  overall
   QA program goal that environmental measurements be  representative,
   accurate, cpmparable, complete and of known quality.
    * These  include analyses of injection fluids, formation  fluids
     and any other aqueous solutions in their terminal  stable  form
     or any of their  intermediary forms.
                                 -2-

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Guidance

This guidance  is based on "Interim Guidelines and Specifications
for Preparing  Quality Assurance Project Plans. *  (QAMS 005/80,
EPA-600/4-83-004, NTIS PB83-170514).  Attachment A follows the
same organization as the QAMs guidance and it is intended to
aid in the preparation of UIC-QA project plans in states that
have not developed their own.  It contains directions and
suggested language that can be be modified by the State for
more relevance.

The QA project plan for chemical analysis must contain the      V
elements listed below.  However, if any of these are duplicated ^~\ ^ .
in other programs they can be incorporated by reference (e.g.   ^ r '
NPDES, or RCRA QA programs).  Furthermore, the preparer can, if ^
warranted, consolidate some of the elements under generic headings.
The RO should  indicate to States what would be acceptable.

    "°    Plan Overview
    i/o  ^/Organization and Responsibility
    ^ °   ^Sampling Procedures
    • °   ^Sample Preservation, Stabilization and Chain of Custody
    "~°   ^Laboratory and Field Equipment Calibration Procedures
    " °   •"Analytical Procedures
    f°   ^Documentation, Data Reduction, Validation and Reporting
    "°   ^Internal Quality Control Checks
    t/o   ^Performance and Systems Audits
    t/o  ^preventive Maintenance
    • °   ^Precision and Accuracy Protocols/Limits
    v°   ^Data Representativeness, Comparability and Completeness
    •v °   "^Corrective Action
    
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by the UIC agency in support of UIC.   In such States, only the
tests that are actually done in support of '-he UIC program
should be covered.  However, the preparer of the plan should
give consideration,  not only to the primary use of the data,
but also to secondary uses.   For example, consideration could be
given to possible applications in enforcement activities (secondary
use) for any data submitted  to support a permit application
(primary use).  In such cases, the SQAO should make sure that
tests done to estimate certain parameters, such as TDS, are
adequate to evaluate contamination episodes or for permit
purposes.

EPA has not established a valid test  for "compatibility" of
injection fluids in  injection formations.  However, if a
compatibility test is required under  a State UIC program, it must
be included in the QA plan.   EPA will revise this guidance in
the future as compatibility  tests are studied.  In general,
operators perform some tests to evaluate tb .=* ease of injection
(e.g., whether there is precipitation of solids in the formation).
Attachment "C" gives a short, discussion of compatibility and a
test which can be done to determine ease of injection.

EPA has not developed or approved specific tests and protocols
to deal with some complex injection fluids.  These will be
made available to the States as they  are developed.
                                       x
RCRA and CERCLA offices in the States or EPA Regions should be
able to provide sampling guidance for "high hazard" samples
taken to analyze Class I hazardous waste injection fluids.
The ROs should include this  information in the guidance .to be
given to States that have HW facilities.

Implementation

The ROs will distribute this guidance to the States.  Upon
receipt, the States  will contact all  persons (e.g., affected
operators, laboratories and  other State offices) involved in
the sampling, testing, processing and reporting of UIC chemical
data.  The implementation of this plan in the States should be
completed within the 1986 grant year.  The RO's UIC section
and QA officer will  determine the adequacy of the State QA
project plan.  For DI States,, the ROs must send the QA project
plan to the Chief, Underground Injection Control Branch in
Headquarters after concurrence from the Regional QA officer.

The ROs will include a condition in the grant agreement or
workplan with respect to the full implementation of the UIC-QA
project plan for chemical test.  This condition should read:
                              -4-

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     ."The State agrees to submit to EPA a QA project plan for
     chemical tests within 120 days after receiving guidance
     from EPA and to implement this plan within the 1986 grant V
     year.  The QA project plan will follow guidance provided
     by EPA on this subject."

The ROs will prepare a QA project plan for DI States and will
send it to the Chief, Underground Injection Control Branch,
EPA Headquarters, no later than 120 days from the receipt of  <~
guidance on the subject.

This guidance will be updated periodically in the future as
warranted.  Examples of programs or special situations will be
incorporated in future guidances.

Since the primary purpose of QA is the improvement of the
quality of the data generated by the States and EPA, the program
should be viewed as a cooperative effort between these two
parties.  The ROs, as the overseeing authority, should remain
flexible enough to encourage initiative on the part of the States
and the regulated community.  The bottom line however, is that
a QA program is necessary to assure effective environmental
programs and EPA, the States and the regulated community are
responsible for implementing such a program.  EPA has made the
obtainment of data of kncwn quality onevof its biggest priorities.

Filing

This guidance should be filed 'under Underground Injection Control
Program Guidance #35 (UICPG #35).

Responsibility

For additional information please contact:

     Mario' Salazar, Environmental Engineer
     401 M Street, S.W.
     Washington, D.C. '20460
     Phone (202) or FTS 382-5561
Attachments

cc: UIC-QA workgroup
                              -5-

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                      ATTACHMENT A
               Instructions and Examples
                   to Be Used in the
                 Preparation of UIC-QA
            Project Plans for Chemical Tests
             Based on QAMS 005/80 "Interim
      Guidelines and Specifications for Preparing
            Quality Assurance Project Plans"
Section    I       Plan Overview                     A.I

          II       Organization and Responsi-        A.3
                   bility

         III       Sampling Procedures               A.4

          IV       Sample Preservation Stabilize^-    A.7
                   tion and Chain of Sustody

           V       Laboratory and Field Equipment    A,10
                   Operation and Calibration
                   Procedures

          VI       Analytical Procedures             A.12

         VII       Documentation, Data Reduction,    A.15
                   Validation and Reporting

        VIII       Internal Quality Control Checks   A.16

          IX       Performance and Systems Audits    A.19

           X       Preventive Maintenance            A.21

          XI       Precision and Accuracy Proto-
                   cols/Limits                       A.22

         XII       Data Representativeness           A.23
                   Comparability and Completeness

        XIII       Corrective Action   .              A.24

         XIV       Quality Assurance Reports         A.25

          XV       Standard Operating Procedures     A.27

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Foreword





     The original intent of Attachment A was to provide the



States and the ROs with a "fill-in-the-blank" guidance document,



which would minimize the effort expended by the States preparing



a Quality Assurance project plan for chemical tests.  However,



as the workgroup became aware of the complexity and relative



differences in the UIC programs, the consensus was reached to



provide a general document with some specific instructions and



illustrative examples.





     As "entioned in the text of the guidance, the QA plan that



each State and each RO develops should i.be designed to meet its



needs.  It is also intended to be a dynamic document which



will change as the UIC program and technology evolve.  It is



not intended to duplicate work done- in support of other EPA



programs such as NPDES, PWSS and RCRA.  The States are encouraqed



to coordinate their QA activities and to avoid, redundancy.

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I.   PLAN OVERVIEW

     Instructions

The preparer should list (or reference) in the QA project plans

if relevant:

a)   The reasons for preparing this plan.  General grant regulations

     (40'CFR 30.503 (e).) reguire that the State prepare a QA

     project plan for all' environmental measurements.  These

     project plans establish a vehicle for assurinq the

     generation of data of known quality through the documentation

     of the processes of sample collection, analyses and data

     handling.
                                                                 w.*}(y •;;
b)   The regulations relevant to the UIC QA program.  The Federal

    •regulations are: 40 CFR 30.503(e), 146.13(b)(1),

     146.33(b)(l) for primacy States; and 40 CFR 144.28ff) and

     146.52(a)(3) for DI States.  The preparer* of the QA proiect

     plan should list the applicable State statute and regula-

     tions/rules.


c)   Measurements in the UIC program which will generate chemical

     data.  Some such activities are:  analyses of formation

     fluids, analyses of injection fluids, analyses of samples

     from monitoring wells, analyses of fluids for aquifer

     exemption justification, analyses involved in ground-water

     contamination episodes and others;

* The person in the State or RO who has been charged with preparing
  the UIC-QA project plan for chemical tests.
                             -A.I-

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d)   Participants in the program.   Examples of these are:



     recognized UIC agencies,  State laboratories, private



     laboratories, well operators,  any contributinq State



     offices and others.



e)   To whom applicable.  All  entities required to submit data



     to the program should be  described.  Data of unknown quality



     are 'not acceptable for submission to the UIC program.  At



     this time,1 there is no explicit regulation in the UIC



     program minimum requirements  requiring the owner or operator



     to comply with specific QA practices outlined in this and



     subsequent guidance.  However, there are several references



     in the UIC regulations requiring the submittal of data of



     known quality (see b) above).   EPA and the State can assure



     compliance with the program by including QA requirements



     as a part of all permits  issued.





f)  How QA requirements will be disseminated to the regulated



    community.  The preparer should indicate what plans have



    been made to disseminate information.  Some vehicles that



    could be used are:



         1.  Newsletters



         2.  Statewide meetings



         3.  Fact Sheets



         4.  Information bulletins to accompany permit apnl icatior.s



         5.  Trade associations



         6.  Operator training
                             -A.2-

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II.  ORGANIZATION AND RESPONSIBILITY


     Instructions


The preparer must name the office or offices responsible for ( /®
UIC-QA chemical tests and indicate how the UIC-QA program will


be implemented.  A split responsibility .situation can arise


when the 1422  (Class I, III, IV and V) program and the 1425


(Class II) program choose to implement different UIC-QA proarams.



Throughout this guidance many different responsibilities are


assigned to the State Quality Assurance Officer (SQAO).  Some


of these responsibilities may be delegated to other program


participants (e.g. laboratory personnel); however, the SQAO

                                       v
should be ultimately.responsible for the adequacy of the QA


program to the RO.



The preparer must also indicate the various offices and agencies


involved in the generation and use of UIC fluid chemical data.


In some States different environmental programs will integrate


many or all their field activities.  In these cases, sampling


for the UIC program  (surveillance) may fall under the responsibi-


lities of a separate agency.  The State (or the RO in DI States)


must ensure that adeguate QA practices are implemented in all


offices contributing to the UIC effort.



The preparer (see footnote on page A.I) must also show how


the State will ensure that all data generated by the operators


will follow the State's QA reguirements.  As mentioned before,
                             -A.3-

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all data submitted as part  of  permit  application,  self-monitoring


and any other UIC activity  are also required  to be covered by


the QA program.   Either the State  or  the  RO in DI  States, must


establish a program to periodically check on  QA compliance by


the operators.



III. SAMPLING PROCEDURES


     Instructions


The State should specify in its QA plan how,  when  and where


the sampling should be done, using permit and generic requirements


as a base.  Some useful examples of general sampling technigues


should be mentioned.  Specific recommendations should also be
                                       i

made.  The State should develop a  short fact  sheet to be used


by operators, which specifies  the  minimum amount of information.


to be included on the sample label.  It  should emphasize the


importance of a specific description on how and where the


sample was taken.



Attachment B  includes:  1)  examples of completed sample  forms;  2)


"Standard Procedures for the Collection of Ground Water  Samples


from Residential and Municipal Wells" which is applicable to a


variety of investigations dealing with inorganic parameters;


3) "Required Containers, Preservation Techniques and Holding


Times"; 4) an example of a "Chain of Custody" form; and


5) a chapter  from a  field handbook (under preparation) with


instructions  for sampling trace organic materials, including
                             -A.4-

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volatile ones.  Furthermore, the first reference in Section VI



of this attachment, also elaborates on the types of sampler



materials to be used.  A survey of these documents should give



the preparer of the QA project plan a fairly complete picture



on sampling techniques to be used in the UIC program.





Some general recommendations that could be made in this section



follow .





     Example



The sampler should coordinate with the laboratory doing the



analysis to ensure proper scheduling.  Attachment C gives the



specified containers, preservation techniques and holding times



for selected samples.  After collecting .all samples they _sho'uld



be handled as few times as possible.   All personnnel should use



extreme care to ensure that samples are not contaminated.








Sample containers should be rinsed with sample water at least



twice before use.  The sampler should make sure that, when



warranted, the ••well is evacuated prior to taking ground water



samples.  Extreme care shall be taken to ensure that all materials



in pumps, tubing, bailers and sample containers do not contaminate



the sample by releasing materials that would interfere with,



add to, or react with the components being tested.  The same



precautions should be taken to prevent any adsorption of the



sample components by. the materials in the pumps, tubing, bailers



and/or sample containers.  The type of equipment and the sample
                             -A.5-

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containers used in the collection and preservation of samples

should be determined by investigating their compatibility

with the expected components in the sample.


All samples should be taken at representative locations.  If

possible, injection fluid samples should be taken out of the

injection line.


     References

The plan preparer should reference or include relevant oortions

of useful publications (in accordance with copvright laws).

Some particularly he.lpful publications are:

* "Manual of Ground Water Sampling Procedures," available from
  NWWA, phone  (614) 846-9355.
                                       V           i
* "Manual of Ground Water Quality:  Monitoring Methodoloay ,'"
  EPA-600/4-76-026.

* "Test Methods for Evaluating Solid Waste - Physical/Chemical
  Methods," SW-846 - 2nd edition.

* "Sampling Ground Water for Organic Contaminants",
  EPA 600/5-80-022.

* "Handbook for Sampling and Sample Preservation of Water and
  Wastewater," EPA-600/4-82-029,  Order PB-83-/24-503, available
  from NTIS.

* 'U.S. Geological Survey 1977, "Handbook of Recommended Methods '
  for Water Data Acquisition,"  USGS Office of Water Data
  Coordinators, Reston, Virginia.

* Wood, W.W.,  1976 "Guidelines for Collection and Field Analyses
  of Ground Water Samples for Selected Unstable Constitutents,"
  U.S. Geological Survey Techniques for Water Resources,
  Investigations Book 1, Chanter D-2.

* "Standard Methods for the Examination of Water and Wastewater,"
  Current Edition

* "Suitability of Containers for Storage of Water Samples,"
  Water Resources Council Technical Paper  16, 1976.
                              -A. 6-

-------
* Morrison, R.D.,  and Brewer, P.E., "Air-lift Samplers for
  Zone-of-Saturation Monitoring." Ground-Water Monitoring
  Review, No. 1, Vol 1, p.52, 1981.

* Claassen, H.C.  "Guidelines and Technigues to Obtain Valid
  Ground-Water Quality Samples." Open-File Report USGS, 1978,
  54 pages.

* Keith, S.V., Wilson, L.D.  Sources of Spatial-Temporal Vari-
  ability in Ground-Water Quality Data and Methods of Control"
  Ground-Water Monitoring Review, Number 3, Volume 2, p.21, 1983.

* Hunkin, G.G.; Reed, T.A.; Branch., G.N, Some Observations on
  Field Exoeriences with Monitoring Wells," Ground-Water Sampling,
  Englewood, CA.;  Ground-Water Monitoring Review, No 1, Vol 1,
  p. 43, 1984.

* "Procedures for the Collection and Preservation of Ground Water
  and Surface Water Samples and for the Installation of Monitoring
  Wells," NTIS, DE84-007264, Bendix Field Engineering Corp.,
  Grand Junction,  CO. January 1984.


IV.  SAMPLE PRESERVATION AND STABILIZATION
     AND CHAIN OF CUSTODY              i

     Instructions

The handling of samples from.the sampling point to the labora-  •

tory is very important.  The preparer should define adequate

preservation, storage and transportation procedures and make

sure that documentation of the handling of the sample will

take place.  The plan should reguire a sampling label (see

Figure  1) and a bound laboratory log book to ensure that all

details associated .with the sampling, transportation and analyses

can be  retraced.  The sampler should also keep a weather-oroof

log book in which the relevant conditions of the sampling

methods are recorded.


Appendix B  includes an example of a chain of custody form as well
                              -A. 7-

-------
as information on preservation techniques.  This chain of custody



form is being used in EPA Region II for special samples to be used



for enforcement cases.





Sample wording of this section follows.



     Example



All samples must have a sampling label containing at least the



information shown in Figure 1.  This label must remain with



the sample throughout its collection,  storage/ transportation



and analysis.  When the sample^ (operator) reports the analysis



to the State, the sampling label should be referenced by its



"Sample ID No." and date of collection and analysis.  The



sampler and/or the laboratory should retain all sampling labels



or the information on them for three years or as required by



the State Quality Assurance Officer (SQAO).  Where samples may



be needed for legal .purposes, "chain-of-custody" procedures



(as defined by the enforcement.agency in the State and/or EPA)



must be used.





All laboratories performing analyses of samples must retain a



"laboratory log" as part of their records.  This log should



show the dates of sample receipt,  preparation, analysis and



results of the sample as well as other relevant information.
                              -A. 8-

-------
(NAME OF SAMPLING 'ORGANIZATION
SAMPLE DESCRIPTION

FACILITY: LOCATION:
WELLS:
DATES:
TIME:
TYPE OF FACILITY: SAMPLING LOCATION:
SAMPLE TYPE: PRESERVATIVE:
SAMPLING METHOD:
SAMPLED BY:
SAMPLE ID NO. :

LAB NAME


)







i

I
E
N
t
I
I
c











*
>
\
\.
*
r
































               Figure 1. Example of General Sample Label
NOTE:  To prevent problems if the label becomes detached from the
sample container, each should be marked with the same symbol.  The
container can be marked with indelible ink, and if used again, the
same number/symbol should be referenced on the label.  There are
certain types of label tape which are solvent resistant, can be ordered
in a roll, preprinted, and written on or stamped with indelible ink.
(Attachment "B" includes an example of a sample label.)
Instructions:
Sample description:
injection or
                     Whether this is a formation,
                     combined fluid sample, etc.
Facility, Location:  Self-explanatory
Wells:  Number of the well sampled, number of wells at the facility
Dates, Time, Type of Facility, Sampling location:  Self-explanatory
Sample type:  Batch, composite, etc.
Sampling method:  Air lift, bailer, swab, etc.
Sampled by, Sample ID No., Lab name, Remarks:  Self-explanatory (See
                                                                     text)
                                 -A. 9-

-------
V.   LABORATORY AND FIELD EQUIPMENT OPERATION AND CALIBRATION
     PROCEDURES

     Instructions

The preparer of the QA plan should include in it the appropriate

SOP and methods which will aid .in assuring that both field and

laboratory equipment are functioning properly. .


The plan should either include or reference the written

calibration procedures, the reference standard^,  and QC samples

used.  The use of these standards and samples is essential to

ensure system control and to measure operator performance.  A

description of a continuous review process over these control

systems should also be included.  These control functions should

include the internal laboratory activities.


Provisions for equipment maintenance, inspection, and testing

procedures must be implemented.  This is necessarv to ensure

that all facility equipment, servicing instruments, and any

other ancillary items are available, properly functioning and

maintained.  A description of how the responsible authority

monitors and controls this vital function shall be included.

Preventive maintenance and inspection procedures must cover

such diverse items as ion chromotographs, gas chromotographs and

other laboratory instruments, the facility high vacuum system,

the water distillation or deionization unit, electronic thermo-

meters, thermostats, pressure gauges and constant voltage

transformers.  An  item of special importance  is the academic
                              -A.10-

-------
training and/or work experience of the analyst needed to operate



the sophisticated equipment which may be required for some



analysis.





The State should develop a SOP for operation of field equipment



used to obtain preliminary water quality data.  Some such equio-



ment may include HACH Chloride kits, field conductivity meters,



portable pH meters, etc.  In the plan, the SQAOs should define



the applicability of the field kits from their experience and



manufacturers' literature.  SPA intends to provide further



guidance on this subject in the future.





A 'field.and laboratory equipment check vl ist( s ) must be developed.



The list(s) should include equipment operatinq parameters, such as



temperature, pressure, flow rate, voltage, etc.  In addition,'



to the check list(s), an equipment maintenance loq book containinq



calibrations and repairs must be established, and it must remain



with the piece of equipment in the lab, or in a safe location



for field equipment.  Maintenance schedules should also follow



manufacturer's recommendations.





Some of the references in Section VI ("Analytical Procedures")



include the calibration procedures and frequency for the equipment



used.  Each laboratory involved in the analysis of UlC-related



samples should have a record showing the dates of calibration



for the preceding three years or longer, as required by the SQAO.



This record should be available for inspection by the SQAO.










                             -A.11-

-------
To comply with this requirement,  it is necessary for all laborato-



ries doing tests required in the  UIC program to agree to:


     0    Retain calibration logs for three years;


     0    Retain laboratory logs  for three years;



     0    Retain sampling labels  or information on them for


          three years;


     0  '  Perform all analytical  tests in accordance with



          methods specified in this plan.




     Example



[Due to the diversity of equipment used in laboratories, it


would be impractical to present a representative example.  The
                                       i

State should prepare this section in accordance with the tvoe



of laboratory equipment it has available.  Field equipment,


especially the so called "kits",  should be periodically checked



aqainst more sophisticated lab equipment and calibrated every



time they are taken out.  For example, titration equipment


used for chloride determination should be checked against



amperometric titrators or more complex/accurate equipment.]




VI.  ANALYTICAL PROCEDURES



     Instructions


The preparer should use this section to give the operators the



range of acceptable procedures.  The laboratory analyst


should use EPA approved procedures and, when these are  not



available, the best available techniques  (see example) .
                              -A.12-

-------
The preparer of, the project plan should keep in mind that some



of the industrial injection streams may contain a wide variety




of compounds and unusually complex analytical techniques may




have to be used.






     Example



All water quality tests required in the UIC program must be



done in accordance with the permit or one of the following methods






1.   Organic and inorganic compounds, water quality measurements:




     40 CFR Part 136 "Guidelines Establishing Test Procedures



     for the Analysis of Pollutants," (as revised on October



     26, 1984 and January 4, 1985), §136.3, Table I.  This



     list references the accepted methods to analyze waters for



     organic and inorganic contaminants.  It also includes




     some physical tests (temperature, specific gravity, etc.).



     This document is available from the SQAO.






2.   Organic compounds, water quality measurements: "Methods for



     Organic Chemical Analysis of Municipal and Industrial



     Wastewater," EPA-600/4-82-057, July 1982,  available from the




     Center for Environmental Research Information (CERI)  26 West



     St. Clair Street,  Cincinnati, Ohio 45268,   Phone:  (513)




     684-7562 or FTS 684-7562.




     NOTE:  This technical report provides procedures that are



     as uniform and cost effective as possible  (with some
                             -A.13-

-------
     minor compromises)  for  the  analysis  of  some  organic

     pollutants.   It also  provides  references  that would be

     helpful to the analyst.

3.    Methods for  the analysis  of inorganic  compounds:   "Methods

     for Chemical Analysis of  Water and Wastes",  EPA-600/4-79-

     020, March 1979; available  from Center  for Environmental

     Research (CERI), 26 West  St. Clair Street, Cincinnati,

     Ohio  45268.  NOTE:  This reference  is  included in 1.

     above and provides  acceptable  analytical  methods.

4.*  Other analyses not  covered  above should be performed in

     accordance with the most  recent edition of "Standard

     Methods for the' Examination of Water and  Wastewaters" :

     American Public Health  Association,  American Water Works

     and the Water Pollution Control Federation.   Other analvses

     not covered above should  be performed  by  the best available

     methods.

 5.* For Class II programs,  analyses which  require a high degree

     of accuracy must be done  as explained  above or in accordance

     with "API Recommended Practice for Analysis of Oil-Field

     Waters" API RP 45.


Note:  Techniques already  approved  and used for other orograms

(RCRA, CERCLA, NPDES, PWSS,  etc.)  should  be deemed acceptable

for the same type of analyses.
* The preparer of the plan should make it clear that the use of
  the last two references above (Nos. 4 and 5) is adequate
  until EPA approves specific tests to be used.
                             -A.14-

-------
VII. DOCUMENTATION, DATA REDUCTION, VALIDATION AND REPORTING

     Instructions

The QA project plan should include detailed documentation of

all samples and methods of collection.  The preparer of the QA

plan should prepare SOPs in which the type of record to be

maintained and the method of storage are defined.


The preparer should also include those mathematical and/or

statistical procedures which are used by the' generators

of data to convert raw data into its final form.  Cross-checkinq

procedures should also be indicated.  If the data are to be

entered into a computer system, 'the SOP should be described.


Validation procedures can be incorporated into the State's data

gathering effort by analyses of split samples, and reolicate

sample analyses, spiked addition recoveries and  intra and

inter laboratory comparisons.  Validation procedures are

described in the EPA document  "Calculation of Precision', Bi-as

and MDL for Chemical and Physical Measurements"  (March 30,

1984) which is available from  the RQAOs.


The State Quality Assurance Officer (SQAO) should prepare

written instructions to validate data.  Examining data for

outliers* (as determined by the SQAO) should be  done routinely.
*Data which are significantly different  from  the maioritv  of
 the other results, as determined by valid statistical  techniques
                             -A.15-

-------
An adequate matrix presentation or other graphic display of



the data can help to identify outliers..  There are a number of



statistical methods for the identification of outliers. 'One



which is widely used is the Standard Deviation method.  The



SQAO should consider the establishment of a formal labora-



tory certification program.  This could be done either by the



incorporation of UIC related laboratories into other certifi-



cation programs such as the one for PWSS or the creation



of a new program which could be expanded in the future to



include all State environmental programs.  The ROs must use



labs certified for other programs (NPDES, PWSS), if available



and applicable, to analyze samples taken to supoort DI programs



The States should also use these labs where applicable.





The State or RO should determine its needs in this area and



include them in the project plan.  The RQAO should be consulted



for assistance.





VIII. INTERNAL QUALITY CONTROL CHECKS



     Instructions



Checks of the data must be done as explained in standard EPA



Quality Control publications (see references below) or by



using other reliable methods.  The establishment of control



charts for instrument calibration is an  important  Internal



Quality Control Check.  Sample wording to this effect  is shown



in the following example.
                             -A.16-

-------
     Example                 ,



All laboratories performing analyses of UIC samples should




maintain a program to frequently check their results.  This



could be done by selecting representative samples of analytical



results for the particular area or type of injection fluid.




Irregular or unusual data should be investigated.  A regular



program of instrument calibration should be developed and



followed.  Quality Control criteria are expl.ained in "Handbook




for Analytical Quality Control in Water and Wastewater Laboratories",



EPA-600/4-79019, March 1979, available from the Center for



Environmental Research Information (CERI), 26 West St. Clair




Street, Cincinnati, Ohio 45268 Phone:  J513) 684-7562 or FTS



684-7562.               ' •                    '



NOTE:  This publication provides information on quality control




measures such-as control of the quality of • the reagents, standardi-



zation of titrants, monitoring of instruments' response, etc.






Practices such as those listed below must be implemented in



laboratories to ensure adequate quality control.






1.  Standard Curve Data - Where applicable, standard curves




    must be checked and calibrated at  least monthly.  This



    requirement applies to atomic emission, ion chromatographic



    and colorimetric methods.  Atomic  absorption curves should



    be obtained daily.
                             -A.17-

-------
2.   Standardization of Titrants  -  When standard solutions


    (titrants)  are used for quantitative analyses to determine


    the concentration of pollutants,  these  titrants must be


    standardized monthly or more frequently if the method


    requires it.  Traceability  to  the National Bureau of


    Standards should be established for all reagent chemicals


    used as standards in the calibration of equipment.



3.   Electrochemical Methods - Electrochemical instruments must


    be standardized each day (or shift)  in  which they are used.

    These standardization procedures  can be found either in the


    methods text used or manufacturer's  instructions for the

                                      •V.
    instrument.'



4.   Analytical  Balances - Because  the balances are the primary


    standard in the laboratory,  care  must be taken to ensure


    their accuracy.  Each balance  should be serviced annually.


    In addition, Class 'S1 weights must be  weighed quarterly to


    document accuracy or to detect problems so corrective


    action can be taken.



5.   Duplicate Analyses - Duplicate analyses must be done on at


    least ten percent (10%) of  the UIC samples received.  If there


    are less than 10 samples in  a  batch, 1  duplicate analysis


    should be done.



    Results of  these analyses must fall within the acceptance
                              -A.18-

-------
    limits for precision defined in the "Precision and Accuracy

    Protocols/Limits," Section XI.


6.  Spiked Sample Analyses - Spiked sample analysis allows the

    laboratory personnel to evaluate the accuracy of the sampling

    method performed on a routine basis.  A spiked sample is

    created by adding a known amount of the constituent being

    analyzed to a representative portion of the oriainal sample.

    The amount of spike should be approximately equal to the

    concentration of the analyte in the original sample.  At

    least 10% spikes or 1 per batch (if less than 10 samples

    per batch) must be run.
                                       s.

    The Regional Quality Assurance Office will make documents

    available outlining the instructions for preparation of

    spiked samples and to evaluate the results of such analyses.

    Section IX outlines how to obtain "QC Samples" to assess

    performance.

7.  Preparation of a Quality Control Manual (QCM) - Each laboratory

    should prepare a QCM to document the responsibilities of

    the laboratory personnel.  Also, all QC checks should

    include acceptance/rejection criteria.


IX.  PERFORMANCE AND SYSTEMS AUDITS

     Instructions

The SQAO should make periodic visits to laboratories doing

analyses of UIC fluid samples.  These visits may be done as




                            -A.19-

-------
part of the ' evaluation audits for several programs (e.g.,

NPDES, PWSS,  RCRA, etc.).  The visits could .include evaluation

of laboratory quality control procedures as well as their

interface with sampling practices.  SQAO visits should be

included in program work plans following recommendations by the

RQAO.  The laboratories should also analyze Q.C. samples

periodically.  These samples will be provided by EPA and made

available to laboratories through the SQAOs .  These samples

would be reflective of everyday samples received in the laboratory

and the concentrations would be known to the SQAO.  The SQAO

should request these QC samples from the RQAO.  Appendix "D"
includes an order form to obtain Q.C. Samples.  This form should
                                       V
be sent to the RQAO.


The SQAO can also recommend candidates to the RQAO for the

"Performance Evaluation Program." The Performance Evaluation

Program sends "blind" samples to the participating labs.  The

labs perform. the analysis and send the result to the Environmental

Monitoring and Support Laboratory (EMSL).  EMSL evaluates the

results and informs the RQAO.  Participation in this program

is limited.


     Example

All laboratories and other parties participating in the collecting,

transporting and analyzing of chemical samples for the UIC  program

are subject to audit visits by the State QA Officer.  These
                             -A.20-

-------
visits would concentrate on assuring that the activity being



performed is in accordance with the State's QA plan 'and scientific



principles.




The SQAO should provide the laboratories with "QC Samples,"



for analysis and reporting of results.  Evaluation would


indicate to the lab and the SQAO the quality of the work done



in the lab and any shortcomings.




The QA should pursue corrective action, if necessary and help



any participant requiring assistance to improve performance.



Please refer to the front of this plan for the name and address



of the State Quality Assurance Officer.




X.   PREVENTIVE MAINTENANCE            -v



     Instructions



The preparer of this plan should address procedures for preventive



maintenance and associated documentation.   The plan should at



least call for laboratories and field units to perform the
                                                      «

maintenance required in the operational manuals for the equipment


used.  Another important consideration would be the. availability



of critical spare parts for the equipment.  The SQAO may want



to require a list of such parts from each  of the participating



laboratories.



     Example



[All laboratories and field units participating in the collection



of environmentally related data for the State UIC program should



have a preventive maintenance program.  A  log must be kept






                             -A.21-

-------
documenting the maintenance.  It would be a good practice



to have.a list of critical spare pa/ts available to the SQAO.]'





XI. PRECISION AND ACCURACY PROTOCOLS/LIMITS



    Instructions



Estimates of data precision and accuracy must be developed in



accordance with EPA guidelines entitled, "Calculating Data



Quality Indicators" and "Establishing Achievable Data Quality



Goals".  These guidelines and updates are available from the RQjjpOs





Laboratory personnel should be consulted with regard to the



selection of analytical methods.  Once the methods are selected,



the detection, precision, and accuracy requirements for these



should be developed and then incorporated into the QA project



plan.  Along with each requirement,  there should be a protocol



to monitor whether these requirements were met.   For example,



intra-laboratory precision .can be monitored by using replicate



samples.   Accuracy can be monitored  with the use of field



blinds, spikes, surrogate spikes, National Bureau of Standards'



Standard Reference Materials (SRMs),  EPA QC reference samples,



etc.  Wherever possible, criteria should be set for the "total



measurement".  This could be accomplished, for example, with



the use of field spikes and replicate samples.  As a minimum,



acceptance criteria should be within plus or minus two standard



deviations of the precision and accuracy data published for



the parameter by EPA.
                             -A.22-

-------
The written and other material mentioned above are available



from the Regional Quality Assurance Officer  (RQAO).





XII. DATA REPRESENTATIVENESS COMPARABILITY AND COMPLETENESS



     Instructions



Data "representativeness" is a qualitative element which refers



to a sample or a group of samples that reflect the characteristic



of the waste stream at the sampling point.   It also includes



how well the sampling point represents the parameters which are



under study.  For example, the representative point to sample



the injection fluid is at the well head.  The permit may specify



sampling points at a facility.  The preparer of the project



plan should provide some guidelines on the proper sampling



location in accordance with local treatment  and construction



practices.  A SOP can be developed for this  purpose.





"Comparability" is also a qualitative characteristic which must



be considered in QA program planning.  Depending on the end use of



data, comparability must be assured for the  project in terms of



sampling plans, analytical methodology, quality.control, data



reporting, etc.  For example, in the example above for



representativeness, in order to have comparability, all samples



must be taken from the same location in the  waste stream and at



the same relative time in the process.  Another comparability



issue would be that data should be reported  in comparable



units.
                             -A.23-

-------
"Completeness" is defined as the amount of valid data obtained

from a measurement system compared to the amount that was

expected and needed to be obtained in meeting the project data

goals.  The determination of data completeness is the responsi-

bility of the sampler (reporting party),  as determined by guidance

and requirements specified by the SQAO.  For examole, if un-

expected events, such as breakdown of equipment, weather conditions

and poor quality of reagents, caused 70%  of the reauired test

to be deleted, the reporting'party (operator) should qualify

the results obtained.  This by no means releases the operator

from the reporting requirements under the UIC proqram.

                                       V
XIII.  CORRECTIVE ACTION               '      -

       Instructions

Whenever data are generated, analyzed and reduced there is a

possibility that some of them may not meet a limit for acceptability

This limit would have been established in accordance with the needs

of the UIC program in the State.  This limit would indicate the

point at which corrective action is required.


The preparer  of the UIC-QA orojet plan should investigate, analyze

and establish the limits for data acceptability beyond which

corrective action is required.  He/she should also offer some

examples of what corrective action can be taken to solve the

problem and offer assistance on a case-by-case basis.
                             -A.24-

-------
Corrective action may also be required as a result of State or

EPA performance audits, system audits, quality control samole

results and laboratory comparision surveys.  An example of the

type of corrective action flow chart that should be developed

follows.

Example
                                       CORRECTIVE ACTION
                                     + 	 	 	 	 	 	 	
 Quality
 Assurance
Management
                     Field and
                     Laboratory
                     Measurements
                            Measure-
                             ment
                            Data
                    Does data
                    exceed con-
                    trol or  fail
                    data Quality
                    Criteria
             YES |Data is    |
             	> flagged and |
                  reported to|
                  management |
                           No
                     Data base
                     and reports
Corrective Actions  Include:
        Revision of Quality Assurance Criteria
        Recalibration or Repair of Equipment;
        Resampling; Revision of Measurement
        Procesures; Training of Personnel
XIV. QUALITY ASSURANCE REPORTS

     Instructions

The preparer of  this plan  should  obtain  agreement  from  the  SQAO
                             -A.25-

-------
and the Director of the UIC program (State or RO) as to the'


schedule for reporting.  A logical alternative would be to


integrate QA reporting with annual UIC reporting by the State


or to consolidate all QA reports for chemical tests for all


environmental programs administered by a single agency.


The report should indicate to EPA that the State is applying


adequate QA techniques to aAl its environmentally related .


measurements.  The State should agree to report to EPA on:


     o  Program highlights;


     o  Approximate number of participating laboratories;


     o  Types of fluid quality tests performed;


     o  Future plans;


     o  Training;


     o  Number of laboratories visited by the SQAO;


     o  Evaluation of performance audit samples.


The reports should be sent to the Regional UIC program office
         »

and the RQAO.  Ir order for the SQAOs to obtain the information


required above, they should ask participating laboratories to


report their activities.  These reoorts should contain at


least the following elements:


     o  Name and location of unit;


     o  Types of analysis done and samples taken;


     o  Number and types of tests done in the reporting period;


     o  Future plans;


     o  Training;
                             -A.26-

-------
     o  Evaluation of performance audit studies.



The laboratory reports should be sent to the SQAO (see beqinninq




of plan) no later than January 31 of. each year for the preceding



year.  The SQAO, in turn, would send the summarized State/Aqency



UIC report to the RO no later than February 28.






XV.  STANDARD OPERATING PROCEDURES (SOPs)
     Instructions



Standard Operating Procedures (SOPs) are very effective in



assuring that certain complex and repetitive tasks are done in



the same manner every time.  The laboratories, sampler^ and/or




operators should pjrepare' SOPs.   The State should decide which



of these SOPs should be sanctioned by the SQAO.






The SOP should provide step-by-step instructions on the handlinq



of the sample, chain of custody, preservation and analytical



procedures, if warranted.  It should be easily understood by



the user and available at each working station.  Appendix D




includes an SOP which was prepared to test for sulfides in



ground water.  It has been modified from the last reference




in Section III ("Sampling Procedures").



   Example



An SOP should be prepared by the operators, samplers and



laboratory personnel for each procedure that is done repeatedly




or routinely.  The SOP should be written in simole terms as to




be understandable to the person doing the work.
                             -A.27-

-------
The operator may develop as.many SOPs  as  needtl,  however, all



SOPs used to develop UIC reporting  data should be available for



inspection by the SQAO.   The  SQAO will, at the request of the



operator, provide guidance  on the preparation of  specific



SOPs.  All SOPs should follow scientific•and EPA-approved



methods and procedures,  as  well as  equipment recommendations



when applicable.
                             -A.28-

-------
                ATTACHMENT B
  I  Examples of Completed Sample Labels

 II .Standard Procedures for the Collection of
     Ground-Water Samples from Residential and
     Municipal Wells

III  Containers, Preservation Techniques and
     Holding Times (with summary page)

 IV  Chain of Custody Form

  V  Sampling, Preservation and Storage Considerations
     for Trace Organic Materials (Including Volatile
     Organics)

-------
 Example,of Complete Sample  Label  (1)   .


                         (NAME OF SAMPLING ORGANIZATION)


 SAMPLE  DESCRIPTION Formation
 STATE:  MT             COUNTY:
FACILITY OR  FIELD:   Cedar Creek Anticline
 LEGAL LOCATION;    SU.  SE. Sect. 19.T»N. R62E
 NAME OF  SAMPLE  SOURCE:  Carter 011
TYPE  OF  SOURCE:  Potential Oil Reservoir
.GEOLOGIC  SOURCE:    Darwin                 SAMPLE INTERVAL:  8320-8349 *
DATE:   11/U/41                      TIME:
SAMPLING  LOCATION:   Insitu/Drill Stem       SAMPLE TYPE:  Formation Water
FIELD TEMP OF  SAMPLE: 153°F	FIELD PH:
Remarks:  Drill  stem test  (DST) flowed for 11/2 hours sample appears to be
          contaminated with mud filtrate.  See completion report for details
          of  DST (attached).
* Depth below ground surface
                                 -B.I-

-------
Example of Complete Sample label (2)


                         (NAME OF SAMPLING ORGANIZATION)


SAMPLE DESCRIPTION   Produced Water
STATE:   WY             COUNTY;    Carbon
FACILITY OR FIELD:   Vertz 011  Field
LEGAL LOCATION:    Section 6. T26N,  R89W
NAME OF SAMPLE SOURCE:  Vertz #47
TYPE OF SOURCE:   Producing 011  Well
GEOLOGIC SOURCE: Tensleep, Amsden, Darwin, and Madison


SAMPLE INTERVAL: Multiple perforation from 5867 .to 6587


DATE:  12/28/81                 	TIME:  2:30 prc
SAMPLING LOCATION:  Heater Treater	SAMPLE TYPE: Formtion Water


FIELD TEMP OF SAMPLE:  60°F                 FIELD PH:     7.2


PRESERVATIVE:                              	
Conments:  Heater Treater (HT) 1s receiving water and oil only from well #47.
          HT 1s pumped every 4-5 days.  HT was pumped out 4 days prior to
          sampling (see attached sampling location description).
* Depth below ground surface
                                  -B.2-

-------
           STANDARD PROCEDURES FOR THE COLLECTION OF
             GROUND-WATER SAMPLES FROM RESIDENTIAL
                      AND MUNICIPAL WELLS*
INTRODUCTION

     This document outlines procedures for the collection of

representative ground-water samples from residential and

municipal wells.  It specifically addresses monitoring of ground-

water quality in relation to the subsurface injection of salt

water.  As such, the procedures presented address only inorganic

parameters and do not consider the more difficult task of

sampling for organics.

     The collection of representative ground-water samples is

neither a straightforward or easily accomplished task.  In

fact, many feel that .it. is impossible to collect a ground-water

sample that is truly representative of aquifer water guality

conditions due to changes which may occur during sample

collection, preparation,  preservation and storage prior to

analysis.  However, certain procedures can be adopted that will

maximize the integrity of the sample.  This document presents

in a step-by-step manner procedures which will ensure not only

the collection of ground-water samples which are representative

as possible but also allow for maximum efficiency in sample

collection.  The following procedures are divided into five

sections.  These are:

     1.  Obtaining background information.

     2.  Obtaining laboratory information and materials.

* This material was prepared for EPA Region V under contract
  with Engineering Enterprizes, Inc., of Norman, OK.
                             -B.3-

-------
     3-.   Sample collectio..,  preparation,  preservation and


         storage.


     4.   Field measurements  of  in  situ  parameters.


     5.   Chain of  custody.procedures.




1.  OBTAINING BACKGROUND INFORMATION


     .The necessary first step  in the  collection of  ground-water


samples is to obtain background information  on the  liquid


suspected of affecting the ground-water quality and specifics


of the area and wells to be  sampled.  This  information can then


be used to design  a sampling program  which will provide the


maximum efficiency of sampling  and improve  the quality of the


collected data.  Information to be obtained  during  this first

                                       i.

phas'e includes:


     o  Identification of parameters  for  analysis;


        For salt water waste streams, the principal parameters


        of interest are pH,  specific  conductance,  alkalinity,
                  *                                              '
                                   o
        Ca, K, Mg, Na, Cl, and  S04- .   Additionally, salt


        water may  contain various  trace metals.  Collection of


        samples for these metals will affect the sampling


        protocol with respect  to preparation and preservation


        of the samples.  If  possible, any other constituents


        in the injected stream  should be  identified in advance.


        This will  allow for  development of  an appropriate


        scheme for preparation  and preservation of  the samples


        for metal  analysis  if  necessary.  The procedures discussed


        in the following sections  will  differentiate between




                            -B.4-

-------
   the principal parameters of the wastes and the


   metals.




o  Scheduling




   Proper scheduling of sampling periods for residential


   municipal wells is important in obtaining representative


   samples.  It is important that a municipal well be


   sampled while it is pumping, because water that has


   been held stagnant in the well casing will not be


   representative.of the aquifer being sampled.  Be sure


   to collect samples from residential wells when the


   water is at equilibrium with the aquifer.  This will
                                  ».

   depend upon the water usage'at the residence.  It is


   best not to take a sample immediately after heavy


   usage (after morning showers), or after a long period


   of little or no usage (usually late to mid-afternoon).


   When sampling a group of residential wells in a particular


   area, be sure to sample them over a relatively short


   period of time.  When collecting more than one round of


   samples, make the sample periods consistent with respect


   to the time of day the samples are taken.




o  Accessibility


   When sampling . residential and municipal wells, site


   accessibility is normally not a problem, especially since


   only a limited amount of equipment has to be brought




                        -B.5-

-------
on-site.  However, accessibility of the well can cause



major problems.  Before attempting to sample a residential



well, determine if the well is physically accessible



for sampling.  For municipal wells, check to see if a



spigot or valve is available from which a sample can



be taken.  In both cases, be sure that the sampling



port or spigot is positioned as close to the wellhead



as possible and be-fore any type of treatment unit,



such as a water softener or filtration.





Materials



•Contact the owner or operators of the wells to determine



what tools, valves, hoses, etc., will be needed.  Wrenches



may be needed for opening and closing- faucets or spigots.



Often ports or valves on municipal wells may be too



large and their use may result in a high volume flow



which will make sampling difficult.  In this case, it



will be necessary to reduce the flow by using appropriate



fittings.  Obtain information from the operator on the



size of the fittings required and on accessibility of



the sampling spigot.  It may be convenient to attach a



section of hose to the line, especially in very cramped



quarters.
                     -B.6-

-------
2.  OBTAINING LABORATORY INFORMATION AND MATERIALS






     The importance of communicating with laboratory personnel



responsible for analysis of the samples prior to sample collection




cannot be overemphasized.  They can be an important source of



information and materials if they understand the specifics of



'the sampling program.  This will not only improve the efficiencv



of the program, but also the accuracy and completeness of. the



results.  It will be necessary to establish with the laboratory




the procedures and analyses which you wish to conduct.  The



laboratory personnel may able to lend guidance or give suggestions




pertaining to particular problem areas which may develop  and



provide written instructions from the laboratory for any  nonroutine



procedures pertaining to sample preparation, preservation and




storage.




     o  Sample bottles .



        Once the  laboratory knows the analyses to be conducted,




        they will be able to supply the appropriate bottles



        and preservatives or inform you as to what you



        should obtain.  The size of the bottle will depend




        on the analysis to be conducted and the analytical



        methods to be employed.  Be sure to collect



        sufficient samples for duplicate analyses should  .




        they be required.  The type of bottles will depend



        upon the  suspected constituents.  For the



        constituents of salt water, linear nolyethelene
                              -B.7-

-------
        bottles are  best.  Wide-mouth bottles  will  provide



        easy access  during both  sampling  and analysis.   The



        amount of  the  sample  needed varies  according  to the



        method to  be used  in  the analysis and  the



        preservation methods.





     o  Sample Care



        In choosing  a  laboratory it may be  necessary  to weigh



        the -efficiency of  using  one near  the sampling site



        versus the greater degree of reliability of a well-



        known but  distant  laboratory to which  samples must



        be shipped.   If the  latter option is used,  make sure



        that the logistics of  transport,  shipping,  and  pickup



        have been  fully worked out sov that  the chain-of-custody



        is not compromised and that sample  preservation times



        are not exceeded.





3.  SAMPLE COLLECTION, PREPARATION, PRESERVATION,  AND STORAGE





     One important goal of sample collection  is to  obtain a



representative sample, of aquifer water by minimizing  changes



that may occur in  the  field  while the sample  is collected,



preserved and stored.   Seemingly small departures  in collect-



ion techniques can significantly affect  the results of the



tests.  Care in handling and cleanliness  must  be maintained



from the time the  sample is  taken until  it  is  delivered to the



laboratory.  Consistency is  the  key  to quality control.  The



following outlined procedures, if adhered to,  should produce
                             -B.8-

-------
samples that are as close as practically possible to representative



aquifer conditions.





     o  Well Evacuation



        As previously mentioned, it is important to remove



        stagnant water from a well that has not recently



        been pumped prior to taking a sample.  This is



        because standing water that has been exposed to



        the atmosphere or has been, in contact with the



        well casing or pump, even for short periods of



        time, will react with these substances, and its



        chemical composition will, be altered.  Contact with



        air will affect pH, alkalinity* and specific con-



        ductance. • Changes in these parameters will in turn



        oxidize certain metal constituents and cause them



        to precipitate.





        The amount of water that should be removed from the



        well is dependent on the diameter and depth of the



        well, the depth to ground water, and the yield of the



        well.  A general rule is to evacuate three to five



        times the volume of water from a well which has been



        inoperative.  To assure adequate evacuation it is a



        standard practice to measure pH, conductivity and



        te'mperature to insure stabilization.  The measurement



        of the well volume and water level should be conducted



        in the following fashion:



             Measure well casing inside diameter.
                             -B.9-

-------
        Determine the  static  water  level.   This

        should be expressed as  feet below  ground

        surface or below casing elevation  depending

       ' upon information available.  (Note that the

        water indicator  used  may have  to be cleaned before

        use in each well.)
                                                       /
        Determine the  total depth of the well.

     -  Calculate the  number  of linear feet of

        static water (difference between static water

        level and total  depth of well).

        Calculate the  static, volume.

The sample should.be taken  as the water  level is rising

in the well bore, i.e.,  as  the  well is filling with fresh

water from the aquifer.



Sampling from residential/municipal wells  can be a very
                                     *
straightforward procedure if  the well  is pumped regularly.

For most residential wells, water should be run for two

minutes prior to sample  collection.  In  most cases, residential

samples can be taken outside  without entering the house.

Besides being convenient, outdoor faucets usually supplv

a more representative sample  by intercepting water from

the well before it has entered the water tank or water

softener.  The faucet should  be checked, however, to

ensure that it is, in fact, the most direct outlet from the
                        -B.10-

-------
Since municipal wells are high volume water producers,



there is no necessity for evacuating the well.  However,



the lines from the wellhead to the sampling port must be



evacuated.  For most residential and municipal wells, the



samples generally can be collected either directly into



the sample bottles, or in cases where sample filtration



is called for, samples can be placed directly into the



filter apparatus.







o  Sample Storage



   Choosing a sample container is of primary importance.



   The material of construction must be nonreactive with



   the sample and especially with the particular parameter



   to be tested.  In general, there are three types of



   construction materials: plastic, glass, and teflon.



   Samples collected for metals and general water quality



   parameters are stored in plastic bottles.  Samples



   collected for organic analysis are routinely placed in



   glass bottles of various types and sizes depending



   upon the particular analysis to be conducted. In most •



   cases, bottles will be supplied by the laboratory



   conducting the analysis.
                        -B.ll-

-------
o Rinsing





  Just prior to filling,  the sample containers are rinsed



  with the water to be sampled.  Enough water is run into



  the container to rinse  the inside and is then dumped



  out.  The lid is rinsed also.  Care is taken not to rest



  the lid on the ground or touch the inside of the lid



  after rinsing.  Rinsing is, of course, omitted if the



  container is pre.treated with preservative.  Care should



  be taken not to come in contact with the sample fluid.





o  Filling Sample Containers



   Bottles should be filled quickly to minimize mixing  •



   with air.  It is helpful to allow the water to overfill



   the container to prevent small bubbles from forming.





o  Filtering



   Whether or not a sample is to be conditioned prior to



   preservation and storage depends upon the analyses



   to be conducted and the type of sample collected.



   Whether or not .a sample is to be filtered will depend



   upon the analyses to be conducted.  If dissolved



   metal constituent concentrations are to be measured,






                        -B.12-

-------
ground-water samples must be filtered in the field


immediately after collection.  Ground waters tend to


be in a more reducing environment than they would be


under standard atmospheric conditions and, as such,


precipitation will occur if the sample is not filtered


and preserved with nitric acid immediately after withdrawal


                         /
Filtering is necessary if the sample is to be analyzed


for dissolved1 constituents.  It is not required if a


total analysis of the sample will be performed.  Certain


metals are adsorbed by suspended sediments and if


filtering does not take place they tend to raise the

                               .\. •
concentration of these constituents in the analysis.


The ions, Ca+2, K+, Mg+2, Na+, Cl~ and S04~2, tend to be


relatively s.table; therefore, sampling for their presence


does not require filtering.  However, for certain


sophisticated testing methods the sample should be


filtered prior to analysis.  Filtering through a 0.45


micron pore size membrane should be performed if the


elements Fe, Mn, Mg, Cd, Cu, As, Se, or B are' involved.


This is done with a device called a vacuum filter.  A


funnel may be helpful to direct the flow of water  into


the filter unit.  Once the sample has been filtered,


it can be transferred to the sample container.  Before


taking the next sample, the filter unit is rinsed with


a very dilute acid solution, followed with deionized


water.  Also, a new filter paper is inserted.





                     -B.13-

-------
o  Sample Preservation



   Complete preservation of  any sample  is  difficult because



   it may be impossible to completely stabilize every



   constituent within a sample.  At best,  preservation



   techniques can only retard the chemical and biological



   changes that continue after the sample  is  removed from



   its environment.   If the  sample environment is significantly



   different from atmospheric conditions,  the sample may



   undergo changes which will render it nonrepresentative



   of its original environment.  Methods of preservation



   are relatively limited and are intended to retard



   biological action, retard hydrolysis of chemical compounds



   and complexes, and reduce volatility of constituents.



   Generally, preservation methods are  limited to pH



   control, chemical addition, refrigeration, and freezing.



   Table 1 in Attachment D gives recommended  container types,



   preservatives, and holding times for a  variety of standard



   water chemical parameters.





   Sample preservation should be performed in the field



   immediately after sample  collection and preparation.



   In many cases where pH control or additions of



   reagents are required, separate bottles and chemical



   preservatives may be supplied by the laboratory.  In



   other cases, the reagents or preservatives may be



   placed in the sample bottle prior to delivery to the site.
                        -B.14-

-------
4.  FIELD MEASUREMENTS OF IN SITU PARAMETERS






     The parameters of temperature, pH, Eh (redox potential),



and EC. (electrical conductivity) begin to change rapidly as



soon as the sample is removed from the well.   In some cases,




it may be desirable to perform in situ measurements before the



samples are brought to the lab.  Field measurements of Eh and pH



are made in a closed, air-tight flow-through cell whenever




possible.  The closed cell prevents the sample from reacting



with the atmosphere and a stirring mechanism ensures that the



sample is consistent throughout.  Numerous devices for measuring




field parameters are available from various manufacturers.




Follow the equipment manual for the particular piece of equipment



you are using.  The required equipment is vulnerable to precontami-




nation and physical abuse;, thus, it is important that meters



for measuring pH, Eh, and EC are calibrated periodicallv as



recommended by the manufacturer with the appropriate liauid



standards.  Allow sufficient time for the electrode to stabilize



before recording the measurement.  The probe or thermometer



should be cleaned and rinsed with distilled water following




each use.






5.  CHAIN-OF-CUSTODY PROCEDURES




     In any activity that may be used to support litigation,




the sampler must be able to provide the chain-of-possession










                             -B.I 5-

-------
and custody of any samples which either are offered as evidence  or



for which the samples for test results are introduced as evidence.



Written procedures must be available and followed whenever



evidence samples are collected, transferred, stored, analyzed



or destroyed.  The primary objective of these proceduress is



to create an accurate written record which can be used to



trace the possession and handling of a sample from the moment  of



its collect i.on through analysis and its introduction as evidence.
                         i


     A sample is defined as being in someone's "custody" if:



     -  It is in one's actual possession; or



        It is in one's view, after beinq in one's



        physical possession; or-



        It is in one"1 s physical possession and then locked



        up so that no one can tamper with it; or



        It is kept in a secured area, restricted to



        authorized personnel only.





     The number of persons involved in collecting and handling



samples should be kept to a minimum.  Field records should  be



completed at the time the sample is collected and should be



signed or initialed, including the date and time, by the samnle



collector(s).  Field records should contain the  following



information:



    • -  Unique sampling or log number;



        Date and time;



        Source of sample  (including name, location  and samole



        type);




                             -B.16-

-------
        Preservative used;



        Analysis required;



     -  Name of collector (s);



        Pertinent field data (pH,  DO, chlorine residual;



        specific conductance, temperature, redox potential, etc.);



        Serial number on seals and transportation cases.





     Each sample must be labeled using waterproof ink and sealed



immediately after it is collected.  Labels should be filled out



before collection to minimize handling of sample container.



     The sample container should then be placed in a transportation



case along with the chain-of-custody record form, pertinent



field record, and analysis request form as needed.  The



transportation case should be sealed or1- locked.  A locked or



sealed chest • eliminates the need for close control of individual



samples.  However, on those occasions when the use of'a chest is



inconvenient, the collector should seal the cap of the  individual



sample container with tape in a way that any tampering would be



easy to detect.



     When transferring the samples, the transferee must sign



and record the date and time on the chain-of-custody record,



which should have been prepared according to enforcement



requirements.  Custody transfers made to a samole custodian in



the field should account for each sample, although samples may



be transferred as a group.  Every person who takes custody must



fill in the appropriate section of the chain-of-custody record.



To minimize custody records, the number of custodians in the



chain-of-possessidn should be minimized.





                             -B.17-

-------
                        Table  I.   Required Containers, Preservation Techniques, and Holding Times
CO
I
Measurement
Table/Par aneter
I A Bacterial Tests
Goliform, fecal
and total
Fecal streptococci

IB Inorganic Tests
Acidity
Alkalinity
Ammonia

Biochemical oxygen
demand
Biochemical oxygen
demand carbonaceous

Bromide


Chemical oxygen
Container Preservative

P, Gool, 4°C
0.008% Na2S2Q25
P, G Gool 4°C
0.008% Na2S202

P, G Gool, 4°C
P, G Gool, 4°C
P, G Gool, 4°C
U2SO4 to pll<2
P, G ,. Gool, 4°C

P, G Gool, 4°C


P, G None required

.
P, G Gaol, 4°C
Maximum
Holding Time

6 hours


6 hours

14 days
14 days
28 days

48 hours

48 hours


28 days


28 days








•





>
'4
>
Q
ft
•z
H
               danand
to pll<2

-------
Table I. Required Containers, Preservation Techniques,  and Holding Times
Measurement
Table/Parameter
IB (Cont.) Inorqanic Tests
Chloride
Chloride
residual
Color
Cyanide, total and
amenable to chlori-
nation
Fluoride
Hardness
Hydrogen ion (pH)
Kjeldahl and organic
Nitrogen
Metals
Ch rani urn VI
Mercury
Container Preservative
P, G None required
P, G . None required
P, G Cool 4°C
P, G Cool 4°C
NaOH to pH> 12
0.6g ascorbic acid
P None required
P, G HNC>3 to pH<2
P, G None required
P, G Cool, 4°C
H2SO4 to pH<2
P, G Cool, 4°C
P, G HNO3 to pH<2
Maximum
Holding Time
28 days
Analyze
immediately
48 hours
14 days6
28 days
6 months
Analyze immediately
28 days
24 hours
28 days

-------
Table I. Required
                                               s,  Preservation Uniques, and hiding
             Measurement
            Table/Parameter
IB(Cbnt.)   Metals,
—          except above
                        Container
                                           Preservative
                            P,
                                                 to pH<2
                                                                                           Maximum
                                                                                         folding Time
6 nonths

Nitrate
1
w
g Nitate-nitrite
i
Nitrite

Oil and grease
Organic carbon

Orthoptosphate
Oxygen, Dissolved
Probe
Winkler

P, G O^01 4°C
Gool 4°C
p G HZS04 to PH<2
1 9
P, G Cbol, 4°C
r*
Gool 4°C
P, G HZS04 to pH<2
P r 0»lf 4°C
HC1 or I12S04 to pH<2
c Filter immediately
' Owl, 4°C
r, Bottle None required
and 'PJp

c; IV >t tie fix on site and
itnr.,. ,i,D[) store in dark
(-.only OTJO.I, 4°C
48 hours
28 days

48 hours
28 days

28 days

48 hours

Analyze
immediately

8 tours
28 days
               Phenols

-------
                          Table  I. Required Online,:,. Preservation Uniques,  and mldi* «
                   Measurement
                  Table/Par ame tier
                                Container
                                                   Preservative
      IB (Oont.)  Phosphorus
                  (elemental)
                  Phosphorus, total
NJ
I-"
I
Residue, total

Residue, Filterable

Residue, Nan-filterable(TSS)

Residue, settleable

Residue, volatile

Silica

Specific conductance

 Sulfate

 Sulfate





 Sulfite


 Surfactants

 Temperature


  Turbidity
                                                        P,  G


                                                        P,  G

                                                        p,  «


                                                        P, G
                                                                        .
                                                                       sodium hydroxide

                                                                       to pH>9
                                                                            required
OX)1, 4°C
Ox»l, 4°C
                                                                              Maximum
                                                                           folding Time
G
P G
r , *J
P, G
P, G
P, G
P, G
P, G
P
P' G
P, G
P, G
Gool, 4°C
Gool,
H2SO4
Gool,
Gool,
Gool,
Gool,
Gool,
Gool,
Gool,
Gool,
4°C
to pH<2
4°C
4°C
4°C
4°C
4°C
4°C
4°C
4°C
Gool, 4°C add
• 	 -,-.„»- it- a nlll5
48 hours
20 days

7 days
7 days
7 days
48 hours
7 days
28 days
28 days
28 days
7 days
 Analyze
   immediately

. 48 hours

 Analyze
   immediately

 48 hours

-------
Sample Preservation and Maximum Holding Times Specific to Class II
Well Samples


     The sampling preservation and maximum holding times are


defined to maintain the integrity of the samples so that accurate


and reliable data will be generated by the laboratories analyzing


such samples.  It is incumbent on the sampling teams to understand


these requirements and plan, the sampling projects so that the


requirements are met.  It is also necessary that the laboratory


personnel understand the requirements and notify clients when


there are problems so that corrective action can be taken.



  i   Sampling containers should be madev from polyethylene with


polyethylene lined lids.  Glass is required only when dissolved


oxygen samples are stabilized in the field and titrated later.


Glass sample.bottles may be used for all other sample types but


polyethylene lined lids are necessary.
                                         *


     When filtration is required, it should be performed on-


site.  -If- conditions preclude field filtration, the samples


must be delivered to facilities and filtered within four(4)


hours.  Samples should be chilled to 4°C during transit.



     Table II summarizes preservation and holding times for some


tests.
                            -B.22-

-------
Parameter
Major Cations

(Na+, K+, Ca+2, Mg+2)

Major Anions

(Cl", S04=, F~, Br~)

Trace Metals

(Fe, Mn, Zn, Pb, Hg)

Alkalinity

Sulfide
PH
Dissolved Oxygen
Specific Conductance

Total Dissolved Solids

Compatability
                           .TABLE II
Preservation
 Technique
  Maximum
Holding Time
 HNC>3 to pH<2.0           6 months



 Chill to 4°C       '     . 1.month



 HN03 to pH < 2.0         6 months



Chill to 4°C             14 days

Chill to 4°C              7 days

2nd Zn Acefrate Reagent

per liter, NaOH to •

pH>9.0

None


Meter method - none

Winkler method - add

MnSC>4 and Azide - NaOH  •

reagents

Chill to 4°C             28 days

Chill to 4°C              7 days

Chill to 4°C             48 hours
   1 hour maximum

   determine on-site

   8 hours
Note:  Holding time and preservation requirements for other parameters

may be obtained from the RQAOs.
                             -B.23-

-------
                                                                                                                     ATTACHMENT   B-III  (summarized   page)
                                                                                 REQUIRED  CONTAINERS,
                                                                                 PRESERVATION  TECHNIQUES,  AND
                                                                                 HOLDING   TIMES
Parameter
Bacterial Itats:

Inorganic Te«la:














M«Ula:7









Winkler








Silica

Suttate
Sulfide 	

Sulfito 	


Turbidity . . 	
Organic lints:*
Volatile Organcs 	 	 	
(EPA) metfiod 624-See Table A
Semi-Volatile Organics plus PCB/Pesticides
(EPA) metnod 62S-Se« Tame B
PwttciOM Testa:
Radiological Teats:

Container'
P.G 	
PG 	
PG ...
PG 	
PG 	
PG 	
PG . .
PG 	
PG 	
PG
PG 	
PG 	
PG 	
P . .
PG 	
PG
PG
PG
PG 	
PQ 	
PG
PG 	
PG 	
Q 	
PG
PG 	

G Bottle ana top
G only 	 	 	
G
PG.
PG 	
PG 	
PG
PG
PG 	
P 	
PG
PG
PG 	

PG 	 	 	
PG
PQ 	 ' . . ..
PG 	
G. Teflon lined seotum ..
G Tellon-tined cap 	
G Teflon-lined cap
PG

Preservation2-3 I
Cool 4'C. 0.008% Na,S70,5 	
Cool 4°C. 0.008% Na,S,03s 	
Cool. 4*C 	
Cool. 4'C 	
Cool. 4'C. H,SO, to pH<2 	
Cod, 4'C 	
None reQuired 	
Cool. 4'C 	
Cool. 4'C. H,SO. 10 pH<2 	
None required .....'. 	 ." 	
None required 	
COOl. 4'C 	
Cooi.4-C.NaOH to pH>!2. O.Sg ascoroc acxj5
None required 	
HNO3, to pH<2 or HjSO4 to pH<2 	
None required 	
Cool, 4'C. H,SO. to pH<2 	
Cool. 4'C 	
HNO,, to PH<2 	
HNO,, to OH<2 	
Cool. 4°C 	
Cool. 4'C. H,S04 to pH<2 	
Cool. 4-C 	
Cool. 4'C. HjSO. to pH<2 	
Cool. 4'C, HCI or H,SO« to pH<2 .: 	
'•Filter immediately. Cool. 4*C 	
None required 	 	 '. 	
• Fix on site anfl store 'n dar*
Cool. 4'C. HjSO. to pH<2 	
Cool. 4'C 	
Cool 4*C HjSO4 to pH<2 	
Cool. 4'C 	
COOl. 4'C 	
Cool 4'C
Cool 4'C 	
Cooi. 4'C 	 : 	
Cool. 4'C 	
Cool 4'C 	
Cod. 4'C 	
Cool. 4'C add zinc acetate dus soaium
hydroxide to pH>9
None required 	
Cool. 4'C 	
None required 	
Cool. 4'C 	
Cool, 4'C. 0.008% NaTS7O,?HCl to pH29 •'" ..
Cool. 4'C, Na,S,O-,? Store m dark 	
Cool. 4-C. pM 5-9'5 	
HNO} to pH<2 	

Maxirr.'jm noictno time*
6 hours.
6 hours.
14 days.
1 4 cays.
28 Qays.
48 hours.
28 days.
48 hours.
28aays.
23 days.
'Analyze immediately.
48 hours.
14 says.*
23cavs.
5 montns.
Analyze immeoiateiy
23 aays. -
24 nours.
29 davs.
6 montns.
48 hours.
28 days.
4fl hours.
28 days.
28 aays.
48 hours. _
Analyze immediate™
9 hours. ^
28 aays.
48 hours.
28aavs.
7 aays.
48 hours.
7 aays
43 aays
7 days.
28 aays.
•28 aavs
28 aays.
7 aays.

Analyze immeaiateiy.
48 hours.
Anatyze immeaiateiy
48 hours
•4 aays.
7 aavs until extraction
40 aays aner
extraction.
7 aays until extraction
40 aays after
extraction.

  ' Potvetnytene I PI of GUts (Q).
  *S*rno»e ornewation snouMl M oertormed Immediately uoon sam-
ple collection for CDmoovie cnerrwcai samoies each anouot snouifl
oe ore*e*v«a at tn* tin* at coHecnon. wnen use Qi an automated;
samoief ma«e* » imoos»»oie to observe eacn aiiauat. ih«n cnemie«i
umotes may EM oreservea Cry maintaining «t **C until comoositing,
•no  samtwe Mxmtng n comoteted.
  >Wheft «ny $*mw« >s io o* sfltooto 9V common c«m*r or Mm
trwouqn m« unttd St*t*« Mans, it mu*i comoty «nn m« 0*oanmt>m
ot Tfansoonsiion nuanjous Mittnais fl«qui4noos i49 CFR Pan 172}.
Th« ot TabM
I), m* Ottica ot Haiaraous Matanais. Mattrtats Transoonatum 8ur*«u.
0*oan*n«m ot Tramoonauon nas t3et*rmm«o mat tn« ntiaraoua Mat-
•n«i« A«quxtioni oo not «oo*v (0 ma toxowtng matariais rfyorocniortc
actd *>$»ioViaoouf 115o»gr«at«fi.*na Sodium nyoroiMMlNaOHl
•" w*t«r MDuttoni at conctn"«uon» ot 0.080*.'. oy *«tqnt or teu ipH
•OOul 12.30 or i««ai.
  *Savno»M snomd o« anwyzed aa soon u OOSSIDM ana* collection
The time* iittM are tn« maximum nmea mai >an>DW« m«y ee n«to
Oatore analysis ana smi M consiaefec *«IKJ S*mo*es mav oe netQ for
longer ovnoos oni> >( the oenmnee. or monnonng laooratorv. nas aata
on tile to snow tnai tne soeo»C typei ot umotes under study are tuoie
IQT me longer time, ana has received  a variance from me Aaejonai
Administrator unoer ^ 136.31 e|. Some simwe* may not o« ftaote (or
me manmum time oenod given m tne Taoie. A oermtne*. or monnonnq
laoorato^v. is ooiigated to noia in* Mmoie 'or a inorter time >i  ou/» wn«n suilide is oreseni Ootwxv
aity  an umotea mav oe tasted «tn <*eo acetate oaoe* oetore OH
adiustm«nis >n ofder to determine it iviit'Oe is pfesent II suitiqe •%
oresent  s ootameo. The umgie is tittered and men
NepH es to tamows to oe *nary/ea oy GC. tC. or GC us
for soecthc comoounds.
  S«mo*e receiving no OH a0)uaimefn musi oe anaiyieo witnm seven
aeya ot lamoung
  '*The on ttiusimvm is not rwuireo n acroiem *>u not o« measured
S«mot«* tor acroie"Qie cnem-
icai category, me soecmeo oreservative ana ma»imum toia^ig times
snouW oe O0serv«d tor oot-mym satequarc ot samc-e •'vegnfv «nef
the anaiytes o> concern iait *ttnm rwo or more cneT^-cai :3iegornq me OH to 6-3. vamotes oreservea m tr^s manne' ~*av oe
seven says Oetore eitracnon ano tor tor TV aavs anei eiiractior
tions to this optional oreservanon ana noiO'^q t:m« c-'ocea^e  a
in  tootnoie  5 i'e me fedu'rem«fit iof 'n>osuitate •ecucitof st
ciwonnet. ana lootnotes 12. <3 i'* me  anai»s-s 31

the'umoie to * 0 : 0 2 to oreveni rearra
  'J?itridS may oe storeo uo to * ?av:
conducieo under an inm 2J nours 0' samoxng
   *The oM adiustment mav o* oe*ro^meo uoon fece-ot at i"*'aooratorv
and may oe om>neo >' m« sarr>os
                                                                           -B.24-

-------
                                                              ATTACHMENT B-IV
                            CHAIN  OF CUSTODY RECORD
                               mVltONMlNUL MOtlCTION A9INCT - HOION H
                               Environmental Services Division
                                       IOISOM, NIW JIlitT  01117
$«••!•
                       •' <••»!••
  fotwi Aii«ai»( l«ip**tlklliiT l*r
                                                                                             Ool.
                  If.
                                             lyt
                                                            041*
                                                                        !«••<« fir Ch««*« •(
 *•••!•
                  ly-
                  ly;
                                              if!
                                                     Tim*
                                                            Oil*
                                           -B.25-
                                                                             f*r CX*P|« •' Cwi'*4y

-------
                                                ATTACHMENT B-V
              SAMPLING,  PRESERVATION AND  STORAGE  CONSIDERATIONS

                         FOR  TRACE ORGANIC MATERIALS


     Organic'compounds in water and wastewater  are  regulated  by  the  Safe'
Drinking Water Act (SDWA) and the Clean Water Act (CWA).

     The SDWA has established maximum  contaminant levels  (1)(2)  for  the
following organic chemicals:

     a)  Chlorinated hydrocarbons:
           Endrin                 Methoxychlor
           Lindane                Toxaphene

     b)  Chlorophenoxys:
           2,4-0                  2,4,5-TP  (Silvex)

     c)  Trihalomethanes:                v
           Trichloromethane       Bromodichloromethane
           Dibromochloromethane   Tribromomethane

     Listed in Table 12.1 are chemicals which have  been  detected in  drinking
water supplies and for which  the possibility of adverse  health effects
exists.  The presence of these chemicals  is  indicative of chemical
pollution; this list 1s  not exhaustive, but  serves  merely as  a guide.(3)

     A court settlement  agreement  involving  the Natural  Resources Defense
Council, et al. and the  U.S.  Environmental Protection Agency  (EPA Consent
Decree) resulted in EPA  publishing a  list of 65 compounds and classes  of
compounds {Table 12.2).   The  Consent Decree  required  that EPA regulate these
compounds via the Federal Water Pollution Control Act (subsequently  amended
by the Clean Water Act).   EPA's expanded  list of organic priority pollutants
(Table 12.3) is an outgrowth  of the Consent  Decree's  list of  65.

     Specific toxic pollutant effluent standards will be promulgated for the
organic priority pollutants,  thus  far  they have been  promulgated (4)(5)(6)
for the following:

                     Aldrin/Dieldrin          Endrin
                     Benzidine               Toxaphene
                     DDT (ODD, DDE)           PCB's
                                -B.26-

-------
 TAflU UM  CHEMICAL INDICATORS OF.  INDUSTRIAL  CONTAMINATION  (23)
I.   MUM\«t1c hAlogenated hydrocarbons:

       Methane  derivatives:
              Qlchlororcethane               Dichlorodlfluoromethane
              Trlchlorofluoromethanu       Carbon Tetrachlorido

        l.thane derivatives:
               1,1-dichloroethane           1,1,1-trichloroethane
              •1,2-dichloroethane           1,1,2-trichloroethane
               hcxachloroethane             1,1,2 ,2-tetrachloroethane

        Unsuturated hydrocarbons:
                Trichloroethylene             1,2-dichloroether,e
                letrachloroethylene           1,3-dichloroprcpene
                Vinyl chloride                Hexachlorobutadiene
                1,1-dichloroethene            2-chlorovinyl  ether

         Other halogenated compounds:
                1,1-dichloropropane           Bis(2-chloroethyl)  ether
                            bis(2-chloroisopropyl) ether
                                            \.
  II-  Cyclic aliphatic compounds:

         Chlorinated hydrocarbons:
                Llndane                      Kepone
                BHC                          Toxaphene

         Cyclodienes:
                Chlordane                    Heptachlor
                Aldrin                       Heptachlor epoxide
                Oieldrin                     Endrin
                         Hexachlorocyclopentadlene

   III.   Aromatic  hydrocarbons:

                 3 ,4-benzofluoranthene        fluoranthene
                 benzo(k)fluoranthene         indeno(l ,2,3,c,d)pyrene
                 1,12-benzoperylene           benzo(a)pyrene

          Benzenes:
                 Benzene                      Ethylbenzene
                 Toluene                      Propylbenzene
                 XyTenes                      Styrene

           Halogenated aromatics:
                  Chlorinated naphthalenes      DDE
                  Chlorobenzene                 ODD
                                  -B.27-

-------
              TABLE  12.1   (continued)
Halogenated aromatics:(continued)
       DicMorobenzenes             Chlorophenols
       Polychlorinated biphenyls    Trichlorobenzenes
       Pentachlorophenol            4-bromopheny1phenyl  ether
       Bromobenzene                 4-chlorphenylphenyl  ether
       DOT                         Hexachlorobenzene

Other aromatic  hydrocarbons:
       Nitrobenzene                 Phthalate  esters
       Oinitrotoluene               Atrazine
                    -B.28-

-------
                           TABLE 12.2  65 TOXIC POLLUTANTS OR CLASSES OF TOXIC POLLUTANTS (21)
VO
I
Acenaphthene
Acrolein
Acrylonitrile
Aldrin/Dieldrln
Antimony and compounds
Arsenic and compounds
Asbestos
Benzene
Benzidine
Beryllium and compounds
Cadmium and compounds
Carbon tetrachloride
Chlordane (technical mixture and metabolites)
Chlorinated benzenes (other.than dichlorobenzenes)
Chlorinated ethanes (including 1.2 dichloroethane
 1,1,1-trichloroethane, and hexachloroethane)
Chloroalkyl ethers (chloromethyl, chloroethyl,
 and mixed ethers)
Chlorinated naphthalene
Chlorinated phenols
Chloroform
2-chlorophenol
Chromium and compounds
Copper and compounds
Cyanides
DDT and metabolites
Dichlorobenzenes (1,2-,1,3- and 1,4-dichlorobenzenes)
Dichlorobenzidine
Dichloroethylenes (1,1- and 1,2-dichloroethylenes)
2,4-dichlorophenol
Dichloropropane and dichloropropene
2,4 Dimethyl phenol
Dinitrotoluene
Diphenylhydrazine
Endosulfan and metabolites
Endrin and metabolites
Ethylbenzene
Fluoranthene
Haloethers
Halomethanes
Heptachlor and metabolites
Hexachlorobutadiene
Hexachlorocyclohexane (all Homers)
Hexachlorocyclopentadiene
Isophorone
Lead and compounds
Mercury and compounds
Naphthalene
Nickel and compounds
Nitrobenzene
Nitrophenols (including 2,4-dinitrophenol,
 dinitrocresol)
Nitrosamines
Pentachlorophenol
Phenol
Phthalate esters
Polychlorinated biphenyls (PCB's)
Polynuclear aromatic hydrocarbons (including
 benzanthracenes, benzopyrenes, benzofluoran-
 thene, chrysenes, dibenzanthracenes and
 indenopyrenes)
Selenium and compounds
Silver and compounds
2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCOO)
TetrachIoroethylene
Thallium and compounds
Toluene
Toxaphene
Trichloroethylene
Vinyl Chloride
Zinc and compounds

-------
                      TABLE  12.3   PRIORITY  POLLUTANTS
I.     Phthalate esters:

        Dimethyl  phthalate                   Oi-n-octyl  phthalate
        Oiethyl phthalate                    B1s(2-*thylhexyl)phthalate
        Di-n-butyl  phthalate                  Butylbenzyl  phthalate

II.   Haloethers

        Bis(2-chloroethy1)ether              Bis(2-chloroethoxy)methane
        Bis(2-chloroisopropyl )ether          4-chlorophenylphenyl ether
        2-chloroethylvinyl ether             4-bromophenylphenyl  ether

III.  Chlorinated hydrocarbons:

        Hexachloroethane                     1,3-dichlorobenzene
        Hexachlorobutadiene                  1,4-dichlorobenzene
        Hexachlorocyclopentadiene             1,2,4-trichlorobenzene
        1,2-dichlorobenzene                  Hexachlorobenzene
                            2-ch'oronaphthalene

IV.   Nitroaromatics and Isophorone:
                                             . v
        Nitrobenzene                         2,4-dinitrotoluere.
        2,6-dinitrotoluene                   Isophorone

V.     Nitrosoamines:

        N-nitrosodimethyl.amine               N-n i t rosodip ropy! ami ne
                            N-nitrosodiphenylamine

VI.   Oioxin:

        2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD)

VII.  Benzidines:

        Benzidine                            3,3-dichlorobenzidine

VIII. Phenols:

        Phenol                               Pentachlorophenol
        2,4-dimethyl phenol                   4-chloro-3-nethy!phenol
        2-chlorophenol                       2-nitrophenol
        2,4-dichlorophenol        .           4-nitrophenol
        2,4,6-trichlorophenol                 2,4-dinitrophenol
                        4,6-dinitro-2-methylphenol
                                    -B.30-

-------
                          TABLE 12.3  (continued)
IX.   Polynuclear aromatics:

        Acenaphthene
        Fluoranthene
        Naphthalene
        Benzo(a)anthracene
        8enzo(a)pyrene
        Benzo(b)f1uoranthene
        Benzo(k)fluoranthene
        Chrysene

X.    Pesticides & PCB's:

        Aldrin
      .  Dieldrin
        Chlordane
        ODD
        DOE
        DDT
        A-endosulfan
        B-endosulfan
        Endosulfan
        Endrin
        Endrln aldehyde
        Heptachlor
        Toxaphene

XI.   Purgeables:

        Benzene
        Chlorobenzene
        Toluene
       1 Ethylbenzene
        Carbon tetrachloride
        1,2-dichloroethane
        1jl,l-trichloroethane
        1,1-dichloroethane
        1,1,2-trichloroethane
        1,1,2,2-tetrachloroethane
        Chloroethane
        Chlorodibromomethane
        Tetrachloroethylene

XII.  Acrolein 4 Acrylonitrile:

        Acrolein
Acenaphthylene
Anthracene
Benzo(g,h,1 )pery1ene
Fluorene
Phenanthrene
Dibenzo(a ,h)anthracene
Indeno(l ,2,3-cd)pyrene
Pyrene
Heptachlor
Alpha-BHC
Beta-BHC
Delta-BHC
Gamma -BHC
Tojaphene
Aroclor
.Aroclor
Aroclor
Aroclor
Aroclor
Aroclor
Aroclor
           epoxide
        1254
        1221
        1232
        1248
        1260
        1016
Chloroform
1,1-dichloroethylene
1,2-transdichloroethylene
1,2-dichloropropane
1,1-dichloropropyiene
Methylchldride
Methylenechloride
Methylbromide
Bromoform
Dichlorobromomethane

Trichloroethylene
Vinyl chloride
Acrylonitrile
                                    -B.31-

-------
     Analytical procedures for the  identification of organic compounds can,
be found in  a  number of publications.(7  - 22)  However, analytical results
are only meaningful if the sample analyzed  is truly a representative sample
of the media you are testing.   Chemical  analysis for organics present at
trace levels places high demands on sampling techniques.


12.1  SAMPLE COLLECTION METHOD

     The method of sampling can either be manual or automatic.  Sampling
practices,  as  specified in Chapter 2,  should be followed, except as
indicated in this chapter.

12_. 1.1  Manual Sampling

     The considerations outlined in Chapter 2 are applicable.  However, -..lie
sample collector and container should  be constructed of b'crosil icate glass
to minimize  sample contamination.  Grab  samples obtained for analyses
of purgeable organics are sealed to eliminate entrapped air.(7)  This
sample collected without headspace, is illustrated in Figure 12.1.
                                Screw cap

                                Teflon/Silicon  Septum
                                (Pi erce  #12722  or equi va
                                 lent)  •

                                Convex Meniscus  (Sample)
                                40 mL  borosilicate glass
                                vial  (Pierce #13075 or
                                equi valent)
                Figure 12.1  Collection Bottle  (21,22)


12.5  SAMPLING  PROCEDURE AND PRETREATMENT  OF  SAMPLE  EQUIPMENT

12.5.1  Pretreatment of Equipment

     The pretreatment technique should be  dictated by  the analyses to be
performed.   The general pretreatment technique for sample and storage
containers  is to:

     1.   Wash bottles with hot detergent water.
     2.   Rinse  thoroughly with tap water followed by three or more rinses
         with orqainic-free water.
                                -B.32-

-------
     3.  Rinse with interference free redistilled solvent such -as acetone or
         methylene chloride and dry in contaminant free air at room
         temperature.  Protect from atmospheric or other sources of
         contamination.  Caps and liners for bottles must also be solvent
.   .      rinsed as above.

     If automatic samplers are to he employed, use the peristaltic pump tvpe
with a single 8-10 liter (2.5 - 3.0-gallons) glass container.  Vacuum tvpe
automatic samplers can be used if sample containers are glass.  The p^o-
cedure outlined above should be followed for the pretreatment of the
containers.  In addition all tubing and other parts of the sampling system
must be scrubbed with hot detergent water and thoroughly rinsed with tap
water and blank water prior to use.  Further rinsing with interference free
acetone or methylene chloride is advised when tubirg and other parts permit,
i.e.» are not susceptible to dissolution by the solvent.

12.5.2. Sampling Procedure

     Purgeables (22)(31)(3?)

     Collect grab samples in glass containers.  The procedure for filling
     and sealing sample containers is as follows:  Slowly fill each con-
     tainer to overflowing.  Carefully set the container on a level surface.
     Place the septum Teflon side down on the convex sample meniscus.   Seal
     the sample with .the screw cap.  To insure~tJhat the sample has been
     properly sealed, invert the sample and lightly tao the lid on a solid
     surface.  The absence of entrapped air bubbles indicates a proper seal.
     If air bubbles are present,-open the bottle, add additional sample, and
     reseal (in same manner as stated above).  The sample must remain
     hermetically sealed until it is analyzed.  Maintain samples at 4°C
     (39 F) during transport and storage prior to analysis.   If the sample  is
     taken from a water tap, turn on the water and permit the system to
     flush.  When the temperature of the water has stabilized, adjust  the
     flow to about 500-mL/minute and collect samples as outlined above.

     Non-Purgeables (22)(32)

     Collect grab samples in glass containers.  Conventional  sampling
     practices should be followed, except that the bottle must not be  pre-
     washed with sample before collection.  Composite samples should be
     collected in refrigerated glass containers in accordance with the
     requirements of the program.   Automatic sampling equipment must be free
     of Tygon and other potential  sources of contamination.


12.6  SAMPLE PRESERVATION AND STORAGE (32)

     Analyze samples as soon as possible.  Preserve and store samples
collected for analyses via EPA's 600 Method Series as described below:
                                  -B.33-

-------
Method 60!^ - Purgeable Halocarbons

The samples must be  iced or refrigerated at 4°C from the time of
collection until extraction.  If the sample contains free or combined
chlorine,.add sodium thoisulfate preservative (10 mg/40 ml will suffice
for up to 5 ppm CU) to the empty sample bottles just prior to shipping

to the sampling site.  .

All samples must be  analyzed within 14 days of collection.

Method 602 - Purgeable Aromatics

Collect about 500 ml sample in a clean container.  Adjust the pH of the
sample to about 2 by adding 1:1 diluted HC1 while stirring vigorously.
If the sample contains free or combined chlorine, add sodium thiosul-
fate pre-.  «rvative (10 mg/40 mi will suffice for up to 5 ppm Cl-0 to the

empty sample bottles just prior to shipping to the sampling site.

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

All samples must be  analyzed within 14 days of collection.
                                              \
Method 603 - Acrolein and Acrylonitrile

The samples must be  iced or refrigerated at 4° from the time of
.collection until extraction.  If the sample contains free or combined
chlorine, add sodium thiosulfate preservative (10 mg/40 ml ,is
sufficient for up to 5 ppm CU) to the empty sample bottles just prior

to shipping to the sampling site.


If acrolein is to be analyzed, collect about 500 ml sample in a clean
glass conatiner.  Adjust the pH of the sample to 4 to 5 using acid or
base, measuring with narrow range pH paper.  Samples for acrolein
analyses  receiving no pH adjustment must be analyzed within three days
of sampling.

All samples must be  analyzed within 14 days of collection.

Method 604  - Phenols

The samples must be  iced or refrigerated at. 4° from the time of
collection until extraction.  At the sampling location fill the glass
container with sample.  Add 80 mg of sodium thiosulfate per liter of
sample.

All samples must be  extracted within seven days and completely analyzed
within 40 days of extraction.
                                 -B.34-

-------
Method 605 - Benzidines

The samples must be iced or refrigerated at 4°C from the time of
collection to extraction.  Benzidine and dichlorobenzidine are easily
oxidized by materials such as free chlorine.  For chlorinated wastes,
immediately add 80 m'g sodium thiosulfate per liter of sample.

If 1,2-diphenylhydrazine is likely to be present, adjust the pH of the
sample to 4 t 0,2 units to prevent rearrangement to benzidine.  The
sample pH should be adjusted to 2-7 with sodium hydroxide or sulfuric
acid.

All samples must be extracted within seven days.  Extracts may be held
up to seven days before analysis if stored under an inert (oxidant
free) atmosphere.  The extract must be protected from light.

Method 606 - Phthalate Esters

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

All samples must be extracted within seven days and completely analyzed
within 40 days of extraction.

Method 607 - Nitrosamines                    v

The samples must be iced or refrigerated at 4°C from the time'of
collection until extraction.  If residual chlorine is present, add
80 mg of sodium thiosulfate per liter of sample.  And, if
diphenylnitrosamine is to be determined, adjust the pH of the water
sample to pH 7 to 10 using sodium hydroxide or sulfuric acid.  Record
the volume of acid or base added.


All samples must be extracted within seven days and completely analyzed
within 40 days of extraction.

Method 608 - Organochlorine Pesticides and RGB's

The samples must be iced or refrigerated at 4°C from the time of
collection until extraction.  If the samples will not be extracted
within 72 hours of collection, the sample should be adjusted to a pH
range of 5.0 - 9.0 with sodium hydroxide or sulfuric acid.   If aldrin
is to be determined, and if residual chlorine is present, add sodium
thiosulfate.

All samples must be extracted within seven days and completely analyzed
within 40 days of extraction.
                                    -B.35-

-------
Method 609 - Nitroaromatks._any Isophorone

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

All samples must be extracted within seven days and completely analyzed.
within 40 days of extraction.

Method 610 - Polynudear Aromatic Hydrocarbons

The samples must be iced or refrigerated at 4°C from the time of
collection until extraction.   PAHs are known to be light sensitive,
therefore, samples, extracts  and standards should be stored in amber or
foil wrapped bottles in order to minimize photolytic decomposition.
Fill the sample bottle and, if residual chlorine i-s present, add 60 mg
of s.odium thiosulfate per lit'rof sample.

All samples must be extracted within seven days, and analysis
completely analyzed within 40 days of extraction.

Method 611 - Haloethers

The samples must be iced or refrigerated at 4°C from the time of
collection until extraction.   If residual chlorine is present, add
80 mg of sodium thiosulfate per liter of water.

All samples must be extracted within seven days and completely analyzed
within 40 day's of extraction.

Method 612 - Chlorinated Hydrocarbons

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

All samples must be extracted within seven days and completely analyzed
within 40 days of extraction.


Method 613 - 2l317,8-Tetrachlorodiben20-p-dioxin

The samples must be iced or refrigerated at 4°c from the time of
collection until extraction.   If residual chlorine is present, add
80 mg of sodium thiosulfate per liter of water.  Protect the sample
from light from the time of collection until analysis.

All samples must be extracted within seven days and completely analyzed
within 40 days of extraction.
                                    -B.36-

-------
Method 624 - Purgeables (GC/MS)   ,

The sample must be iced or refrigerated at 4°C from the time of
collection until extraction.  If the sample contains residual chlorine,
add sodium thiosulfate preservative (10 mg/40 ml is sufficient for up
to 5 ppm Clp) to the empty sample bottles just prior to shipping to the
sample site, fill with sample just to overflowing, seal the bottle, and
shake vigorously for one minute.

Experimental evidence indicates that some aromatic compounds, notably
benzene, toluene, and ethylbenzene are susceptible to rapid biological
degradation under-certain environmental conditions.(3)  Refrigeration
alone may not be adequate to preserve these compounds in wastewaters
for more than seven days.  For this reason, a separate sample should be
collected, acidified, and analyzed when these aromatics are to be
determined.  Collect about 500 ml of sample in a clean container.
Adjust the pH of the sample to about 2 by adding HC1 (1+1) while
stirring.  Check pH with narrow range (l.i to 2.8) pH caper.  Fill a
sample container as described in Section 9.2.  If chlorine residual is
present, add sodium thiosulfate to another sample container and fill as
in Section 9.2 and mix thoroughly.

A^l samples must be analyzed within 14 days of collection.
                                             i.
Method 625 - Base/Neutrals, Acids and Pesticides _(G.C/M_S)

The samples must be iced or refrigerated at 4°C from the time of
collection until extraction.  The sample must be protected from light.
If the sample contains residual chlorine, add 80 mg of sodium
thiosulfate per liter of sample.

All samples must be extracted within seven days and completely analyzed
within 40 days of extraction.
                               -B.37-

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                     ATTACHMENT C




                    COMPATIBILITY






 I  Compatibility in the Hydrogeological Environment




II  Compatibility for Ease of Injection

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I. .  COMPATIBILITY IN THE HYDROGEOLOGICAL ENVIRONMENT*      '


     In designing an injection well,' injection fluid and formation

fluid interactions must be accounted for.  These interactions may

lead to severe reduction in formation permeability or to a loss

of structural integrity within the formation itself.  Fluid and

formation compatibility problems are specific to the particular

formation and waste involved.  Their prediction and solution

require site-specific studies.  Specific problems associated

with such compatibility include plugging of the injection formation

with suspended solids, precipitation and polymerization of the

waste fluid, growth of biologic organisms within the formation,

and dissolution of the formation matrix.


     In' some cases, the injection, fluid may react directly with
                                      4.

the rock matrix.  One common problem is the swellinq of clays

from contact with the injection fluid.  Affected clays can

significantly reduce the permeability of the formation.  In other

instances,, polar-organic compounds can be adsorbed by the rocks,

particularly silicates, and can significantly reduce the permeability

of the formation.


     The injection of acids may result in dissolution of the rock

matrix.  In the case of certain cemented material, dissolution

can result in the migration of particles which then block pore

spaces and reduce permeability.  Dissolution of the confining


* This material was extracted from various reports prepared bv
  Geraghty and Miller, Inc. for EPA-ODW under contract #68-01-5971.
  This material only addresses compatibility in what relates to
  "ease of injection".  It does not address more complex problems
  such as waste interactions, chemical, gradients, etc.  EPA will
  develop criteria on these in the future.


                              -C.I-

-------
formation can allow the migration of injection fluid from out of


the injection formation.  In addition,  under certain conditions

CC>2 gas can be formed, which may interfere with injection and may


cause "blow-outs".



     To avoid interaction problems,  the injection and confining


formations should have their respective formation fluid and rock


matricies tested for compatibility with the.proposed injection


(or similar) fluid.  Drilling a borehole offers an excellent

opportunity to collect data relevant to a number of important


parameters of the formations penetrated.  The following are the


major fluid and rock matrix sampling techniques:



A.   Drill Cuttings
                                      i
     Drilling techniques produce cuttings which can be collected


and analyzed.  Cuttings produced during drilling accumulate in


the hole and are removed at intervals by bailing..  In rotary


drilling, the cuttings are collected from the "shaleshaker" .


The cuttings obtained provide samples representative of the


formations penetrated.



     Cuttings are normally examined at the site under low-cower


magnification to identify rock type, grain size, color, and


mineralogy.  Testing the samples with acid can be used to determine


carbonate material.  Exposing cuttings to the injection fluid


will allow other useful observations regarding comoatibility.
                              -C.2-

-------
     Cuttings must be disposed of properly once they have outlived



their usefulness.



B.   Coring



     Geologic cores taken while drilling provide lithologic and



hydrologic information superior to that obtained from the analysis



of drill cuttings.  Coring is accomplished thr.ough the use of a



special drilling bit and a.coring barrel which is attached to



the end of the drill pipe.  As the bit cuts into the rock, an



inner core is left intact and pushed into the core barrel.





     Techniques are also available to take cores from the sides



of a borehole after drilling is completed.  These sidewall ceres



are generally taken to provide infbrmat'ion about formations from



which cores were not taken during drilling.  Sidewall. cprinq is



accomplished by driving a wireline coring device which contains



small hollow cylinders into the formation by an explosive charge.



Sidewall coring is limited to relatively soft materials.





     Examination of conventional cores can provide substantial



amounts of data valuable to the design and the construction of



injection wells.  Visual examination of cores can reveal  fractures,



bedding features, and solution cavities; laboratory examination



can determine porosity, grain size, permeability, and formation-



fluid quality.  In situ behavior of the injection and confining



formations can be simulated in the laboratory using conventional



core samples and representative injection fluid.
                              -C.3-

-------
     Data obtained from sidewall cores are not as reliable as



those obtained from conventional cores due partly to the relatively



small size of the sample.   Formations are disturbed substantially



during coring, and the more permeable formations sampled have



generally been invaded with drilling fluid.





C.   Fluid Sampling



     Some of the methods for obtaining formation-fluid samples



are drill-stem testing, swabbing,  bailing, and air-lift.



     Drill-stem testing is a technique whereby a zone in an open



borehole is isolated by an expandable packer or packers and fluid



from the formation allowed to flow through a valve into a drill



pipe.  Similar to this,, there is a device which can be lowered



into the borehole on a wire line rather than on a drill pipe.  la



this case, the sample is limited to the amount that can be



contained in the testing device (no more than 5 gallons).





     Swabbing is a method  of producing fluid similar to pumping



a well.  In swabbing, fluid is lifted from the borehole through



drill pipe, casing, or tubing by a swab that falls freely downward



through the pipe and its contained fluid, but which seats against



the pipe walls on the up-stroke, drawing a volume of fluid above



it as it is raised.  Swabbing is preferable to drill-stem testing



where unconsolidated formations cause testing to be difficult.



Swabbing may also be used  in conjunction with drill-stem testing
                              -C.4-

-------
to increase the volume of fluid obtained.  The advantage of
swabbing is that it can be continued until all drilling mud has
been drawn from the pipe, thus allowing the chemistry of the
formation water sampled to reach a steady state.  This procedure
helps to insure that a representative sample of formation water
is obtained.

     Bailing may be used to obtain formation water samples, but
care 'must be taken to insure that the water sample is representative
of the formation of interest and not of another formation also
draining into the borehole.   This problem is reduced in holes in
which casing is driven since the casing acts to isolate the lowest
formation from the other water-producing formations.
                                       i.
     In air-lift (or gas-lift) sampling, fluid can be obtained by
injecting gas under pressure into the well.  The gas forces the
fluids in the well to rise to the surface.  This air-lift sampling
has limits similar to those  encountered with bailing.
                              -C.5-

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II.  •COMPATIBILITY TEST FOR EASE  OF INJECTION*






A.  Scope and Application




     1.  This method is designed  to qualitatively determine the



         compatibility of waters  by mixing two representative



         samples and evaluating the effects over a specific time.






     2.  The method is only applicable to the UIC program and  is  an




         approximation of the interactions which may occur in  the



         injection zone.






3.  Summary of Method






     1.  Equal volumes of. injection and formation fluids



         are mixed together under controlled laboratory conditions



         The mix is then allowed  to stand undisturbed for 20




         days and is visually observed periodically.  In addition,




         portions of the samples  are analyzed for iron and calcium



         before mixing to determine if these constituents are



         being precipitated.




C.  Comments



    ~. 1.  Because this is a qualitative method, experience in




         performing the test is invaluable.






D.  Sample Handling and Preservation










* Prepared by Tom Steibel, EPA Region VIII.
                              -C.6-

-------
     1.  Samples must be taken in one liter polyethylene or glass



         containers and care should be taken to eliminate air



         spaces in the bottles;



     2.  Samples must be refrigerated or chilled to 4°C with



         ice during storage or transit, and maximum holdinq times



         prior to beginning analysis is 48 hours;



     3.  The subsurface environment should be simulated to



         reflect actual conditions as much as oossible.





E.  Equipment



     1.  pH meter;



     2.  Refrigerator;



     3. . Three 'or four liter glass beaker with watch glass;



     4.  The equipment and reagents necessary for the



         analysis of iron and calcium.



F.  Procedure



    Before mixing the pH and the concentration of iron and calcium.



    should be determined.



     1;  Carefully pour one liter of each samole of water together



         in the three or four liter beaker.  Mix thorouq'hlv



         with a glass rod.  Allow solids to settle.



     2.  Using a serological pipette, remove enough of the



         mixture from the supernatant to analyze pH, iron and



         calcium. Cover mixture with watch glass.



     3.  Obtain the pH, iron and calcium concentrations by an



         acceptable technique and enter these values on the samnle



         record form along with any observations of the mixture.





                              -C.7-

-------
     4.   Carefully place  beaker  in  refrigerator.





     5.   On days 3, 7,  11,  14, and  20,  repeat  steos 2 and 3.



H.  Precision and Accuracy



    There are no proven methods  for evaluating the precision



    or accuracy for compatability.   The precision and accuracy



    for pH, iron and calcium determinations  is listed in Section VI



    of the UI  Quality  Assurance Criteria.
                              -C.8-

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                          COMPATIBILITY
                        SAMPLE RECORD FORM
Injection Water Sample Number:
Aquifer Water Sample Number:
Date Sampled:
Date Test Began:
Analyst:
                 Date
     Time Samoled:
     Time Test Began:
PH
Ca
Fe   Observations
Day 1





Day 3





Day 7
Day 14





Day 20








Refrigerator Temperature:=
          (Acceptable range = 2-5°C)
                              -C.9-

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               ATTACHMENT D






 I.   Quality Control Sample Request Form




II.   Example of an SOP

-------
                                                         ATTACHMENT D-I
ASE PRINT OR TYPE.
4
                                  QUALITY CONTROL SAMPLE REQUEST

                                  	  Telephone
                                                               Form Approved O.M.B. 2000-0139
                                                                                 EXD. 4-30-86'
Company	
Laboratory
Address
                                         State
                                                           Zip Code
City
Approval of Laboratory Director	
Please indicate Programs for which  QC  samples  are requested:     Q Ambient Monitoring
   Drinking Water   Q Wastewater  Q Toxics  (TSCA) •  Q Solid Waste/Hazardous Wastes (RCRA)

           WATER QUALITY/WATER POLLUTION SAMPLES                    WATER SUPPLY SABLES
	  Demand
"EWAPI Reference Oils
  	  Arabian Light Crude
  	  Prudhoe Bay Crude
  	  South Louisiana Crude
  	  No. 2 Fuel (high arom.)
  	  No. 6 Fuel (high vise.)
           Bunker C
       LAS
       Mineral
       Mun. Digested Sludge
       Nutrients
       Oil & Grease
       Pesticides in Fish
       PCBs in Fish
       PCBs in Sediments
       Phenols (4AAP Method)
       Residues
       Other
                                                 in Cap^c.
                                                 in Hydraul
                                                    Trans.
                                                    in
1016
1015
1016
1242 in Capac.
1242 in Hydraul
1242 in Trans.
1?54
1254
1254
1260
                                                 i n Capac.
                                                 in Hydraul
                                                    Trans.
                                                    Capac.
                                                    in
                                                    in
                                            1260 in Hydraul,
                                            1260 in trans.
                                     'Trace Metals WP -  I   •
                                     Trace-Metals WP -  II
                                     Trace Metals WP -  III
                                     Trace Metals in Fish
                                     Vol atile Organics
                                     Other
    PRIORITY POLLUTANTS/HAZARDOUS WASTESyTQXIC  CHEMICALS
       n-Alkanes
       Aromatic Purgeables
       Chlorinated Hydrocarbons
       Chi. Hyd. Pest. WP - I
       Chi. Hyd. Pest. WP - II
       Chi. Hyd. Pest. WP - III
       Cyani de
       Dichl orobenzenes
       EP Metals
       GC/MS Acids
       GC/MS Base Neutrals - I
       GC/MS Base Neutrals - II
       GC/MS Base Neutrals - III
       GC/MS.Pesticides
       GC/MS Pesticides
       GC/MS Purgeables
       GC/MS Purgeables
       GC/MS Purgeables
       GC/MS Purgeables -
                       I
                       II
                       I
                       II
                       III
                       IV
                                        Haloethers
                                        Halo. Puraeables - I
                                        Nitroaro. 4 Isophorone
                                       (specific Aroclors)
                                          Aroclor 1016
                                          Aroclor 1221
                                       __  Aroclor 1232
                                       __  Aroclor P42
                                       _  Aroclor 1248
                                       __  Aroclor 1254
                                       __  Aroclor 1250
                                       __  Aroclor 1252
                                        Phenols (GC)
                                        Phthalate Esters
                                        Polynuclear Aromatics I
                                        Polynuclear Aromatics II
                                        Polynuclear Aro. SRM 1647
                                        Other 	
                                        Other
WS Corrosivity/Sodium
WS Herbi ci des
WS Nitrate/Fluoride
WS Chi. Hyd. Pest. I
WS Chi . Hyd. Pest. II
WS Res. Free Chlorine
WS Temik
WS Trace Metals  •
WS Tri ha 1 am ethanes
WS Turbidity
Other 	
Other
                                                                            SAMPLES
                                                                      Chlorophyll Fluoro.
                                                                      Chlorophyll Soectro.
                                                                      Phytopl ankton
                                                                      Simulated Plankton
                                                                      Other _ .
                                                                      Other
DATE REQUESTED:  	
EPA-360 (Cin)  (Rev.  6/83,  Pt.  1)
                                                   DATE SHIPPED:
                                           -D.I-

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APPENDIX D-II

Example of a SOP


Sampling for Sulfide

The following procedure is recommended for collecting samples

for sulfide analysis:

    1.  Have reagent-grade zinc acetate and IN NaOH available  in
        the field.

    2.  Add 2 g of reagent-grade zinc acetate to a 100-ml
        polyethylene bcttle.'

    3.  Measure the pH of the sample (see Korte and Ealey,  1983)

    4.  Collect the sample by flowing it through the filter
        holder and directly into the sample bottle as described ,
        previously.  If the sample pH is >7, fill sample bottle
        to top and close tightly.
                                       \.
    5.  If the sample pH is <7, neutralize with NaOH solution.
        The final pH should be >7.

    6.  Store sample away from natural light, and analyze as
        soon as possible.
                              -D.2-

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               ATTACHMENT £

DRAFT OUTLINE  OF ITEMS TO BE ADDRESSED
 IN THE QUALITY  ASSURANCE PROJECT PLAN
   FOR THE NATIONAL PESTICIDE  SURVEY

     QUALITY ASSURANCE  PROJECT PLAN
       GROUND WATER  SUPPLY SURVEY

   FINAL REPORT  — DETERMINATION'OF THE
     QUALITY OF  GROUND WATER SUPPLIES

-------
                    DRAFT OUTLINE  OF  ITEMS TO BE ADDRESSED

                                    IN THE

                        QUALITY ASSURANCE PROJECT PLAN

                                   FOR THE

                          NATIONAL PESTI-CIDE SURVEY


                                      By

                              Task Group Leaders

                         Office of Pesticide Programs
                                     and
                           Office  of  Drinking Water
                                                               Project NPS
                                                               Section No  1
                                                               Revision No.
                                                               Month Year
                                                               Page 1 of 1
OPP PROJECT NUMBER

ODW PROJECT NUMBER


PROJECT PERIOD
APPROVALS:

Director, Hazard Evaluation Division,  OPP  ?




Quality Assurance Officer,  OPP:




Director, Criteria and Standards Division, ODW ?




Quality Assurance Officer,  ODW:




                                -5.1-
DATE
DATE
DATE
DATE

-------
                                                                Project NPS
                                                                Section No. 2
                                                                Revision No.
                                                                Month Year
                                                                Page 1 of 2
                                  SECTION 2

                              TABLE OF CONTENTS




 Title  Page

 Table  of Contents

'Project Description  .

 Project Organization  and Responsibility

 QA Objectives  for  Measurement Data

 Sampling Procedures

 Sample Custody
                                            V
 Calibration  Procedures  and Frequency

 Analytical Procedures

 Data Reduction,  Validation, and Reporting

 Internal Quality Control Checks

 Performance  and  System  Audits

 Preventive Maintenance

 •Specific Routine Procedures Used to Assess Data
   Precision, Accuracy,  and Completeness

 Corrective Action

 Ojjality Assurance  Reports to Management


 Appendices:

 A  (Section) 6.0,  Quality Assurance Project Plans Versus
    Project Work  Plans,  from the EPA-QAMS Guidelines
    (QAMS-005/80)

 B  Standard  Operating Procedures
SECTION

   1

   2

   3

   4

   S

   6

   7

   8

   9

  10

  11

  12

  13


  14

  15

  16
                                -E.2-

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                                                          Project NPS .
                                                          Section No  2
                                                          Revision No
                                                          Month Year
                                                          Page 2 of 2
                            DISTRIBUTION
Steering Committe for the NPS:

     Stuart Cohen (OPP), Co-chairman
     Arthur Perler (ODW), Co-chariman
     Peter Kuch (OPP)
     George Denning (ODW)
     Herbert Brass (ODW)

Task Group Chairpersons for the NPS:

     Stuart Cohen (OPP):  Analyte Selection, Geophysical Characterization
     Peter Kuch (OPP):  Pesticide Usage  Information
     George Denning (ODW):  Sample Sites Location, OMB Submission
     William Coniglio .(ODW): Occurrence Data
     Kris Khanna (ODW):  Health Advisories
     John Trax (ODW):  State Liaison
     Herbert Brass (ODW):  Analytical Methods and Sampling,.Analytical
       Contractor Selection and Management
     Irvn'n Pomerantz (ODW):' Quality Assurance Project Plan
     Elizabeth Leovey-
-------
                                                               Project NPS
                                                               Section'No.. 3
                                                               Revision No
                                                               Month' Year
                                                               Page 1 of 3
                                 SECTION 3
                            PROJECT DESCRIPTION

3.1  Data Quality Objectives for the Project
     A summary  of the  statement of the Data Quality Objectives (DQOs) for the
     National  Pesticide  Survey (NPS) should be in this section.  The DQO state-
     ment includes:
     0  Statement of Project Objectives
        (intended use  of the data)
     0  Design  of the  Data Collection Scheme
        (selection of  analytes, of types of ^samples, of sites, etc.)
     0  Statement of the Data Quality Objectives
        (precision, accuracy, representativeness, comparability,
        completeness in  relation to the data collection plan)
3.2  Quality Assurance Project Plan for the Project
     Development of the  DQO statement precedes the development of a QA Project
     Plan.  After decisions are made aoout project objectives, project design,
     and data collection quality objectives, plans can be made to conduct the
     project in a manner to assure that the collected data does meet the stated
     needs.
3.3  Outline of the QA Project Plan for the NPS
     The following outline of issues/procedures that need to be addressed in
     order to plan for the conduct of the NPS was developed according to the
     EPA QAMS Guidelines (QAMS-005/80) and the recent experience of the Office
     of Drinking Water in planning and conducting the National Inorganics and
                                  -E.4-

-------
                                                                Project NPS
                                                                Section No. 3
                                                                Revision No.
                                                                Month Year
                                                                Page 2 of 3
   -  Radionuclides Survey (NIRS).   It is  to  be  reviewed  by OOW/OPP Managers,
     Task Group Chairpersons,  HED  Ground  Water  Team,  and QA personnel  for
     clarity, accuracy and completeness.  The final outline will  include
     their input and will serve  as a  comprehensive check list  for those who
     plan the operational phases of the project.
3.4  Documentation of the QA Project  Plan for the NPS
     EPA Quality Assurance Policy  requires documentation of the QA plans for
     environmental data collection projects, and the  identification of the
     key persons who will be responsible  for the associated activities.  The
     QAMS-005/80 format includes the  various^ activities  that require planning.
     Documentation of the plans  can be in various forms.
     3.4.1  Direct Presentation
            Information about  the  planned conduct of  an  activity  can be pre-
            sented in the text of  the QA  Project Plan.
     3.4.2  Reference to Work  Plan Documents
            Presentation of information in a Project  Work Plan document can
            be referenced in the applicable  section of the master QA Project
            Plan.  The Work Plan document should be readily available  in a
            permanent file of  survey  records, through a  designated custodian.
            The cover page of  the  document should be  appended  to  the plan to
            facilitate retrieval.   The reference in the  master QA plan must
            be very clear (page  number and location in the work plan);
                               -E.5-

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                                                          Project NPS
                                                          Section No. 3
                                                          Revision No.
                                                          Month Year   '
                                                          Page 3 of 3
       Additionally, a "QA Project Plan locator page" should be inserted
       at the  beginning of the Work Plan document to assure traceability
       of the  applicable section.   Appendix A,  (Section) "6.0 Quality
       Assurance Project Plans Versus Project Work Plans" from the QAHS-
       005/80  Guidelines, contains information about relating project
       planning documents to- sections in a master QA Project Plan.
3.4.3  References  to Standard Operating Procedures (SOPs)
       Presentation of information in an SOP document can be referenced
       in the  applicable section of the master QA Project Plan.  The SOP
       should  be readily available in as-permanent file of survey records,
       through a designated custodian.  The cover page should be appended
       to the  plan to facilitate locating/retrieving it in the file of
       survey  records.  Appendix B, "Standard. Operating Procedures,"
       contains information about relating SOPs to sections in a master
       QA Project  Plan.
                               -E.6-

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                                                               Project NPS
                                                               Section No. 4
                                                               Revision. No.
                                                               Month Year
                                                               Page 1 of 1
                                  SECTION 4

                  PROJECT  ORGANIZATION AND RESPONSIBILITIES


     This section  should present  the roles of the Office of Pesticide Programs

and the Office of  Drinking Water  for this project.  It should include the

roles of the Divisions  and/or  Branches and/or groups within each Office that

have been assigned key  responsibilities, and also the functions of QA personnel

in each Office. Names  of  Directors, Chiefs, Group Chairpersons, and. QA

Officers should appear  with  their respective organizational listings.  Tables

or Charts should be developed  to  show line authority for the conduct of the

project.
                                    -S.7-

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                                                               Project NPS
                                                              . Section No. 5
                                                               Revision No.
                                                               Month Year
                                                               Page 1 of 8
                                 SECTION 5
                      QA  OBJECTIVES FOR MEASUREMENT DATA

     This section addresses the analytical methods selected to measure the
analytes of interest,  the minimum reporting limits to be used for analytical
results, and the precision, accuracy, comparability, representativeness and
completeness objectives  for the measurement data to be generated during the
survey.   Following is  an  outline of issues to be addressed/information to be
obtained for these aspects of project planning.
5.1  Methodology
     0  Criteria used  to  select methodology fbr the analytes chosen during
        the development of the Data Quality Objectives (DQOs) for the NPS.
     0  Status of selected methods as standard or non-standard for pesticides
        in water or in drinking water.
     0  Generation of  precision and accuracy data for non-standard or non-
        approved methods  may be required so the EMSL-CI Equivalency Staff can
        statistically  compare the new method to an accepted method.  If a
        totally new method is required for any NPS analytes, the criteria for
        acceptable precision and accuracy needs to be set.  The precision and
        accuracy objectives stated in the DQOs for the NPS can serve as a
  — -    guideline to needs.
     0  Tables for Section 5 should include a listing of the types of
        methodology to be used, the analytes to be-measured with each type,
                               -E.8-

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                                                                Project NPS
                                                                Section No.  5
                                                                Revision No.
                                                                Month  Year
                                                                Page 2 of 8
        the source of each method and its (numerical)  identification  in  the

        referenced source.  An example format is shown in Table 5.1.

5.2  Minimum Reporting Limits

     0  Until survey analysts can generate minimum report limits,  the method

        statements of detection limits might be  used as guideline  analytical

        information for survey designers.

     0  Prior to the survey, participating analysts should generate the

        minimum reporting limits they can achieve for  survey  analytes with

        the selected methodology and the equipment they will  use during  the
                                            s.
        survey.  (All the NIRS analysts used the procedure in Appendix A of

        EPA-600/4-82-057, "Methods for Organic Chemical Analysis of Municipal

        and Industrial Wastewater.")

     0  Minimum reporting limits for each analyte are  included in  the format

        shown in Table 5.1.

5.3  Precision and Accuracy

     0  Until survey analysts can generate precision and accuracy  data,  the

        method statements of precision and accuracy might be  used  as  guideline

        analytical information for survey designers.

     0  Prior to the survey, participating analysts should analyze standard

_ -     solutions to generate precision and accuracy data, and calculate statis-

        tics to indicate the quality of data they can  achieve for  survey

        analytes with the selected methodology and the equipment they will
                                -E.9-

-------
                                                               Project NPS
                                                               Section No. 5
                                                               Revision No.
                                                               Month Year
                                                               Page 3 of 8
        use  during  the  survey.  The solutions should undergo any pre-treatments

        (e.g.,  concentration procedures) that are planned for survey samples.

        The  concentrations of the standard solutions used to generate the

        data should be  reported and should be at the level expected in survey

        samples.  Estimates of expected concentrations might be available

        from survey designers.

     0   At least  one concentration was analyzed on seven different days by NIRS

        analysts.   For  most types of analyses, two concentration levels were

        analyzed  and reported.  Survey planners designated the statistics to

        be calculated.  The Table 5.1 format includes precision and accuracy
                                           L
        statistics  and  the concentrations) of the standard solution(s) used /

        to generate the data for each analyte.

5.4  Comparability

     5.4.1  Comparable  Application of Selected Methodology

            0  Standard Operating Procedures (SOPs) Required and Reviewed
               (See Appendix B)

               -  Any deviations from a selected method should be known.

               -  If more than one laboratory is using a method,
                 significant differences can be resolved.

            0  Precision and Accuracy Data Required

_ -            -  Serves as a check on acceptable application of
                 analytical method.
                               -E.10-

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                                                           Project NPS
                                                           Section No.  5
                                                           Revision No.
                                                           Month Year
                                                           Page .4 of 8
5.4.2  Comparable Generation of Criteria Data Prior to Survey
       All analysts should use the same procedures to generate data and
       to calculate minimum reporting limits and precision and accuracy
       statistics, regardless of the type of analytical  method used.
5.4.3  Comparable Pre-Treatments of Samples                •'
       0  Familiarity "with the methodologies and review of the SOPs from
          the laboratories will help identify issues about pre-treatments.
       0  If a pre-treatment is presented as an option in any of the
          analytical procedures, it may be possible to establish a pro-
          tocol to minimize analytical  time, to ensure a consistent
                                       i
          response to the variant, and  to provide for the treatment only
          as necessary.
       0  Data handlers need to be alerted about segregating data repre-
          senting treated samples from  data reported for non-treated
          samples for the same analyte(s).
       0  Pre-treatments conducted by more than one laboratory should be
          conducted in a comparable manner.  Review of the SOPs and,  to
          some extent, comparison of the precision and accuracy data
          generated from pre-treated solutions by the laboratories can
          provide a basis for planning/ensuring comparability.
5.4.4  Comparable Spiking Concentrations
       0  Since the amount of spike used affects the magnitude of a sub-
          sequent percent recovery calculation, standardization of the
                             -5.11-

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                                                          Project NPS
                                                          Section No- 5
                                                          Revision No.
                                                          Month Year
                                                          Page 5 of 8
          amount  that will be used by the laboratories for survey samples
          should  be established.  This will provide a comparable basis
          for  using the recovery data to characterize the quality of
          survey  data at the end of the project.
       0   NIRS analysts report detailed information about spiking
          operations.  An example of the bench sheet for reporting the
          information is in Table 5.2.
5.4.5  Comparable Acquisition of Reported Data
       The data user should be informed about how a reported analytical
                                       V
       result  was obtained.  Laboratory SOPs should include this informa-
       tion and it should be included in reports of the data to the
       user.   Is  the result routinely:
            0   from one analysis of one sample?
            0   an average from one analysis each of field replicates?
            0   an average from one analysis each of two or more
               extracts from one sample?
            0   an average of two or more quantifications (e.g.,
               GC runs) of aliquots from one processed sample?
            0   or other possibilities, depending on the nature
               of the analysis?
5.4.6  Comparable Reporting Standards
       0   Identification of the type of data if some is produced from
          pre-treated samples and some is not for the same analyte.
       0   Units to be used.
                            -E.12-

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                                                                Project NPS
                                                                Section No.  5
                                                                Revision No.
                                                                Month Year
                                                                Page 6 of 8
            0  Significant figures to be reported.

            0  Correction factors may be an issue.   If so,  should they  be

               reported with the raw data or be applied prior to reporting?

            0  Other issues pertinent to the methodology to be used.

5.5  Representativeness During Analytical Operations

     Analysts are responsible for ensuring that they use a  representative

     aliquot of any sample(s) they analyze.

5.6  Completeness of Valid Data Obtained
                                                                  7
     Participating analysts should submit their estimate of the percentage  of

     samples' they receive for which they can obtain valid data.  Estimates

     should be based on their previous experience in conducting the  analyses

     they will perform on survey samples.
                                  -E.13-

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                                                                         Project NFS
                                                                         Section No.  5
                                                                         Revision No.
                                                                         Month Year
                                                                         Page 7 of 8
   Parameter
     and
EPA Methodology^3'

FOUR ELEMENTS,
  Atomic Absorption-
  Furrice Technique:

  Arsenic (206.2)

  Cadmium (213.2)

  Lead (239.2)

  Selenium (270.2)
                                        TABLE 5.1

                                       INORGANICS*
  Minimum         Cone.  (mg/L)
 Reporting            for            Precision
Limit (mg/L)(b)   P&A Statistics*^    (% RSD)(d'
Accuracy
{% REH6'
ONE ELEMENT,
  Atomic Absorption-
  Cold Vapor Technique:

  Mercury, Total  (245.1)
THIRTY-TWO ELEMENTS AND SILICA,
  Inductively Coupled
  Plasma-Atomic
  Emission Spectrometry:

  Aluminum (200.7)

  Antimony (200.7)

  Barium (200.7)

  Beryliurn (200.7)


*
Footnotes for Table 5.1 are at the end  of Table  5.2,
                                            -2.14-

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                                                               TABLE 5.2



                                                         SAMPLE  0
Spiked
Data
Arsenic


Selenium


Lead Cadmium
       Analyst
       Date of Analysis
       Concentration of
       Unspiked  Sample mg/L
 i
Id
U1
I
       Spike Volume
       Spike Concentration
       Concentration
       Sample  Plus  Spike mg/L
       Concentration of
       Spiked  Sample Found
       Volume of  Sample
       Calculated  %
       Recovery	
                             Date Reviewed hy:


                             Additional  Comments;
Date:
-O 3C 70 trt -O
(u o n> n> -i
in 3 < o o
n> r«- -•• ri- tj.
  3- v> —•• o>
CD   -•• o o
  -< O 3 c*
O (D 3
-h Q»   Z Z
  -I Z O -O
CD   O •  (/I

       cn

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                                                               Project  NPS
                                                               Section  No   6
                                                               Revision No.
                                                               Month Year
                                                               Page 1 of 4
                                 SECTION 6
                             SANPLING PROCEDURES

6.1  Sites
     A description of the criteria used to select sampling  sites.   If  this  is
     included in Section 3, that section can be referenced.
6.2  Type of Samples
     Grab?  Raw?  Finished?   Ground?  Surface?
6.3  Number of Samples Per Site
     Survey samples required  from each site, including any  duplicates  required
     for individual analytical methods.     »•
6.4  Collection of Duplicate  Samples
     The rate of collection' and procedure' to select  sites for  collection  of
     duplicate samples to be  analyzed for quality control purposes.  (If  the
     procedure to select the  sites is in Section 3,  that section  can be
     referenced.)
6.5  Sample Collectors
     0  Who will  collect the  samples?
     0  How will  sample collectors  be  "recruited"?
     0  Do collectors need  special  training?
6.6  Scheduling System for  Sample Collection
     0  The analytical capacities of participating laboratories  and  the
        allowable holding times  for samples govern the  rate  at which samples
        should be scheduled for  collection.
     0  A system for control  of  the rate  should be planned.

                              -E.16-

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                                                                Project NPS
                                                                Section No.  6
                                                               .Revision No.
                                                                Month Year
                                                                Page 2 of 4
6.7  Sampling Materials
     0  Required supplies:  containers,  preservation equipment for collectors,
        preservation,chemicals, etc.
     0  Required preparation of containers or equipment (e.g., special  cleaning,
        rinses, etc.)
     0  Pre-survey checks on quality  of supplies.
6.8  Field Blanks
     0  Preparation and rate of usage.
     0  Any treatments to be done in  the field, (e.g., addition of a preservative)
6.9  Shipment of Sampling Materials
     0  Contents of sampling kits           v
     0  Destination
     0  Any arrangements for second-party distribution to collectors
6.10 Collection Procedures
     0  Reference the source(s) of the description(s) of collection procedurets):
        -  Analytical  Method
        -  EPA 600/4-82-029, "Handbook for Sampling and Sample
           Preservation of Water and  Wastewater"
        -  EPA 600/8-80-038, "Manual  of Analytical  Methods for
           the Analysis of Pesticides in Humans and Environmental
           Samples"
""      -  ASTM Annual Book of Standards Part 31,  03370-76 "Standard
           Practices for Sampling Water"
        -  Other
                                  -E.17-

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                                                               Project NPS
                                                               Section No. 6
                                                               Revision No.
                                                               Month Year
                                                               Page 3 of 4
     0  If a non-standard procedure is to be used, it should be described
        either in an Appendix to the Plan or in Task Group records that are
        readily available in a permanent file of survey records, through a
        designated custodian.  In the latter case, a traceable reference to
        the Task Group  record is sufficient for this item in the Plan.  (See
        Appendix A).                       •       .
     0  Pre-survey tests of the comparability of collection procedu.es in
        cases where alternatives are expedient or when a non-standard
        procedure is under consideration.
     0  Development of  a "Sampling Instructions" packet for sample co1 lectors.
6.11 Preservation                          l
     0  Chemical additions required for analytes of interest.
     0  Department of Transportation regulations may affect plans or require
        a waiver for shipment of preservatives, or preserved samples.
     0  Icing requirements.
6.12 Transport of Samples and Field Blanks to Laboratories
     0  Mode (holding times may affect choice).
     0  Information and shipping materials needed by field personnel.
     0  Arrangements for payment of shipping charges.
— •  °  Decision on destination - All sent to TSD for distribution or some/all
        sent directly from the field to the analytical laboratories?
                                 -E.18-

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                                                                Project NPS
                                                                Section No.  6
                                                                Revision No.
                                                                Month Year
                                                                Page 4 of 4
6.13 Checks or Treatments of Samples Prior to Distribution to Analysts
     0  There may be a need to check some common condition of samples, e.g.,
        the pH if samples are acidified in the field.   In this case,  plans
        could be made for a central  laboratory to check the condition and
        keep records for all the samples, or else for  designated persons  in
        each analytical laboratory to check and keep records.
     0  .Checks (e.g., for residual chlorine) or pre-treatments that are only
        required for some types of analyses would probably be done in the
        laboratory responsible for those analyses.   These method-specific
        checks or pre-treatments should be discussed elsewhere (Section 9) in
        the Plan.
6.14 Storage of Samples and Field Blanks Prior to Analysis
     0  Any special conditions required.
6.15 Holding Times
     0  Maximum holding times according to analytes from time of collection  to
        beginning of analyses.
6.16 Disposal of Samples
     0  Who will  be responsible for disposal?
     0  Who will  be responsible for releasing samples  for disposal?
— -  °  Are special techniques required for disposal of pesticide samples?
     0  Are containers to be returned to TSD?
                              -E.19-

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                                                                Project NPS
                                                                Section No. 7
                                                                Revision No.
                                                                Month Yea.   •
                                                                Page  1 of 5
                                 SECTION 7

                                SAMPLE  CUSTODY


     If samples are needed  for  legal purposes  (e.g.,  enforcement),  "chain-of-

custody" procedures as defined  by the Office of Enforcement  should  be planned.

A manual describing the required procedures is available  from  that  Office.

Survey designers should specify if  the  procedures  are necessary.

     For any project, plans need to be  made to document the  identity  of each

sample and to keep records  that describe each  sample  and  trace each through

the collection-to-disposal  processes presented in  Section 6, "Sampling
                                           \.      •                            .
Procedures."  Persons should be designated  to  be  responsible for  the  samples,'

to keep suitable records about  the  samples  while  in their custody,  and to

move them along to the next process.  All records  should  be made  in ink and,

whenever feasible, kept in  permanently-bound books.   Dates and signatures

should be required.

     Survey planners should also devise a system  for  tracking  the entire

sample stream during the project so they can arrange  a steady  flow  of samples

to the laboratories within  holding  times, and  ensure  the  timely completion  of

the project.

i.l  Field Operations

     0  System and person(s) responsible for record-keeping  about the sources

        of collected samples.  If information  is  required from the  private

        sector (plant manager,  well owner,  etc.),  OMB approval is probably

        required.



                              -E.20-

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                                                                Project  NPS
                                                                Section  No. 7
                                                                Revision No.
                                                                Month Year
                                                                Page,2 of 5
     0  System for sample identification.
     0  System for record-keeping  by  the  sample  collector  about  sample
        collection information  and, as  appropriate,  field  measurement and
        preservation information.  Signature  of  sample  collector should  be
        required.
     0  System and person(s')  responsible  for  any transport records  that  need
        to be kept, or if signatures  are  required.
7.2  Laboratory Operations
     0  Designation of person(s) to receive samples  and log them in.  Specify
        information to be recorded.
                                           i
     0  System and person(s)  responsible  for  re-labeling audit samples (field
        blanks, duplicates,  blinds) if  they are  to be disguised  as  regular
        survey samples.   Include a system  to  notify  handlers of  survey data so
        they can distinguish  audit data from'  survey  sample data.
     0  System, person(s) responsible,  and record-keeping  for any checks on
        some condition common to all  samples  (e.g.,  pH), if required, and for
        reporting  the results to analysts, if necessary.
     0  System, person(s) responsible,  and record-keeping  for any storage of
        samples and/or for their distribution to analysts  or to  other labora-
        tories.  If samples  are distributed to.other laboratories,  each  should
        have a Sample Custodian who maintains a  log  of  samples received  and
        is responsible for their distribution to analysts  and for their  final
        deposition.
                               -E.21-

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                                                               Project NPS
                                                               Section No. 7
                                                               Revision No.
                                                               Month Year
                                                               Page 3 of 5
     0  Analysts  are  responsible for maintaining traceable records about any
        treatments of a  sample while it is in their custody.
     0  System, person(s)  responsible, and record-keeping for storage/disposal
        of any unused sample matter and for sample containers and any other
        sampling  equipment.
7.3  Overall  Sample Tracking System
     0  A system  for  tracking sample-handling operations from the shipment of
        collection kits  through disposal of analyzed samples is highly recom-
        mended.   Such a  system is in use for the NIRS.  It requires input
        from key  survey  personnel, and has proven to be very effective in
        controlling the  rate of sample collection according to the analytical
        capacities of participating laboratories, in assuring that back-logged
        samples can be analyzed within holding times, in keeping laboratory
        supervisors informed about the progress of their analysts in processing
        samples,  and  in  presenting reports to ODW management about the status
        of survey operations.
     0  Figure 7.1 is an example of the monthly progress report for NIRS that
        is sent to all analysts, laboratory chiefs and QA officers, and TSD
        survey managers.   It communicates information about shipment of
        sample kits,  the number of samples received to date by each laboratory,
        the number of samples processed by each laboratory through data
        transmittal to TSD, and the sample receipts anticipated for the next
        month.
                                 -E.22-

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                                                                Project  NPS
                                                                Section  No.  7
                                                                Revision No.
                                                                Month  Year
                                                                Page 4 of 5
     0  Figure 16.1 is an example of a ISO quarterly  report on  the  NIRS  that

        includes summary statistics about sampling  operations.

7.4  Permanent Filing of Sample Handling Records

     0  All records should be made in ink and,  whenever  feasible, kept in

        permanently-bound books.

     0  Record books should be filed alono. with other survey  records  and

        identified in a manner to facilitate  their  later use, if  required.

        References to the location of analysts' notebooks may be  used if

        participating laboratories maintain their own permanent file  of

        analytical records.
                                           i
     0  A person should be identified in the  final  project  report as  custodian

        of the records, in case acce.ss to the records is needed at  some

        future time.
                                 -E.23-

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                                                               Revision No.
                                                               Month Year
                                                               Page 5 of 5

                               FIGURE 7.1
   'i
   ?    UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
                            CINCINNATI. OHIO
                       Technical Support Division
                        Office of Drinking Water
                            OFFICE OF WATER
             26 W, St. Clair Street, Cincinnati, OH  45268
DATE:     August 16, 1984

SUBJECT:  First Monthly Progress Report of the NIRS

FROM:     Edward M. Click, ChemistP/fll/Q
          Drinking Water Quality ArSessrrfefit Branch

TO:      Addressees
This is the first monthly progress report (of many)  for  the  NIR  survey.
This report will hopefully keep you aware of the status  of sample
shipments and redepts on a monthly basis.

The following table will detail the current status of the survey relating
to the shipment/receipt of samples and the analytical data that  has  been
submitted for verification and Input into the computer.   The effective
date of this memo is 8-6-84.
LABORATORY       SAMPLES RECEIVED    DATA RECEIVED   DATA VALIDATED

TSD                       27              11               0

MERL                      27               0               0

EMSL-IAS-ICP              25               0               0

EMSL-ES-ICP                200

EMSL-IAS-RAD              27               0               0

EERF-RAD                   0               00


To date, 91 shipment sets have been sent to the states for later  sampling,
The anticipated sample load for the month of August is 29.  The antici-
pated sample load for the month of September, at this time, 1s 65.

As always, 1f I can be of assistance, don't hesitate to call or stop  by.


Addressees:



                                  -E.23a-

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                                                               Project NPS
                                                               Section No- 8
                                                               Revision No.
                                                               Month Year
                                                               Page 1 of .1
                                 SECTION 8
                     CALIBRATION PROCEDURES AND FREQUENCY
     The participating  laboratory(ies) should provide information about the
calibration of any piece  of equipment that will be used for measurement
procedures during a project.
8.1  Type of Information  to be Provided
     0  Information about any solutions that will be used to calibrate or
        check the performance of the equipment (e.g., calibration solutions,
        internal  standard spiking solutions, equipment performance check
        solutions).  Traceability to a recognized source of standard materials
        is also of interest.
     0  A description of  the procedure(s) that will be used to,  perform the
        calibration or performance check.
     0  The criteria or the planned frequency for recallbrations.
8.2  Location of the Information
     A written Standard Operating Procedure (SOP) that includes the cited  infor-
     mation for equipment that will be used may be referenced rather than
     repeating the information here.  Each referenced SOP should be:
        0  the one that will be used during the project;
        0  readily available in a permanent file of survey records, through
           a designated custodian.
     See Appendix B, "Standard Operating Procedures."
                                   -E.23b-

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                                                                Project  NPS
                                                                Section  No  9
                                                                Revision No.
                                                                Month  Year
                                                                Page 1 of 2
                                  SECTION 9

                              ANALYTICAL METHODS


     Although standard measurement methods are usually  selected for a  data

collection project,  they often contain options because  of sample matrix  vari-

ables, the availability of alternative equipment,  etc.   Some selected  method-

ology may be for state-of-the-art analyses that are subject to continuous

analyst improvement.  A copy of a selected method,  then, cannot serve  as an

unequivocal description of how an analyst will conduct  an analysis  on  project

samples.  The participating laboratory(ies) should  provide information about

how each analyte or characteristic (e.g., pH}  will  be measured.

9.1  Type of Information to be Provided

     0  Information about reagents that will be used.

     0  Identification of equipment that will  be used.

     0  The stepwise procedure for any pre-treatment of samples (e.g.,

        extraction,  digestion).

     0  The stepwise procedure that the analyst will use for measurements

        on project samples, including any pre-analysis  checks (e.g., for

        residual chlorine) that will  be made.

     0  Criteria that will be used if judgements about  optional steps  need

 — "    to be made.
                               -E.23c-

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                                                               Project NPS
                                                               Section No. 9
                                                               Revision No.
                                                               Month Year
                                                               Page 2 of 2
9.2  Location of the  Information
     A written Standard  Operating Procedure (SOP) that includes the cited
     information for  an  analyte or characteristic that will be measured may
     be referenced rather than repeating the information here.  Each referenced
     SOP should be:
        0  the one that  will be used during the project;
        0  readily available in a permanent file of survey records, through
           a designated  custodian.
     See Appendix B,  "Standard Operating Procedures."
                                -E.23d-

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                                                               Project NPS
                                                               Section No. 10
                                                               .Revi si on No.
                                                               Month Year
                                                               Page 1 of 4
                                  SECTION  10
                   DATA REDUCTION,  VALIDATION  AND  REPORTING

     Survey planners need to develop  processing  and management  systems  for
each type of data required for a project.
10.1  Types of Data That Require Processing and  Management
      10.1.1  Data Collected Prior to Collection/Analyses of Project
              Samples
              0  Measurements required to  plan the design of the  sampling
                 program.
              0  Measurements for procedure or method  equivalency checks
                 for field and/or analytical operations.
              0  Measurements to establish minimum reporting limits for
                 measurements on project samples.
              0  Measurements to establish precision and accuracy capabilities
                 for measurements on  project samples.
      10.1.2  Sample Background Data
              0  Information about the source  of the sample (e.g., plant
                 treatments, well information).
      10.1.3  Sample Collection Data
_ -           °  Results from any measurements made in the  field.
              0  Outcomes from adding preservatives.
              c  Information specific to the project.
                               -E.23e-

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                                                         Project NPS
                                                         Section No.  lJ
                                                         Revision No.
                                                         Month Year
                                                         Page 2 of 4
10.1.4  Sample Treatment Data

        0   Measurements made because of pre-analytical checks or

           treatments of samples.

10.1.5  Analytical  Data for Samples

        Data handling (reduction, validation and reporting) procedures

        for analytical results are usually documented in a laboratory's

        Standard Operating Procedure (SOP) for each measurement method

        and/or in their Laboratory QA Program statement.  These docu-

        ments may be referenced  for analytical data rather than repeating

        the'information in this  section.  See Appendix B, "Standard

        Operating Procedures."

10.1.6  Analytical  Data for QC Check Samples

        0   Data handling procedures within a laboratory for results

           from internal QC check samples are usually documented  in  an

           SOP for a measurement method.  See the  above item about

           referencing SOPs.

       .°   Results from internal QC check samples  reported by laboratories-

           to external project managers.
                                                                         w
        0   Results reported for  audit QC check samples provided by

           external  sources (e.g., EPA performance evaluation samples;

           blanks,  duplicates or blinds provided by project managers to

           look like  "regular" samples).
                         -E.23f-

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                                                                Project NPS
                                                                Section No. 10
                                                                Revision No.
                                                                Month Yea•
                                                                Page 3 of 4
10.2  Data .Handling for Each Type of Data
      10.2.1  Reduction of the Data
              0  Standard for significant  figures.
              0  Standard procedure for rounding-off  operations.
              0  Equations to calculate values  from data  (e.g., concentration
                 of an analyte).
              0  Any other treatments specific  to the type  of  data.
      10.2.2  Validation of the Data
              0  Criteria or cross-checks  to  validate the integrity  of  the
                 data during collection, transfer, reduction,  storage and
                 reporting operations.
              0  System to ensure that data obtained/generated from  non-
                 uniform procedures is  segregated from "regular"  data.  An
                 example is ta-gging data from a  digested  sample if data for
                 the analyte is usually obtained from non-digested samples.
              0  Methods to screen data for conformity to specified  standards
                 (e.g., significant figures,  units to be  used  for reporting).
              0  System to check  for completeness of  data.
              0  Methods to identify and treat  outliers,  inconsistent data,
                 etc.
              0  System for originators of data  to check  interim  records or
                 outputs for error.
                                -E.23g-

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                                                               Project NFS
                                                               Section No.  10
                                                               Revision No.
                                                               Month Year
                                                               Page 4 of 4
              0   System of periodic audits of data bases for error and the
                 cause of the error.
              0   Identification of the person(s) responsible for any of the
                 planned validations.
      10.2.3   Reporting of the Data
              0   Identification of reports to be made.
                 -   Immediate reports to appropriate officials when analytical
                    results exceed established "alert" criteria (e.g., MCLs,
                    Health Advisory action levels).
                 -   Interim reports of project data to management.
                 -   Reports to officials associated with the sites sampled
                                          i
                    during the survey,
                 -   Final report of data from the project.
                 -   Other reports appropriate to the project.
              0   Formats for reporting the data to ensure that uniform and
                 complete information is reported.
              0   Identification of the person(s) who are to prepare reports.
              0   Identification of the person(s) who are to receive reports.
10.3  Managing the  Data Flow for a Project
      The overall scheme of data flow for a project should be planned starting
      with its collectors or generators through its receipt by the data user.
      (A flow chart is usually needed.)
      0  Include  the names of key individuals who reduce the data, validate
         the  data or deal with the data in any manner.
      0  Completely identify computers and data bases that will be used.

                               -E.23h-

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                                                                Project NPS
                                                                Section No.  11
                                                                Revision No.
                                                                Month  Year
                                                                Page 1 of 2
                                  SECTION 11
                       INTERNAL QUALITY CONTROL  CHECKS
     For each measurement method that will  be used  during  a  project,  the
participating laboratory(ies) should provide information about the  internal
quality control checks that the analyst will  apply  to check  the quality of
the measurements made )n project samples.
11.1 Checks That Might be Planned
     0  Analysis of various types of blanks or treated  sample  aliquots to
        monitor for interferences.
     0  Analysis of duplicate aliquots from one  sample  to  assess precision.
                                            i
     0  Analysis of QC samples, laboratory  control  standards,  spiked  samples,
        etc., to assess accuracy.
     0  Other checks appropriate for monitoring  variables  pertinent to a
        particular measurement method.
11.2 Information to be Provided for Each Check
     0  The purpose of the check.
     0  The planned frequency of the check.
     0  As applicable, the source and/or the concentration of  the solution
        used.
     0  The criteria for acceptability of results of the check.
     0  The course of action if acceptance  criteria are not  met (corrective
        action in the laboratory).
                            -E.24-

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                                                               Project NPS
                                                               Section No.  li
                                                               Revision No.
                                                               Month Year
                                                               Page 2 of 2
     0   The system  for  reporting results from the checks to laboratory
        supervisors (QC reports to laboratory management).
     0   The location  of records about the checks.
11.3 Location of the  Information
     A  written Standard Operating Procedure (SOP) that includes  the cited
     information for  a  measurement method that will be used may  be- refer-
     enced rather than  repeating the information here.  Each referenced  SOP
     should be:
        0  the one  that will be used during the project;
        0  readily  available in a permanent'-file of survey records, through
           a designated custodian.
     See Appendix B,  "Standard Operating Procedures."
                             -2'. 25-

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                                                               Project NPS
                                                               Section No  12
                                                               Revision No.
                                                               Month Year
                                                               Page 1 of 2
                                  SECTION  12
                        PERFORMANCE  AND  SYSTEM  AUDITS

     Survey planners need to provide audit materials and/or  the  resources to
evaluate the performance of critical  project  operations.   (Section 14 deals
with procedures to assess audit data after it is  collected.)
12.1 Audits for Field Operations
     0  Field (shipping) blanks
     0  .Checks on the addition of preservative(s)
     0  Collection of duplicate samples  for analyses,  especially  if  volatile
        compounds are of interest          s.
12.2 Audits for Analytical Operations
     12.2.1  Audit Samples Disguised as  Field Samples  (Blinds)
             0  Field (shipping) blanks
             0  Duplicate samples
             0  Laboratory-prepared  blanks
             0  Standard solutions from  EPA,  NBS,  etc.,  sources
     12.2.2  Analyses by an Independent  Laboratory
           -  °  Duplicate samples collected in  the field.
             0  Splits of audit samples  provided  by survey managers  to
                principal laboratories.
     12.2.3  Performance Evaluation  Studies
             0  Participation in EPA Studies  or other  evaluation programs.
                          -E.26-

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                                                               Project NFS
                                                               Section No. 12
                                                               Revision No.
                                                               Month Year
                                                               Page 2 of 2
12.3 Audits for Data Management Operations
     0  Second party audits at any level of operations that include
        data handling.
     0  Types of systems that might be checked are listed in Section 10.2.2,
        "Validation of  the Data."
12.4 System Audits
     12.4.1  In-house Laboratories
             Supervisors and/or QA personnel should conduct system
             audits as  part of the routine QA activities for the
             laboratory.  Types and frequency would be included in
             the laboratory's QA Program statement.  (See Appendix B).
     12.4.2  Contract Laboratories
             An on-site system audit of the laboratory is usually a
             pre-award  requirement.  Additional system audits may be
             conducted  by the project officer during the term of
             the contract.
                             -E.27-

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                                                                Project NPS
                                                                Section No. 13
                                                                Revision No.
                                                                Month Year
                                                                Page 1 of 2
                                  SECTION 13
                            PREVENTIVE MAINTENANCE

     Any equipment used for measurement procedures should be subjected to any
kind of maintenance that will help assure its continued, quality operation.
The participating laboratory(ies) should provide maintenance information for
any equipment that will be 'used for a project.
13.1 Type of Information to be Provided
     0  Maintenance procedures that will be conducted.
     0  The person responsible for conducting the maintenance.
     0  The schedule or frequency of the maintenance.
                                            i
     0  Critical spare parts on hand and/or back-up equipment that is
        available to assure continuous operations.
13.2 Location of the Information
     A written Standard Operating Procedure (SOP) or a Laboratory QA Program
     statement that includes the cited information for equipment that will  be
     used may be referenced rather than repeating the information here.   Each
     referenced SOP or QA Program should be:
        0  the one that will be used during the project;
        0  readily available in a permanent file of survey records,  through
           a designated custodian.
     See Appendix B, "Standard Operating Procedures."
                                -S.28-

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                                                               Project KIPS
                                                               Section No. 13
                                                               Revi si on No.
                                                               Month Year
                                                               Page 2 of 2
13.3 Equipment Failures  During a Project
   - Survey planners  should establish a system for the immediate report of
     significant equipment downtime that becomes necessary during a project.
     The scheduling of  sample collection may need adjustment because of
     allowable holding  times.
                               -E.29-

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                                                                project
                                                                Section No.  14
                                                                Revision No.
                                                                Month Year
                                                                Page 1 of 2
                                  SECTION 14
                     SPECIFIC ROUTINE PROCEDURES USED TO
               ASSESS DATA PRECISION, ACCURACY AND COMPLETENESS

     Survey planners need to choose the procedures they will  use to assess
the precision and accuracy of project data and its completeness in  reference
to the data collection scheme.  Statements for all three of these data  quality
indicators should accompany any report of data from project samples.
14.1  Types of Data to be Assessed
      (Section 10.1 includes subdivisions of these types.)
      14.1.1  Data collected prior to the main project.
      14.1.2  Data about the sample source.
                                            i              '•-
      14.1.3  Data from field operations.
      14.1.4  Data from pre-analytical checks or treatments of samples.
      14.1.5  Data from analysis or measurements of samples.
      14.1.6  Data from QC check and audit samples.
14.2  Types of Assessments
      14.2.1  Precision, accuracy and completeness of data.
      14.2.2  Other Statistical Treatments
            -  °  Tests of significance
              0  Confidence limits
              0  Testing for outliers
                                     -E.30-

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                                                                Project NFS
                                                                Section No. 14
                                                                Revision No.
                                                                Month  Year
                                                              ,  Page 2 of 2
14.3  Procedures to be Selected
      14.3.1  Methods  used  to  gather the data for calculations.
      14.3.2  Equations to  calculate the assessments.
      14.3.3  Standards for significant figures in  data  used  to
              calculate the assessments.
      14.3.4  Standards for significant figures used to  report
            ,  assessment statistics.

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                                                                Project NPS
                                                                Section No. 15
                                                                Revision No.
                                                                Month Year
                                                                Page 1 of 3
                                  SECTION 15

                              CORRECTIVE ACTION


     As decisions are made about the requirements for sampling,  analyses,  and

data handling, plans should be made to provide checks and procedures  for

corrective action to ensure that activities  are conducted as  envisioned.

15.1  Elements of Plans for Corrective Action

      0  What is the standard for acceptable performance?  ("See  15.2).

      0  What check can be made?

      0  Who is responsible for monitoring the system or operation?

      0  Who needs to know about the problem so it can be corrected

         (communication chain)?             t

      0  What procedure can be used to correct the problem?

      0  Who is responsible for oversight to assure that the  problem  is

         corrected?

15.2  Standards for Common Operations
                                                                     »
      15.2.1  Sampling Operations

              0  Collection Techniques

                 -  Type of sample required
            f
                 -  Type of analyte of interest

_ .           °  Rate of Sample Collection

                 -  Holding times required

                 -  Laboratory capabilities
                            -E.32-

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                                                         Project NFS
                                                         Section No.  15
                                                         Revision  No.
                                                         Month Year
                                                         Page 2 of 3  .
        0   Measurements in the field

           -   Precision, accuracy, completeness

        0   Addition of Preservatives

           -   Outcome required

        0   Transportation

           -   Preservation required

           -   Holding times

           -   Availability of mode

        0   Storage of Samples

           -   Preservation condition required

15.2.2  Laboratory Operations        >.

        0   Analyses and Measurements

           -   Standard methodology (comparability)

           -   Minimum reporting limits

           -   Precision, accuracy, completeness.  [Laboratory
                                                   »

              Standard Operating procedures usually  include  a

              plan for corrective action based on internal QC

              checks (see Appendix B).  An additional  system for

              external (audit) checks on these standards  should

              be planned by project managers (Section  12).]
                       -E.33-

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                                                         Project NFS
                                                         Section No. 15
                                                         Revision No.
                                                         Month Year
                                                         Page 3 of 3
15.2.3  Data Management Operations
        0  Reduction,  Validation, Reporting
           -  Integrity
           -  Comparability  (standards  for rounding, calculating,
              etc.)
           -  Completeness
           -  User needs
        0  Section 10.2.2 includes  checks to be planned for data handling.
                          -E.34-

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                                                                Project  NFS
                                                                Section  No.  16
                                                                Revision No.
                                                                Month Year   .
                                                                Page 1 of 4
                                  SECTION 16

                   QUALITY ASSURANCE REPORTS  TO MANAGEMENT



16.1  Content of Periodic Reports

      0  Assessment of measurement data in terms of  accuracy,  precision,  and

        .completeness.                         /

      0  Results" of performance audits.

      0  Results of system audits, as appropriate.

      0  Significant QA problems and their resolution  or, if  appropriate,

         recommended solutions.

      0  Figure 16.1 is an example copy of a  TSD quarterly  report  on  the  NIRS,

16.2  Mechanism for Periodic Reports

      0  How often will reports be made?

      0  Who prepares the report?

      0  Who receives the report?
                          a
16.3  Content for Final Report on Project

      0  A separate section on QA should be included in  the final  report.

      0  The QA section should include a summary of  the  data  quality  infor-

         mation contained in the periodic reports.
                            -E.35-

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                                                                   Project NPS
                                                                   Section No. 16
                                                                   Revision No.
                                                                   Month Year
                                                                   Page 2 of 4
                                  FIGURE 16. L,


Project 82A:  National  Inorganics and  Rad1onuc11des Survey  (NIRS)


Description:

     The project 1s  primarily designed to provide, through  a national  sam-
pling survey, Information on the occurrence In drinking water of several
radlonuclldes (especially rad1um>228)  And on gross alpha and beta  radiation
levels.  Rad1um-228  data will also  be  used to Investigate the feasibility
of using a geological  model to  predlcythe occurrence of rad1um-228.   In
addition to the radlonucllde determinations, occurrence Information  for
thirty-seven Inorganic species  will  be gathered.  This information 1s  needed
to provide sound guidance to the Office of Drinking Water In making  regula-
tory decisions.

Status:

     The sampling phase of  the  survey  was started on July 1, 1984.   Summary
statistics, as of September 22, 1984,  describing the current status  are
presented 1n Table 1.


                                Table 1    '  .

               National Inorganics  and RadlonucMdes Survey
                      Project Status (as of 9/21/84)
          Number of weeks  Into  survey                       12
          Number o.* sites  sampled                           92

          Number duplicates  received                        13

          Number field blanks received                       1

          Total  samples received                           106

          •Number sampling  kits  shipped                    >300

          Number add shipments                            62

          Turn-around documents mailed                     294
          Turn-around documents returned*                   56

          Number schedule  forms returned by  states          29
      *Ne* York, which  h«s  sampled  48  sites,
       will  be returning  turn-around documents
       at a  later t1«e.
                           -E.36-

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                                                                     Project NPS
                                                                     Section No. 16
                                                                     Revision No.
                                                                     Month Year
                                                                     Page  3 of 4
     To date, sampling materials (bottles, cubltalners, shipping containers,
Instructions, etc.) for over 300 sites have been distributed.  This trans-
lates fnto about Z5X of sampling materials having been distributed during
the first Hi of the project period.  No shipments of sampling materials to
states have been significantly delayed or lost.  Thus, all Indications are
that there will be no significant problems 1n the distribution of sampling
•aterlals for tne NIRS project.

     The return of sawples to TSD 1s progressing very well.  There have been
no samples lost or seriously delayed, and ill samples received have been in
good condition.  All samples received to date have been adequately acidified
in the field.  Thus, there are no problems anticipated with sample preserva-
tion.  In addition, no samples have leaked or been lost due to Improperly
fitting or tightened cubitainer caps.  This 1s probably due 1n part to the
use of the "CAPLUG' Insert.  One sample leaked slightly due to a small per-
foration of unknown origin 1n the cubitainer wafll, but sufficient sample
remained for analyses.
                     •
     Several computer programs have been completed which are designed to In-
put, store, and process sampling schedule Information.  The organization of
these programs allow both a historical listing of what happened and a future
projection of anticipated sampling.  The high priority candidates (I.e.,
those that are targeted to be sampled in the month or quarter 1n which the
project week falls) are Identified and listed for convenience 1n arranging
schedules.  These listings have become very valuable 1n controlling the num-
ber of samples that might go astray and/or 1n quickly resolving problems.

     A pair of programs has been developed which permit the generation of data
entry screen forms for Inputting a wide variety of data.  These programs can
be used for many different projects and applications Including the data entry
for the NIRS project.

     Cooperation from the states has been excellent and far exceeds expecta-
tions.  While there are about 15 states that have not yet been 1n contact
with TSD, most of the others have sent back schedule fonas or Indicated that
they were flexible and would be willing to adjust their schedule to accortno-
date our needs.  At this point, there are enough sites scheduled to maintain
t relatively uniform sample flow for at least three months.

     A status report on the NIRS project has been prepared which contains addi-
tional Information on the project.

Anticipated Activity:

     1.   Continue the sampling program, analysis, data entry, and state
          and regional contacts.
                                 -E.37

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                                                            Project NFS
                                                            Section No. 16
                                                            Revision No.
                                                            Month  Year
                                                            Page 4 of 4
2.   Continue  software development for scheduling and data handling,
     Including development of user documentation for the generalized
     data entry programs.

3.   Continue  to nonltor the quality assurance of the survey.  Spedfi
     cally, to undertake a study of the quality and completeness of
     Information being returned on NIRS survey forms and to prepare
     a report  describing results, conclusions, and recommendations
     by December 31,  1984.
                                   J.P. Longtln
                                   J.B. Walasek
                         -E.38-

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                                                             Project NPS
                                                             Appendix A
                                                             Revision No.
                                                             Month Year
                                                             Page 1 of 1
- 6.0   QUALITY ASSURANCE PROJECT PLANS VERSUS PROJECT WORK PLANS

       This document provides guidance  for  the  preparation of QA Project
 Plans  and describes  16  components  which  must  be  Included.   Histori-
 cally,  »ost  project  managers  have  routinely  Included the  majority  of
 the£e 16 elements 1n  their project work plans.   In practice, 1t is fre-
 quently  difficult  to separate  Important  quality  assurance  and quality
 control functions and to isolate  these  functions  from technical perfor-
 mance activities.  For those projects where  this  1s the case, it 1s not
 deemed  necessary  to replicate  the  narrative  in  the  Quality Assurance
 Project Plan section.

       In  Instances  where  specific QA/QC protocols are addressed  as  an
                                         *
 Integral part of the  technical  work  plan,  1t is only  necessary to cite
 the page  number  and  location  in  the work  plan 1n  the specific subsec-
 tion designated for this  purpose.

       It must be stressed, however,  that whenever  this approach is used
 a "QA Project Plan locator page" must be inserted  into the  project work
 plan  Immediately  following the  table of  contents.  This  locator  page
 must list each of the Items required for the QA Project  Plan  and  state
 the section and pages 1n  the  project plan where the  Item is described.
 If a QA  Project  Plan  Item 1s not applicable to  the work plan  in  ques-
 tion,  the words 'not  applicable"  should be inserted next to the appro-
 priate component on the locator page and  the reason why  this component
 1s not  applicable  should  be briefly  stated  in the  appropriate subsec-
 tion 1n the QA Project Plan proper.
  FROM:   EPA-QAMS Guidelines (QAMS-005/80)
                           -E.39-

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                                                                Project NPS
                                                                Appendix B
                                                                Revision No.
                                                                Month Year
                                                                Page A of 5
                        STANDARD OPERATING PROCEDURES

     Several sections 1n the QAMS-005/80 guideline format for QA Project
Plans deal with activities that are exclusively  part of analytical  or
measurement activities.   These are:
          Section 8, Calibration Procedures and  Frequency
          Section 9, Analytical Procedures
          Section 11, Internal Quality Control Checks
          Section 13, Preventive Maintenance
Other sections deal with activities that are also  conducted as part of either
the  analytical process or the internal quality control  check system for
analyses.  These are:
            .  •       .    •        •          s.
          Section 10, Data Reduction,  Validation,  Reporting
          Section 14, Specific Routine Procedures  Used  to
                        Assess Data Precision, Accuracy and
                        Completeness
          Section 15, Corrective Action
          Section 16, QA Reports to Management
The  information that is cited in the outlines.for  these eight sections, as
required  for analytical  procedures, is usually included in Standard Operating
Procedure (SOP) documents that a laboratory develops for analyses conducted
by their  staff or for the QA program conducted by  the laboratory.
     The SOP for an analysis might be a totally  original write-up,  even though
'a standard analytical method is addressed.  Another approach to SOP documenta-
tion is the thorough annotation of a copy of the standard method, with original
sections  added to document laboratory-specific protocols.
                              -E.40-

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                                                                Project NFS
                                                                Appendix B
                                                                Revision No.
                                                                Month Year
                                                                Page 2 of 5
     Standard methods usually include sections  dealing with:
          0  Calibrations
          0  Stepwise Analytical  Procedures
          8  Internal Quality Control Checks
          0  Data Reduction (calculation of results)
These sections can be annotated by the analyst  to describe how the analysis
will be conducted for a project.
     Additional SOP information that usually requires specific,  added input
by the analyst or other laboratory personnel is:
          0  Preventive Maintenance
          0  Data Validation and Reporting
          0  Specific Procedures to Assess Data Precision,
               Accuracy, and Completeness
          0  Corrective Action
          0  QA Reports to Management       l
Some laboratories have these operations standardized and documented in a
statement of the laboratory QA Program.
     Copies of SOP information should be provided by  the participating labora-
tory(ies) to project managers well before the operational  phase of a project.
Those responsible for oversight of analytical operations need time to review
each SOP in case any changes are required in the operations.
     Ideally, each laboratory will have SOPs on file and available when the
participation commitment is made.  If laboratories are secured by contract,
3t)P' information can be required in the request for proposals  by requiring a
QA Project Plan on the mandatory "QA Form QAR-C" (copy attached).  The type
of information that should be included in each  section of the submitted plan
                             -E.41-

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                                                               Project NPS
                                                               Appendix B
                                                               Revision No.
                                                               Month Year
                                                               Page 3 of 5
is Itemized in each  corresponding section of this outlined project plan.   If

the proposer has  SOPs  that contain the required information,  the person can

reference the SOPs in  the appropriate sections of the project plan and attach

the entire SOPs as appendices.
                              -2.42-

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                                                                   Appendix o
                                                                   Revision No.
             QUALITY ASSURANCE REVIEW KB EXTRAMURAL PROJECTS      Month Year

                               (CONTRACTS)               ,          Page 4 of 5
I.  GENERAL

    Descriptive Title:

    Sponsoring Program Office:

    Approximate Dollar Amount:

    Duration:
II.  THIS CONTRACT REQUIRES ENVIRONMENTAL MEASUREMENTS     _^	
     (If yes, complete fora; if no, sign fora and        •   Yes     173"
     submit with procurement request)
III.  QUALITY ASSURANCE REQUIREMENTS
      (Projects involving environmental measurements)       Yes     No

      a.  Submission of a written quality assurance (QA)
          program plan (ccmaitsent of the offerer's
          management to meet the QA requirements of the
         'scope of work) is to be included in the
          contract 'proposal.
                                                i
      b.  Submission of a written QA project plar is to
          be included in the contract proposal.

      c.  A written QA project plan is required as a
          part of the contract.

      d.  Performance on available audit'samples or
          devices shall be required as part of the
          evaluation criteria (see list on reverse
          side).

      e.  An on-site evaluation of proposer's facilities
          will be made to ensure that a QA system is
          operational and exhibits the capability for
          successful completion of this project (see
          schedule on reverse side).

     "f.  QA reports will be required (see schedule on
          reverse side).
QA Form QAP.-C, Revision No. 1, 1981
                                  -S.43-

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17.   Dni?.'*IlTATION (Projects . v/olving environmental zeas ur events)
                                                                 project
                                                                 Appendix B
                                                                 Revisfon No.
                                                                 Month Year
                                                                 Page 5 of 5
    ' Percentage of techr.ical evaluation zoints a5Si*r.=d
     to QA

     Project Officer estimate of percentage of cost
     allocated to environrental raeasuretents
             OC Reference        Split Samples      Henuired    FPJT'UT'CT
                                      for              for
                    .C— 9  '       Cross-^Coc'c&r'' son
              (Yes or No;         CTes or Hoi      (les or, :io)
QA System Audits are. required:  Preaward 	; during contract:

QA Reports are required:  With Progress Reports	: with ?inal  Repc


The signatures below verify that the QA requirements have been  establi;

QA Officer:                             Project Officer:
Sisr.a?ure                    Date       Si»r.ature                     Date

After sifir^tures, a copy of this fora ciust be included with  the Request for
Proposal arc sent to the Contracts Office and a copy placed  on file with
the'QA Officer.
OA ?cns QAR-C
                                  -E.44-

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                     QUALITY ASSURANCE PROJECT PLAN

                       GROUND WATER SUPPLY SURVEY
              Mary Ann Feige, Quality Assurance Coordinator
                                  and
                    J. Wayne Mello, Project Engineer
                      Water  Supply Technology Branch
                        Technical Support Division
                        Office  of Drinking Water
                            Office of Water
                   U.S.  Environmental' Protection Agency
                            Cincinnati, Ohio
                                                                   r i
                                                                   Section  0
                                                                   Revision1No.  1
                                                                   May 1983
                                                                   Page 1 of 2
Project Number:   FY  '81  -  81,  FY  '82  - 82B, FY  '83 - 828

Project Period:   October 1980  - February  1983



APPROVALS:


Branch Chief, WSTB  V^Wx,  \l//^^2L^^     Date
                                                            '    /
Branch Chief, DWQ& OeUW^ Q 6/Ut
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                                 CONTENTS
                                                                    Section u
                                                                    .Revision No.  1
                                                                    May  1983
                                                                    Page  2 of  2
Distribution
Introduction
Project Description
Project Organization and Responsibilities
Quality Assurance Objectives for Measurement Data
Sampling Procedures
Sample Custody
Calibration Procedures and Frequency
Analytical Procedures
Data Reduction, Validation, and Reporting
Internal Quality Control Checks
Performance and System Audits               ^
Preventive Maintenance
Specific Routine Procedures Used to Assess Data
  Precision, Accuracy, and Completeness
Corrective Action
Quality Assurance Reports to Management
SECTION

   1
   2
   3
   4
   5
   6
   7
   8
   9
  10
  11
  12
  13  .

  14
  15
  16
APPENDICES:

A.  Ground Water Supply Survey, Status Report #1, February  1981
B.  Sampling and Shipping Instructions for the Ground Water Supply
    Survey, December 22, 1980
C.  Contract #68-03-3031, Determination of the Water Quality of
    Ground Water Supplies (selected pages)
0.  B.A. Kingsley, et al., "Determination of the Quality of Ground
    Water Supplies," January 1983
                                  -E.48-

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                                                          Section 1
                                                          Revision No.
                                                          May 1983
                                                          Page 1 of 1
                    SECTION 1

                  DISTRIBUTION
James J. Westrick, Chief, WSTB, TSD
0. Wayne Mello, Project Engineer, WSTB, TSD
Herbert 0. Brass, Chief, OWQAB, TSD  '
Robert F. Thomas, Contract Project Officer, DWQAB, TSD
Mary Ann Feige, Quality Assurance Coordinator (until. 1/82), TSD
Audrey D. Kroner, Quality Assurance Coordinator (after 1/32), TSD
Lowell A. Van Den Berg, Director, TSD
Irvnn Pomerantz, Quality Assurance Officer, ODW
                        -S.50-

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Project GWSS
Section 2  '
  vision No. 1'
   . 1983
   e 1 of 1
                                          SECTION 2

                                         INTRODUCTION
               Volatile organic contaminants (VOCs) are a general  category of
          synthetic organic chemicals which include low molecular weight, volatile
          halogenated aliphatic and aromatic compounds.  Many VOCs are commonly
          used industrial, commercial, and household solvents which have been
          detected frequently in ground water supplies.  Numerous  incidents of con-
          tamination of well  water by such VOCs as trichloroethylene, 1,1,1-trichloro-
          ethane, tetrachloroethylene, benzene, xylene,, etc., have been reported
          across the country.

               Many of the VOCs are adverse to human health in some measure; some
          VOCs are known or' suspected carcinogens.  Therefore, the Environmental
          Protection Agency is considering various regulatory alternatives for
          limiting public exposure to VOCs in drinfcing water.  In  order to develop
          a sensible, technically sound regulatory posture, the Agency must have a
          strong base of data on the occurrence of VOCs in drinking water.  To
          supplement the data which have been gathered in previous EPA surveys'and
          various State investigations, the EPA, Office of Drinking Water (ODW),
          Technical Support Division (TSD), Cincinnati, Ohio, conducted an extensive
          sampling and analysis program to examine the occurrence of VOCs in drinking
          water from ground water sources.

               The following Quality Assurance Project Plan covering the sampling
          and measuring activity requirements for the survey is in accordance with
          EPA policy requirements that each office or laboratory generating environ-
          mental data has the responsibility to implement minimum procedures which
          assure that the precision, accuracy, completeness, representativeness,
          and comparability of its data are known and documented.
                                            -E.51-

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                                                                    Section 3
                                                                    Revision No.
                                                                    May 1983
                                                                    Page 1 of m
                                SECTION  3

                           PROJECT DESCRIPTION
     The Technical  Support  Division  (TSD),  Office  of  Drinking Water,
conducted a national  survey  of water  supplies using ground  water sources.
Samples from approximately  1,000  ground water systems w=re  to be analyzed
to determine total  organic  carbon  (TOC) levels and the 'presence of purgeable
volatile organic chemicals  (VOCs).   The major objectives  of the survey
were:

         (1)  to provide  data on  the  frequency and magnitude of
              occurrence  of  VOCs  in  systems  using  ground  water; and

         (2)  to provide  the states  information  on systems  suspected
              of being contaminated  by purgeable VOCs.

     The survey was divided  into  two  parts.  A random sample of 500
systems was selected for  sampling  from the  national inventory of public
water systems.  In  the second part of the survey,  the states were asked
to select 500 suspect supplies for inclusion in  the program (see Appendix
A).

     Information packages were distributed  to all  the states and Puerto Rico.
AIT regions and participating states  were contacted to discuss and schedule
the sampling efforts.  TSD  supplied  sampling kits  and arranged with the
regions, states or  local  utilities to have  the samples collected.  Appendix
B is a copy of the  instructions for  sampling and shipping.

     Samples were analyzed  for purgeable  halocarbons  and  aromatics and
for total organic carbon.  Residual  chlorine was also measured in samples
from chlorinated supplies to provide  information supplemental to the tri-
halomethane data.  The analyses were  conducted by  SRI International under
contract #68-03-3031, "Determination  of the  Water  Quality of Ground Water

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Project GWSS.
 ection 3
   ision No.
    1983
 "age 2 of 2
          Supplies" (Appendix C).  TSD analyzed some duplicate samples for quality
          control, and supplied the contractor with blind samples, shipping blanks
          and standards' for quality assurance purposes.

               TSD prepared periodic reports of data for submission to the cognizant
          regional offices, states, and local utilities.

               EPA response on samples containing VOCs depended on the risk associ-
          ated with the level of contamination (see Appendix A).  This ranged frorr
          simply reporting the data to the utility, state and region in periodic
          reports in the case of very low risk contamination,,to immediate reporting
          to the state and region in the case of high risk levels.  TSD personnel
          were available on a limited basis to assist states and utilities in the
          investigation of contamination incidents.  This assistance was in the
          form of advice on sampling and analytical procedures, treatment methods,
          ground water investigation techniques, and analytical assistance.  Resam-
          pling on request to assist a state was also Available on a limited basis
          during the first phase of the survey.

               Selected sites found to be contaminated during the first'phase of
          sampling were resampled.  This resample consisted of collecting water
          samples from the original sample point and at a number of well  heads,
          if possible.  The number of resamples was negotiated by the Project
          Engineer and the state contact person.

               At the end of the project, TSD conducted appropriate statistical
          analyses of the data and prepared a summary report for submittal to the
          Director, Office of Drinking Water.  The contractor prepared a final report
          on the analytical and quality control program for the survey (Appendix 0).
                                            -E.53-

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                                                                    Section 4
                                                                    Revision No.
                                                                    May 1983
                                                                    Page 1 of \
                                SECTION  4

                PROJECT ORGANIZATION  AND RESPONSIBILITIES
     A schematic showing project  organization  and  line  authority is shown
in Figure 1.

     The Ground Water Supply  Survey  was  conducted  under the  c jeral 1
management of Lowell  Van Den  Berg, Director, Technical  Support  Division.
This management function consisted of  coordination  of the  efforts of
various Divisions of  the Office of Drinking Water  and reporting progress
to the Director, Office of  Drinking  Water.

     James Westrick,  Chief, Water Supply Technology Branch (WST1?),  was
responsible for the work performed by  WSTB staff  in conducting  the  survey
and for preparing the final reports.   Wayne ^ello,  Project Engineer (WSTB),
was responsible for scheduling the sampling with-state  personnel, supplying
sampling materials, receiving samples,  shipping samples to the  analytical
contractor, preparing periodic reports  of the  data  for  distribution to
participating regions, states, and utilities,  responding immediately to
evidence of serious contamination (including prompt notification and any
resampling), conducting statistical  analyses of the data,  and  assisting
in the preparation of the final report  and papers  for presentation  and
publication in the technical  literature.

     Herbert Brass, Chief,  Drinking  Water Quality  Assessment Branch
(DWQAB), was responsible for  the  work  performed by  DWQAB staff  during the
conduct of the survey.  Robert Thomas,  Contract Project Officer (DWQAB),
was responsible for overseeing the contract laboratory  activities to
assure the quality of the analytical data.  The chemists (DWQAB) who
prepared blind samples and  conducted the analyses  of quality control check
samples upon direction by the Contract  Project Officer  were:

          Michael Weisner - preparation  of blind  samples at  beginning
            of survey; analysis of purgeable halocarbons and aromatics
                                 -E.54-

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Project GWSS
Section 4   ' .
Revision.No. 1
   ' 1983
   e 2 of .3
                    Candy Miller - analysis of purgeable halocarbons and
                      aromatics
                    Robert Streicher - analysis of purgeable halocarbons
                      and aromatics
                    Kerry Sweeney - analysis of total organic carbon

          Richard Johnston and Waymon Wallace (WSTB) prepared the shipping blanks.

               Barbara Kingsley, Contract Project Manager for SRI, International, was
          directly responsible for all analytical data generated for survey samples,
          for reporting (monthly) technical progress and quality control results,
          for reporting sample data, and for preparing a final report on the ana-
          lytical and quality control program of SRI, International for the survey.
          The chemists (SRI, International) who conducted the analyses of survey
          samples and quality control check samples were:

                    Barbara Kingsley - analysis of purgeable halocarbons and
                      aromatics                       v
                    Christina Gin Avanzino - analysis of purgeable halocarbons
                      and aromatics
                    Curtis Beeman - confirmatory analysis of purgeable halocarbcns
                      and aromatics
                    Robert Emerson - analysis of total organic carbon and residual
                      chlorine

               The Office of Program Development and Evaluation had the responsibility
          for generating and updating the random sample and for providing input to
          the statistical analysis phase of the project.  The Health Effects Branch
          of the Criteria and Standards Division provided health effects guidance
          to regions and states upon the discovery .during this survey of a serious
          contamination problem.
                                            -E.55-

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                                                                                        Section  4
                                                                                        Revision No.
                                                                                        May  1983
                                                                                        Page  3 of  3
                                    OFFICE  OF DRINKING WATER
                                     VICTOR KIMM, DIRECTOR
                                                            Office of Program Development
                                                                  and Evaluation
                                                              Arnold Kuzmack, Director
           Criteria, and Standards Division
             Joseph Cotruvo, Director
                  Technical Support Division
                 Lowell Van Den Berg, Director
               Health Effects Branch
              William Lappenbusch, Chief
Quality Assurance Coordinator
 Mary Ann Feige  (until  1/82)
 Audrey Kroner  (after  1/82)
Water Supply  Technology
        Branch
 James Westricfc,  Chief
Drinking Water Quality
  Assessment Srancn
 Herbert Brass, Chief
                                           Project  Engineer
                                             Wayne  Mello
                                           Sanitary Engineer
                                            OWQAB Analysts
                                   Contract Project Officer
                                    RoDert Thomas, Chemist
                                  Contract  Project  Manager
                                           (SRI)
                                      Barbara  Kingsley
                              Figure 1.  Project Organization
                                               _r>  c /•
                                               — _. .jo —

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Project GWSS
Section 5
   ision No. 1
    1983
   e-1 of 3
                                          SECTION 5

                      QUALITY ASSURANCE OBJECTIVES FOR MEASUREMENT  DATA
          A.   ,Methodology

               Purgeable Halocarbons were analyzed using  EPA Method  502.1,  "The
               Determination of Halogenated Chemicals in  Water  by  the  Purge and
               Trap Method," (1981).   See Section 9.

               Purgeable Aromatics were analyzed using  EPA Method  503.1,  "The
               Analysis of Aromatic Chemical  Indicators of Industrial  Contamination
               in Water by the Purge and Trap Method,"  (1981).   See  Section 9.

               Total Organic Carbon was determined usiVig  EPA's  "Total  Organic
               Carbon, Low Level Method" (1978) and the "Dohrmann  DC-54 Ultra
               Low Level. Total Organic Carbon Analyzer  System Equipment
               Manual ," 2nd ed. (1978).

               Residual Chlorine was determined with the  Hach CN-70  Test  Kit.   This
               testing was a check for the presence of  chlorine in samples  from
               supplies that pr.actice  chlorination.
                                                          »
          B.   Precision

               •The contract stipulated the precision requirement  for analyses  of
               replicate samples for purgeable organics at ± 40%  difference wnen
               compound concentrations determined were  below 5  ug/L  and ± 20%  for
               concentrations above 5  ug/L.   Precision  for analyses  of replicate
               samples for TOC initially was  to be within ± 10% for  concentrations
               below 200 ug/L and ± 5% for concentrations above 200' ug/L.   By  mutual
               agreement between the TSD Contract Project Officer  and  the SRI
               Contract Project Manager, the  precision  for TOC  analyses could  be
               within ± 20% for concentrations below 300  ug/L and  ±  10% for concen-
               trations above 300 ug/L.
                                            -E.57-

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                                                                    Revision  No.
                                                                    May 1983
                                                                    Page 2 of  3
C.  .  Accuracy

     The accuracy requirement  for  EMSL  QC  samples  for purgeable organics
     was ± 40% and ± 20% difference  for concentrations below and above
     5 wg/L,  respectively.   Accuracy  for EMSL  QC samples  for TOC initially
     was to be ± 20% and ± 10% for concentrations  below and above
     200 ug/L, respectively.   By mutual  agreement  between TiD and SRI,
     the final accuracy requirement  for TOC was  ±  20% for concentrations
     below 300 wg/L and ± 10%  for  concentrations above 300 ug/L.

0.    Completeness

     The quantity of data generated  during this  project should provide a
     high degree of confidence that  estimates  of nationwide occurrence of
     synthetic volatile organic contaminants made  from these data are
     accurate.  Sample aizes of 200  systems that serve more than 10,000
     persons  and of 300 systems that  serve less  than  10,000 persons were
     selected on the basis of  occurrence frequencies  found in tha Community
     Water Supply Survey (CWSS) of 1978.  Those  sample sizes should allow
    . at least 95% confidence that  errors of the  estimates of occurrence
     frequencies would be no more  than  ± 15% for the  larger systems and
     ± 30% for the smaller systems.

E.    Representativeness
           *
     The total number of samples to  be-analyzed  was  limited by the contract
     funds available, and a balance  was struck between random samples for
     nationwide occurrence estimates  and suspect sites for investigating
     the upper range of contamination levels.  To  obtain  information from
     a maximum number of supplies  within the available resources, it was
     decided  to collect one sample of finished water  from each utility at
     a point  near the entrance to  the distribution system.  The VOC
     concentrations in water supplies from a single  well  that is not
     pumped continuously can vary  depending on pumping rate and schedule,
     and the  hydrodynamics of  the  plume of contamination.  If multiple
     wells supply a system at  a single  entry point and some wells are
                                  -S.58-

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Project GWSS
    ti'on'5
    si-on No. 1
  .  1983
Page 3 of 3
               contaminated while others are not, the VOC concentration in the
               sample at the entry point could vary greatly, depending on which
               wells were in operation at the time of sampling.  In systems with
               more than one entry point, a single sample would obviously represent
               only those wells contributing to that entry point.  With these limi-
               tations in mind, a sample of finished water taken at or near a point
               of•entry provides a reasonable compromise between the information
               obtained from a single sample from a single well and that from mul-
               •tiple samples taken throughout the system.

          E.   Comparability

               Sampling, analysis, and reporting units are those in the approved
               methodology.                          ' *•
                                            -E.59-

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                                                                    Project GWSS
                                                                    Section 6
                                                                    Revision Nq^
                                                                    May 1983
                                                                    Page 1 of 2
                                SECTION  6

                           SAMPLING  PROCEDURES
     A sampling kit was prepared  at  TSD  for  each  sampl ing'location.
Amber bottles of 60 ml and  250 ml capacity were dosed  with  a  preservative
(mercuric chloride at  10 ing/L)., capped with  teflon  septa  and  screw caps,
labeled with preprinted labels which  had been  stamped  with  the sample
identification numbers, and secured  in "styrofoam"  boxes.   The styrofoam
boxes had been custom  molded to hold  the proper number of  bottles.  A
shipping blank (250 ml bottle containing organic-free  water and preserv-
ative) was also included with the sampling kit.   The shipping blanks were
to remain with the sampling kit through  all  stages  of  transportation and
storage.  Any possibilities of contamination from the  surroundings could
be investigated by analysis of these  blanks.

     The-bottles, along with a plastic bag and> tie,  a  sampling site  data
sheet (Appendix B), sampling and  shipping'instructions (.Appendix 8), and
shipping labels and forms were shipped to the  sample collectors on av
schedule which had been prearranged  with the states.   The  sample collectors
took the samples, filled in the labels and site data sheets,  iced and
secured the boxes, and delivered  them to an  overnight  freight delivery
service.  The samples  were  shipped to TSD except  for a few  samples collected
during the second phase of  the survey from sites  located  near the contract
laboratory.  Those samples  were shipped  directly  to  the contractor.   All
shipping costs were paid by EPA.

     When samples arrived at TSD, they were  unpacked,  logged  in, and any
unusual circumstances  were  noted. The sample  bottles  were  then placed in
storage in a cold room free of organic vapor contamination  until they
were repacked in ice for overnight shipment  to the  chemical analysis
contract laboratory.  Replicate samples  were collected at  each site  so
half the bottles were  shipped to  the  contract  laboratory  and  half were
held in cold storage at TSD. This was necessary  for occasional analysis
of sample duplicates by TSD chemists  or  for  quick-response, in-house
verification of contract laboratory  results.
                                  -E.60-

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Project GWSS
Section 6
Revision No.

     2 of 2
               When samples were received at the contract laboratory, they were
          logged and inspected, then immediately stored in a walk-in refrigerator
          maintained at 4°C.  All primary analyses were completed within one month
          of samp.le collection.

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                                                                    Section 7
                                                                    Revision No.
                                                                    May 1983
                                                                    Page 1•of 2
                                SECTION 7

                              SAMPLE CUSTODY
     Samples were Qollected  by  plant,  state or EPA personnel.   The sample
collector signed tfne .identification label on each sample  bottle.   His
name was also recorded  on  the Ground Water Survey Data  Sheet  (see Appendix
B) which was part of  the sampling kit  sent to each sampling location.
The data sheet was stamped with the same  identification number  as that on
the sample bottles in the  kit.  Either the sample collector or  utility
personnel completed the form and  returned it to the  Project Engineer.

     The Project Engineer  maintained a log of receipt of  these  data sheets
and kept the forms in labeled binders.  He also entered information from
these sheets for each sample into the  EPA computer system, an  IBM 360  at
Research Triangle Park.  These  items included date sampled, location of
sample point, the number of  wells in the  system, the number of  wells
contributing to the sample,  the depth  of  the wells,  treatment,  proximity
to industry, etc.

     The 'Project Engineer  maintained a log of all survey  samples  received
at TSD»  He was responsible  for shipping  samples to  the contract  laboratory
and maintained a file of all shipping  records.  He also was the custodian
of the replicate samples held in  cold  storage at TSD.

     When the samples were shipped to  the contract laboratory,  the TSD
Project Officer logged  pertinent  sample information  into  the  TSD  laboratory
data system (HP 3354) for  tracking purposes.

     When samples arrived  at the  contract laboratory, the Contract Project
Manager logged their  receipt, served as custodian of the  samples  during
storage, and distributed them to  the analysts.  Disposal  of the samples
after analysis was at the  direction of the TSD Contract Project Officer.
                              -E.62-

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Project GWSS
     «on ,7
     ion No. 1
     983
Page 2 of 2
               Replicates of.samples stored at TSD that were chosen for quality
          control check analysis were distributed to the analysts by the Project
          Engineer at the direction of the TSD Contract Project Officer.  The  latter
          also directed-disposal of samples after analysis.

               After sample analyses were confirmed, one 60 ml vial and one 250 ml.
          vial of sample from each site were retained in 4°C storage at TSD.   These
          will remain in storage until  the TSD Contract Project Officer releases
          them for disposal.  .

               All tire survey data sheets and TSD sample handling records are  in
          files kept by the TSD Project Engineer.
                                            -S.63-

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                                                                    Section 8
                                                                    Revision No.
                                                                    May 1983
                                                                    Page 1 of 1
                                SECTION 8

                   CALIBRATION  PROCEDURES AND FREQUENCY
     The methods used to  analyze  survey  samples  are  listed  in  Section 5.
Each method includes  specific calibration procedures  and  the frequency
for performance.  The Contract  Project Manager was  responsible for meeting
this contract provision to  assure that the  >nalytical  systems  were in
control.  The TSO Contract  Project  Officer  used  the  data  reported by SRI,
International for the required  quality control analyses  (Section  11) to
check that the analytical systems of  the contract laboratory were indeed
in control during analyses  of survey  samples.
                                  -E.64-

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Project GWSS
Section 9
    «sion No. 1
    1983
     1 of 1
                                          SECTION 9

                                    ANALYTICAL PROCEDURES
               The analytical procedures were.those approved by the EPA; they are
          listed in Section 5.  For this survey, the procedures for purge'able
          halocarbons (502.1) and aromatics (503.1) were combined by 'pi acing'the.
          respective detectors in series (the PID, then the Coulson) and using one
          gas chromatograph.  This cut the analysis time almost in half.   It also
          provided additional confirmatory analytical data.  This method had been
          shown by SRI to be comparable to the individually-applied EPA methods.
          The procedure is included in a paper "Gas Chromatographic Analysis of
          Purgeable Halocarbon and Aromatic Compounds in Drinking Water Using Two
          Detectors in Series," Kingsley, et al., in "Water Chlorination,.  Environ-
          mental Impact and' Health Effects," Vol. 4, Btook  1, R.L. Jolley,  Ed., Ann
          Arbor Science Publishers, Ann Arbor, MI (1983),  p. 593.  A'copy  is .in  the
          TSD files for contract #68-03-3031.
                                            -E.65-

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                                                                    section  lu
                                                                    Revision No.
                                                                    May 1983  ,
                                                                    Page 1 of 2
                                SECTION  10

                DATA REDUCTION,  VALIDATION,  AND  REPORTING
A.   Sample Background Data

     Information from the data  sheets  submitted  by  the  sample collectors
    •was entered into the computer  by  the  TSD  Project  Engineer.   After
     entry, the printouts were  checked against tne  handwritten copy. ,
     After all  the field data were  entered into  the EPA computer system,
    • several  checks were'made to  test  its  validity.   One test performed
     was to determine if the population figure given was the total  popu-
     lation served or if it was the number of  service  connections.   This
     was done by dividing the total  production (MGD) by the total  popula-
     tion figure.   If the, result  was below 25  gallons.per day per  person
     (gpdc) or over 200 gpdc, the state was called  to  verify the population
     figures.  Any necessary corrections were  made  in  the. data•file. •

     The other field data, such as  number  of well's,  depth of wells,
     treatment, or proximity to industry will  not be double checked at
     this time.

8.   Analytical Data

     Results  from each analysis were calculated  by  the  contractor's
     individual analysts and submitted to  the  Contract  Project Manager
     for review.  The data were objectively reviewed for completeness,
   ,  calculation accuracy, and  conformity  to specific  standards, for
     example, significant figures.   The contract laboratory was  provided
     access to the EPA computer system (IBM 360  at  Research Triangle Park),
     so their Project Manager could enter  the  data  in  a format specified
     by the TSD Contract Project  Officer.   After data  entry and  before.
     permanent storage in a data  file, all  new entries  were printed on
     the Project Manager's data terminal and checked for accuracy.
     Appropriate changes were made  if  necessary.  Then  the sample  data
     were stored in the designated  data file.
                                  -E.66-

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Project GWSS
Section 10
    lion No.
    P1983
  re 2 of 2
               The ISO Contract Project Officer periodically reviewed all data
               entered by the contractor into the EPA data system.  These data
               included the results of duplicate analyses, duplicate samples also
               analyzed by TSO, confirmatory analyses, "blind" unknowns sent to the
               contractor by TSD, and analyses of shipping blanks.  Furthermore,
               monthly reports were submitted by the contractor which contained the
               results of EMSl quality control samples that were analyzed twice
               monthly for each analytical system employed.  From all of these
               data, the Project Officer determined: (1) any potential problem
               areas; (2) the precision and accuracy of the analyses; and (3) the
               adherence to quality assurance guidelines set forth in the written
               contract.  The sample results were then accepted or rejected on the
               basis of these determinations.  If accepted, the results were fina-
               lized and verified again by the Contract Project Manager as being
               final.  If rejected, then the compound or parameter in question was .
               listed as being "not analyzed," and corrective action was initiated.

          C.   Collating Sample Background Data and Analytical Data

               After sample and analytical data had been entered.and validated, the '
               program to collate the site data and the analytical data was performed.
               Every 100th data line, was checked to see if the analytical data for
               that sample matched with its site information.  If the match was
               correct, the data processing for that group of data was considered
               correct.

          D.   Reporting Survey Results

               The validated sample background data and analytical results for the
               thirty-four organic compounds selected for analysis in the survey
               were compiled and reported at the end of the project in "The Ground
               Water Supply Survey, Summary of Volatile Organic Contaminant Occurrence
               Data," January 1983.  (The Total Organic Carbon data were of secondary
               interest so are not included in this report.)  The report also contains
               the results of tests of significance of the differences in frequency
               of occurrence of compounds, point estimates of the probability of VOC
               occurrence and the confidence limits of the estimates.

               Any additional access to the sample background data and analytical
               results in the IBM 360 data base will be through the Project Engineer.
                                            -S.67-

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                                                                    project
                                                                    Section  11
                                                                    Revisi.on  No.  1
                                                                    May 1983
                                                                    Page 1 of
                                SECTION  11

                     INTERNAL  QUALITY  CONTROL  CHECKS
     Internal  quality control  was  tracked  by  SRI,  International  by dupli-
cate analysis  of survey samples  and  by  analyzing quality control  samples
as stipulated  in the analytical  contract  (Appendix C).   All  samples found
or suspected to contain the  organics  of interest were reanalyzed for
confirmation.   The results from  duplicate  analyses were entered into the
EPA computer system by the Contract  Project Manager.   The results of
analyses of quality control  samples  were  reported  to  the TSD Contract
Project Officer in monthly progress  reports.   The  TSD Contract Project
Officer used these data as described  in Section  10.   In addition, quality
control was tracked by TSD-with  duplicate  samples  and blinds which were
analyzed by both SRI and TSD.  The use  of  these  data  is also described in
Section 10.

     At the conclusion of the  survey, the  contractor  prepared a' report on
the' quality control applied  during the  project (Appendix 0), in order to
substantiate the quality of  the  data  generated.
                                  -E.68-

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Project GWSS
     «on 12
     ion 'No. ,1
     983
Page 1 -of 1
                                       •   SECTION   12

                                PERFORMANCE AND SYSTEM  AUDITS
               Performance evaluation samples were analyzed by SRI,  International
          and the data evaluated by TSD before the analytical contract was  awarded,
          A pre-award site visit was made by Herb Brass, Chief, OWQAB, in combina-
          tion with a meeting to final.ize aspects of the Community Water  Supply
          Survey contract.  Site visits by the TSD Contract Project  Officer contin-
          ued on ah annual basis after the contract was awarded.
                                            -E.69-

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                                                                    Section  13
                                                                    Revision No.
                                                                    May 1983
                                                                    Page 1 of
                                SECTION  13

                          PREVENTIVE  MAINTENANCE
     The Project Manager for  SRI,  International  was  responsible for
assuring that the equipment used  for  the  required  analytical  work was
properly maintained.   The TSD Contract  Project  Officer used the data
the quality control  analyses  reported by  the  contractor and TSD analysts
(Section 11) to check that the analytical  systems  of the contract labora
tory were in control  during analyses  of survey  samples.
                                 -E.70-

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• Project GWSS
 Section 14
     «sion No. 1
     1983
      1 of 1   .
                                           SECTION 14   '

                           SPECIFIC ROUTINE PROCEDURES USED TO ASSESS
                           DATA PRECISION, ACCURACY, AND COMPLETENESS
           A.   Analytical Data

                The analytical contract (Appendix. C) stipulated % difference (relative
                range) between duplicates as the precision statistic to be used.  For
                most of the quality control checks, enough data were generated to jus-
                tify using %  relative standard deviation as the precision statistic.
                The accuracy  statistic used was % error, with signed results to dis-
                tinguish positive and negative error.  The formulas for these statis-
                tics are included in the final report (Appendix D) prepared by the
                contract laboratory about the quality assurance program they conducted
               .during the generation of analytical data for this survey.

           8.   Survey Results

                The survey was conducted to gather occurrence data.  Treatment of the
                results was a matter of sorting the data (random - nonrandom, popula-
                tion categories, etc.) to report the results.  See the January 1983
                report, "Summary of Volatile Organic Contaminant Occurrence Data."
                Statistical inferences (tests of significance, etc.) drawn from the
                data were calculated according to Miller, I. and Freund, J.E.,
                Probability and Statistics for Engineers, Prentice-Hall, Inc.,
                Englewood Cliffs, N.J., 1965.
                                             -S.71-

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                                                                    Project GWSS
                                                                    Section 15
                                                                    Revision No.  1
                                                                    May 1983
                                                                    Page 1 of
                                SECTION  15

                            CORRECTIVE ACTION
     Any.questions  or problems  about  sample  collection  were  handled on a
case-by-case basis  by the  Project  Engineer.   If  a  shipping blank  contained
detectable levels  of organics,  the Contract  Project  Manager  contacted che
TSD Contract Project Officer  and a joint  decision  was made concerning the
sample collected at the same  time.

     If the TSD Contract  Project Officer  determined  that  sample  results
should be rejected  based  on quality assurance  guidelines, the  TSD Project
Officer and the Contract  Project Manager  determined  the proper course of
corrective action.   The contract laboratory stock whatever steps  were
necessary to correct any  analytical problems.   Samples  held  in reserve at
the contractor's laboratory or  at  TSD were then  reanalyzed if  the storage
time was not excessive.  If the reserve samples  were not  usable,  the site
was resampled if possible.
                                 -E.72-

-------
Project GWSS
Section 16
Revision No. 1
    1983
     1 of 1
                                          SECTION 16

                           QUALITY ASSURANCE REPORTS TO MANAGEMENT
               Monthly reports on technical progress and quality control were
          submitted by the Contract Project Manager through the SRI, International
          Laboratory Director to the TSD Contract Project Officer.  After completion
          of the analyses of survey samp-les, the contractor submitted a summary
          report (Appendix D) about the analytical procedures used to perform the
          analyses and the results obtained from the analytical quality control
          program.  The summary report prepared by TSD at the completion of the
          project contains a section on the quality assurance program for the
          survey.
                                            .-E.73-

-------
                                                                       Project GWSS
                                                                       Appendix A
                                                                       Revision No.  1
 y'P"4v,                                                                May 1983
»H  4\ \                                                               Page 1 of 7
$ $32 /    UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
 *     *'*"                         CINCINNATI. OHiO H26B
                             Technical Support Division
                             Office of Drinking Water
                       OFFICE OF WATER AND WASTE MANAGEMENT
                      5555 Ridge Road, Cincinnati, OH 45268
                            GROUND WATER SUPPLY SURVEY

                                 STATUS REPORT |1
                                 (February 1981)


      The national Ground Water Supply Survey (GWSS) is now underway and this  is

 the first of several planned status reports on its progress.  The GWSS has four

 objectives.  It will be used to describe,the national  occurrence levels and

 frequency of synthetic organic pollution found in drinking water supplied froc

 the ground.  It will improve Federal  and State responses to newly identifies
                                                k
 contamination incidents.   It will  stimulate and enhance State ground water

 contamination detection and control activities.  And,  it should improve our

 ability to predict where  ground water pollution is likely to be found in .the

 future.


      In early November 1980 the Office of Drinking Water (ODW) announced its

 proposal for a ground water supply survey and  requested the advice and cooper-

 ation of all fifty States and Puerto  Rico.   By  mid December, most of tne"States

 had sent written continents and all  had been contacted.   Over forty States are

 cooperating in the implementation  of  the survey,  and all  but four intend to take

 part in follow-up activites  when a contaminated  supply is identified.


      Of the  1,000 systems to  be surveyed,  nearly  13% have been sent the sampling

 package.   By the first  week  in  February,  82  sample sets had been forwarded to

 the analytical  laboratory.  At  present,  152  systems have  been scheduled to take



                                     _T7  74 _
           ,          •                 JJ . / *t ~"

-------
. Project GWSS
   pendi'x A
    i-sion No. 1
   'y 1983
 Page 2 of 7
. rro
   ,
        samples, filling up the analytical schedule through the first week in March.
        The sampling schedule is continuing to fill, and if your State has a particular
        future date in mind, please call us to ensure adequate planning.  .When a sched-
        ule is established, please make every effort to collect samples wtthin that time
        period.  If you must change the schedule, let us know as soon as possible.   The
        laboratory can analyze only a certain number of samples per week so scheduling
        for a relatively uniform work load is extremely important.

             The analytical results of the samplinc  will be forwarded routinely on  a
        bimonthly basis.  The first analytical  report is expected  out in April.   Perti-
        nent results'will  be forwarded to each  State and Region.   Special  actions will be
        taken if a high level  of contamination  is found.  Those actions are discussed
        toward the end of  this report.

        Questions and Answers

             As a result of the  comments received in December,  and  from early  experience
        from the first several  Sample  collections, a number of  specific  questions have
        come up.   Although  not every State  or Region is  affected by  these  issues, quite
        a  few are,  and  attention to them is  important.   The questions  are:

             Q -  The survey design allows  for  only  one  sampling point  for
                 each system.   There  are many  shortcomings with this  type  of
                  survey design.  For  example,  if a  supply  uses multiple
                 wells, from what  point  should the  sample  be drawn?   What  are
                 the  reasons for the  single sample  design,  and can  it be
                 changed?

            A -  Extensive discussion preceded the  decision to use  the single
                 sample design.  The most compelling argument in favor of  the
                 selected design is resources.   Only 1,000 water samples can
                 be  analyzed.   Considering the multi-objective nature of the
                 GWSS, the single  sample per system approach best serves to
                 support a broad initiative on ground water quality.  With
                                               -S.75-

-------
                                                                  Project  GWSS
                                                                  Appendix A
                                                                  Revision No.
                                                                  May  1983
     respect to the multiple well question, a sampling p.oint        ^e
     should be chosen which represents the largest possible num-
     ber of wells.  The analytical methods in use are very sensi-
     tive, so that if. one of several wells contributing to the
     sampling point is significantly contaminated, some contami-
     nation will be found.  As described later, the single sample
     is being used as a screening device and confirmatory analysis
     will be carried out when significant pollution is found.

Q -  What is the purpose of doing both a random and a non-
     random .sample, and are the results going to be com-
     bined?

A -  The random sample is being done for the express purpose
     of determining'the national occurrence of drinking water
     contamination by synthetic organic chemicals.  Onl^ this
     data will be used in the development of national  economic
     impacts and estimates of national  occurrence needed to help
     decide whether or not to write a regulation, and how a
     regulation might be designed.

     The nonrandom sample has different purposes.  It should
     provide information on the upper range of contamination
    .levels, help States to provide added public health protec-
     tion by searching for contamination, assist EPA and States
     in, developing a  predictive capability for locating contami-
     nated sites, and may help in structuring future national
     guidance and regulations.


Q -  What is the purpose of the primary and secondary  lists of
     systems, and how are they used?

A -  The random sample was drawn nationally,  and consists  of
     about 500 systems.   Naturally,  not every system will  be
     able to participate,  so a second list of 250 systems  was
     drawn to back up the  primary list.   These systems  were drawn
     randomly from the whole nation,  so it is possible  that a
     particular State will  have a listing which  is not  very
     representative within that State.   This  is  to be  expected.
     In terms of the  use  of these lists,  the  primary list  should
     be fully used if at  all  possible.   However,  when  a name
     cannot  be used from  the primary  list,  one from the secondary
     list should be used.   Only in this  way can  the "randomness"
     be maintained.   Another feature  of  the random sample  is that
     the sample is broken  into subgroups.   One is the  group of
     systems which serve  fewer than  10,000 people,  the  other is
     systems which serve more  than 10,000 people.   When replacing
     a  system from the primary  list  by  a  system  from the secon-
     dary list,  the size  breakdown must  be maintained.   Replace  a
     small  system with a  small  system;  replace a  large  system
     with a  large  system.   If you  run out  of  replacements,  please
     let us  know.
                                  -E.76-

-------
project
Appendix A
Revision No. 1
May 1983   .
   e 4 of 7
             Q -  A small number of criteria were suggested for use when
                  selecting water supplies as part of the nonrandom sample.
                  Are these to be the- only criteria, or can a State use others
                  as well?

             A -  By no means should a State feel constrained by the criteria
                  ODW suggested.   We recognize that State personnel are far
                  more knowledgeable on conditions that may lead to contami-
                  nation of ground water,  and expect other criteria to be used
                  as well.  An essential  point we would like maintained is
                  that the systems chosen  be those for which there is no
                  existing water  quality  data, but which are suspected to be
                  contaminated by organic  chemicals.   In addition, we want to
                  know just what  criteria  actually were used to select the
                  systems.  When  you have  completed selection of the nonrandom
                  systems in your State,  please briefly describe- the selection
                  process to us.

             Q  -  State and Regional  resources for surveys and  follow-up of
                  -contamination found  are  not unlimited,  and usually are
                  allocated well  ahead of  time.   This survey will, in some
                  cases,  place severe  burdens on States resources.   What
                  can EPA provide to ease  these burdens?

             A  -  We have a genuine  concern  about the impact on resources, and
                  this survey has required ODW to reprogram some work as well.
                  In terms of assistance,  half of the samples being examined are
                  being selected  by  the States but analysed by  EPA.   This  is an
                  expensive task'which may support work a  State otherwise  would
                  have to do,  or  may not be  able to do.   Beyond analytical
                  support for initial  and  confirmatory  samples,  we are unable to
                  help financially.

                  However,  contamination of  drinking  water supplies  by harmful
                  organic chemicals  is  an  important public  health  matter.
                  Where detected,  serious  incidents of  contamination must  be
                  dealt with  to protect public health.  Such  responses will
                  require a  concerted  State-Federal  effort.  We  must all  plan
                  to take part  in this  work,  especially on  follow  up in  inci-
                  dents of  detected  contamination.

       Follow-up  When Contamination Is Found
            One of the important aspects of the GWSS is follow-up when a case of ground

       water contamination is found.  The local response will vary from State to State

       and system to system, depending on many factors.  This issue is so important

       that a draft guidance on the matter will be circulated for comment soon.  Final




                                         -E.77-

-------
                                                                      Project .GWSS
                                                                      Appendix  A
                                                                     .Revision  No.  1
                                                                      May 1983  '
                                                                      Page 5 of 7
guidance will  be issued separately.   In the meantime, ODW has developed  an

approach for timely notification of Regions and States, based on  the  degree of

risk imposed by the contamination  found.



     In essence, when a sample  is  found to have high levels  of  contamination,

EPA or the State will analyze an additional water sample taken  from the  identi-

cal original sampling point.  Additional EPA fallow-up analysis on the water

system will usually not be possible,  and should be discussed by the State  and

Region on a case-by-case basis.  Generally, system level follow-up is a  State

responsibility.

                                                V
     Specifically EPA response  to  a high level will be as follows.  For  contami-

nants which are known or suspected carcinogens, and when the concentration found

is associated with a lifetime risk to the community at the level  shown in  the

column titled "Risk Level," the actions shown  in the "Action" column  below will

be taken by EPA.  The lifetime  risk is the probability of illness over a 70-

year period.  A 10"  risk level is equal to a  one in one-hundred-thousand  chance

of illness.


      Risk Level                                      Action

     10                                Alert  call from laboratory to ODW;
     (moderate risk)                   immediate Regional and  State  notification.

     10"5 - 106                        Notification by laboratory to ODW
     (relatively low risk)             in its weekly report: Regional and
                                       State  notification within one week.

     Less than 10                      Notification to ODW, Regions  and
     (very low risk)                   States in bimonthly  report.
                                        -E.78-

-------
 pject. GWSS
   eridix A                         •     ,
   i si on No. 1          '
May 198'3
Page 6 of 7 por contaminants which are noncarcinogenic toxins, and 'when the risk to

       the community is at the level shown in the column titled "Risk Level," the •

       actions shown in the "Action" column will be taken by EPA.
              Risk Level

            At or near 10-day SNARL
            (Suggested No Adverse
            Response Level)

            Between ADI (Acceptable
            Daily Intake) and 10-day SNARL
            Less than ADI
           Action

 Alert call from laboratory; immediate
 Regional and State notification;
 development of new SNARL (if necessary).

 Notification by laboratory to ODW in
 its weekly report; Regional and State
 notification within one week.

 Notification to ODW,  Regions and States
 in bimonthly report.
                 When there is  a mixture of two or more chemicals  which are
                 potential carcinogens,  the risk will  be treated additively.
                 For noncarcinogens  no additive assumption will  be made,  for
                 purpose of notification.

                 The water analyses  will  measure the  concentration of the
                 chemicals listed below.   The status  of formal  nealth advisories
                 is indicated  in the group headings.
            Chemicals Covered  by  TTHH  MCL

            bromoform
            bromodichloronethane
            chloroform
            dibromochloromethahe
       SNARLS  Or  Criteria Documents
       To  Be Available  By August 1981

       1,2-dibromo-3-chloropropane (June)
       1,2-dichloroethane (March)
       1,1-dichloroethylene (March)
       cis-1,2-dichloroethylene (March)
       trans-1,2-dichloroethylene (April)
       benzene  (March)
       toluene  (August)
       o-xylene (March)
       m-xylene (March)
 SNARLS  Presently  Available

 carbon  tetrachloride
 methylene  chloride
 tetrachloroethylene
 1,1,1-trichloroethane
 trichloroethylene

 Health  Effects  Criteria Documents

 vinyl chloride

 Chemicals  Rarely  Found And Which
 hay Be  Evaluated  After August  ijSl

 dichloroiodomethane
 bromobenzene
£-ch1orotoluene
£-chlorotoluene
 ethyl benzene
 iso-propylbenzene
_n-propyl benzene
Ttyrene
 1,1-dichloroethane
                                            -E.79-

-------
p-xylene (March)
chlorobenzene
1,2-dichlorobenzene
1,3-dichlorobenzene
1,4-dichlorobenzene
1,2-dichloropropane
1,1,2,2-tetrachloroethane
1,1,1,2-tetrachloroethane .
1,1,2-trichloroethane
trichlorobenzene isomers  "
                                                                     Project GWSS
                                                                     Appendix A
                                                                     Revision No.  1
                                                                     May 1983
                                                                     Page 7 of ?•
     If you have further questions, please contact Lowell A. Van Den Berg,
Director, TSD, ODW,  5555 Ridge Road, Cincinnati, OH 45268 (513-684-4374).
For questions concerning sampling and scheduling contact J. Wayne Mello  at
513-684-4445. '.
                                       Lowell A. Van Den Berg, Director
                                       Technical Support Division

-------
                                                                          Project GUSS
                                                                         • Appendix B
                                                                         • Revision No.  1
                                                                          May 1983
                                                                          Page  1  of 16
        *
I 5SfaL •   UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
 *'«« «*&*•'•'                         CINCINNATI. OHIO 4SJM
                               Technical  Support  Division
                               Office of  Drinking Water
           • •             OFFICE OF  WATER  AND  WASTE MANAGEMENT
                        5555 Ridge  Avenue,  Cincinnati OH 45268
       DATE:      December  22,  1980

       SUBJECT:   Sampling  and  Shipping  Instructions  for tne Ground Water
                 Supply Survey

       FROM:      Lowell A. Van Den Berg, Director,
                 Technical Support Division        *•

       TO:        Ground Water  Supply Survey Sample^Collectors


       Attached  are  instructions  for collection and  shipment of water samples
       for the Ground Water Supply Survey.  This survey is being conducted by
       the Office of Drinking  Water, US EPA, 1n cooperation with stats agen-
       cies and  Regional offices  of EPA.  It is important to read the sam-
       pling  instructions thoroughly to become familiar with the procedures
       and requirements.

       You will  also find a data  sheet which,, when completed, will provide in-
       formation on  the sampling  site and on the water system.  Please fill in
       the information as completely and accurately  as you can, or have some-
       one knowledgeable about the system provide the information.  The data
       will be useful in Identifying the sample and  describing the system from
       which  the sample was taken.  This Information, combined with the analyt-
       ical results, will provide an assessment of the state of the nation's
       ground water  supplies.

      The contamination of ground water by man-made organic chemicals is a
       problem that  has only recently been recognized.  We hope the data
       developed by this survey will greatly increase our knowledge of the
       extent of the problem.

      We are grateful  for your help 1n providing the samples and the system
       Information.  Your assistance 1n these matters 1s essential to the
       success of the project.
                                      -E.82-  '

-------
Project  GWSS
Appendix B
    ision No.  1
     1983
   ge  2  of  16
                                W31OM, SCLKD'WCTER SJMtt 0*7* 9tE£T
   SWP1E ID:
           act:
                                                        IB
                                                    SAWL2C
   HVC GT SAMPLER:
                                                           NO:
        MO ACCRCSS or Sfsr» tezx
           PIANT
                                                          MO ACOtCSS OP
                                                                          JO:
   HELD
                                 ODUfflf:
        WRSISITif:
                                                               OLCR:
        QiLCW?JE RESIOSU.:
                            nvz
T01X.
        iromnr TME oxer rcrvr or
              (WX5RESS IT APPICPRlXIt)
   1.   APFBCBCIMATtrr HW «»« PCCPU2 DOC THE HkTS* SICSHJl SERVE (INGifflOC PUROUSJ3 WCCT
                DEPTH
                 rmnr
3.   ?OR SOI
       1.
       2.
       3.
       4.
       s.
       «.
       7.
       9.
       9.
       10.
                              me
                                           SYSTDI aw?
                                              or \st
  4.  CW3X WE Niraor cr
                               WIICH ccKiwawt THE MWOMW cr
                                                   ' -E . SX-
                                                                    CDttTNUC CN BACK  IT
                                                                     TO THE

-------
                                                                                              Project. GWSS
                                                                                              Appendix B
                                                                                              Revision No.  1
                                                                                              May  1983
                                                                                              Page  3  of 16
5.   FOR V€ZiS NOT USED AT LEAST SEC !CNTHS EACH YEAR. \«V ARE THEY SOT 'JSTD
          (E.G. SEASCNAL VARIATION W C6HAND, aONTAMTNATION,  EQUI7MENT 7FCBUJB, ETC.)
6.   WAI WPE OP 3DII. IS -SIS. WJCR OVERBURDEN. MOVE THE AQUIFERS FTCH WIOJ VATER IS ORAWT?
          (E.G. OMT, SAND, LOAM. OTHER)
7.   WAT IS 'SE AVERKZ »JLY P5COUCT1W OF THE SYSTEH?
                                                                        O» fWff LCCATIOS XES TSE WV.TSR HJTTER THE DISTR1BLTIC« SfSTSf?     _

10.  ARE THERE RESS7.OIJS CR H3LDTC 71>ffUTIES TO WHICH THE WCER IS
                BETCRE IT IS mSTRIBUTEO?          •              i.         • ttS             NO
U.  r*yS THE VBVTER SYSTa CSLCRIWJE?                            YES     ' _ HO
          U 30. 'AT VHAI POINTS IS THE TREAT«jr JM^hSiS IS CHtrKDanai D3JE, AND
          WAT PCf« CF CHLCRIHE IS USED AT EACH fQINT?
12.  OTHER THAN CHLCKDaTTCU, WAT 75EAT-ENT5 ARE USED?

                       (OTHER THAN CaLdONEI             H.

                                     .                  I.   PCX RDOWM.
     S.   CaMUtATICH                                   3.   ACnVMSO AUWXNA

     C.   gyp'p||g/T?ffTPM                                 K.   CDMCSICN Q3R3CL

     o.__rnaj«aTCN                                    u.    ruxmrg Acornos

     £.__ UUB SODA 3CPTEHHC                           M.  _HirHItE RBOWO.

     r.____IO« EXCHANGE SUKramC                        N.   CBANULAR ACrTVATED GNRSDN

     C.   AERA33OM                                     0.   OfflER (SPEdFif) _

13.  V»»X PERCSWXZ Of THE V*TER IS WEATEW  _

14.  IS TREATMENT CCNOXTED AT EACH WCi OR ARE THERE CEKIRAL TKEA3HEHT LOCXT1CHS7       EACH      CEKTRA1
                                                                                       HEU.      LOCATING
          IP CanSAL TREA3XJJT UX3OTOS. H»  MANY?  _
                                                   -S.84-

-------
     «ject GWSS
     endix B
     ision No.  1
 May 1983
'Page 4  of 16
  15.  IS THERE ANY OHESCIAL OR INDUSTRIAL ACTIVITY  IN CLOSE PROXaiTY TO ANY OF THE VGiS?       YES  	W
            (WITHIN 10 MXLES1

                XT 90. INDICATE THE DISTANCE BE3VCEN TaAT ACnVTTY AND WE WELLS:                 i

                     ED) MANY WELLS ARE WITHIN THE FOLLOWING DISTVCSS     	
                           FIO1 Oa«E?CX. CR OOUSTRIM. ACTIVITY?        • WITHIN  Ifl  1/2-1
                                                                          • tOLSS      MILES   KH£S

                «KT  a THE >»3UR£ CP THE OK3C2AL OR DCUSTRIM. ACTTVITY?
    -   '         (INDICATE HOW DISTANT THE ACTIVITY  IS  nO4 TSE >iEAR£ST «2i)

                                                                                      WTTHIN 3     3-10
                                                                                       MILES
                                       A.  OfK ClEANtNC 3U5IKESS

                                       B.  AVTATICS FACIUT1ES

                                       C.  HACHINE 5CFS

                                       D.  WTTAL FAHRICATICN

                                       K.  ELECTJCPIATUC

                                       P.  i^
                                       G.  CHEMICAL PUNTS

                                       B.  CUMPS/LANOnLLS

                                       I.  BRZAPCCUS WASTE

                                                STDANZ OR DISPOSAL

                                       J.  INDUSTRIAL SEPTIC TNKS

                                       R.  «ME SEfmC TANKS
                                       L.  IHDJSTRIAL PITS, POCE AND IAEZZK5

                                       M.  OiaER (SPEdTTI _
  16.  HAS THESE BEEH ANY CTCSW PECARDDC THE QALITT OP THE DRINKING WATER?             T2S          >O
                              TASTE AND ODOR)
           IT SO, WHAT WERE THE CHARACTERISTICS OF THE WATER QUALITY PROBLEM?
                 KACE THIS QKXX SHEET D» THE ATTACHED ENVELOPE AND HAH. IT AS f no TO THE DATE OP

                SAMPUNG AS POSSIBLE.  IP tO} >OULD U7Z A SOMAR7 OP THE STUDY RBULTS CHECK HERE


                                                           -E.85-

-------
                                                                       Project GWSS
                                                                       Appendix B
                                                                       Revision No.  1
                                                                       May 1983
                                                                       Page 5  f 16
                                                 December 16,  198.0
                                  SAMPLING INSTRUCTIONS


      A sample  of  the  finished drinking water should be collected  at  a  point
 as  close  as  possible  to the  entrance to the distribution  system  (such  as  after
.the clear well, or.distribution manifold) but also at a convenient point  for
 sample collection.  The time of collection will depend on the  operation of the
 facility.   If  pumping is continuous, the collection can be  at  any time; but  "f
 pumping only occurs during a certain time of day, say 8:00  am  to  5:00  pm, coilec*.
 the sample during the last hours of pumping (4:00 - 5:00  pm) if possible.  This
 procedure will  produce a water sample representing a larger area  of  the aquifer.

      The  procedures for the  collection of drinking water  samples  to  be
 analyzed  for organic  contamination may be different from-those with  wh-ich you
 are familiar.   First,  the sample bottles should not be rinsed, because they
 contain preservatives.  Second, all sample bottles should be filled  completely,
 so  a few  drops  of water run  over the top.  Carefully put  the cap  and teflon
 septum back  over  the  top and seal.  CAUTIONS:

      T.  The white, shiny side of .the septum should not be  visible when the
          vial  is  capped.

      2.  No  air bubble should be present when the vial is turned  over.  If
          an  air Duooie is present, remove the cap and septum and  make  up  the
      difference with  additional water, then recap.

      3.  Do  not tighten caps too much, they break easily.

      The  sampling box contains the following Hems:

      3-60 ml vials:   Preserved with 0.5 ml of mercuric chloride.  These will
                      be analyzed for 11 aromatic compounds.

      4-60 ml vials:   These will be analyzed for 26 volatile halocarbons.

      1-60 ml vial:    Preserved with 0.5 ml of sodium thiosulfate.  This
                      vial may be analyzed at a future date  for the quenched
                      trihalomethanes.

      3-250 ml  vials:  Preserved with 1 ml of mercuric chloride.   These  will
                      be analyzed for total organic carbon (TOC).

      1-250 ml  vial:   This vial contains blank water.  This  vial  should not
                      be opened, but it should be carried  along with  the other
                      vials.  This is done to determine the  possibility of con-
                      tamination from the surrounding environment.


                                       -E.86-

-------
   *VP
«
Project GWSS
Appertdix B
  vision No. 1
    1983
  ge 6 of 16
             - Data  Sheet

             - Pictorial  Sheet on the Collection of Organics

             - Return Shipment Labels

             - Return Envelope

             Before  sample collection, fill  out the sample labels,  using a waterproof
        pen  (if  nothing else, a hard ball  point pen will  work).   A  dry label  is easier
        to fill  in than a .wet one.

             Also, either before or after collection,  please a«sk the person you ara
        working  with at the utility to fill  in the enclosed data sheet.  Some  of the
        questions ne/she may not be able to  answer.  Please encourage him/her to provide
        as much  of the information as possible.  Completeness in filling out  this data
        sheet will help greatly in the interpretation  of  the resultant data.

             After all samples are collected,  repack them into the  Styrofoam  box and
        fill  with ice.  The smaller size ice works better than the  larger cubes.  Close
        the  plastic  bag around the Styrofoam box using the enclosed twist tie.   Before
        the  box  is to be shipped, tightly tape the box shut.

             Shipping:

             To  reduce the cost of shipping  these samples back to the Cincinnati  Lab,
        combined shipments are recommended,  i.e., if more than one  site can be col-
        lected within 1-3 days, wait until all are collected and tape the boxes together
        before' shipping them.  If  samples can be collected over several  days,  don't
        seal  the first samples collected until they are ready for shipment.  All  samples
        should be kept iced until then.   Also, if samples are to be collected on a
        Friday,  wait until Monday to ship them.  This  will avoid samples setting on
        some loading dock over the weekend.  Again, make  sure all samples are kept iced
        and  stored in an organics-free area  (do not store with solvents, paints,  or
        other organic chemicals).

             All shipments should be sent collect to the  Cincinnati Lab via either
        Federal  Express or Purolator to avoid  billing  problems.   We have accounts with
        either of these firms and they are very cooperative.  Also, If you are collect-
        ing-samples  in an area that isn't served by either, if at all possible wait .
        until you are in one of those cities before shipping the samples to us.  A list
        of cities serviced by Federal Express  and Purolator in your State is  enclosed.
        If time  will not permit you to do so,  ship the sample collect to me by any air
        freight  service that will get the sample to me overnight.   Again, if  samples
        have to  be held, keep them iced and  stored in  an  organics-free area.

             The data packet should be mailed  in the enclosed envelope.

             Your cooperation in this effort will be greatly appreciated.  If at any
        time you have questions, please call,  Wayne Hello, collect, at (513)  634-4445.
                                                -E.87-

-------
I
w
•
oo
oo
I
                                                          LOCATION  OF CITIES
                                                          SERVICED  BY EITHER
                                                    FEDERAL  EXPRESS OR  PUROLATOR
-a 3 "XI f> -o
tu o> rt> "O -j
l£) << < T3 O
fO   -.. n> c_j.
   ,_. en 3 rt>
—I 10 —•• Q- O
   00 O -•• H-
O C*> 3 X
-»>        CD
     -z. co z:
H^   O   Crt
en   •    t/>

-------
Project GWSS
Appendix B
  'ision No. 1
    1983
 ige 8 of 16
      CITIES SERVICED
         BY EITHER
FEDERAL EXPRESS OR PUROLATOR
                                               TELEPHONE NUMBERS FOR
                                                  PICK UP SERVICE
      AREA  SERVED


      A1 abatna
      •   Anniston
         Birmingham
         Midland City/Dothan
         Florence
         Gadsden
         Huntsville
         Mobile
         Montgomery

      Alaska

         Anchorage
         Fairbanks

      Arizona

         Phoenix
         Tucson

      Arkansas

         Fayetteville
         Little Rock
         Pine Bluff

      California

         Anaheim
         Bakersfield
         Burbank
         Fresno
         Long Beach
         Los Angeles
         Modesto
         Napa
         Oakland
         Ontario
         Oxnard
         Sacramento
         San Diego
         San Francisco
         San Jose
         Santa Barbara
         Santa Cruz,
         Santa Rosa-
         Stockton

      Colorado

         Colorado Springs
         Denver
         Fort Collins
         Greeley
         Dnahln
              PUROLATOR
FEDERAL EXPRESS
              205-328-8370
              205-983-3602

              205-328-8370
              205-328-8370
              205-666-3947
              205-265-7208
              602-267-1467
              602-792-0290
              501-664-8100
              501-664-8100
              213-673-1200
              213-673-1200
              415-952-0880
              303-287-0395
                                                -E.89-
 800-238-9070
 205-591-7745

 800-238-9070
 800-238-9070
 .205-772-0131
 205-342-7990
 205-288-8274
                                 907-243-3322 (Info)
                                 907-452-1186 (Info)
 602-894-9681
 602-294-2691
 501-372-7201
 800-238-9070
 213-594-6813
 805-393-5580
 213-849-319J
 209-252-4091
 213-594-6813
 213-776-4111
 209-982-5781
 800-852-7707
 415-568-2380
 213-331-0768
 800-852-7707
 916-392-9360
 714-297-0386
 415-877-9000
 408-279-8870
 805-964-0736
 800-852-7707
 800-852-7707
 209-982-5781
 303-574-6850
 303-320-8320
 800-824-7831
 800-824-7831
 800-824-7831

-------
                                         TELEPHONE NUMBERS FOR
                                           PICK UP SERVICE
AREA SERVED

Connecticut
    Bridgeport
    Bristol
    Hartford
    New Britain
    New Haven
    New London
    Norwalk
    Stamford
    Waterbury

Delaware
    Wilmington

District of Columbia

Florida
    Daytona Beach
    Fort Lauderdale
    Fort Myers
    Gainesville
    Jacksonville
    Lakeland
    Melbourne/TItusville
    Miami
    Orlando
    Pensacola
    Sarasota
    St. Petersburg
    Tallahassee
    Tampa
    West Palm Beach

Georgia
    Albany
    Athens
    Atlanta
    Augusta
    Columbus
    Macon
    Savannah

Hawaii
    Honolulu
PUROLATOR
FEDERAL EXPRESS
203-527-2100
203-847-3883
703-836-4542
305-525-3339
813-332-3132

904-389-5524
305-949-2226
305-896-1676
904-477-2276

813-823-5806
904-576-7174
813-879-5960
 912-883-5223

 404-763-8500
 404-793-2189
 404-323-6071
 912-788-5152
 912-964-6174
 203-579-1911
 203-728-1221
 203-728-1221
 203-728-1221
 203-469-2347
 800-526-3900
 800-431-1186
 800-431-1186
 203-753-4087
 302-652-1803

 703-691-1901
 800-238-9070
 305-525-4287

 800-238-9070
 904-757-0800
 813-682-6076
 800-238-9070
 305-371-8500
 305-857-3420
 800-238-9070
 8T3-746-9211
 813-821-4572

 813-885-2783
 800-238-9070
  800-238-9070
  404-452-0314
  912-781-8794
  912-964-9261
                    808-836-2303
                                                                       Project GWSS
                                                                       Appendix B
                                                                       Revision No.  1
                                                                       May  1983
                                                                       Page 9 of 16
                                        -E.90-

-------
Project GWSS
Appendix B
 ^vision No.
    1983
 Tge 10 of 16
1
                                              TELEPHONE NUMBERS FOR
                                                 PICK UP SERVICE
      AREA  SERVED
      Idaho

      Illinois
                           PUROLATOR
FEDERAL EXPRESS
          81oomi ngton/Norroal
          Chicago
          Decatur
          Moline/
          Peori a
          Rockford
          Springfield
      Indiana
         .Bloomington
          Evansville
          Fort Wayne
          Gary
          Indianapolis
          Kokoroo
          Lafayette/West Lafayette
          Michigan City
          Muncie/Anderson
          South Bend
          Terre Haute
      Iowa
          Cedar Rapids
          Davenport
          Des Moines
          Sioux City

      Kansas
          Topeka
          Wichita

      Kentucky
          Lexi ngton
          Louisville
          Owensboro
          Paducah

      Louisiana
         Baton Rouge
         Lafayette
         Lake Charles
         Monroe
         New Orleans
         Shreveport
                               None
                           312-738-6480

                           309-788-0428
                           309-829-4366
                           815-965-4377
                            812-424-7516
                            219-484-5724

                            317-634-1161
                            219-233-1406
                            319-356-8635

                            515-287-4000
                            712-252-2729
                            816-471-0057
                            816-471-0057
                            606-259-0406
                            502-637-9791

                            502-442-9555
                            318-322-2309
                            504-466-6256
                            318-742-7268
                                                                None
 800-526-3940
 312-686-6886
 800-526-3940
 309-797-9706
 309-697-5910
 815-874-9591
 217-753-3626
 800-526-3940
 812-426-1461
 219-747-1637
 312-686-6886
 317-2*8-1251
 800-526-3940
 800-526-3940
 800-525-3940
 800-525-3940
 219-234-0023
 800-526-3940
 319-366-8613
 309-797-9706
 515-280-8001
 800-526-3940
 316-945-5201
 606-253-2488
 502-361-2326
 812-426-1461
 504-924-0347
 800-238-9070
 800-238-9070

 504-733-3724
 318-227-1903
                                      -E.91-

-------
                                                                Project GWSS
                                                                Appendix B
                                                                Revision No. 1
                                                                May 1983 '
                                                                P, ne 11 of 16
                                        TELEPHONE NUMBERS FOR
                                           PICK UP SERVICE
AREA SERVED
Maine            ,
    Bangor
    Lewi ston
    Portland

Maryland
    Baltimore
    Gaithersburg
    Hagerstown

Massachusetts
    Boston
    Brockton
    Fall River
    Fltchburg
    P1ttsf1eld
    Springfield
    Worcester

Michigan

    Ann Arbor
    Battle Creek/Kalawazoo
    Benton Harbor
    Detroit
    Flint
    Grand Rapids
    Jackson
    Lansing
    Muskegon
    Saginaw/Bay City

Minnesota

    Duluth
    Minneapolis/St. Paul
    Rochester

Mississippi
    B11ox1/Gulfport
    Jackson
    Pascagoula
PUROLATOR
FEDERAL EXPRESS
207-784-0110
301-488-2020
617-269-7000
617-853-2458
313-542-6223

616-698-9500

517-321-6184
218-727-2798
612-721-6201
507-282-2559
601-939-6080
 207-947-6749

 207-775-7755
 301-760-8750
 703-691-1901
 800-526-39C ^
 617-662-0200
 617-662-0200
 800-556-6553
 617-662-0200
 800-526-3900
 413-736-3220
 617-393-6166
 313-941-7010
 616-968-0385
 800-526-3940
 313-941-7010
 313-767-4003
 616-455-1012
 800-526-3940
 517-394-6440
 800-526-3940
 517-695-6150
 612-340-0887
 800-238-9070
 601-932-3310
 800-238-9070
Missouri
    Kansas City
    St. Louis
    Springfield
816-471-0057
314-776-1110
 816-471-7110
 314-367-8278
 417-869-8422
                               -E.92-

-------
 Project GWSS
Appendix B
^•vision No.
•By 1983
^age 12 of 16
    1
                                               TELEPHONE NUMBERS FOR
                                                  PICK UP SERVICE
       AREA  SERVED
       Montana

       Nebrasks
          Lincoln
          Omaha

       Nevada
          Las Vegas
          Reno

       New Hampshire
          Manchester
          Nashua
                               PUROLATOR
FEDERAL EXPRESS
                                 None
                               712-323-1678
                               603-668-1773
       New Jersey
                    City
Atlantic
Camden
Edison
Jersey City
New Brunswick
Newark
Paterson
Teterboro
Trenton
Vine!and/Millvi lie
                                         201-967-9474
      New Mexico
          Albuquerque
          Sante Fe
      New York
          AT bany
          Binghamton
          Buffalo
          Elmira
          Fanningdale
          Garden City
          Long  Island
          New York City
          Newburgh/Poughk eeps1e
          Rochester-
          Syracuse
          Utica
          White Plains
                               505-345-7777




                               518-785-3676

                               716-685-4911
                               516-349-8383
                               212-392-6150

                               716-225-1505
                               315-437-7361

                               914-592-2171
      None
 800-526-3940
 712-347-6890
                                                  702-736-6161
                                                  702-323-3664
 603-669-6672
 603-669-6672
 800-942-
 609-662-
 201-923-
 201-923-
 201-923-
 201-923-
 201-923-
 201-923-
 609-587-
 800-942-
7717
•5682
^6000
,6000
•6000
•6000
,6000
•6000
7678
7717
 505-344-2321
 505-344-2321
 518-783-1155
 607-729-5218
 716-632-6200
 800-526-3900
 516-454.0300
 516-454-0300

 212-777-6500
 914-564-6850
 716-546-8080
 315-463-6647
 800-526-3900
 914-835-0030
                                          -£.93-

-------
                                                                  Project GWSS
                                                                  Appendix B
                                                                  Revision No. 1
                                                                  May 1983
                                                                  Page 13 of  16
                                        TELEPHONE NUMBERS FOR
                                           PICK UP SERVICE
AREA SERVED

North Carolina

    Ashevllle
    Burlington
    Charlotte
    Fayettevllle
    Greensboro
    Raleigh/Durham
    Salisbury

North Dakota
    Fargo
PUROLATOR
704-525-1127

704-525-1127

919-467-2241
919-467-2241
701-237-3239
FEDERAL EXPRESS
 800-238-9070
 919-855-5340
 704-394-5101
 800-238-9070
 919-855-5340
 919-781-9060
 800-238-9070
Ohio
    Akron
    Belpre
    Canton
    Cincinnati
    Cleveland
    Columbus
    Dayton
    Hamilton
 .  Lima
    Loral n*
    Mansfield
    Marion
    Springfield
    Steubenvllle
    Toledo
    Youngstown

Oklahoma

    Oklahoma City
    Tulsa

Oregon

    Portland
    Salem
614-423-9580
216-456-7188
513-621-3720
216-431-0500
614-471-4126
513-898-1070
419-865-8200
405-672-5539
918-836-8719
503-283-1220
 216-733-8341

 216-494-3691
 606-283-2922
 216-361-0872
 614-475-8314
 513-898-1693
 606-283-2922
 800-526-3940
 216-361-0872
 419-524-2143
 800-526-3940
 513-898-1693
 412-923-2130
 4.19-865-0265
 216-759-8222
 405-682-3681
 918-836-0241
 503-257-6611
 800-824-7831
                                    -E.94-

-------
Project GWSS
  pendix B
  " ision No. 1
    1983
Page 14 of 16
                                              TELEPHONE NUMBERS FOR
                                                  PICK UP  SERVICE
AREA SERVED:
Pennsylvania
Al 1 entown
Altoona
Erie
Harrisburg
King of Prussia
Lancaster
Philadelphia
Pittsburgh
Reading
Seneca
Tyrone
WHkes-Barre/Scranton
Williams port
PUROLATOR

215-791-1621

814-453-6032 ,
717-939-1351


215-825-5710
412-366-7970

814-676-0606
814-684-0729
717-655-8696
717-326-1303
FEDERAL EXPRESS

. 215-435-7651
800-526-3900
814-833-5660
717-944-0401
215-923-3085
717-944-0401
215-923-3085
412-923-2130
215-435-7651


717-346-7011
800-526-3900
      Puerto Rico

          San Juan

      Rhode Island

          Providence

      South Carolina

          Anderson
          Charleston
          Columbia
          Greenville/Spartanburg

      South Dakota

          Sioux Falls

      Tennessee

          Bristol
          Chattanooga
          Clarksville
          Jackson
          Johnson City
          K1 ngsport
          Knoxvillo
          Memphis
          Nashville
401-463-6720
803-791-5800
803-791-5800
803-791-5800
605-339-9110




515-629-9736

901-423-0605
615-525-5181
901-365-1670
615-226-0930
                   800-238-3064
401-738-4401
800-238-9070
800-238-9070
803-254-0201
803-238-8191
615-323-7117
615-892-2760
800-542-5171

615-323-7117
615-323-7117
615-970-2761
901-345-3810
615-361-4121
                                        -E.95-

-------
                                 3
                                        TELEPHONE NUMBERS FOR
                                        .   PICK UP SERVICE
                                     Project GWSS
                                     Appendix B
                                    'Revision No. 1
                                     May 1983
                                    .Page 15 of 16
AREA SERVED
PtJROLATOR
FEDERAL EXPRESS
Texas
    Afliarillo
    Austin
    Beaumont
    Brownsville
    Corpus Chrlsti
    Dallas
    El Paso
    Fort Worth
    Galveston
    Harlingen
    Houston
    Longview
    Lobbock
    McAl1 en
    Midland/Odessa
    San Antonio
    Sherman
    Temple
806-374-4930
512-928-4970
214-438-4713
915-565-2256
214-438-4713
713-869-6405

806-747-3601


512-227-5113
Utah
    Provo/Orem
    Salt Lake City

Vermont
    Burl ingtbn

Virginia
    Bristol
    Charlottesville
    Lynchburg
    Newport News
    Norfolk
    Petersburg
    Richmond
    Roanoke

Washington
    Bremerton
    Olympia
    Seattle
    Spokane
    Tacoma

West Virginia
    Charleston/Dunfaar
    Huntington
804-853-6754

804-644-4086
703-985-0525
206-325-5400
509-535-3521
 304-768-9796
 304-768-9796
 806-335-1641
 512-474-8029
 713-842-5892
 512-541-6721
 512-851-2836
 214-358-5271
 915-778-5435
 817-332-6293
 800-238-9070
 512-423-8835
 713-667-2500
 800-238-9070
 806-747-1752
 512-687-4792
 800-238-5355 (Info)
 512-824-9488
 214-358-5271
 512-474-8029
                   800-824-7831
                   801-532-6590
                   802-864-0074
 615-323-7117
 800-238-5355  (Info)
 800-238-9070
 804-857-5967
 804-857-5967
 804-222-6765
 804-222-6765
 703-342-7851
 206-762-5811
 206-762-5811
 206-762-5811
 800-238-5355  (Info)
 206-762-5811
                                      -E.96-

-------
  §oject GWSS
  pendix B
  vision No. 1
May 1983
Page 16 of 16
                                              TELEPHONE NUMBERS FOR
                                                 PICK UP SERVICE
      AREA SERVED
      Wisconsin
          Appleton/Oshkosh
          Green Bay
        .*Janesvi11e/Be1oit
        ,  Kenosha
          Madison
          Milwaukee
          Racine
          Schofield

      Wyomi ng
PUROLATOR
                                                          FEDERAL EXPRESS
414-731-5769
414-468-7159
608-241-4106
414-342-9330

715-359-4210

    None
414-739-8033
414-432-3260
608-241-2825
414-481-8680
508-241-2825
414-481-8680
414-481-8680
    None
                                         -E.97-

-------
Project GWSS
••^^^MY'S*
^^R-n3_3031 SI
USUeO IT COCE
AWARD/CONTRACT Appenaix C
Revision No. 1.
2 (MtCTivf B»H }. IfOuisniOM/culCHAif MOUtSl'MOJICT NO
!P 2 9 1980 cr Rn-ru?R

«'egotiated Contracts Branch
3 jn tracts Manager.ent Division
Invironnental Protection Agency
Jincinnati, Ohio 45268
COnTtACTOt CODE
r // «/>.' rf-« */«* 3 ;
fAC.ii.ni' cooc
™, .-_,.,„ _^
SRI INTERNATIONAL
l^n "uit ^^ Ravenswood Avenue
*.j 2:p"^.i Menlo Park, CA
L ' .J
i SHI* TO/MSAit tot com
i. r»a •tocL'tiwixi WAS r~"[ AovdTiste


i: fATK»£NT Will If »"0f IT
' «c."j'l!«o<:'oiNo. Ma^ 1983 •
•»"HC Page 1 of 10
COOK j ; | ' uci..."
OT**(* l \<*
n*"-'
1
H/A
10 iUtoK IMVQlCIi 'J <•?»• -"'"' ."•••^T

1
ACCOUNTING OPERATION'S OFFICE
Environtrtcnt.nl Protection Agency
Cincinnati, Oil A52f>8
n HJ ».»no ^nuAWT TO ^ '° UiC "" '"" ^ ?1FJ1 T"1>-J-^ PRICE -
CO «' u.i.c. J" u«10) INOFFINITF. OUANTITY
        feSO/10308    BOOOOA    68033031    OB64*.nM051    25.32    $275,000    060812HO
AQ
•


1*
TITLZ: DITEF.MINAT10N OF THE "WATER QUALITY OF
GROUND WATER SUPPLIES
*7he figures vere arrived at on an average basis,
hovever, the Contractor is responsible for the
number of analyses.
Order of Precedence - In the event of an inconsi
of this contract, the inconsistency shall be res
following order: (a) the schedule including the
(b) the General Provisions; (c) the other provis
incorporated by reference or otherwise; and (d)
OUAMT1TT
5000 AN
8500 AN

n
MY?
\LY?

•i*
ES (MINIMI1?1)
F.S (MAXIMUM)

70
;;«.:".

ttency between the provisions
slved by giving -precedence in the
Statement) or 1 Scope of T.,'crk;
.ons of thje contract whether
:he specificaiions. j
i
51
                                                                              TOtAl AMOUNT O' COM'»»O  S
                                                                               2/3,000
                         CONTR.»«'
                                                                 •t*««. «« *•••*? •«t«^*4 •« t» ita* •*«»• U«*«4 •*••* •*»< •*
                                                                 Tw» «w«f4 <•«••<«••«•• tk« i»«Mi«• H
                                                                 *M C***«M<»«»* » M**C*««*>**  *M«  r*tf •<•»•.  *•« (»|  •».«
                                                             •y^-'
J4.
       M.in.im-r
                                             J»
                                                                    ' Of
                                                                            V^ES  W.  HF.TSF.R
                                                                            Jf  3»ll JICN

                                                                            2  9 19DO

-------
 Project  GWSS
 Appendix C
 Revision No. 1
 May  1983
 Page 2 of 10

    ARTICLE VII
                031
                                 SPECIAL PPCVISIONS
                                                                        4  OF  in
                              -  PAYMENTS
    The contractor shall  be paid,  upon submission of proper  invoices or vouchers, the
    prices stipulated below for  the following items delivered and acccplcci loss deductions
    if any, as herein provided:
\.
 Case  Period

 SamjjVc_Sct

 Source  of supply
'raw water/finished  water
 Halocarbons
                                                                                Trie !.•
  Parameters  to  be  Dctcrmiiiert_

  1  - Bromoform
  2  - Bromodichloromcthane
  3  - Carbon  Tetrochloridc
  4  - Chlorobenzene
..  5  - Chloroform
  6  - Dibromochloromcthone
  7  - 1,2-Dibromo-3-chloropropane
  0  - 1,2-Dichlorobenzene
  9  - 1,3-Dichlorobenzcnc
10  - 1 ,4-Dichlorobcnzenc
11  - 1,1-Dichloroethano
12  - 1,2-Dichloroethane
13  - 1 ,1-Dichloroethylene
14  - c_ijs_-1 ,2-DicMoroethylene
15  - trnns^-1 ,2-Dichloroctnylene
16  - V,~2-Oichloropropane
17  - Methylene  Chloride
18  - 1,1,2,2-Tetrachloroothnnc
19  - 1,1,1,2-Tetrachlorocthanc
20  - Tetrachloroethylcnt
21  - 1 ,1,1-Trichlorouthane
22  - 1 ,1 ,2-Trichloroetluinc
23  - Trichloroethylene
24  - Vinyl Chloride
25  - Dichlwoiodon.ethaTie
26  - Bromobenzine
                                                                             Per
                                                                           $50.00
2.  Source of supply
    raw water/finished water
    Aroma tics
                                     1  -  Benzene
                                     2  -  o_-chlorotnlucne
                                     3  -  p-chlorotoluene
                                     4  -  tthylbcnzene
                                     5  -  ij£-fjropylbenzene
                                     6  -  n-(>ropylbenzene
                                     7  -  styrene
                                     B  -  Toluene
                                     9  -  o-Xylcne
                                    10  -  n«-Xylcne
                                    11  -  p-Xylene
                                    12  -  Trichlorobenzenc Isomcrs
                                                                            e.50.00
3.  Source of supply
    raw water/finished water
                                    Total  oryanic carbon
                                     5-45.00
                                    pprvTSTON? FOR NEOTTTATTTi

-------
                                     SPSCM. PTCVTSICNS
                                                                               Project GWSS
                                                                               Appendix C
                                                                               Revision No. 1
                                                                               May 1983
                                                                               Page 3 of 10
A.   Source  of suooly
     raw  water/finished water

5.   Confirmatory Analysis
     (Dual Colupn -  101)
6.   Confirmatory (GC/MS)
70   Quality  Control
     (Quplicate-10-)
8.   Qua!ity  Control
  .   (reference samples)
          Free and combined chlorine
          residual
         Halocaroons
         Aromatics

         Halocjrbons
         AromatiCS'
         Halocarsons
         Aromatics
         Total Organic Carton
         Free and Ccmoined chlorine
          residual
         Halociroons
         AromatiCS
         Total Craani,c Carton
         Free and Com-oined chlorine
          residual
S  60.00
                                                                            S   O'} .DO
S 2 u5 .00
S  50.00
                                                                            S    3.70
S . 55.00
                                                                                  o A
     An original  and 3 codes of each voucher shall  be submitted to the Accounting
     Operations  Office set forth 1n Blocit *12 on Page 1  (Star.cara Fora 25).
     ARTICLE  VIII
- PP.njF.CT DIRECTOR
     The -performance  of  the work  required by  this  contract  shall bn  conducted
     under the direction  of Dr. Dale M.  Coulson.   The r.ov<«rnrH.'nt  reserves  the  rip'-it
     to approve any successor to  Dr. Coulson.
                                    PSCV1S1CNS FOR MECCT

                                           -E.100-

-------
Project GWSS
   Kendix C
   ision No. l
    1983
Pa9e 4 of 10                   STATEMENT .OF WORK


 The  contractor,  employing  gas chroma tography, will analyze raw and finished
 ground water  samples.

 Samples shall  be provided  by EPA to the contractor.  Samples to be analyzed
 for  aromatic  compounds will have a suitable preservative such as nitric acid
 or mercuric chloride added at the time of sample collection.  Samples will be
 stored at 4°C  after collection and must be stored at this temperature until
 analysis.  Samples will he provided to the contract laboratory within seven (7)
 days after collection and must be analyzed within thirty (30)  cnlend.ir days nfter
 collection.


 The  goal of the  program is to provide quantitative data on a broad range of
 purgeable organic compounds.  Total organic carbon and free and combined
 chlorine residual . measurements are also to be performed.  Additional p"rgeable
 compounds are  to be reported, though not necessarily identified, by comparison
 to internal standard(s) and the development of retention indicies.  The relative
 peak area compared to that of a known concentration of an internal standard
 should also be reported.
                                    *
 During the period of performance del ivery orders will be issued for the following-
 'types of analyses.  (Reference Payment Article Items 1 thru 4).  The purae end
 trap gas chromatographic procedure employing an electrolytic conductivity dc.tector
 is to be  used for the analyses of .halocarbons.  Attachment 1 (paragraphs a, 5, 6, 7,
 3 &  9).  The more selective and sensitive photoionazation detector should be employed
 for  the analyses of aromatic compounds rather than a flame ionization detector (Fib)
 --sample measurements.  Attachment 1 (10).

 During the period of performance delivery orders will be issued for the following
 types of analyses.  (Reference Payment Article Items 5 and 6).  It is realized that
 in certain cases, a second gas chromatographic column will be required for confirmatory
 analyses and  in  some cases gas chromatography/mass spectromttry (GC/MS) will be
 required for positive identifications.  These .analyses should be quantitative
 \r\ nature and  be restricted to sample sets 1 and 2 and to specific
 compounds identified in Tohlc 1.  Dual column confirmatory determinations
 shall be performed on 10^ of the samples.   Gas chr«mato«jraphy/mass
 spectrometry confirmatory analyses shall be performed on 5" of the
 Samples.  The  project Officer in conjunction with the contractor
 will  select samples to be analyzed by CC/t'S.  Detection and quantification
 limits for thr onjanic compuonds listed in Table I must bo equal to
 or less than 0.1 - 0.5 u'j/1 and 0.5 ug/1 respectively.   Generally,
 detection limits for additional  compounds  reported must be equal or
 less than 0.5  ug/1.  However, during the course of the contract, the detection
 and quantitation limits should be expected to be improved.

       Low-level  total organic carbon determinations shall be made
 according to the  specified  method. Attachment I (11)  Samples will
 be preserved hy EPA at the  time of collection.  Minimum detection
 and quantification limits of 50 and 100  uy/1 must be achieved.

       Free and combined residual chlorine measurements shall be
 made  according to the specified method.  Attachment I (12)  Minimum
 detection and  quantification limits of 50 and 100 ug/1 must be
 achieved.                                                        EXHIBIT A
                                                                 Contract No.  6S-03-3031
                                                                 Pap.e  1 of 2

-------
                                                                         Project  GWSS
                                                                         Appendix  C
_  ,.    .                                                                 Revision  No.  1
Quality Assurance                                                   'May  1983

During the period  of performance delivery  orders  will  be  issued  for the Page 5.of 10
following  types of analyses.   (Reference  Payment Article Itfe.-;s  7  i  8).
The following items shall  be  performed  by the  contractor for  quality.
assurance  purposes:

 a.    The  contractor  shall  analyze in duplicate a  total of 101  of
      each sample  set  listed  in Table 1.  The  initial 10 samples  in
      each set  shall be  analyzed  in duplicate  to hctter define
      precision  of  the analyticjl  laboratory.  Prt'cision for  all
      compounds  quantitatively analyzer',for shall bo as given in
      Table  II.   In addition, [TA may collect  (in  duplicate)  and
      analyze 5-10!; of all  samples.

 b.    During the contract period, when analytical data are being
      obtained,  the contractor will quantitatively analyze, twice
      per  month  and in duplicdte, reference samples supplied by EPA.
      This requirement will apply for each instrument bciny employed
      by the? contractor  in  the study.  Four samples arc roc-'i  red as
      Outlined  in Table  111.  Precision requirements will  be as
      stated in  Table  II.  'Accuracy requirements (Table 111) will be
      based on the .avera^s obtained by qualified testing  laboratories
      who  have previously analyzed the reference samples.
                                                    EXHIBIT A
                                                    Contrnct No. 68-03-3031
                                                    A/7/80
                                                    Page 2 of 2
                                     -E.102-

-------
Project GWSS .
   endix C
   Ision No. 1.
PageTof 10                     REPORTS OF WORK


     Compilation of Data

            All generated data will be inputed by the contractor into a
     data handling system that is compatible with a 370/108 IBM System.
     The contractor will also Suhniit monthly to [PA interim «uul final
     printouts of all dota plus a macjnetic tape of interim and final
     data.
     Reports

     The major reporting effort, Analytical Results are to be submitted
     to the project officer on: a monthly basis.  Six copies of the
     monthly report are to be provided within 15 (calendar days) after
     the end of the period being reported.  The contractor, for each
     preceding month, shall provide the project officer with the following;
                                 %
      a.   Entry of data into an appropriate data system

      b.   A copy of the computer printout.            s.         .       .
      c.-   Duplicate determination data.
      d.   Confirmatory analyses data.
      e.   Quality control data -- precision and accuracy.
      f.   Details of progress, accomplishments, and problem areas.
      g.   examples of analog outputs of data gathered in the preceding
           month.

      At the direction of the project officer, the contractor shall
      provide an example of how final reported values for specific
      samples are obtained.  The contractor must save all raw data
      outputs for a period of one year after completion of the contract.
      All or part of these data shall be made available to EPA on request.
      All data may be transferred to EPA on request.
             •
      A summarized report is to be submitted to the project officer
      consisting of:           confirmatory analyses, quality control, .
      and any additional pertinent experimental data.  The report shall
      include a detailed description of the methods used, modifications
      made to established procedures, difficulties encountered, and, if
      any, recommendations for future analytical development work.

      Reports shall be prepared in accordance with CPA Manual entitled,
      "Science and Technical Pufolicaiton" TN3 dated May 14, 1974.
                                         -E.103-
                                                         EX1UBIT B
                                                         Contract No. 68-03-3031
                                                         A/7/80
                                                         Page 1 of 1

-------
                                                                      Project GWSS
                                                                      Appendix C
                                                                      Revision No.  1
                                                                      May 1983
                                                      ,                'Page 7 of 10
                              Attachment I
1.   US Environmental Protection Agency, "National  Interim Primary
     Drinking Water Rpgul aliens," Fed.  Register,  £0(2*0),  59566-59588
     (December 24, 1975).

2.   US Environmental Protection Agency, "Interim Primary  Drinking Water
     P.egul ationo; Control of Organic Chemical  Contaminants in Drinking
     Water," Fed. Register £3(28),  5756-5780 (February 9,  1978).

3.   US Environmental Protection Agency, "National  Interim Primary
     Drinking Water Regulations; Control of Tribal omet.hanes in Drinking
     Water; Final Rule," Fed. Register  44(231),  68624-68707 (November
     29, 1979).

4.   US Environmental Protection Agency, "Sampling  and Analysis Pro-
     cedures for Screening of Industrial Effluents  for Priority Pol-
     lutants," Environmental Monitoring and Support Laboratory, Cin-
     cinnati , Ohio (April 1977).
                            *
5-   Dollar, T. A. and J. J. Lichtenberg, "Determining Volatile Organics
     at the Microgram-per Litre Level  in Water by Gas Chrowatoyraphy,"
     0. AWWA, 66 739 (1974).

6.   Cellar, T. A., J. J. Lkhtenbcrg and R.  C. Kroner,  "The Occurrence
     of Qrganohalides in Chlorinated Drinking Water," J. AWWA _66_ 703
     (1974).                                       .   '

7.   Brass, M. ,0. , M. A. Feige, T.  Malloran,  J. W.  Mello,  D.  Munch and
     R. F. Thomas, "The National Organic Monitoring Survey:  Samplings
     and Analyses for Purgeable Organic Compounds," in "Drinking  Water
     Quality Enhancement Through Source Protection,"  Robert Pojasek,
     Editor, Ann Arbor Science Publishers,  Ann Arbor, Ml  ('1977).

8.   L'S Environmental Protection Agency "Guidel ines Establishing  Test
     Procedures for the Analysis of Pollutants; Proposed Regulations,"
     Fed.  Register £4(233), 69464-69575 (December 3,  1979),  Methods 601
     and 602.

9.   US Environmental Protection Agency "The  Analysis of Malogenated
     Chemical  Indicators of Industrial  Contamination  by the Purge and
     Trap Method," Environmental Monitoring and Support Laboratory,
 "'   Cincinnati, Oil (April  1900) (DRAFT).

10.  US environmental Protection Agency "The  Analysis of Aromatic Indi-
     cators of Industrial Contamination in  Water  by the Purye and Trap
     Method,"  Environmental Monitoring  and  Support  Laboratory, Cincinnati,
     Oil (April 1980)  (DRAFT).

                                                ATTACHMENT T
                                                Contract  No.  6R-03-3031
                              -E.104-           A/7/80
                                                Page 1 of  2

-------
project  GWSS
"" pendix C
  Ins ion No. 1
Jay 1983
Page 8 of 10
        11.   US Environmental  Protection Agency "Method for the  Low  Level  Determi
             nation of Total Organic Carbon," Environmental Monitoring  and
             Support Laboratory, Cincinnati, OH (April  1978).

        1.2.   US Environmental Protection Agency, "Methods for Chemical  Analyses
             of VJater and Wastes," Environmental Monitoring and Support Labora-
             tory, Cincinnati, OH  (1978).
                                                          ATTACHMENT I
                                                          Contract No. 68-03-3031
                                                          4/7/80
                                                          Page 2 of 2
                                            -E.105-

-------
                            TABLE 11

                   Minimum Precision  Requirements
                                                                      Project GWSS
                                                                      Appendix C
                                                                      Revision No. 1
                                                                      May 1983
                                                                      Page 9 of 10
      Sample Set'
Precision Requirements
           1


           2


           3


           4
20* above
40% below
20% above
40% below

 5X above
10% below
10% above
5 ug/1
5 us/1

5 ug/1
5 uij/1

200 ug/1
200 ug/1

100' ug/1
a - See Table I.
b - Measured as the percent difference between the  two values
    obtained.  The average of  the two values  shall  be used to base
    the percentage difference.   Thus,

    Percentage Difference
V2 - V1 x 100
Vl
+ V2
2
    where V.  and V- are the experimentally  determined  concentrations,
                                                 TABLE II
                                                 Contract No. 68-03-3031
                                                 4/7/80
                                                 Page 1 of 1
                                    -E.106-

-------
Project GWSS
Appendix C
 'vision No. 1
    1983
 5ge 10 of 10
                                     TABU  III
          Required Reference Sample Analyses and Accuracy Requirements
           1.  Purgeable Organic Halocarbons -- two samples each containing
               compounds at different concentrations; accuracy requirements
               ^ 20% above 5 ug/1 and ^ 40% below 5 ug/1.

           2.  Purgeahic Aromatic Compounds -- two samples each containing
               compounds at different concentrations; accuracy requirements
               j* 20% above 5 ufj/1 and +_ 40% below 5 ug/1.

           3.  Total Organic Carbon -- two samples, each containing
               different TUC concentrations; accuracy requirements
               +_ 10% above 200 u«j/l  and +_ 20% below 200 ug/1.
           4.  Tree and ccrnbinet! clilorinc residual -- o^e sample; accuracy
               requirements * 107..
           a.  To be onaly:ed twice a month- in duplicate.
           b.  For each analytical system being employed.
           c.  Accuracy based on the averages of testing laboratories who
               have previously analyzed these reference samples.
                                                       TABLE III
                                                       Contract No.  68-03-3031
                                                       6/7/80
                                                       Page 1 of 1
                                           -E.107-

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                                                      Project GWSS
                                                      Appendix D
                                                      Revision No. 1
                                                      May  1983
                                                      Page  1 of 54
January 19, 1983


Final Report



DETERMINATION OF TEE QUALITY OF GROUND WATER SUPPLIES

By:  B. A. Kings ley, C.  Gin Avanzino,
     C. W. Beeman,  and R.  M. Emerson
Prepared for:
                               i
U.S. ENVIRONMENTAL PROTECTION AGENCY
Technical Support Division-Office of Water Supply
26 West St. Clair Street
Cincinnati, Ohio 45268
Attention:  Mr. Robert Thomas
            Project Officer

EPA Contract No. 68-03-3031
SRI International Project No. PYU-2250
Approved:
M. E. Hill, Laboratory Director
Chemistry Laboratory

G. R. Abrahamson
Vice President
Physical Sciences Division
                   -E.108-

-------
Project GWSS
   endix 0                                                        .
   1ST on NO; 1                                             EPA Report No.
    1983                                                   January 1983
Page 2 of 54 '
                   DETERMINATION OF THE QUALITY OF GR01TND WATER SUPPLIES



                                             BY •

              B. A. Kingsley, C.  Gin Avanzino,  C.  W.  Beeman,  and R.  M.  Emerson

                                     SRI International
                               Menlo Park, California  94025



                                EPA Contract No.  68-03-3031



                                                       i
                                       Project  Officer

                                       Robert  Thomas
                                 Technical Support Division
                                   Office of Water Supply
                                  26 West St. Clair Street
                                   Cincinnati,  Ohio  45268
                            Office of Water and Waste Management
                            U.S. Environmental Protection Agency
                                   Cincinnati, Ohio 45268
                                          -3.109-

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                                                                 Project  GWSS
                                                                 Appendix  D
                                                                 Revision  No.  1|
                                                                 May  1983
                                                                 Page  3 of 54
                             DISCLAIMER
     This report has been reviewed  by  the  Technical  Support
Division, Office of Drinking Water, U.S. Environmental  Protection
Agency, and approved for publication.   Approval does  not  signify
that the contents necessarily reflect  the  views and  policies  of
the U.S. Environmental Protection Agency,  nor does mention of
trade names or commercial products  constitute endorsement or
recommendation for use.
                                 ii
                               -E.110-

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  pject GWSS
—pendix D
Revision No.  1
May 1983
Page 4 of 54                       ,     ,
                                         FORZWAHD
                                  (to be supplied by USEPA)
                                              111


                                             -E.lll-

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                                                                       Project  GWSS
                                                                       Appendix D
                                                                       Revision No.  !•
                                                                       May  1983
                                                                       Page  5 of 54
                                   ABSTRACT
     The Ground Water Supply Survey  was  initiated  to assess  the  quality of
ground-source drinking water with respect to  purgeable halocarbon and aromatic
compounds and total organic carbon.   In  the first  phase of this  survey, the
U.S. Environmental Protection Agency,  in cooperation with  the  States, collected
samples from approximately 1000 water supplies.  Half of these supplies were
randomly selected to provide a representative survey of the  nation's  ground
water sources*  Of these sources,  40Z were systems serving populations of
10,000 or more, and 60Z were smaller systems.  The remaining water supplies
were selected because of suspected chemical contamination.   Many of the sup-
plies found to contain purgeable organic compounds will be resampled during a
second phase of this survey, now in  progress.

     3urge and 'trap preconcentration methods  were  used for the purgeables  gas
chromatographic analyses.  A serially interfaced photoionization/electrolytic
conductivity detector system was developed and used to detect  and quantify 37
target compounds.  An extensive quality  assurance  program was  incorporated into
the analytical scheme.  All data were entered directly from  SRI  International
into an EPA-maintained data file.

     This final report, covering the first phase of the survey,  summarizes the
procedures used to perform these analyses and thf  results  obtained as part of
the quality assurance program.  Results  of sample  analyses are not discussed.

     This report was submitted in fulfillment of EPA Contract  No. 68-03-3031 by
SRI International under sponsorship  of the U.S. Environmental  Protection
Agency, Office of Drinking Water,  Technical Support Division.  This report
covers the period from October 1,  1980,  to January 31, 1982.   Work was com-
pleted on February 15, 1982.
                                      iv

-------
Project GWSS
Appendix D
 evisipn No. 1
    1983
   e 6 of 54  '
                                           CONTENTS           '         '
                                                                                Page

       Forevard	    ill
       Abstract	     iv
       Figures	•	     vi
       Tables	    vii
       Acknowledgments	   vlii
             1  Introduction	      1
             2  Conclusions and Recommendations	      2
             3  Experimental Procedures	•     3
                Analytical Procedures	      3
                Sample Collection and Storage	      3
                Purgeable Halocarbon and Aromatic Compounds..	      3
                     General Procedures and instrumentation	      3
                     Standards Preparation	 	      7
                     Analytical Procedures	      7
                          Analytical Conditions	      7
                          Calibration	      9
                          Compound Identification and Quantification	     13
                          Interferences	     14
                Residual Chlorine	     15
                Total Organic Carbon	     16
                     General Procedures	*	     16
                     Analytical Procedures'	     17
                          Calibration	     17
                          Calculation of TOC Concentration	     18
             4  Quality Assurance	     19
                Reference Samples	     19
                Duplicate Analyses	     22
                Split Sample Analyses	     24
                Blind Sample Analyses	     24
                Confinflatory Analyses	     24
                     Second Column Confirmatory Analyses	     24
                          Halocarbons Confirmatory Analyses	     24
                          Aroma tics Confirmatory Analyses	     31
                        .  Comparison of Primary and Second Column
                            Confirmatory Analyses	     31
                     Gas Chromatography/Mass Spectrometry Confirmatory
                       Analyses	     31
                Data Reporting Errors	     42
             5  Reporting of Data	     43

       Re f erences	     44
                                          -E.113-

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                                                                      Project GWSS
                                                                      Appendix D
                                                                      Revision No. 1
                                                                      May.1983
                                                                      Page 7 of 54
                                    FIGURES   '

Number

   1     Block diagram of GC/PID/E1CD  instrumentation	,
     •
   2     Diagram of modified photoionization  detector  connections.
         Chromatograms  obtained  by  purge/trap GC/PID/E1CD  analysis
         of 1 ppb standard mixture  of  halocarbon and aromatic
         compounds using 12 SP-1000 on Carbopack B column..;	     10

         Chromatograms  obtained  by  purge/trap GC/PID/E1CD  analysis
         of a 1 ppb standard mixture of halocarbon and  aromatic
         compounds using an n-octane on Poracil C column	:.     28

         Chromatograms  obtained  by  purge/trap GC/PID/E1CD  analysis
         of a 1 ppb standard mixture of aromatic and halocarbon
         compounds using a 5? SP1200/5Z Bentone 34 on Supelcoport
         column	     32
                                      vi


                                     -E.114-

-------
Project GWSS .
Appendix 0
Revision No. 1
    1983
     3 of 54
        Number
                                            TABLES
1

2 "

3

4
5
6
7
8
9
•-
10

11
12
13
14

15
16
17
18
19
20



Analytical Conditions for Primary Analysis of Halocarbons

Calibration Data and Quantification Limits for
GC/PID/E1CD Primary System 	
Retention Order and Detector Response of Selected
Purgeables Using GC/PID/E1CD System 	
Halocarbons Reference Sample Analyses — Primary Column 	
Aromatics Reference Sample Analyses — Primary Column 	
TOC Reference Sample Analyses 	 • 	
Precision of Duplicate Analyses 	 	 	 	
Comparison of Data Obtained for Split Sample Analyses 	
Comparison of Concentrations (ppb) Determined from
Blind Sample Analyses 	 « 	 	 • 	
Analytical Conditions for Confirmatory Analysis
of Halocarbons. 	 	
Halocarbons Reference Sample Analyses — Confirmatory Column....
Analytical Conditions for Confirmatory Analysis of Aromatics..
Aromatics Reference Sample Analyses — Confirmatory Column 	
Precision Between Primary and Second Column Confirmatory
Analyses 	
Analytical Conditions for GC/MS 	
Calibration Data and Quantification Limits for GC/MS System...
Reference Samples Analyses— GC/MS 	
Precision Between Primary and GC/MS Confirmatory Analyses 	

Relative Retention Times for Quantified Compounds Using
GC/PID/E1CD 	
vii
-E.115-

8

11

12
20
21
22
23
25

26

27
30
33
33

34
35
37
38
39
40

41



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                                                                       Project  GWSS
                                                                       Appendix D
                                                                       Revision No. 1
                                                                       May  1983
                                                                       Page  9 of 54
                                ACKNOWLEDGMENTS
     The authors would like to acknowledge the staff members at SRI
International and the Technical  Support Division, Office of Drinking Water of
the OTs. Environnmetal Protection  Agency, for their efforts, comments, and
criticisms of this work.  At SRI  we extend special recognition  to Dr. Dale  M.
Coulson for his guidance  and support in this work.

     At EPA we especially appreciate the guidance of the Project Officer,
Robert Thomas, and Wayne  Mello for providing some of the statistical analyses
included in this report.

     In addition, we extend our  thanks to the personnel of the fifty states who
provided the samples used for this study.
                                     viii

                                  -E.116-

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   tject GWSS
   endix D
   ision No. 1
May 1983
Page 10 of 54
                                          SECTION 1
                                         INTRODUCTION
           The Office of Drinking Water of the U.S. Environmental Protection Agency
       (EPA),* in cooperation with the States, has undertaken a survey of the quality
       of the nation's drinking water derived from ground water sources.  The goals of
       the Ground Water Supply Survey (GWSS) are to (1) augment the current pollution
       occurrence data base for ground water supplies, (2) improve Federal and State
       responses to pollution incidents, (3) stimulate State ground water quality
       activities, and (4) develop improved identification of heavily polluted ground
       water sources.

            For the first phase of the GWSS, approximately 1000 ground water supplies
       were sampled.  Half of these supplies were randomly selected, with 200 repre-
       senting systems serving populations of 10,000 or more and 300 systems serving
       smaller populations.  The remaining water supplies were selected by the States
       and EPA because of suspected contamination.

            All samples were analyzed for purgeable halogenated and aromatic organic
       chemicals and  for total organic carbon.  Residua! chlorine' concentrations were
       measured at the time of analysis for those systems that add a disinfectant.
       These analyses were performed at SRI International under contract to the EPA,
       Office of Drinking Water, Technical Support Division (TSD),  Cincinnati, Ohio.

            Phase 1 of this survey has now been completed.  Sixteen monthly reports
       have been submitted, describing in detail the analytical procedures used, prob-
       lems encountered, data acquired, and results obtained from the quality
       assurance program. This final report is intended to summarize the work done
       during this phase of the GWSS.

            Phase 2,  now under way, will continue these analyses, resampling many of
       the systems where contamination was identified during this initial phase in  an
       effort to locate the specific sites of contamination and to monitor any changes
       in types or concentrations of pollutants.
                                              1
                                          -E.117-

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                                                                       Project GWSS
                                                                       Appendix D
                                                                       Revision No.  1
                                                                       May 1983
                                                                       Page 11 -of 54
                                   SECTION  2

                        CONCLUSIONS AND  RECOMMENDATIONS
     All data generated in this  survey were  analyzed by  the EPA Technical
Support Division (TSD).  Although  conclusions  regarding  the results of the
sample analyses are beyond the scope  of  this project, SRI  International can
make certain recommendations based on its  experience with  these analyses:

     (1)  Resampling of contaminated  supplies, now under way,
          should provide the information necessary to pinpoint  the
          location of the offending well(s)  in a  ground  water
          system.  It is recommended  that, whenever possible,
          samples from heavily contaminated  wells be obtained and
          analyzed for the semivolatile  (extractable) organics
          using gas chromatography/mass  spectrometry (GC/MS)
          techniques, since the  purgeahles data obtained may be a
          good indication of further  contamination.

     (2)  The serial gas chrooatography/photoionization  detector/
          electrolytic conductivity detector (GC/PID/E1CD) system
          developed for these analyses provided significantly more
          information for compound identification than is  avail-
          able from separate'GC/PID and  GC/E1CD analyses.   This
          system is recommended  for future work of this  type.            :

     (3)  It is recommended that dichloromethane  be eliminated
          from the list of target  compounds  or that its  quantifi-
          cation limit be raised significantly.   This compound  is
        .  present in the environments of most  laboratories
          involved in water analyses, including some water utili-
          ties.  Low level occurrence data are almost meaningless.
          Field blanks analyzed  in this  work routinely contained
          2-3 ppb of this compound.
                                   -E.118-

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Project GWSS
Appendix D   ;
Revision No. 1
    1983
     12 of 54
                                         SECTION .3
                                  EXPERIMENTAL PROCEDURES
      ANALYTICAL PROCEDURES
            *                                                 '            ,

           All water samples collected for this phase of the survey were analyzed for
      purgeable halocarbon and aromatic compounds and for total organic carbon
      (TOC).  The concentrations of residual free and total chlorine were determined
      at the time of purgeables analysis for those samples to which disinfectant had
      been added.  Second column confirmatory analyses were performed for all samples
      found to contain compounds other than the trihalomethanes (THMs) and for other
      samples as necessary.  Selected samples were also analyzed by GC/MS. These
      confirmatory analyses are discussed in detail in Section 4 as a part of the
      quality assurance program.

      SAMPLE COLLECTION AND STORAGE

           Samples were collected in 60- and 250-ml headspacs-free, screw cap septum-
      sealed bottles with Teflon-lined septa.  Samples intended for purgeables and
      TOC analyses were preserved with mercuric chloride (10 ppm> to inhibit bac-
      terial growth, since some data indicate losses of aromatic compounds by bio-
      degradation  (1).  Additional bottles of sample containing no preservative were
      collected  for residual chlorine measurements.  Field blanks (TSD generated
      Milli-Q processed water) accompanied the water samples at all times.

           Field collected samples were first shipped iced by overnight air express
      to TSD, where they were inspected, sorted, and temporarily stored.  Backup
      samples were kept at TSD. Sample sets were then replaced in ice before shipment
      to SRI, again by overnight air express.  A standard sample set for a ground
      water site consisted of one 250-ml and two 60-ral sample bottles containing
      mercuric chloride preservative, one 60-ml bottle without mercuric chloride
      preservative, and a 250-ml field blank.  After being logged and inspected, the
      samples were immediately stored in a walk-in refrigerator maintained at 4°C.'
      Additional bottles of SRI-generated blank water were stored in this refrigera-
      tor to monitor for contamination during storage.  This refrigerator is equipped
      with alarm, and automatic shutoff systems to prevent accidental freezing or
      overheating  of the samples.

           All primary analyses were completed within one month of sample collection.

      PURGEABLE HALOCARBON AND AROMATIC COMPOUNDS

      General Procedures and Instrumentation

           The purge/trap technique (2-4) was used to concentrate the purgeables from
      25-ml water  samples before gas chromatographic analysis.
                                             3


                                         -E.119-

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                                                                        Project GWSS
                                                                        Appendix D
                                                                        Revision No. 1
                                                                        May 1983 .
                                                                        Page 13 of 54
     The. original analytical scheme specified separate purge/trap GC analyses
for halocarbon and for aromatic compounds,  using electrolytic conductivity
detection (E1CD) and photoionization detection (PID),  respectively."  However,
at the initial project meeting before beginning the  analyses, SRI proposed the
use of a serially interfaced PID/E1CD system that allows detection of all these
compounds in a single analysis.  Data obtained from  analyses of EPA supplied
Reference Samples using this system were presented,  showing the required accu-
racy and precision with no loss of sensitivity.  Further, SRI agreed to analyze
an initial batch of samples using both the  serial detector procedure and sep-
arate *E1CD analyses for halocarbons.  The results of these analyses demonstra-
ted that data obtained using the GC/PID/E1CD system  was equivalent to the data
derived from separate analyses.  Subsequently, all analyses were performed
using the dual detector system (5).

     Over the period of this study, a number of samples have been analyzed by
both SRI and TSD as a part of the quality assurance  program.  (The data
obtained fron these analyses are pi_sented  in Tables 8 and 9 of Section 4.)
The SRI values were obtained using the serial detectors, and the TSD data were
obtained from separate analyses for halocarbon and aromatic compounds.  These
data also demonstrate the equivalence of the procedures.

     The instrumentation used, shown in Figure 1, consisted of the following
components:  a Tekmar LSC-II purge/tr^p unit; a Hewlett-Packard 584QA gas chro-
matograph with recording integrator; an HNU high temperature photoionization
detector (PID), mpdel PI-51-02, with a 10.2-eV lamp; a detector interface unit;
a Coulson electrolytic conductivity detector (E1CD); and an additional Hewlett-
Packard model 3380A recording integrator.  The sorbent trap in the LSC-II was
filled with two-thirds Tenax GC/one-third coconut charcoal (6, 7).  The glass
vessel was wrapped with heating tape to allow complete drying of the vessel
during the trap bake-out cycle.

     The photoionization detector was modified to eliminate leaks.  The modifi-
cations made, shown as shaded areas in Figure 2, provided the leak-tight system
necessary to allow the gas stream to pass to the second detector.  The transfer
line from the GC column is connected directly to the deter.tor inlet tube by a
1/16-in. Swagelok union.  The Swagelok nut  attached  to the inlet tube is held
rigidly in place by a hexagonal opening in  the plate attached firmly to the
•detector base, preventing damage to the glass-lined  inlet tube when the trans- '
fer line is attached.  A Teflon 0-ring is inserted at the base of the UV lamp
window to provide a better seal between the lamp and the detector cell.  The
PID was operated at 2008C.

     A modified heated transfer block was also installed between the PID and
the E1CD.  A glass transfer tube delivers the effluent from the PID into the
heated zone of the E1CD furnace. Additional helium (35 cm^/min) is added within
the transfer block to sweep the PID effluent into the glass transfer tube.

     Two identical systems were used for these analyses:  one for the primary
analyses and the other for second-column confirmations.
                                       4
                                   -E.120-

-------
Project  GWSS
Appendix 0
«i si on No.  1
    1983
    j  14  of 54
                        Purge/trap unit
                           Gas chromatograph
                                                  PID    PiD/EICD     EICD
                                                          Interface'
                                                           Sweep
                                                           Helium
                                                   Y               7
                                                     Recording integrators
                                                                   JA-325522-32A

                          FIGURE 1  DIAGRAM OF GC/PID/ElCD INSTRUMENTATION
                                               -E.12. 1-

-------
          Quartz
        Window
 Glass-lined
   Stainless
  Steel Inlet
  Hold-down Plate
Cut to Fit 1/16 in.
     Swagelok Nut
                             A
                                      10.2 eV  Lamp
                                     .Teflon 0-ring Seal

d


I





To PID/EICD
Interface
                                 1/16 in.iss Swagelok Union
                                ,1/16 in. ss Transfer Line
                                 from GC Column
                                                JA-325522-33A


 FIGURE 2  DIAGRAM OF MODIFIED PHOTOIONIZATION DETECTOR
           CONNECTIONS
                                                                          owoo
                                                                 Appendix D
                                                                 Revision No.  1
                                                                 May  1983
                                                                 Page  .15 of  54
                          -E.122-

-------
project
Appendix D
Revision No. 1
May 1983
    ' 16 of 54
       Standards  Preparation

            All standard solutions  were prepared  in methanol  (Burdick & Jackson, dis-
       tilled-in-glass).  An aliquot  of this methanol was tested for contamination
       before use by spiking -10 ul into water and analyzing  the solution by  the pro-
       cedures described below for  sample  and standard analyses.

            Stock standards were prepared  by placing about 9  ml of methanol in a 10-ml
       volumetric flask, which was  then stoppered and weighed.  One to two drops of
       the  desired compound were added to  the flask, using a  disposable pipette with
       the  tip barely above the surface of the methanol.  The stopper was replaced and
       the  flask  was reweighed.  The  concentration of the standard was calculated from
       the  weight difference.  The  flask was,then filled to the mark with methanol,
       and  the contents  were mixed  by inverting the flask three times.  These stock
       standards, at concentrations of 1 to 2 mg/ml  fcgAil),  were transferred to 10-ml
       crimp-top  vials and stored refrigerated in dessicators containing activated
       -arbon. Stock standards of  vinyl chloride were purchased in sealed glass vials
       containing 0.1 mg/ml of vinyl  chloride in  tnethanol (Chera Service, West Chester,
       Pennsylvania) to  avoid problems associated with handling and preparing stan-
       dards of this gas.

            Working standard mixes  were prepared  by adding aliquots of the desired
       stock standards to methanol.  Several different mixes  were used to avoid inter-
       ferences.   The concentration of each compound in these working standard mixes
       was  6.0 ±  0.2 ng/ul.   These standards were used until they failed to give
       satisfactory results when compared  with the Reference  Samples.  Vinyl chloride
       working standards were prepared immediately before use because radical changes
       in concentration  of this compound could be noticed within one hour of prepara-
       tion.  The remaining stock standard was discarded once the glass seal was bro-
       ken.

            Blank water  was generated using a Milli-0 reverse osmosis system  (Milli-
       pC  ., Bedford, MA).  The blank water used  for purgeables standards was kept
       unaer continuous  nitrogen purge.

       Analytical Procedures

            The same procedures (2-4) were used for analysis  of samples and of stan-
       dards.  Standards were prepared by  spiking the desired amount of working stan-
       dard mixture into 25 ml of blank water in  a 30-ml gas-tight syringe with an
       inert valve.

            Samples were carefully  poured  into a  30-ml gas-tight syringe.  After the
       headspace  was eliminated, the  volume was adjusted to 25 ml.  Five microliters
       of the internal standard mixture containing 10 ngAil each of 2-bromo-l-chloro-
       propane (BCP) and a ,a,a-trifluorotoluene (TFT) in methanol was added through
       the syringe valve using a 10-til syringe.   Sample syringes were rinsed with
       blank water and dried in a 110*C oven between samples.

            Analytical Conditions—The conditions used for the primary purgeables
       analyses are shown in Table  1.
                                             7

                                          -E.123-

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                                                                         Project GWSS
                                                                         Appendix D
                                                                         Revision No.
                                                                         May 1983
                                                                         Page 17 of. 54
            TABLE 1.  ANALYTICAL CONDITIONS FOR PRIMARY ANALYSIS OF
                             HALOCARBONS AND AROMATICS
Sample volume:

Internal standards:


Purge:
      «
Desorption:

Chromatographic system

     Column:


     Carrier:


     Temperature program:
     Analysis time:
25ml

50 ng 2-Bromo-l-chloropropane (2 ppb)
50 ng a p. ,a-Trif luorotoluene (2  ppb)

Helium at  40  cm^/min for  10 min

A minutes  at  180°C
1.8-n by 2-mm I.D.  glass  packed with
IX SP-1000 on 60/80 Carbopack B

Helium at 35 cur/min (26  cur/min through     ^
the LSC-II,  9 cm /min directly into injector)

Initial temperature 60"C  for 10 min (including
the 4-roin desorption),  programmed at 7°C/min for
10 min, then 12°C/minxto  final temperature of
200°C
55 min
At the beginning of an analysis, the purge vessel of  the LSC-II was filled with
25 ml of sample or standard, and the purge cycle, the GC program,  and the sec-
ond recording integrator were started simultaneously.  The sample  was purged
with helium for 10 minutes while the purged organics  were collected on the  •
sorbent trap.  At the end of the purge cycle,  the aorbent trap was sealed off
and rapidly heated to 100*C, then switched into the GC carrier stream and
heated to 180"C, while the collected sample was thermally desorbed onto the
head of the gas chromatographic column.  At the end of 4 min,  the  sorbent trap
was switched out of the GC carrier stream.  The GC column was  then temperature
programmed as shown in Table 1 and held at the final  temperature until after
the expected elution time of p-dichlorobenzene (55 min).

     During the desorption period, the sample  was drained from the vessel.,  At
the completion of desorption, the sorbent trap was heated to 220*C, and the
purge vessel was heated to 110°C while the vessel and trap were purged with
helium (-100 cm3 /min) for 20 min.   All valve  switching and heating were per-
formed automatically by the LSC-II and an auxiliary  timer and heater.
 Use  of  the extra helium sweep in the injector significantly improved the
 shape of  early-eluting peaks using this gas chromatograph.
                                    -E.124-

-------
Project GWSS
Appendix D
Revision No. 1
    »1983
   e 18 of 54
          Chroraatograms  obtained  fron analysis ~f a 1 ppb standard.mixture  of halo-
      carbon and aromatic compounds using the OC/PID/E1CD system are shown in Figure
      3.  The  circled numbers refer to ID numbers in Tables 2 and 3.  These  chromato-
      grams indicate a number of opportunities for compound misidentif icat'ion as a
      result of either coelution or close retention times.  For example, vinyl chlor-
      ide (No. 3) and dichlorodifluoromethane (No. 4) are not resolved.  Dichloro-
      iodo'raethane (No. 22)  is poorly  resolved from the internal standard BCP (No.
      21).  Tetrachloroethylene (No.  25) and 1,1,2,2-tetrachloroethane  (No.  26), and
      n-propylbenzene (No.  38) and o-chlorotoluene (No.  37) are also unresolved.
      Trichlproethylene  (No. 17) and  benzene (No. 18) elute very closely.  However,
      in each  case, one  of  the pair causes a response on only one detector,  while the
      other causes both  detectors  to  respond.  In addition, for compounds that cause
      both E1CD and PID  response,-  the difference in retention times between  the two
      detectors is very  reproducible.  This information  has been very helpful in
      identifiying compounds in complex samples.

          Calibration-—The system was calibrated by analyzing spiked standards.
      Calibration factors were decennined by analysis of standards spiked into blank
      water at concentrations of 0.5, 1, 2, 3, and 10 ppb.  At least two analyses
      were performed at  each level. For each compound, area counts were plotted ver-
      sus concentration  (ppb).  The slope of the regression line was then calculated,
      and the  inverse was used as  a calibration factor (R), having the units ppb/area
      count.

          In  general, calibration factors for the halogenated alkanes and alkenes
      and chlorobenzene  were calculated from the E1CD calibration, whereas the PID
      calibration was used for the aromatic compounds, including the other halogen-
      ated aromatics.  Dichloroiodomethane was an exception.  At low concentrations,
      this THM was poorly resolved from the internal standard BCP in the E1CD chro-
      matogram, and its  concentration was frequently determined using a calibration
      factor calcxilated  from the PIT), where BCP Caused no interference. Calibration
      factors  from both  detectors  were used for the applicable compounds if  needed
      for clarification.

          Typical calibration data are shown in Table 2.  Quantification limits were
      at least two times the minimum  detectable concentration.  The 0.2-ppb  quantifi-
      cation limit was set  as a reasonable and convenient minimum for the halocarbon
      compounds.  However,  for many of the halgenated compounds, detection limits
      were much lower  than 0.3 ppb.   The 0.5-ppb limits  for the aromatic compounds
      were set to accommodate fluctuations in the PID lamp intensity over time.
      There were a number of exceptions.  For example, the quantification limit for
      vinyl chloride was set at 1  ppb even though much smaller amounts of this com-
      pound could be easily detected  in the E1CD chromatogram. However, because of
      the frequently observed coeluting freon (dichlorodifluoromethane), detection of
      a peak in the less sensitive PID chromatogram was  necessary for identification
      of vinyl chloride.

          There were  several cases of anomolous response in the halocarbon  data.
      The tetrachloroethane isomers show a 4:1 ratio in  E1CD response factors, and
      the trichloroethane isomers  have a nearly 2:1 response factor ratio.   This
      problem  was noted  early in the  contract period, and standards prepared by TSD
      were analyzed, giving the same  results.  TSD had reported 1:1 ratios for each
      of  these isomeric  pairs.  Although these differences have never been resolved,


                                            9
                                          -E.125-

-------
Q
U
UJ

LU
10

O
Q.
co
LU
tr
                                                                      Project GWSS
                                                                      Appendix D
                                                                      Revision No.  1
                                                                      May  1983
                                                                      Page  19 of  54'
UJ
V)

1
l/J
               20
                                      30
                              TIME (min)
40          50

        JA-32S522-34A
  FIGURE 3
CHROMATOGRAMS OBTAINED BY PURGE/TRAP GC/PIO/EICO ANALYSIS
OF 1 ppb STANDARD MIXTURE OF HALOCARBON AND AROMATIC
COMPOUNDS USING 1% SP1000 ON CARBOPACK B COLUMN
Numbers in circles refer to ID numbers in Tables 2 and 3.

                     10

                  -E.126-

-------
Project GWSS
Appendix 0
Revision No.  1
     1983
    e 20 of  54
                                TABLE 2.  CALIBRATION DATA AND QUANTIFICATION LIMITS
                                              FOR GC/PID/E1CS PRIMARY STSTZM
ID
Number
Compound
R* (xlO6)
Quantification
Limit (ppb)
Electrolytic conductivity detector
3
6
7
8
9,10
11
12
13
14
15
16
17 .
19
20
21
22
23
24
25
26
29
-
Vinyl chloride
Dichloroaethane
1 ,1-Dichloroethylene
1,1-Dlchloroe thane
ci«-, trana-Dichloroethylene
Chloroform
l,2-Dichloro«thane
1 , 1 , 1-Trichloroethane
Carbon tetrachloride
Broaodichloroae thane
1 , 2-Di chloropropane
Trichloroethylene
• Dlbrooochloromethane
1,1,2-Tricbloroethane
2-Brooo-l-chloropropane CISTD)
Dlchlorolodome thane
Bronoform
1,1.1,2-Tetrach lor o« thane
Tetrachloroethylene
1,1,2,2-Tetraehloroethane
Chlorobenzene
1,2-DibronD-i-chloropropane
Photolonization detector
18
27
28
30
31
32
33
35,36
37
38
39
40
41
42
Benzene
o.a.o-Trlfluorotoluene (ISTD)
Toluene
Ethylbenzene
Bronobenzene
I»op ropy Ibenzene
a-lylene
o-, p-Xylenes
o-Chlorotoluene
o-Propy Ibenzene
p-Chloro toluene
a-Dichlorobenzeae
o-Dichlorobenzene
p-Dichlorobenzene
9.8
4.5
9.8
3.7
7.6
3.4
8.3
5.2
3.5
5.6
5.8
3.7
10
9.8
-
22
29
4.2
3.1
16
9.2
ISO
R jxlO5)
1.7
-
1.6
1.9
2.4

1.6
1.7
c
e
c
c
e
c
\
lb
0.2
0.2
0.2
0.2
0.5
0.2
0.2
0.2
0.2
0.2
0.5
0.5
1
1.0
1.0
0.2
0.2
0.5
0.5
5

0.5
-
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
                     "Calibration  factor* calculated aa deteribed in text have units ppb/are*
                      count*.

                      Mo quantification limit vaa aet for dichloroaethane became of posaible
                      background contamination.

                     ^Because of poor integration of theae late-e'luting conpounda, concentrations
                      of theae rarely observed compound* were  determined by manual Integration
                      with a atandard analysed the aaae day.
                                                        11

                                                     -E.127-

-------
              TABLZ 3.
                                  OIBE* AMD  DETECTOR RESPONSE or SILECTED FUXCZAJUS
                                     OSIHC CC/PID/Eld) STSTW
                                                                               rrujeut,  onoo
                                                                               Appendix D
                                                                               Revision No.   1
                                                                               May  1983  .     •
                                                                               Page  21  of   54
                                             Relative Retention Tlat  on Colu
                                                                                    Detector Reeponee
n
No.
i
2
3
4
5
'6
7
8
9
10
Covpouad
ChloroM thane
BromoMtheae
Vinyl Chloride
DtcblorodlfluoroMthaae
Qilaroe thane
DlchloroBC thane
1 , 1-01 chloroe thy lene
1,1-Dlchlaroe thane
traaa-Dlchloroethylme
cle-Dl chloroe thylene
AC
0.069
0.086
0.100 (0.097)
0.100
0.129
0.199
0.360 (0.356)
0.459
0.516 (0.512)
0.516 (0.512)
Bd
0.177
0.294
0.177 (0.170)
0.101
0.411
0.497
0.323 (0.318)
0.657
0.448 (0.444)
0.620 (0.621)
c* ra
«o'
ID
HD +
RD
ID
HD
HD +
HD
HD +
0.710 (0.704) »
UCD
4-
+
+
^.
+
+
»
•*•
+
+
11    Qtlorefor*
12    1,2-DlchloTMthnM
13    1.1,1-TrichlortMtfaaM
14    Carbon Tttrachloridi
15    lroaodlchlorc»th«o«

16    1,2-Dlchloropropan*
17    Trichloro«thTl«n«
18    Dcax«iM
19    DlbronochloroMChant
                     0.550
                     0.591
                     0.650
                     0.670
                     0.703

                     0.760
                 0.797  (0.796)
                     0.813
                 '   0.820
                                                        0.620
                                                        0.889
                                                        0.680
                                                        0.325
                                                        0.796

                                                        1.00
                                                    0.680 (0.678)
                                                        0.870
                                                        0.972
     ID
    0.433
     ID
    0.426
     H>

    1.00
0.646 (0.630)
    0.630
     HO
20
21
22
23
24
25
26
27
23
29
X
31
32
33
34
35
36
37
38
39
40
41
42
1 , 1 , 2-Tri chloroethaoe
2-Broeo-l-chioropropant (ISTD)
DlchlorolodoMthnt
Bromof on
l,l.l,2-T«trachloroe thane
Tttrachloroethylene
1,1,2.2-Tatrachlorotthane
a.a.a-TniluoTotolueae (ISTD)
Toluene
Qilorobeazen*
Ethylbenxene
Broaobeazeiie
laopropylbenxen*
e-Iy'itne
Scyrene
o-Xylene
p-Zylene
o-Ch lore toluene
o—Propy loeaxene
^•Gblorotolueac
•-D1 chlorobenxene
o-Dlchlorobeniene
p-Wchlorobenxen.
0.820
0.860
0.902
0.912
0.912
0.981 (0.983)
0.981
1.00
1.02
1.08 (1.08)
1.18
1.23 (1.23)
1.31
1.41
1.41
1.49
1.49
1.60 (1.58)
1.58
1.71 (1.72)
1.71 (1.72)
1.80
1.83
1.08
1.12
1.04 (1.04)
1.12
1.12
0.796 (0.796)
1.33
1.00
1.12
1.12 (1.12)
1.28 ^
KD
KD
1.36
HD
l.U
1.36
KD
KD
ND
KD
HD
KD
1.77 +
1.42 - +
2.13 (2.16) f +
2.48 - *
1.77 - *
1.16 U.J1-) + +
2.99 - *
1.00 + +
1.21 +
1.37 (2.41) + +
1.91 +
3.42 (3.50) •» »
2.37 +
2.23 *
2.86 +
2.37 +
2.07 »
3.23 (3.30) * *
2.78 t-
3.23 (3.30) * *
3.88 (3.98) i- +
5.28 (5.43) + +
3.42 (3.50) + +
     i»«  r«t«ntlon
dittetot.  Wh«r« f
tlCD.
in an
 nvabtn  «rt
                                    to int«rn«l itwuUrd a,a,«-trlfluorotolu«ii« u»taj th«
                                   ra, tb« firtc oiafacr npr**«nu r»L«civ«  r»t«ntlon tlat for
          t»u»«»  rMpoBM (•*•)  or dou not e«u«< rwpoea* (-) en IndleiMd detector.
 ?rt»«r7 «B«lytie»l coluan:  1.8 m by 2-«s 1.2.  |lui paelud »lth II SP-1000 ea 60/80 C«rbop«ck 8, held
 et 60 C for 10 mln, then teasencure pretraaaed at 7*C/mln for 10 mia,  UMa 12'C/mia to • fiaal tcat>«ri-
 tur« of 200*C.

Salocartcne eonflr»etory eolian: 1.8 » 'by 2-M l.D. il«. peeked with  o-aetaae on PoreeU C. held at
 50 C for * mln,  then tcBBeratur«prosra«ed at 44c/«la  to i final tevperatur* of 140*C.

*Aroaetie« eonflr»etorr column:   1.8 • by 2-
-------
Project GWSS
   endix D
   jsion NO'. 1
    1983 '  .
 age 22 of 54
      quantification of these compounds is not affected.  (In factj of these com-
      pounds, only 1,1,1-trichloroethane was observed in any real water sample during
      this survey.)

           More important is the very poor response obtained for l,2-dibromo-3-
      chlpropropane (DBCP).  The insensitivity to this compound is especially dis-
      turbing because the chronic exposure concern level (see Section 5) for this
      compound has been set at 0.05 ppb.  The major losses of this compound during
      analysis appear to' lie within the purge/trap system, since the detection limit
      by dir,ect injection is estimated at 12 ng.  This amount would be equivalent to
      0.5 ppb in a 25-ml water sample.  The poor sensitivity toward this compound is
      probably caused by a combination of low purging efficiency and losses within
      the LSC-II.  Similar results were obtained on both GC/PID/E1CD systems in oper-
      ation.  The GC/MS employs a manual purge trap system and demonstrates the same
      poor sensitivity.

           After the calibration was completed, quality control Reference Samples
      were analyzed (see Section 4).  If the results of these analyses met the per-
      formance criteria, sample analysis was begun.

           The calibration factors varied over time with changing detector response
      and column age.  In fact, PID calibration factors were usually recalculated
      daily because considerable variation was observed.  Both E1CD and PID calibra-
      tion factors were monitored by daily analysis of spiked standards.  If the
      calibration factors failed to give the correct concentrations for the daily
      standard (error greater .than 202), more calibration analyses were performed and
      additional quality control Reference Samples were analyzed.

           Of the two internal standards used, BCP was detected only by the E1CD,
      whereas TFT was detected by both the F.LCD and PID.  When the GC/PID/E1CD system
      is used, TFT is a more suitable internal standard for both halocarbon and aro-
      matic compounds because the relative retention times (RRTs) calculated relative
      to this compound better indicate the elution order of all the compounds of
      interest for all the columns used in this work.  Relative retention times cal-
      culated with respect to TFT are shown in Table 3 for a number of compounds in
      addition to those to be quantified in this survey.  Relative retention times
      for the primary chromatographic column are shown in Column A of this table.
      Also shown are the response for each compound for each detector (+ or -) and
      the relative retention times of each compound on one or more of the confirma-
      tory columns discussed in Section A.

           Compound Identification and Quantification—All compounds were identified
      by comparing the retention time of the observed peak with the known retention
      times obtained from standards within a II retention time window.  (Relative
      retention times were used only as an extra check in cases of closely eluting
      compounds.)  The concentration of a compound was determined by applying the
      appropriate calibration factor to the chromatographic area:


                                  Cone (ppb)   »  Area x R                           (1)
                                            13
                                         -E.129-

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                                                                          Project
                                                                          Appendix  0
                                                                          Revision  No.  1
                                                                          May 1983
                                                                          Page 23 of  54
Both operations (comparison of retention times  and calculation of
concentration) were performed automatically  by  external  standard calibration
factors entered into the integrators.   All data were  carefully check-ed for
accuracy because slight variations  in  retention time  could sometimes result in
an incorrect identification, and poor  integration could  yield incorrect concen-
tration data.  Chromatograms from both detectors  were compared for consistency
of "response for applicable compounds.

     Occasional samples contained compounds  at  concentrations greatly exceeding
the range of the calibration data,  sometimes causing  signal saturation.  In
such cases additional standards were prepared and analyzed at concentrations
near the estimated concentration of the sample.  In cases of signal saturation,
the sample was reanalyzed using an  attenuated detector signal and quantified
against a similar standard analyzed under the same conditions.

     When unidentified peaks were observed in either  PID or E1CD chromatograms,
they were reported by relative retention time and relative area (TLA).  For
unknown E1CD peaks, the relative retention times  were calculated relative to
BCP; PID unknowns were reported relative to  TFT.   Relative areas (RA) were
calculated by assuming that the unknown compound  had  a response equal to that
of the aplicable internal standard:


                 RA - (Area(unknown)/Area(ISTD)]  x Conc(ISTD)               (2)


Subsequent analyses of these samples by GC/MS have resulted in identification •
of most of the unknown compounds observed.

     Interferences—Many-of. the problems of  misidentification caused by poor
resolution or coelution were solvable  by comparing the E1CD and PIT) chromato-
grams.  However, four potential interference problems remain:


     (I)  High concentrations of chloroform  could mask small quanti-
          ties of 1,2-dichloroethane.   Fortunately, these ground water
          samples seldom had chloroform concentrations in excess of 40
          ppb, where such interference would require  raising the
          detection limit for 1,2-dichloroethane.  Any samples con-
          taining chloroform at concentrations  greater than 40 ppb
          were reanalyzed using a different  chromatographic column (as
          described in Section 4),  and the presence or absence of this
          compound was determined from the results of the second anal-
          ysis.

     (2)  Two of the other trihalomethanes coelute with  other com-
          pounds:  dibromochloromethane with 1,1,2-trichloroethane and
          bromoform with 1,1,1,2-tetrachloroethane.  Because the THMs
          are so often present in chlorinated waters, confirmatory
          analyses were not routinely  performed to prove the identifi-
          cation.  However, the concentrations  of the four more common
          THMs usually follow a pattern of either increasing or
          decreasing concentration with increase  in the  number of


                                      14
                                    -E.130-

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Project GWSS
Appendix D
Revision No. 1
    1983
     24 of 54
  KKVl

*
                bromine atoms per molecule.  Any samples that did not follow
                these trends were reanalyzed using the confirmatory
                column.  Although this approach was definitely subjective",
                it was not possible to reanalyze all samples containing
                these two THMs.  As noted above, neither 1,1,2-trichloro-
                ethane nor 1,1,1,2-tetrachloroethane was observed in any of
                the actual water samples analyzed in this survey even though
                most of the samples contained no THMs.  One blind sample
                (see Section 4) containing 1,1,1,2-tetrachloroethane was
                analyzed.  The apparent occurrence of bromoform at a concen-
                tration of 18 pph with no other THMs triggered a second
                column confirmatory analysis, resulting in correct identifi-
                cation of the tetrachloroethane.  However, there Is the
                possibility that these compounds could have remained unde-
                tected in THM-containing samples. •

           (3)  A more interesting case of compound misidentification caused
                by interference occurred when numerous samples with high THM
                levels appeared to contain small amounts of 1,2-dichloropro-
                pane.  This compound closely elutes with dibroroochloro—
                methane on the confirmatory column, and initially it was
                thought that the identification was not being confirmed
                using this column because of interference of this TOM at
                high levels.  However, all samples of this type did contain
                the same unknown peak in the confirmatory column chromato-
                gram.  It is suspected that this compound is actually the
                chlorination product dichloroacetonitrile (DCAN), although
                only one such sample contained this compound at a concentra-.
                tion sufficient for identification by GC/MS.  At the time
                these analyses were performed, no authentic DCAN standard
                was available to allow determination of its response.

           (4)  The other cases of coelution indicated in Table 3 could be
                resolved by reanalysis of the samples using one or both of
                the confirmatory columns, as discussed in Section 4.

      RESIDUAL CHLORINE

           Free and total residual chlorine concentrations were measured for samples
      from water systems using chlorination.  Because of concern about biodegradation
      of some of the compounds of interest, particularly the aromatics, these
      measurements were made at the time of purgeables analysis in order to determine
      whether or not the residual chlorine was still providing protection from chis
      source of sample degradation.

           The DPD (N,N-diethyl-p-phenylenediamihe) colorimetric method was used for
      these measurements.  This method uses the reaction of HOC1, OC1~, and chlor-
      amines with DPD to form a pink solution.  Values for free chlorine are obtained
      by reaction of DPD with HOC1 and/or OC1~ in a buffered solution (pH 6.3-6.5).
      For total chlorine measurements, KI is added to the sample along with the buf-
      fer and DPD.  The I~ catalyzes the reaction between the chloramines and DPD, so
      that the total chlorine value measures the amount of HOC1, OC1~, and chlor-
      amines in the solution.
                                            15
                                          -E.131-

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-Project GWSS
Appendix D
Revision No. 1
May 1983
Page 26 of 54
     Stock standards were prepared by weighing 50 to 200 mg KHP and diluting to
     100 ml with blank water in a volumetric flask.  The stock was stored in an amber
     glass bottle in the dark when not in use.  The standard was replaced when ana-
     lyses of Reference Standards (Section 4) failed to yield correct results.
     Working standards were prepared by dilution of an appropriate aliquot of the
     stock standard with blank water immediately before use.

          The TOC oxidizing reagent was a solution of potassium persulfate
     (K,S20g) (Gold Label, 99.95Z-100.05Z purity, Fisher Scientific Co., Fairlawn,
     NJ) ana 85Z phosphoric acid (HjPO^) , reagent grade (Mallinckrodt, Parris, NY);
     5 g of potassium persulfate and 3 ml (5 g) of phosphoric acid were diluted to
     100 ml with blank water in a volumetric flask.   The reagent was stored in an
     amber glass bottle and replaced every two weeks.

     Analytical Procedures

          Ten ml of sample was introduced into the sparger, and 0.5 ml of TOC oxi-
     dizing agent was added.  As the analysis began, the sample was purged with
     helium.  The purgeable components of the sample first passed through a lithium
     hydroxide scrubber, which removed the inorganic C02, then through a
     pyrolysis/reduction system where the gas stream was joined with a stream of
     hydrogen.  The combined gases passed over a nickel catalyst that converted the
     purgeable organic carbon to methane, which was detected by flame ionization.
     The integrated signal from the detector gave a response proportional to the ?OC
     concentration in the sample.

          The water sample passed through a reaction coil where the nonpiirgeable
     organic carbon was exposed to intense ultraviolet illumination in the presence
     of the acidified oxidizing reagent.  The nonpurgeable organic carbon was thus
     converted to C02, and the sample was transferred to a second sparger where the
     CO 2 was purged with helium.  The C02 was then passed through the
     pyrolysis/reduction system where it was converted to methane and measured by
     the flame ionization detector.  The integrated signal was added to that from
     the POC measurement, resulting in the concentration of total organic carbon
     (TOC).

          This procedure, performed automatically by the DC-54, was repeated until
     two sequential analyses gave concentrations within the required level of
     precision (10Z for TOC levels above 300 ug/liter and 20Z below that level).

          Calibration—The system clean-up and calibration procedure specified in
     the manufacturer's operation manual (9) were used.  The procedure consists of
     three parts:  (1) balancing the totalizer circuit in the totalizer/reaction
     module, (2) establishing a system blank, and (3) calibrating the system with a
     carbon standard.

          A detailed procedure for balancing  the totalizer circuit is given in the
     manufacturer's operating manual  (9).  Since it was seldom necessary, the pro-
     cedure will not be explained here.

          The  system blank (SB) was established by recirculating a blank water sam-
     ple through the system until a TOC level of <0.005 ± 0.005 ppm C was achieved
      for two consecutive analyses. This is a  correction value to be subtracted from


                                           17
                                        -E.132-

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                                                                          Project  GWSS
                                                                          Appendix D
                                                                          Revision No.  1
                                                                          May  1983
                                                                          Page  25  of  54
     The Each CN-70 Test Kit (Hach Chemical Company, Ames, Iowa) was used for
these analyses.  The intensities of the colored solutions were visually com-
pared with a color wheel provided with the kit.  Values of free and total
chlorine were reported over the range of 0.1 to 3.0 mg/liter (ppm).

TOTAC;. ORGANIC CARBON

General Procedures

     All water samples were analyzed using a standard EPA method (8) and a
Dohrmann DC-54 ultralow-level total organic carbon analyzer.  The sparger used
allowed transfer of the entire sample, including suspended solids, through the
UV reaction chamber during the nonpurgeable organic carbon (NPOC) part rf the
analysis cycle.

     This sparger was further modified at SRI to improve the precision obtained
in the analyses of some samples.  In the early stages of this work, it was
noticed that analysis of certain samples yielded data with very poor
precision.  Initially, it was thought that the lack of precision was caused by
suspended solids in the sample, since this phenomenon was never observed with
standards or Reference Samples, and not all samplesvexhibited this behavior.
Erratic data were not obtained when the standard glass-fritted sparger was
used.  However, careful observation of the analysis process revealed that a
small amount of sample backed up through the sparger side arm and into the UV
reaction chamber when a sample was loaded and the helium purge begun.
Lengthening the sparger side-arms by 2.5 in. prevented sample backup and made
an immediate improvement in the precision of analyses.  It is suspected that
the lack of precision was caused by nonpurged carbon dioxide present in that
part of the sample that was observed to back up into the reaction chamber, thus
escaping the purgeable organic carbon (POC) helium purge.  Since both calibra-
tion standards and Reference Samples were prepared with nitrogen-purged water
having a much  lower carbon dioxide concentration, the sample backup was not a
problem with these analyses.

     Water used for standards and reagents was obtained from a Milli-Q RO sys-
tem and kept under continuous nitrogen purge until used.  Potassium hydrogen
phthalate  (KHP:  CgH.O.K) (Aldrich Chemical Co., Inc., Milwaukee, WI) was used
as the calibration standard.  The concentration of this standard, expressed in
sag/liter, parts per million of carbon (ppm C) was calculated as shown below.


                 mg C/liter  -  Wt^ ° * 12  x  103  -  ppm C                (3)


where
     Wt  -  weight of KHP in grams
      n  «  number of carbon atoms per molecule (8 for KHP)
     12  »  atomic weight of carbon
     MW  -  molecular weight of KHP (204)
      V  -  volume of water in liter.
                                      16

-------
                                                                         Appendix D .
                                                                         Revision No. 1
                                                                         May 1983
                                                                         Page 27 of .54
the results of subsequent analyses.  This procedure also derafbonizes  the sys-
tem of accumulated residue*

     The system was calibrated daily using KHP  standard
containing -1.2 ppm C. Calibration at  this concentration resulted  in linear
response over a concentration range of 0.200  to 12 ppm C.

     Calculation of TOO Concentration—The TOC  concentration  of  a  sample was
determined by correcting the digital readout  from the DC-54 using  the  corrected
system.blank (SB) obtained for that day:

                       (ppm)   »  (TOC  from digital readout) - SB             (A)
                                      18
                                   -E.134-

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Project GWSS
Appendix D
Revision No. 1
    1983
   e 28 of 54
                                           SECTION 4

                                       QUALITY ASSURANCE


            The  following  quality  assurance  protocol was established to monitor the
       quality of data  generated in  these  analyses.

            Reference sample analysis:   Four times per month using each
                                         instrument.
                 Aromatics:  one concentration  level
                 Ralocarbons and total organic  carbon: two concentration levels

            Duplicate analyses:  10Z of samples analyzed

            Blind sample analyses

            Split sample analyses

            Confirmatory analyses
                  (1)   Second chromatographic column
                  (2)  GC/MS


        REFERENCE SAMPLES

            Concentrates containing  standard mixtures of some of  the more  frequently
        observed  halocarbon and aromatic compounds were provided by TSD as  needed.  The
        concentrates were diluted with methanol  (1:10 and 1:20 for the halocarbon mix-
        ture and  1:10  for the aromatics), and the  diluted concentrates were spiked into
        blank  water  as'needed to provide Reference Samples.  Reference Samples for TOC
        measurements were prepared  immediately before use by diluting 0.5 ml of the
        concentrate  into 50 ml  or 250 ml of blank  water for high and low level measure-
        ments,  respectively.  The remainder of the TOC concentrate was transferred to a
        crimp-top vial and  stored in  a refrigerator until needed for the next set of
        Reference Sample analyses.  Once opened, a vial of concentrate was  used for
        about  one month, then replaced with a new  vial.

            Reference Samples  were,  in general, analyzed weekly using each instrument
        in use at that time for sample analysis.  The contract specified that precision
        and accuracy (error) measurements be  within 40Z for purgeable concentrations
        less than 5  ppb and 20% for concentrations above that level.  Precision was
        defined as  the difference between duplicate values, divided by the  average of
        the two (expressed  as a percent).  This  measurement of precision is appropriate
        for biweekly duplicate  measurements.   However, since single Reference Samples,
        were analyzed  weekly  for the  purgeables, the precision of  the measurements is
        better expressed by the coefficient of variation (100 times the standard devia-
        tion,  divided  by the mean value).  The error was to be calculated with ref-
        erence to average values obtained from interlaboratory tests.  Since none was
        available,  the error was calculated as 100 times the absolute value of the
        difference between  the  expected and mean concentration, divided by  the expected
        concentrations.   These  data,  along  with  the range of values found in these
        analyses, are  summarized in Tables  4  and 5 for halocarbons and aromatics,
                                              19
                                          -E.135-

-------
                                        TABLE 4.  HALOCARBONS REFERENCE SAMPLE ANALYSES—PRIMARY COLUMN
U)

Low Level8
Expected Concentration Found

Chloroform
1,2-Dlchloroe thane
1,1,1-Trlchloroe thane
Carbon tetrachloride
Bromodichlorome thane
Trichloroethylene -
Dlb romochlo rome thane
Bromoform
Tetrachloroethylene
Cone.
(ppb)
8.2
3.3
1.3
1.5
l.A
2.3
2.1
1.7
1.1
Range
6.1 -9.2
2. A -3.6
0.85-2.0
1.2 -1.8
0.96-1.6
1.7 -2.6
1.0 -2.5
0.59-2.0
0.82-1. A
Mean
7.2
2.9
1.1
l.A
l.A
2.0
1.7
1.6
1.0
CVC
12
10
22
10
11
9
17
18
11
(ppb)
X
Errord
-12
-r-12
-15
-6.7
0
-13
-19
-5.9
-9.1
Expected
Cone.
(ppb)
3A
1A
5.6
6.2
6.0
9.1
8.5
7.0
A. A
High Level6
Concentration Found (ppb)
Range
25-36
9.9-15
3,7-8.0
5.1-7.3
5.1-7.5
7.A-10
5.3-8.9
5.1-8.2
3. 6-5. A
Mean
31
13
5.0
6. A
6. A
8.7
7.1
6.9
A. 3
CVC
9
11
20
a
9
6
11
10
8
X
Error4
-8.B
-7.1
-11
3.2
6.7
-A. A
-16
-l.A
-2.3

                 48 analyses.
                                                                            **

                 47 analyses.

                j»
                 Coefficient of  variation:  100 times  the standard deviation divided by the mean value.


                 Error expressed as  100 times the difference between the expected and mean measured  concentrations,

                 divided by the  expected concentration.
                                                                                                                             -O 2 73 3> -u
                                                                                                                             o> cu m -o -t
                                                                                                                             IQ "< < T3 O
                                                                                                                             n>   -»• a> <->•
                                                                                                                                t-' t/i 3 n>
                                                                                                                             (Si IO -•• CL O
                                                                                                                             10 oo o -••€-«•
                                                                                                                                cj r> x
                                                                                                                             o       cr>
                                                                                                                             -*   -z.
-------
Project GWSS
Appendix D
Revision No. 1
    1983
     30 of 54
       respectively.   For all halocarbon  compounds, the errors calculated averaged
       -11Z  for  the low level and -5Z  for the high level.  While these data
       demonstrate a  slight negative bias, the accuracy and precision requirements
       were  easily met.   No bias was observed for the aromatic compounds.


         !    TABLE 5.   AROMATICS REFERENCE SAMPLE ANALYSES—PRIMARY COLUMN

-
Benzene
Toluene
Ethylbenzene
Total xylenes
Expected
Cone.
8.7
5.3
5.9
7.5
Concentration Found (ppb)u
Range
6.9-12
3.5-6.5
4.3-6.7
5.0-8.5
Mean
Cone.
9.5
5.1
5.9
7.2
C7*
13
14
10
13
Z
Error0
9.2
-3.9
0
-4.0

       a52  analyses.
        Coefficient  of  variation: 100 times the standard deviation divided by the
        mean value.
       cError expressed as  100  times the difference between the expected and mean
        measured  concentrations, divided by the expectediconcentration.


            Precision and accuracy  requirements for TOC Reference Samples were 10%
       above 300  ppb and 20Z below  that level.  .These measurements were made in
       duplicate,  biweekly. The definition of precision specified in the contract was
       the  same as for  the  purgeables (i.e., the difference divided by the average).
       This definition  is suitable  for the biweekly duplicate measurements made, but
       precision  was reported as the coefficient of variation on a monthly basis.  The
       coefficient of variation is  also used in Table 6 to express the precision of
       all  TOC measurements made over the course of this study.  This table also shows
       the  range  of  values  found and the accuracy of the mean value.  TOC Reference
       Sample analyses  demonstrated precision and accuracy (error) well below that
       required.

            No Reference Samples were provided for residual chlorine measurements.

            Reference Samples were  also analyzed using the confirmatory
       chromatographic  columns  and  GC/MS. These data are represented in the
       appropriate sections below.
                                            21
                                         -E.137-

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                                                                       Project  GWSS
                                                                       Appendix D
                                                                       Revision' No.  1
                                                                       May  1983
                                                                       Page  31  of  54
                      TABLE  6.  TOC REFERENCE SAMPLE ANALYSES



,
H±gh level0
Low level6
Expected
Cone.
(ppn)
3.05
0.610


Range
2.87-3.11
0. 580-0. 645
Concentration Found
Mean
Cone. CVa
3.00 . 2.1
0.606 2.8
(ppn)
Z
Error
-1.6
-0.66
•
aCoefficient of variation:   100  times  the standard deviation divided  by the
 mean value.
^Error express^J as 100 times Che difference between the expected  and mean
 measured concentrations,  divided by the expected concentration.

C44 analyses.


DUPLICATE ANALYSES                                                          '.

     Approximately 102 of  the purgeables analyses were performed in
duplicate.  Most of these  were selected at  random^(i.e., every  tenth  sample);
however, some of the duplicate purgeables data  reported represent  analyses that
were repeated for specific purposes.   The most  common reasons were signal
saturation for one of the  compounds and failure of the integrator  to  report an
area for an off-scale peak.  (Nonintegrated on-scale peaks were manually
integrated.)  failure of peak recognition,  an occasional problem with the
HP3380A integrators used for the E1CD  chromatograms, presented  difficulties
mainly with chloroform because only the first eluting peak was  affected and the
other peaks were seldom off-scale.  In such cases duplicate data were reported
for the other compounds, and the concentration  of the compound  in  question was
reported as "greater than" some  value.  Occasionally a second bottle  of sample
was used for the duplicate analysis.   This  was  usually done when the  results of
a confirmatory analysis, using a different  bottle of sample, gave  results  very
different from those obtained in the first  analysis.  Duplicate analyses were
also performed when laboratory contamination was suspected.  However, such data
were reported only if the  suspicion proved  false.  (Data from proven  cases of
laboratory contamination were detected from the file.)

     Because of the nature of the analysis, all TOC concentrations were
determined in duplicate. For these measurements, duplicate data were  reported
for every tenth sample analyzed.

     Duplicate measurements of free and residual chlorine were  performed and
reported for every tenth sample.

     The contract provides that  precision between duplicate values for the
purgeables analyses by 201 for concentrations above 5 ppb and 40Z  below that
concentration level.  Precision  requirements  for TOC measurements  are 10Z  above
300 ppb and 20Z below that level.   (Precision is defined as the difference
divided by the average, expressed as a percent.)  A summary of  the precision
data obtained is shown in  Table  7.  The trihalomethanes have been  excluded from
                                      22
                                     -E.138-

-------
I
PI
Ul

VD

I
                                                                        TABLE 7.  PRECISION OF DUPLICATE ANALYSES


Concentration
15 ppb

Nunfcer
Muaber Meeting Range of
Duplicate Precision Precision Mean
Coapound Pairs" Criteria1" Values0 Precision0
Vinyl chloride
1 , 1-Dlchloroe thy lena
1,1-Dlchloroathana
1,2-Dlchloroethylena
1 , 2-Dlchloro* thane
1.1,1-Trlchloroe thane
Carbon tatrachlorlda
1 , 2-DlchloropropaiM
Trlchloro« thy lane
Tetrachloroethylena
Chlorobenc-na
•roanbaniaoa
Toluana .
•-Xylan*
o-.p-Iylaoaa
o-Dlchlorobaniand
Total organic carbon
1
6
11
14
1
12
8
2
a
a
2
i
2
)
3
2

11
1 (1001)
5 (83X) A
10 (9 IX)
13 (92X)
1 (100X)
11 (92X)
B (100X) 2
2 (100X)
8 (100X)
8 (100X)
2 (1001)
0 (OX)
2 (100X)
3 (100X) 3
3 (100X)
2 (1001) 3
Concentration
10 (81X)
36
.6-51
0-53
0-43
0
0-41
.0-38
0-1.2
0-37
0-27
11-23
67
8-20
.3-35
13-20
.8-20
1300 ppb
0-13
-
29
17
13
—
14
17
0.6
22
13
17
—
14
17
17
12

3.6
Concentration >5 ppb '
Number
Umber Meeting Range of
Duplicate Precision Precision Mean
Pairs* Criteria0 Valu«ac Pracialon'
I 0 34 —
0 _____
n „,_, __ — „
6 4 (67X) 0-22 11
0 — — —
2 2 (100X) 5.4-5.7 5.5
0 _ —
0 — — —
8 7 (B8X) 2.5-24 13
1 1 (100X) 17
0 — — —
0 — — —
0 « — •. ii -
0 ______
0 —— 	 _
Concentration > 300 ppb
74 69 (93X) 0-6.7 2.0
      70 > TO
      fD XJ  -»
	    •*£ *JU  (^
 0>    -•• 0) 0.
   i-i in 3  tt>
• CO U3 -«• Q. O
 ro oo o -••<-»•
   CO 3 "X
 O          G)
 -h   ZO E
      o    co
 tn   •     co
                               er of tl_*a co-pound found at or shove the quantification Unit In both •nalyaea. aeparated  Into high and
                           low rangea.

                           Hinder of tlaea prcclalon between duplicate valuea net contractual precision  criteria:' purgaablea - 40X for
                           concentration <5 ppb and 20X above that level.  TOC:  10X <300 ppb and 51 above that  level.

                           For each pair, precision calculated aa 100 tleee the abaolute value of their  difference,  divided by their
                           average.  The range of the precision valuea and mean precision value are shown for  each parameter.

-------
                                                                        Appendix D
                                                                        Revision No. 1
                                                                        May 1983
                                                                        Page 33 of 54
this summary because duplicate analyses were  not  alwrvs  performed on the same
day and THM formation did continue  in some  of these  Suspies.   For purgeables,
the range, success at meeting precision requirements,  and  mean precision values
are given for each compound for which duplicate data were  obtained,  divided
into concentrations above and below 5 ppb.  These data demonstrate that the
precision goals were, in general, met for duplicate  analyses:   the mean
precision values for all compounds  averaged 16Z for  concentrations less than 5
ppV and 10Z for higher concentrations.

SPLIT .SAMPLE ANALYSES

     Split samples were real water  samples  that were analyzed  by  both TSD and
SRI.  In most cases samples were selected for split  analysis at TSD  on the
basis of data reported by SKI. The results of these analyses  are given in
Table 8.  Note that detection limits are different for some compounds and that
only qualitative data were available at TSD for certain  compounds at the
beginning of the study.  TSD data for purgeables  were  obtained by separate
GC/E1CD and GC/PID analyses.  While no formal precii'on  requirements were set
for split analyses, these comparative data  helped demonstrate  the equivalence
of data obtained by the two methods.

BLIND SAMPLE ANALYSES

     Blind samples were blank water dosed at  TSD  with  known concentrations of
analytes and senr to SRI as samples.  Only,  five such samples were analyzed, all
early in the contract period.  The  results  of these  analyses are  shown in Table 9.
Since the results of these analyses were satisfactory, shipment of blind
samples was discontinued.

CONFIRMATORY ANALYSES

Second Column Confirmatory Analyses

     All samples found or suspected to contain pugeable  aromatic  and halocarbon
compounds other than the THMs were  reanalyzed using  different  chromatographic
columns that elute the compounds  in different orders'.  In  addition,  all samples
containing chloroform at concentrations greater than 40  ppb were  reanalyzed
using the confirmatory column because chloroform  at  this concentration level
could mask small quantities of 1,2-dichloroethane.   Confirmatory  analyses were
also performed, for samples containing unknown peaks  and  DCIM.   Approximately
one-third of the samples were reanalyzed for  halocarbons,  and  6J  for aromatics.

     Halocarbons Confirmatory Analyses—A chromatographic  column  of  n-octane on
Porasil C was specified for second  column halocarbon analyses. The  analytical
and calibration procedures described for primary  analyses  were used  for second
column confirmations.  Only electrolytic conductivity  detection was  specified
for these analyses; however, once the PID was installed  in the system it became
apparent that use of the two detectors allowed confirmation of a  greater number
of compounds than was possible by E1CD alone.
                                      24
                                     -E.140-

-------
                                                                                                 Of MIA OITAII4W tM irUt UUftl AlULtlU |c«*e«lt«tl»«.
                                                                                                                                                                                                                               o>
                                                                                                                                                                                                                              ia
                                                                                                                                                                                                                               n>
                                                                                                                                                                                                                               t*J UJ —•• D. O
                                                                                                                                                                                                                               4^ CD O  -«• r+
                                                                                                                                                                                                                                   l*J 3  X
                                                                                                                                                                                                                               O              CD
                                                                                                                                                                                                                               -*>     =Z O 3-:
                                                                                                                                                                                                                                       O      (/>
                                                                                                                                                                                                                               O1     •       t/1
 I
M
             U>
^ |i 1 !l !i
1.1/1
1.4/1
l.ll/t.4l I.M/t



i i
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i
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i.n/i.il


Si
|3
1.41/0. 41
1. 1/4.1
1. 41/1.1



|i i
It 5'
S • A^M
t.44/1.41
1.4/1.1



t. 11/0.44
i j | i Si
1 Z i l .-




I.1IM.1I

i.i/i.t it/n 1.1/1.1 »w«t
l.Vt.H l.ll/l.l 1.4/4.41
I.H/t.ll I.U/I.I4 I.V1
W I.U/t.ll I.WI.II l.ll/o
11 4.1/4.1
II I.M/I.M 1.14/t.ll l.t/l
II I.M/a.tl
14 1.4/1.1 l.ll/t
U
1* I.I/I.I I.I/I
II I.M/I.M Ill/in 1.441/1
U
It l.ll/l.ll
M
t
14 l.ll/l.ll

1

11
I.M/I.4I
1
11
II/U

I.1I/I.4I

IVII

I.I/I. 1
l.t/l. 1
t. 4/1.1

I.I/I.I
ll/ll

• 1.4/1. 1
1.40/1.11





1.1/1. I

<«. !)>/•. M
It/4*








l.l/l.l



1.14/I.M
0.40/t.M
II

II


14

II

M

II
                                                                             t.14/0.14

                                                                             1.44/1.14
                                                      I.I/I.I
                                                                  I.I/I.I

                                                                  I.I/I.I
t.11/0.44

  1.4/1.4
                                    I.N/l.n

                                      ll/ll
                                                                                                                                11/41
I.I/I.I

4.W4.I
                                                                                                                                            t. it/i. ii
                                                                                                                                                                   l.t/l.t   t.M/(«».l)*
                                                                                                                                                        I.M/(.l.t)>



                                                                                                                                                         4.1/1.1
                                                                     luIlM 11.11.
                                                                                                                                            CC/tlt/IICB «.l

-------
                          TABLE  9.   COMPARISON OF  CONCENTRATIONS  (ppb)  DETERMINED FROM BLIND SAMPLE ANALYSES*
i
M
N5

I
        K)
        a\


els-, trana-
Dlchlor oe thy lene
Chloroform
1,1, 1-Trlchloroe thane
Carbon tetrachlorlde
Bromodlchloromethane
Tr Ichloroe thy lene
Dlbromochloromethane
Dichlorolodome thane
Bromoform
1,1,1, 2-Tet rachloroethane
Tetrachloroe thy lene
Chlorobenzene
Benzene
Toluene
Ethylbenzene
m-Xylene
p-Dl chlorobenzene
Total organic carbon
Cone, (ppro)
Sample 1
(<0.5)b/0.27





1.6/1.6


(<0.5) /0.50

1.4/1.3
13/13
1.6/1.2
11/11

5.0/4.0
Sample 2 Sample 3 Sample. 4
61/49 7.5/9.0
7.7/10 1.7/1.6
1.7/1.2
3.5/2.2
1.7/1.7
1.8/1.6
••
2.1/1.5
2.2/2.3
3.9/3.6 1.3/1.4
5.6/5.0
0.97/1.2 1.1/1.1
6.4/5^2 5.5/5.2
1.5/1.6 0.94/1.0
5.1/4.6 17/21
4.6^/4.7
1.15/0.98 NAd/2.0 0.30/(<0.2)b
Sample 5
1.4/1.5

9.6/12
0.9/1.2

0.77/0.92

1.1/1.3








2.4/2.3

The first number given was determined from analysis at TSD and the second reported by
b
Mot reported below quantification limit.
Only dosed concentration available from TSD.
d
Not reported.
SRI.
~O 2 73 J> TO
a> cv to ~a ~i
id "< < "O O
fl> — *• rt> <—».
'*-• in 3 tt>
to vo -•• Q- n
in Oo o •-•• rt
W 3 X
0 CD
-•> Z O E
O to
in • i/i

-------
  pject GWSS
   lendix D
	 ision No.  1
May 1983
Page 36 of  54
           The analytical conditions used are summarized in Table 10.  Chromatograms
      obtained by.analysis of a 1 ppb standard mixture of halocarbon compounds and
      selected aromatics are shown in Figure 4.  The circled, numbers in the figure
      correspond  to the ID numbers in Tables 2 and  3.  Relative retention time data
      relative to TFT for this column are shown in  Column B of Table 3, although this
      internal standard (ID 27) potentially interferes with a number of the halocar-
      bon; compounds of interest and was not normally included in confirmatory
      halocarbon  analyses.
         TABLE 10.  ANALYTICAL CONDITIONS FOR CONFIRMATORY ANALYSIS OF HALOCARBONS
         Sample volume:
         Internal standards:

         Purge:
         Desorption:
         Chromatographic system

              Column:

              Carrier:

              Temperature  program:


              Analysis  time:
25 ml
50 ng 2-Bromo-l-chloropropane

Helium at 40 cm^/min for 10 min
4 minutes at 180*C
1.8-m by 2-mm I.D. glass packed with n-octane
on Porasil C        ^
Helium at 40 cm^/min (28 cur/min through the
LSC-II; 12 cm^/min directly into injector)
Initial temperature 50*C for 4 min (during
desorption), programmed at 4*C/m'in to final
temperature of 140*C
30 min
           Although  this  column  is useful for confirmatory analyses because of the
       very different elution order of the halocarbon compounds, there are an
       unfortunately  large number of coelutions in the E1CD chromatograms:

           (1)   Chloroform and cis-1,2-dichloroethylene
           (2)   1,1,1-trichloroethane and trichloroethylene
           (3)   Bromodichloromethane and tetrachloroethylene
           (4)   Bromofonn, 1,1,1,2-tetrachloroethane, the internal
                 standard  BCP, and chlorobenzene.


       In  cases  (1) through (3),  the first compound of the pair causes only E1CD
       response,  whereas the second causes a response on both detectors.  In the case
       (4), only  chlorobenzene shows significant response on the PID.  (Bromoform and
       1,1,1,2-tetrachloroethane  also coelute on the primary column, so the n-octane
       column  is  useless for resolving questions involving this pair of compounds.)
       Information gained  using both detectors has been particularly useful in
       confirming the presence of cis-1,2-dichloroethylene and tetrachloroethylene
       since most of  the chlorinated waters also contained THMs.  Trichloroethylene
       and 1,1,1-trichloroethane  were also frequently observed in the same sample.
                                            27

                                           -E. 143-

-------
                                                                 Project GWSS
                                                                 Appendix  D
                                                                 Revision  No.. 1
                                                                 May  1983
                                                                 Page  37 of 54
   o
   o
   LU
   V)

   O
   CL

   UJ
   tr
   LU
   CO

   O
   a.
   to
                    10
20
                          TIME (min)
     30

JA-32SS23-3SA
FIGURE 4  CHROMATOGRAMS OBTAINED BY PURGE/TRAP GC/PID/E1CO
         ANALYSIS OF A 1 ppb STANDARD MIXTURE OF HALOCARBON
         AND AROMATIC COMPOUNDS USING AN n-OCTANE ON PORASIL
         C COLUMN

         Circled number* refer to ID numbers in Tiblej 2 tnd 3.

                            28
                          -E.144.

-------
Project GWSS
    •ndix 0
    sion No. 1
    1983
Page 38 of 54
           The availability of  the  PID  chromatogram  for these analyses has also been
      useful  for  confirming arotnatics identifications in certain cases.  Benzene and
      trichloroethylene  (ID 18  and  17,  respectively), and  toluene and
      tetrachloroethylene  (ID 28  and 25)  are not resolved  on the Bentone column
      nonnally used  for  aromatics confirmatory  analyses, but are well resolved on  the
      n-octane column.   Use of  the  PID  chroreatogratn  allows conf irraation of the
      aromatics identifications under these conditions.

           Procedures  similar to  those  described for the primary analyses were used
      for  compound identification and quantification, except that concentrations were
      calculated  using the  response from  both detectors for applicable compounds.

           For example,  if  a peak corresponding to the trichloroethylene (A)
      'retention time was observed on the  PID chroreatogram, the concentration of this
      compound was calculated using the areas from each chroma1. ogr am and the two
      values  were compared.  If they differed by more than 40X (100 times their
      difference  divided by their average), it  was assumed that 1,1,1-trichloroethane
      (B)  was present.   The concentration of the latter compound could then be
      calculated  as  follows:

                                                            R-(EICD)
                        ConcB -  [ConcA(ElCD) - ConcA(PID)]                      (5)
       where  subscript  A refers  to  the  compound  showing both PID and E1CD response
       (trichloroethylene in  this example)  and subscript B  to the coeluting compound
       having only  E1CD response (1,1,1-trichloroethane here); concA (PID) and concA
       (E1CD) refer to  concentrations of  A  calculated  from  the PID and E1CD chroma-
       tographic  areas,  respectively; and R  and 1L. are the calibration factors for
       compounds  A  and  B calculated for the tlCD.

           If the  difference in the concentrations of the  A compound calculated using
       both detectors was less than 40Z,  only the A compound was reported (using the
       PID calculation), and  the other  compound  was shown as "not reported".

           The Reference Samples described for  the primary analyses were analyzed
       using  the  confirmatory halocarbons system.  The calculation method described
       above  was  used for quantification  of 1,1,1-trichloroethane and
       trichloroethylene and  of  bromodichlorome thane and tetrachloroethylene.  A
       summary of the results of these  analyses  is shown in Table 11.
                                             29

                                            -E.145-

-------
TABLE 11.  HALOCARBONS REFERENCE SAMPLE ANALYSES—CONFIRMATORY COLUMN




Halocarbona
Chloroform
1,2-Dichloroethane
1,1,1-Trichloroethane"
Carbon tetrachloride
Broaodlchloroue thane
Trlchloroethylene
Dlb ronoch loroMe th ane
Bronofora
Tetrachloroethylene


Expected
Cone.
(PPM
8:2
3.3
1.3
1.5
1.4
2.3
2.1
1.7
1.1

Low

Level*


Concentration Found

Range
6.9-11
2.1-3.9
0.8-1.4
1.1-1.8
1.2-2.4
1.5-2.6
1.4-2.5
1.2-2.1
0.82-1.4

Mean
8.0
2.9
1.1
1.4
1.8
2.2
1.8
1.7
1.1

CVC
13
14
14
16
21
14
16
17
14


(ppb)
I
Error
-2.5
-12
-15
-6.7
29
-4.3
-14
0
0


Expected
Cone.
(ppb)
34
14
5.6
6.2
6.0
9.1
8.5
7.0
4.4

High

Levelb


Concentration Found


Range Mean
21-36
10-16
2.5-7.3
4.9-9.4
4.5-10
7.6-11
5.8-8.9
5.8-9.4
4.0-6.1
33
13
5.1
6.2
7.2
8.6
7.7
7.4
4.9

CVC
7
11
23
18
22
11
11
10
U


(ppb)
Z



Error
-2
-7
-8
0
20
-5
-9
-5
11
.9
.1
.9


.5
.4
.7


*19 analyses.
19 analyses.






Coefficient of variation: 100 times the standard
Error expressed as 100
divided by the expected
tines the
difference






deviation divided by the
between the
expected
and mean


Man value.












found concentrations,
concentration.
Quantified using response from both PID and

































E1CD,











as described In text.


































































X> 3
Hi OJ
10 l<
CD
I— '
co ȣ>
 oo
CO
o
-t>
en
;o» -o
(D ^O 1
< ~o o
-"• n> <^.

* C^

-------
Project GWSS
Appendix D
Revision No. 1
May 1983
     40 of 54

          Aromatlcs  Confirmatory Analyses'—Second column confirmations for the
     aromatic  compounds  employed a column of  SZ SP 1200/51 Bentone 34.  Procedures
     used were similar to those described for primary analyses.  The analytical
     conditions used are shown in Table  12.   Although signals from both detectors
     were monitored  during these analyses, only the PID (signal was ordinarily
     required  for  identification and quantification of the aromatic compounds.
     Chromatograms obtained by analysis  of a  1 ppb standard of the aromatic and
     selected  halocarbon compounds are shown  in Figure 5.  Circled numbers refer to
     the ID  numbers  in Tables 2 and 3.   Retention time data relative to TFT for this
     column, are shown in column C of Table 3.

          In a few cases this column was used to confirm halocarbon identifications
     that were not resolvable using the  n-octane column.  Aa noted previously, bro-
     moform  and 1,1,1,2-tetrachloroethane (ID 23 and 24, respectively) coelute on
     both the  primary and halocarbons confirmatory systems and both showed only E1CD
     response.  They are, however, resolved on the Bentone column.

          The  procedures described for the primary analyses were used to identify
     and quantify  compounds observed in  these analyses.

          The  Reference  Samples described earlier were analyzed using the aromatics
     confirmatory  system.  A summary of  all such analyses is presented in Table 13.

          Comparison of  Primary and Second Column Confirmatory Analyses—A measure
     of the  precision between the primary and second column confirmatory analyses is
     shown  in  Table  14.   For each of the confirmed identifications, precision was
     calculated as the difference between the two values, divided by their average,
     expressed as  a  percent.  For all compounds, the mean precision between primary
     and confirmatory analyses averaged  242 for concentrations below 5 ppb and 17%
     for higher concentrations.

     Gas Chromatography/Mas3 Spectrometry Confirmatory Analyses

          Forty-six  samples were individually selected for GC/MS analysis by consul-
     tation with the Project Officer.  Identification of unknowns was emphasized.
     Other  selected  samples contained infrequently observed compounds or were con-
     taminated with  a variety of pollutants.

          A Finnigan 3200 GC/MS with a 6100 Alpha 16 Data System was used for these
     analyses.  Samples  were analyzed in three sets.  For the first set of samples,
     the system was  equipped with a semiautomated Tekaar-LSC-I purge/trap
     analyzer.  The  LSC-I contributed a  high  background level of toluene and was
     replaced  with a manual purge/trap system for the remaining two sets of analy-
     ses.   The manual system consisted of a 6-port Carle valve, a standard purge
     vessel (identical to those used for the  other GC analyses), and a U-shaped
     glass  sorbent trap  containing Tenax-GC and coconut charcoal.  The trap was
     wrapped with heating tape and heated by  use of a Varlac.  Analytical conditions
     are shown In Table  15.
                                            31
                                            -E.147-

-------
    TABLE 12.
                                                        Project  GWSS
                                                        Appendix  D
                                                        Revision  No.  1
                                                        May  1983
                                                       • Page 41  of  54
ANALTTICAL CONDITIONS FOR CONFIRMATORY ANALYSIS OF AROMATICS
Sample volume:
Internal standards:
Purge:
Desorptlon:
Chromatographic system
     Column:

     Carrier:

     Temperature program:

     Analysis time:
              25 ml
              50 ng  a ,cz ,a-Trif luorotoluene
              Helium at 40 co^/min for 10 min
              4 minutes at 180°C
              1.8-m by 2-tnra I.T).  glass packed with
              5Z SP-1200/5Z Bentone 34 on Supelcoport (100/120)
              Helium at 40 cuP/min (28 cm^/min through the
              LSC-II; 12 cm3/rain  directly into injector
              Initial temperature 60°C for 4 min (during
              desorption), programmed at 3*C/min to final
              temperature of 110°C
              32 min
      TABLE 13.  AROMATICS REFERENCE SAMPLE ANALYSES—CONFIRMATORY COLUMN



Compound
Benzene
Toluene
Ethylbenzene
Total xylenes
Expected
Cone.
(ppm)
8.7
5.3
5.9
7.5
Concentration Found (ppb)a

Range
8.0-11
4.3-6.5
5.4-7.0
7.0-8.8
Mean
Cone.
9.8
5.6
6.5
8.0

cvb
10
12
8
9
Z
Errorc
13
5.7
10
6.7

all analyses.
 Coefficient of variation:  100 times the standard deviation divided by the
 mean value.
cError expressed as 100 times the difference betveen the expected and mean
 found concentrations, divided by the expected concentration.
                                      32
                                     -E.148-

-------
Project GWSS
Appendix D
Revision No.  1
     1983
      42 of  54
                           o
                           o
                           o
                           Q.
                           1/5
                           LU
                                                           20

                                                  TIME (min)
 30

JA-22SO-1
                   FIGURE 5  CHROMATOGRAMS OBTAINED BY PURGE/TRAP GC/PIO/EICO ANALYSIS

                            OF A 1 ppb STANDARD MIXTURE OF AROMATIC AND HALOCARBON

                            COMPOUNDS USING A 5% SP1200/5* BENTONE 34 ON SUPELCOPORT COLUMN

                            Circled numbers refer to ID numberi in T»bles 2 *nd 3.

                                                   33
                                                -E.149-

-------
TABLE 14.  PRECISION BETWEEN PRIMARY AND SECOND COLUMN COHF1RHATORY ANALYSES
Concentration 15 ppb
Total Nunber Nunber
Concentration >S ppb
Nunfcer


of Confirmed Conflrned Range of Mean Confirmed - Range of Mean
Identifications* Identifications8 Precision Values'" Precision'* Identlf Icatlons^Preclslon Value*" precision'1
Trlchloroethylene
Tetrachloroethylene
1,1,1-Trlchloroethane
1,2-Dtchloroethylene
(cia and trana)
1,1-Dlchloroe thane
Carbon tetrachlorlde
1,1-Dlchloroe thy lene
o-, p-Xylenes
at- Xy lene
1 , 2-Dlchloroe thane
Benzene
Toluene
1,2-Dlchloropropane
p-Dlchlorobentene
Vinyl chloride
Ethylbenzene
Bronobenzene
Chlorobenzene
o-Dlchlorobenzeoe
1 , 2-DlbroBO- 3-chloro-
propane
n-Propylbenzeoe
o-Chloro toluene
Nunber of times the
99
78
70
59

33
30
23
19
17
16
14
14
13
10
8
7
6
2
2

1
1
1
compound was observed at
74
65
63
47

33
27
22
19
16
15
11
12
12
10
7
7
5
2
2

Oc
1
1
0-74
0-70
0-98
0-110

0-135
4.9-53
0-141
0-35
0-57
3.0-48
0-63
1.8-45
5.7-71
1.3-80
8.7-45
0-76 „.
0-42
0-25
38-40

~
~
—
or above the quantification
16
15
21
23

24
23
34
11
18
22
20
21
24
22
23
31
21
13
39

~
70
8
25
13
7
12

0
3
1
0
1
1
3
2
1
0
1
0
1
0
0

1
0
.0 0
0-44 14
9.1-37 19
4.7-66 25
0-38 14

—
0-22 12
12
—
20
— 20
8.7-33 24
0
28
_-
«.o
—
30
—
_

9.5
—
—



- -




















limit in both analyaea.
b
X Precision calculated for each pair of analyses as 100 times the absolute value
value. The range of
Quantification Halt







precision value* and the
for thla compound was 5







mean
ppb.







precision value are shown for
















of their difference,
each compound.








divided by their average
TD 3; TO
<£ *< <.
| 	 , (/J
.p>. ID -'•
CO 00 O
CO 3
o
0
en •

~i> ~T3
*^J ™J
*o o
ft) <-_*.
a a>
o O
-•• rt
X
cn
CO
. CO

-------
Project GWSS
Appendix D
  yision No. 1
    1983
   re '44 of 54
nypt
   «i

   •=
                         TABLE 15.  ANALYTICAL CONDITIONS FOR CC/MS
       Sample  volume:
       Internal  standards:

       Purge:
       Desorption:
       Chromatographic  system
            Column:

            Carrier:
            Temperature program:


            Analysis  time:
       Mass  spectrometer
            Mode:
            Electron  energy:
            Seconds/scan:'
            Mass range:
                                    25 ml
                                    250  ng 2-Bromo-l-chloropropane;
                                    87 ng   a ,
-------
                                                                        Kroject
                                                                        Appendix D
                                                                        Revision No.  1
                                                                        May 1983
                                                                        Page 45 of  54
where RF is the external standard typt  response factor,  RRF is the response
factor, relative to TFT, Area(cpd) and  conc(cpd)  are  the area of the primary
characteristic ion (from the reconstructed ion current chromatogram) and the
concentration of the compound of interest, and Area(TFT) and conc(TFT) are the
corresponding parameters for the internal standard a ,
-------
Project GWSS
   endix D
   3 si on No.
    1983
  "ge 46 of 54
1
            TABLE  16.   CALIBRATION  DATA AND QUANTIFICATION LIMITS FOR GC/MS SYSTEM

Compound
Vinyl chloride
Dichlorome thane
1,1-Dichloroethylene
1,1-Dichloroethane
1 ,2-Dichloroethylene
Chloroform
1 ,2-Dichloroe thane
1,1, 1-Tr ichloroethane
Carbon tetrachloride
Bromodichlorome thane
1 ,2-Dichloropropane
Trichloroethylene
Dibromochloromethane
Dichloroiodiomethane .
Broroof orm
1,1,1,2-Tetrachloroethane
Tetrachloroethylene
Chlorobenzene
1 ,2-Dibromo-3-chloropropane
Benzene
Toluene
Ethylbenzene
Bromobenzene
Isopropylbenzene
m-Xylene
Styrene
°~> p~Xylenes
n-Propylbenzene
o-Chlorotoluene
p-Chlorotoluene
m-Dichlorobenzene
• o-Di chlorobenzene
p-Dlchlorobenzene
m/e
62
84
96
63
96
83
62
97
117
83
63
130
. 129
83
173
131
166
112
157
78
91
91
158
105
91
104
91
120
126
126
147
146
146
Quantification
RF Limit (ppb)
2400
4010
1018
2790
1480
4290
1460
2370
3650
1860
1310
2920
940
4
384
ND*
3190
; 4340
75
5970
7500
7600
ND
ND
5820
2710
5960
ND
6400
6800
ND
ND
3830
0.4
1
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4
•0.5
0.4
1.0
5
1.0
1
0.4
0.4
4
0.3
0.3
0.3
0.5
0.5
0.3
0.5
0.3
0.5
0.5
0.5
0.5
0.5
0.5

                 determined for this set of analyses because compound was  not
             observed in primary GC/PID/E1CD analyses of these  samples.
                                             37
                                          -E.153-

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                                               TABLE 17.  REFERENCE SAMPLES ANALYSES—GC/MS
   00
Ln
.O
1




Halocarbona
Chloroform
1,2-Dichloroe thane
1,1,1-Trichloroe thane
Carbon tetrachlorlde
Bromodichlorome thane
Trlchloroethylene
Dlbromochloromethane
Bromofona
Tetrachloroethylene
A
Aromatlce
Benzene
Toluene
Ethylbenzene
Total Xylenes

Low Level8
Expected Concentration Found
Cone.
(ppb) Range Mean CVC
8.2 6.6-8.1 7.5 10
3.3 2.9-3.4 3.1 9
1.3 1.1-1.2 1.1 5
1.5 1.3-1.7 1.5 13
1.4 1.4-1.5 1.4 4
2.3 1.6-2.2 1.9 16
2.1 1.1-1.5 1.3 16
1.7 1.5-1.9 1.7 10
11 1111 10 *k
• 1 1 * Z~ A • J 1 • * 3
8.7 7.0-9.0 7.9 10
5.3 4.1-4.7 4.4 6
5.9 5.5-6.5 5.9 6
7.5 5.9-7.8 6.9 9
.
High Lavelb
(ppb) Expected Concentration Found (ppb)
Z Cone. ,
Error (ppb) Range Mean CVC Error
-8.5 34 29-31 30 4 -12
-6.1 14 12-14 13 9 -7.1
-15 5.6 4.1-5.3 4.8 13 -14
0 6.2 5.5-7 6.1 13 -1.6
0 6.0 6.7-7.3 6.9 5 15
-17 9.1 8.1-9.6 9.1 10 0
-38 8.5 6.8-7.7 7.2 6 -15
0 7.0 6.8-9.5 8.0 17 14

"
-



3 analyses.
3 analyses.




Coefficient of variation: 100 times the standard deviation divided by the mean value.
Z Error calculated as 100 times the difference between
divided by the expected
e,
6 analyses, except for






concentration.
toluene (4) .






the expected and found concentrations,
Ol Ql 0) T) -)
IO << < T3 O
fl> —•• <~>.
•— • 1/1 3 fP
•£* VO — '• d. O
~-J 00 O -'• rfr
U> 3 X
o . en
-«. 2: o s:
o oo

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    ject  GWSS
    endix 0
  vision No. 1
May 1983
Page 48  of  54
                     TABU 18.  PRECISION BrtVEEH FRBUXT ATO CC/KS CONniMXTOKT AHULTSES

Concentration < 5
Compound
Vinyl ehloridt
1 ,l-Diehloroethylene
1,1-Dlchloroethane
cir- or trans-Dichloro-
ethyl ene
1.2 -01 chroroe thane
1 ,1 ,1-Trichloroetha.ae
Carbon tetrachlorlde
1 ,2-Dichloropropane
Trichloroethylene
Tetrachloroethylene
1 , 2-Br oao-3-«hloro-
propane
Benzene
Toluene
Sthylbenxene
Broao benzene
«-Xyl«n«
o-, p-Xyl«n««
p-Di chlor ebencene
MuBlwr
of pair*4
4
3
10

4
11
2
0
9
6
0
3
2
2
4
2
4
2
ppb
Z Tkrecl«lon
tonge
6.9-29
8.0-100
C-66

15^32
2.0-70
29-92
-
C-«S
16-110
—
19-40
11-51
31-54
27-100
6.8-13
2.2-60
18-27
Mean
17
43
19

23
22
60
'. -
29
55
—
30
31
42
49
9.9
24
22
Concentration > 5 ppb
Berber
of ?min*
1
1
1
5
0
3
0
1
s. 7
3
1
2
0
0
0
0
0
0
2 Preciilon
Range Mean
82
' - 8.3
7.7
9.2-52 21
-
15-32 26
-
49

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                                                                            Project  GWSS
                                                                            Appendix D
                                                                            Revision No.  1
                                                                            May  1983 .
                                                                            Page  49  of  54'
      TABLE 19.  UNKNOWN COMPOUNDS IN SAMPLES IDENTIFIED  BT GC/MS ANALTSIS
KIT*, Primary CC/PID/E1CD
Relative to Internal Standard
Pound in
Identification Saaple No.
DlfluoroMttiane



Chloromcthone . '

Chlorodi f luorove thane

Chloroflaoroaethane


Chloro« thane

Dichlor of luoroae thane




Trichlorofluorone thane


l,2-Dlchloro-l,l,2-trlfluoroethane
l,l,2-trichloro-l,2,2-trifluoro*thane
Dichloroacetonltrlle
Dichloropropene (any of 3 iaoaer*)
Tetrahydrofuran'
Diethyl ether*

Cyclohixaned
Methylcyclobexaned
4-11ethy 1-2-pentaoone
314
6«T - •-_,. •
700 "
894
267
676
390
888
700
888 '
894
770
888
22
118
575
727
888
575
676 i
727
888
377
919
40
899
888
894
771
771
673
BCPb
0.35
. 0.35
0.35
0.35
0.35
0.35
0.35
0.35
0.35
0.35
0.35
0.40
0.40
0.44
0.44
0.44
0.44
0.44
0.55
0.55
0.55
0.65
0.76
0.92
1.08
'
-
-
•
-
~
TTTC
-
-
-
-
-
-
-
-
-
-
-
-
-
-
•-
-
-
-
-
-
'

-
-
-
0.60
0.65
0.65
•0.71
0.93
0.97
*Relativ« retention timet calculated include the 10-aln purge tia

fegkT 'reported relative, to BCF ufing E1CD chromatograa.

e*RT-reported relative i to TTT  uilng PID ehromatogroa.

dldenxification confined by analyiia of authentic ttandard.
                                    4Q
                               -E.156-

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        TABLE 20.  RELATIVE  RETENTION TIMES FOR QUANTIFIED COMPOUNDS USING GC/PID/E1CD SYSTEM*

ID
Number
Compound
RRTb
Electrolytic conductivity detector
3
6
7
8
9,10
11
12
13
14
15
16
17
19
20
21
22
23
24
25
26
29
—
Vinyl chloride
Dlchlorome thane
1 , 1-Dlchloroethylene
1, 1-Dlchloroethane
els-, trans-Dichloroethylene
Chloroform
1,2-Dichloroethane
1,1,1-Trlchloroe thane
Carbon tetrachlorlde
Bromodlchlorome thane
1 ,2-Dlchloropropane
Trlchloroethylene
Dlbromochloromethane
1,1,2-Trlchloroe thane
2-Bromo-l-chloropropane (ISTD)
Dlchlorolodpme thane
Bromofona • ., , •,•
1,1,1 2-Tetrachl6roethane
Tetrachlbroethylene
1,1, 2, 2-Tetrachloroethane
Chlorobenzene .
l,2-Dlbjomo-3-chlloropropane
0.376
0.457
0.589
0.670
0.717
0.745
0.779
0.827
0.843
0,871
0.91R
0.947
0.967
0.967
1.000
1.010
1.042
1.042
1.099
1.099
1.177
1.259
ID
Number
Compound
RRT0
Photolonlzatlon detector
18
27
28
30
31
32
33
35,36
37
38
39
40
41
42



*"




Benzene
a ,a ,a-Tr If luorotoluene (ISTD)
Toluene
Ethylbenzene
Bromobenzene
Is opropyl benzene
m-Xylene
o-, p-Xylene
o-Chlorotoluene
n-Proy pi benzene
p-Chloro toluene
m-Dl chlorobenzene
o-Dt chlorobenzene
p-Di chlorobenzene






.

0.862
1.000
1.023
1.132
1.172
1^231
1.308
1.367
1.436
1.436
1.553
1.553
1.591
1.616








'., ^ • ,
*ID number* correspond -tofnumbered peaks In Figure 3.
.               ? .   ; •  f ' '
 Relative retention  tlinpe; for  halocarbon compounds relative to Internal standard  2-bromo-l-chloro-
 propane using E1CD.  Times calculated Include 10-mln purge time.

cRelatlve retention  times for  aromatic compounds relative to Internal standard o ft /x-trlfluorotoluene
 using PID.  Times calculated  Include  the 10-tnln purge time.
                                                                                                               __
                                                                                                               fU (0 T3 I
                                                                                                              «< < X3 O
                                                                                                             n>   -<•
                                                                                                               (-> 10 3 (D
                                                                                                             tr> 10 -*• tx o
                                                                                                             O CD O -»• r+
                                                                                                               OJ 3 X
                                                                                                             o       cr>
                                                                                                             01
                                                                                                                     oo
                                                                                                                     to

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                                                                       Project GWSS
                                                                       Appendix D
                                                                       Revision No.  1
                                                                       May 1983
                                                                       Page 51 of 54
DATA REPORTING ERRORS
     The reported data were monitored  for  transcription or reportiftg errors  by
tracing data for every tenth sample  from the original notebook entries  through
the computer-data file*  Ninety-seven  identification numbers  (172  separate
analyses) were checked.  No significant errors were found.
                                      42
                                     i S8-

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Pro


  .
Project GWSS
   endix D
   ision No.
 'ay 1983
Page 52 of 54
1
                                           SECTION 5

                                       REPORTING OP DATA
            All sample data,  Including the results of purgeables primary,  duplicate,
        second column confirmatory,  and GC/MS analyses, and TOC and residual.chlprine
        primary and duplicate  analyses, were entered directly from SRI into fhg;. prpJect
        data file maintained at the  EPA computer facility-in Research Triangle  Park,
        North  Carolina.  The data entry format was established by TSD. :.to accommodate a
        Texas  Instruments Silent 700 terminal.  This system proved to be a  very effi-
        cient  method of data transmittal.

            Although all samples were analyzed within 30 days of collection, data were
        entered only after they had  been carefully checked and entered into the project
        notebooks.  Delays were as long as four weeks.  However,  when unusually contam-
        inated samples were encountered, TSD was alerted within 48 hours by
        telephone.  The criteria for phone alert were established after consultation
        with the Project Officer and were based on EPA guidelines that considered both
        acute  and chronic toxicity factors and potential carcinogenic risks (10).  The
        phone  alert criteria used were as follows:
                 1,2-Dibrono-3-chloropropane
                 Vinyl chloride
                 1,1-Dichlproethylene
                 1,1-Di chloroethane
                 1,2-Dlchloropropane
                 Xylenes (total isomers)
                 Carbon tetrachloride
                 Tetrachloroethylene
                 Trichloroethylene
                 1,2-01chloroethylene
                 Chlorobenzene
                 1,1,1-Trichloroethane

                 Other target compounds (separately)
                 Combinations of target compounds
                   (total cone)"1"
                                                          Observed Cone,  (ppb)

                                                                     5*
                                                                    10
                                                                    10
                                                                    10
                                                                    10
                                                                    10
                                                                    20
                                                                    20
                                                                    50
                                                                    50
                                                                    50
                                                                   100

                                                                    20
                                                                    50
             After the data were received by the Project Officer,  all identifications
        (other than THMs) were verified during the biweekly phone  conversations.   This
        review allowed correction of data transmission errors that occasionally occur-
        red.  Data were regarded final only after completion of second column confirma-
        tory analyses.
         Detection limit in these analyses.
        "^Excluding THMs.
                                              43
                                          -E.159

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                                                                              .  u
                                                                      Revision  No.  1
                                                                      'May 1983
                                                                      Page 53 of  54
                                  REFERENCES


1.   Brass, H. J.,  E. M.  Click,  D.  J.  Munch,  J. W. Munch,  and M.  . .  Feige.  The
     Decomposition of Low Molecular-Weight  Aromatic  Compounds in Stored Water
     Samples," presented  at the  Third  Conference on  Water  Chlorination:   Envir-
     onmental Impact and  Health  Effects,  October 28-November 2,  1979,  Colorado
     Springs, Colorado.

2.   Bellar, T. A.  and J. J. Lichtenberg.   "Determining Volatile Organics at
     the Microgram-per-Liter Level  in  Water by Gas Chromatography,"  J. Am.
     Water Works Assoc.  66:739 (197*)

3.   "The Determination of Halogenated Chemical Indicators of Industrial Con-
     tamination in Water  by Purge and  Trap, Method 502.1," U.S.  EPA  Environmen-
     tal Monitoring and Support  Laboratory, Cincinnati, Ohio (1980).

4.   "The Determination of Aromatic Chemical  Indicators of Industrial Con-
     tamination in Water by Purge and  Trap, Method 502.2," U.S.  EPA  Environ-
     mental Monitoring and Support  Laboratory, Cincinnati, Ohio  '1979).

5.   Kingsley, B. A., C.  Gin, D. Coulson, and R..Thomas.  "Gas Chromatographic
     Analysis of Purgeable Halocarhon  and Aromatic Compounds in  Drinking Water
     Using Two Detectors  in Series," presented at the  Fourth Conference on
     Water Chlorination:   Environmental Impact and Health  Effects,  October 18-
     23, 1981, Pacific Grove, California.

6.   Boland, P. A., B. A. Kingsley, D. F. Stiverfe, and I.  A. Pomerantz.   "Pro-
     tocol for1 the Analysis of a Broad Range  of Specific Organic Compounds in
     Drinking Water," in  Advances in the Identification and Analysis of Organic
     Pollutants in Water, Vol. 2, L. J. Keith, ed.  (Ann Arbor, Michigan:  Ann
     Arbor Science Publishers, Inc. 1981),  Chap. 44.

7.   Kingsley, B. A., C.  Gin, W. R. Peifer, D. F. Stivers, S. H. Allen,  H. J.
     Brass, E. M. Click,  and M.  J.  Weisner.   "A Cooperative Quality  Assurance
     Program for Monitoring Contract Laboratory Performance," in Advances in
     the Identification and Analysis of Organic Pollutants in Water, Vol. 2,  L.
     J. Keith, ed. (Ann Arbor, Michigan:  Ann Arbor  Science Publishers,  Inc.  ,
     1981), Chap. 45.

8.   "Total Organic Carbon, Low Level, Method," U.S. EPA Envitonmental Monitor-
     ing and Support Laboratory, Cincinnati,  Ohio (1978).

9.   "Dohnnann DC-54 Ultra Low Level Total  Organic Carbon  Analyzer System
     Equipment Manual," 2nd ed.  (1978), pp. 2-14, 2-15.

10.  "Guidance on Response to Contamination Detected in the Ground Water Supply
     Survey," U.S. EPA (internal EPA memo), Draft, April 29, 1981.
                                      44
                                  -E.160-

-------