United States Office of 8olld Watt* and Office of Research and
Environmental Protection Emergency Response Development
Agency Washington DC 20460 Washington DC 20460
Superfund EPA/540/X-88/004 April 1988
For Internal Use Only
&ERA Protocol for a
Chemical Treatment
Demonstration Plan
SUPERFUND INNOVATIVE
TECHNOLOGY EVALUATION
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PROTOCOL FOR A CHEMICAL TREATMENT
DEMONSTRATION PLAN
U.S. ENVIRONMENTAL PROTECTION AGENCY
26 WEST MARTIN LUTHER KING DRIVE
CINCINNATI, OHIO 45268
April 1988
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PREFACE
This document was developed for the U.S. Environmental Protection Agency
by PEI Associates, Inc., under Contract No. 68-03-3413, Work Assignment No.
0-1. The document is intended to provide guidance for the development of
demonstration plans for chemical treatment under the Superfund Innovative
Technologies Evaluation (SITE) Program. Its purpose is to provide direction
to the EPA and SITE Evaluation Contractor on the content, general format, and
kinds of information that must be developed for each chemical technology
demonstration, so that the demonstration can proceed in a technically sound
manner.
ii
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CONTENTS
Page
Preface i i
Figures v
Tables vi
Acknowledgement vii
1. Introduction 1
1.1 Overview of SITE program 1
1.2 Definition of responsibilities of EPA and
the Developer 3
1.3 Purpose and use of the protocol document 4
2. Factors Affecting Technology Demonstration 7
2.1 Process characteristics 7
2.2 Testing site acceptability 8
3. Test Plan 11
3.1 Technology description 11
3.2 Testing approach 16
3.3 Field demonstration preparation 18
3.4 Field demonstration implementation 21
3.5 Document tests and prepare reports 22
3.6 Management and schedule 23
4. Guideline Document for Health and Safety Plan
for Evaluation of Chemical Technologies 27
4.1 Introduction 27
4.2 Project description 27
4.3 Project objectives 29
4.4 Safe work practices 29
4.5 Control 31
4.6 Hazard evaluation 37
4.7 Personal protection equipment 44
4.8 Education and training 55
4.9 Communication procedures 57
4.10 Decontamination procedures 59
4.11 Site plan 62
4.12 References for Section 4 64
(continued)
i ii
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CONTENTS (continued)
5. Guideline Document for Quality Assurance Project Plan
for Evaluation of Chemical Technologies 65
5.1 Project description 65
5.2 Organizational chart and delineation of
QA/QC responsibilities 69
5.3 Quality assurance objectives 69
5.4 Site selection and sampling procedures 77
5.5 Analytical procedures and calibration 105
5.6 Data reduction, validation, and reporting 112
5.7 Internal quality control checks 116
5.8 Performance and system audits 118
5.9 Calculation of data quality indicators: specific
routine procedures used to assess data precision,
accuracy, completeness, and method detection limit 120
5.10 Corrective action 123
5.11 Quality control reports 125
5.12 References for Section 5 126
5.13 Annotated glossary of terms 126
i v
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FIGURES
Number Page
3-1 Schematic of Unit Operations in a Treatment
Process 13
3-2 Proposed Reaction Mechanism 17
3-3 Process Diagram 17
3-4 Location of Sampling Points in a Hypothetical
Chemical Treatment Process 19
3-5 Organization of Responsibilities for Field
Demonstrations Conducted Under the EPA SITE Program 24
3-6 Project Schedule 26
4-1 Hazardous Substance Data Sheet 42
5-1 Quality Assurance Project Approval Form 66
5-2 Sample Project Schedule 68
5-3 Sample Project Organization Scheme 70
5-4 Air Sampling Apparatus 86
5-5 Method 5 Sampling Train 87
5-6 Thief Sampler 90
5-7 Sampling Triers 92
5-8 Weighted Bottle Sampler 94
5-9 Dipper 94
5-10 Sample Bottle Label 100
5-11 Chain-of-Custody Record 101
5-12 Sample Receipt Form 102
5-13 Sample Checkout Log 103
5-14 Data Reporting Scheme 115
v
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TABLES
Number Page
1-1 Areas of Responsibility of the EPA PM and
the Developer Under the SITE Program 5
3-1 Capital and Operating Costs for EAF Recycling
Process 15
4-1 Protective Clothing and Accessories 46
5-1 Example of Definition of QA/QC Responsibilities 71
5-2 QA Objectives for Precision, Accuracy, Completeness
and Method Detection Limit 74
5-3 Precision, Accuracy, and Method Detection Limit QA
Objectives for Project-Specific Chlorinated Solvents 76
5-4 Summary of Proposed Sampling Program 80
5-5 Bibliography for Ambient Air Sampling Procedures 88
5-6 Recommended Collection Volumes for Metal Determinations 89
5-7 Required Containers, Preservation Techniques, and
Holding Times 98
5-8 Sample Preparation and Analytical Methods 107
5-9 Sample Field Equipment Calibration Checklist 109
5-10 Maintenance Procedures and Schedule for Major
Instrumentation 119
vi
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ACKNOWLEDGEMENTS
This report was prepared for the U.S. Environmental Protection Agency
Hazardous Waste Engineering Research Laboratory under Contract No. 68-03-
3413. The EPA Project Officer was Mr. Eugene Harris and the EPA Technical
Project Monitor was Ms. Norma Lewis. PEI Associates, Inc., was the prime
contractor and SCS Engineers was the major subcontractor.
Ms. Catherine Hartman was PEl's Project Manager. SCS's efforts were
managed by Mr. James Sta»nm. Key technical investigators included Ms. Roxanne
Sukol and Ms. Catherine Chambers of PEI. We gratefully acknowledge the
assistance given by Ms. Martha Phillips, technical editor at PEI.
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SECTION 1
INTRODUCTION
1.1 OVERVIEW OF SITE PROGRAM
The Congress and EPA have expressed concern over the use of land-based
disposal and containment technologies to mitigate problems caused by releases
of hazardous substances at Superfund sites. Through legislation, Congress
has mandated a program entitled Superfund Innovative Technologies Evaluation
(SITE Program) to accelerate the development and demonstration of new or
innovative technologies. The emphasis of the SITE Program is on technologies
that deal with the treatment or destruction of hazardous substances.
The SITE Program has four objectives:
° To identify and, where possible, remove impediments to the develop-
ment and commercial use of alternative technologfes.
° To conduct a demonstration program of the more promising innovative
technologies to establish reliable performance and cost information
for site characterization and decision making regarding technology
applicability.
° To develop procedures and policies that encourage selection of
available alternative treatment remedies at Superfund sites.
° To structure a development program that nurtures emerging tech-
nologies.
The protocol guidance provided by this document is offered to assist those
involved in the SITE demonstration program and the development program.
Demonstration Program
The focus of the demonstration portion of the SITE Program is on pilot-
scale or full-scale tests of new or innovative technologies. The technolo-
gies the EPA selects for demonstration in the SITE Program will already have
undergone laboratory bench-scale testing. The main objective of the demon-
stration program is to collect reliable performance and cost data on
1
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innovative alternative technologies to permit their consideration by Super-
fund decision-making personnel. Because the emphasis is on the collection of
quality performance data, sampling and analysis procedures are of primary
importance. Therefore, quality assurance/quality control (QA/QC) procedures
must be strictly followed throughout the demonstration program.
The demonstration program will provide sufficient data on performance,
cost-effectiveness, and reliability to allow potential users to make sound
judgments regarding the applicability of a technology for a specific site and
to compare its effectiveness with that of other alternatives. An evaluation
of the technology demonstration will include characterizing the performance,
determining the possible need for pre- and post-processing of wastes, identi-
fying the site-specific wastes and media to which the process can be applied,
determining potential operating problems and solutions, and establishing the
approximate capital and operating costs. The evaluation will identify gov-
ernmental policy and regulatory requirements applicable to the technology and
the hazardous substances being treated/destroyed. The demonstration will
permit some evaluation of long-term operating and maintenance costs.
Demonstrations will take place either at actual hazardous waste or
Superfund locations or at locations that duplicate or closely simulate the
wastes and conditions found at Superfund sites. This will enhance reliabili-
ty of the information collected and its acceptance by the user community.
Development Program
Although the emphasis of the SITE Program is on demonstration of full-
scale technologies, there is a need for further development of technologies
that are not yet ready for full-scale demonstration. Such technologies may
currently be undergoing continued development in the private sector; they may
also include some on which further development is halted because of a limited
market, inadequate funds, or perceived institutional impediments. The SITE
Program will focus on those developing technologies that would meet a need at
Superfund locations because of the inadequacy of existing technologies. The
EPA will provide technical and financial assistance to further the develop-
ment of selected promising technologies to ensure their continuing progress
toward commercialization.
2
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1.2 DEFINITION OF RESPONSIBILITIES OF EPA AND THE DEVELOPER
Under the SITE Program, private firms that have developed a technology
to a point where it is ready for pilot- or full-scale demonstration may apply
to EPA for participation in the SITE Program. A private firm that EPA has
selected to participate in the SITE Program is referred to as the "Devel-
oper."
The EPA will also select a consulting firm to assist the Agency in
conducting the SITE Program; this firm is referred to as the Contractor. The
EPA, the Contractor, and the Developer will work together as a team in con-
ducting the technology demonstrations.
The EPA's responsibility in carrying out the SITE Program entails a
broad scope of work. The EPA Project Manager (PM) is responsible for over-
seeing the technology demonstration and for completing individual tasks as
described here. Many of these tasks may be delegated to the Contractor, but
the EPA PM will still have ultimate responsibility for them. The EPA PM will
assign the Contractor to develop the Test Plan, Health and Safety Plan, Sam-
pling and Analysis Plan, and Quality Assurance Project Plan for each technol-
ogy demonstration. The EPA PM will review these plans and will approve them
only after determining that they provide sufficient and appropriate guidance
to assure the collection of quality data on technology performance and cost.
The plans will be based on information the Contractor obtains from the Devel-
oper. Through the SITE Contractor, the EPA PM will document the experimental
conditions and the results obtained during the demonstration and will verify
that the approved plans were followed.
The Contractor will prepare a comprehensive report that includes a
description of the technology, copies of the plans mentioned in the preceding
paragraph, the test conditions, the performance data, cost estimates, test
results, and the conclusions drawn. The Contractor will-submit the report to
the EPA PM for approval and revisions before it is issued as a final report.
Additional details regarding EPA's and the Contractor's scope of work are
addressed, as appropriate, in other sections of this document.
The Developer's responsibilities will encompass all the tasks necessary
to conduct a demonstration of the technology at the selected location and
3
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with the selected wastes. The Developer is also responsible for decontamina-
tion of equipment and personnel in accordance with EPA guidelines.
Table 1-1 lists some, but not all, of the typical responsibilities of
the Developer and the EPA PM. These are described in more detail in Section
2.2 and throughout this document.
1.3 PURPOSE AND USE OF THIS PROTOCOL DOCUMENT
This document provides protocol guidance for the Test Plan, Quality
Assurance Project Plan (which must include a Sampling and Analysis Plan), and
Health and Safety Plan that the Contractor must prepare for each chemical
technology demonstrated under the EPA SITE Program. Its purpose is to pro-
vide guidance on the content, general format, and kinds of information that
must be developed for each technology demonstration. These plans are pre-
pared to ensure that verifiable performance and cost data are collected for
each technology and that the field work is conducted in accordance with rec-
ommended protocols for health and safety, sampling and analysis, and quality
assurance/quality control (QA/QC). Each plan is prepared by the Contractor
and submitted to the EPA PM for review. The EPA PM must approve the plans
before the demonstration can proceed. This guidance document has been pre-
pared to facilitate the preparation, review, and approval process so that the
demonstration can proceed in a technically sound manner.
The generic plans presented herein are intended to serve as guides. The
user will need to modify the contents to fit the specific technology in-
volved. EPA recognizes that, especially with regard to chemical technolo-
gies, even a single process may be configured in several different ways to
meet the diverse requirements for treatment in different hazardous waste
scenarios. The examples provided throughout this document do not collective-
ly represent any single technology.
This protocol guidance is organized into three main sections following
Section 2, which covers generic factors affecting a technology demonstration.
Section 3 presents a sample Test Plan, Section 4 a sample Health and Safety
Plan, and Section 5 a sample Quality Assurance Project Plan.
The Test Plan describes the technology, scope of work, and technical ap-
proach, and outlines the schedule, management and staffing, and budget. The
Health and Safety Plan addresses protocols for personnel protection, the lev-
els of protection required, and decontamination procedures. The Quality
4
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TABLE 1-1. AREAS OF RESPONSIBILITY OF THE EPA PM
AND THE DEVELOPER UNDER THE SITE PROGRAM
EPA
Developer
Initial work items
Organize kickoff meeting
Take baseline samples for site characteriza-
tion or pretreatment needs
Assist Developer in acquiring required permits
Demonstration plan
Coordinate, review, and approve Sampling &
Analysis (S&A) Plan
Develop Health & Safety (H&S) Plan for EPA
personnel
Coordinate overall H&S program
Develop and approve QA/QC program
Site preparation
Prepare site in accordance with Developer's
"List of Needs"
Excavate waste material and bring to process
developers
Demonstration
Carry out S&A in accordance with QAPP
Provide H&S training
Arrange for QA/QC audit
Supply site H&S officer
Post demonstration site cleanup
Arrange for disposal of waste material
Report preparation
Prepare S&A report
Prepare final technology evaluation report
g
Provide technology descrip-
tion
Conduct initial site visit
Attend kickoff meeting
Supply "list of needs" to
EPA
Meet permitting and other
regulatory requirements
Implement H&S program for
Developer's personnel
Pretreat feed material
Bear costs of operating the
technology during the
demonstration
Decontaminate and
demobilize equipment
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Assurance Project Plan, which includes a Sampling and Analysis Plan, address-
es the essential elements for the collection of representative samples by
acceptable reproducible methods; the selection of standard methods for analy-
sis, chain-of-custody, and sample preservation; and Category II QA/QC re-
quirements (blanks, matrix spike, matrix spike duplicates, and other required
protocols). The Quality Assurance Project Plans are of utmost importance in
the SITE Program technology demonstrations. Strict adherence to the approved
plans is essential to obtaining quality performance data on each technology.
For the convenience of the user, the three plans are presented in a
manner that permits the use of one plan at a time. Users should follow the
protocol guidance presented for the general organization and scope and then
adapt specific details to meet their own particular technology requirements.
6
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SECTION 2
FACTORS AFFECTING TECHNOLOGY DEMONSTRATION
Several factors affect the planning and execution of a technology dem-
onstration. The EPA and the Developer must recognize and consider these
factors in the development of the Test, Health and Safety, and Quality Assur-
ance Project Plans. The factors are briefly discussed in this section and
referred to throughout this document.
2.1 PROCESS CHARACTERISTICS
Several process characteristics affect the duration, cost, and complex-
ity of a technology demonstration. For example, one such characteristic is
whether the process operates in a batch or continuous mode. For batch pro-
cesses, data from several consistently operated runs must be collected to
provide enough data for comprehensive statistical analysis. For continuous
processes, some initial run time is required to allow the system to reach
equilibrium. Thereafter, the testing begins and continues until a predeter-
mined number of samples of various types have been collected to provide
statistically significant data. If a process upset occurs, the process must
be restarted and allowed to reach equilibrium again before more sampling can
be conducted.
The size, type, and configuration of equipment affect implementation of
the technology demonstration. For example, the use of a large mixer might
require the construction of a concrete foundation, pad, and berms before the
mixer can be moved to the site. Heavy equipment (cranes, etc.) may also be
required. Sufficient time and resources must be provided to accommodate such
preparatory work. Demobilization of large equipment can also be complex if
heavy equipment is required.
7
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The variability of process performance should be defined and considered
in designing the test plans. The greater the variability in a process, the
greater the duration of the test and the number of samples required to obtain
scientifically valid data.
The effect of variations in the process should be assessed. For exam-
ple, if changes in the waste feed material will significantly affect perform-
ance, some pretreatment in the form of sizing, crushing, blending, drying,
chemical addition, or other steps may be warranted. The Developer will
advise EPA of the need for pretreatment of waste feed.
Another factor that will affect the technology demonstration is the De-
veloper's budget. The Test Plan and QA Project Plan (Sampling and Analysis)
will define the number and duration of runs and the required number of samples
(based on the amount of data needed to conduct a scientifically valid evalua-
tion). If the cost of conducting the demonstration according to the EPA-
approved plans exceeds budget, the Developer may want to decrease the test
duration. The EPA must ensure, however, that plan modifications to meet
budget constraints will still result in a valid demonstration that complies
with SITE Program objectives.
2.2 TESTING SITE ACCEPTABILITY
In addition to the technology requirements of a suitable location for a
SITE Program technology demonstration (discussed in Section 3), several
nontechnical site characteristics must be considered early in the planning.
These relate to the political acceptability of conducting experiments at a
particular site and whether permits must be obtained.
As part of the SITE Program, the SITE personnel will work with the
Regional Community Relations person to meet with the community before a
demonstration. The SITE personnel or Regional Community Relations person
will explain the scope, purpose, and applications of the technology to be
demonstrated, as well as the need for the overall program.
In some cases, it may be necessary to obtain permits to conduct the
demonstration. The EPA will determine the need for permits; however, the
Developer will be responsible for obtaining them. The applications for any
required permits should be prepared and submitted early in the planning. No
permitting will be necessary for demonstrations carried out at NPL Superfund
sites. Nevertheless, the Office of Solid Waste and Emergency Response
8
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(OSWER) will conform to the functional equivalent of any applicable or rele-
vant and appropriate laws and regulations, as required by the Superfund
Amendments and Reauthorization Act (SARA) of 1986 or by the National Oil and
Hazardous Substances Pollution Contingency Plan (NCP)(40 CFR Part 300).
Permits will be required for demonstrations conducted either at offsite
private facilities owned by the Developer (e.g., at its manufacturing or
research facility) or at a commercial offsite facility. In these cases, the
Developer or facility owner will be responsible for obtaining the permit;
however, OSWER may provide some assistance.
Occasionally, demonstrations will be conducted at EPA Office of Research
and Development (ORD) Test and Evaluation (T&E) facilities. This will be
determined by the safety requirements, the need for specialized equipment or
facilities, the QA/QC needs, or cost considerations. T&E facilities should
already have basic permits that will require, at most, only modification for
demonstration activities. In these cases, ORD will be responsible for ob-
taining any permit modifications. Such facilities also have modern pollution
control and safety equipment in place, which means that technologies can be
tested for full determination of their capabilities without fear of pollutant
releases. These facilities therefore would be readily available for moder-
ate-sized demonstration activities under safe and controlled conditions and
at a lower cost. In some cases, EPA believes that tests at a T&E facility
may be necessary prior to a field demonstration to determine appropriate
design details or operating conditions. Such tests can also be used as a
post-test, followup study to determine the flexibility of a technology to
treat additional wastes and/or media. These tests might be conducted with
the demonstration equipment or with pilot-scale equipment. In any event, the
demonstration will normally be conducted on waste obtained from a hazardous
waste site. The results of these demonstrations must be shown to be applica-
ble to "real world" situations at actual Superfund sites regardless of where
the demonstration is performed.
The Office of Research and Development is currently considering several
facilities for possible development as T&E facilities for SITE demonstra-
tions, e.g., the Kill Creek T&E Facility and the Center Hill T&E Facility,
Cincinnati, Ohio; the Combustion Research Facility (CRF), Pine Bluff, Ar-
kansas; the Edison, New Jersey, facility; and the Air and Energy Engineering
Research Laboratory, Research Triangle Park, North Carolina.
9
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The permits that may be required include both Federal and State permits
under RCRA (RCRA manifests, RD&D permits, TSDF permits, generator permits),
NPDES permits, and air permits. The Developer will provide auxiliary equip-
ment or modify the experimental system as necessary to meet permit require-
ments .
10
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SECTION 3
TEST PLAN
3.1 TECHNOLOGY DESCRIPTION
The EPA PM and the Contractor should review the plans for the technology
demonstration with the Developer and prepare a list of specific objectives
for the demonstration design. After defining the project objectives, the EPA
PM should review the objectives of the SITE Program to ensure that the project
goals are consistent with the overall SITE Program goals. The specific
project objectives must further the objectives of the SITE Program.
The Developer will develop the technology description, including an
engineering design for the field demonstration, and the EPA PM will review
the design for completeness, technical adequacy, and applicability.
The Developer should review existing performance data on the technology
to provide information enabling rational selection of design assumptions.
For example, previous work on a chemical treatment process may have indicated
a pH range necessary for the process to proceed; thus, the design would in-
clude a determination of the required pH adjustments.
The EPA PM, the Contractor, and the Developer should determine the need
for presampling and analysis to characterize the site more fully before the
demonstration is begun. The EPA will conduct all sampling and analysis to
determine the Developer's need to pretreat any material and for site charac-
terization. Developers are encouraged to conduct any additional sampling and
analysis for their own benefit. If these sampling efforts indicate that
waste pretreatment is required, EPA will conduct the pretreatment work.
The operating conditions, which will be addressed in the design, include
waste characterization. For example, a particular chemical dechlorination
process may be applicable to a wide variety of halogenated organic compounds,
including PCBs, ethylene dibromide, chlorinated dioxins, and chlorinated
dibenzofurans; however, the same process may not adequately treat hydroxylated
aromatic compounds such as pentachlorophenol, hexachlorophene, and phenols.
11
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The Developer should define the operating parameters, which will be
reviewed carefully by EPA. In a study of a chemical degradation process for
~
PCBs, the following daily operational parameters were determined:
1) Weight of contaminated soil charged to the mixer.
2) Weight of each reagent chemical charged to the mixer.
3) The pH of soil and reagent mixture in the reactor before and after
heat-up.
4) Temperature of mixer contents monitored with time during heat-up,
hold, and cool-down.
5) Volume of condensate collected during process.
6) Volume of reagent recovered from treated soil.
7) Volume of acid added to soil to adjust pH to pH 9.
8) Weight of treated soil discharged from mixer.
The development of mass and energy balances around a process is essen-
tial to the design because it provides the database needed for selection and
sizing of the equipment and instrumentation. Figure 3-1 is a schematic show-
ing the unit operations in a treatment process. The tabular information at
the bottom of the figure shows the amounts of soil and reagents that go into
and out of each unit.
A flow diagram that includes mass and energy balances allows the design
engineer to specify instrumentation. These specifications should be detailed
enough to include types and capacities of pumps and gauges and other instru-
ments. Piping and instrumentation diagrams should show the configuration,
sizing, and materials of construction (PVC, carbon steel, stainless steel,
etc.) of the piping.
The equipment specifications should address the various types of equip-
ment, the size of each unit, the material of construction, and the location
Copa, W. M., Ph.D., et al. Powdered Activated Carbon Treatment (PACT™) of
Leachate from the Stringfellow Quarry. Taken From Incineration and
Treatment of Hazardous Waste. Proceedings of the Eleventh Annual Research
Symposium. EPA 600/9-85-028. September 1985.
12
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VENT TO
ATMOSPHERE
NIXTOX
45% KOH
DMSO
PEG
SOIL
HEAT
COOLING
REACTOR
IX-
3-SCREEN
SIEVE
CONDENSATE
HOLDING TANK
SOLIDS
DRAINED
REAGENT HOLDING
HOLDING
NOTE: ITEM NO. 7A REPRESENTS REACTOR CONTENTS PRIOR TO HEATING
ITEM NO. 7B REPRESENTS REACTOR CONTENTS AFTER HEATING
TOTAL REACTOR CAPACITY: 4.6 fl3
WORKING REACTOR CAPACITY: 2.76 ft3
o
©
©
©
©
©
©
©
©® *©
©• ©
©
TOTAL SOIL
107.7
-
_
-
-
-
107.7
96.9
-
_
9Q.9
DRY SOIL
66.9
-
_
-
-
-
96.9
-
-
_
-
WATER IN SOIL
10.6
-
-
-
-
-
10.8
-
10.8
_
-
TOTAL KOH
-
35.9
-
-
-
35.9
35.9
16.2
-
8.1
8.1
DRY KOH
-
ie.2
-
-
-
16.2
16.2
-
-
_
-
WATER IN KOH
-
19.7
-
19.7
19.7
-
1S.7
-
-
DMSO
-
-
35.0
-
-
35.9
35.9
35.9
-
17.8
17.8
PEG
-
-
-
18.0
-
18.0
18.0
18.0
-
9.0
9.0
TMH
-
-
-
18.0
10.0
18.0
18.0
-
9.0
9.0
TOTAL WATER
10.8
19.7
-
-
-
19.7
30.5
0
30.5
15.3
15.3
HEATING UNIT (u)
50,000 Blu/hr
50 fcyhr STEAM
CONDENSER /O.
UNIT viy
30,000 Btu/hr
ALL VALUES ARE pound* PER BATCH REACTOR
Figure 3-1. Schematic of unit operations in a treatment process.
13
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of each piece in the overall process. They should also include the manu-
facturer (supplier).
The equipment specifications usually include a waste feed system unless
the feed is manual or the technology involves an in situ process. If a waste
feed system does exist, the Developer should characterize it similarly to the
rest of the process (i.e., supply unit dimensions, method of operation,
construction materials, etc.). The EPA PM should check all piping, equip-
ment, and instrumentation specifications for waste, reagent, and product com-
patibility.
A pollution control system may be required to control volatile emis-
sions, particulates, runoff, seepage, releases, etc. The complexity of such
controls varies with the process. An in situ soil treatment might require
control of runoff in the event of a heavy rain. Such control might consist
of a proper slope of the soil plot and a runoff collection system. Pollution
controls on a pressurized pilot-scale reactor, however, may include a con-
denser followed by a molecular sieve and activated carbon to collect and
treat emissions. The EPA PM should review the pollution controls to ensure
compliance with applicable regulations.
The utilities necessary to conduct the demonstration should be specified
in the design so that the site can be adequately prepared for the demonstra-
tion. Specific requirements for water, electricity, steam, etc, must be
addressed in the actual equipment design, such as specific voltage and wat-
tage requirements, or required water supply flow rates.
The Developer's design should include a site layout showing the location
and approximate size of each piece of equipment, as well as support equipment
and supplies (e.g., a lab trailer, office trailer, decontamination station,
waste storage area, drums, tanks, parking area). The layout also should in-
clude the contaminated and the uncontaminated zones, if they are sufficiently
defined at this stage.
While demonstrating performance of a treatment technology is the primary
objective of the demonstration program, another important objective is to
estimate the cost of the technology. The summary in Table 3-1 is an example
of a cost estimate for an electric arc furnace (EAF) recycling process. This
estimate presents both capital and operating costs for three plant sizes.
14
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TABLE 3-1. CAPITAL AND OPERATING COSTS FOR EAF RECYCLING PROCESSc
Cost component
Small facility Medium facility
costs costs
Large facility
costs
Capital (Installed) Costs
Fixed capital investment
(FCI)
Working capital costs
(15% of FCI)
TOTAL CAPITAL COST
Annualized Costs
Annualized capital cost
(5 yr at 12%)
Operating costs
Raw maternal
O&M labor0
Electricity
Water
O&M supplies
(10% of FCI)
Lab charges ($l/ton)
Miscellaneous costs/
credits
Local taxes and insur-
ance (3% of FCI)
Plant overhead (15% of
operating costs)
Home office management
and administration (25
of operating costs)
Credit for sale of high
zinc dust ($10/ton)
Transport of high zinc
dust
TOTAL ANNUALIZED COST
Unit cost for processed
dust
$70,000
10,500
$80,500
$22,500
0
33,280
2,000
250
7,000
1,000
2,100
6,500
10,900
(10,000)
10,000
$85,530/yr
$85.50/ton
$130,000
19,500
$149,500
$ 41,700
0
33,280
6,000
750
13,000
3,000
3,900
8,400
14,000
(30,000)
30,000
$124,030/yr
$41.34/ton
$200,000
30,000
$230,000
$ 64,220
0
66,560
18,000
2,250
20,000
9,000
6,000
17,370
28,950
(90,000)
90,000
$232,350/yr
$25.82/ton
Adapted from E. R. Krishnan
Includes onsite supervision
et al. PEI Associates, Inc.
and clerical, 2080 h/yr/person at $16/h.
15
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Capital costs generally include engineering design, equipment purchase, and
installation/fabrication; operating costs include operation and maintenance.
Where possible, life-cycle cost estimates should be included.
The following is an example of a technology description:
"Chemical Treatment of Chlorinated Organics in Soils Using Potassium
Polyethylene Glycol (KPEG)"
Chlorinated dioxins (such as TCDD) and polychlorinated biphenyl {PCB)
wastes and contamination of water and soils are a serious concern in
many areas of the country because of the high toxicity of these com-
pounds and the very limited treatment or disposal options currently
available for them. Some laboratory-scale research has been completed
on a chemical destruction technique to dechlorinate dioxins and PCBs and
render them far less hazardous. The chemical decontamination process
has been successfully demonstrated on a small scale on contaminated
soils. The process involves the addition of potassium polyethylene
glycol (KPEG) to contaminated soils. The chlorinated dioxins or PCBs
dechlorinate to form water-soluble compounds under relatively mild
conditions of temperature and pressure. The soils are then washed
counter currently with water to remove the soluble dechlorinated prod-
ucts and to recover the reagents.
The basics of chemical soil decontamination are straightforward. Con-
taminated soil is mixed with an alkaline reagent consisting of potassium
hydroxide in a solution of mixed polyethylene glycol and dimethyl sulf-
oxide. The reagent mixture dechlorinates the aryl halide to form a PEG
ether, which may further degrade to form a totally dechlorinated spe-
cies. This mechanism is shown in Figure 3-2. A schematic diagram of
the process is shown in Figure 3-3.
3.2 TESTING APPROACH
The Test Plan should identify all the controls and variables in the
process and indicate any variables to be tested during the demonstration. In
a chemical treatment technology, reagent ratios and pressure may be held
constant while reaction vessel temperature is varied. Or the reagent mixture
may be changed while all other variables (temperature, pressure, mixing time,
etc.) are held constant. By manipulating only one variable at a time and
collecting sufficient performance data for that particular scenario before it
is changed, reliable data or system performance will be generated.
The Test Plan should define the range of performance for each variable
tested; if temperature is a variable, the plan should state (for example)
that Runs 1 through 10 will be conducted at 100°C, Runs 11 through 20 will be
16
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CI
ROH+KOH DMSO
CI
R0K+ ioi 10
crvVVrci
DMSO
~
ROK + HOH
CMC *kcl
FIGURE 3-2. PROPOSED REACTION MECHANISM.
The soil/reagent mixture is heated to 30°C to 150°C, and mixing takes
place until the reaction has been completed. At the end of the reac-
tion, reagent is recovered by decantation and washing the soil with
several volumes of water. The decontaminated soil is then discharged
and the reagent is recycled for reuse, as shown in the process diagram
in Figure 3-3.
MAKEUP WATER
WATER
VAPOR
COfsDENSCR
CONTAMINATED
SOIL
MIX
REACT ,
DECANT
REAG£NT
HEATER
~ FIRST
WASH
SECOND
WASH
—r
T"
CLEAN
SOIL
FIGURE 3-3. PROCESS DIAGRAM.
The KPEG treatment is capable of detoxifying or destroying a wide
variety of halogenated organic compounds, including PCBs, ethylene
dibromide, chlorinated dioxins, and chlorinated dibenzofurans;
exceptions include hydroxylated aromatic compounds such as
pentachlorophenol, hexachlorophene, and phenols and related compounds
such as 2,4-D and 2,4,5-T.
17
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conducted at 140°C, and Runs 21 through 30 will be conducted at 180°C. Rang-
es for control parameters also should be defined. If pressure is identified
as a constant, the plan should state for example that the process will be run
at a slight pressure of 5 to 10 psi. It should also state the basis for
concluding that operation within a defined pressure range does not signifi-
cantly affect the process so that the EPA PM can judge whether or not such a
factor is indeed a control parameter.
The Test Plan should list the controls, the variable to be changed, and
the expected range of performance for each test run in the field demonstra-
tion.
Sampling and analysis are key steps in the SITE Program demonstrations.
Every unit operation input and output should be sampled so that changes in
the process can be characterized. Figure 3-4 presents a simplified example.
Samples would be taken at each point identified by a number. In some cases,
the reactor must be sampled many times. If a reaction occurs in steps or
over a period of time, it may be advisable to take samples at periodic inter-
vals (e.g., every 15 minutes or every hour) to provide sufficient data for
development of a reaction curve. If progressive dechlorination occurs,
analysis of the concentrations of each of the subsequent dechlorination
intermediates would provide valuable data on the kinetics of the process that
might be used later for further optimization of the process. Operating
parameters (i.e., temperature, pressure, mixing speed, etc.) also should be
monitored so that data on all controls and variables are recorded and docu-
mented. Ambient air monitoring at most field demonstrations is also recom-
mended as a safety measure for determining any potential exposure of the
field crew to air toxics. The specific parameters monitored will vary with
the technology; however, the main contaminants generally should be measured,
as well as the more general indicators such as volatile organic compounds
(VOCs) or particulates.
3.3 FIELD DEMONSTRATION PREPARATION
The Developer has primary responsibility for the field demonstration,
and the EPA PM is responsible for overseeing these efforts. The Developer
will identify the resources required for conducting the field demonstration
18
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TO ATMOSPHERE
LIQUIDS
REAGENTS
WASH
MIXER
LIQUIDS/SOLIDS
, SEPARATOR
RECYCLE
LIQUIDS
SOLIDS
DISPOSAL
CARBON FILTER
CONDENSER
REACTOR
DISPOSAL
Figure 3-4. Location of sampling points in a hypothetical
chemical treatment process.
TO
DISPOSAL
19
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and will document them in the form of a "needs list." The needs list can be
divided into site-preparation needs and technology-demonstration needs.
The site preparation needs list should identify the items or site char-
acteristics necessary for the performance of a technology demonstration. The
list might include such items as:
1) Suitable waste supply. Quantity and quality of waste needed and
any seasonal restrictions on obtaining or using the waste should be
defined.
2) Access roads sufficient for the equipment.
3) A firm and level site for all equipment.
4) Availability and proximity of necessary support services or skills.
5) Site security to prevent accidents and to minimize vandalism.
The technology-demonstration needs list can be developed under the main
categories of utilities, facilities, equipment, and supplies. The technology
demonstration needs list includes items such as the following:
1) Utilities
° Fuel (liquid propane, natural gas, diesel oil, gasoline,
kerosene, etc.)
° Water (city, well, or bottled drinking water; deionized water;
softened water; etc.)
° Electricity (utility-supplied or generator-supplied, 110V,
220V, or 440V, etc.)
° Telephone (portable or stationary)
2) Facilities
° Waste storage and handling areas (sheds, bermed/lined pits,
etc.)
° Residual storage area (bermed/lined pits, etc.)
° Mobile or stationary laboratory
0 Personnel changing, eating, and showering areas (lockers,
showers, etc.)
° Office
° Decontamination station
° Secure storage area for equipment and supplies
° Appropriate on- or offsite disposal facilities (landfills,
incinerators, etc.)
20
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3) Equipment:
° Heavy equipment (bulldozers, cranes, backhoes, drum grapplers,
forklifts, etc.)
0 Experiment-related equipment (reactors, agitators, tanks,
drums, dumpsters, conveyors, scaffolding, scales, etc.)
0 Sampling and analytical equipment (samplers, gas chromato-
graph, atomic absorption spectrophotometer, pH meter, balance,
etc.)
° Safety equipment (shower, eye-wash station, fire extinguisher,
etc.)
4) Supplies:
° Reagents
° Chemicals
0 Personal protective equipment
0 Sampling bottles, labels, forms, notebooks, etc.
° Office supplies
The EPA is responsible for all site preparation, including but not
limited to such things as gaining permission to enter the site, arranging for
physical access to the site, utility hookups, secure storage areas for equip-
ment, providing a cleared and level work site, and conducting any necessary
excavations to bring contaminated waste to the technology demonstration unit.
In addition, the EPA must obtain waste for pretreatment and conduct sampling
and analysis to characterize the waste. The Developer will estimate types
and quantities of wastes any byproducts for which EPA must arrange disposal.
EPA will arrange for suitable storage, treatment, and disposal of all residues
or byproducts.
3.4 FIELD DEMONSTRATION IMPLEMENTATION
The Developer is responsible for the performance and staffing of this
task, and the SITE Contractor is responsible for overseeing it for the EPA.
The task includes setup, shakedown, test runs, decontamination, and demobili-
zation of the field demonstration equipment. The EPA will provide the staff
for monitoring and evaluating the demonstration.
When the Developer's team arrives at the site, the EPA PM will establish
routines for implementing the health and safety, sampling and analysis,
QA/OC, and documentation procedures as explained in the plans, and review
them with the field crew. This review by the EPA PM is conducted in addition
to OSHA-required training.
21
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The Contractor will set up a decontamination station and provide appro-
priate supplies, the Developer will be responsible for proper decontamination
of its personnel and equipment, and the EPA will supervise decontamination
operations.
The final aspect of the field demonstration will be demobilization of
equipment and personnel. Rented supplies and equipment will be returned by
appropriate parties. EPA will return their own rental equipment. A check-
list should be developed for all major equipment to ensure protection of the
equipment during demobilization.
3.5 DOCUMENT TESTS AND PREPARE REPORTS
Inasmuch as the overall objective of the SITE Program is to provide
valid performance and cost data on the field demonstrations, the written
documentation and final reports will serve as the "product" of the Program.
The EPA has primary responsibility for documentation of the technology
demonstration. The EPA Contractor will prepare data sheets specific to the
tests to be run. Monitoring data sheets, sampling data sheets, and analyti-
cal results sheets be prepared and filled out for each run. In addition,
each member of the field team will be issued a numbered daily logbook in
which to document test conditions, samples taken, problems encountered,
corrective actions taken, results obtained (if known at the time), and pro-
cedures. The EPA will document the extent to which all provisions in the
Test Plan, Health and Safety Plan, and QA Project Plan are followed. Any
deviations from the approved plans must be documented, along with the reasons
for these deviations and any known or likely impacts on the process. The
daily logbooks should describe any equipment or instrumentation failures or
operating difficulties and document all instruments readings during process
operation. Pictures, slides, and/or video tapes will be prepared as appro-
priate, and will be made part of the permanent documentation file.
The EPA will prepare data summaries with all monitoring and analysis
results to be used ultimately in the comprehensive reports prepared by the
EPA. The technical report should address, at a minimum, the following
topics:
22
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0 Description of technology
0 Objectives of field demonstration
0 Design
0 Operations
0 Results - performance
0 Results - costs
° Conclusions and recommendations
° Appendices
Test Plan
Quality Assurance Project Plan
The Technical Report will be reviewed by the EPA PM and (as directed)
others in EPA Headquarters, Regional offices, State agencies, the Developer's
firm, or other involved parties. In some instances, EPA may request a peer
review.
The review comments of various parties will be submitted to the EPA PM,
who will direct the EPA Contractor to respond to them as appropriate. The
EPA Contractor will then submit a revised final report to the EPA PM.
In addition to the technical report, EPA intends to develop an Applica-
tion Analysis Report describing the types of wastes that were treated during
the technology demonstration and the types of wastes that might be treated.
The objective is to provide information about applications of the technology
to other waste/matrix scenarios.
3.6 MANAGEMENT AND SCHEDULE
The EPA PM, the EPA Contractor, and the Developer will all participate
in the SITE Program technology demonstrations. Each party has specific
responsibilities, as summarized in Figure 3-5. Overall responsibility for
management lies with the EPA PM; however, EPA will delegate the execution of
many of the task areas to the SITE Contractor. The EPA will also be respon-
sible for approving all plans, procedures, and reports.
The Developer will design the equipment, prepare it for the field demon-
stration, and operate the process. Responsibilities also include decon-
tamination and demobilization after the demonstration is completed.
23
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EPA PROJECT MANAGER
1. Overall supervision of and responsibility (or project
2. Work with EPA Headquarters and Regional staff personnel
3. Coordinate meetings
4. Assist in meeting regulatory (state and federal) requirements
5. Approval of plans, reports, and procedures
6. Coordinate with Developer
7. Assignment of tasks to Contractor and Developer
SfTE CONTRACTOR
1.
Preparation of technology description (obtained from
Developer)
2.
Meeting site preparation needs for demonstration
3.
Preparing information for Regional needs (specifically com-
munity relations)
4.
Preparation of technology objectives
5.
Review of design
6.
Preparation of Test Plan
7.
Preparation of H & S plan
8.
Supplying on site H & S and QA/QC officers
9.
Preparation of QA/QC Plan, including sampling and
analysis procedures.
10.
Taking samples, including following chain-of-custody pro-
cedures and some analyses
11.
Training of field crew
12.
Conducting H & S daily meetings
13.
Documentation and reporting
TECHNOLOGY DEVELOPER
1.
Provide technology description to SITE Contractor and
coordinate with EPA PM
2.
Design demonstration
3.
Meet permitting and other regulatory requirements
4.
Prepare for field demonstration
5.
Pretreat feed material
6.
Operate process
7.
Decontamination and demobilization
Figure 3-5. Organization of responsibilities for field demonstrations conducted
under the EPA SITE Program.
24
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Figure 3-6 is a sample schedule to serve as a guide for developing the
specific schedule for a given demonstration. An individual project may take
more or less time than that shown in the figure, depending on such factors as
the complexity of the technology, the reaction time of the process, and the
need to obtain permits.
25
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Responsible
party
Sep Oct Nov Dec
Apr. May Jun. Jul Aug. Sep Oct. Nov. Dec
Apr Jun. Jul Aug
ro
cr>
1 Accept Developer
2 Issue Wk. Assign. #1
3 Additional Data Co faction
4 Site Requirement to Region
5 Regions Review Site Data
6 Review Regional Responses
7 HQ Evaluate Sita/Tech. Mix
S Select Site
9 Initiate Coop Agreement
10 Developer Review/Sign
11 HQ Review/Sign
12 Intergovernmental Review
13 Haaponaa to States
14 Prepare for Public Comment
15 Announce Comment Period
16 Pubic Comment Period
17 Area Reqxxtee Summary
18 negulaimy Compiance
19 Obtain Developer's Op Plan
20 Prepare QA/QC Plan
21 Pripare Health/Safety Plan
22 Prepare SarpVAnaVws Plan
23 Review QAOC Plan
24 Review Haalh/Safety Plan
25 newew Samp-/Ana lysis Plan
26 Accept QA/QC Plan
27 Accept Heath/Safety Plan
28 Accept SampVAnalysis Plan
29 Proper* Final Demo Plan
30 Review Final Demo Plan
31 Accept Fmai Demo Plan
32 (sane Wfc Awgn «2
33 Site Preparation
34 Developer Mobilzaton
35 Implement Demonstration
36 Evaluate Technology
37 Demoblzation/Dnposal
38 Prepare Draft Report
39 Prepare Final Report
<0>
<0>
(0)
(S)
(R)
(S)
(S)
(S)
(0)
P)
P)
(S)
(S)
(S)
(S)
(S)
(S)
(O)
(D)
(0)
p>
(O)
P)
P>
P>
P)
P>
P)
CO)
P)
P>
p>
(D)
P)
P)
P)
(O) ORD (Indudes Contractor)
(S) OSWER
(R) Region
(D) Developer
(G) General Administrative
Figure 3-6. Project schedule.
-------
SECTION 4
GUIDELINE DOCUMENT FOR HEALTH AND SAFETY PLAN
FOR EVALUATION OF CHEMICAL TECHNOLOGIES
4.1 INTRODUCTION
The contents of a Health arid Safety (H&S) Plan will vary from project to
project; however, it must include key elements to enable the preparation of a
complete health and safety program. The purpose of this generic H&S Plan is
to provide a framework for the formulation of a site- or project-specific H&S
Plan. It is important to note that any contractor is responsible for the
health and safety of his/her employees; this includes medical monitoring.
4.2 PROJECT DESCRIPTION
Location
The H&S Plan should include a detailed description of the location of
the technology demonstration and the surrounding geographic area. In addi-
tion to a written description, it should include maps showing the demonstra-
tion area and the general surrounding area. These maps should highlight
roads, railroads, airports, hospitals, fire departments, and the locations of
other emergency equipment.
If the demonstration is housed indoors, the square footage of the build-
ing(s) involved in the project also must be described. If the demonstration
is slated for a specific site (i.e., a landfill), the affected area must be
designated. The description should also note such site-specific character-
istics as:
0 Adjacent buildings (or rooms).
c Presence of structures other than buildings (towers, etc.).
° Presence of other wastes or reagents (not a part of the demonstra-
tion).
27
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0 Identification of contamination and decontamination zones.
° Presence of heavy equipment dedicated to the site.
° Location of the waste to be treated.
In addition to site-specific information, the H&S Plan should consider
the surrounding area and its population. In a worst-case accident scenario,
local residents and property will be affected. This point is especially
important in an outdoor demonstration.
Process Description
A chemical process is a series of unit operations and/or unit processes,
the products (and byproducts) of which result from the following:
1. One or more chemical or physiochemical changes.
2. The extraction, separation, or purification of a product with or
without the aid of chemical reactions.
3. The preparation of a specific product from a mixture of materials
(either natural or synthetic in origin).
For the SITE Program, the chemical technology will use the waste as a
feed stream and transform the hazardous constituents of the waste into a more
desirable form.
The type of process used in the technology will affect its operation and
inherent hazards. A chemical process may be operated in either a batch or
continuous mode. In a batch process, the feed (the waste) is charged into
the system at the beginning of the process and the products are removed
simultaneously some time later.* In a continuous process, the inputs and
outputs flow continuously throughout the duration of the processing opera-
tion.*
Either type of process may be operated safely; however, a continuous
process is more difficult to control than a batch process. The lessened
degree of control can tend to compound hazards during the processing of
waste. The designated Safety Officer should note this tendency and be
familiar with the chemical process and its operations before the onsite
testing is begun.
A chemical process may use one or more of the following pieces of equip-
ment:^
28
-------
c Columns
Vessels
° Reactor
° Heat Exchangers
° Pumps and Compressors
0 Process Instrumentation
The Safety Officer should identify all process equipment used in a given
chemical technology and define any associated hazards.
4.3 PROJECT OBJECTIVES
In this section, the H&S Plan will outline the project and its objec-
tives. The project objectives should be clearly summarized early in the H&S
Plan so that users can review the H&S procedures with the objectives in mind.
All onsite personnel should be aware of the process and its operating charac-
teristics (heat, odors, noise, etc.); the number (and length) of trial runs
in the project; specific waste components; waste byproducts produced by
processing; project milestones; and the impact of this project on waste
treatment. Each worker should be oriented to the health and safety factors
pertaining to each phase of the project. All onsite personnel should be made
aware of any changes to project outlines or scope and the effect of the
changes on the health and safety procedures. Having been educated on all
aspects of the project, a worker will be better equipped to make an intel-
ligent decision in the event of an accident or emergency.
4.4 SAFE WORK PRACTICES
The major goal of a H&S Plan is to inform personnel of the techniques
and/or equipment that will guard them from site-specific hazards. Common
safe work practices are equally important during day-to-day operations. Such
safe work practices, as described in OSHA/EPA's "Occupational Safety and
Health Guidance Manual for Hazardous Waste Site Activities," include, but
are not limited to the following:
1) A daily safety meeting should be held to inform and review with
workers the activities planned for the day and the associated
safety issues.
29
-------
Eating, drinking, chewing gum or tobacco, smoking, or any practice
that increases the probability of hand-to-mouth transfer and inges-
tion of material is prohibited in any area designated as contami-
nated.
At a minimum, personnel must wash their hands and faces thoroughly
upon leaving the work area. For those undergoing higher degrees of
potential exposure, full showers (or baths) are required.
Whenever decontamination procedures for outer garments are in
effect, the entire body should be thoroughly washed as soon as
possible after the protective garment is removed and disposed of in
a proper manner.
No facial hair that interferes with a satisfactory fit of the
mask-to-face seal is allowed on personnel required to wear respira-
tors.
Contact with contaminated or suspected contaminated surfaces should
be avoided when possible. Personnel should avoid walking through
puddles, leachate, or discolored surfaces; kneeling on ground; and
leaning, sitting, or placing equipment on drums, process equipment,
or the ground/flooring.
Because some medicines and alcohol can worsen the effects from
exposure to toxic chemicals, prescribed drugs must not be taken by
personnel on duty where the potential for absorption, inhalation,
or ingestion of toxic substances exists unless specifically approved
by a qualified physician. The intake of alcoholic beverage/illegal
substance is prohibited during work hours.
All field personnel must be trained and have medical examination
verification. They also must be familiar with standard operating
procedures and any site-specific instructions and information
contained in the SITE Safety Plan.
All personnel must follow the instructions contained in the SITE
Safety Plan.
All personnel assigned to a site must be adequately trained and
thoroughly briefed on anticipated hazards, equipment to be worn,
safety practices to be followed, emergency procedures, and communi-
cations.
Any necessary respiratory protective devices and clothing must be
worn by all personnel going into areas designated as requiring such
protective equipment.
30
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12) Onsite personnel must use the buddy system when wearing respiratory
protective equipment. In the event of an accident, a third person,
suitably equipped as a safety backup, is required during initial
entries.
13) Visual contact should be maintained between pairs on site and with
safety personnel.
14) During continual operations, onsite workers should act as safety
backup to each other. Offsite personnel provide emergency assist-
ance.
15) Personnel should practice unfamiliar operations before actually
performing them.
16) Entrance and exit locations must be designated and emergency escape
routes delineated. Warning signals for site evacuation must be
established.
17) Communications (by radios, hand signals, signs5 or other means)
must be maintained between initial entry members at all times.
Emergency communications should be prearranged in case of radio
failure, necessity for evacuation of site, or other reasons.
18) For outside demonstrations, wind indicators visible to all person-
nel should be strategically located throughout the site.
19) The number of personnel and the amount of equipment in the contami-
nated area should be held to a minimum consistent with effective
site operation.
20) Procedures for leaving a contaminated area must be planned and
implemented before the site is entered. Work areas and decontamina-
tion procedures must be established based on expected site conditions.
21) Disposable time devices should be used to document and reference
times during such events as sampling, trial runs, and emergency
situations.
4.5 CONTROL
For a demonstration to proceed safely, it must be performed in a con-
trolled environment. A controlled environment means that the site is oper-
ated by a defined staff of professionals and skilled workers, including a
designated Safety Officer. Further, all activities must be organized and
implemented from a centralized command location. Finally, all site bound-
aries and perimeters must be accurately defined, and access to these areas
31
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must be tightly regulated. Enforcement of the criteria described in the
following subsections should help to ensure the completion of a safe demon-
stration .
Key Safety Personnel
During the demonstration, safety is the responsibility of the Safety
Officer. This individual has the authority to suspend the demonstration
temporarily if there appears to be a threat to health or safety. The Safety
Officer (who will have beer, selected by the EPA or its designated representa-
tives) has the authority and responsibility for the following:
0 Upgrading the level of protection when necessary.
° Requiring additional monitoring.
° Suspending operations for any health and/or safety reason.
The Safety Officer, or his/her appointed representative, will be respon-
sible for planning and execution of the overall site safety policy. He/she
will be responsible for making project-level decisions regarding safety rules
and operations.
The Safety Officer will also have primary responsibility for the follow-
ing:
1) Assuring that appropriate personal protective equipment is avail-
able and properly utilized by all site personnel.
2) Assuring that site personnel are aware of the provisions of the H&S
Plan, are instructed in the work practices necessary to ensure
safety, and are trained in planned procedures for dealing with
emergencies.
3) Assuring that personnel are aware of the potential hazards asso-
ciated with the demonstration and the site.
4) Supervising the monitoring of safety performance by all personnel
to ensure that required work practices are employed.
5) Correcting any work practices or conditions that may result in
injury to personnel or exposure to hazardous substances.
The Safety Officer or an appointed representative will plan and super-
vise specific safety activities in support of the work performed at the proj-
ect demonstration in accordance with the H&S Plan. The Safety Officer will
32
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have the authority to make changes to the H&S Plan where required by un-
foreseen, site-specific conditions.
At the demonstration site, the Safety Officer shall:
1) Conduct site monitoring of personnel hazards to determine the
degree of hazard present.
2) Determine personnel protection levels and necessary clothing and
equipment to ensure the safety of personnel.
3) Evaluate chemical hazard and weather (if applicable) information,
and recommend to the EPA PM any necessary modifications to work
plans and personnel protection levels to maintain personnel safety.
4) Monitor the safety performance of all personnel to ensure that the
required practices are adhered to.
Site Boundaries/Perimeters
The information presented here has been paraphrased from Section 6 of
the Hazardous Materials Incident Response Manual established by EPA's Office
of Emergency and Remedial Response. These guidelines were established for
investigation and cleanup of uncontrolled hazardous waste sites; however, the
same precepts are applicable to demonstrations operated under the SITE Pro-
gram. The Safety Officer must determine the applicability of these prin-
ciples based on the site and type of technology involved.
One important means of preventing or reducing the migration of contami-
nants is to delineate zones on the site where the prescribed operations are
to occur. Movement of personnel and equipment between zones and onto the
site itself should be limited by access control points. Three contiguous
zones are recommended: Zone 1: Exclusion Zone, Zone 2: Contamination
Reduction Zone, and Zone 3: Support Zone. Each is discussed in the follow-
ing sections.
3
Zone 1: Exclusion Zone --
The Exclusion Zone, the innermost of the three zones, is the area where
contamination does or could occur. All people entering the Exclusion Zone
must wear prescribed levels of protection. An entry and exit check point
must be established at the periphery of this zone to regulate the flow of
personnel and equipment into and out of the zone and to verify that the
established entry and exit procedures are followed.
33
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The outer boundary of Zone 1, called the Hotline, is established ini-
tially through a visual survey of the immediate environs of the site and a
determination of where the hazardous substances are located or where any
material has leaked or spilled. The Safety Officer also should provide
guidance for determining the boundaries and should indicate the presence of
any organic or inorganic vapors/gases or particulates in the air, combustible
gases, and radiation resulting from water and soil contamination.
Additional factors that should be considered include how much distance
is required to prevent fire or an explosion from affecting personnel outside
the zone, the physical area necessary to conduct the demonstration, and the
potential for contaminants to be blown from the area. Once the Hotline has
been determined, it should be physically secured, fenced, or well defined by
landmarks. During subsequent site operations, the boundary may be modified
or adjusted as indicated by the Safety Officer.
All personnel within the Exclusion Zone must wear the required level of
protection. Personal protective equipment is stipulated on the basis of
site-specific conditions, including the type of work to be done and the
hazards that might be encountered. Frequently, different levels of protec-
tion are justified within the Exclusion Zone. Subareas should be specified
and conspicuously marked as to whether Level A, B, or C protection is re-
quired. The level of protection is determined by the measured concentration
of substances in air, the potential for contamination, and the known or
suspected presence of highly toxic substances.
Job assignments also may influence the level of protection required in
the Exclusion Zone. For example, collecting samples from open containers
might require Level B protection, whereas Level C protection might be suf-
ficient for walk-through ambient air monitoring. The assignment of different
levels of protection within the Exclusion Zone, as appropriate, generally
allows a more flexible, more effective, and less costly operation while still
maintaining a high degree of safety.
3
Zone 2: Contamination Reduction Zone --
The Contamination Reduction Zone, which lies between the Exclusion Zone
and the Support Zone, provides a transition between contaminated and clean
34
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zones. By serving as a buffer, this intermediate zone reduces the probabili-
ty of the clean zone becoming contaminated or being affected by other exist-
ing hazards. It provides additional assurance that the physical transfer of
contaminating substances on people, equipment, or in the air is limited
through a combination of factors, including decontamination, distance between
Exclusion and Support Zones, air dilution, zone restrictions, and work func-
tions.
Initially, the Contamination Reduction Zone is considered an uncontami-
nated area. At the boundary between the Exclusion and Contamination Reduc-
tion Zones, Contamination Reduction Corridors (decontamination stations) are
established, one for personnel and one for heavy equipment. Depending on the
size of the operation, more than two corridors may be necessary. Exit from
the Exclusion Zone is through a Contamination Reduction Corridor. As opera-
tions proceed, however, the area around the decontamination station may be-
come contaminated, although to a much lesser degree than the Exclusion Zone.
The amount of contaminants present should decrease from the Hotline to the
Support Zone because of the distance involved and the decontamination proce-
dures used.
3
Zone 3: Support Zone --
The Support Zone {at the outermost part of the site), is considered a
contamination-free or clean area. Support equipment (command post, equipment
trailer, etc.) is located in this zone. Traffic is restricted to authorized
response personnel. Normal work clothes are appropriate within this zone,
but potentially contaminated personal clothing, equipment, and samples must
be left in the Contamination Reduction Zone until they are decontaminated.
The location of the command post and other support facilities in the
Support Zone depends on a number of factors, including:
0 Accessibility: Open space available, topography, location of
roads, or other limitations.
0 Wind direction: The preferred location of support facilities is
upwind of the Exclusion Zone; however, shifts in wind direction and
other conditions may be such that an ideal location cannot be based
on wind direction alone.
35
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The boundary between the Support Zone and the Contamination Reduction
Zone, called the Contamination Control Line, separates the possibly low-
contamination area from the clean Support Zone. Access to the Contamination
Reduction Zone from the Support Zone is through a control point. Personnel
entering this zone might be required to wear the prescribed personal protec-
tive equipment for persons working in the Contamination Reduction Zone.
Anyone entering the Support Zone is required to remove any protective equip-
ment worn in the Contamination Reduction Zone.
3
Command Post --
The Command Post should be located in the clean work area. Operational
activities in the office and command post include:
1) Supervision of demonstration operations.
2) Maintenance of communication, including emergencies of communica-
tion.
3) Recordkeeping (e.g., chain-of-custody records, daily logbooks,
accident reports, equipment records, H&S Plan, etc).
4) Interfacing with government agencies, medical personnel, the media,
and other interested parties.
3
Discussion of Boundaries and Work Areas —
The use of a three-zone system, access control points, and exacting
decontamination procedures provides reasonable assurance against the trans-
location of contaminating substances. This site control system is based on a
worst-case situation. Site control and decontamination procedures may be
less stringent if more definitive information is available on the types of
substances involved and the hazards they present. This information can be
obtained through air monitoring, instrument survey, and sampling, and from
available technical data concerning the characteristics and behavior of
material present.
The distance between the Hotline, the Contamination Control Line, and
the Command Post, and the size and shape of each zone must be based on site-
specific considerations. Assuring that the distances between zone boundaries
36
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are sufficient to allow room for the necessary operations, to provide ade-
quate distances to prevent the spread of contaminants, and to eliminate the
possibility of injury due to explosion or fire requires considerable judge-
ment. For long-term operations, reasonable methods (for example, air sur-
veillance and visible deterioration} would have to be developed to determine
if material is being transferred between zones and to assist in modifying
site boundaries.
The following criteria should be considered in establishing area dimen-
sions and boundaries:
1) Physical and topographical features of the site.
2) Weather conditions (if applicable).
3) Field/laboratory measurements of air contaminants and environmental
samples.
4) Air dispersion calculations.
5) Potential for explosion and flying debris.
6) Physical, chemical, toxicological, and other characteristics of the
substances present.
7) Cleanup activities required.
8) Potential for fire.
9) Area needed for conducting operations.
10) Potential for exposure.
11) Proximity to residential or industrial areas.
4.6 HAZARD EVALUATION
The evaluation of potential hazards is an important first step in secur-
ing a safe demonstration site. The exposure to one or more hazardous mate-
rials represents a significant threat to the health of both onsite personnel
and neighboring residents. After identifying all hazardous materials, the
Safety Officer must assemble pertinent toxicological, physical, and chemical
37
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data. In addition to exposure to hazardous materials, the more traditional
hazards (such as explosion, fire, and heavy equipment accidents) must be
identified and minimized to the extent possible.
Hazardous Materials
During the planning stages of a demonstration, the hazardous materials
that may be involved with the project must be inventoried. The inventory
should include every hazardous material used in the technology plus those
within the waste involved in the demonstration. The list of substances that
might be involved in a technology demonstration could number less than 10 to
more than 100. These hazardous substances may be organic or inorganic in
nature, and they may exist as a single compound or as a component in a mix-
ture of compounds. The chemical compounds used may exist in one or more
phases (solid, liquid, or gas). All of these factors must be considered when
assembling a list of chemical compounds of concern.
Each substance also must be properly identified with a label. Symbols,
numbers, and colors can be used to provide the following important informa-
tion :
0 Hazard identification
° Degree of danger it posed by exposure or contact
° Required actions should an accident or overexposure occur
If a substance is transferred from a large container to a small container,
the smaller container also must be properly labeled.
Concentrations
After completing the list of all hazardous substances involved in a
specific demonstration, the Safety Officer must establish the likely range of
concentration of each substance. Such information is necessary for designat-
ing levels of personal protection during normal operations, cleanup, and
emergency situations. In addition to concentration data, a definition of
regulatory exposure limits is needed. These limits should include, but not
be limited to, the following:
1) The OSHA permissible exposure limits (PELs) representing the time-
weighted average (TWA) exposures during an 8-hour working day in a
40-hour workweek and allowable excursions for designated periods of
38
-------
time at specified concentrations above the TWA concentrations
(providing the TWA is not exceeded during the 8-hour day). The
PELs are set forth in OSHA regulations in 29 CFR Part 1910, Subpart
Z.
2) Exposure limits recommended by the National Institute for Occu-
pational Safety and Health (NIOSH) based on criteria documents and
the January 1981 publication "Occupational Health Guidelines for
Chemical Hazards." The values by the Standards Completion Program
(SCP) recommended concentrations for IDLH (Immediately Dangerous to
Life and Health) which represent the maximum level from which an
individual could escape within 30 minutes without any escape-im-
pairing symptoms or irreversible health effects. Other TWA values
and excursion limits may also be referenced when OSHA PEL values
are not available and NIOSH has no recommended values.
3) Threshold Limit Values (TLVs) recommended by the American Con-
ference of Governmental Industrial Hygienists (ACGIH) for TWA and
excursion limits (current edition). Where available, these values
may be used when OSHA and NIOSH have no established or recommended
values.
4
Primary Hazards
It is important that all primary hazards be identified during the plan-
ning stages of a technology demonstration. An initial site survey and
review of demonstration work scope should be useful in determining hazardous
or potentially hazardous conditions. The main effort should focus on rapid
identification of the primary hazards that may affect the public, site per-
sonnel, and the environment. Of major concern are the real or potential
dangers from fire, explosion, airborne contaminants, and (to a lesser degree)
radiation and oxygen-deficient atmospheres.
4
Organic Vapors and Gases --
If known organic substances are involved and the materials could be
volatile or become airborne, measurements for organics in the air should be
made with one or more appropriate and properly calibrated survey instruments.
If it is not known whether any organic vapors/gases are present, instru-
ments such as a photoionizer (e.g., HNU Systems) or a portable gas chromato-
graph (e.g., a Foxboro Systems OVA) should be operated in the total readout
mode to detect organic vapors. If the constituents can be identified, the
readout indicates the total airborne substances to which the instrument is
responding. Identification of the individual vapor/gas constituents permits
the instruments to be calibrated to these substances and used for more spe-
cific and accurate analysis.
39
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Sufficient data should be obtained during the initial entry to map or
screen the site for various levels of organic vapors. These gross measure-
ments may be used on a preliminary basis to 1) to determine levels of per-
sonal protection, 2) establish site work zones, and 3) select candidate areas
for more thorough qualitative and quantitative studies. Very high readings
on the HNU or OVA also may indicate the displacement of oxygen or the pres-
ence of combustible vapors.
4
Inorganic Vapors and Gases --
Very few direct-reading instruments are capable of detecting and quan-
tifying nonspecific inorganic vapors and gases. Currently, the HNU photo-
ionizer has very limited detection capability, whereas the Foxboro OVA has
none. If specific inorganics are known or suspected to be present, measure-
ments should be made with appropriate instruments, if available. Colori-
metric tubes are practical only if the substances involved are known or can
be narrowed to a few.
4
Radiation --
Although many sites will not require radiation monitoring, this type of
monitoring should be incorporated into the Site Plan where radioactive mate-
rials could be present (e.g., fires at warehouses or hazardous material
storage facilities, transportation incidents involving unknown materials, or
abandoned waste sites).
4
Oxygen Deficiency --
Normal air contains about 20.5 percent by volume of oxygen. At or below
19.5 percent oxygen air-supplied respiratory protective equipment is needed.
Oxygen measurements are particularly important when work is performed in
enclosed spaces, low-lying areas, or in the vicinity of accidents that have
produced heavier-than-air vapors that could displace ambient air. These
oxygen-deficient areas are also prime locations for taking further organic
vapor and combustible gas measurements because the air has been displaced by
other substances. Oxygen-enriched atmospheres increase the potential for
fires.
4
Combustible Gases —
40
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The presence or absence of combustible vapors or gases must be deter-
mined. If readings approach or exceed 10 percent of the lower explosive
limit (LEL), extreme caution should be exercised in continuing the investi-
gation. If readings approach or exceed 25 percent of the LEL, personnel
should be withdrawn immediately. Before any onsite activities are resumed,
project personnel (in consultation with experts in fire or explosion preven-
tion) must develop procedures for continuing operations.
4
Visual Observations --
While on site, the project team should make visual observations to
assist in the evaluation of site hazards (e.g., dead fish or animals; land
features; wind direction; labels on containers indicating explosive, flam-
mable, toxic, or corrosive materials; conditions conducive to splash or other
contact with unconfined liquids, sludges, or solids; and other general con-
ditions).
4
Direct-Reading Instruments --
Because direct-reading field instruments will not detect or measure
all organic vapors, inorganic vapors, gases, or particulates, negative read-
ings should not be interpreted as indications of the complete absence of
airborne toxic substances. Negative results can only be verified by collect-
ing air samples and analyzing them in a laboratory.
Hazardous Substance Information Forms
After all hazardous substances and situations have been identified, this
information must be organized into a useful form. Use of a hazardous sub-
stance data sheet (HSDS) will ensure that all important information for a
given substance has been gathered. This sheet should include physical/chem-
ical properties, hazardous characteristics, safety information, and site-
specific notes. Figure 4-1 is a sample hazardous substance data sheet.
Process Safety Audit
A process safety audit should be an integral part of any hazard evalua-
tion program. The process safety audit comprises an evaluation of the de-
sign, construction, and operation of a process from a safety point of view.
One or more engineers (not involved with the demonstration) should review
both process drawings and equipment in a pipe-by-pipe, valve-by-valve inspec-
tion that includes:
41
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NAME OF SUBSTANCE:
COMMON:
I. PHYSICAL/CHEMICAL PROPERTIES:
Normal Physical State: Cas
Molecular Weight
Density
Specific Gravity
Solubility: Water
Solubility:
Boiling Point
Melting Point
Vapor Pressure (mmHg)
Vapor Density
Flash Point OC/CC
Other:
CHEMICAL:
Li qui d
Solid
e
gm/ml
/ C
/ c
/ C
/ C
/ C
/ C
/ c
/ C
SOURCE
2. HAZARDOUS CHARACTERISTICS
A.
B.
TOX 1COLOG1CAL HAZARD
HAZARD
1nhalation
Yes
No
1ngest i on
Yes
No
Skin/Eye Absorption
Yes
No
Skin/Eye Contact
Yes
No
Carci nogenic
Yes
No
Teratogenic
Yes
No
Mutagenic
Yes
No
Aquatic
Yes
No
Other:
Yes
No
FIRE HAZARD
HAZARD
Combusti bi1i ty
Yes
No
Toxic Byproducts
Yes
No
Other:
Yes
No
Yes
No
Flammable/Explosive
Yes
No
C.
lfl/lel
UFL/UEL
REACTIVITY HAZARD
Water
Other:
HAZARD
Yes No
Yes No
Yes No
Yes No
CONCENTRATIONS
SOURCE
CONCENTRATIONS
SOURCE
CONCENTRATIONS
SOURCE
Figure 4-1. Hazardous Substance Data Sheet.
42
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NAME OF SUBSTANCE:
D. CORROSIVE HAZARD HAZARD pH SOURCE
Acid Yes No
Base Yes No
Neutralizing Agent:
RADIOACTIVE HAZARD
HAZARD
Background
Yes
No
Alpha Particles
Yes
No
Beta Particles
Yes
No
Carnna Radiation
Yes
No
3. INCIDENT RELATED:
Quantity involved:
Release Information:
Monitoring/Sampling Recommended:
EXPOSURE RATE SOURCE
-------
1. Checking the proper sizing of piping, valves, fittings, etc.
2. Checking to ensure the proper use of materials for construction.
3. Checking to ensure that all conditions described on the as-built
drawings actually exist on site.
4. Checking to ensure the proper installation of all process equipment.
5. Checking to ensure that process equipment is properly plumbed
(i.e., inlet piping is connected to pump inlet and outlet piping is
connected to pump outlet).
6. Checking to ensure that all Federal, State, and local regulations
are met concerning safety, fire, and other codes.
Safety audits should be tailored to meet the individual needs of a given
technology. They should be conducted on a regular basis, and records from
each audit should be kept on file.
4.7 PERSONAL PROTECTION EQUIPMENT
All onsite personnel must wear protective equipment when involved in
activities in areas where known or suspected atmospheric contamination,
vapors, gases, or particulates may be generated or when such activities could
result in direct contact with skin-affecting substances. Full-face-piece
respirators will protect lungs, gastrointestinal tract, and eyes against
airborne toxicants. Chemical-resistant clothing will protect the skin from
possible contact with skin-destructive and/or absorbable chemicals. As
always, good personal hygiene will limit or eliminate the ingestion of mate-
rials by unsuspecting workers.
The Safety Officer (or his designated representative) is responsible for
ensuring the health, safety, and efficiency of the team. He/she will deter-
mine the level of personal protection necessary for the health and safety of
the team based on many criteria, some of which are also used in boundary
determinations. These factors include characteristics of the demonstration
process, types and amounts of hazardous waste present at the site, surface
air and wind characteristics, the location of the site relative to human
traffic, and overt signs of hazards to life and health. Any team member can
seek to upgrade the level of protection through consultation with the Safety
44
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Officer, and an agreement regarding the desired level will be reached before
the team member enters the exclusion area.
All personal protection equipment will be stored and maintained in the
Support Zone (Zone 3). In the case of an outside demonstration, equipment
may be stored in the command post to protect it against weather, vandalism,
or theft.
4
Levels of Protection
Personal protection equipment for the protection of team members against
exposure to hazardous materials is divided into four categories. The EPA
endorses the philosophy of providing a higher-than-required degree of pro-
tection until support data prove this degree is not needed, rather than
providing a lower degree of protection only to find that the support data
substantiate the need for upgraded protection. The four categories of pro-
tection are designated A, B, C, and D. Level A provides the highest degree
of protection, including the self-contained breathing apparatus (SCBA). The
degree of protection decreases from Level A to Level D. The decision to use
a given level of protection is based on the total atmospheric vapor/gas
concentration for a specific area. Table 4-1 gives a general outline of
personal protective clothing and accessories. The following subsections
present criteria for the use of this clothing and equipment for each level of
protection.
Level A Protection-
Level A protection provides the highest degree of protection of the
respiratory tract, skin, and eyes, provided the inherent limitations of the
equipment are not exceeded. Level A protection must be used when the concen-
tration of total vapors/gases in air is in the range of 500 to 1000 parts per
million (ppm) based on the following criteria:
1) Although Level A provides protection against air concentrations
greater than 1000 ppm for most substances, an operational restric-
tion of 1000 ppm is established as a warning flag for the following
reasons:
0 To evaluate the need to enter environments with unknown con-
centrations greater than 1000 ppm.
° To identify the specific constituents contributing to the
total concentration and their associated toxic properties.
45
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TABLE 4-1. PROTECTIVE CLOTHING AND ACCESSORIES
body part
PROTECTED
TYPE OF CLOTHING
OR ACCESSORY
DESCRIPTION
TYPE OF PROTECTION USE CONSIDERATIONS
Full Body
Fully-encapsulating
suit
One-piece garment. Boots
and gloves may be integral,
attached and replaceable, or
separata
Protects against splashes,
dust, gases, and vapors.
Does not allow body heat to
escape. May contribute to
heat stress in wearer, par-
ticularly if worn in conjunc-
tion with a closed-«ircuit
SCBA; a cooling garment
may be needed. Impairs
worker mobility, vision, and
communication.
Non -encapsulating
suit
Jacket, hood, pants, or bib
overalls, and one-piece
coveralls.
Protects against splashes,
dust, and other materials
but not against gases and
vapors. Does not protect
parts of head or neck.
Do not use where gas-tight
or pervasive splashing
protection is required.
May contribute to heat
stress in wearer.
Tape-seal connections
between pant cuffs and
boots and between gloves
and sleeves.
Aprons, leggings,
and sleeve
protectors
Fully sleeved and gloved
apron.
Separate coverings for arms
and legs.
Commonly worn over non-
encapsulating suit.
Provides additional splash
protection of chest, fore-
arms, and legs.
Whenever possible, should
be used over a non-encap-
sulating suit (instead of
using a fully-encapsulating
suit) to minimize potential
for heat stress.
Useful for sampling, label-
ing, and analysis opera-
tions. Should be used only
when there is a low proba-
bility of total body contact
with contaminants.
Firefighters'
protective clothing
Gloves, helmet, running or
bunker coat, running or
bunker pants (NFPA No.
1971, 1972, 1973), and
boots.
Protects against heat, hot
water, and some particles.
Does not protect against
gases and vapors, or
chemical permeation or
degradation. NFPA Stan-
dard No. 1971 specifies
that a garment consist of
an outer shell, an inner
liner, and a vapor barrier
with a minimum water
penetration of 25 lbs/in'
(1.8 kg/cm1) to prevent
the passage of hot water.
Decontamination is difficult.
Should not be worn in areas
where protection against
gases, vapors, chemical
splashes, or permeation is
required.
Proximity garment
(approach suit)
One- or two-piece
overgarment with boot
covers, gloves, and hood of
aluminized nylon or cotton
fabric.
Normally worn over other
protective clothing, such as
chemical-protective cloth-
ing. firefighters' bunker
gear, or flame-retardant
coveralls.
Protects against brief
exposure to radiant heat.
Does not protect against
chemical permeation or
degradation.
Can be custom-
manufactured to protect
against some chemical
contaminants.
Auxiliary cooling and an
SCBA should be used if the
wearer may be exposed to a
toxic atmosphere or needs
more than 2 or 3 minutes of
protection.
Blast and
fragmentation suit
Blast and fragmentation
vests and clothing, bomb
blankets, and bomb carriers.
Provides some protection
against very small detona-
tions. Bomb blankets and
baskets can help redirect
a blast.
Does not provide
hearing protection.
(continued)
46
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TABLE 4-1 (continued)
BODY PART
PROTECTED
TYPE OF CLOTHING
OR ACCESSORY
DESCRIPTION
TYPE OF PROTECTION
USE CONSIDERATIONS
Full Body
(cont.)
Radiation-
contBminBtion pro-
tective suit
Various types of protective
clothing designed to
prevent contamination of
the body by radioactive
particles.
Protects against alpha
and beta panicles. Does
NOT protect against
gamma radiation.
Designed to prevent skin
contamination. If radiation
is detected on site, consult
an experienced radiation
expert and evacuate person-
nel until the radiation haz-
ard has been evaluated.
Flame/fire retardant
coveralls
Normally worn as an
undergarment.
Provides protection from
flash fires.
Adds bulk and may exacer-
bate heat stress problems
and impair mobility.
Flotation gear
Life jackets or work vests.
(Commonly worn under-
neath chemical protective
clothing to prevent flotation
gear degradation by
chemicals.)
Adds 15.5 to 25 lbs (7 to
11.3 kg) of buoyancy to
personnel working in or
around water.
Adds bulk and restricts
mobility.
Must meet USCG standards
(4b CFR Part 160).
Cooling garment
One of three methods:
IDA pump circulates cool
dry air throughout the suit
or portions of it via an air
line. Cooling may be
enhanced by use of a vor-
tex cooler, refrigeration
coils, or a heat exchanger.
12) A jacket or vest having
pockets into which packets
of ice are inserted.
(3) A pump circulates
chilled water from a
water/ice reservoir and
through circulating tubes,
which cover part of the
body (generally the upper
torso only).
Removes excess heat
generated by worker
activity, the equipment, or
the environment.
(1) F\jmps circulating cool
air require 10 to 20 ft' (0.3
to 0.6 m') of respirable air
per minute, so they are
often uneconomical for use
at a waste site.
(2) Jackets or vests pose
ice storage and recharge
problems.
(3) Pumps circulating
chilled water pose ice stor-
age problems. The pump
and battery add bulk and
weight.
Head
Safety helmet (hard
hat)
For example, a hard plastic
or rubber helmet.
Protects the head from
blows.
Helmet shall meet OSHA
standard 29 CFR Part
1910.135.
Helmet liner
Insulates against cold.
Does not protect against
chemical splashes.
Hood
Commonly worn with a
Protects against chemical
helmet.
splashes, particulates,
and rain.
Protective hair
covering
Protects against chemical
contamination of hair.
Prevents the entangle-
ment of hair in machinery
or equipment.
Prevents hair from inter-
fering with vision and
with the functioning of
respiratory protective
devices.
Particularly important for
workers with long hair.
Eyes and
Face"
Face shield
Full-face coverage,
eight-inch minimum.
Protects against chemical
splashes.
Does not protect ade-
quately against
projectiles.
Face shields and splash
hoods must be suitably sup-
ported to prevent them from
shifting and exposing por-
tions of the face or obscur-
ing vision. Provides limited
eye protection.
*AII eye and face protection must meet OSHA standard 29 CFR Part 1910.133.
(continued)
47
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TABLE 4-1 (continued)
BODY PART
PROTECTED
TYPE OF CLOTHING
OR ACCESSORY
DESCRIPTION
TYPE OF PROTECTION
USE CONSIDERATIONS
Eyes and
Face Icont.)
Splash hood
Protacts against chemical
splashes.
Does not protect
adequately against
projectiles.
Safety glasses
Protect eyes against large
particles and projectiles.
If lasers are used to survey
a site, workers should wear
special protective lenses.
Goggles
Depending on their con-
struction, goggles can
protect against vaporized
chemicals, splashes, large
particles, and projectiles
(if constructed with
impact-resistant lenses).
Sweat bands
Prevents sweat-induced
eye irritation and vision
impairment.
Ears
Ear plugs and muffs
Protect against physiolog-
ical damage and psycho-
logical disturbance
Must comply with OSHA
regulation 29 CFR Part
1910.95. Can interfere with
communication.
Use of ear plug* should be
carefully reviewed by a
health and safety profes-
sional because chemical
contaminants could be
introduced into the ear.
Headphones
Radio headset with throat
microphone
Provide some hearing
protection while enabling
communication.
Highly desirable^ particularly
if emergency conditions
Hands and
Arms
Gloves and sleeves
May be integral, attached,
or separate from other
protective clothing.
Protect hands and arms
from chemical contact.
Wear jacket cuffs over glove
cuffs to prevent liquid from
entering the glove.
Tape-seal gloves to sleeves
to provide additional
protection.
Overgloves.
Provide supplemental pro-
tection to the wearer and
protect more expensive
undergarments from abra-
sions, tears, and
contamination.
Disposable gloves.
Should be used whenever
possible to reduce decon-
tamination needs.
Foot
Safety boots
Boots constructed of
chemical-resistant material.
Protect feet from contact
with chemicals.
Boots constructed with
some steel materials (eg.,
toes, shanks, insoles).
Protect feet from com-
pression, crushing, or
puncture by falling, mov-
ing, or sharp objects.
All boots must at least meet
the specifications required
under OSHA 29 CFR Part
1910.136 and ahould pro-
vide good traction.
Boots constructed from
nonconductive, spark
resistant materials or
coatings.
Protect the wearer
against electrical hazards
and prevent ignition of
combustible gases or
vapors.
(continued)
48
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TABLE 4-1 (continued)
BODY PART
PROTECTED
TYPE OF CLOTHING
OR ACCESSORY
DESCRIPTION
TYPE OF PROTECTION
USE CONSIDERATIONS
Foot (cont.)
Disposable shoe or
boot covers
Made of a variety of
materials. Slip over the
shoe or boot.
Protect safety boots from
contamination.
Protect feet from contact
with chemicals.
Covers may be disposed of
after use, facilitating
decontamination.
General
Knife
Allows a person in a fully-
encapsulating suit to cut
his or her way out of the
suit in the event of an
emergency or equipment
failure.
Should be carried and used
with caution to avoid
puncturing the suit.
Flashlight or lantern
Enhances visibility in
buildings, enclosed
spaces, and the dark.
Must be intrinsically safe or
explosion-proof for use in
combustible atmospheres.
Sealing the flashlight in a
plastic bag facilitates
decontamination.
Only electrical equipment
approved as intrinsically
safe, or approved for the
class and group of hazard
as defined in Article 500 of
the National Electrical Code,
may be used.
Personal dosimeter
Measures worker expo-
sure to ionizing radiation
and to certain chemicals.
To estimate actual body
exposure, the dosimeter
should be placed inside the
fully-encapsulating suit.
Personal locator
beacon
Operated by sound, radio,
or light.
Enables emergency per-
sonnel to locate victim.
Two-way radio
Enables field workers of
communicate with per-
sonnel in the Support
Zone.
Safety belts, har-
nesses, and lifelin-
Enable personnel to work
in elevated areas or enter
confined areas and pre-
vent falls. Belts may be
used to carry tools and
equipment.
Must be constructed of
spark-free hardware and
chemical-resistant materials
to provide proper protec-
tion. Must meet OSHA
standards in 29 CFR Part
1926.104.
49
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0 To make more precise determinations of concentrations of
constituents.
° To evaluate the calibration and/or sensitivity error asso-
ciated with the instrument(s).
° To evaluate instrument sensitivity to wind velocity, humidity,
temperature, etc.
2) A limit of 500 ppm total vapors/gases in air was selected as the
value at which upgrading from Level B to Level A should be consid-
ered. This concentration was selected to provide full protection
of the skin until the constituents can be identified and measured
and substances affecting the skin are excluded.
3) The range of 500 to 1000 ppm is sufficiently conservative to pro-
vide a safe margin of protection if readings should be low because
of instrument error, calibration, and sensitivity; if higher than
anticipated concentrations were to occur; and if substances that
are highly toxic to the skin should be present.
4) A range of concentrations that would provide adequate protection
from exposure to particulates has not been strictly defined. The
opportunity for exposure to high levels of airborne particulate
matter is low for most SITE demonstrations. Guidance for exposure
to airborne particulates can be found in "Threshold Limit Value for
Chemical Substances in the Work Environment," by American Confer-
ence of Governmental Industrial Hygienists, 1987-88.
Typically, high ambient air contaminant concentrations have been found
only in closed buildings when containers were being opened, when personnel
were working in the spilled contaminants, or when organic vapors/ gases were
released in transportation accidents.
In a decision concerning the requirement for Level A protection, the
negative aspects also should be considered; e.g., the higher probability of
accidents due to cumbersome equipment and, more important, the physical
stress caused by heat buildup in fully encapsulating suits. The use of Level
A protection will also increase the time required to perform most work tasks.
Level A personal protective equipment includes:
1) SCBA
2) Fully encapsulated suit
3) Coveralls, cotton, white
4) Underwear, cotton
50
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5) Gloves, surgical
6) Boots, neoprene, steel toe and shank
7) Booties, butyl rubber or PVC
8} Gloves, disposable (optional)
9) Booties, disposable (optional)
10) Hard hat (optional)
Level B Protection--
Level B protection represents the minimum protection recommended for
initial entry to an open site where the type, concentration, and presence of
airborne vapors are unknown. This level of protection provides a high degree
of respiratory protection. Skin and eyes are also protected, but a small
portion of the body (neck and sides of head) may be exposed. The use of a
separate hood or hooded, chemical-resistant jacket would further reduce the
potential for exposure to this area of the body. Level B impermeable pro-
tective clothing also increases the probability of heat stress.
A limit of 500 ppm has been selected as a decision point for a careful
evaluation of the risks associated with higher concentrations. The following
factors should be weighed carefully when downgrading to Level B is being
considered:
1) Whether a person wearing Level B protection may be required to
enter areas with unknown concentrations that could exceed 500 ppm.
2) The probability that the substance present are severe skin hazards.
3) The work involved and the increased probability of exposure.
4) The need for qualitative and quantitative identification of the
specific components.
5) Inherent limitations of the instruments used for air monitoring.
6) Instrument sensitivity to winds, humidity, temperature, and other
factors.
Level B personal protective equipment includes:
1) Pressure-demand airline respirator
2) Apron or long-sleeved jacket and pants, butyl rubber or neoprene.
3) Gloves, butyl rubber or neoprene
4) Gloves, surgical
5) Boots, butyl rubber or neoprene, steel toe and shank
51
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6) Booties, butyl rubber or neoprene
7) Coveralls, chemical-resistant (optional)
8) Underwear, cotton (optional)
9) Booties, disposable (optional)
10) Gloves, disposable (optional)
11) Hard hat (with face shield - optional)
12) Escape mask (5 minutes)
Level C Protection-
Level C skin protection is identical to Level B protection, assuming the
same type of chemical protective clothing is worn, but Level C provides less
protection against inhalation hazards. A range of background to 5 ppm above
ambient background concentrations of vapors/gases in the atmosphere has been
established as guidance for the selection of Level C protection. Air concen-
trations of unidentified vapors/gases approaching or exceeding 5 ppm would
warrant upgrading respiratory protection to a self-contained breathing appa-
ratus.
A full-face, air-purifying mask equipped with an organic vapor canister
(or a combined organic vapor/particulate canister) provides protection
against low concentrations of most common organic vapors/gases. Among the
substances against which full-face, canister-equipped masks will not protect
are substances that have very low TLV or IDLH concentrations. Every effort
should be made to identify the individual constituents and the presence of
particulates contributing to the total vapor readings of a few parts per
million before respiratory protective equipment is selected. It is exceed-
ingly difficult, however, to obtain a constant, real-time identification of
all components in a vapor cloud with concentrations of a few parts per mil-
lion at a site where ambient concentrations are constantly changing. If
highly toxic substances have been ruled out, but ambient levels of a few
parts per million persist, one should not assume that the wearing of only a
self-contained breathing apparatus is sufficient. The continuous use of air-
purifying masks in vapor/gas concentrations of a few parts per million pro-
vides reasonable assurance that the respiratory tract is protected, as long
as the absence of highly toxic substances has been confirmed.
52
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Level C personal protective equipment includes:
1) Full-face respirator (appropriate cartridge must be selected)
2) Escape mask (optional)
3) Gloves, butyl rubber or neoprene
4) Gloves, surgical
5) Boot, butyl rubber or neoprene, steel toe and shank
6) Booties, butyl rubber or neoprene (optional)
7) Coveralls, chemical-resistant (optional)
8) Underwear, cotton (optional)
9) Booties, disposable (optional)
10) Gloves, disposable (optional)
11) Hard hat (with face shield - optional)
12) Splash-proof goggles (optional)
Level D Protection-
Level D protection should be used only in ambient settings, and should
be chosen only after laboratory analysis has verified that ambient or back-
ground conditions exist.
Level D equipment includes:
1) Boots/shoes, safety leather or chemical-resistant, with steel
toes
2) Safety glasses (optional)
3) Hard hat (optional)
4) Full-face respirator (readily available) (optional)
5) Escape mask (optional)
6) Work gloves (optional)
5
Basic Personal Protective Equipment for Chemical Technologies
The preceding subsections have covered the use of personal protective
equipment for scenarios where chemicals are or have been released to the
environment in an uncontrolled manner. Numerous chemical technologies in-
volve processes that operate in a closed loop (closed to the environment)
format. Just as a chemical processing area is different from a hazardous
waste site, the needs for personal protective equipment are also different.
53
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The general types of protection for a chemical processing area include:
1) Ear plugs and ear muffs
2) Spectacles, goggles, and face shields
3) Safety helmets (hard hats)
4) Gloves
5) Boots
Hearing Protection-
Hearing loss is one of the least obvious health problems associated with
chemical processing. All site personnel must be made aware of the hazards of
high noise levels from the operations of pumps, compressors, mixers, etc.
Regulations established by OSHA require that workplace noise exposure levels
not exceed 85 dB.
Eye and Face Protection-
Protective eye wear is probably the most important of all the personal
protective equipment. Glasses worn for everyday use are not suited for a
processing environment. Regulations established by OSHA require that appro-
priate safety eye wear conform to ANSI test standards. Materials of con-
struction include heat-treated glass or thermoplastics (e.g., polycarbonate).
Head Protection-
Safety helmets protect the head from Injuries caused by the impact or
penetration of falling objects. They also provide some degree of protection
from high voltage shock and burns. A safety helmet consists of a hard resil-
ient shell and a suspension system. Safety helmet shells may be constructed
of plastic, fiberglass, polyester resins, or aluminum. The material selected
will depend on the working environment. For example, a polyethylene helmet
will offer a reasonable degree of protection from attack by various solvents.
Most suspension systems are made of a woven nylon webbing and plastic system.
Safety helmets are classified by ANSI as providing A, B, or C safety
protection. Class A helmets reduce the impact of falling objects and offer
limited voltage protection. Class B helmets are designed to reduce the
danger of exposure to high voltages. Class C helmets offer no electrical
protection and should only be used in situations where the hazard potential
is minimal.
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Hand Protection-
Hand protection (gloves), one of the oldest forms of personal protection
equipment, falls into two major categories: 1) that which protects the
worker from hazards, and 2) that which protects the process from outside
contamination. The gloves must be able to protect workers from chemical
exposure, cuts, abrasion, vibration, and electrical hazards.
Foot Protection-
Safety boots (or shoes) are used to protect personnel from injuries
resulting from falling objects, stepping on sharp objects, and objects rol-
ling over the foot. They can also provide protection from exposure to bio-
logical/chemical hazards, slipping, heat (or cold), and electrical (or static
electricity) hazards. Protective footwear must be used in wet environments,
especially where asbestos or known carcinogens may be encountered.
4.8 EDUCATION AND TRAINING
OSHA requires that all hazardous waste operators receive from 24 to 48
hours of training before being permitted to engage in hazardous waste opera-
tions that could expose them to safety and health hazards (29 CFR Part 1910,
Federal Register, Volume 51, No. 244, December 19, 1986). The Developer must
ensure that its own field staff are properly trained and that they partici-
pate in a medical surveillance program. The SITE Contractor is responsible
for training its own field staff and for ensuring the adequacy of the train-
ing of all demonstration participants.
An additional part of the training will involve the EPA PM's review of
the following procedure with the SITE Program technology evaluation field
staff: health and safety; sampling and analysis; QA/QC and operating proce-
dures; and equipment assembly, startup, shakedown, and disassembly proce-
dures.
Equipment
Primary personnel with an alternate backup should be trained in the use
of any and all task-related equipment. This type of equipment may include:
1) Material-handling devices
2) Process instrumentation
55
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3) Monitoring devices
4) Power and hand tools
5) Heavy equipment (i.e., forklifts, skid movers, etc.)
In addition to work-related training, all personnel should be trained in
the use of personal protective equipment, in the performance of primary
first-aid functions, and in site evacuation procedures.
Safe Practices/Procedures
The topic of safe practices/procedures is site- and task-specific.
Personnel working in proximity to chemical processing equipment should be
sensitive to the following conditions:
1) Unusual buildup of localized heat. This situation is often a
precursor to explosion or fire. Supervisory personnel should be
notified of this condition immediately.
2) Unusual or strained sound from pumps or motors. This may indicate
the clogging or freezing of equipment. Supervisors should be
notified immediately.
3) Unusual or strong odors. Although chemical processes may be res-
ponsible for mild odors, unusual or stronger-than-normal odors may
indicate that a reaction vessel, pipe, pump seal, etc. is leaking.
4) Leaking pipes. Chemical processes may require the use of overhead
process or utility piping. Thus, leaking pipes may drip hazardous
materials on unsuspecting site personnel.
5) Unusual hot or cold surfaces. Large amounts of heat may have to be
added or removed from some chemical processes. Extreme care should
be used around hot or cold surfaces.
6) Pressurized vessels. In some chemical processes, reaction vessels
may be required for operation at pressures in excess of 100 psi.
Extreme care should be used when work is done near pressurized
vessels or pipes.
Advanced First Aid
Situations may arise that require the use of advanced first aid. The
Safety Officer or his representative should be trained in these procedures.
Site personnel should be discouraged from performing advanced first aid
techniques unless they demonstrate prior knowledge and training in this area.
The misapplication of advanced techniques can cause further harm to an in-
jured person.
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Chemical Education
Chemical education for onsite personnel should be developed on the basis
of those chemicals involved in the technology demonstrated. The extent of
individual training should vary with the degree of potential hazard or
exposure. All new employees must be trained promptly, and all personnel (new
and old) should be retrained at regular intervals.
Training sessions (or meetings) must address the following issues:
1) A list of all chemicals an individual is likely to encounter in the
course of a technology demonstration.
2) A brief discussion of the chemicals and their properties.
3) How to identify each of the chemicals.
4) The effects of uncontrolled exposure and how to identify uncon-
trolled exposure.
5) Procedures for reporting a chemical exposure.
6) Protective measures that must be followed to prevent exposure.
Onsite personnel must be trained to read and understand labels and
material safety data sheets (MSDSs). The training sessions should outline
the basic points of any applicable Federal, State, or local right-to-know
laws. Each program should be tailored so that workers learn about the chemi-
cals with which they will work directly.
4.9 COMMUNICATION PROCEDURES
This section outlines communication needs and procedures during normal
operations and during emergency conditions. In the event of an emergency,
the command post must request outside assistance, regardless of site condi-
tions.
Radio Communications
Radio communication between work areas enables instantaneous transfer
information during trial runs of the technology. Process workers can also
use the radio to request additional waste or processing reagents, consult
with engineers in the command post, ask for emergency aid, monitor safety and
progress, and solve minor problems.
57
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Alarm Systems
The alarm system should provide warning to personnel in all areas.
Warning devices, such as hand-held horns, should be placed in all work areas.
Chemical processes for which such process alarms should be considered might
exhibit one or more of the following characteristics:
1) The potential for rapid heat generation, resulting in explosion or
fire.
2) Processes that are sensitive to changes in pH. Changes in pH might
change the process chemistry and thereby generate unwanted or
dangerous products.
3) Processes that require thorough mixing. The lack of mixing might
lead to conditions similar to those above.
4) Processes using reagents that are extremely corrosive or reactive.
In addition, automatic alarms should be assigned to those process para-
meters (temperature, pH, etc.) that have an impact on normal operations in
order to warn onsite personnel of operational problems as well as emergency
conditions.
Hand Signal
Hand signals should be established as a backup measure in the event of
radio failure. All site personnel should be trained in the use of sight-
specific hand signals, to be presented and reviewed regularly by the Safety
Officer.
Disposable Timepieces
Advances in computer chip technology have enabled the manufacture of
small, lightweight, disposable timepieces. These timepieces should be placed
on logbooks and personal protection suits so that site personnel can document
the time that specific events (sampling, etc.) take place and be aware of
workshift changes or breaks. The use of such timepieces should increase the
efficiency of a project.
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4.10 DECONTAMINATION PROCEDURES4
Standard Level and Appropriate Decontamination Protocols
All site personnel must go through appropriate decontamination proce-
dures before leaving the site. Decontamination areas should be set up in
appropriate zones, and receptacles should be provided for all disposable
clothing. Conventional trash cans lined with heavy-duty polyethylene trash
bags should be used for this purpose. Wash tubs containing a detergent-water
solution or an appropriate decontamination solution and soft-bristle brushes
should be used to decontaminate reusable personal protective clothing and
boots. After the detergent-water washing, an intermediate rinse is applied
when applicable. Clean potable water should be used for the final rinsing.
Monitoring equipment should be brushed to remove any obvious contamina-
tion. All heavy equipment must be decontaminated before it is removed from
the site. This should include manual removal of gross contamination with
shovels, etc., followed by a steam or high-pressure wash; particular atten-
tion should be given to tracks, wheels, and undercarriages.
The wash waters used and all disposable items should be collected for
disposal in accordance with applicable State and Federal regulations and
policies.
Decontamination procedures are based on the level of personal protection
equipment being worn and the degree of exposure. As a general rule, the
personnel who perform decontamination activities are outfitted in one level
of protection below that worn by the personnel being decontaminated; i.e., if
personnel entering the decontamination line are outfitted with Level B pro-
tection equipment the decontamination personnel would normally wear Level C
equipment. Higher or lower levels of protection for decontamination person-
nel may be determined in the field based on the types of contaminants (if
any) found, air monitoring, results, etc.
Decontamination Solutions
Decontamination solutions are prepared to react with, neutralize, or
remove physically specific contaminants at a site. All such solutions should
be individually marked and coded. Only trained personnel should administer
decontamination procedures. All decontamination solutions and rinse waters
should be collected for proper disposal. The following are four examples of
59
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decontamination solutions:
1) Light contamination: A detergent-based solution.
2) Organic contamination: A detergent-based solution.
3) Acid and alkali contamination: A trisodium phosphate-based solu-
tion.
4) Organophosphate or cyanide contamination: A calcium hypochlorite-
based solution.
Emergency Decontamination
It is difficult to outline procedures that deal specifically with emer-
gency situations because the responses of man and machine during such condi-
tions cannot be predicted. A high percentage of emergencies will be medical
in nature; thus, decontamination must be improvised to adapt to the emer-
gency.
The decontamination effort may aggravate or cause more serious health
effects. If prompt life-saving first aid and medical treatment are required,
decontamination procedures should be omitted. Whenever possible, site per-
sonnel should accompany contaminated victims to the medical facility to
advise on matters involving decontamination.
Physical injuries can range from a sprained ankle to a compound frac-
ture, from a minor cut to massive bleeding. Depending on the seriousness of
the injury, trained response personnel may give treatment at the site. For
more serious injuries, additional assistance may be required at the site or
the victim may have to be treated at a medical facility.
Lifesaving care should be instituted immediately with no consideration
being given to decontamination. The inured person's outside garments may be
removed (depending on the weather) if such removal does not cause a delay,
Interfere with treatment, or aggravate the problem. Respirators and backpack
assemblies must always be removed. Fully encapsulating suits or chemical -
resistant clothing can be cut away. If the outer contaminated garments can-
not be safely removed, the individual should be wrapped in plastic, rubber,
or blankets to prevent contamination of the inside of an ambulance and the
medical personnel. In this case, outside garments would be removed at the
medical facility. No attempt should be made to wash or rinse the victim at
the site unless the individual is known to have been contaminated with an
60
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extremely toxic or corrosive material that could also cause severe injury or
loss of life. In the case of minor medical problems or injuries, the normal
decontamination procedure should be followed.
Heat-related illnesses range from heat fatigue to heat stroke. When
heat stroke (the most serious of these illnesses) occurs, treatment must be
prompt to prevent irreversible damage or death. Protective clothing may have
to be cut off. Less serious forms of heat stress also require prompt atten-
tion, or they may lead to a heat stroke. Unless the victim is obviously
contaminated, decontamination should be omitted or minimized and treatment
begun immediately.
Injuries resulting from exposure to chemicals can be divided into two
categories:
1) Injuries from direct contact, such as acid burns or inhalation of
toxic chemicals.
2) Potential injury due to gross contamination of clothing or equip-
ment.
If a person has inhaled contaminants, only qualified physicians can ren-
der treatment. If the contaminant is on the skin or 1n the eyes, immediate
measures must be taken to counteract the substance's effect. First aid
treatment usually consists of flooding the affected area with water; however,
for a few chemicals, water may cause more severe problems.
When protective clothing is grossly contaminated, contaminants may be
transferred to treatment personnel or the wearer and cause injuries. Unless
severe medical problems have occurred simultaneously with the splashes,
protective clothing should be washed off as rapidly as possible and carefully
removed.
General Decontamination Protocol and Equipment
Decontamination procedures may have to be adapted to meet conditions
found at the site. Certain conditions can intensify or lessen the degree of
decontamination. Adaptation of decontamination procedures should be based on
the following factors:
1) Type of Contaminant. The extent of personnel decontamination de-
pends on the effects the particular contaminant involved has on the
body. All contaminants do not exhibit the same degree of toxicity
(or other hazard). Whenever it is known or suspected that person-
nel could become contaminated with highly toxic or skin-destructive
61
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substances, a full decontamination procedure should be followed.
If less hazardous materials are involved, the procedure can be
downgraded.
2) Amount of Contamination. The amount of contamination on protective
clothing usually can be determined visually. If the clothing is
badly contaminated, thorough decontamination is generally required.
3) Level of Protection. The level of protection and specific pieces
of clothing worn determine, on a preliminary basis, the layout of
the decontamination line. Each level of protection introduces
different problems in the decontamination and doffing of the equip-
ment.
4) Work Function. The work each person does determines the potential
for contact with hazardous materials and, in turn, dictates the
layout of the decontamination line.
5) Location of Contamination. Contamination on the upper areas of
protective clothing poses a greater risk to the worker because
volatile compounds may generate a hazardous breathing concentration
both for the worker and for the decontamination personnel. The
probability of contact with skin when doffing the upper part of
clothing is also greater.
6) Reason for Leaving Site. The reason for leaving the Exclusion Zone
also determines the need for and extent of decontamination. A
worker leaving the Exclusion Zone to pick up or drop off tools or
instruments and immediately returning may not require decontamina-
tion. A worker leaving to get a new air cylinder or to change a
respirator or canister, however, may require some degree of decon-
tamination. Individuals departing the Exclusion Zone for a break,
lunch, or at the end of the day, must be thoroughly decontaminated.
7) Equipment. Selection of decontamination equipment, materials, and
supplies is generally based on availability. Other considerations
are ease of equipment decontamination or disposability. Most
equipment and supplies can be easily procured. Decontamination
equipment can include soft-bristle scrub brushes, long-handled
brushes, buckets, garden sprayers, large galvanized wash tubs,
stock tanks, children's wading pools, large plastic garbage cans,
plastic bags, and paper or cloth towels.
4.11 SITE PLAN
The site specific H&S Plan should contain the following information.
Designated Safety Officer
The site plan must contain the name, address, and phone number(s) of the
Safety Officer.
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Site-specific Information
1) Maps/directions to all areas of the demonstration site.
2) Details regarding local fire departments, including the name of the
chief, phone numbers, etc. The Safety Officer should notify local
authorities prior to starting the first test run.
3) The presence and requirements of local ambulance services. The
Safety Officer snould notify the ambulance services prior to the
first test run.
4) A list of the full complement of first aid equipment kept on site.
5) Emergency medical information, including hospitals, doctors, ambu-
lance services, emergency phone numbers, including medical facili-
ties, fire departments, utilities, etc.
6) A complete list of monitoring instruments required by site condi-
tions. This list would include explosimeters, organic vapor
meters, pH meters, etc.
7) Site-specific emergency procedures.
Medical Monitoring
All site personnel should be involved in a personal monitoring program.
This program should include a baseline physical and routine followup exams,
including:
° Occupational and general medical history
° Physical examination
° CBC and differential
° Methemoglobin
0 Blood chemistry screen
0 Urinalysis
° Blood lead
° Heavy metal screen (Cd, Hg, As)
° Stool for occult blood
° Chest x-ray
EKG
° Spirometry (screening)
° Vision screen tonometer
° Audiogram
63
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Urine phenol
Dicubaine cholinesterase
Emergency Medical Care
During each technology demonstration, the Safety Officer should ensure
that one or more onsite personnel are trained as an Emergency Medical
Technician.
4.12 REFERENCES FOR SECTION 4
1. Felder and Rousseau. Elementary Principles of Chemical Processes.
J. Wiley and Son, Inc., New York. 1978.
2. Peters and Timmerhaus. Plant Design and Economics for Chemical
Engineers. McGraw-Hill Co., New York. 1980.
3. U.S. Environmental Protection Agency. Office of Emergency and Remedial
Response Hazardous Materials Incident Response Manual. October 1987.
4. National Institute for Occupational Safety and Health. Occupational
Safety and Health Guidance Manual for Hazardous Waste Site Activities.
1985.
5. Plant Engineering. Personal Protective Equipment, A Basic Selection and
Application Guide. Jeanie Katzel, Sr. Editor. Vol. 39, Page 48-56,
October 1985.
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Section No. 5
Revision No. 1
Date: April 29, 1988
Page 1 of 64
SECTION 5
GUIDELINE DOCUMENT FOR QUALITY ASSURANCE PROJECT PLAN
FOR EVALUATION OF CHEMICAL TECHNOLOGIES
The intent of this plan is to assist the Project Manager in preparing a
Quality Assurance Project Plan (QAPP) for a specific chemical technology SITE
demonstration. Because it is structured to encompass all aspects of "Interim
Guidelines and Specifications for Preparing Quality Assurance Project Plans"
(QAMS-005/80), it should allow for the development of a QAPP that will satis-
fy all Category II requirements.
In addition to standard QAPP requirements, this plan addresses sampling
and analysis (S&A) requirements. Sampling and analyzing raw waste, interme-
diate products, final products (treated waste), and byproducts are critical
functions in a technology demonstration. These S&A guidelines should provide
a framework for the formulation of specific S&A goals.
During the development of this plan, the Developer must work closely
with the EPA (or its representative). Ultimately, the EPA (or the Contrac-
tor) will be responsible for both the sampling and analysis functions and the
quality assurance aspects of the demonstration.
Figure 5-1 shows an example QAPP approval form for a Category II pro-
ject. This form must contain the names, signature, and date of signature of
appropriate managerial and QA personnel. In addition to this approval form,
the table of contents should contain a distribution list containing the names
and titles of all pertinent managerial and QA personnel who receive the QAPP.
5.1 PROJECT DESCRIPTION
A QAPP must reflect a complete understanding of the project and its
objective. This section of the plan should provide a general description of
the project that includes the following:
65
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Section No. 5
Revision No. 1
Date: April 29, 1988
Page 2 of CT—
QUALITY ASSURANCE PROJECT PLAN APPROVAL FORM
for
HWERL Contracts/IAG's/Cooperative Agreements/ln-house Projects
Lab Workplan No: Task Start Date:
(for measurement, data gathering, anchor data generation
Project Category: activities)
OA ID No: Date QAPP Received:
Task Title:
Technical Project Officer:
Contractor:
APPROVALS:
Contractor Project/Task Manager
Signature
Date
Contractor QA Manager
Signature
Date
Affiliate Task Manager*
Signature
Date
Other (as appropriate)
Signature
Date
HWERL Technical Project Officer
Signature
Date
HWERL Branch or Staff Chief"
Signature
Date
HWERL Quality Asurance Officer Signature Date
* Approval signature is required for any ancillary sampling, analytical, or data gathering support provided by a
subcontractor or HWERL principal investigator.
** Approval signature from the HWERL Branch or Staff Chief is required for Category I, II, and III extramural projects
and for all in-house projects.
HWERL (QAPP AF)
(October 1986)
Figure 5-1. Quality Assurance Project Plan Approval Form.
66
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Section No. 5
Revision No. 1
Date: April 29, 1988
Page 3 oT 64
1) Project background. This should include a brief outline of the
project history and all parties involved with the project.
2) Experimental design of the process. The plan should include a
brief review of the demonstration process, equipment, and chemical
reagents that will be used.
3) Project data base. The plan should cover the intended use and
ultimate application of the project data. The project description
should clearly define each type of critical measurement to be made,
each type of matrix (air, water, soil, biota, etc.) to be sampled
for measurement, and each type of system condition (e.g., facility
or process controls and operating parameters) to be monitored on a
routine basis. The project description should clearly distinguish
between critical measurements and system conditions. Critical
measurements are those that have a direct impact on the technical
objectives of a project (see Quality Assurance Procedures for
HWERL, Reference 1). Sampling objectives should encompass the
collection of data required for the performance of a mass and
energy balance. Project hypotheses also should be presented.
4) Project timing. The plan should include a flow diagram or table
showing the sequence of events and the estimated completion time of
project tasks. Management tools, such as Critical Path Charts, may
be included in this section.
5) Startup and completion dates. In addition to Item 4 above, the
plan should include anticipated project startup and completion
dates. Task-specific startup and completion dates also should be
included in this section. Figure 5-2 shows a sample project sched-
ule highlighting project milestones.
The S&A Plan for a technology demonstration must address the operation
of a chemical unit to which one or more reagents are added, heat is added or
withdrawn, and mixing or agitation is applied. Each of these actions will
initiate a physical or chemical change in the waste being treated. The
real-time measurement and monitoring of these changes will provide the pro-
ject team with information regarding the success or failure of a given trial
run. For example, a sudden drop in pH to very low levels might negate or
alter subsequent process reactions. The following list presents examples of
parameters that could be monitored during a chemical process demonstration.
This list is not inclusive; monitoring parameters should be developed to
apply to the specific process being demonstrated.
67
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Section No. 5
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Page 4 o? 64
Elapsed time, weeks
Task Description
TASK I Pretest Site
Survey
M2
TASK II Preparation of
QA/QC Plan
M3
TASK III Offsite
Preparation
M4
M5 M6
M7
TASK IV Onsite
Test Work
M8
TASK V Analysis
M9
M9
M9 M10 M11
M12
TASK VI Data Reduction
and Reporting
^ MOO - Project-Specific Milestone
Figure 5-2. Sample project schedule.
68
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Section No. 5
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Page 5 of 64
pH
° Temperature
0 Oxygen production
° By-product production
0 Carbon dioxide production
By monitoring changes in the operating parameters, the project team may
be able to mitigate or correct a problem with the process demonstration.
Also, a review of monitoring information can provide a basis for the solution
of the problem. The inclusion of process measurements should be considered
in the development of specific sampling and analysis objectives.
5.2 ORGANIZATIONAL CHART AND DELINEATION OF QA/QC RESPONSIBILITIES
The QAPP should list and briefly describe the responsibilites of all
personnel whose task it is to ensure the collection of valid measurement data
and to make routine assessments of measurement systems for precision and ac-
curacy. This group of persons, which should be listed in a table or on a
chart showing project organization and lines of authority (see Figure 5-3),
would include the EPA Project Manager and Quality Assurance Officer. It is
important that the specific QA/QC responsibilities within this group be
delineated, as shown in Table 5-1. It is highly desirable for the QA Officer
to work independently of the rest of the project team to minimize the risk of
conflict of interest within the project team.
If subcontractors are used, particular attention should be given to how
QA/QC activities will be monitored throughout the subcontractor's portion of
the project. The subcontractor should be included in the organization chart,
along with the appropriate line of authority. The specific functions (e.g.,
analysis, engineering) performed by the subcontractor also should be listed.
5.3 QUALITY ASSURANCE OBJECTIVES
The quality assurance objectives of a demonstration will depend on the
types of sampling and analysis involved. Although sampling and analysis
functions will vary widely throughout the program, the S&A Plan must consider
and list each critical measurement. Critical measurements are defined as all
measuring, data gathering, or data generation activities that have a direct
impact on the technical objectives. Sampling must provide information on the
69
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Section No. 5
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Page 6 of 64
EPA
QA
OFFICER
EPA
PROJECT
MANAGER
ENGINEERING
MANAGER
ANALYTICAL
MANAGER
EPA CONTRACTOR
PROJECT
MANAGER
DEVELOPER
FIELD
MANAGER
EPA
CONTRACTOR
QA OFFICER
Figure 5-3. Sample project organization scheme.
70
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Section No. 5
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Page 7 of 64
TABLE 5-1. EXAMPLE OF DEFINITION OF QA/QC RESPONSIBILITIES
EPA Contractor QA Officer
° Collection of valid measurement data
° Routine assessment of measurement systems for precision and accuracy
EPA Contractor Project Manager
0 Documentation
0 Reporting
EPA Contractor Analytical Manager
° Sampling
0 Sample custody
0 Sample preparation
° Sample analysis
° Data reduction
° Data storage and retrieval
characteristics of the waste prior to, during, and following treatment.
Sampling must also characterize intermediate products and byproducts.
In conjunction with each parameter, the QAPP must assign QA objectives
to ensure that each of the project's technical goals is met. In general, the
QA objectives established for each type of critical measurement should be
based on prior knowledge of the measurement system being used; method valida-
tion studies in which replicates, spikes, standards, calibrations, recovery
studies, etc., are used; and the requirements of the specific project. Where
possible, these objectives should be expressed in terms of precision, accura-
cy, completeness, representativeness, comparability, and, where applicable,
method detection limit.
The two estimators of precision are relative percent difference (RPD)
and relative standard deviation (RSD). The former is the appropriate esti-
mator when duplicate observations are used to determine precision; the latter
is the more appropriate estimator of precision where more than two replicate
observations are made. Precision objectives for most listed measurements
(except pH) are presented as RPD of field duplicates. Precision objectives
for pH are listed in pH units and expressed as limits for field duplicates.
Accuracy objectives for organic and metals determinations are given as
percentage recovery range of laboratory matrix spikes. Accuracy objectives
71
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Section No. 5
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Pa9e 8 of 64
for cation exchange capacity and alkalinity measurements are given as per-
centage bias as determined by analysis of standard reference materials (e.g.,
EPA QC check samples). Accuracy objectives for pH are given in pH units and
expressed as bias limits as determined by analysis of standard reference
materials (e.g., EPA QC check samples).
For a Category II project, completeness entails a comparison of the
amount of valid data obtained with the amount of valid data planned to be
obtained. Completeness must be defined for a Category II project. Complete-
ness is affected by both controllable and uncontrollable factors. Total
completeness addresses dropped samples, mechanical failures, holidays, no
sample available, etc. In other words, any time a sample is extracted, but
for any reason does not produce a result, it is "not completed." For
Category II projects, completeness entails an assessment of the amount of
valid data obtained compared to the amount of data that was planned to be
obtained to achieve a particular statistical level of confidence. Generally,
a level of 90 to 95 percent completeness is used as an objective.
For certain kinds of critical measurements (such as determination of
overall process efficiencies, rates, mass balances, etc.) or the character-
ization of certain kinds of physical properties, some data quality indicators
may not be quantifiable. To cover this possibility, the QAPP should include
a qualitative statement of data quality requirements. For example, consider
a project in which a chemical treatment technology is designed to field-test
the rate of a dechlorination of PCBs in soil media. In such a project, it
may be necessary to establish a data acceptability criterion for a total
chlorine mass balance, in addition to individual method precision and accura-
cy objectives to ensure an appropriate level of significance for the dechlo-
rination process. A qualitative statement of data quality requirements for
total chlorine mass balance might be written as follows:
The acceptability of treatment efficiency data will be determined by
total chlorine mass balance. Data will be acceptable if at least 75
percent of the total organic chlorine component initially present can be
accounted for in the total chlorine mass balance at the end of each
sampling period after control sample effects have been taken into ac-
count.
72
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Section No. 5
Revision No. 1
Date: April 29, 1988
Page 9 of 64
The QA objectives for representativeness and comparability are generally
not quantifiable; therefore, these should be discussed qualitatively in the
text.
All critical measurements must be such that results are representative
of the media (air, water, etc.) and conditions being measured. Any deviation
from approved procedures must be documented and factored into the process
before conclusions are drawn. Unless otherwise specified, all data must be
calculated and reported in units consistent with other demonstrations report-
ing similar data so that data bases can be compared. The use of officially
approved EPA methods (or equivalent) also aids in the relative comparison of
data from one project to another. The QA objectives established for each
critical measurement parameter should be based on prior knowledge of the
measurement being used.
In chemical method validation studies, replicates,•spikes, standards,
calibrations, recovery studies, etc., should be used with particular emphasis
on the requirements of the specific project. The QAPP also should define a
subset of samples that require analysis by a referee lab. When quantifica-
tion is impossible, this section should include a qualitative statement of
data duality requirements for the affected parameter.
Table 5-2 presents an example of QA objectives for measuring parameters
likely to be of interest in aqueous, solid, and sludge samples. Table 5-3
presents QA objectives for determining selected chlorinated organics. The
QAPP should provide project-specific tables for each aspect of the demon-
stration.
The Plan should include a statement explaining the overall impact on the
project should one or more QA objectives not be met, even after corrective
action measures have been taken.
For a Category II QAPP, the overall project impact of not meeting the
specified QA objectives is usually a reduction in the ranges of validity
(e.g., confidence level) and the applicability of the data below the level
needed to achieve the technical or regulatory project goals. Data that fail
to meet QA objectives usually must be accompanied by detailed qualifying
statements that explain the reasons for the failure and describe the limita-
tions on the validity and use of the data. Satisfactory qualifying state-
ments are typically predicated on a comprehensive set of corrective actions.
73
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TABLE 5-2. QA OBJECTIVES FOR PRECISION
AND METHOD DETFCTION LII
Critical Matrix type Method reference
measurement
Volatile
Water
EPA Method 601
(Ref. 5)
chlorinated
Soi 1
SW-846
Method
8010
(Ref.
4)
hydrocarbons
Purge-and-
Water/soi1
SW-846
Method
5030
(Ref.
4)
trap
Semivolatile
Water
EPA Method 612 (Ref. 6)
chlorinated
Soil
SW-846
Method
8120
(Ref.
4)
hydrocarbons
Sonication
Soil
SW-846
Method
3550
(Ref.
4)
extraction
Metals
Antimony
Water/soil
SW-846
Method
7040
(Ref.
4)
Arsenic
Water/soil
SW-846
Method
7060
(Ref.
4)
Barium
Water/soil
SW-846
Method
7080
(Ref.
4)
Beryllium
Water/soil
SW-846
Method
7090
(Ref.
4)
Cadmiurn
Water/soil
SW-846
Method
7130
(Ref.
4)
Chromium
Water/soil
SW-846
Method
7190
(Ref.
4)
Copper
Water/soil
SW-846
Method
7210
(Ref.
4)
Lead
Water/soil
SW-846
Method
7420
(Ref.
4)
Mercury
Water/soil
SW-846
Method
7470
(Ref.
4)
Nickel
Water/soil
SW-846
Method
7520
(Ref.
4)
Selenium
Water/soil
SW-846
Method
7740
(Ref.
4)
Silver
Water/soil
SW-846
Method
7760
(Ref.
4)
Thallium
Water/soil
SW-846
Method
7841
(Ref.
4)
Zinc
Water/soil
SW-846
Method
7950
(Ref.
4)
Digestion
Water
SW-846
Method
3005
(Ref.
4)
Digestion
Water
SW-846
Method
3010
(Ref.
4)
(continued)
ACCURACY, COMPLETENESS,
T (MPL)
Units MDL Preci- Accuracy'3 Complete-
sion ness, %
ug/1iter
yg/kg
90
90
90
vig/1 iter
yg/kg
c
c
90
90
85
d
800
40
40-115
90
d
5
30
65-130
90
d
500
20
75-125
90
d
40
20
80-120
90
d
20
20
80-120
90
d
200
30
70-130
90
d
100
20
80-120
90
d
500
30
70-120
90
d
0.5
35
75-120
90
d
200
25
80-120
90
d
10
50
35-125
90
d
50
30
55-130
90
d
20
50
40-150
90
d
20
35
60-140
90
90
90
TJDZIW
Q)
Ol
(D
O)
(£3
c+
<
o
(D
r+
•.
l/>
—i.
O
o
3
»—•
3
O
ZZ.
>ZO
¦a
O
•
-s
•
O
1
ro
K£>
•
i—»
cn
CTi
»—»
to
00
00
-------
TABLE 5-2. (continued)
Critical
measurement
Matrix type
Method reference
Units
MDL
Preci-
sion
Accuracy
Complete-
ness, %
^4
Ol
Digestion
Digestion
Chloride
Chloride resi-
dual (RsC^)
PH
Cation exchange
capacity (CEC)
Acidity
Alkalinity
Total dis-
solved solids
(TDS)
Water
Soil
Water/soi1
Water/soi1
Water
Soi 1
Soi 1
Water
Water
Water
SW-846 Method 3020 (Ref. 4)
SW-846 Method 3050 (Ref. 4)
EPA Method 325.1 (Ref. 6)
EPA Method 330.2 (Ref. 6)
e
e
1.0
0.2
EPA Method 150.1 (Ref. 6) pH units
SW-846 Method 9045 (Ref. 4) pH units
SW-846 Method 9080 (Ref. 4) meg/100 g 0.05
EPA Method 305.1 (Ref. 6) mg/liter 5
EPA Method 310.1 (Ref. 6) mg/liter 5
EPA Method 160.3 (Ref. 6) mg/liter 5
15
20
±0.02!
±0.02
30
20
20
30
80-120
70-130
±0.04;*
±0.049
±40h
±25'
i
As Percent Recovery Range of laboratory matrix spikes, unless otherwise noted.
c QA objectives or organic analyte measurements are presented in Table 5-3.
^ As ug/liter for water samples; as pg/kg for soil samples.
e As mg/liter for water samples; as mg/kg for soil samples.
^ Expressed in pH units as limits for field duplicates.
9 Expressed in pH units as bias for measurement of standard QC check sample.
^ As percent bias for measurement of standard QC check sample.
1 Not available for method.
90
90
90
90
90
90
80
90
90
90
As Relative Percent Difference (RPD) of field duplicates, unless otherwise noted.
-0 0
OO
Q)
0)
ro
1—»
-P*
<0
00
CO
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Section No. 5
Revision No. 1
Date: April 29, 1988
Page 12 of 64~
TABLE 5-3. PRECISION, ACCURACY, AND METHOD DETECTION LIMIT
QA OBJECTIVES FOR PROJECT-SPECIFIC CHLORINATED ORGANICS
Precision Accuracy,
Analyte MDLa RPD % recovery
Volatile Chlorinated Hydrocarbons
Carbon tetrachloride
Chlorobenzene
Chloroethane
2-Chloroethylvinyl ether
Chloroform
Chloromethane
Dibromochloromethane
1.2-Dichlorobenzene
1.3-Dichlorobenzene
1-4-Dichlorobenzene
1.1-Dichloroethane
1.2-Dichloroethane
1.1-Dichloroethene
trans-1,2-Dichloroethene
1.2-Dichloropropane
cis-l,3-Dichloropropene
trans-1,3-Dichloropropene
Methylene chloride
1,1,2,2-Tetrachloroethane
Tetrachloroethane
1.1.1-Trichloroethane
1.1.2-Trichloroethane
Trichloroethene
Trichlorofluoromethane
Vinyl chloride
Semivolatile Chlorinated Hydrocarbons
2-Chloronaphthalene
1.80
50
5-155
1,2-Dichlorobenzene
2.20
40
5-175
1,3-Dichlorobenzene
2.30
35
>0-160
1,4-Di chlorobenzene
2.50
30
10-145
Hexachlorobenzene
0.10
35
10-165
Hexachlorobutadiene
0.70
30
>0-145
Hexachloroethane
0.80
35
>0-120
1,2,4-Trichlorobenzene
0.10
45
5-145
a MDL units are pg/1iter for water samples, yg/kg for low-level soils.
0.20 45 40-150
0.35 40 35-155
0.90 35 40-145
0.30 60 10-190
0.10 35 45-140
0.20 60 >0-200
0.20 50 20-195
0.30 45 >0-210
0.65 70 5-190
0.50 45 35-150
0.20 25 40-140
0.10 40 45-150
0.25 50 25-170
0.25 50 35-160
0.15 40 40-165
0.90 60 20-180
0.75 60 20-180
0.50 35 20-175
0.10 70 5-190
0.10 45 20-170
0.10 40 35-145
0.10 30 30-145
0.25 35 30-150
1.00 50 15-165
0.40 45 20-170
76
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Section No. 5
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Page 13 o? 64
These usually include a verification or demonstration that the analytical
measurement system was and is in control, a complete repreparation and re-
analysis of the affected samples, a thorough validation check of data from
both original and reanalyzed samples, and full documentation of results for
both original and reanalysis data. Statements outlining a mechanism for
reporting the additional requirements to meet the specified QA objectives and
to achieve project goals also should be included.
5.4 SITE SELECTION AND SAMPLING PROCEDURES
This section should include a scientifically credible plan for site
selection and sampling. First, the scientific, regulatory, and program
objectives must be defined, and then a sampling plan should be developed to
meet those objectives.
Scientific, Regulatory, and Program Objectives
The scientific, regulatory, and program objectives for sampling should
be clearly stated. For example, the sampling objectives for a PCB treatment
technology might be to demonstrate that PCBs in soil can be reduced to less
than 2 parts per million. Thus, the sampling scheme should be designed pri-
marily to obtain initial and final PCB concentrations in soil. Additional
sampling to monitor PCB levels over time of the treatment probably also
should be included.
Regulatory objectives generally relate to applicable, relevant, and
appropriate Federal or State environmental standards. Scientific objectives
may encompass any other critical measurement data. For example, the level of
oxygen in a system or the system temperature are critical to a reaction; the
objectives for monitoring such parameters would include the range of allow-
able values.
The major objective of the SITE Program is to provide treatment technol-
ogies necessary to implement cleanup standards that require a greater reli-
ance on permanent remedies at Superfund sites. The demonstration program is
designed to provide sound engineering and cost data on selected technologies.
Monitoring objectives should focus on providing information on system per-
formance and reliability.
77
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Section No. 5
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Page 14 o? 64
Selection of Sampling Locations
The techniques or guidelines used to select sampling locations should be
described. The complexity of selecting sampling locations varies with the
type of technology and whether it is conducted in vessels or in situ, is a
continuous or a batch operation, etc. Sampling locations for a treatment
technology conducted in a vessel are usually collected from one or more sam-
pling ports. Selection of sampling locations for an in situ process requires
that a grid be developed with designated sampling points. Monitoring a batch
process requires that each batch be sampled before, after, and usually during
the treatment process. A continuous process is usually sampled at constant
time intervals. Including a description of the procedure for selecting sam-
pling locations in the QAPP will promote consistency in the approach.
Sample Types
The sampling plan should include all types of samples relevant to a
chemical technology. These may include the following:
Gas samples: Liquid samples: Solid samples:
Ambient air Reagents (new) Waste (untreated)
Emissions Reagents (used) Waste (treated)
Waste (untreated) Sludges/residues (i.e., filter
Waste (treated) cake, etc.)
Condensate Soil (untreated)
Effluents Soil (treated)
Groundwater
Surface water
Sampling Strategy
The sampling strategy is key to a demonstration evaluation program. It
must be well conceived so that all critical measurements are made and suffi-
cient samples are taken to be representative. The sampling strategy should
address the following:
° Types of strategy (e.g., simple, stratified, or systematic random
sampling).
° Sampling frequencies or sampling counts for each sample type.
Types of Strategy--
The characteristics of the technology determine the types of samples
78
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Section No. 5
Revision No. 1
Date: April 29, 1988
Paige 15 o? 64
taken. For example, grab samples taken at a sampling port would be appropri-
ate for the well-mixed liquid contents of a vessel equipped with an operating
agitator and operating in the batch mode. Sampling a stratified lagoon,
however, might require obtaining a sample profile by collecting samples from
layers in the waste at various depths. The sampling strategy for a continu-
ous operation might entail taking samples at specified time intervals.
Sampling strategies are presented in Section 1.1.3 of "Test Methods for
Evaluating Solid Waste," SW-846, 1986. Each strategy includes instructions
on how to choose the necessary number of samples based on available prelimi-
nary information about the item that is to be sampled. Such information can
be obtained through an initial round of sampling, or it can be estimated.
The informational requirements of the sampling strategy should be kept in
mind during the design of the sampling plan.
In the case of dynamic matrices (such as reactors, piping, etc.), the
use of grab samples may be appropriate. The plan must address both the
frequency and number of grab samples that should be taken in a given situa-
tion. A deep groundwater well that has been in service for some time may
require only a single grab sample, whereas a batch manufacturing process may
require many and frequent grab samples (e.g., one sample every 15 minutes
over an 8-hour period). Whenever possible, charts, maps, sampling grids,
flow diagrams, and/or tables delineating sampling program operations should
be included in the plan.
Sampling Frequencies or Counts--
The sampling frequencies or counts of various sample types are deter-
mined by the characteristics of the technology. Generally, sampling schemes
are designed to sample every stream going into a system and all streams
coming out of a system, with emphasis on the waste(s) in and the waste(s)
out. Table 5-4 is an example of a proposed sampling program for a treatment
process. A similar table should be prepared for each QAPP developed under
the SITE Program.
Sampling Procedures and Volumes
Sampling procedures should be taken from SW-846, 3rd Edition, 1986, if
applicable; additional procedures should be based on the guidelines and
recommendations provided in the following bibliography:
79
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Section No. 5
Revision No. 1
Date: April 29, 1988
Page 16 of 64
Water
Guidelines Establishing Test Procedures for the Analysis of Pollut-
ants Under the Clean Water Act, Federal Register, Volume 49, Number
209, October 26, 1984.
Methods for Chemical Analysis of Water and Wastes, EPA-600/4-79-
020, March 1983.
Handbook for Sampling and Sample Preservation of Water and Waste-
water, EPA-600/4-82-029, September 1982.
Handbook for Analytical Quality Control in Water and Wastewater
Laboratories, EPA-600/4-79-019, March 1979.
Water, Solids, Slurries
Test Methods for Evaluating Solid Waste, SW-846, 3rd Edition,
November 1986.
Air
Quality Assurance Handbook for Air Pollution Measurement Systems:
Volume I - Principles, EPA-600/9-76-005, March 1976.
Volume II - Ambient Air-Specific Methods, EPA-600/4-77- 027a, May
1977.
Volume III - Stationary Source-Specific Methods, EPA-600/4-77-027b,
August 1977.
TABLE 5-4. SUMMARY OF PROPOSED SAMPLING PROGRAM
No. of
Sampling location Classification samples
Raw feed tank
RF
6
Oxidized liquor filtrate
OF
3
Oxidized liquor filter cake
OC
3
Filter cake
FC
6
Effluent
EF
6
Blanks
BL
3
Total
27
a RF = Raw feed or influent
FC =
Filter cake
OF = Oxidized liquor filtrate
EF =
Effluent
OC = Oxidized liquor filter cake
BL =
Blank
80
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Section No. 5
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Date: April 29, 1988
Page 17 of 64 ~
When standard EPA-approved procedures are used, the standard method
should be referenced, usually in a table. When nonstandard procedures are
used, the entire sampling procedure should be described in the text.
Solid and liquid samples may be taken under a variety of situations.
Samples are most likely to be taken from containers and reaction vessels (or
tanks) during a SITE project. The following subsections provide some sam-
pling guidelines.
Sampling From Containers--
As used here, the term container refers to receptacles designed for
transporting materials (e.g., drums and other smaller receptacles as opposed
to stationary tanks). Weighted bottles, Coliwasas, drum thiefs, or triers
are the suggested sampling devices for the sampling of containers. (These
devices are discussed in later sections.)
The sampling strategy for containers varies according to 1) the number
of containers to be sampled, and 2) access to the containers. If the waste
is contained in several containers, ideally every container will be sampled.
If the large number of containers or cost factors makes this impossible, a
subset of individual containers must be randomly selected for sampling. This
can be done by assigning each container a number and then randomly choosing a
set of numbers for sampling.
Access to a container will affect the number of samples that can be tak-
en from the container and the location within the container from which sam-
ples can be taken. Ideally, several samples should be taken from both verti-
cal and horizontal locations throughout the waste container. The number of
samples required for reliable sampling will vary depending on the distribu-
tion of the waste components in the container. When the content of the waste
is unknown, a sufficient number and distribution of samples should be taken
to address any possible vertical anomalies in the waste. Containerized
wastes tend to be nonrandomly heterogeneous in a vertical rather than a hori-
zontal direction because of 1) settling of the solids and the denser phases
of liquids, and 2) variation in the content of the waste as it entered the
container. Bags, paper drums, and open-headed steel drums (the entire top of
which can be removed) generally do not restrict access to the waste and
therefore do not limit sampling.
81
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Section No. 5
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Page 18 o7 64
When access to a container is unlimited, a three-dimensional, simple,
random-sampling strategy, in which the container is divided by constructing
an imaginary three-dimensional grid, can be used to obtain a representative
set of samples. This strategy involves the following steps:
1) The top surface of the waste is divided into a grid whose sections
either approximate the size of the sampling device or are larger
than the sampling device if the container is large. (Cylindrical
containers can be divided into imaginary concentric circles, which
are then further divided into grids of equal size.)
2) Each section is assigned a number.
3) The height of the container is then divided into imaginary levels
that are at least as large as the vertical space required by the
chosen sampling device.
4) Each of these imaginary levels is assigned a number.
5) Specific levels and grid locations are then selected for sampling
by using a random number table or random number generator.
Another appropriate sampling approach is the two-dimensional, simple,
random-sampling strategy, which can usually yield a more precise sampling
when fewer samples are collected. This strategy involves:
1) Dividing the top surface of the waste into an imaginary grid as in
the three-dimensional strategy.
2) Selecting grid sections for sampling by using random number tables
or random number generators.
3) Sampling each selected grid point in a vertical manner along the
entire length from top to bottom with a sampling device such as a
Drum Thief or a Coliwasa.
Some containers (e.g., drums with bung openings) limit access to the
contained waste and restrict sampling to a single vertical plane. Samples
taken in this manner can be considered representative of the entire container
only if the waste is known to be homogeneous. Precautions must be taken
during the sampling of any type of steel drum because the drum may explode or
expel gases or pressurized liquids.
Sampling From Reactors and Tanks--
Reactors and tanks are essentially large containers. Reactors are
usually equipped for agitation and may have heating or cooling sources.
Tanks are used for "holding" or storing process mixtures. Because of their
82
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Section No. 5
Revision No. 1
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Page 19 of 64~
similarity, the considerations involved in sampling these vessels are much
the same as those for sampling containers. As with containers, the goal is
to acquire a sufficient number of samples from different locations within the
waste to provide analytical data that are representative of the contents of
the entire vessel. If the vessel is operating under mixed conditions, it is
considered a homogeneous system; however, if the mixing conditions are ob-
served to be operating poorly, this assumption does not apply. Poor mixing
conditions are indicated by an inadequate number of mixing blades, inadequate
power input, or obstructions within the vessel that permit the development of
pockets of unmixed fluid.
The accessibility of the vessel contents also will affect the sampling
methodology. If the vessel is an open one allowing unrestricted access, a
representative set of samples is usually best obtained by use of the three-
dimensional, simple, random-sampling strategy described in Section 1.4.1 of
Publication SW-846, which was described earlier.
A less comprehensive sampling approach may be appropriate if information
regarding the distribution of waste components is known or assumed (e.g.,
vertical compositing will yield a representative sample). In such cases, a
two-dimensional simple random sampling strategy may be appropriate. This
strategy was also described earlier. If the waste components are known to
consist of two or more discrete strata, a more precise representation of the
tank contents can be obtained by using a stratified random sampling strategy
(i.e., sampling each stratum separately by using the two- or three- dimen-
sional simple random sampling strategy).
Some vessels permit only limited access to their contents, which re-
stricts the locations within the vessel from which samples can be taken. If
sampling is restricted, the sampling strategy must be to take at least suffi-
cient samples to address the potential vertical anomalies in the waste so
sampling can be considered representative. Contained wastes tend to display
vertical rather than horizontal nonrandom heterogeneity as a result of the
settling of suspended solids or denser liquid phases. If access restricts
the sampling of a portion of the vessel contents (e.g., in an open vessel,
the size of the vessel may restrict sampling to the perimeter of the vessel;
83
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Section No. 5
Revision No. I
Date: April 29, 1988
Page 20 o? 64
in a closed vessel, the only access to the waste may be through inspection
ports), the resulting analytical data will only be considered representative
of the accessed area, not of the entire vessel contents unless the vessel
contents are known to be homogeneous.
The most appropriate type of sampling device for vessels depends on the
vessel's parameters. In general, subsurface samplers (i.e., pond samplers)
are used to sample shallow vessels, whereas weighted bottles are normally
used to sample vessels deeper than 5 ft. Dippers are useful for sampling
pipe effluents.
Sampling of In Situ Treatments--
Potential SITE projects may address the in situ treatment of contaminat-
ed soils or sludges. In this case, materials sampled may either be solid or
semisolid in nature.
A random three-dimensional sampling approach is best suited for in situ
treatments. A three-dimensional sampling approach involves establishing an
imaginary three-dimensional grid of sampling points in the contaminated area.
Sampling points are then selected by using a random number generator or
table. The sampling grid is generated by assembling maps and general soil
information for the area. The map is divided into 2 two-dimensional grids
with sections of equal size. These sections are then assigned numbers se-
quentially. Next, the depth to which sampling will take place is determined
and subdivided into equal levels, which also are sequentially numbered. The
horizontal and vertical sampling coordinates are then selected.
Hollow-stem augers combined with split-spoon samplers are used when
sampling to depths greater than 5 ft. Shallow sampling devices are discussed
in succeeding subsections.
Air Sampling Procedures--
This subsection outlines the various air sampling procedures that may be
required for a SITE demonstration. Each technology has its own sampling
requirements. Air sampling can be simplified by generating a complete list
of compounds and estimates of their concentrations that may be emitted during
84
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Section No. 5
Revision No. I
Date: April 29, 1988
Page 21 of 64
treatment with a specific technology. An example might be the monitoring of
emissions of methylene chloride from an in situ treatment of contaminated
soil. In this case, the compound is known and the amount of methylene chlo-
ride may be estimated. The sampling and analysis may be performed to verify
actual conditions. Air sampling data will be critical to the performance of
a material balance. The protocol presented herein is meant to serve as an
example from which a specific air sampling program may be designed.
Air sampling may take many different forms, including sampling gases,
particulate emissions, and ambient air. A specific chemical technology may
not require all of these; however, an overview of the method required for
each is presented.
The sampling of gases for organic constituents entails the use of EPA
Method 25, which is described in the Federal Register, Volume 44, No. 195,
pages 57808-57822. This method applies to the measurement of total gaseous
nonmethane organics from source emissions. The procedure involves drawing a
sample through a chilled condensate trap into a gas collection tank. A
simplified diagram of the sampling apparatus is shown in Figure 5-4.
The sampling of particulate emissions entails the use of EPA Method 5,
which is described in the Federal Register, Volume 42, No. 160, pages 41777
through 41782. This method applies to the determination of particulate emis-
sions from a stationary source. This procedure provides for the measurement
of particulate matter in air as it is collected on a glass fiber filter. The
amount of particulates is determined gravimetrically after the removal of
uncombined water. A diagram of a Method 5 sampling train configured for
stack testing is presented in Figure 5-5.
Ambient air sampling encompasses several sampling procedures. The
following points must be considered in the design of an ambient air sampling
program:
° Sampling locations
Frequency of sampling
0 Pollutant to be measured
0 Specific procedures
85
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Section No. 5
Revision No. 1
Date: April 29, 1988
Page 22 of 64
VACUUM
GAUGE
FLOW RATE
CONTROLLER
PROBE
EXTENSION
(IF REQUIRED)
CONNECTOR
PROBE
ON/OFF
FLOW
VALVE
QUICK
CONNECT
STACK
WALL
DRY ICE
AREA
CONDENSATE
TRAP
EVACUATED
SAMPLE
TANK
Figure 5-4. Air sampling apparatus.
86
-------
00
^4
«=C[|)I
M TEMPERATURE SENSOR
< PROBE
* PITOTTUBE
HEATED
IMPING ER TRAIN OPTIONAL, MAY BE REPLACED
THERMOMETER BY AN EQUIVALENT CONDENSER
TEMPERATURE
SENSOR ^ STACK WALL
PROBE
TYPES
PITOT
TUBE
- j incnwumcicn w ¦ '"*
J AREA / /
^ J . FILTER HOLDER /
THERMOMETER
AIRTIGHT
PUMP
VACUUM
LINE
CHECK
VALVE
PITOT
MANOMETER §_
WPINGERS
ICE WATER BATH
THERMOMETERS
BYPASS
VALVE VACUUM GAUGE
MAIN VALVE
DRY GAS
METER
Figure 5-5. Method 5 sampling train.
TD O
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-------
Section No. 5
Revision No. 1
Date; April 29, 1988"
Page 24 oT 64
The bibliography presented in Table 5-5 should assist in the assembly of an
ambient air sartp 1 i 11 t ,
Sampling Volun.ts--
The volume of a sample for analysis should be sufficient to carry out
all of the tests required. Test methods and laboratories can usually specify
the necessary volume of the samples.
TABLE 5-5. BIBLIOGRAPHY FOR AMBIENT AIR SAMPLING PROCEDURES
Condition
Reference
Airborne particulates
Clements, J. B. Extraction of Airborne Particulates
with Benzene, Ca-1. Research Triangle Park, NC.
1972.
Hydrocarbons
Federal Register, Vol. 36, No. 84, April 30, 1971.
Fugitive particulates
Cowhers, C., et al. Development of Emission Factors
for Fugitive Dust Sources. EPA-450/3-74-037, 1974.
General
Jarke, F. H., Ambient Air Monitoring at Hazardous
Waste Facilities. In: Proceedings of 78th Meeting
of Air Pollution Control Association, 1985.
Modeling
Thibodeaux, J., and S.T. Hwang. Landfarming of
Petroleum Waste--Modeling the Air Emission Problem.
Environmental Progress. 1982.
The sampling volumes required depend on the number of different sample
preparation procedures needed for analysis. Such techniques Include graph-
ite-furnace atomic adsorption spectrometry (GFAA), flame atomic absorption
spectrometry (FLAA), inductively coupled argon plasma emission spectrometry
(ICP), hydride-generation atomic absorption spectrometry (HGAA), and cold-
vapor atomic absorption spectrometry (CVAA), each of which entails a dif-
ferent digestion procedure. The volumes shown in Table 5-6 represent those
required for individual digestion procedures and recommended sample collec-
tion volumes for metals determinations.
88
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Section No. 5
Revision No. 1
Date; April 29, 1988
Page 25 of 64
TABLE 5-6. RECOMMENDED COLLECTION VOLUMES FOR METAL DETERMINATIONS
Digestion vol-
ume required, Collection
Measurement ml volume, ml
Metals (except hexavalent chromium and mercury)
Total recoverable 100 600
Dissolved 100 600
Suspended 100 600
Total 100 600
Chromium IV 100 400
Mercury
Total 100 400
Dissolved 100 400
a Solid samples must be at least 200 g, and they usually require no
preservation other than storing at 4°C until analyzed.
Sampling Containers and Equipment
The sampling equipment and the preparation and cleaning procedures
should be discussed in the text. The containers used for sample collection,
transportation, and storage for each sample type should also be described.
Sampling Equipment for Solids—
Organization of solid waste sampling equipment is based on the size of
the solids being sampled, their moisture content, and their degree of com-
paction. Sampling equipment for solids includes a drum thief, a trier, an
auger, a scoop, and a shovel. This equipment is referenced in EPA SW-846,
"Testing Methods for Evaluating Solid Waste." Each piece is briefly de-
scribed in this subsection.
Drum Thief--A drum thief consists of two slotted concentric tubes, usu-
ally made of stainless steel or brass. The outer tube has a conical pointed
tip that permits the sampler to penetrate the material being sampled. The
inner tube is rotated to open and close the sampler (see Figure 5-6).
89
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Page 26 of 64 ~
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Section No. 5
Revision No. 1
Date: April 29, 1988
Page 27 o? 64
Trier--A trier consists of a tube cut in half lengthwise and having a
sharpened tip that allows the sampler to cut into sticky solids and to loosen
soil (see Figure 5-7). A trier samples moist or sticky solids with a parti-
cle diameter of less than one-half the diameter of the trier.
Auger--An auger, which consists of sharpened spiral blades attached to a
hard metal central shaft, is used to sample hard or packed solid wastes or
soil.
Scoop and shovel—Scoops and shovels are used to sample granular or
powdered material in bins, shallow containers, and conveyer belts.
Sampling Equipment for Liquids—
Organization of liquid-sampling equipment depends on the type of con-
tainer in which the liquid is stored. Liquid sampling will apply to many
aspects of a biological technology, including:
1) Sampling of containerized waste prior to treatment.
2) Sampling of liquid-based treatment schemes.
3) Sampling of holding vessels that contain process byproducts.
Liquid-sampling equipment includes a composite liquid sampler (Coli-
wasa), a weighted bottle, and a dipper. This equipment is referenced from
EPA SW-846, "Testing Methods for Evaluating Solid Waste." Each of these
three equipment items is briefly described in this subsection.
Composite liquid waste sampler (Coliwasa)--The Coliwasa is used to
sample free-flowing liquids and slurries in drums, shallow open-top tanks,
pits, and similar containers. It is especially useful for sampling wastes
that comprise several immiscible liquid phases.
The Coliwasa consists of a glass, plastic, or metal tube equipped with
an end closure that can be opened and closed while the tube is submerged in
the material to be sampled.
A more detailed discussion of the Coliwasa can be found in the U.S. EPA
600/2-80-018 report entitled "Samplers and Sampling Procedures for Hazardous
Waste Streams." A modification of the device is described in "Evaluation of
91
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Section No. 5
Revision No. 1
Date: April 29, 1988
Page 28 o7 64
C3
H
i i
60 -100 cm
1.27-2.54 cm
Figure 5-7. Sampling triers.
i
5.08 - 7.62 cm
122-183 cm
(48 - 72 in.)
«T
92
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Section No. 5
Revision No. 1
Date: April 29, 1988
Page 29 o? 64
the Procedures for Identification of Hazardous Wastes," by L. R. Williams, et
al. (EPA 600/4-81-027 April 1981).
Some experienced sampling personnel find the Coliwasa cumbersome and
difficult to clean or dispose of after use.
Weighted bottle--This sampler consists of a glass or plastic bottle,
sinker, stopper, and a line that is used to lower, raise, and open the bot-
tle. The weighted bottle, which is used to sample liquids and free-flowing
slurries, is built to the specifications in ASTM Methods D 270 and E 300.
Figure 5-8 shows the configuration of this type of sampler.
Dipper--The dipper, shown in Figure 5-9, consists of a glass or plastic
beaker clamped to the end of a two- or three-piece telescoping aluminum or
fiberglass pole that serves as the handle. A dipper is used to sample
liquids and free-flowing slurries. Dippers are not available commercially
and must be fabricated to conform to individual specifications.
Sample Containers--
In the measurement of trace metals, containers can introduce either
positive or negative errors by 1) contributing contaminants through leaching
or surface desorption, and 2) depleting concentrations through adsorption.
Therefore, particular attention must be given to the collection and treatment
of a sample prior to its analysis. The following cleaning treatment sequence
has been determined to be adequate to minimize contamination in the sample
bottle, whether it is borosilicate glass, linear polyethylene, polypropylene,
or Teflon: detergent (tap water), 1:1 nitric acid (tap water), 1:1 hydro-
chloric acid (tap water), and deionized water.
Standard 40-ml, screw-cap, glass volatile organics analysis (V0A) vials
with Teflon-faced silicone septa may be used for both liquid and solid matri-
ces. The vials and septa should be washed with soap and water and rinsed
with distilled, deionized water. After the vials and septa have been thor-
oughly cleaned, they should be placed in a muffle furnace and dried at 105°C
for approximately 1 hour. (Note: The septa must not be heated for an ex-
tended period of time (i.e., more than 1 hour) because the silicone begins to
degrade at 105°C.)
93
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Section No. 5
Revision No. 1
Date: April 29, 1988
Page 30 o? 64
CORK
WASHER
PIN
NUT
Figure 5-8. Weighted bottle sampler.
,VARIGRIP CLAMP
BOLT HOLES
BEAKER
150 TO 600 ml
TELESCOPING ALUMINUM POLE
2.5 TO 4.5 m (8 TO 15 ft)
Figure 5-9. Dipper.
94
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Section No. 5
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Date: April 29, 1988
Page 31 of 64 ~
During sample collection, liquids and solids should be gently introduced
into the vials to reduce any agitation that might drive off volatile com-
pounds. Liquid samples should be poured into the vials without introducing
air bubbles into the vial. Should bubbling result from overly aggressive
pouring, the sample must be poured out and the vial refilled. Each VOA vial
should be filled until the meniscus formed is higher than the lip of the
vial. The screw-top lid with the septum (Teflon side toward the sample)
should then be tightened onto the vial. After the lid is tightened, the vial
should be inverted and tapped to check for air bubbles. If any air bubbles
are present, the sample must be retaken. Two VOA vials should be filled at
each sampling site.
The VOA vials for samples that have solid or semisolid (sludge) matrices
should be filled to the extent possible. During the filling process, the
vials should be lightly tapped to eliminate as much free air space as possi-
ble. Two vials should be filled at each sampling site.
When the VOA vials are filled, they should be immediately labeled at the
point at which the sample is collected. They should not be filled near a
running motor or any type of exhaust system because discharged fumes and
vapors can contaminate the samples. The two vials from each sampling site
should then be sealed in separate plastic bags to prevent cross-contamination
between samples, particularly if the sample waste is suspected of containing
high levels of volatile organics. (Activated carbon may be included in the
bags to prevent cross-contamination from highly contaminated samples.) The
VOA samples also can be contaminated by diffusion of volatile organics
through the septum during shipment and storage. A trip blank prepared from
distilled deionized water should be kept on hand throughout the sampling,
storage, and shipping process to monitor for possible contamination.
Containers used to collect samples for determination of semivolatile or-
ganic compounds should be washed with soap and water and rinsed with methanol
(or isopropanol). The sample containers should be glass or Teflon and have
screw-top covers with Teflon liners. When Teflon is not available, solvent-
rinsed aluminum foil may be used as a liner. Plastic containers or lids must
not be used for sample storage because samples could become contaminated by
the phthalate esters and other hydrocarbons within the plastic.
95
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Section No. 5
Revision No. 1
Date; April 29, 1988
Page 32 o? 64
Four liters of aqueous liquids are required for semivolatile analysis,
and 250-ml wide-mouth bottles are generally used for solids and sludges.
Sample containers should be filled carefully to prevent any portion of the
collected sample from coming in contact with the sampler's gloves and thereby
causing contamination. Samples should not be collected or stored in the
presence of exhaust fumes. If a sample comes in contact with the sampler
(when an automatic sampler is used), reagent water should be run through the
sampler and the sample should be used as a field blank.
Cleaning and Storage of Lab Glassware--
In the analysis of samples containing contaminants in the parts-per-
bi111on (ppb) range, the use of scrupulously clean glassware is mandatory.
Failure to use clean glassware can lead to a myriad of problems in the inter-
pretation of the final chromatograms as a result of extraneous peaks caused
by contamination. Particular care must be taken with glassware such as
Soxhlet extractors, Kuderna-Danish evaporative concentrators, sampling-train
components, or any other glassware that comes in contact with an extract that
will be evaporated to a lesser volume. The process of concentrating the
compounds of interest in this operation may similarly concentrate and thereby
seriously distort the results.
The basic cleaning steps are as follows:
1) Removal of surface residuals immediately after use.
2) Hot soaking to loosen and flotate most particulate matter.
3) Hot-water rinse to flush away floating particulates.
4) Soaking with an oxidizing agent to destroy traces of organic com-
pounds.
5) Hot-water rinse to flush away materials loosened by soaking in a
deep penetrant.
6) Distilled-water rinse to remove metallic deposits from the tap
water.
7) Methanol rinse to flush off any final traces of organic materials
and to remove the water.
8) Flushing the item immediately before use with some of the same
solvent that will be used in the analysis.
96
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Section No. 5
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Pa9e 33 of 64
The preparation of sample containers should include Items 1 through 6
above. In addition to those steps, all glassware (except glass/metal con-
tainers) must be sterilized in an autoclave for 60 minutes at a temperature
of 170°C. Glass/metal containers should be heated to 170°C in an autoclave
for a minimum of 2 hours. Plastic sample containers may be sterilized in an
autoclave at 121°C for 15 minutes, or ethylene oxide gas sterilization can be
used.
Sample Preservation
Table 5-7 presents the required containers, preservation procedures, and
holding times for aqueous samples. (Additional requirements can be found in
Table 2-16 of SW-846, 3rd Edition.) Corresponding procedures for solids,
nonaqueous liquids, slurries, particulates, and vapor samples may vary widely
depending on the nature of the sample. Generally, solids, sludges, and non-
aqueous liquids can be placed in glass containers with Teflon-lined caps and
cooled to 4°C without jeopardizing the sample. Special samples, such as
those collected in Tenax tubes, require special preparation and handling
procedures, which are described in the methods. Separate samples must be
obtained for analysis when the toxicity characteristic leaching procedure
(TCLP) and zero-headspace extraction (ZHE) are of interest. No preservatives
are added. The TCLP samples require 100 g; ZHE samples require 25 g. The
ZHE sample is taken and bottled in the same way as are other samples for
volatile organic analysis. Both TCLP and ZHE samples are stored and shipped
at 4°C.
Sample Custody
An important part of the quality assurance program is assuring the in-
tegrity of the sample from collection to data reporting. This includes being
able to trace the possession and handling of samples from the time of collec-
tion through analysis and final disposition. This documentation of the
sample's history is referred to as "chain of custody." The components of the
chain of custody (field-sampling protocol sample seals, sample labels with
the sample number, a field logbook, chain-of-custody records, and sample
analysis requests) and the procedures for their use are described in the
following subsections.
97
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TABLE 5-7. REQUIRED CONTAINERS, PRESERVATION TECHNIQUES, AND HOLDING TIMES
VO
00
Measurement parameter
Container3
Preservation''
Maximum holding times0
Purgeable organics fEPA
Method 8240)
Teflon-
G
¦1 ined
septum
Cool to 4°C, protect
from light
14 days
Extractable organics (EPA
Method 8250)
Teflon-
G
¦ 1 ined
cap
Cool to 4°C, protect
from light
7 days until extraction,
40 days after extraction
Pesticides, PCB's
(EPA Method 8080)
Teflon-
G
¦ 1ined
cap
Cool to 4°C
pH 5 to 9
7 days until extraction,
40 days after collection
Metals (except mercury-
chromium VI)
P.G
HNOj to pH less than 2
6 months
Mercury (EPA Method 7470)
P.G
HNOj to pH less than 2
28 days
Chromium VI
P,G
Cool, 4°C
24 hours
pH
P.G
None required
Analyze water inmediate-
ly (on site); none
specified for soil
Residue
P.G
Cool, 4"C
7 days
Organic carbon, total
P.G
Cool, 4'C, HC1 or H2S0„
to pH less than 2
28 days
Cyanide, total
P.G
Cool to 4°C; NaOH to pH
greater than 12
14 days
Sulfide
P.G
Cool to 4°C; add zinc
acetate plus NaOH to
pH greater than 9
7 days
a Polyethylene (P) or glass (G).
k Sample should be preserved immediately upon sample collection.
c Samples should be analyzed as soon as possible after collection. The times 1
times that samples may be held before analysis and still be considered valid,
the maximum holding times will be flagged.
d Add 0.08% Na2S2Oz if residual chlorine may be present in aqueous samples.
e 0.6 g of ascorbic acid in aqueous samples.
isted are the maximum
All data obtained beyond
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Section No. 5
Revision No. 1
Date: April 29, 1988
Page 35 o7 64
Field Sampling Protocol--
Chain-of-custody procedures begin with the preparation of reagents or
supplies that eventually become a part of the sample (such as filters or
absorbing reagents). The sample collector is responsible for initiating
chain-of-custody procedures and documenting the sample source. Sample col-
lection must be performed in accordance with standard sampling procedures.
If these procedures are changed, a written justification for the deviation
must be entered into the field survey log. After the sample is collected, it
must be prepared in accordance with applicable sampling instructions (i.e.,
fixation, addition of preservative), labeled, sealed, and stored or shipped
in a manner that will maintain the chain of custody.
Chain of Custody--
Chain of custody is the aspect of sample handling assurance that docu-
ments the custody chain that the sample follows. The chain-of-custody form
documents where the sample originated, who authorized and who performed
transmittals, how and when the sample was received, and who received it.
Documentation must be clear.
After the chain-of-custody form is completed, each sample must be logged
in on a sample receipt form and assigned a unique identification number. The
sample receipt form identifies the condition of each sample and designates
the analyses to be run. The sample description and project requirements must
then be entered into the sample log, which also includes project number,
date, and the analyses required. The sample is then properly stored accord-
ing to prior transmitted instructions.
A sample checkout log form must be used for internal chain-of-custody
tracking of samples placed in and taken out of sample refrigerators and
secured storage areas. The person putting the sample in or taking it out of
the designated location indicates this transaction with his/her initials, the
date, and any pertinent comments. Examples of labels, chain-of-custody
forms, sample receipt forms, and sample checkout log forms are shown in
Figures 5-10 through 5-13, respectively.
99
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Section No. 5
Revision No. 1
Date: April 29, 1988
Page 36 o? 64
Project Number:
Site:
Site Description:
Analysis:
Sampler:
Date: / / Time:
Sample Type:
Preserv:
am/pm
C/G
Figure 5-10. Sample bottle label.
When the sample analyses are completed and the sample is consumed, or
discarded, the Sample Custodian logs and initials it accordingly. Only the
Laboratory Director is authorized to transmit or discard samples, and then,
only as authorized by the Laboratory Project Manager.
Sample Seals-
Sample seals are used to guard against and to detect unauthorized tam-
pering of the samples between the time of collection and analysis. Items
such as gummed paper seals and custody tape are used for this purpose. The
seal is attached such that it.must be broken to open the sample container.
Seals should be affixed to containers before the samples leave the custody of
the sampling personnel. Shipping containers should also contain seals to
discourage and detect possible tampering.
Logbooks—
All information pertinent to a demonstration is recorded in ink in a
bound, consecutively page-numbered logbook. Corrections should be lined out,
not erased, and then be initialed and dated. Entries in a logbook should
include the following, as applicable:
1) Location, description, and photographs (if applicable) of the
sampling point. If the sample is obtained from a monitoring well,
entry will include the well number.
2) Type of waste (e.g., ground water, soil, leachate, sludge, or
wastewater).
3) Number and volume of sample taken.
4) Date and time of collection.
5) Collector's sample identification number(s).
100
-------
CHAIN-OF-CUSTODY RECORD
Samplers signature
Project No.
Sample
No.
Seq.
No.
Date
Time
Sample location
Sample type
No. of
conts.
Remarks
TOTAL NUMBER OF CONTAINERS
Relinquished fay (sign)
Date
Time
Received by (sign)
Relinquished by (sign)
Date
Tne
Received by (sign)
Relinquished by (sign)
Date
Time
Received by
Relinquished by
Date
Tme
Received by (sign)
Method of shipment
Shipped by (sign)
Received for laboratory (sign)
Time Date
"DD3JW
b ai it (t
(A (+< n
fD (T> -J* r+
-i- o
O 3
3
CO
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Figure 5-11. Chain-of-custody record.
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Section No. 5
Revision No. 1
Date: April 29, 1988
Page 38 o? 64
Client: Project No.:.
Date Logged:.
Logged by:
Shipper:
007156
Condition of samples:
SAMPLES RECEIVED
Client ID
Sample no.
Analyses requested
Date of
disposal
Type and volume
of container
Figure 5-12. Sample receipt form.
102
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Section No. 5
Revision No. 1
Date: April 29, 1988
Page 39 o? 64
Location:.
Project:
Date/lnHials
Sampie
Numbers
Notes
Figure 5-13. Sample checkout log.
103
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6) Sample distribution and how transported; (e.g., name of the labo-
ratory, the cartage agent (Federal Express, United Parcel, etc.).
7) References, material for the sampling site, such as maps or
photographs.
8) Field observations.
9) Any field measurement made (e.g., pH, flammability, explosivity,
and water depth).
10) The signature of the person responsible for and the date of the
observation.
Summary--
Sampling situations vary widely. No general rules can be set to specify
the extent of information that must be entered in a logbook. Nevertheless,
records must contain sufficient information to allow someone to reconstruct
the sampling activity without having to rely on the collector's memory. The
logbooks should be kept in a safe place for protection.
The samples must be delivered to the laboratory for analysis within the
specified allowable holding time and be accompanied by the chain-of-custody
record. Samples must be packaged and shipped according to U.S. Department of
Transportation and EPA regulations, and they must be delivered to the person
authorized to receive samples at the laboratory.
Sampling Protocol for System Conditions
In addition to the collection of critical measurement data, monitoring
the operation of system parameters is important. These parameters may vary
greatly and they are normally monitored by process instrumentation. Instru-
ments should be used to measure such variables as temperature, pressure,
density, viscosity, specific heat, conductivity, pH, humidity, dew point,
liquid level, flow rate, chemical composition, and moisture content. Process
instruments, which are generally designed for broad application, may continu-
ously record data on a strip chart (or some other medium). They also are
used to control the operation of the process.
104
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For example, process instrumentation might be used to measure pH in the
biological degradation of phenol in soil. This hypothetical batch process
might entail mixing microbial cultures into fixed volumes of contaminated
soil. This process allows the microbes to break down phenol into various
short-chain fatty acids (such as acetic acid) in a pH range of 6 to 9.
Because the production of these fatty acids tends to lower the pH of the
system, however, a buffer solution must be added to the mixing vessel. The
use of pH monitoring equipment would permit the real-time measurement during
processing, and the output from the pH equipment could be recorded on a
strip chart for permanent storage. The pH measurements could also be used to
control the addition of buffer solution. In this example, the measurement of
process pH has provided the following:
1) The real-time measurement of the system's pH.
2) A permanent record of the system's pH on a strip chart.
3) The content of the addition of buffer solution to the process
vessel.
For system conditions that are monitored on a routine basis (e.g.,
facility, design, or process controls and operating parameters), this section
of the QAPP should include only the following items:
0 Identification of all system condition data to be collected, de-
scriptions of the collection methods, and a discussion of the
reasons for collecting these data.
0 Illustrations that accurately depict the monitoring locations at
which the data will be collected.
0 Specification of the frequencies of data collection.
5.5 ANALYTICAL PROCEDURES AND CALIBRATION
This section of the QAPP should include a description of or reference to
an appropriate analytical method for each type of critical measurement to be
made. The calibration procedures and frequency of calibration also should be
discussed or referenced for each system, instrument, device, or technique
used to obtain critical measurement data.
105
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Officially approved EPA analytical methods and procedures should be
selected for use if they are available and applicable. Previously validated
methods should be used whenever possible. When standard EPA-approved methods
are used, their descriptions can be referenced rather than included in the
QAPP. (Approved methods include those in References 2 through 5.) The
selected method must be appropriate for determination of the specific ana-
lytes of interest in the sample matrix involved.
When nonstandard methods of analysis are used, the QAPP must include
detailed descriptions of the method, the standard operating procedure for
implementing the method, and the pertinent validation data, either in this
section or as an appendix.
Table 5-8 presents an example of the sample-preparation and analytical
methods chosen for a project. All the methods listed are from U.S. EPA's
"Test Methods for Evaluating Solid Waste", Third Edition, SW-846, November
1986, and "Methods for Chemical Analysis of Water and Wastes", EPA-600/4-
79-020, March 1983. Each method includes a detailed discussion of the ana-
lytical procedures.
The correct calibration, operation, and maintenance of field equipment
used to make measurements at the sites are extremely important throughout the
demonstration. (The use of the term "calibration" is more generally appli-
cable to chemical methodologies and field instrumentation.) Table 5-9 pro-
vides a sample list of field measurement equipment and corresponding Standard
Operating Procedures (SOPs), field calibration procedures, and frequency of
calibration.
Before onsite activities begin, specific personnel should be assigned
responsibility for each piece of field measurement equipment. These persons
should become familiar with the operation, calibration, and maintenance pro-
cedures for the items assigned to them. Calibration and maintenance activi-
ties are recorded in the daily logbooks.
Laboratory Calibration Procedures
Detailed calibration procedures for all sampling and analytical equip-
ment required for a demonstration are provided in the respective analytical
methods and should be included in the site-specific QAPP. This subsection
provides general calibration procedures for the analytical instrumentation
used in a wide variety of analytical methods.
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TABLE 5-8. SAMPLE PREPARATION AND ANALYTICAL METHODS3
Preparation method Analytical
Parameter class Liquid Solid method
BDAT List
Volatiles NA NA 8240
Semivolatiles 3520 3550 8270
Alcohols NA NA Direct injection
with a GC/FID
Metals
Antimony 3005 3005 6010
Arsenic 3050 3050 7060
Barium 3005 3050 6010
Beryllium 3005 3050 6010
Cadmium 3005 3050 6010
Chromium(T) 3005 3050 6010
Chromium(VI) NA NA 7196
Copper 3005 3050 6010
Lead 3020 3050 7421
Mercury 7470 7471 NA
Nickel 3005 3050 6010
Osmium 3005 3050 7550
Selenium 3050 3050 7740
Silver 3020 3020 6010
Thallium 3020 3050 7841
Vanadium 3005 3050 6010
Zinc 3005 3050 6010
Inorganics (other than metals)
Cyanide(T) NA NA 9010
Cyanide(A) NA NA 9010
Fluoride NA NA 340.2
Sulfide NA NA 9030
Organochlorine pesticides 3520 3550 8080
Phenoxyacetic acid herbicides NA NA 8150
Organophosphorus insecticides 3520 3550 8140
PCBs 3520 3550 8080
Dioxins and furans NA NA 8280
(continued)
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Section No. 5
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TABLE 5-8 (continued)
Parameter class
Preparation method
Liquid Solid
Analytical
method
OAQPS List
Volatiles
Semivolatiles
Ammonia
Alcohols
PCBs
Dioxins and furans
NA
3520
NA
NA
3520
NA
NA
3550
NA
NA
3550
NA
8240
8270
350.2
b
8080
8280
POC
NPOC
TCLP List
Volatiles NA NA
Semivolatiles 3520 NA
Metals
Arsenic 3050 NA
Barium 3005 NA
Cadmium 3005 NA
Chromium 3005 NA
Lead 3020 NA
Mercury 7470 NA
Selenium 3050 NA
Silver 3020 NA
Alcohols NA NA
Organochlorine pesticides 3520 NA
Phenoxyacetic acid herbicides NA NA
Others
pH NA 9045
Chloride 300.0 Water ex-
traction
Total residue NA NA
COD NA NA
TOC NA NA
Ethylenediamine 3520 3550
Tartaric acid 3520 3550
Ash (after ignition at 550°C)
8240
8270
7060
6010
6010
6010
7421
7470
7740
6010
8240
8080
8150
9040
NA
160.3
410.3
415.1
8270
8270
160.4
Methods from "Test Methods for Evaluating Solid Waste", 3rd ed., SW-846,
November 1986 and EPA 600/4-79-020, "Methods for Chemical Analysis of
Water and Wastes".
108
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TABLE 5-9. SAMPLE FIELD EQUIPMENT CALIBRATION CHECKLIST
Instrument
SOP
Calibration Procedure
Frequency
HNU Model Pl-101
trace gas ana-
lyzer
See HNU instruc-
tion manual,
See HNU instruction manual, pp. 3-1 to 3-6 and
8-1 to 8-10 for calibration gas procedures
Zero instrument
Daily
Daily or after
4 hours of use
o
pH meter
Per manufacturer's
instructions
Conductivity meter
Per manufacturer1s
instructions
Immerse electrodes in buffer solution of known
pH, adjust meter to proper reading. Remove and
rinse electrodes. Immerse in second buffer so-
lution of a known pH, adjust meter. Standard
buffer solutions should bracket the sample pH.
Repeat above until readings are within 0.05
units of buffer solution values. All solutions
should be at ambient temperature
Obtain correction factor by comparing observed
reading with a standard salt solution and dis-
tilled or deionized water
Daily or after
4 hours of use
Dai ly
Zero instrument
Daily or after
4 hours of use
MSA Model 53 ex-
plosimeter
Foxboro/Century
organic vapor
analyzer, Model
0VA-108
Per procedures
stated on meter
Per Foxboro/Cen-
tury instruction
and service manual
Number MI-2R900AD
Per procedures stated on meter
See Foxboro/Century i
manual, pp. 7 to 9
nstruction and service
Daily
Dai ly
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-------
Section No. 5
Revision No. 1
Date: April 29, 1988
Page 46 of 64
Plasma Emission Spectrometer--
A plasma emission spectrometer, which operates under the same general
principles as a UV light spectrometer, may be used to analyze for a variety
of inorganic constituents. The general calibration procedure for the plasma
emission spectrometer is as follows:
1) The instrument should be set up and programmed according to the
procedures contained in the instrument operating manual.
2) Instrument linearity and detection limits are determined quarterly.
3) All calibration standards, the calibration blank, control samples,
and regular samples are spiked with the internal standard.
4) All standards and samples are analyzed in duplicate, and a blank
rinse is used between each sample and standard.
5) The first run of each analysis is a signal compensation blank,
followed by a calibration blank and mixed calibration standards
(5 ppm) for each element to be analyzed.
6) An independent control sample is run after the calibration stan-
dards, after every 10 to 15 samples, and after the last sample. If
the results of this standard fail to agree within +10 percent of
the accepted value, the previous 10 to 15 samples must be reana-
lyzed.
7) Each matrix is spiked with the elements being analyzed to determine
any matrix interferences (acceptable recovery is 75 to 125 per-
cent). At least 1 sample in 20 is spiked in duplicate.
8) Any sample exceeding the linear range for one or more elements is
diluted and reanalyzed.
Other Inorganic Methods--
The following are general calibration procedures for other inorganic
methods:
1) Analytical balances are checked with Class 5 weights each day they
are used. If a trend toward inaccuracy is found and cannot be
corrected by laboratory personnel, professional service must be
obtained. The balances are professionally serviced and checked
against NBS-certified weights each year.
2) Atomic absorption spectrophotometers are used in a number of EPA-
approved methods, including 7060, 7080, 7130, and a variety of
other metal analyses. Atomic absorption spectrophotometers are
calibrated for each metal analyzed, and a record is kept of instru-
ment response. A minimum of a blank plus four upscale points are
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used for calibration. This full set of standards is analyzed
initially and then periodically during a large set of samples and
after the last sample. Should a lack of sensitivity or other
malfunction be detected that cannot be corrected in-house, profes-
sional services must be obtained.
3) Ultraviolet/visible (UV) spectrophotometers may be used to analyze
for a variety of ions, e.g., the permanganate ion. The UV spectro-
photometers are checked with standard color cuvettes each day they
are used and are checked for minor and grating alignment monthly.
A full set of calibration standards (consisting of a blank and at
least four upscale points) is analyzed to establish the calibration
curve. A check sample is analyzed after every tenth sample and
after the last sample. If the results of this check sample fail to
agree within +10 percent of the accepted value, the instrument is
recalibrated and the previous 10 samples are reanalyzed. Concen-
trations of the standards are as specified in the method. Service
criteria are the same as those described for the other instruments.
4) The ion chromatograph is calibrated each day it is used. A minimum
of a blank and four upscale points are used to establish the cali-
bration curve. A check sample is analyzed after every tenth sample
and after the last sample. If the results of this check sample
fail to agree within +10 percent of the accepted value, the instru-
ment is recalibrated and the previous 10 samples are reanalyzed.
Organic Methods—
The following are general calibration procedures for organic methods:
1) The high-pressure liquid chromatograph (HPLC) and the standard gas
chromatographs (GCs) are calibrated each day analyses are per-
formed. These instruments provide for the separation and analysis
of numerous organic-based compounds, such as polychlorinated bi-
phenyls (PCBs) (EPA Method 8080). At a minimum, a blank and five
upscale points are used to establish the calibration curve. One of
the calibration standards is reanalyzed after every tenth sample
and after the last sample to establish the continuing validity of
the initial curve. The criterion for continuing validity is spec-
ified in the individual methods. If the criterion is not met, the
instrument is recalibrated and the previous 10 samples are reana-
lyzed.
2) The GC/mass spectrometers (GC/MS) provide for analysis of volatile
and semi volatile organic compounds as outlined in EPA procedure
8240. The GC/MS's are checked for mass calibration with FC-43 each
analysis day and are tuned to the criteria specified in the method
with BFB or DFTPP (4-bromoflurobenzene or decafluorotriphenylphos-
phine) depending on whether samples are intended for volatile or
semivolatile analysis. Calibration requires a minimum of a blank
and three upscale points and the use of the internal standard
method of determining response factors. Continuing calibration is
based on satisfactory agreement of a daily check standard. The
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requirements for satisfactory agreement are specified in the QA
plan for the project or the specified method. If satisfactory
agreement is not obtained, the instrument is recalibrated before
proceeding with the analyses.
Preventive Maintenance
The preventive maintenance of analytical, laboratory, and operational
process equipment is important to the success of the demonstration. The
Contractor and Developer should assemble and regularly review a maintenance
checklist to include the following:
1) A complete list of all operational process and analytical laborato-
ry equipment and its location.
2) Frequency and description of each preventive maintenance activity,
e.g.:
XYZ Sampling Pump: Check seals Weekly
Repack bearing Monthly
3) The individual designated to perform each preventive maintenance
task.
Spare parts for process equipment, analytical equipment, and sample
collection must be inventoried on a regular basis. Although it is not neces-
sary to keep an onsite supply of those equipment parts that are stocked
locally, a supply of hard-to-find parts should be kept on site for emergency
repair. Availability of spare parts is essential to the implementation of a
preventive maintenance program.
5.6 DATA REDUCTION, VALIDATION, AND REPORTING
For all laboratory data generated and processed to be scientifically
valid, defensible, and comparable, the correct equations and procedures must
be used to prepare those data. Each method presented in Reference 2 is
accompanied by a set of calculations and appropriate forms for data pre-
sentation. Each analytical method presented in SW-846 provides detailed
instructions for calculating concentrations of specific analytes. The fol-
lowing subsections also present general criteria concerning the processing of
data.
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Data Reduction
Analytical results should be reduced to concentration units specified in
the analytical procedure, as cited in SW-846 (or a similar reference). If
units are not specified in the analytical procedure, data from the analysis
of water samples should be reported in milligrams/liter for inorganic param-
eters and micrograms/1 iter for organic parameters. Data from the analysis of
solid samples should be converted to units of milligrams/kilogram for inor-
ganic parameters by use of the following equation:
Xw = £xv x V * d,f'^ 1 w
where X = Reported value, mg/kg
w
Xy = Reported sample value, mg/liter
V = Sample volume, liters
d.f. = Dilution factor
w = Sample weight, kg
This same basic equation is used for organic concentrations, except that Xw
will be in units of micrograms/kilogram and Xy will be in units of micro-
grams/1 iter.
Data Validation
Data validation is the process of screening data and accepting or re-
jecting these data on the basis of sound criteria. The QA personnel should
use validation methods and criteria that are appropriate for the type of data
involved and purpose of the measurement. Validation procedures should in-
clude the following:
1) Ensuring adherence to the specified sampling, preparation, cleanup,
and analysis procedures.
2) Examining precision, accuracy, and other QC data generated during
the project.
3) Ensuring the use of properly calibrated and maintained sampling
equipment and analytical instrumentation.
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Outlier data may be thought of as QC data that fall outside of a spe-
cific QA objective window for accuracy or precision. Such data should be
identified during the daily examination of QC data. When outlier data are
identified, an investigation should be conducted to isolate the causes, and
the results should be promptly reported to the Project Manager (or his repre-
sentative). If possible, affected samples should be reanalyzed. If reanal-
ysis corrects the problem, then only the reanalysis data should be reported.
If both sets of analysis contain the outlier, both results should be report-
ed, and the outlier should be identified in the final report. If reanalysis
is not possible, the initial results should be reported, and the outlier
should be identified in the final report. Records of all data should be
maintained, even those judged to be "outlying" or of spurious value. The
persons validating the data should be sufficiently knowledgeable with regard
to the technical work to be able to identify questionable values.
Analytical data generated in this program are considered useful if the
quality control data for a spiked sample achieve the precision and accuracy
goals stated in the site-specific QA plans and the sample was analyzed within
the maximum holding time. Spiked laboratory-pure water should be used in
assessing data usefulness when the sample itself cannot be spiked because of
its physical nature or the nature of the analysis parameters. If the pre-
cision and accuracy do not achieve the QA objectives, these data should be
flagged, and the impact of not meeting the QA objectives should be deline-
ated.
Problems of this type may be identified by the analysts or their super-
visor, who may take the corrective action specified in the specific QA Plan.
The QA Officer must be notified when this occurs. When corrective action is
needed, sufficient reanalyses must be performed to establish whether the
deviant QC result was caused by the sample matrix or by an out-of-control
analysis. Out-of-control analyses must be repeated.
Data Reporting
Figure 5-14 presents a flow chart depicting the data-reporting scheme.
Data will be reported in standard units, usually as micrograms/1 iter or
milligrams/liter for trace analytes. Any necessary deviations from SW-846
procedures should be fully documented.
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Page t? 1 o? 64
NO
YES
QC RESULTS
UNACCEPTABLE
QC RESULTS
ACCEPTABLE
DATA
UNACCEPTABLE
DATA
ACCEPTABLE
PRECISION AND
ACCURACY
ACHIEVED?
REVIEW DATA, REANALYZE
IF NECESSARY AND IF
POSSIBLE
SAMPLE PREPARATION
AND ANALYSIS
PROCEED WITH DATA
REDUCTION, REPORT
ALL VALUES IN
APPROPRIATE UNITS
REVIEW
QC DATA
REVIEW DATA.
REANALYZE
IF NECESSARY
REVIEW DATA, REANALYZE
IF NECESSARY AND IF
POSSIBLE
DATA REVIEWED
BY CONTRACTOR
PROJECT MANAGER
VALIDATED DATA
ENTERED INTO
PROJECT FILE
DATA REPORTED
IN TECHNICAL REPORT
Figure 5-14. Data reporting scheme.
115
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5.7 INTERNAL QUALITY CONTROL CHECKS
The QA Project Plan for each task should specify the internal quality
control measures that will be used to ensure optimum valid data collection.
The QA Plan should specify the appropriate QC checks, the control limits, and
the planned corrective action to be used if control limits are exceeded. The
quality control checks outlined in the following subsections are oriented
toward chemical testing. Similar QC checks are not as specifically defined
for biological tests. It is important that the Developer review all biologi-
cal evaluations with appropriate laboratory personnel to ensure that appro-
priate measures are being taken during each analysis.
Internal Quality Control Measures
Internal quality control procedures for analytical programs are sum-
marized in this subsection. The analytical QC program should make use of QC
samples whose values are known, calibration check samples, method blanks,
replicate aliquot analyses, surrogate spikes, and matrix spikes.
Known QC samples, called laboratory control standards (LCS) or standard
reference solutions or laboratory-purewater spikes, are prepared by adding
known quantities of EMSL-Cincinnati, NBS Standard Reference, or independently
prepared stock materials to deionized water. The LCS are routinely used to
establish that an instrument or procedure is in control before sample anal-
ysis begins. The analysts report the LCS result to the QC clerk, who plots
it on the control chart.
A calibration check sample is one of the working calibration standards
periodically used to check that the original calibration is still valid.
A method or reagent blank consists of deionized water carried through
the entire preparation and analysis procedure. Analytical results should not
be corrected for the method blank. Instead, both the uncorrected sample
results and the blank results will be reported. Method blank samples for
organic compositional analysis should be analyzed for volatile, base-neutral/
acid, and PCB fractions. For inorganic analysis, separate method blanks for
flame, furnace, and cold vapor digestates should be analyzed.
At least one sample, chosen at random, should undergo a complete dupli-
cate analysis. Replicate aliquots of actual samples or QC samples are ana-
lyzed so that the precision of the analytical procedure can be estimated.
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A surrogate spike compound is one that mimics the behavior of target
analytes in terms of stability, preparation losses, measurement artifacts,
etc., but does not interfere with the target analyte measurement. The surro-
gate spiking procedure should be used in the analysis of volatile and base-
neutral fractions by GC/MS. Recovery data should be included in the QA/QC
section of the final report.
A matrix spike sample is prepared by adding known amounts of the target
analyte(s) to an aliquot of an actual sample. As indicated in SW-846 (3rd
Edition), duplicate matrix spikes of a field sample are generally used to
determine both precision and accuracy (percentage recovery). The frequency
varies between 1 in 10 and 1 in ZQ samples of a given matrix type, depending
on the particular procedure.
Type and Frequency of Use of QC Measures
A minimum standard for the type and frequency of use of each QC measure
should be presented. These requirements may be revised depending on the
timing and scope of the demonstration. Any alterations to these measures
require EPA approval. The following is a schedule of instrument QC checks
and their frequency:
1) Calibrations (or calibration checks) should be performed at least
daily. Laboratory personnel should consult standard operating
procedures and manufacturers' literature to define specific in-
tervals.
2) An LCS analysis value within control limits is performed daily
before sample analysis is begun.
3) A calibration check or an LCS sample within the original value of
the method limit is run after every 10 samples (inorganic analy-
sis).
4) An appropriate calibration check or LCS samples may be run as often
as every five samples for some organic analyses, whereas only a
daily calibration check sample may be run for other organic anal-
yses (such as GC/MS).
5) A method blank is used with each analysis batch (20 or less sam-
ples). The preparation and/or extraction dates should match those
of the samples they represent.
6) Surrogate spikes are used in all organic GC/MS analyses.
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7) Ten percent of all inorganic samples and five percent of all or-
ganic samples (or a minimum of one per sample batch of 20 or less,
whichever is greater) should be split in the laboratory into three
aliquots prior to the first sample preparation or extraction step
in the procedure. Two aliquots should be spiked with the same
amount of the desired constituents (duplicate matrix spikes).
Duplicate matrix spikes are used to determine precision and ac-
curacy (percentage recovery).
8) A trip blank should be used during each sampling episode. Trip
blanks should be prepared beforehand in the laboratory, carried
into the field, and then returned to the laboratory for analysis.
A trip blank provides a check on sample contamination resulting
from sample transport or shipping and from site conditions.
Special QC Considerations
Reagents used in the laboratory are normally of analytical reagent grade
or higher purity; each lot of acid and solvent used is checked for accepta-
bility prior to its use. All reagents should be labeled with the date re-
ceived and date opened. Deionized water quality should be routinely checked.
Subcontractor laboratories should make at least those QC checks outlined
here and report the results of all QC samples with the data. No field spikes
are planned because it is difficult to spike samples accurately in the field.
In the laboratory, preventive maintenance should include attention to
glassware, water supply, reagents, and analytical balances, as well as the
more complex instrumentation. Table 5-10 summarizes the preventive mainte-
nance procedures for the instruments expected to be used during a demonstra-
tion.
5.8 PERFORMANCE AND SYSTEM AUDITS
The QA plan should describe the internal performance evaluation and
technical system audits for monitoring the capacity and performance of each
critical measurement system. Internal laboratory quality control checks,
including analysis of duplicates, spikes, and blanks, are described in Sub-
section 5.9. Data generated as part of the internal quality control program
should be reviewed by the QA Officer (or a subcontractor's QA Officer) and
the Contractor Project Manager to assure the absence of systematic bias or
trends and to ensure that appropriate corrective actions are taken as re-
quired. Quality problems identified and necessary corrective actions taken
should be included in the SITE report.
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29,
W
1988
"64
TABLE 5-10. MAINTENANCE PROCEDURES AND SCHEDULE FOR MAJOR INSTRUMENTATION
Instrumentation
Maintenance procedure/schedule
Spare parts
GC/MS
Inductively-
coupled plasma
spectrometer
Perkin-Elmer model
atomic absorption
spectrophotometer
graphite furnace
GC
1. Replace pump oils annually.
2. Change septa daily.
3. Change gas line dryers quarterly.
4. Replace electron multiplier as needed.
1. Clean optical surfaces monthly or as
needed.
2. Clean torch assembly when discolored
or after 8 h of running high-dis-
solved-solids samples.
1. Clean optical surfaces weekly.
2. Condition graphite tube before
starting analysis.
3. Check condition of graphite contact
rings weekly; replace if pitted or
worn.
4. Clean atomizer windows weekly or as
needed.
1. Change septa daily.
2. Check syringe for burrs daily.
3. Change gas line dryers quarterly.
4. Leak check when installing a new
analytical column.
5. Periodically check inlet system for
residue buildup.
Syringes
Septa
Columns
Liquid nitrogen
Autosampler
tubing
Liquid argon
Injector tubes
Spare windows
RF coil
Graphite tubes
Graphite contact
rings
Autosampler
tubing
Syringes
Columns
Septa
Swagelok
fittings
FID jets
Injection port
liners
A technical systems audit consists of an evaluation of all components of
a critical measurement system. It includes a careful evaluation of both
field and laboratory quality control procedures. Normally, system audits are
performed before or shortly after a system is operational. In addition,
secondary audits should be made on a regularly scheduled basis during the
lifetime of the project. An onsite systems audit also may be a requirement
for many formal laboratory certification programs.
The field activities of a subcontractor should be audited internally at
least once by the Contractor to assure that the required equipment and proce-
dures for sample collection, preservation, shipping, handling, and documenta-
tion are being used. Audit results should be reported on a regular basis and
also be included in the final SITE report.
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5.9 CALCULATION OF DATA QUALITY INDICATORS: SPECIFIC ROUTINE PROCEDURES
USED TO ASSESS DATA PRECISION, ACCURACY, COMPLETENESS, AND METHOD
DETECTION LIMIT
The quality control activities undertaken during the demonstration
should include:
1) Ongoing activities to assure that measurement systems are under
control.
2) Activities specific to a given treatment technology evaluation
experiment.
The ongoing quality control activities consist principally of evaluating
data obtained (when possible) from the following sampling categories:
0 Calibration standards 0 Laboratory blanks
0 Surrogate spikes 0 Control standards
0 Matrix spikes 0 Field samples
° Duplicate analyses
Procedures used to evaluate these data should include calculations of arith-
metic means, standard deviations, relative percent difference (relative
range) if less than three data points, comparison of differences between
duplicate analyses, and spike sample values expressed as percentage recovery.
These values should be included as an appendix in each SITE report.
Project-specific data evaluation procedures depend on the demonstration
and, in turn, on the types and numbers of field samples to be collected. In
general, the overall objectives of the technology demonstration probably
should include a comparison of concentrations of one or more measurement
parameters in a waste before and after treatment and qualitative and quanti-
tative determination of accompanying emissions, byproducts, etc. For the
most part, the statistical procedures used for this work are expected to be
simple and straightforward. For example, they should Include calculation of
limits of detection, limits of quantification, standard deviation, and rela-
tive percent difference (relative range), and an evaluation by least-squares
linear regression. In all cases, these procedures should be taken from ap-
propriate EPA documents and manuals for the media under investigation. Over-
all guidance should be obtained from the EPA document entitled "Calculation
of Precision, Bias, and Method Retention Limit for Chemical and Physical Mea-
surements," issued on March 30, 1984, as Chapter 5 in the EPA Quality Assur-
ance Manual.
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Precision
Precision should be estimated by the analysis of replicate samples. If
three or more values are determined, they should be expressed as the standard
deviation, s, which is determined by the following equation:
N , N 2
Z X/ - 1 E X.
S = i = 1 1 N 1 - 1 1
N - 1
where S = standard deviation
X. = individual measurement result
N1 = number of measurements
Relative standard deviation may also be reported. If so, it should be
calculated as follows:
RSD = 100 * |
where RSD = relative standard deviation, expressed in percent
S = standard deviation
X = arithmetic mean of replicate measurement
If only two values are determined, precision should be estimated by
calculating the relative percent difference (relative range) with the fol-
lowing equation:
(D, - DJ (100)
RPD = -
(Dj + D2)/2
where RPD = relative percent difference
D. = the larger of the two observed values
D^ = the smaller of the two observed values
Accuracy
Accuracy should be estimated from the analysis of QC samples whose true
values are known, surrogate spike recoveries, or matrix spike recoveries, and
it should be expressed as percentage recovery. The formulas for calculating
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these values are as follows:
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1) For QC samples:
* _ mn ,measured valueA
Percentage recovery = 100 ( trye Vj^ue )
2) For surrogate spikes:
Percentage recovery = 100 (""true^a 1 ue^U&)
3) For matrix spikes:
C, - C
Percentage recovery = 100 (——-)
where C. = value of spiked aliquot
C = value of unspiked aliquot
= value for spike added
Completeness
Completeness should be reported as the percentage of all measurements
made whose results are judged to be valid. The following formula should be
used to estimate completeness:
C = 100 (^)
where C = percent completeness
V = number of measurements judged valid
T = total number of measurements
Method Detection Limit (MDL)
This approach for determining MDL and method quantitation limit (MQL) is
taken from Chapter 1 of SW-846 (3rd Edition).
The detection and quantification limits of analytes are evaluated by
determining the noise level for each analyte. If an analyte is present, the
noise level adjacent in retention time to the analyte peak may be used. For
wave length dispersive instrumentation, multiple determinations of digestates
with no detectable analyte may be used to establish the noise level. The
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method of standard additions should then be used to determine the calibration
curve for the digestate or extracted sample in which the analyte was not
detected. The slope of the calibration curve, m, should be used to calculate
MDL and MQL by using the following:
m = slope of calibration line
Sg = standard deviation of the average noise level
MDL (MQL) = KSg/m
For K = 3; MDL = method detection limit
For K = 5; MQL = method quantitation limit
The methods given in SW-846 (3rd edition) generally provide MDLs and practi-
cal quantitation limits (PQLs) for various matrices. Each laboratory must
determine the MDLs for the methods and explain the procedure used to obtain
them. These values cannot necessarily be obtained for all samples. The
impact of varying matrices on MDLs should be addressed in the Developer's
laboratory report.
5.10 CORRECTIVE ACTION
An analyst who obtains a value that fails to meet specifications for
accuracy or precision should immediately notify the QA Officer, who will then
take the following steps to correct the deficiency:
1) Review the calculations for calculating and transcribing errors.
2) Review the analysis with the analyst to determine whether any pro-
cedural errors were made.
3) Examine reagents and equipment to determine if they were func-
tioning and were used properly.
4) Examine the instrumentation for calibration and signal response.
If calculation errors were found and corrected, no further action would
be taken. If other causes were responsible, analyses would be rerun to
obtain results within specifications or to document that the sample matrix is
the cause of the problem.
When these procedures fail to reveal an apparent problem, the Quality
Assurance Officer and the Project Manager must determine the appropriate
action to be taken.
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Because of its generic nature, this QA Plan cannot address every situa-
tion that may arise with the wide variety of sample types and analyses
included in a particular demonstration. Therefore, the following cases are
given as illustrations to assist in determining what corrective actions
should be applied.
Examples of Out-of-Control Events and Corrective Actions
The following are general examples of out-of-control events and appro-
priate corrective actions:
1) Two testing laboratories do not agree in the determination of fecal
coliform. The failure to dechlorinate samples or inaccurate tem-
perature control may have caused the discrepancies. Laboratory
personnel should review all procedures to ensure that the test is
administered correctly.
2) The percent difference for response factors on GC/MS calibration
check standards is greater than 20 percent. This is considered a
warning limit. If the percent difference is greater than 25,
corrective action must be taken. If the source of the problem
cannot be determined after corrective action, a new initial cali-
bration must be generated before sample analyses are continued.
3) The laboratory method blank exceeds the required criteria. The
source of contamination must be investigated, and appropriate
corrective measures must be taken and documented before sample
analysis proceeds. Samples processed with an out-of-control method
blank must be reanalyzed.
4) The analytical spike value for a graphite furnace metals analysis
of a sample is not within the required 75 to 125 percent recovery
window. The sample is diluted and another analytical spike is
prepared and analyzed. If the spike value is still not within the
required percent recovery window, the method of standard addition
must be used for the sample analysis.
General
Because of the wide variety and total number of samples that must be
analyzed for a demonstration within a very short time period, the QA objec-
tive is to apply currently accepted procedures and to obtain the best results
possible with those procedures. The development of new procedures is not
possible, but corrective action must be sufficient to show that the analyti-
cal procedures are in a state of statistical control and that QC results out-
side the QA objectives are due to problems in the sample matrix. Some of the
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methods call for analyzing all samples by the method of standard addition if
certain criteria are not met. Depending on the sample load and how critical
the deadlines are, EPA QA personnel may waive this requirement. Sufficient
spikes and/or reanalyses should be run to document these problems; however,
it may be impossible to resolve them prior to the deadlines.
5.11 QUALITY CONTROL REPORTS
General
During the course of the project, a reporting mechanism must be in place
to keep demonstration management and EPA informed of analytical progress, any
problems, and the results of QA/QC assessments. These reports should address
progress, data quality, analytical problems, and possible corrective action
procedures and should include an up-to-date assessment of data quality in
terms of precision, accuracy, completeness, and MDLs attained. Significant
problems that come to light during the demonstration should be relayed to the
EPA Project Manager. Also, any planned deviations to the approved QA Plan
should first be cleared with the EPA Project Manager.
Final Reports
In the final demonstration report, a separate QA section should sum-
marize the data quality information (including audit reports, if audits were
conducted) obtained for each site. The QA section should contain the follow-
ing:
1) A data quality statement for precision.
2) A data quality statement for accuracy.
3) A discussion of the QA objectives that were met and those not met.
4) If QA objectives were not met, a discussion of that impact on the
project.
In addition to the final SITE report, EPA intends to develop an Applica-
tion Analysis Report for each technology demonstration. This reoprt will
address the application of the technology to other waste/matrix scenarios
based on the demonstration results.
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5.12 REFERENCES FOR SECTION 5
1. Simes, G.F. Quality Assurance Procedures for HWERL. Hazardous Waste
Engineering Research Library, Office of Research and Development, U.S.
Environmental Protection Agency, August 26, 1985 (revised October 10,
1986). HWERL Document Control No. OAP-0006-GFS. 1986.
2. U.S. Environmental Protection Agency. Test Methods for Evaluating Solid
Waste, Volumes 1A-1C: Laboratory Manual, Physical/Chemical Methods,
SW-846, Third Edition. Office of Solid Waste. Document Control No.
955-001-00000-1. 1986.
3. American Water Works Association. Standard Methods for the Examination
of Water and Wastewater. 16th Edition. 1985.
4. Guidelines Establishing Test Procedures for the Analysis of Pollutants
Under the Clean Water Act. 40 CFR Part 136. Federal Register, Vol. 49
(209), Friday, October 26, 1984. Appendix A—Methods for Organic Chem-
ical Analysis of Municipal and Industrial Wastewater. 1984.
5. U.S. Environmental Protection Agency. Methods for the Chemical Analysis
of Water and Wastes. EPA-600/4-79-020 (revised March 1983). Environ-
mental Monitoring and Support Laboratory, Cincinnati. 1983, and sub-
sequent EPA-600/4 Technical Additions thereto.
5.13 ANNOTATED GLOSSARY OF TERMS
Blank - A blank is an artifical sample designed to monitor the introduction
of artifacts into the process. For aqueous samples, reagent water is
used as a blank matrix; however, a universal blank matrix does not exist
for solid samples; therefore, no matrix is used. The blank is taken
through the appropriate steps of the process.
A reagent blank is an aliquot of analyte-free water or solvent analyzed
with the analytical batch. Field blanks are aliquots of analyte-free
water or solvents brought to the field in sealed containers and trans-
ported back to the laboratory with the sample containers. Trip blanks
and equipment blanks are two specific types of field blanks. Trip
blanks are not opened in the field. They serve as a check on sample
contamination originating from sample transport, shipping and from site
conditions. Equipment blanks are opened in the field and the contents
are poured appropriately over or through the sample collection device,
collected in a sample container, and returned to the laboratory as a
sample. Equipment blanks serve as a check on sampling device clean-
liness.
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Calibration Standards and Devices (traceable) - Working standards or devices
used for calibration purposes that are themselves calibrated or checked
against a material or device with a known, true, reference value.
Collocated Samples - Air samples collected at the same time and location with
adequate distance between them to preclude airflow interference. The
difference in measured concentrations between the two collocated sam-
plers is used to assess precision.
Control Charts - A quality control tool used to track the performance of
field and laboratory instruments. After an instrument is calibrated,
calibration limits are set (e.g., ±7.5 percent) as a control measure.
If the limits are exceeded, the control charts indicate the instrument
must be recalibrated.
Independent Multilaboratory Analysis for Interlaboratory Comparison Studies -
Used to determine precision between laboratories by using the same
analytical methods and procedures and split samples or replicates. This
also helps detect a laboratory bias (should any particular lab be sig-
nificantly different), which could then be addressed.
Independent Multimethod Analysis - Used to determine the accuracy of a par-
ticular analytical method; may be used to study the appropriateness of a
given method or procedure with a given matrix or background.
In-House Proficiency Testing Program - A program to determine and document
the analysts' capabilities in the lab by incorporating practice runs of
documented procedures and replicate or split samples, which are analyzed
by different analysts to assess the individual analyst's accuracy and
intralaboratory precision. This emphasizes to the analyst the impor-
tance of quality work and gives impetus to appropriate corrective action
and further training as necessary.
Internal Standard - Known amount of a known compound (very similar in charac-
teristics or behavior to a target compound) that is added to the sample
immediately prior to analysis to provide a relative measure of instru-
ment and analytical variability.
Laboratory Pure Water Spikes - Reagent, analyte-free, or laboratory pure
water means distilled or deionized water or Type II reagent water that
is free of contaminants that could interfere with the analytical test in
question. Laboratory-pure-water spikes are made by adding a predeter-
mined quantity of stock solution of certain analytes to the laboratory
pure water prior to sample extraction/digestion and analysis.
Matrix/Spike Duplicate Analysis - In matrix/spike duplicate analysis, prede-
termined quantities of stock solutions of certain analytes are added to
a sample matrix prior to sample extraction/digestion and analysis. Sam-
ples are split into duplicates, spiked, and analyzed. Percent recov-
eries are calculated for each of the analytes detected. The relative
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percent difference between the samples is calculated and used to assess
analytical precision. The concentration of the spike should be at the
regulatory standard level or the estimated or actual method quantifi-
cation limit. When the concentration of the analyte in the sample is
greater than 0.1 percent, no spike of the analyte is necessary.
Reagent Checks - Reagents are analyzed prior to use to document impurity-free
reagents (especially useful to document the absence to any target anal-
yses). The reagents are certified to be of a known and acceptable
quality.
Replicate Check Standard - Appropriate standard (may be laboratory pure water
spike or independently prepared reference standard) that is run in
replicate to generate precision data at a given concentration. This
standard may be used to bracket field samples and blanks to demonstrate
acceptable analytical precision throughout the run.
Replicate Sample - A replicate sample is a sample prepared by dividing a
sample into two or more separate aliquots. Duplicate samples are con-
sidered to be two replicates.
Split Samples - Respresentative subsamples taken from the same sample. Split
samples are normally provided when two or more parties are interested in
analyzing the samples independently. Individual laboratories routinely
split samples to perform matrix spikes and matrix spike duplicate anal-
yses.
Surrogates - Surrogates are organic compounds that are similar to analytes of
interest in chemical composition, extraction, and chromatography, but
that are not normally found in environmental samples. These compounds
are spiked samples prior to analysis. Percent recoveries are calculated
for each surrogate.
Zero and Span Gases - At regular Intervals between instrument calibrations,
zero and span gases are used to check the calibration of an instrument.
Zero-air, verified to be free of contaminants that would cause detect-
able responses in the instrument, is used to establish the baseline
response for the contaminant of interest. Span gas, consisting of a
relatively pure concentration of the contaminant of interest, is used to
provide a single upscale recorder response in the range of 70 to 90
percent. The recorder response is used to determine the calibration
relationship of the instrument.
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