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.
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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:
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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
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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.
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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
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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,
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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
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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-
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* 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-
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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-
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(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)
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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-
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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.
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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) .
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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
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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.
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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
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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-
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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.
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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
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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
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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
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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
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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.
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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.
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"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.
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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
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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-
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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.
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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.
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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-
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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
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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-
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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
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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
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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
$«••!•
•' <••»!••
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-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-
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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-
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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-
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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-
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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-
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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-
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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-
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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-
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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-
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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
-------
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-
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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-
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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-
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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-
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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-
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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-
-------
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-
-------
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-
-------
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
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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-
-------
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-
-------
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-
-------
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-
-------
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-
-------
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-
-------
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-
-------
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-
-------
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-
-------
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
-------
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-
-------
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-
-------
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.
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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.
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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."
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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.
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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."
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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.
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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).
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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.
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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.
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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).
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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.
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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.
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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.
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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
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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
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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).]
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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.
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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.
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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.
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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.
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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
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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)
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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.
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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
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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
-------
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
-------
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).
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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.
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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. ' *•
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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.
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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.
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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.
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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.
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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.
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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.
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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.
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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
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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-
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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
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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
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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-
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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
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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
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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
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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
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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
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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.
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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
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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
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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
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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
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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.
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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-
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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
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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
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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-
-------
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
S !J
•
i
M U/ll
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-
-------
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
-------
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
-------
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-
-------
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
-------
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-
-------
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
-------
. 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-
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