MIDWEST RESEARCH INSTITUTE
VERIFICATION OF PCB SPILL CLEANUP BY
SAMPLING AND ANALYSIS
DRAFT INTERIM REPORT NO. 2
TASK 37
EPA Prime Contract No. 68-02-3938
MRI Project No. 8201-A(37)
May 7, 1985
Prepared for
U.S. Environmental Protection Agency
Office of Toxic Substances
Field Studies Branch (TS-798)
401 M Street, S.W.
Washington, D.C. 20460
Attn: Mr. Daniel T. Heggem
MIDWEST RESEARCH INSTITUTE 425 VOLKER BOULEVARD, KANSAS CITY MISSOURI 64110 • 816 753-7600
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MRI WASHINGTON, D.C. 20006-Suite 250, 1750 K Street, NW. • 202 293-3800
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VERIFICATION OF PCB SPILL CLEANUP BY
SAMPLING AND ANALYSIS
Bruce A.
Mitchell 0.
Stephen E.
Gary L.
David C.
Bradley D.
Boomer
Erickson
Swanson
Kelso
Cox
Schultz
DRAFT INTERIM REPORT NO. 2
TASK 37
EPA Prime Contract No. 68-02-3938
MRI Project No. 8201-A(37)
May 7, 1985
Prepared for
U.S. Environmental Protection Agency
Office of Toxic Substances
Field Studies Branch (TS-798)
401 M Street, S.W.
Washington, D.C. 20460
Attn: Mr. Daniel T. Heggem
MIDWEST RESEARCH INSTITUTE 425 VOLKER BOULEVARD, KANSAS CITY, MISSOURI 64110 • 816 753-7600
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DISCLAIMER
This document is a preliminary draft. It has not been released
formally by the Office of Toxic Substances, Office of Pesticides and Toxic
Substances, U.S. Environmental Protection Agency, and should not at this
stage be construed to represent Agency policy. It is being circulated for
comments on its technical merit and policy implications.
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PREFACE
This Draft Interim Report was prepared for the Environmental Pro-
tection Agency under EPA Contract No. 68-02-3938, Work Assignment 37. The
work assignment is being directed by Mitchell D. Erickson. This report was
prepared by Dr. Erickson, Bruce Boomer, Gary Kelso, and Steve Swanson of
Midwest Research Institute (MRI). The sampling design (Section IV.A) was
written by David C. Cox and Bradley 0. Schultz of the Washington Consulting
Group, 1625 I Street, N.W. , Washington, D.C. 20006, under subcontract to
Battelle Columbus Laboratories, Subcontract No. F4138(8149)435, EPA Contract
No. 68-01—6721 with the Design and Development Branch, Exposure Evaluation
Division. The EPA Task Managers, Daniel T. Heggern and John H. Smith, of the
Office of Toxic Substances, provided helpful guidance and technical inforina-
ti on.
MIDWEST RESEARCH INSTITUTE
Clarence L. Haile
De y Pr ram Manager
ohn E. Goi
Program Manager
Approved:
James L. Spigarelli, Director
Chemical and Biological Sciences
i)epartment
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TABLE OF CONTENTS
Page
I. Introduction. . . . . . 1
II. Summary . . . . 1
III. Overview of PCB Spills and Cleanup Activities 3
A. Introduction to PCB Spills and Cleanup . . . . . 3
1. Current Trends 3
2. Limitations of This Overview 3
B. Components of the Cleanup Process 4
1. Health and Safety 4
2. Reporting the Spill 4
3. Quick Response/Securing the Site 6
4. Determination of Materials Spilled/Cleanup
Plan 6
5. Cleanup Procedures 6
6. Proper Disposal of Removed PCB Materials. . . 7
7. Sampling and Analysis 7
8. Remedial Action 8
9. Site Restoration 8
10. Records 8
11. Miscellaneous Considerations 8
IV. Guidelines on Sampling and Analysis . . 9
A. Sampling Design. . . . . . . . 9
1. Proposed Sampling Design 9
2. Sample Size and Design Layout in the Field. . 11
3. Compositing Strategy for Analysis of Samples. 1]
4. Calculations of Average Number of Analyses,
and Error Probabilities 25
B. Sampling Techniques . . . . 26
1. Solids Sampling 26
2. Water Sampling 34
3. Surface Sampling . 35
C. Analytical Techniques . . . 35
1. Gas Chromatography (GC) . . . . . . . 40
2. Thin-Layer Chromatography (TLC) . . . 42
3. Total Organic Halide Analyses . . . . . . 43
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Page
D. Selection of Appropriate Methods 43
1. Criteria for Selection
2. Selection of Instrumental Techniques.
3. Selection of Methods
4. Implementation of Methods
E. Quality Assurance 47
1. Quality Assurance Plan.
2. Quality Control . .
F. Documentation and Records.
G. Reporting Results
47
48
51
52
V. References.
52
TABLE OF CONTENTS (concluded)
43
• 44
• 44
• . 46
iv
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I. INTRODUCTION
The U.S. Environmental Protection Agency (EPA) under the authority
of the Toxic Substances Control Act (TSCA) Section 6(e) and 40 CFR Section
761.60(d), has determined that polychlorinated biphenyl (PCB) spills must be
controlled and cleaned up whenever the spill incident poses a substantial risk
to human health or the environment. The Office of Toxic Substances COTS) has
been requested to provide written guidelines for cleaning up PCB spills, with
particular emphasis on the sampling design and sampling and analysis methods
to be used for the cleanup of PCB spills.
This work assignment is divided into two phases. The reports of
Phase I are presented in Draft Interim Report No. 1, Revision No. 1, “Cleanup
of PCB Spills from Capacitors and Transformers,” by Gary L. Kelso, Mitchell
D. Erickson, Bruce A. Boomer, Stephen E. Swanson, David C. Cox, and Bradley
D. Schultz, submitted to EPA on January 9, 1985. Phase I consists of a review
and technical evaluation of the available documentation on PCB spill cleanup,
contacts with EPA regional offices and industry experts, and preparation of
preliminary guidelines for the cleanup of PCB spills. The document was aimed
at providing guidance in all aspects of spill cleanup for those organizations
which do not already have working PCB spill cleanup programs.
Phase II, reported in this document, reviews the available sampling
and analysis methodology for assessing the extent of spill cleanup by EPA en-
forcement officials. This report includes some of the information from the
Phase I report, incorporates comments on the Phase I report and the general
issue which were received at a working conference on February 26-27, 1985,
and addresses the issue from the perspective of developing legally defensible
data for enforcement purposes.
This report, intended primarily for EPA enforcement personnel, out-
lines specific sampling and analysis methods to determine compliance with EPA
policy on the cleanup of PCB spills. The sampling and analysis methods can
be used to determine the residual levels of PCBs at a spill site following
the completion of cleanup activities. Although the methodologies outlined in
this document are applicable to PCB spills in general, specific incidents may
require special efforts beyond the scope of this report. Future changes in
EPA policy may affect some of the information presented in this document.
Following a summary of the report (Section II), Section III presents
an overview of PCB spilis and cleanup activities. The guidelines on sampling
and analysis (Section IV) includes discussion of sampling design, sampling
techniques, analysis, and quality assurance.
II. SUMMARY
This report presents the results of Phase II of this work assign-
ment. Phase I consisted of a review and technical evaluation of the avail-
able documentation on PCB spill cleanup, contacts with EPA regional offices,
and preparation of preliminary guidelines for the cleanup of PCB spills.
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Phase II (this document) reviews the available sampling and analysis rnethodol-
ogy for assessing the extent of spill cleanup by EPA enforcement officials.
The report incorporates some of the information from the Phase I report and
general issues received at a working conference on PCB spills.
The EPA has set reporting requirements for PCB spills and views PCB
spills as improper disposal of PCBs. Cleanup activities have not been stan-
dardized since PCB spills are generally unique situations evaluated on a case-
by-case basis by both the PCB owner (or his contractor) and the responsible
EPA regional office. Components of the cleanup process may include health
and safety; reporting the spill; quick response/securing the site; determina-
tion of materials spilled; cleanup procedures; proper disposal of removed PCB
materials; and sampling and analysis. The actual level of action is dependent
on the amount of spilled liquid, PCB concentration, spill area and dispersion
potential, and potential human exposure.
A sampling design is proposed for use by EPA enforcement staff in
detecting residual PCB contamination above an allowable limit after cleanup
of a spill site is completed. The proposed design involves sampling on a
hexagonal grid centered on the cleanup area and extending just beyond its
boundaries. Guidance is provided for centering the design on the spill site
and for staking out the sampling locations, taking possible obstacles into
account. Compositing strategies in which several samples are pooled and
analyzed together, are recommended for each of the three proposed designs.
Since an enforcement finding of noncompliance must be legally defensible, the
sampling design emphasizes the control of the false positive rate , the proba-
bility of concluding that PCBs are present above the allowable limit when, in
fact, they are not.
Sampling and analysis techniques are described for PCB-contaminated
solids (soil, sediment, etc.), water, oils, surface wipes, and vegetation. A
number of analytical methods are referenced; appropriate enforcement methods
were selected based on reliability. Since GC/ECD is highly reliable, widely
used, and is included in many standard methods, it is a primary recommended
method for most spill situations. Secondary methods may be useful for con-
firmatory analyses or for special situations when the primary method is not
applicable.
Quality assurance (QA) must be applied throughout the entire moni-
toring program. Quality control (QC) measures, including protocols, certifi-
cation and performance checks, procedural QC, sample QC, and sample custody
as appropriate, should be stipulated in the QA plan.
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III. OVERVIEW OF PCB SPILLS AND CLEANUP ACTIVITIES
A. Introduction to PCB Spills and Cleanup
The EPA has established requirements for reporting PCB spills based
on the amount of material spilled and disposal requirements for the spilled
PCBs and materials contaminated by the spill. Under TSCA regulations [ 40 CFR
761.30(a)(1)(iii) and 40 CFR 761.60d], PCB spills are viewed as improper
disposal of PCBs. Although specific PCB cleanup requirements are not
established in the TSCA regulations, each regional administrator is given
authority by policy to enforce adequate clean-up of PCB spills to protect
human health and the environment.
1. Current Trends
Due to regional variations in PCB spill policy and the lack of a
national PCB cleanup policy, PCB cleanup activities have not been standard-
ized. Individual companies owning PCB equipment and contract cleanup com-
panies have developed their own procedures and policies for PCB cleanup
activities keyed to satisfying the requirements of the appropriate EPA
regional office. In addition, the EPA regional offices typically have pro-
vided suggestions for companies unfamiliar with PCB cleanup.
PCB spills are generally viewed as unique situations to be evalu-
ated on a case-by-case basis by both the PCB owner (or his contractor) and
the EPA regional office. However, a general framework is often used to ap-
proach the problem. Most cleanup activities involve quick response, removal
or cleaning of suspected contaminated material, and post-cleanup sampling to
document adequate cleanup. Major considerations involved in the cleanup
process include minimizing environmental dispersion, minimizing any present
or future human exposure to PCBs, protecting the health and safety of the
cleanup crew, and properly disposing contaminated materials.
The involvement of EPA regional offices is typically limited to
phone conversations often including a follow-up call to receive the ana-
lytical results of the post-cleanup sampling. If the EPA representative is
not satisfied with the reported data, additional documentation, sampling and
analysis, or cleanup (followed by further sampling and analysis) may be re-
quested.
In cases of special concern (e.g. , large spills), EPA regional of-
fices may work more closely with the PCB owner or contractor in planning the
cleanup, sampling and analysis activities, and on-site inspections.
2. Limitations of This Overview
The general discussion in this chapter refer to the procedures,
policy, and considerations that seem to be widely used at present by PCB
owners and spill cleanup contractors in meeting the requirements of the EPA
regional offices. The activities described do not involve EPA regulations or
policy except where indicated, since the EPA has not established requirements
on PCB cleanup procedures.
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Table 1 categorizes PCB spills into approximate levels of action
for PCB spill cleanup based on concern. Potential environmental problems in-
crease with increases in PCB concentrations, amount of spilled liquid, spill
area and dispersion potential, and potential human exposure. The three spill
types presented in Table 1 are based on very rough estimates. Severity in
one key item such as human exposure could raise a spill to a Type 3 (i. e.
requiring special attention). On the other hand a spill of a large volume of
liquid may be considered a Type 2 spill due to a relatively low concentration
of PCBs. The three categories are only approximate and are intended to demon-
strate the flexibility needed in responding to PCB spills. EPA regional of-
fices should provide guidance on spill cleanup activities whenever questions
develop.
The situations described in this chapter are limited to recent PCB
spills of similar magnitude to the reported spills associated with PCB oil
transformers and capacitors (i.e., Type 2 in Table 1). Unusually severe spill
incidents (Type 3 in Table 1) involving large volumes of PCBs, a large spill
area, a high probability of significant human exposure, and/or severe en-
vironmental or transportation scenarios may require special considerations,
beyond the scope of this discussion.
Spills below the reporting requirements (< 10 lb or approximately 1
gal.), especially those involving mineral oil transformers, are typically not
subject to the detail of effort outlined in this chapter. Although cleanup
of these smaller spills (Type 1 in Table 1) is required if the concentration
of PCBs in the spilled material is > 50 ppm, the spill and the cleanup
activities normally are not reported to EPA.
Future changes in EPA policy may invalidate some of the discussions
appearing in this chapter. For example, if EPA adopts any type of formal
categorization scheme for PCB spills, some of the assumptions made in this
chapter may become inappropriate.
B. Components of the Cleanup Process
1. Health and Safety
Protection of the health and safety of the clean-up crew during the
PCB cleanup operation is an important concern. References discussing health
and safety considerations relevant to some PCB spill incidents include NIOSH
Criteria for A Recommended Standard for Exposure to Polychlorinated Biphenyls
( PCBs ) (1977c) and Health Hazards and Evaluation Report No. 80-85-745 (NIOSH
1980). The appropriate level of health and safety protection is dependent
upon the specifics of the spill.
2. Reporting the Spill
If the regulatory limits are exceeded, the spill must be reported
to federal, state, and local authorities as applicable. Under EPA regulations
[ Fed. Reg. 50:13456-13475], spills over 10 lb must be reported to The National
Response Center. The toll free phone number is (800) 424-8802.
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Table 1. Approximate Levels of Action for PCB Spill Cleanup Based on Concern
Notes: Type 1 spill is usually not reported.
• Type 2 spill is reported and discussed in this chapter.
• Type 3 spill is not discussed in this chapter and may require special
EPA assistance.
• “Severity” in one key item may raise the spill to a higher risk category.
0,
Categories of increasing concern
Type 1
Type
2
Type 3
Approximate gallons of
spilled liquid
< 1
> 1
> 5
Area of spill (sq ft)
< 250
250 (avg.)
> 1,000
PCB concentration in
spilled liquid
(ppm)
< 500
> 50
Variable or high
Types of spilled
liquid
Mineral oil
variable)
(or
Variable
Variable, Askarel
Exposure scenario
Various
Various
Special concern for high
exposure situations
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3. Quick Response/Securing the Site
Quick response is desirable to mitigate the dispersion of the
spilled material and to secure the site. Federal regulations require that
cleanup actions commence within 48 hr of discovery of a spill [ 40 CFR
761.30(a)(1) (iii)]. More rapid response is highly preferable.
f quick response allows removal or cleaning of the PCB-contaminated
material before it is dispersed by wind, rain, seepage, and other natural
causes or by humans or animals. In securing the site, the cleanup crew
determines the spill boundaries, prevents unauthorized access to the spill
site, and notifies all parties involved.
The methods used to secure the site will vary on a case-by-case
basis, depending on the specific circumstances. The extent of the spill is
usually determined by visual inspection with the addition of a buffer area
that may include PCBs finely dispersed from splattering. Evaluating the ex-
tent of the spill involves considerable judgment, ihcluding consideration
of the cause of the spill, weather conditions, and specifics of the site.
Field analysis kits may aid the crew in determining the extent of
the spill in some instances. The field kits, when used properly, can serve
as a screening tool. The need for quick response has limited the usefulness
of the more accurate field analytical techniques such as field gas chroma-
tography. Practical problems associated with availability of the equipment
and trained staff, set-up time, and cost have limit d the use of such tech-
niques at this time.
4. Determination of Materials Spilled/Cleanup Plan
After securing the site, the response crew will either (a) immedi-
ately proceed with the cleanup operation, or (b) identify the materials
spilled and formulate an appropriate cleanup plan. A suitable cleanup plan
can be developed by identifying the type of PCB material (i.e., mineral oil,
PCB oil, Askarel) and considering such factors as the volume spillec, area
of the spill, and site characteristics.
Based on reasoning similar to Table 1, the crew leader can determine
the necessary level of effort in accordance with the policy of the PCB owner
and the regional EPA office. He can determine if additional guidance is
needed, plan the sampling and analysis, and make other decisions related to
the level of effort and procedures needed.
5. Cleanup Procedures
The cleanup procedure may include, but may not necessarily be limited
to, the following activities:
Removal or repair of failed/damaged PCB equipment,
Physical removal of contaminated vegetation;
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Physical removal of contaminated soils, liquids, etc.
• Decontamination, encapsulation, or physical removal (as appro-
priate) of contaminated surfaces, and
• Decontamination or removal of all equipment potentially con-
taminated during the cleanup procedures.
The specific procedures used in a cleanup are selected by the PCB
owner or the cleanup contractor. Key considerations include removal of PCBs
from the site to achieve the standards required by the EPA region, company,
or other applicable control authority; avoidance of unintentional cross con-
tamination or dispersion of PCBs from workers’ shoes, contaminated equipment,
spilled cleaning solvents, rags, and other sources; and protection of workers’
health.
The cleanup crew shall make every possible effort to keep the spilled
PCBs out of sewers and waterways. If this has already occurred, the crew needs
to contact the local authorities. Water is never used for cleaning equipment
or the spill site.
A simple PCB spill cleanup may involve the removal of the leaking
equipment, removal of contaminated sod and soil by shovel, cleaning pavement
with an absorbant material and solvents, and decontamination or disposal of
the workers’ equipment (shovels, shoes, gloves, rags, plastic sheets, etc.).
More complicated situations may include decontamina tion of cars, fences,
buildings, trees and shrubs, electrical equipment, or water (in pools or
bodies of water).
In some cases, adequate decontamination of surfaces (pavements,
walls, etc.) may not be possible. An alternate to physical removal of the
surface material is encapsulation of the contaminated area under a coating
impervious to PCBs. EPA Regional Offices may offer advice on this subject.
6. Proper Disposal of Removed PCB Materials
All PCB-contaminated materials removed from the spill site, must be
shipped and disposed in accordance with relevant federal, state, and local
regulations. TSCA Regulations [ 40 CFR 761.60] outline the requirements for
the disposal of PCBs, PCB articles, and PCB containers in an incinerator, high
efficiency boiler, chemical waste landfill, or an approved alternative method.
Facility requirements for incineration and chemical waste landfills are
presented in 40 CFR 761.70 and 40 CFR 761.75, respectively.
7. Sampling and Analysis
Although sampling and analysis will be discussed in detail in
Chapter IV, this discussion gives an overview of applicable considerations
and current practice. Sampling and analysis may not always be needed
(especially for the spills described as Type 1 in Table 1), but enforcement
authorities or property owners may ask for proof that the spill site has been
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adequately decontaminated. This can be accomplished by taking a number of
samples representative of the area contaminated by the spill. Samples should
represent the full extent of the spill, both horizontal and vertical, as well
as the types of materials in the spill area (soil, surfaces, water, etc.).
Sampling design and technique as well as sample handling and preser-
vation should incorporate acceptable procedures for each matrix to be sampled
and concern for the adequacy and accuracy for the samples in the final analysis.
Analysis of the samples for PCB content should be performed by
trained personnel using acceptable procedures with due consideration of qual-
ity assurance and quality control.
Further discussion of sampling and analysis (applicable to EPA en-
forcement activities) appears in Chapter IV.
8. Remedial Action I
If the analysis results indicate the cleanup was not in compliance
with designated cleanup levels, additional cleanup is needed. Additional sam-
pling can pinpoint the location of remaining contaminated areas if the original
sampling plan was inadequate. If additional cleanup is needed, the cleanup
crew will continue as before, removing more material or cleaning surfaces more
thoroughly. Remedial action will be followed by additional sampling and anal-
ysis to verify the adequacy of the cleanup.
9. Site Restoration
This is not addressed under TSCA and is a matter to be settled be-
tween the company responsible for the PCB spill and the property owner.
10. Records
Although there are no TSCI\ requirements for records of PCB cleanup
activities except for documentation of PCBs stored or transported for dis-
posal [ 40 CFR 761.80(a)], the PCB owner must keep records of the spill cleanup
in case of future questions or concern. Relevant information may include
dates, a description of the activities, records of shipment and disposal of
PCB-contaminated materials, and a report of collected samples and results of
analysis.
11. Miscellaneous Considerations
a. Expeditious and effective action are desired throughout
the cleanup process to minimize the concern of the public, especially res-
idents near the site or individuals with a special interest in the site.
Likewise, speed and effectiveness in the cleanup may prevent any future con-
cern or action related to the PCB spill.
b. Education and training of the spill response crews and re-
sponsible staff members is a constant concern. The employees need sufficient
training to make proper judgements and to know when additional assistance or
guidance is needed.
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IV. GUIDELINES ON SAMPLING AND ANALYSIS
Reliable analytical measurements of environmental samples are an
essential ingredient of sound decisions for safeguarding public health and
improving the quality of the environment. Effective enforcement monitoring
should follow the general operational model for conducting analytical measure-
ments of environmental samples, including: planning, quality assurance/quality
control, verification and validation, precision and accuracy, sampling, mea-
surements, documentation, and reporting. Although many options are available
when analyzing environmental samples, differing degrees of reliability, dictated
by the objectives, time, and resources available, influence the protocol chosen
for enforcement monitoring. The following section outlines the factors crit-
ically influencing the outcome and reliability of enforcement monitoring of
PCB spill cleanup.
A. Sampling Design
This section presents a sampling scheme, to be used by EPA Enforce-
ment Staff, for detecting residual PCB contamination above the allowable limit
after cleanup operations have been completed. Two types of error traceable
to sampling and analysis are possible. The first is false positive , i.e.
concluding that PCBs are present at levels above the allowable limit when, in
fact, they are not. The false positive rate for the present situation should
be low, because an enforcement finding of noncompliance must be legally de-
fensible, that is, a violator must not be able to claim that the sampling re-
sults could easily have been obtained by chance alone.
The second type of error possible is a false negative , i.e., failure
to detect the presence of PCB levels above the allowable limit. The false
negative rate will depend on the size of the contaminated area and on the
level of contamination. For large areas contaminated at levels well above
the allowable limit, the false negative rate must, of course, be low, to en-
sure that serious violators are caught. The false negative rate can be higher
for slightly contaminated areas or for small areas. In the extreme case, no
sampling scheme will be able to detect a tiny contaminated area with much re-
liability.
1. Proposed Sampling Design
In practice, the contaminated area from a spill will be irregular
in shape. In order to standardize sample design and layout in the field, and
to protect against underestimation of the spill area by the cleanup contractor,
we are proposing to sample within a circular area surrounding the contaminated
area. Guidance on choosing the center and radius of the circle, as well as
the number of sample points to be used is provided in Section 2 below. We
modeled the detection problem as follows: try to detect a circular area of
uniform residual contamination whose center is randomly placed within the
sampling circle. The implicit assumption that residual contamination is
equally likely to be present anywhere within the sampling area is reasonable,
at least as a first approximation (Lingle, 1985). This is because more ef-
fort is likely to have been expended in cleaning up the areas which were ob-
viously highly contaminated.
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Two general types of design are possible for the detection problem
we have posed: grid designs and random designs. Random designs have two
disadvantages compared to grid designs. First, they are more difficult to
implement in the field, since the sampling crew must be trained to generate
random locations onsite, and since the resulting pattern is irregular.
Second, grid designs are more efficient in certain senses than random de-
signs. This is because random designs do not result in even spacing of sam-
ple points, but rather in a clustering effect which may over-sample some
areas at the expense of others. As an illustration, a grid design is certain
to detect a sufficiently large circle while some random designs are not. For
example, our suggested design below with a sample size of 19 is certain to
detect an area of radius 2.8 ft. By contrast, a design based on a simple
random sample of 19 points has a 21% chance of failing to detect such an area.
We are therefore proposing a grid design. A hexagonal grid based
on equilateral triangles has two advantages for this problem. First, such a
grid minimizes the circular area certain to be detected (among all grids with
the same number of points covering the same area). Second, some previous ex-
perience (Mason 1982; Matern 1960) suggests that the hexagonal grid performs
well for certain soil sampling problems. The hexagonal grid may, at first
sight, appear to be complicated to lay out in the field. Guidance is provided
in Section 2 below and shows, we believe, that the hexagonal grid is quite
practical in the field and is not significantly more difficult to deploy than
other types of grid.
The smallest hexagonal grid has 7 points, 1 the next 19 points, the
third 37 points. In general, the nth grid has 3n 2 + 3n + 1 points. To com-
pletely specify a hexagonal grid, the spacing d (distance between adjacent
points) must be determined. We chose d to minimize, as far as possible, the
size of the residual contaminated circle which is certain to be detected.
Values of d so chosen, together with number of sampling points and radius of
smallest circle certain to be detected are shown in Table 2 for a sampling
circle of radius 10 ft. For a general sampling circle of radius r feet, the
numbers in the table must be adjusted proportionally. For example, the grid
spacing for a circle of radius 20 ft for the 7-point design is
d = (20)(0.87) = 17.4 ft.
Table 2. Parameters of Hexagonal Sampling Designs
Design
no.
No. of
points
Spacing d (ft)
Smallest radius
certain to be
detected
1
7
8.6
5.0
2
19
4.8
2.8
3
37
3.3
1.9
n
3 2 + 3 + 1
10(n 2 1/3)1/2
10(3n 2 + 1)1/2
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The first three hexagonal designs are shown in Figures 1 to 3. Re-
member that these are scaled for a sampling circle of radius 10 ft. The choice
of sample size depends on the cost of analyzing each sample and the reliability
of detection desired for various residually contaminated areas. Subsection 2
below provides some suggested sample sizes for different spill areas, based on
the distribution of spill areas provided by the Utility Solid Waste Activities
Group (USWAG 1984; Lingle 1985).
2. Sample Size and Design Layout in the Field
a. Sample Size
The distribution of cleanup areas for PCB capacitor spill sites,
based on data collected by USWAG (1984) is shown in Table 3. Based on this
distribution, we recommend the sample sizes found in Table 4. For all except
the very smallest spills a sample size of 19 is recommended. For spills under
25 ft 2 , 7 samples should suffice, while for very large spills over 1,000 ft 2 ,
37 samples should be taken. From Table 3, 37 samples will be required in only
about 4% of spills (provided the distribution of spill areas sampled by EPA
enforcement staff follows Table 3).
b. Design Layout in the Field
The first step in laying out the design for an irregularly-shaped
spill area is to determine the center and radius of the sampling circle which
is to be drawn surrounding the spill area. The following approach is recom-
mended:
(a) Draw the longest dimension, L 1 , of the spill area.
(b) Determine the midpoint, P, of L 1 .
(c) Draw a second dimension, L 2 , through P perpendicular to
L 1 .
(d) The midpoint, C, of L 2 is the required center.
(e) The distance from C to the extremes of L 1 is the required
radius, r.
Figure 4 gives some examples of the procedure, and demonstrates that the center
and radius are reasonable for most spill shapes. Even if the center determined
is slightly off, the sampling design will not be adversely affected.
Once the sampling radius r has been determined, and the sample
size selected based on Table 4, the grid spacing can be found from Table 2.
Example: Suppose r = 5 ft. Then the sampling area is
(3.14)(5 2 )ft 2 = 78.5 ft 2 . Thus, a sample size of 19 should be
used. The grid spacing is d = (4.8/1O)(5)ft = 2.4 ft.
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—10 • — — — — — — I — — — I — I . I — I — I — I . I . I — I • I
x
Figure 1. Location of sample points in 7 sample point plan.
A square represents a sample location. The outer boundary of the contam-
inated area is assumed to be 10 ft from the spill site.
12
-------
V
10
—10 j1.1 .1 .1 .I .I*I.11 I .I 111 .1111
ř (1) ot\ O O
.... I I I I I I I I
x
Figure 2. Location of sample points in 19 sample point plan.
A square represents a sample location. The outer boundary of the contam-
inated area is assumed to be 10 ft from the spill site.
13
-------
:L 0 0 0
0 0 0 0
—10
I I I I I I I I I
Figure 3. Location of sample points in 37 sample point plan.
A square represents a sample location. The outer boundary of the contam-
inated area is assumed to be 10 ft from the spill site.
14
-------
Table 3. Distribution of PCB Capacitor-Spill
Cleanup Areas Based on 73 Cases
Cleanup area (ft 2 )
Percent of cases
100
50.7
101-200
23.3
201-300
4.1
301-400
2.7
401-500
4.1
501-600
4.1
601-700
0
701-800
1.4
801-900
2.7
901-1,000
2.7
1,001-1,100
0
1,101-1,200
2.7
1,201-1,600
0
1,601-1,700
1.4
Table 4.
Recommended
Sample Sizes
Sampling area
(ft 2 )
Sample size
25
7
25-1,000
19
1,000
37
15
-------
Figure 4. Locating the center of an irregularly-shaped spill area.
L 1 p
/
/
16
-------
To find the sampling locations, first lay out a baseline di-
ameter of the sampling circle; this diameter can be chosen randomly or for
the convenience of the samplers. This baseline should be used as the hor-
izontal diameter of the grids as shown in Figures 1 through 3. Once the
sampling locations on the grid diameter have been staked out, the remaining
samples are located one at a time, always using two existing locations to
stake out a new sampling point.
Example : Refer to Figure 5 and consider the problem of
staking out locations 5 and 6 once locations 1 through 4 have
been found. For location 5, attach a piece of rope or sur-
veyor’s chain to the stakes at each location 3 and 4. Draw
the ropes (chains) taut horizontally until their endpoints
meet, at location 5. Stake out and label the new location.
To find location 6, use locations 3 and 5 in the same way.
By proceeding one step at a time as indicated in the example,
the entire grid can be laid out systematically. As an aid, a copy of the ap-
propriate Figures 1 through 3 should be labeled before starting to determine
the order and numbering of the layout.
In practice, various obstacles may be encountered in trying to
lay out the sampling grid. Many “obstacles” can be handled by taking a dif-
ferent type of sample, e.g., if a fire hydrant is located at a point in a sam-
pling grid otherwise consisting of soil samples, then a wipe sample should be
taken at the hydrant, rather than taking a sample of nearby soil. The ob-
stacle most likely to be encountered is a vertical surface such as a wall.
To determine the sampling point on such a surface, simply draw taut the ropes
(chains) of length d attached to two nearby stakes and find the point on the
vertical surface where their common ends touch. See Figure 6 for an illustra-
tion of the procedure.
3. Compositing Strategy for Analysis of Samples
Once the samples have been collected at a site, the goal of the
analysis effort is to determine whether at least one sample has a PCB con-
centration above the allowable limit. A finding of even one unacceptably
contaminated sample will trigger a requirement for the responsible party to
reclean the entire spill area. Thus, it is not important to determine pre-
cisely which samples are contaminatd or even exactly how many. This means
that the cost of analysis can be substantially reduced by employing composit-
jj g strategies, in which groups of samples are thoroughly mixed and evaluated
in a single analysis. Then only if the composite or group shows a suspiciously
high level, the individual samples are analyzed one by one to find out if in-
deed a single sample has an unacceptably high level of PCB.
For purposes of this discussion, we will assume that the maximum
allowable PCB concentration in a single sample is 10 ppm. This is a reason-
able level for soil samples (the predominant type). Different levels may be
required for water samples or wipe samples. However, the calculations can
easily be adapted to those cases. The proposed analytical method for soil
samples has not been validated; however, existing data and the best judgement
17
-------
o 0 0 0
c i 0 a
o 0 0 0
o ci o
o 0 0 0
0 0 0 0
o 0 0 0
‘ (‘)Co \ O)O
I I I I I I I / /
Figure 5. Locating a new sampling point.
0 0
10
9
8
7
6
5
4
3
2
I
0
—I
-2
-3
—4
-5
-6
-7
—8
-g
—10
0
2
c i 0
0
0
18
-------
Figure 6. Location of a sampling point on a vertical surface.
19
-------
of chemists experienced in PCB analyses indicate that performance criteria of
80% accuracy and 30% standard deviation should be attainable for concentra-
tions above 1 ppm.
To protect against false positive findings due to analytical error,
the measured PCB level in a single sample must exceed some cutoff greater than
10 ppm for a finding of contamination. For example, suppose that a 5% false
positive rate for a single sample were desired. Then, using standard sta-
tistical techniques, the cutoff level for a single sample is
(0.8)(10) + (1.645)(O.3)(0.8)910) = 11.9 ppm.
Thus, if the measured level in a single sample is 11.9 ppm or greater, one
can be 95% sure that the true level is 10 ppm or greater. In general, the
cutoff is
(0.8)(10) + k(O.3)(0.8)(10) = 8 + 2.4k
where k chosen to control the false positive rate for the complete set of
analyses.
Now suppose that a composite of in samples is analyzed. The true
PCB level in the composite (assuming perfect mixing) is simply the average of
the m levels of the individual samples. Let X be the measured PCB level in
the composite. If X (8 + 2.4k)/m, then all m individual samples are rated
clean. If X > (8 + 2.4k)/m, then one or more indivjidual samples be con-
taminated. The next step is to analyze all m samples individually.
The applicability of compositing is potentially limited by the size
of the individual specimens and by the performance of the analytical method
at low levels of the analyte. First, the individual specimens must be large
enough so that the composite can be formed while leaving enough material for
individual analyses if needed. In the present situation, adequacy of speci-
men sizes should not be a problem. The second limiting factor is the analyt-
ical method. Here, we can be sure of performance down to about 1 ppm. Since
the assumed permissible level is 10 ppm, no more than about 10 specimens
should be composited at a time.
In cornpositing specimens, the location of the sampling points to be
grouped should be taken into account. If a substantial residual area of con-
tamination is present, then contaminated samples will be found close together
Thus, contiguous specimens should be composited, if feasible, in order to max-
imize the potential reduction in the number of analyses produced by the corn-
positing strategy. Rather than describe a (very complicated) algorithm for
choosing specimens to composite, we have graphically indicated some possible
compositing strategies in Figures 7 through 10. Based on the error probabil-
ity calculations presented in Section 4 below, we recommend the compositing
strategies shown in Table 5. For details on the reduction in number of analy-
ses expected to result (as compared to individual analyses), see Section 4.
20
-------
—2
-3
—4
—5
-6
—7
-I
-9
—10
x
Figure 7. Location of sample points in a 7 sample point plan,
with detail of a 2 group compositing design.
4I) 0
21
-------
V
A
Figure 8. Location of sample points in a 19 sample point plan,
with detail of a 2 group compositing design.
—4
—
-6
—7
—O
—9
-10
o a -. 0 ‘L, •‘) • (I•) 40 ‘\ Q U 0
, I I I I I I I I
22
-------
x
Figure 9. Location of sample points in a 19 sample point plan,
with detail of a 2 group compositing design.
c Q).Q \ (p (1) A) fl .., c ••. ( , A) (r) (O \ ‘b 0) Q
— I I I I I f I I
23
-------
Figure 10.
Location of sample points in 37 sample point plan,
with detail of a 4 group compositing design.
—2
—3
—4
-5
—6
—7
-8
-g
—10
, , , I I I I I /
24
-------
Table 5. Recommended Compositing Strategies
Sample size
Compositing
strategy
7
One
group of
7
19
One
group of
10,
one of
9
37
Three groups
of
9, one of 10
4. Calculations of Average Number of Analyses, and Error Probabil-
ities
Estimates of expected number of analyses and probabilities of false
positives (incorrectly deciding the site is contaminated above the limit),
and false negatives (failure to detect residual contamination) errors were
obtained for various scenarios. The calculations were performed by Monte Carlo
simulation using 5,000 trials for each combination of sample size, compositing
strategy, level, and extent of residual contamination. The computations were
based on the following assumptions:
a. Only soil samples are involved. In practice other types
of samples will often be obtained and analyzed. Although the results of this
section are not directly applicable to such cases, theydo indicate in gen-
eral terms the type of accuracy obtainable and the potential cost savings
from coinpositing.
b. If the true PCB level in a sample is C, then the measured
value is a normally distributed random variable with mean 0.8C and standard
deviation (O.3)(O.8C) = O.24C. This accounts for random measurement error.
c. The maximum allowable level in a single sample is 10 ppm.
The cutoff on the measured value for a single sample for a finding of noncom-
pliance is (0.8)(10) + (2.576)(0.3)(0.8)(1O) = 14.2 ppm. This corresponds to
a single-sample false positive rate of 0.5%.
d. The residual contamination present is modeled as a randomly
placed circle of radius r and uniform contamination level X; both r and X can
be varied. The PCB level outside the randomly placed circle of contamination
is zero.
e. Analysis of samples is terminated as soon as a positive re-
sult is obtained on any individual specimen. If a composite reads positive,
it is broken down into individual specimens and these are analyzed before any
other composite.
f. The compositing strategies used are shown in Figures 7
through 10.
25
-------
The results of our calculations are shown in Tables 6 through 12.
Tables 6 through 8 show the performance of the compositing strategies recom-
mended in Section 3. Tables 9 through 12 indicate why the compositing strate-
gies of Section 3 are optimal (subject to the constraint of never compositing
more than 10 samples) for each sample size.
The major conclusions that can be drawn fromthese results are as
follows. First, the proposed cutoff on the measured PCB level for a finding
of noncompliance for a single sample, 14.2 ppm, is successful in controlling
the overall false positive rate of the sampling scheme. For example, when an
area half the size of the entire site remains contaminated just at the allow-
able limit of 10 ppm, the false positive rate is 1% for the 7-point design,
3% for the 19-point design, and 6% for the 37-point design.
Second, the detection capabilities of the design appear satisfactory,
bearing in mind the difficulty of detecting randomly-located contamination
without exhaustive sampling. As an example, the proposed 19-point design can
detect 50 ppm contamination present in 9% of the cleanup area with 97.5% re-
liability. Reliability is 95% for 20 ppm contamination present in 25% of the
area.
Third, the proposed compositing strategies are quite effective in
reducing the number of analyses needed to reach a decision in all cases ex-
cept those involving large areas contaminated near the cutoff of 10 ppm. For
example, for contaminated levels of 25 ppm or greater, the expected number of
analyses to reach a decision never exceeds 5 for the 7-point design, or 7 for
the 19-point design and the 37-point design. Larger number of analyses are
needed in marginal cases, up to 23 for the 37-point design when 50% of the
area is contaminated at 10 ppm.
B. Sampling Techniques
The types of media to be sampled will include soil, water, vegeta-
tion and solid surfaces (concrete, asphalt, wood, etc.). General sampling
methods are described below. Additional sampling guidance documents are avail-
able (Mason 1982, USWAG 1984).
1. Solids Sampling
When soil, sand, or sediment samples are to be taken, a surface
scrape samples should be collected. Using a 10 cm x 10 cm (100 cm 2 ) template
to mark the area to be sampled, the surface should be scraped to a depth of
1 cm with a stainless steel trowel or similar implement. This should yield
at least 100 g soil. If more sample is required, expand the area but do not
sample deeper. Use a disposable template or thoroughly clean the template
between samples to prevent contamination of subsequent samples. The sample
should be scraped directly into a precleaned glass bottle. If it is free-
flowing, the sample should be thoroughly homogenized by tumbling. If not,
successive subdivision in a stainless steel bowl should be used to create a
representative subsample.
26
-------
Table 6. Performance of Sampling Strategy with
7 Points Composited Together
X R: 1 3 5 7
4 1.00 1.00 1.00 1.08
0.000 0.000 0.000 0.000
8 1.00 1.00 1.42 4.00
0.000 0.000 0.000 0.000
10 1.01 1.01 1.84 5.04
0.000 0.000 0.001 0.009
12 1.03 1.21 2.25 5.40
0.000 0.001 0.015 0.088
14 1.10 1.62 2.88 5.16
0.004 0.020 0.081 0.284
16 1.14 1.98 3.56 4.76
0.009 0.059 0.205 0.521
20 1.26 2.56 4.26 4.05
0.029 0.206 0.482 0.774
25 1.27 2.84 4.47 3.65
0.047 0.351 0.746 0.910
50 1.29 2.87 4.52 3.46
0.069 0.473 0.972 0.991
500 1.30 2.91 4.47 3.38
0.075 0.487 0.999 0.000
Note: Top number = average number of analyses. Bottom number = probability
of declaring out of compliance (for levels of PCB, x, 10 ppm and below this
will be the probability of false positive; for levels above 10 this will be
the probability of detection). R = radius of contaminated circle iii feet;
X PCB contamination level in ppm.
27
-------
Table 7. Performance of Sampling Strategy with
19 Points, 2 Composites
X R: 1 3 5 7
4 2.00 2.00 3.28 7.37
0.000 0.000 0.000 0.000
8 2.00 3.04 9.12 13.13
0.000 0.000 0.000 0.000
10 2.02 3.74 10.48 14.13
0.000 0.002 0.014 0.029
12 2.07 4.49 10.68 12.82
0.000 0.026 0.150 0.272
14 2.31 5.04 9.32 9.41
0.006 0.115 0.460 0.686
16 2.54 5.83 7.59 6.59
0.023 0.261 0.737 0.909
20 2.74 6.25 5.47 4.25
0.072 0.556 0.949 0.992
25 2.79 6.33 4.50 3.45
0.123 0.780 0.991 0.999
50 2.81 6.04 4.01 3.04
0.168 0.975 0.999 1.000
500 2.82 5.98 3.97 3.03
0.166 0.998 1.000 1.000
Note: Top number = average number of analyses. Bottom number probability
of declaring out of compliance (for levels of PCB, x, 10 ppm and below this
will be the probability of false positive; for levels above 10 this will be
the probability of detection). R = radius of contaminated circle in feet;
X = PCB contamination level in ppm.
28
-------
Table 8. Performance of Sampling Strategy with
37 Points, 4 Composites
X R: 1 3 5 7
4 4.00 4.35 9.67 15.58
0.000 0.000 0.000 0.000
8 4.00 9.03 15.94 22.02
0.000 0.000 0.000 0.000
10 4.02 10.50 17.17 22.96
0.000 0.009 0.029 0.056
12 4.16 10.97 15.74 17.83
0.001 0.108 0.309 0.479
14 4.56 10.24 11.27 10.32
0.014 0.358 0.723 0.898
16 4.90 9.04 7.87 6.43
0.044 0.620 0.937 0.991
20 5.22 7.25 5.51 4.33
0.137 0.888 0.996 1.000
25 5.31 6.44 4.67 3.57
0.237 0.968 0.999 1.000
50 5.22 5.86 4.20 3.09
0.331 0.997 1.000 1.000
500 5.25 5.86 4.13 3.08
0.350 0.999 1.000 1.000
Note: Top number = average number of analyses. Bottom number = probability
of declaring out of compliance (for levels of PCB, x, 10 ppm and below this
will be the probability of false positive; for levels above 10 this will be
the probability of detection). R = radius of contaminated circle in feet;
X = PCB contamination level in ppm.
29
-------
Table 9. Comparison of Sampling Designs for r = 1 (1% of Spill Site Size)
Level of
contaminated
area, x
1
7
Group,
points
2
7
Groups,
points
Individually,
7 points
2
19
Groups,
points
6
19
Groups,
points
Individually,
19 points
4 :
1.00
0.000
2.00
0.000
7.00
0.000
2.00
0.000
6.00
0.000
19.00
0.000
8 :
1.00
0.000
2.00
0.000
7.00
0.000
2.00
0.000
6.00
0.000
19.00
0.000
10 :
1.01
0.000
2.00
0.000
7.00
0.001
2.02
0.000
6.01
0.000
19.00
0.001
12 :
1.03
0.000
2.02
0.000
6.98
0.005
2.07
0.000
6.03
0.000
18.93
0.008
14 :
1.10
0.004
2.05
0.004
6.96
0.013
2.31
0.006
6.08
0.005
18.74
0.029
16
:
1.14
0.009
2.07
0.010
6.92
0.026
2.54
0.023
6.12
0.019
18.46
0.063
20
:
1.26
0.029
2.12
0.029
6.88
0.043
2’.74
0.072
6.08
0.070
18.06
0.110
25
:
1.27
0.047
2.12
0.048
6.84
0.052
2.79
0.123
6.00
0.121
17.75
0.143
50
:
1.29
0.069
2.12
0.066
6.80
0.067
2.81
0.168
5.94
0.166
17.49
0.173
500
:
1.30
0.075
2.13
0.071
6.81
0.063
2.82
0.166
5.93
0.167
17.46
0.177
—
number o
f
-- -
Note: Top number = average analyses; bottom number probability of declaring
out of compliance (for levels of PCB, x, 10 ppm and below this will be the probability of
false positive; for levels above 10 this will be the probability of detection).
30
-------
Table 10. Comparison of Sampling Designs for r = 3 (9% of Spill Site Size)
Level
contami
area,
of
nated
x
1
7
Group,
points
2
7
Groups,
points
Individually,
7 points
2
19
Groups,
points
6
19
Groups,
points
Individually,
19 points
4
:
1.00
0.000
2.00
0.000
7.00
0.000
2.00
0.000
6.00
0.000
19.00
0.000
8
:
1.00
0.000
2.00
0.000
7.00
0.000
3.04
0.000
6.19
0.000
19.00
0.000
10
:
1.01
0.000
2.01
0.000
6.99
0.001
3.74
0.002
6.34
0.002
18.96
0.004
12
:
1.21
0.001
2.10
0.001
6.91
0.027
4 .49
0.026
6.53
0.015
18.40
0.067
14
:
1.62
0.020
2.31
0.020
6.69
0.099
5.04
0.115
6.77
0.087
16.90
0.232
16
:
1.98
0.059
2.48
0.059
6.49
0.165
5.83
0.261
6.80
0.224
14.86
0.448
20
:
2.56
0.206
2.73
0.206
6.06
0.314
6.25
0.556
6.36
0.533
11.89
0.731
25
:
2.84
0.351
2.82
0.350
5.65
0.426
6.33
0.780
5.83
0.781
10.22
0.874
50
:
2.87
0.473
2.79
0.473
5.45
0.494
6.04
0.975
5.20
0.976
8.94
0.990
500
:
2.91
0.487
2.81
0.488
5.46
0.499
5.98
0.998
5.13
0.999
8.62
0.999
Note: Top number = average number of analyses; bottom number probability of declaring
out of compliance (for levels of PCB, x, 10 ppm and below this will be the probability of
false positive; for levels above 10 this will be the probability of detection).
31
-------
Table 11. Comparison of Sampling Designs for r = 5 (25% of Spill Site Size)
Level
contami
area,
of
nated
x
1 Group,
7 points
2 Groups,
7 points
Individually,
7 points
2 Groups,
19 points
6
19
Groups,
points
Individually,
19 points
4
:
1.00
0.000
2.00
0.000
7.00
0.000
3.28
0.000
6.08
0.000
19.00
0.000
8
:
1.42
0.000
2.13
0.000
7.00
0.000
9.12
0.000
7.73
0.000
19.00
0.000
10
:
1.84
0.001
2.26
0.000
6.98
0.005
10.48
0.014
8.47
0.010
18.83
0.017
12
:
2.25
0.015
2.46
0.010
6.81
0.063
10.68
0.150
8.53
0.117
17.31
0.180
14
:
2.88
0.081
2.83
0.068
6.29
0.219
9.32
0.460
7.87
0.384
13.72
0.516
16
:
3.56
0.205
3.22
0.183
5.64
0.409
7.59
0.737
6.85
0.653
10.58
0.761
20
:
4.26
0.482
3.56
0.466
4.68
0.684
5.47
0.949
5.49
0.919
6.25
0.962
25
:
4.47
0.746
3.54
0.745
4.12
0.854
4.50
0.991
4.70
0.988
4.35
0.995
50
:
4.52
0.972
3.47
0.969
3.58
0.987
4.01
0.999
4.24
0.999
3.34
1.000
500
:
4.47
0.999
3.44
0.999
3.50
1.000
3.97
1.000
4.17
1.000
3.23
1.000
Note: iop number = average number of analyses; bottom number probability of declaring
out of compliance (for levels of PCB, x, 10 ppm and below this will be the probability of
false positive; for levels above 10 this will be the probability of detection).
32
-------
Table 12. Comparison of Sampling Designs for r = 7 (50% of Spill Site Size)
Level
contami
area,
of
nated
x
1
7
Group,
points
2
7
Groups,
points
Individually, 2
7 points 19
Groups,
points
6
19
Groups,
points
Individually,
19 points
4
:
1.08
0.000
2.02
0.000
7.00
0.000
7.37
0.000
6.31
0.000
19.00
0.000
8
:
4.00
0.000
2.98
0.000
7.00
0.000
13.13
0.000
9.78
0.000
19.00
0.000
10
:
5.04
0.009
3.55
0.006
6.96
0.013
14.13
0.029
10.83
0.022
18.73
0.030
12
:
5.40
0.088
3.81
0.067
6.61
0.118
12.82
0.272
10.42
0.226
16.15
0.296
14
:
5.16
0.284
3.96
0.216
5.79
0.349
9.41
0.686
8.47
0.623
11.34
0.705
16
:
4.76
0.521
3.90
0.441
4.82
0.579
6.59
0.909
6.43
0.876
7.14
0.921
20
:
4.05
0.774
3.58
0.747
3.53
0.849
4.25
0.992
4.45
0.991
3.74
0.994
25
:
3.65
0.910
3.18
0.895
2.87
0.951
3.45
0.999
3.77
0.999
2.61
1.000
50
:
3.46
0.910
2.94
0.895
2.40
0.997
3.04
1.000
3.29
1.000
2.10
1.000
500
:
3.38
1.000
2.88
1.000
2.39
1.000
3.03
1.090
3.31
1.000
2.02
1.000
T
number of ana
lyses; bottom
Note: op number = average number = probability of declaring
out of compliance (for levels of PCB, x, 10 ppm and below this will be the probability of
false positive; for levels above 10 this will be the probability of detection).
33
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In some cases, such as sod, scrape samples may not be appropriate.
For these cases, core samples, not more than 5 cm deep, should be taken using
a soil coring device. These core samples should be well—homogenized in a
stainless steel bowl by successive subdivision. A portion of each sample
should then be removed, weighed and analyzed.
Samples should be stored at 4°C in precleaned glass bottles. Be-
fore collection of verification samples, this equipment must be used to gen-
erate a field blank as described in Section IV.E.
2. Water Sampling
a. Surface Sampling
If PCBs dissolved in a hydrocarbon oil were spilled, they will
most likely be dispersed on the surface. Therefore, a surface water collec-
tion technique should be used. Surface water samples should be collected by
grab techniques. Where appropriate, the precleaned glass sample bottle may
be dipped directly into the body of water at the designated sample collection
point. A sample is collected from the water surface by gently lowering a pre-
cleaned sample bottle horizontally into the water until water begins to run
into it. The bottle is then slowly turned upright keeping the lip just under
the surface so that the entire sample is collected from the surface.
b. Subsurface Sampling
If the PCBs were in an Askarel or other heavier-than-water
matrix, the PCBs will sink. In these cases water nea ’ the bottom should be
collected. To collect subsurface water, the bottle should be lowered to the
specified depth with the cap on. The cap is then removed, the bottle allowed
to fill, and the bottle brought to the surface.
c. Other Sampling Approaches
When the above approaches are not feasible, other dippers,
tubes, siphons, pumps, etc. , may be used to transfer the water to the sample
bottle. The sampling system should be of stainless steel, Teflon, or other
inert, impervious, and noncontaminating material. Before collection of sam-
ples, this equipment must be used to generate a field blank as described in
Section IV.E.
d. Sample Preservation
The bottle is then lifted out of the water, capped with a PTFE-
or foil-lined lid, identified with a sample number, and stored at approximately
4°C until analysis to retard bacterial growth.
34
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3. Surface Sampling
a. Wipe Samples
If the surface to be sampled is smooth and impervious (e.g.
rain gutters, aluminum house siding), a wipe sample should indicate whether
the cleanup has sufficiently removed the PCBs. These surfaces should be sam-
pled by first applying an appropriate solvent (e.g., hexane) to a piece of
11 cm filter paper (e.g. , Whatman 40 ashless, or Whatman “50” smear tabs) or
gauze pad. This moistened filter paper or gauze pad is held with a pair of
stainless steel forceps and used to thoroughly swab a 100-cm 2 area as mea-
sured by a sampling template.
Care must be taken to assure proper use of a sampling template.
Different templates may be used for the variously shaped areas which must be
sampled. A 100 cm 2 area may be a 10 cm x 10 cm square, a rectangle (e.g.
1 cm x 100 cm or 5 cm x 20 cm), or any other shape. The use of a template
assists the sampler in the collection of a 100 cm 2 sample and in the selec-
tion of representative sampling sites. When a template is used it must be
thoroughly cleaned between samples to prevent contamination of subsequent
samples by the template.
The wipe samples should be stored in precleaned glass jars at 4°C.
Before collection of verification samples, the selected filter paper or gauze
pad and solvent should be used to generate a field blank as described in Sec-
tion IV.E.
b. Sampling Porous Surfaces
Wipe sampling is inappropriate for surfaces which are porous
and would absorb PCBs. These include wood and asphalt. Where possible, a
discrete object (e.g. , a paving brick) may be removed. Otherwise, chisels,
drills, saws, etc., may be used to remove a sufficient sample for analysis.
Samples near (generally less than 1 cm deep) the surface most likely to be
contaminated with PCBs should be collected. Where possible, the sample col-
lection should be as unobtrusive as possible.
C. Analytical Techniques
A number of analytical techniques have been used for analysis of
PCBs in the types of samples which may be associated with PCB spills. Some
of the candidate analytical methods are listed in Table 13. The analysis
method(s) most appropriate for a given spill will depend upon a number of
factors. These include sensitivity required, precision and accuracy required,
potential interferents, ultimate use of the data, experience of the analyst,
availability of laboratory equipment, and number of samples to be analyzed.
As shown in Table 13, many analytical methods are available. The
general analytical techniques are discussed and then compared below.
35
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Table 13 Standard Procedures of Analysis for PCBs
Procedure Determination Quanti tati on
designation Matrix Extraction Cleanupc method Qual. method LOD QC Reference
03534-80 Water Hexane/CH 2 C1 2 (Florisil) PGC/ECDd No Total area or 0.1 pg/i No ASTM, 1981a
(Silica Gel) Webb-McCall
608 Water CH 2 C 1 2 (Florisil) PGC/ECO No Area 0.04-0,15 pg/L Yes EPA, 1984a,
(S removal) Longbottom and
Lichtenberg, 1982
625 Water CH 2 C 1 2 None PGC/EIMS Yes Area 30-36 pg/L Yes EPA, 1984b,
(CGC) Longbottom and
Lichtenberg,
1982
304h Water Hexane/ Florisil/ PGC/ECD Yes Summed areas NS Yes EPA, 1978
CH 2 C1 2 silica gel or HECO or Webb-McCall
(85/15) (CH 3 CN)
(S removal)
EPA (by- Water Several Several HRGC/EIMS Yes md. peaks NS Yes Erickson et al
products) 1982, 1983d,
EPA, 1984c
ANSI Water Hexane (H 2 S0 4 ) PGC/ECD No Single peak or 2 ppm Yes ANSI, 1974
(Saponification) summed peaks
Alumina
Monsanto Water Hexane Alumina PGC/ECD No Individual or 2 ppb No Moein, 1976
total peak
heights
UK-DOE Water Hexane Silica gel PGC/ECO No NS 106 ng/L No UK-DOE, 1979;
Devenish and
Han ing-Bowen,
1980
03304-74 Air DI PGC/ECD No Total area NS Yes ASTM, 198]b
Water Hexane (H 2 50 4 )
Soil, H 2 0/CH 3 CN (Saponification)
sediment (Alumina)
EPA (homolog) Solids and Several Several HRGC/EIMS Yes md peaks MS Yes Erickson et al
liquids 1985a
EPA 625-S Sludge CH 2 C1 2 Florisil, HRGC/EIMS or Yes Area MS Yes Haile and
Silica gel, PGC/EIMS Lopez-Avila,
or GPC 1984
-------
Table 13 (Continued)
Procedure Determination Quantitation
designation Matrix Extraction Cleanup method Qual method LOU QC Reference
EPA Sludge Hexane/ GPC PGC/ECD Yes Peak area or US Yes Rodriguez
(Halocarbon) CH 2 C1 2 / S removal peak height et al. , 1980
acetone
(83/15/2)
Priority Sludge CH 2 C1 2 GPC PGC/EIMS Yes MS MS Yes EPA, 1979c
Pollutant (base/
neutral
and acid
fractions)
6100 Sludge CH 2 Cl 2 GPC HRGC/EIMS Yes NS NS Yes Ballinger, 1978
(3 fractions) Silica gel or PGC/EIMS
8080 Solid waste CH 2 C1 2 (Florisil) PGC/ECD No Area 1 pg/g Yes EPA, 1982e
8250 Solid waste CH 2 C1 2 None PGC/EIMS No MS 1 pg/g Yes EPA, 1982e
c 8270 Solid waste CHC1 2 None CGC/EIMS NO NS 1 pg/g Yes EPA, 1982e
EPA (spills) Unspecified Hexane/ (CH 3 CN) PGC/ECD No Total area or MS Plo Beard and
acetone (Florisil) Webb-McCall Schaum, 1978
(Silica gel)
(Mercury)
EPA Soil and Acetone! Florisil PGC/ECD No Computer MS Yes EPA, 1982d
Sediment Hexane Silica gel
(S removal) -
Monsanto Sediment CH 3 CN Saponification PGC/ECD No individual or 2 ppb No 1oein, 1976
H 2 S0 4 total peak
Alumina heights
ANSI Sediment, CH 3 CN Saponification PGC/ECD No Single peak or 2 ppm Yes ANSI, 1974
soil 112504 summed peaks
Alumina
EPA (by- Air collected Hexane (H 2 S0 4 ) HRGC/EIMS Yes md. peaks 1 15 Yes Erickson et al
products) on Florisil or (Florisil) 1982, 1983d,
XAD-2 Erickson, 1984b
EPA (ambient Air near haz- Ilexane! Alumina PGC/ECD No Total area or 10-50 ng!in 3 No Lewis, 1982
air) ardous waste ether peak height
sites col-
lected on P1W
-------
Quantitation
method 100
Reference
Table 13 (Continued)
Procedure
designation
Matrix
Extraction
CleanupC
Determination
method
Qual
EPA (stack)
Incinerator
emissions
and ambient
air collected
on Florisil
Hexane
(H 2 S0 4 )
Perchiorina-
tion PGC/ECD
No
Area
10 ng
EPA
Combustion
sources
collected
on Florisil
Pentane or
CH 2 C 1 2
(FlorisIl/
silica gel)
PGC/MS
Yes
Area/homolog
0 1 nq/inj
EPA (incin—
Stack gas
Pentane/
PGC/MS
Yes
Single peak
MS
erators)
methanol
ANSI
Air
(to luene
impinger)
-
(H 2 5 0 4 )
(Saponification)
(Alumina)
PGC/ECD
No
Single peak
2 ppb
NIOSH
(P&CPN 244)
Air collected
on Florisil
Hexane
None
PGC/ECD
No
Peak height or
area from stan-
dard curve or
Webb-McCall
0 01 mg/rn 3
NIOSH
Air collected
Hexane
None
PGC/ECD
No
Peak height or
0 01 mg/rn 3
(P&CAM 253)
on Florisil
Perchlorina-
tion
area from stan
dard curve
EPA (gas) -
Natural gas
sampled with
Florisil
Hexane
H 2 S0 4 -
- PGC/ECD -
Total area, peak
height or Webb-
McCall
(Perchlorination)
0 1-2 pg/rn 3
EPA [ 5,A,(3)]
Blood
Hexane
(Florisil)
PGC/ECD
No
NS
MS
EPA [ 5,A,(1)]
Adipose
Pet ether!
CH 3 CN
Florisil
PGC/ECD
No
MS
MS
EPA (9,D)
Adipose
Pet. ether/
CH 3 CN
Saponification
Florisil
TLC
No
Semiquant.
10 ppm
EPA (9,B)
Milk
Acetone!
hexane
CH 3 CN
Florisil
Silica acid
PGC/ECD
Yes
md peaks
50 ppb
QC
No Haile and
Baladi, 1977;
Beard and Schaum,
1978
No levins et al.
1979
Yes Beard and
Schaum, 1978
Yes ANSI, 1974
No NIOSH, 1977a
Mo NIOSH, 1977b,c
No Harris et al
1981
No
Yes
No
Yes
Watts, 1980
Watts, 1980
Watts, 1980
Watts, 1980
Sherma, 1981
-------
Table 13 (Continued)
Procedure Determination
designation Matrix Extraction CleanupC method Qual
ADAC (29) Food CH 3 CN/Pet. Florisil MgO/ PGC/ECD No
ether Celite
Saponi fi cation
Japan Food Pet. ether! Silica gel PGC/ECD Yes
CH 3 CN Saponi fication
(Florisil)
PAM Food Pet ether! Silicic acid PGC/ECD No
CH 3 CN (Saponification) (PGC/HECD)
(Oxidation) (NP-TIC)
(Florisil) (RP—TLC)
Paper and Saponifica- Florisil MgO! PGC/ECO No
paperboard tion Celite
Saponi fication
Capacitor 01 b None SCOT HRGC/FID No
Askarels
Mineral oil Dilute with Florisil slurry PGC/ECD Yes
hexane or (H 2 S0 4 ) (PGC/HECD)
isooctane (Florisil column)
Transformer DI (H 2 S0 4 ) PGC/HECD No
fluids or (Florisil) or /ECD or
waste oils (Alumina) /EIMS
(Silica gel) (HRGC)
(GPC), (CH 3 CN) - - - - —
EPA (by- Products or Several Several HRGC/EIMS Yes
products) wastes
DCMA 3 pigment A. Hexane/ None PGC/ECD No
types H 2 S0 4
B CH 2 C1 2 Florisil
DOW Chlorinated DI None PGC/EIMS Yes
benzenes
EPA (isomer Unspecified Not addressed Not addressed HRGC/EIMS Yes
groups)
Source. N LI Erickson, Ihe Analytical Chemistry of PCBs , Butterworths, Boston, MA,
a No specilic details
b Direct injection or dilute and inject.
c Techniques in parentheses are described as optional in the procedure
d Or PGC with microcoulornetric or electrolytic conductivity
AOAC (29)
03303- 74
D4059-83
EPA (oil)
Quanti tation
method
LOD
QC
Reference
Total area or
NSa
No
AOAC, 1980a
md peaks
Summed areas
NS
No
Tanabe, 1976
perch lorination
Area
NS
No
FDA, 1977
Total area or
NSa
No
AOAC, 198Ob
md peaks
Total area
2.8 x 108 mol/L
Ho
ASTM, 1980a
md. peaks or
SO ppm
No
ASTM, 1983
Webb-McCall
Total area or
1 mg/kg
Yes
EPA, 1981
Webb-McCall
Bellar and
Lichtenberg,
1981
md peaks
MS
Yes
Erickson et al
1982, 1983d;
Erickson, 1984a
,
10 isomers
. 1 ppm!homolog
Yes
DCMA, 1982
Total peak
MS
Yes
Dow, 1981
height/homolog
md peaks
MS
Yes
EPA, 1984d
1985, in press
-------
1. Gas Chromatography (GC )
As can be seen in Table 13, analysis of PCBs by gas chromatography
is frequently the method of choice. PCBs are chromatographed using either
packed or capillary columns and may be detected using either specific detec-
tors or mass spectrometry. A comprehensive method for analysis of PCBs in
transformer fluid and waste oils was developed by Bellar and Lichtenberg
(1982). This method describes six different cleanup techniques, recommends
three GC detectors, and suggests procedures for GC calibration and for mea-
surement of precision and accuracy. This method also discusses several cal-
culation methods.
a. Gas Chromatograph/Electron Capture Detection
Packed column gas chromatography with electron capture detec-
tion (GC/ECD) is generally the method of choice for analysis of spill site
samples, transformer oils, and other similar matric s which must be analyzed
for PCB content prior to disposal (Copland and Gohmann 1982). GC/ECD is very
sensitive, highly selective against hydrocarbon background, and relatively
inexpensive to operate. The technique is most appropriate when the PCB resi-
due resembles an Aroclor standard and other halogenated compounds do not inter-
fere.
While it is considered a selective detector, ECO also detects
non-PCB compounds such as halogenated pesticides, polychiorinated naphthal-
enes, chloroaromatics, phthalate and adipate esters, and other compounds.
These compounds may be differentiated from PCBs only by chrornatographic re-
tention time. Elemental sulfur can interfere with PCB analysis in sediment
and other samples which have been subjected to anaerobic degradation condi-
tions. There are also common interferences which do not give discrete peaks.
An example of a nonspecific interference is mineral oil (ASTM 1983). Mineral
oil, a complex mixture of hydrocarbons, can cause a general suppression of
ECD response. Mineral oils from transformers often contain PCBs as a result
of cross-contamination of transformer oils.
A major disadvantage of ECD is the range of response factors
which different PCB congeners exhibit. Zitko et al. (1971) and Hattori et al.
(1981) published response factors ranges of about 540 and 9000, respectively.
Boe and Egaas (1979), Onsuka et al. (1983) and Singer et al. (1983) have also
published ECU response factors. The range of response factors seriously in-
hibits reliable quantitation.
When PCBs are analyzed by packed column gas chromatography,
the PCBs are usually quantitated by total areas or individual peaks. In the
total areas method, the areas of all peaks in a retention window are summed
and this total compared with the corresponding response of an Aroclor stan-
dard. With the individual peak quantitation method, response factors are
calculated for each peak in the packed column chromátograrn. The most prom-
inent individual peak quantitation method was originated by Webb and McCall
(1973). These results may be reported as an Aroclor concentration or as
total PCB. Packed column GC techniques are generally useful for quantitation
40
-------
of samples which resemble pure Aroclors but are prone to errors from inter-
fering compounds or from PCB mixtures that do not resemble pure Aroclors
(Albro 1979). For this reason analysts have been using capillary gas chro-
matography for the analysis of PCB5. Capillary gas chromatography offers the
analyst the ability to separate most of the individual PCB isomers. Bush
et al. (1982) has proposed a method of obtaining “total PCB” values by inte-
gration of all PCB peaks, using response factors generated from an Aroclor
mixture. Zell and Ballschmiter (1980) have developed a simplified approach
where only a selected few “diagnostic peaks” are quantitated. In a similar
approach Tuinstra et al. (1983) have quantitated six specific, diagnostic con-
geners which appear to be useful for regulatory cutoff analyses.
b. GC/Hall Electrolytic Conductivity Detector
Electrolytic conductivity detectors have also been used with
packed column gas chromatography to selectively detect PCBs (Webb and McCall
1973, Sawyer 1978). The Hall electrolytic conductivity detector (HECD) mea-
sures the change in conductivity of a solution containing HC1 or HBr which is
formed by pyrolysis of halogenated organic GC effluents. The HECD exhibits
105_106 selectivity for halogenated compounds over other compounds. It also
gives a linear response over at least a 10 range. HECD and ECO were com-
pared for their use in detecting PCBs in waste oil, hydraulic fluid, capacitor
fluid, and transformer oil (Sonchik et al. 1984). They found both detectors
acceptable, but noted that the HECD gave higher results with less precision
than the ECO. The method detection limits ranged from 3-12 ppm for HECD and
2-4 ppm for [ CD. Greater than 100% recovery of spikes analyzed by HECO indi-
cated a nonspecific response to non-PCB components, since extraneous peaks
were not observed. Another comparison of HECD and ECO for the analysis of
PCBs in oils at the 30-500 ppm levels found that the type of detector made no
significant difference in the results (Levine et al. 1983). The authors noted
that higher accuracy had been expected from the more specific HECD. They
postulated that the cleanup procedures (Florisil, alumina, and sulfuric acid)
all had effectively removed the non-PCB species which would have caused
interferences in the ECD and reduced its accuracy.
c. GC/Mass Spectrometry
Highly specific identification of PCBs is performed by GC with
mass spectrometric (GC/MS) detection. High resolution gas chromatography is
generally used with mass spectrometry, so individual PCB isomers may be
separated and identified. A GC/MS produces a chromatogram consisting of data
points at about 1-s intervals, which are actually full mass spectra. The data
are stored by a computer and may be retrieved in a variety of ways. The data
file contains information on the amount of compound (signal intensity),
molecular weight (parent ion), and chemical composition (fragmentation pat-
terns and isotopic clusters).
GC/MS is particularly suited to detection of PCBs because of
its intense molecular ion and the characteristic chlorine cluster Chlorine
has two naturally occurring isotopes, 35 C1 and 37 C1, which occur in a ratio
of 100:33. Thus, a molecule with one chlorine atom will have a parent ion,
M, and an M+2 peak at 33% relative intensity. With two chlorine atoms, M+2
has an intensity of 66% and M+4, 11%.
41
-------
Because of its expense, complexity of data, and lack of sensi-
tivity, GC/MS has not been used as extensively as other GC methods (particu-
larly GC/ECD), despite its inherently higher information content. As the
above factors have been improved, GC/MS has become much more popular for
analysis of PCBs, and will probably continue to increase in importance. Sev-
eral factors including the introduction of routine instruments without costly
accessories, decreasing data system costs, and mass-marketing, have combined
to keep the costs of GC/MS down while prices of other instruments have risen
steadily. With larger data systems and more versatile and Huser_friendlyhl
software, the large amount of data is more easily handled. However, data re-
duction of a GC/MS chromatograni still requires substantially more time than
for a GC/ECD chromatogram. In addition, the sensitivity of GC/MS has im-
proved.
d. Field-Portable Gas Chromatography Instrumentation
Gas chromatography may be used for analysis of samples in the
field. Gas chromatography is a well-established laboratory technique, and
portable instruments with electron capture detectors are available (Splittler
1983, Colby et al. 1983, Picker and Colby 1984). A field-portable GC/ECD
was used to obtain rapid measurements of PCBs in sediment and soil (Spittler
1983). The sample preparation consisted of a single solvent extraction. The
PCBs were eluted from the GC within 9 mm. In a 6-h period, 40 soils and
10 QC samples were analyzed, with concentrations ranging from 0.2 to 24,000
ppm. The use of field analysis permits real-time decisions in a cleanup op-
eration and reduces the need for either return visits to a site.
Mobile mass spectrometers are also available. An atmospheric
pressure chemical ionization mass spectrometer, marketed by SCIEX, has been
mounted in a van and used for in situ analyses of soil and clay (Lovett et al.
1983). The instrument has apparently been used for field determination of
PCBs in a variety of emergency response situations, including hazardous waste
site cleanups. Other, more conventional mass spectrometers, should also be
amenable to use in the field.
2. Thin-Layer Chromatography (TLC )
Thin—layer chromatography is a well-established analytical tech-
nique which has been used for the determination of PCBs for many years.
Since the publication of a TLC method for PCBs by Mulhern (Muihern 1968,
Muihern et al. 1971), several researchers have used TLC to measure PCBs in
various matrices. Methods have been reported by Willis and Addison (1972)
for the analysis of Aroclor mixtures, by Piechalak (1984) for the analysis of
soils, and by Stahr (1984) for the analysis of PCB containing oils. Even with
a densitometer to measure the intensity of the spots, TLC is not generally
considered quantitative. Order-of-magnitude estimates of the concentration
are certainly obtainable, but the precision and accuracy probably do not
approach that of the gas chromatographic methods.
42
-------
A spill site sample extract will probably need to be cleaned up
before TLC analysis. Levine et al. (1983) have published a comparison of
various cleanup procedures. Stahr (1984) has compared the Levine sulfuric
acid cleanup to a SepPak® C 18 cleanup method.
Different TLC techniques have been used to improve the sensitivity
and selectivity of the method. Several researchers have reported that the
use of reverse-phase TLC (C 18 -bonded phase) achieves a better separation
of PCBs from interferences (DeVos and Peet 1971, DeVos 1972, Stalling and
Huckins 1973, Brinkman et al. 1976). Koch (1979) has reported an order of
magnitude improvement in the PCB limit of detection through use of circular
TLC. The two most common methods of visualization are fluorescence (Kan et al.
1973, Ueta et a]. 1974) and reaction with AgNO 3 followed by UV irradiation
(DeVos and Peet 1971, DeVos 1972, Kawabata 1974, Stahr 1984).
No direct comparison of the performance of TLC with other techniques
for analysis of samples from spill sites has been made. Two studies (Bush et
al. 1975, Collins et al. 1972) compared TLC and GC/ECD. In both studies, the
PCB values obtained were comparable. However, the study by Bush et al. indi-
cated that the TLC results were generally lower than GC/ECD.
3. Total Organic Halide Analyses
Total organic halide analysis can be used to estimate PCB concen-
trations for guiding field work, but is not appropriate for verification or
enforcement analyses. A total organic halide analysis indicates the presence
of chlorine and sometimes the other halogens. Many of the techniques also
detect inorganic chlorides (e.g., sodium chloride; common table salt). The
reduction of organochlorine to free chloride ion with metallic sodium can be
used for PCB analysis. The free chloride ions can be then detected calori-
metrically (Chlor-N-Oil®) or by a chloride ion-specific electrode (McGraw-
Edison). The performance of these kits has not been tested with any matrix
other than mineral oil. X—ray fluorescence (XRF) has also been studied as a
PCB screening technique (McQuade 1982, Schwalb and Marquez 1982).
D. Selection of Appropriate Methods
1. Criteria for Selection
The primary criterion for an enforcement method is that the data be
highly reliable (i.e., they are legally defensible). This does not necessarily
imply that the most exotic, state-of-the-art methods be employed; rather that
the methods have a sound scientific basis and validation data to support their
use. Many other criteria also enter into selection of a method, including
accuracy, precision, reproducibility, comparability, consistency across ma-
trices, availability, and cost.
For PCB spills, it is assumed that the spills will be relatively
fresh and therefore that PCB mixtures will generally resemble those in com-
mercial products (i.e., Aroclor®). It is further assumed that, for most of
the matrices likely to be encountered, the levels of interferences will be
relatively low.
43
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2. Selection of Instrumental Techniques
Based upon the above criteria and assumptions, either GC/ECD or
GC/MS should provide suitable data. Since GC/ECD is included in more stan-
dard methods and since the technique is more widely used, it appears to be
the technique of choice. The primary methods recommended below are all based
on GC/ECD instrumental analysis. Some of the secondary and confirmatory tech-
niques are based on GC/EIMS.
3. Selection of Methods
Ideally, a standard method would be available for each matrix likely
to be encountered in a PCB spill. The matrices of concern include solids (soil,
sand, sediment, bricks, asphalt, wood, etc.), water, oil, surface wipes, and
vegetation. The methods for these matrices are summarized in Table 14 and
discussed in detail below. A primary recommended method is given and should
be used in most spill instances. The secondary method may be useful for con-
firmatory analyses, or where the situation (e.g. , high level of interferences)
indicates that the primary method is not applicable.
a. Solids (Soil, Sand, Sediment, Bricks, Asphalt, Wood, Etc. )
EPA Method 8080 from SW-846 (USEPA 1982e) is the primary recom-
mended method. The secondary methods, Method 8250 and Method 8270, are GC/MS
analogs. Method 8080 entails an acetone/hexane (1:1) extraction, a Florisil
column chromatographic cleanup, and a GC/ECD instrurpental determination. A
total area quantitation versus Aroclor standards is specified. No qualitative
criteria are supplied. A detection limit of 1 pg/g is prescribed. No valida-
tion data are available.
Bulk samples (bricks, asphalt, wood, etc.) should be readily
extractable using a Soxhiet extractor according to EPA Method 8080 (USEPA
1982e). The sample must be crushed and subsampled to ensure proper solvent
contact.
b. Water
EPA Method 608 (USEPA 1984e) is recommended as the primary
method. This is one of the “priority pollutant” methods and involves extrac-
tion of water samples with dichlorornethane. An optional Florisil column
chromatographic cleanup and also an optional sulfur removal are given. Sam-
ples are analyzed by GC/ECD and quantitated against the total area of Aroclor
standards. No qualitative criteria are given. This method has been exten-
sively validated and complex recovery and precision equations are given in
the method for seven Aroclor mixtures. The average recovery is about 86% and
average overall precision about ± 26%. The average recovery and precision
for the more common Aroclors (1242, 1254, and 1260) are about 78% and ± 26%,
respectively. Detection limits are not given in the current version (USEPA
1984a), although they were listed as between 0.04 and 0.15 ig/L for the seven
Aroclor mixtures listed as priority pollutants in the method validation study
(Millar et al. 1984).
44
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Table 14. Summary of Recommended Analytical Methods
Primary method (GC/ECD) Secondary method
Matrix Designation Reference Designation GC detector Reference
Solids 8080 USEPA 1982e 8250, 8270 MS USEPA 1982e
Water 608 (JSEPA 1984a 625 MS USEPA 1984b
Oil “oil” USEPA 1931a; “oil” MS USEPA 1981a;
Bellar and Bellar and
Lichtenberg, Lichtenberg,
1981 1981
Surface Hexane extrac- None Hexane extrac- MS None
wipes tion/608 tion/625
Vegetation AOAC (29) AOAC 1980a None None None
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c. Oils
Spilled oil samples should be analyzed according to an EPA
method (Bellar and Lichtenberg 1981). The method is written for transformer
fluids and waste oils, but should also be applicable to other similar oils
such as capacitor fluids. In this method, samples are diluted by an appro-
priate factor (e.g. , 1:1000). Six optional cleanup techniques are given.
The sample may be analyzed by GC/ECD as the primary method. Secondary instru-
mental choices, also presented in the method, are GC/HECD, GC/MS, and capil-
lary GC/MS. PCBs are quantitated by either total areas or the Webb-McCall
(1973) method. No qualitative criteria are given. QC criteria are given. A
detection limit of 1 mg/kg is stated, although it is highly dependent on the
amount of dilution required. An interlaboratory validation study (Sonchik
and Ronan 1984) indicated 81 to 126% recoveries for different PCB mixtures,
with an average of 97% for Aroclors 1242, 1254, and 1260, as measured by ECD.
The overall method precision ranged from ± 11 to ± 55%, with an average of
± 12% for Aroclors 1242, 1254, and 1260. The method validation statistics
were presented in more detail as regression equations.
d. Surface Wipes
No standard method is available for analysis of PCBs collected
on surface wipes. However, since this matrix should be relatively clean and
easily extractable, a simple hexane extraction should be sufficient. Samples
should be analyzed according to EPA Method 608 (USEPA 1984a), except for
Section 10.1 through 10.3. In lieu of these sections, the sample should be
extracted three times with 25 to 50 rnL of hexane. The sample can be extracted
by shaking for at least 1 mm per extraction in the’ wide-mouthed jar used for
sample storage. Note that the rinses should be with hexane so that solvent
exchange from methylene chloride to hexane (Section 10.7) is not necessary.
This method is proposed in this document and has not been validated.
e. Vegetation
The AOAC (1980a) procedure for food is recommended for analysis
of vegetation (leaves, vegetables, etc.). This method involves extraction of
a macerated sample with acetonitrile. The acetonitrile is diluted with water
and the PCBs extracted into petroleum ether. The concentrated extract is
cleaned up by Florisil column chromatography by elution with a mixture of ethyl
ether and petroleum ether. The sample is analyzed by GC/ECD with quantitation
by total areas or individual peak heights as compared to Aroclor standards.
No qualitative criteria are given. Validation studies with chicken fat and
fish (Sawyer 1973) are not relevant to the types of matrices to be encountered
in PCB spills.
4. Implementation of Methods
Each laboratory is responsible for generating reliable data. The
first step is preparation of an in-house protocol. This detailed 11 cookbook”
is based on methods cited above, but specifies which options must be followed
and provides more detail in the conduct of the techniques. It is essential
that a written protocol be prepared for auditing puprposes.
46
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Each laboratory is responsible for generating validation data to
demonstrate the performance of the method in the laboratory. This can be
done before processing of samples; however, it is often impractical. Valida-
tion of method performance (replicates, spikes, QC samples, etc.) while ana-
lyzing field samples is acceptable.
Changes in the above methods are acceptable, provided the changes
are documented and also provided that they do not affect performance. Some
minor changes (e.g. , substitution of hexane for petroleum ether) do not
generally require validation. More significant changes (e.g., substitution
of a HECD for ECD) will require documentation of equivalent performance.
E. Quality Assurance
Quality assurance must be applied throughout the entire monitoring
program including the sample planning and collection phase, the laboratory
analysis phase, and the data processing and interpretation phase.
Each participating EPA or EPA contract laboratory must develop a
quality assurance plan (QAP) according to EPA guidelines (USEPA 1980). Ad-
ditional guidance is also available (USEPA 1983). The quality assurance plan
must be submitted to the regional QA officer or other appropriate QA official
for approval prior to analysis of samples.
1. Quality Assurance Plan
The elements of a QAP (U.S. EPA, 1980) include:
Title page
Table of contents
Project description
Project organization and responsibility
QA objectives for measurement data in terms of precision, ac-
curacy, completeness, representativeness, and comparability
Sampl ing procedures
Sample tracking and traceability
Calibration procedures and frequency
Analytical procedures
Data reduction, validation and reporting
Internal quality control checks
Performance and system audits
Preventive maintenance
Specific routine procedures used to assess data precision,
accuracy and completeness
Corrective action
Quality assurance reports to management
47
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2. Quality Control
Each laboratory that uses this method must operate a formal quality
control (QC) program. The minimum requirements of this program consist of an
initial and continuing demonstration of acceptable laboratory performance by
the analysis of check samples, spiked blanks, and field blanks. The labora-
tory must maintain performance records which define the quality of data that
are generated.
The exact quality control measures will depend on the laboratory,
type and number of samples, and client requirements. The QC measures should
be stipulated in the QA Plan. The QC measures discussed below are given for
example only. Laboratories must decide on which of the measures below, or
additional measures, will be required for each situation.
a. Protocols
Virtually all of the available PCB methods contain numerous
options and general instructions. Effective implementation by a laboratory
requires the preparation of a detailed analysis protocol which may be followed
unambiguously in the laboratory. This document should contain working instruc-
tions for all steps of the analysis. This document also forms the basis for
conducting an audit.
b. Certification and Performance Checks
Prior to the analysis of samples, the laboratory must define
its routine performance. At a minimum, this must include demonstration of
acceptable response factor precision with at least three replicate analyses
of a calibration solution; and analysis of a blind QC check sample (e.g. , the
response factor calibration solution at unknown concentration submitted by an
independent QA officer). Acceptable criteria for the precision and the ac-
curacy of the QC check sample analysis must be presented in the QA plan.
Ongoing performance checks should include periodic repetition
of the initial demonstration or more elaborate measures. More elaborate mea-
sures may include control charts and analysis of QA check samples containing
unknown PCBs, and possibly with matrix interferences.
c. Procedural QC
The various steps of the analytical procedure should have qual-
ity control measures. These include, but are not limited to, the following:
Instrumental Performance : Instrumental performance cri-
teria and a system for routinely monitoring the performance should be set out
in the QA Plan. Corrective action for when performance does not meet the
criteria should also be stipulated.
48
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Qualitative Identification : Any questionable results
should be confirmed by a second analytical method. A least 10% of the
identifications, as well as any questionable results, should be confirmed by
a second analyst.
Quantitation : At least 10% of all calculations must be
checked. The results should be manually checked after any changes in com-
puter quantitation routines.
d. Sample QC
Each sample and each sample set must have QC measures applied
to it to establish the data quality for each analysis result. The following
should be considered when preparing the QA plan:
Field Blanks : Field blanks are analyzed to demonstrate
that the sample collection equipment has not been cqntaminated. A field blank
may be generated by using the sampling equipment to collect a blank sample
(e.g. , using the water sampling equipment to sample laboratory reagent grade
water) or by extracting the sampling equipment (e.g., extracting a sheet of
filter paper from the lot used to collect wipe samples). A field blank must
be collected and analyzed for each type of sample collected.
Replicate Samples : One sample from each batch of 20 or
fewer will be analyzed in triplicate. The sample is divided into three rep-
licate subsamples and all these subsamples carried through the analytical
procedure. The results of these analyses must be comparable within the limits
required for spiked samples.
Analysis of Spiked Samples : The sensitivity and re-
producibility must be demonstrated for any method used to report verification
data. This can be done by analyzing spiked blanks near the required detec-
tion limit. To demonstrate the ability of the method to reproducibly detect
the spiked sample, one or more spiked samples should be analyzed in at least
triplicate for each group of 20 or fewer samples within each sample type col-
lected. Samples will be spiked with a PCB mixture similar to that spilled
(e.g., Aroclor 1260). Example concentrations are:
Matrix Spike Level
Soil, etc. 10 pg/g (10 ppm)
Water 100 pg/L (100 ppb))
Wipes 100 pg/wipe (100 pg/100 cm 2 )
Quantitative techniques must detect the spike level within ±30% for all spiked
samples.
49
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e. Sample Custody
As part of the Quality Assurance Plan, the chain-of-custody
protocol must be described. A chain-of-custody provides defensible proof of
the sample and data integrity. The less rigorous sample traceability docu-
mentation merely provides a record of when operations were performed and by
whom. Sample traceability is not acceptable for enforcement activities.
Chain-of-custody is required for analyses which may result in
legal proceedings and where the data may be subject to legal scrutiny.
Chain-of-custody provides conclusive written proof that samples are taken,
transferred, prepared, and analyzed in an unbroken line as a means to maintain
sample integrity. A sample is in custody if:
- It is in the possession of an authorized individual;
- It is in the field of vision of an authorized
individual;
- It is in a designated secure area; or
- It has been placed in a locked container by an
authorized individual.
A typical chain-of-custody protocol contains the follow-
ing elements:
1. Unique sample identification numbers.
2. Records of sample container preparation and integrity
prior to sampling.
3. Records of the sample collection such as:
- Specific location of sampling.
- Date of collection.
- Exact time of collection.
- Type of sample taken (e.g., air, water, soil).
- Initialing each entry.
- Entering pertinent information on chain-of-
custody record.
- Maintaining the samples in one’s possession or
under lock and key.
- Transporting or shipping the samples to the
analysis laboratory.
50
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- Filling out the chain-of-custody records.
— The chain—of-custody records must accompany the
samples.
4. Unbroken custody during shipping. Complete shipping
records must be retained; samples must be shipped in
locked or sealed (evidence tape) containers.
5. Laboratory chain-of-custody procedures consist of:
- Receiving the samples.
— Checking each sample for tampering.
- Checking each sample against the chain-of-custody
records.
- Checking each sample and noting its condition.
- Assigning a sample custodian who will be
responsible for maintaining chain-of-custody.
- Maintaining the sign—offs for every transfer of
each sample on the chain—of-custody record.
- Ensuring that all manipulations of the sample
are duly recorded in a laboratory notebook along
with sample number and date. These manipulations
will be verified by the program manager or a
designee.
F. Documentation and Records
Each laboratory is responsible for maintaining complete records of
the analysis. A detailed documentation plan should be prepared as part of
the QAP. Laboratory notebooks should be used for handwritten records. Digi-
tal or other GC/MS data must be archived on magnetic tape, disk, or a similar
device. Hard copy printouts may also be kept if desired. Hard copy analog
data from strip chart recorders must be archived. QA records should also be
retai ned.
The documentation must completely describe how the analysis was
performed. Any variances from a standard protocol must be noted and fully
described. Where a procedure lists options (e.g., sample cleanup), the op-
tion used and specifics (solvent volumes, digestion times, etc.) must be
stated.
The remaining samples and extracts should be archived for at least
2 months or until the analysis report is approved by the client organization
(whichever is longer) and then disposed unless other arrangements are made.
51
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The magnetic disks or tapes, hard copy chromatograms, hard copy spectra, quan-
titation reports, work sheets, etc. , must be archived for at least 3 years.
All calculations used to determine final concentrations must be documented.
An example of each type of calculation should be submitted with each verifi-
cation spot.
G. Reporting Results
Results of analysis will normally be reported as follows:
Matrix Reporting Units
Soil, etc. pg PCB/g of sample (ppm)
Water mg PCB/L of sample (ppm)
Surfaces (wipes) pg PCB/wipe (pg PCB/100 cm 2 )
In some cases, the results are to be reported by homolog. In this
case, 11 values are reported per sample: one each for the 10 homologs and
one for the total. Some TSCA analyses require reporting the results in terms
of resolvable gas chromatographic peak (U.S. EPA, 1982c, 1984e). In these
cases, the number of results reported equals the number of peaks observed on
the chromatogram. These analyses are generally associated with a regulatory
cutoff (e.g., 2 pg/g per resolvable chrornatographic peak (U.S. EPA, 1982c,
1984). In these cases it may be sufficient, depending on the client organi-
zation’s request, to report only those peaks which are above the regulatory
cutoff.
Even if an Aroclor is used as the quantitation standard, the re-
suits are never to be reported as “pg Aroclor®/g sample.” TSCA regulates all
PCBs, not merely a specific commercial mixture.
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