. if- t"
vvEPA
United States
Environmental Protection
Agency
Office of Research and
Development
Washington, DC 20460
EPA/600/8-91/066
February 1991
Preparation Aids for the
Development of
Category IV Quality
Assurance Project Plans
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EPA/600/8-91/006
February 1991
PREPARATION AIDS
FOR THE DEVELOPMENT OF
CATEGORY IV
QUALITY ASSURANCE PROJECT PLANS
by
Guy F. Simes
Risk Reduction Engineering Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, OH 45268
Printed on Recycled Paper
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This material has been funded by the United States Environmental
Protection Agency. Although it has been subject to the Agency's review,
and has been approved for publication as an EPA document, it does not
necessarily reflect EPA policy.
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Foreword
Today's rapidly developing and changing technologies and industrial
products and practices frequently carry with them the increased generation
of materials that, if improperly dealt with, can threaten both public health
and the environment. The U.S. Environmental Protection Agency is
charged by Congress with protecting the Nation's land, air, and water
systems. Under a mandate of national environmental laws, the Agency
strives to formulate and implement actions leading to a compatible balance
between human activities and the ability of natural systems to support and
nurture life. These laws direct the EPA to perform research to define our
environmental problems, measure the impacts, and search for solutions.
The Risk Reduction Engineering Laboratory is responsible for planning,
implementing, and managing the research, development, and
demonstration programs to provide an authoritative, defensible
engineering basis in support of the policies, programs, and regulations of
the EPA with respect to drinking water, wastewater, pesticides, toxic
substances, solid and hazardous wastes, and Superfund-related activities.
This publication is one of the products of a quality assurance outreach
program that provides a vital communication link between the researcher
and the user community.
Perhaps the greatest benefit to the users of this document comes from its
emphasis on up-front planning — do the right thing, right, the first time.
While this sounds straightforward, managers know that determining the
right course in a complex and uncertain situation is anything but simple.
Determining customer requirements up-front, and then having the
processes and procedures in place to accomplish them, averts costly
mistakes. Resources are conserved in two ways: by avoiding rework to
correct efforts that do not initially meet management or customer
specifications; and by performing to the specifications required and not
beyond them. In these ways, this "Preparation Aids" document can help
management achieve its mission with more effective utilization of
diminishing resources.
E. Timothy Oppelt, Director
Risk Reduction Engineering Laboratory
Ml
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Abstract
Data collection activities performed for the Risk Reduction Engineering
Laboratory (RREL) of the U.S. Environmental Protection Agency are
divided into four categories, depending on the intended use of the data.
Quality Assurance (QA) Project Plans are written to ensure that project
needs will be met and that quality control procedures are sufficient for
obtaining data of known quality. The level of QA required, however,
depends on the project category selected for a given project. Projects that
produce results for the purpose of assessing suppositions are identified as
Category IV projects. "Pure" research and development projects
frequently fit into mis category.
To assist professional scientists and engineers in preparing QA Project
Plans, separate guidance manuals in an easy-to-read format have been
developed for each category. The Category IV manual contains detailed
descriptions of each of the five required elements of a Category IV QA
Project Plan. Also included are definitions and explanations of frequently
used terms, examples of QA forms and charts, sample equations, and
numerous types of tables suggested for summarizing information.
IV
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Contents
Foreword ,
Abstract
Figures
Tables
Acknowledgments
0.0 Introduction
1.0 Project Description
2.0 Quality Assurance Objectives
3.0 Sampling and Analytical Procedures
4.0 Approach to QA/QC
5.0 References
Page
iii
iv
vi
vii
viii
1
7
11
19
29
35
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Figures
Number
0-1 QA Project Plan Approval Form
Page
5
VI
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Tables
Number
2-1
2-2
2-3
3-1
3-2
3-3
Page
QA Objectives for Precision, Accuracy, and Method
Detection Limits 13
QA Objectives for Precision, Accuracy, and Detection Limits -
Alternate Form 14
Required Detection Limits for Volatile Chlorinated Organic
Compounds 15
Summary of Laboratory Analyses and Sample Quantity Requirements 20
Required Containers, Preservation Techniques, and Holding Times 21
Typical Summary of Standard Methods and Procedures !.. 23
vu
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Acknowledgments
The extensive technical contributions of Dr. John R. Wallace of Maxwell
Laboratories and the assistance of Robert Banner, Ann Kem, and William
Mueller of the USEPA in reviewing the document are gratefully
acknowledged. Grateful appreciation is, also, extended to the excellent
editorial and technical comments provided by Dr. Monica Nees.
VUl
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SECTION 0.0
INTRODUCTION
0.1 PURPOSE OF THE QUALITY ASSURANCE PROJECT PLAN (QAPjP)
The purpose of a QA Project Plan is to relate project objectives to specific measurements
required to achieve those objectives. The QA Project Plan must provide sufficient detail to
demonstrate the following:
• Intended measurements are appropriate for achieving project objectives;
• Quality control procedures are sufficient for obtaining data of known and
adequate quality; and
• Such data will be defensible if challenged technically or legally.
Environmental projects require the coordinated efforts of numerous individuals, including
regulators, managers, engineers, scientists, statisticians, and economists. The QA Project Plan
must integrate the requirements of everyone involved, in a form that permits an easy and painless
review. It must also provide unambiguous instructions to the sampling team, the analytical
laboratory, and any other parties responsible for data generation. Finally, the QA Project Plan
must provide sufficient detail to allow a thorough, detailed review by an independent party not
involved in the project implementation.
0.2 QUALITY ASSURANCE CATEGORIES
Because the end use of the data determines the degree of quality assurance that is required,
RREL uses four categories in its QA Program:
CATEGORY I PROJECTS require the most rigorous and detailed QA, since
the resulting data must be both legally and scientifically defensible. Category I
projects include enforcement actions and projects of significant national or
congressional visibility. Such projects are typically monitored by the Adminis-
trator. Category I projects must produce results mat are autonomous; that is,
results that can prove or disprove a hypothesis without reference to comple-
mentary projects.
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CATEGORY H PROJECTS are those producing results that complement other
inputs. These projects are of sufficient scope and substance that their results
could be combined with those from other projects of similar scope to produce
information for making rules, regulations, or policies. Projects that do not fit this
pattern, but have high visibility, would also be included in this category.
CATEGORY HI PROJECTS are those producing results used to evaluate and
select basic options, or to perform feasibility studies or preliminary assessments
of unexplored areas which might lead to further work.
CATEGORY IV PROJECTS are those producing results for the purpose of
assessing suppositions.
The RREL Technical Project Manager is responsible for assigning the category that accurately
reflects the intended use of the data and the type of work being done.
This document addresses only Category IV requirements; separate documents are available for
each of the remaining categories. Be sure to use the Preparation Aids document for the correct
category.
0.3 UNDERLYING LOGIC AND ORGANIZATION OF A QA PROJECT PLAN
A QA Project Plan, regardless of category, must cover the following topics:
• Process being tested and the objectives of the test (i.e., the hypothesis
to be tested);
• Measurements that will be taken to achieve those objectives;
• Quality of data that will be required and how that quality will be obtained; and
• How data will be recorded, calculated, reviewed, and reported in a defensible
manner.
The QA Project Plan is organized according to the topics discussed in the body of this report.
To be an effective communication tool, the QA Project Plan must be concise, but still contain
essential experimental detail.
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Be sure to include:
Any project-specific information necessary for the sampling team, analyt-
ical laboratory, data reduction team, and all otlier project participants.
However, assume these parties are familiar with standard methods,
Any deviations from standard methods or procedures, or clarification #f
such documents whenever there are ambiguities, ;
Equations for all project-specific calculations and data reductions*
But don't be repetitious:
Bo not discuss the same subject matter more than once in a QA Project
Plan, Although the required elements of the QA Project Plan may appear
to overlap in some cases, repetition leads to confusion, and to documents
too long for effective communication, If you are unsure where a subject
should be treated, discuss it once and cross-reference that discussion in the
other sections.
Do not repeat material from a Sampling Plan* If a separate Sampling
Plan has been generated, reference the section and page number in the QA
Project Plan, as needed.
Do not repeat material from standard methods that are available from the
EPA or the Code of federal Regulations, Provide detailed citations and
assume that the analyst and reviewer have these methods «n*hand*
0.4 CATEGORY IV FORMAT NOTES
All Category IV QA Project Plans must incorporate the following format requirements:
• Title page.
• QA Project Plan Approval Form (see Figure 0-1).
• Distribution list to ensure that key personnel will receive current copies and
updates.
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• Table of Contents as shown at the beginning of this document. If a given
element is not applicable, the text of the Category IV QA Project Plan should
explain its omission.
0.5 QA PROJECT PLAN APPROVAL FORM (SIGNATURE PAGE)
It is important that the project principals understand and agree on the experimental approach.
For this reason, the QA Project Plan Approval Form must be signed by key project personnel as
well as key personnel from any subcontractors. These signatures—which must be obtained
before the final QA Project Plan is submitted—indicate that the key personnel have read the
appropriate sections of the QA Project Plan and are committed to implementing the plan.
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QUALITY ASSURANCE PROJECT PLAN APPROVAL FORM
for
RREL Contracts/IAGs/Cooperatlve Agreements/In-house Projects
RREL QA ID No:.
Contractor:
RREL Project Category:
RREL Lab Workplan No:
QA Project Plan Title:.
Revision Date:
COMMITMENT TO IMPLEMENT THE ABOVE QA PROJECT PLAN:
Contractor's Project/Task Manager (print)
Contractor's QA Manager (print)
Other as Appropriate/Affiliation* (print)
Other as Appropriate/Affiliation* (print)
Signature
Signature
Signature
Signature
Date
Date
Date
Date
Other as Appropriate/Affiliation* (print)
Signature
Date
* Commitment signature Is required for any ancillary sampling, analytical, or data
gathering support provided by a subcontractor or RREL principal Investigator.
APPROVAL TO PROCEED IN ACCORDANCE TO THE ABOVE QA PROJECT PLAN:
RREL Technical Project Manager (print)
Signature
Date
CONCURRENCES:
RREL Section or Branch Chief (print)
Guv Slmea
Signature
RREL QA Manager
Signature
Date
Date
RREL (QAPJP AF)
(March 1989)
Figure 0-1. Quality Assurance Project Plan Approval Form
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SECTION 1.0
PROJECT DESCRIPTION
This section describes the process or environmental system that is to be tested, the key personnel,
the project objectives, a summary of the experimental design, and the proposed project schedule.
This section typically contains the subsections listed below, plus others at the principal
investigators discretion.
1.1 GENERAL OVERVIEW
This section provides a brief synopsis of the overall project; In one to two paragraphs describe
the programmatic and regulatory setting in which the project is going to be carried out. The
purpose(s) of the study should be described, along with the decisions that are to be made and the
hypothesis to be tested. Other anticipated uses of the data should also be noted. Explain the
consequences of drawing incorrect conclusions or making invalid decisions. The type of process
or environmental system that is to be tested should also be described briefly. Describe the
general characteristics of any feed and discharge streams, including the anticipated concentration
ranges of the pollutants of interest.
1.1.1 The Process
This section describes the process, site, facility, or environmental system that will be tested.
Include flow diagrams, maps, charts, etc., as needed. Approximate mass or volumetric flow rates
should be indicated to permit proper evaluation of the sampling and process monitoring
procedures. For flow processes, indicate sampling points with alphanumeric designations.
This section should contain enough material to permit a technical reviewer who is unfamiliar
with the specific project to assess the proposed sampling and analytical strategy.
1.1.2 Statement of Project Objectives
All project objectives should be summarized and stated clearly in this section. Avoid scattering
statements of project objectives throughout the various sections of the QA Project Plan, or
among several documents. Statements of objectives, when scattered among various subsections,
often result in an unfocused effort and hinder document review.
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Project objectives should be stated in numerical terms whenever possible:
Poor Statement: The bio-oxidation procedure will be characterized with respect
to its ability to remove semivolatile organic compounds.
Better Statement: The major objective is to demonstrate a bio-oxidation
efficiency of 95 percent for the compounds listed in Table...
Best Statement: The objective is to demonstrate a bio-oxidation efficiency of
90 percent or higher at a confidence level of 95 per cent for the compounds listed
in Table...
For Category IV projects, however, some objectives cannot be stated in entirely quantitative
terms. For example, one objective for a biotreatment project might be to determine the dominant
microbiological species in a reactor. Or, for a test of a new incinerator design, one might wish to
determine the range of combustion conditions that result in molten ("slagging") ash.
It is common to rank project objectives according to importance. Although this ranking is not
essential, it does help to focus effort on the primary goals of the project.
1.2 EXPERIMENTAL DESIGN
List all measurements that are anticipated during the project, then classify them as critical or
noncritical measurements. Critical measurements are those that are necessary to achieve
project objectives; they may include both on-site process measurements and chemical
measurements. Thus, for a test of an electric arc furnace as a means of incinerating organics, the
rates of consumption of shield gas (e.g., argon) and electric power are as important as the feed
rate and concentration of pollutant. Noncritical measurements are those used for process
control or general background readings.
It is common practice to test pollution control equipment or processes in different operating
modes or stages. For example, an incinerator might be operated under warm-up conditions,
followed by incineration tests at three different feed rates. The various test conditions should be
summarized in this section. If possible, indicate the length of time anticipated for each test
condition. When appropriate, indicate how equilibrium conditions will be established before
sample collection begins.
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Example: Total hydrocarbons in the stack gas will be monitored continuously.
Sampling will not begin until THCs concentrations are stable within ±5 percent
over a three-hour period.
Summarize the number of measurements that are planned for each sample (air, water, soil, etc.)
for each test condition. For Category IV projects, the optimum number of samples will often not
be known until initial results are obtained. In this case, describe how the number of samples for
each test condition will be determined during execution of the project.
1.3 SCHEDULE
Indicate start-up and ending dates, including dates of preliminary studies and field and laboratory
activities.
1.4 PROJECT ORGANIZATION AND RESPONSIBILITIES
This section should demonstrate that the project organization is adequate to accomplish the
intended goals. This is most easily accomplished by listing all key personnel and their assigned
responsibilities. Include telephone numbers and geographic locations. For organizationally
complex projects, an organizational chart can be helpful.
Be sure to:
• Include enough information in this section to permit 9 technical person
unfamiliar with your project to evaluate ttie sampling and analytical
: approach*
* Avoid repeating material from a sampling or analytical plan. Complete a
necessary description onee, then cite it in all other documents. Repeating
material inevitably leads to confusion add w£$tes the valuable time of
project participants, typists, and reviewers* Most importantly, essential
details are readily overlooked when buried in repetitious or «verl£lengthj
documentation.
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SECTION 2.0
QUALITY ASSURANCE OBJECTIVES
Quality assurance objectives are specifications that measurements must meet in order to achieve
project objectives. For example, in ordering a pump for a chemical plant, factors such as
capacity, pressure, and materials of construction must be specified. Similarly, precision, accu-
racy, detection limits, and completeness must be specified for physical/chemical measurements.
Additional analytical requirements are described qualitatively in terms of representativeness and
comparability. Quality assurance objectives are needed for all critical measurements (see Section
1.2) and for each type of sample matrix (soil, water, biota, etc.). Be sure to include quality
assurance objectives for physical as well as chemical measurements.
Once QA objectives are set, the measurement systems are designed to meet them. The project
manager, analytical chemists, and other principals must agree on the feasibility and appro-
priateness of these objectives.
2.1 DETERMINING QA OBJECTIVES
QA objectives must be defined in terms of project requirements, and not in terms of the
capabilities of the intended test methods. Of course, the QA objectives must be achievable by
available methods, and for this reason it is important that the laboratory review the QA
objectives. When QA objectives exceed the capabilities of available methods, either the methods
must be modified or the test plan must compensate for these deficiencies. Modifications may
often be as simple as collecting a larger sample. However, if nonstandard or significantly
modified test methods are required, the QA Project Plan must include laboratory validation data
to prove that the method is capable of achieving the desired performance.
The following are examples of how QA objectives can be determined:
Example 1: Low temperature stripping of carbon disulfldefrom soil.
The first objective of this project is to identify procedures capable of removing 99 percent
of the CS2from the contaminated soil. The untreated soils contain 150 mglkg ofCS2,
and consequently the treated soils should contain no more than 1.0% of this amount, or
£1.5 mglkg ofCS2. To allow a reasonable margin of safety, the detection limit of 0.1
mglkg is required for total CS2 in soils.
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A second objective of this project is to demonstrate that leachate from the treated soil
contains less than 4,8 mg/L ofCS2 as required by land disposal regulations (40 CFR
268.41). For this purpose a detection limit of'0.5 mg/L is required for CS2 in leachate.
Example 2: Biological treatment ofpentachlorophenol (PCP).
Previous experience with similar processes has indicated that the concentration of
pollutant in the effluent typically varies by a factor of two under stable operating
conditions with uniform feed. To assure that the analytical error is significantly less than
the natural process variability, the precision of the analytical methods should be
significantly less than this value, or approximately ± 30 percent or less.
Category IV projects are allowed a wide range in defining the specific QA objectives and
methods involved, but project-specific QA objectives and methods must still be established.
2.2 QUANTITATIVE QA OBJECTIVES: PRECISION, ACCURACY,
METHOD DETECTION LIMIT, AND COMPLETENESS
QA objectives for precision, accuracy, method detection limit, and completeness should be
presented in a QA objectives table similar to those shown in Tables 2-1 through 2-3. Be sure to
include QA objectives for all matrix types and to indicate the units in which these QA objectives
are given. Summary tables are very helpful to the laboratory which must meet these objectives.
Because precision and accuracy can be measured in various ways, explain the method to be used.
If precision, for instance, is to be determined by duplicates, explain whether sample splitting
will occur in the laboratory, during sampling, or at some other stage. Then summarize all such
information in either text or tabular format.
The following statements are examples of descriptions for precision, accuracy, and method
detection limits:
Examples: Precision objectives for all the listed methods except those for pH are
presented as relative percent difference (RPD) of field duplicates. Precision objectives
forpH are listed inpH units and expressed as limits for field duplicates.
Precision objectives for unconfined compressive strength are given as relative standard
deviation for triplicate sets.
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Table 2-2. QA Objectives for Precision, Accuracy, and Detection Limits -- Alternate Form
Data
Quality Parameter
Method of
Determination
Frequency
Required
Objective3^1)
Precision
- Water
- TCLP leachates
Accuracy
- Water & TCLP leachates
- Water & TCLP leachates
- Water
- MMS train
Detection limits
- Water
- MMS train
Semivolatile Organic Compounds
Field duplicate
Duplicate leaching
of laboratory - split
sample
Laboratory matrix
spike
Surrogate
NIST standard
reference materials
Spike of XAD resin
7 analyses of
spiked clean water
3 analyses of
spiked XAD
I/test condition
I/test condition
1 water/test
condition
1 leachate/test
condition
All samples
I/project
3/project
1 before project
1 before project
RPD<50
RPD<60
Recovery = 50-150%
Recovery = 50-150%
(b)
Recovery = 50-150%
Recovery = 50-150%
MDL £ 10 jig/L, neutrals
MDL i 20 vgfL, phenols
MDL £ 100 *tg/L, bases
MDL i 20 itg
a RPD=relative percent difference.
MDL s method detection limit
b As specified in Method 8270.
Note(l) Objectives must be met for all critical measurements. (See Section 1.2 of this document.)
Note (2) MDLs must be calculated according to Equation (8), Section 4.0 of this document, which takes into
account the number of low-level samples analyzed.
areNOT^iiecessadiy those fiiat wetM be employed
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Table 2-3. Required Detection Limits for Volatile Chlorinated Organic Compounds2
Compound
Regulatory
Threshold (*tg/L)
Required
MDL (jig/L)
1,1,1-Trichloroethane
1,1-Dichloroethane
1,1-Dichloroethene
Vinyl chloride
1,2-Dichloroethane
Perchloroethylene
5
5
5
2
1
5
0.5
0.5
0.5
0.2
0.1
0.5
Method detection limits for these compounds are critical and will be determined experimentally by the
laboratory before sample collection is started. MDLs must be well below the Regulatory Threshold in
order to demonstrate that treated waters meet discharge limits.
This table itJneantto iSustete typical format.
The tests listed are NGTiaecessarSy those thai would be, employed
',.,2 ,' , for a process of^as type.
Accuracy objectives for organic compounds and metals are given as percent recovery
range of laboratory matrix spikes. Accuracy objectives for temperature measurements
are absolute deviations in ' C.
Detection limits are defined as the method detection limit (MDL) multiplied by the
dilution factor required to analyze the sample. MDLs -will be determined by replicate
extraction and analysis of three identical spiked samples ofXAD resin.
When analyzing for a large number of organic compounds by GC or GC/MS, it is usually
unnecessary to list QA objectives for each compound separately. Instead, list QA objectives
according to compound type as was done for the semivolatile detection limits in Table 2-2. In
other cases, for example, where detection limits are derived from applicable regulations, list
detection limits for individual compounds, as is shown in Table 2-3.
15
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Finally, the author of the QA Project Plan must explain how the QA objectives are to be
interpreted in a statistical sense. QA objectives are often interpreted in a sense that all data must
fall within these goals; for such projects any data that fail to satisfy the QA objectives are
rejected and corrective action is undertaken. However, other interpretations are possible. For
example, the project requirements may be satisfied if the average recovery is within the
objectives; that is, excursions beyond the objectives might be permitted, but the average recovery
would have to satisfy the goals described in this table. Whatever the case, it is important to
describe in this section how tabulated QA objectives will be interpreted.
2.3 QUALITATIVE QA OBJECTIVES: COMPARABILITY AND
REPRESENTATIVENESS
Comparability is the degree to which one data set can be compared to another. For instance, to
evaluate an environmental cleanup process, analyses of the feed and discharge streams must be
comparable. Similarly, to perform a nationwide environmental survey, methods used at different
locations must be comparable. Comparability is achieved by the use of consistent methods and
by traceability of standards to a reliable source.
Representativeness is the degree to which a sample or group of samples is indicative of the popu-
lation being studied. An environmental sample is representative for a parameter of interest when
the average value obtained from a group of such samples tends towards the true value of that
parameter in the actual environment, as the number of representative samples is increased.
Representativeness is normally achieved by collecting a sufficiently large number of unbiased
samples.
The QA Project Plan should demonstrate that adequate comparability and representativeness will
be achieved.
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2.4 OTHER QA OB JECTIVES
Some projects may require additional QA objectives, such as mass balances. Requirements for
all additional QA measurements should be stated in this section.
Example: Soil Washing for Removal ofPCP.
A mass balance will be calculated according to the following expression:
Mass Balance = Mass ofPCP in output streams/mass ofPCP in input streams
For this test to be successful, mass balance should be between 50 and 150
percent. The specific equations for calculating the influent and effluent masses in
terms of the measured quantities are given in Section _._ of this QA Project Plan.
2.5 WHAT IF QA OBJECTIVES ARE NOT MET?
This section should include a discussion of the impact of not meeting one or more QA objectives.
Will the project be a complete loss? Will some, but not all, of the project goals still be realized?
Will the statistical confidence level be reduced? Are there legal or regulatory ramifications?
Answers to such questions help provide a critical perspective on the QA Program.
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SECTION 3.0
SAMPLING AND ANALYTICAL PROCEDURES
This section should describe or reference the procedures that will be used for sampling and
analysis.
3.1 SAMPLING PROCEDURES
This section describes the specific procedures that will be used for collecting and preserving
samples.
• Discuss each sampling procedure that will be employed. For EPA-approved
procedures, a reference is sufficient Other sampling procedures should be
summarized in the text; additional details should be provided in an Appendix.
(Copies of ASTM sampling procedures are frequently appended.)
• Prepare a list of analytes, sample volumes to be collected, and the amount of
sample that is required for each analysis (see Table 3-1). Specify whether the
required amount is intended for matrix spike/matrix spike duplicate determin-
ations or for a single determination only. Be sure to have your laboratory
manager review this table to ensure that the sample volume or mass are
sufficient for all intended analyses.
• Describe any compositing or sample splitting procedures that will be employed
. in the field or laboratory.
• Discuss any sampling equipment that will be used, and how this equipment
will be calibrated.
• Describe containers used for sample collection, transport, and storage for each
sample type and cleaning procedures to prevent sample contamination. Include
sample preservation methods and holding times, noting all reagents, equip-
ment, supplies, etc., required for sample preservation, and also the specific
time requirements for shipping samples to the laboratory. Note refrigeration
conditions and holding times that will be employed. (See, for example, Table
3-2.)
• Include procedures for recording sample history, sampling conditions, and any
other pertinent information.
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Table 3-1. Summary of Laboratory Analyses and Sample Quantity Requirements
Stream
Sampling Method Analysis Parameter
Sample Quantity
Container Size Required for Analysis^'
Test soil
Treated soil
Scrubber makeup
scrubber liquor
Scrubber solids
Stack
Shelby tubes
ASTM-C172/
composite^
Grab
Thief
Method 5
Midget M-5@)
Metals trains
Modified Method 5
NIOSH-IOOS^2)
Semivolatiles
Volatiles
Metals scan
Dioxins/furans
EP toxicity
TCLP
Higher heating value
Chlorine
Moisture
Semivolatiles
Volatiles
Metals scan
Dioxins/furans
TCLP
Semivolatiles
Volatiles
Metals scan
Dioxins/furans
Semivolatiles
Volatiles
Metals scan
Dioxins/furans
Paniculate
HC1
Metals
Semivolatiles
Dioxins/furans
Volatiles
250 mL
250 mL
250 mL
250 mL
250 mL
250 mL
250 mL
250 mL
250 mL
250 mL
250 mL
250 mL
250 mL
250 mL
1 L
40 mL VGA vial
1 L
1 L
250 mL
250 mL
250 mL
250 mL
50 g
50 g
100 g
50 g
250 g
500 g
250 g
250 g
100 g
50 g
50 g
100 g
50 g
500 g
1 L
40 mL VGA vial
1 L
1 L
50 g
50 g
100 g
50 g
900 L
900 L
900 L
3000 L
3000 L
20 L
Note (1) Indicate whether the listed quantity suffices for replicates, spikes, and other QC purposes, or if it is
sufficient for only a single analysis. In the latter case, indicate how extra material will be provided for
QC purposes.
Note (2) Copies of these methods would have to be appended because they are not readily available.
- v J; ^$ps tafefe'fcaaaatto IS«st$te typical format, vf
lEhe test$!ste<| are NOTHeoessarJly those feat wbald be e*»|>!
-^' ^ .,*•,' 'v;"_^ s * fora praeess ofl&is tvpel -
20
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Table 3-2. Required Containers, Preservation Techniques, and Holding Times
Measurement
Type"
Preservation13
Maximum Holding Times0
Extractable organics
Pesticides, PCBs
Metals (except mercury
and chromium VI)
G Coolto4'C,
Teflon-lined septum protect from light
G Coolto4'C,
Teflon-lined septum pH 5-9
P,G
HNO3topH<2
7 days until extraction,
40 days after extraction
7 days until extraction,
40 days after extraction
6 months
Mercury
Chromium VI
pH
Residue
Organic carbon, total
Sulfide
P,G
P,G
P,G
P,G
P,G
P,G
HNO3topH<2
Cool, 4 "C
None required
Cool,4°C
Cool,4'C,HClor
H2SO4topH<2
Coolto4'C;
add zinc acetate plus
NaOHtopH>9
28 days
24 hours
Analyze water immediately
(on site); none specified for soil
7 days
28 days
7 days
a Polyethylene (P) or glass (G).
Sample will be preserved immediately upon sample collection.
c Samples will be analyzed as soon as possible after collection. The times listed are the maximum times that
samples will be held before analysis and still be considered valid. All data obtained beyond the maximum
holding times will be flagged.
- This table is meantto illustrate typical format.
The tests !iste# are NOT necessarily those that would be employed "
-'" ~'~", for access of this tygfr
21
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3.2 PROCESS MEASUREMENTS
For field projects, prepare a table of all process measurements that will be taken while on site.
Such measurements might include flow rate, pressure, temperature, or power consumption, as
appropriate. For each measurement note the location of the measurement, the procedure, the
frequency of measurement, and the responsible party.
3.3 ANALYTICAL PROCEDURES AND CALIBRATION
This section of the QA Project Plan should describe all of the field and laboratory measurement
procedures for both chemical and physical measurements. Sample preparation methods and
cleanup procedures (such as extraction, digestion, column cleaning, etc.) should also be included.
The purpose of this section is to ensure that all methods are appropriate for their intended use and
are described in sufficient detail.
Requirements of this section can often be largely satisfied by referencing appropriate standard
methods. Most RREL projects rely heavily on EPA-approved methods that have been validated
for environmental samples. Standardized procedures from other organizations, such as the
ASTM and the American Public Health Association, are also commonly employed. When
standard methods are unavailable, nonstandard methods must be used and described in detail. It
is essential to consult the analytical laboratory and other measurement specialists for
guidance during preparation of this section because these specialists know the intricacies
and limitations of the methods.
Begin this section with a summary table of all measurements to be made. Specify the parameter
to be measured, the sample type, the method number (when available), the method title, a method
type, and a reference. (See Table 3-3 as an example.) Note the revision number of the method or
the edition number of a publication, because nominally identical methods are modified somewhat
by updates. Provide the additional project-specific information in the text of this section.
3.3.1 EPA-Approved or Other Validated Standard Methods
EPA-approved or similar validated methods can be incorporated by reference, thereby greatly
minimizing the effort required to complete this section. Once a method is cited, do not repeat
information that is already found in the method. Some additional information is almost always
required, however, to assure that project-specific requirements will be met. The following
considerations apply:
22
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• Some EPA-promulgated methods contain only general procedure descriptions
and lack specific QC requirements or applicable validation data. For example,
EPA Method 18 provides general requirements for GC analysis of stack gases,
but contains no QC requirements. For such methods, validation data pertinent
to the specific project must be appended. Alternately, a preliminary method
validation can be specified as a subtask of the project; in that case, however,
specific procedures and acceptance criteria for method validation must also be
included as part of the QA Project Plan.
« Other EPA-approved standard methods, such as those found in Standard
Methods for the Examination of Water and Wastewater, give operating
procedures but omit most QC and calibration requirements. This missing
information must be provided either in this section or in Section 4.0 of the QA
Project Plan. As a minimum, be sure to specify the frequency, acceptance
criteria, and corrective action plans for all QC procedures and calibrations.
• It is not necessary to include copies of methods or sections of methods from
SW-846, the Code of Federal Regulations, Standard Methods for the
Examination of Water and Wastewater, or Methods for Chemical Analysis of
Water and Waste because these sources are readily available. However, do
append ASTM and NIOSH procedures because they may not be so readily
available to other project principals or reviewers.
• EPA-approved or similarly validated methods that are significantly modified
are considered to be unvalidated methods and are treated as described in
Section 3.3.2.
• Certain EPA methods such as those found in SW-846 specify most operating
details, including quality control and calibration requirements. Such
procedures, however, frequently allow the user to specify certain other options
to satisfy project objectives. For example, for multianalyte methods such as
GC/MS, the user will typically specify the target compound list that is required
for the project. Matrix spike compounds are chosen from the compounds of
interest to the particular project, and are not necessarily those recommended in
the method. Also list the project-specific target compounds to be used as
calibration check compounds and matrix spike compounds. Specify the
acceptance criteria for matrix spike compounds. In certain cases, isotopically
labeled forms of the project analytes may be included as surrogates.
The following is an example of how one might specify various options allowed by Method 8080,
a validated method from SW-846 which contains QC and calibration requirements:
25
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Example: Method 8080.
This method will be employed to determine the 19 pesticides listed in Table _-_ of
this QA Project Plan. Although PCBs can also be determined by this method, the
GC -will not be calibrated for these products unless they are observed. The matrix
spike compounds will be the six critical pesticides listed previously in this QA
Project Plan. The surrogates will be tetrachlorometaxylene (not dibutyl-
chlorendate). Detection will be by ECD. Quantitation will be by external
calibration. Acceptance criteria for surrogate recovery will not be determined by
control charts, but must be within a 50-150 percent range. Acceptance criteria for
matrix spike/matrix spike duplicates are those stated in Table _-_ of this QA
Project Plan. Extraction and cleanup procedures are described below...
3.3.2 Nonstandard or Modified Methods
Category IV projects must sometimes employ analytical methods that have not yet been
validated for the intended application. In such cases, describe the intended procedure, state how
it will be validated, and specify what criteria must be met before it is accepted.
Category IV projects are allowed wide latitude in selecting specific methods to be used. Specific
methods, however, must be established. If appropriate EPA-approved methods are available for
a particular critical measurement, their use should be considered but is not necessarily required.
3.3.3 Calibration Procedure and Frequency
This section covers calibration procedures for each analytical or measurement system used to
obtain data for critical measurements.
• In the case of standard EPA-approved methods that include calibration
procedures, a reference to that method suffices. For nonstandard methods that
are appended to the QA Project Plan, reference can be made to a Standard
Operating Procedure (SOP). Describe all other calibration procedures in this
section.
• A list of calibration standards, including source, traceability, and verification
of purity, must be included.
• For process measurements (e.g., flow, mass, etc.) and for chemical or physical
analyses, specify the planned frequency of initial and continuing calibration
checks and the acceptance criteria for all calibration measurements.
26
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For physical measurements such as temperature and pressure, calibration statements can be quite
brief.
Example: All thermocouples intended for use in the range 50°Cto 350' C will be
calibrated versus an N 1ST-traceable thermometer at a minimum of two
temperatures, by placing both in an oven simultaneously and noting any
difference between readings. The thermocouple readout must be within 2 ° C of
the corrected mercury thermometer or the thermocouple device will be replaced
or corrected.
27
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SECTION 4.0
APPROACH TO QA/QC
Category IV projects are allowed a wide latitude in defining the specific data reduction,
validation, and reporting procedures and requirements. Specific procedures and requirements,
however, must be established. This section should describe the calculation procedures that will
be employed, the type and frequency of QC procedures, and formulas for calculating data quality
indicators.
4.1 CALCULATION OF RESULTS
In most cases, the designated analytical methods specify procedures for calculating concen-
trations in individual samples; such information should not be repeated here. This section is
primarily reserved to show how analytical results will be manipulated to prove or disprove a
hypothesis. This section should provide formulas and summarize any statistical procedures for
reducing the data, including units and definitions of terms. Also define procedures that will be
employed for determining outliers or flagging data.
Example: For each treatment condition, the control efficiency, E, will be
calculated from the following equation:
E = C /C.
out in
where C denotes concentration. The uncertainty in this number will be expressed
as a confidence range:
where E is the average control efficiency for a given operating condition, s is the
sample standard deviation, and n is the number of times a given operating
condition is tested.
If mass balance calculations are required, provide exact formulas relating the mass balance to the
individual measurements that will be made.
29
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Also specify data reporting requirements at this point. Indicate the units for each measurement
and each matrix, and whether data will be reported on a wet, dry, or some other basis. List the
deliverables that will be expected from the laboratory and from the field operation, and
summarize the data deliverables that will be included in the final report. Will the data package
include all raw data, sufficient to recalculate the results if necessary? What type of QC data will
be reported? Will analytical and other measurement data be partially reduced before they are
reported, or will all individual measurements be reported?
Example: The final report will contain the following analytical data:
• All analytical results from all primary samples. Data judged to be outliers will
be included, along with a justification for excluding this information from
further interpretation.
• All individual results from standard reference materials, independent check
samples, replicates, and matrix spikes, including both initial and final concen-
trations.
• Data from continuous emission monitors, reported as 15-minute averages and,
where appropriate, summarized graphically.
For most RREL projects, this section should contain a statement that the final report will include
a QA section covering QA/QC activities and results. These results must be readily correlated to
the primary data and must clearly indicate the limitations of the data and the range of validity of
the conclusions.
The final report should also include a summary of the original QA objectives, and a statement of
whether or not these objectives were met. If QA objectives were not met, explain how not
meeting the project's QA objectives affected the outcome.
4.2 INTERNAL QUALITY CONTROL
This section describes the nature and frequency of all QC methods that will be followed for both
field and laboratory activities. Bear in mind that the QC procedures specified here should follow
from the QA objectives stated in Section 2.0. That is, Section 2.0 specifies analytical require-
ments, while Section 4.0 describes how these specifications will be met.
30
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Examples of QC checks that should be considered include the following:
• Samples
- Collocated, split, replicate
• Spikes
- Matrix spikes and matrix spike duplicates
- Spiked blanks
- Surrogates and internal standards
• Blanks
- Sampling, field, trip, method, reagent, instrument
- Zero and span gases
• Others
- Standard reference materials (complex natural materials, pure solutions)
- Mass tuning for mass analysis
- Confirmation on second column for gas chromatographic analyses
- Control charts
- Independent check standard
- Determinations of detection limits
- Calibration standards
- Proficiency testing of analysts
- Any additional checks required by the special needs of your project
Include QC checks for process measurements as well.
The use of ambiguous terms is a common problem in this section. The terms "duplicate" and
"replicate" are particularly troublesome. The text must explain the exact point in the process
where replication occurs. Does "replicate" refer to samples collected simultaneously or sequen-
tially in the field; to samples collected at the same sampling point but at different times; to
samples that are split upon receipt in the laboratory; or to samples collected under yet another
splitting protocol? The term "QC check sample" is equally ambiguous unless it is fully defined.
Also be sure to give complete details on matrix spiking.
31
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Similarly, there are numerous types of blanks; the exact procedure for preparing these blanks
must also be described. Do not assume that a term such as "field blank" will mean the same to
the sampling team and to a reviewer as it does to you.
Either in this section or in Section 2.0, be sure to specify what compounds or elements will be
used as matrix spikes and surrogates, and describe the point in the analytical process at which
they will be added. If the standard methods recommend surrogate and matrix spike compounds
that are suitable, incorporate them by reference. More typically for RREL projects, at least some
of the matrix spike compounds must be selected on a project-specific basis.
Be sure to:
• Identify the slages at which replication and spiking occiir* Avoid using
terms such as "sample replicate" without explaining how such replication
will be performed. "s /
Explain in detail how blanks will be prepared.
4.3 CALCULATION OF DATA QUALITY INDICATORS
This section describes how data quality indicators will be calculated and reported. As a
minimum, equations must be provided for precision, accuracy, completeness, and detection
limits. In addition, equations must be given for other project-specific calculations, such as mass
balance, emission rates, confidence ranges, etc.
4.3.1 Precision
If calculated from duplicate measurements, relative percent difference is the normal measure of
precision:
- C)
100%
RPD =
(C-L + C2)/2
(1)
where:
RPD = relative percent difference
C1 = larger of the two observed values
C2 = smaller of the two observed values.
32
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If calculated from three or more replicates, use relative standard deviation rather than RPD:
RSD = (s/y) x 100%
where: RSD = relative standard deviation
s = standard deviation
y = mean of replicate analyses.
Standard deviation is defined as follows:
(2)
o —
n
Z
1=1
(y± - y)2
n _ 1
where:
s
Yi
y
n
standard deviation
measured value of the fth replicate
mean of replicate measurements
number of replicates.
(3)
For measurements, such as pH, where the absolute variation is more appropriate, precision is
usually reported as the absolute range, D, of duplicate measurements:
D =
(4)
where:
D = absolute range
m-^ = first measurement
iri2 = second measurement
The standard deviation, s, given above, can also be used.
4.3.2 Accuracy
For measurements where matrix spikes are used, calculate the percent recovery as follows:
%R = 100% x
S - U
sa
(5)
33
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where: %R = percent recovery
S = measured concentration in spiked aliquot
U = measured concentration in unspiked aliquot
C ,, = actual concentration of spike added.
S3.
When a standard reference material (SRM) is used:
%R = 100% x
m
srm
(6)
where: %R = percent recovery
C = measured concentration of SRM
C0,™ = actual concentration of SRM.
o J-ill
4.3.3 Completeness
Completeness is defined as foUows for all measurements:
%C = 100% x
(-I-)
(7)
where:
%C = percent completeness
V = number of measurements judged valid
T = total number of measurements
4.3.4 Method Detection Limit (MDL)
MDL is defined as follows for all measurements:
= ^11-1,1-0=0.99)
x s
(8)
where:
s —
(n-l,l-a=0.99)
method detection limit
standard deviation of the replicate analyses
Students' t-value for a one-sided 99% confidence level and a
standard deviation estimate with n-1 degrees of freedom.
34
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SECTION 5.0
REFERENCES
References, if any, can be included in the body of the text, as footnotes, or collected in this
section. If a reference is not readily available, attach a copy to the QA Project Plan. References
must uniquely identify the cited material. In particular, when citing various compendia of
standard methods published by the EPA, ASTM, American Public Health Association, etc., be
sure to include the edition number since such methods can change substantially from one edition
to the next.
Following are references applying to Table 3-3 of this document
1. American Society for Testing and Materials. Annual Book of Standards. ASTM.
Philadelphia, PA. Parts 14 and 19 (updated yearly).
2. U.S. Environmental Protection Agency. "A Procedure for Estimating Monofilled Solid
Waste Leachate Composition" Technical Resource Document SW-924, 2nd ed.
Hazardous Waste Engineering Research Laboratory, Office of Research and
Development. Cincinnati, OH, and Office of Solid Waste and Emergency Response.
Washington, DC, 1986.
3. American Nuclear Society. ANSI/ANS-16.1-1988. American National Standard
Measurement of the Leachabitity of Solidified Low-Level Radioactive Wastes by a Short-
Term Test Procedure, American Nuclear Society. LaGrange Park, IL, 1986.
4. U.S. Environmental Protection Agency. Office of Solid Waste. Test Methods for
Evaluating Solid Waste, 3rd ed. Available from U.S. Government Printing Office.
Washington, DC, 1986.
5. Alford-Stevens, A., T. A. Bellar, J. W. Eichelberger, and W. L. Budde. Method 680,
Determination of Pesticides and PCB in Water and Soil/Sediment by Gas
ChromatographylMass Spectrometry. Available from the U.S. Environmental Protection
Agency. Cincinnati, OH, 1985.
6. Klute, A. (Ed.). Methods of Soil Analysis, Part I. American Society of Agronomy.
Madison, WI, 1986.
35
•&U.S. GOVERNMENT PRINTING OFFICE: 1993 - 750-002/60183
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