United States Office of Research and EPA/600/R-98/1173
Environmental Protection Development December 1998
Agency Washington, D.C. 20460
4>EPA Environmental Technology
Verification Report
Immunoassay Kit
EnviroLogix, Inc.
PCB in Soil Tube Assay
ETV ETV ET
-------
EPA/600/R-98/173
December 1998
Environmental Technology
Verification Report
Immunoassay Kit
EnviroLogix, Inc.
PCB in Soil Tube Assay
By
Amy B. Dindal
Charles K. Bayne, Ph.D.
Roger A. Jenkins, Ph.D.
Oak Ridge National Laboratory
Oak Ridge Tennessee 37831-6120
Eric N. Koglin
U.S. Environmental Protection Agency
Environmental Sciences Division
National Exposure Research Laboratory
Las Vegas, Nevada 89193-3478
This demonstration was conducted in cooperation with
U.S. Department of Energy
David Bottrell, Project Officer
Cloverleaf Building, 19901 Germantown Road
Germantown, Maryland 20874
Superfund Innovative Technology
Evaluation Program
oml
-------
Notice
The U.S. Environmental Protection Agency (EPA), through its Office of Research and Development
(ORD), and the U.S. Department of Energy's Environmental Management (EM) Program, funded and
managed, through Interagency Agreement No. DW89937854 with Oak Ridge National Laboratory, the
verification effort described herein. This report has been peer and administratively reviewed and has been
approved for publication as an EPA document. Mention of trade names or commercial products does not
constitute endorsement or recommendation for use of a specific product.
-------
„.«,.„, UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
^ ^B
^ ^k mr Office of Research and Development
- t>JM6*r "S Washington, D.C. 20460
ENVIRONMENTAL TECHNOLOGY VERIFICATION PROGRAM
VERIFICATION STATEMENT
TECHNOLOGY TYPE: POLYCHLORINATED BIPHENYL (PCB) FIELD ANALYTICAL
TECHNIQUES
APPLICATION: MEASUREMENT OF PCBs IN SOILS AND SOLVENT EXTRACTS
TECHNOLOGY NAME: PCB IN SOIL TUBE ASSAY
COMPANY: ENVIROLOGIX INC.
ADDRESS: 55 INDUSTRIAL WAY
PORTLAND, ME 04103
PHONE: (207) 797-0300
The U.S. Environmental Protection Agency (EPA) has created a program to facilitate the deployment of innovative
technologies through performance verification and information dissemination. The goal of the Environmental Technology
Verification (ETV) Program is to further environmental protection by substantially accelerating the acceptance and use
of improved and more cost-effective technologies. The ETV Program is intended to assist and inform those involved in
the design, distribution, permitting, and purchase of environmental technologies. This document summarizes the results
of a demonstration of EnviroLogix Inc. PCB in Soil Tube Assay.
PROGRAM OPERATION
EPA, in partnership with recognized testing organizations, objectively and systematically evaluates the performance of
innovative technologies. Together, with the full participation of the technology developer, they develop plans, conduct
tests, collect and analyze data, and report findings. The evaluations are conducted according to a rigorous demonstration
plan and established protocols for quality assurance. EPA's National Exposure Research Laboratory, which conducts
demonstrations of field characterization and monitoring technologies, with the support of the U.S. Department of
Energy's (DOE) Environmental Management (EM) program, selected Oak Ridge National Laboratory (ORNL) as the
testing organization for the performance verification of polychlorinated biphenyls (PCBs) field analytical techniques.
DEMONSTRATION DESCRIPTION
In July 1997, the performance of six PCB field analytical techniques was determined under field conditions. In September
1998, the performance of EnviroLogix Inc.'s PCB in Soil Tube Assay kit was evaluated similarly. Each technology was
independently evaluated by comparing field analysis results with those obtained using approved reference methods.
Performance evaluation (PE) samples were also used to assess independently the accuracy and comparability of each
technology.
The demonstration was designed to detect and measure PCBs in soil and solvent extracts. For EnviroLogix, the
demonstration was conducted at ORNL in Oak Ridge, Tennessee, from September 21 through 25, 1998. The study was
conducted under two environmental conditions. The first site was outdoors, with naturally fluctuating temperatures and
relative humidity conditions. The second site was inside a controlled environmental chamber, with generally cooler
temperatures and lower relative humidities. Multiple soil types, collected from sites in Ohio, Kentucky, and Tennessee,
were analyzed in this study. Solutions of PCBs were also analyzed to simulate extracted surface wipe samples. The
results of the soil and extract analyses conducted under field conditions by the technology were compared with results
from analyses of homogenous replicate samples conducted by conventional EPA SW-846 methodology in an approved
EPA-VS-SCM-29 The accompanying notice is an integral part of this verification statement. December 1998
iii
-------
reference laboratory. Details of the demonstration, including a data summary and discussion of results, may be found
in the report entitled Environmental Technology Verification Report: Immunoassay Kit, EnviroLogix Inc., PCB in Soil
Tube Assay, EPA/600/R-98/173.
TECHNOLOGY DESCRIPTION
The EnviroLogix PCB in Soil Tube Assay applies the principles of enzyme linked immunosorbent assay (ELISA) to the
determination of PCB. In such an assay, an enzyme has been chemically linked to a PCB molecule or PCB analog to
create a labeled PCB reagent. The labeled PCB reagent (called a conjugate) is mixed with an extract of native sample
containing the PCB contaminant. A portion of the mixture is applied to a surface (i.e., the inside of a test tube) to which
an antibody specific for PCB has been affixed. The native PCB and PCB-enzyme conjugate compete for a limited
number of antibody sites. After a period of time, the solution is washed away, and what remains is either PCB-antibody
complexes or enzyme-PCB-antibody complexes attached to the test surface. The proportion of the two complexes on
the test surface is determined by the amount of native PCB in the original sample. The enzyme present on the test surface
is used to catalyze a color change reaction in a solution added to the test surface. Because the amount of enzyme present
is inversely proportional to the concentration of native PCB contaminant, the amount of color development is inversely
proportional to the concentration of PCB contaminant. The color development is quantified through the use of a hand-held
photometer.
The EnviroLogix PCB in Soil Tube Assay is designed for semi-quantitative field screening for PCBs in soil. The kit is
supplied with calibrators equivalent to 1 part per million (ppm) and 10 ppm PCB (Aroclor 1254) in soil. These
calibrators are used to evaluate threshold levels of 1 and 10 ppm. A threshold level of 50 ppm can also be evaluated
using the 10 ppm calibrator by preparing a 1:5 sample extract dilution into methanol. For the extract samples, the
threshold levels are 0.4, 4, and 20 (ig/mL.
VERIFICATION OF PERFORMANCE
The following performance characteristics of the PCB in Soil Tube Assay were observed:
Throughput: Throughput was 8 samples/hour under outdoor conditions and 7 samples/hour under chamber conditions
for one operator. This rate included sample preparation and analysis.
Ease of Use: One operator analyzed samples during the demonstration. Minimal training (4 h) is required to operate the
kit, provided the user has a fundamental understanding of basic chemical and field analytical techniques.
Completeness: The PCB in Soil Tube Assay generated results for all 232 PCB samples for a completeness of 100%.
False positive/negative results: All of the blank samples (soils and extracts) were reported as the lowest reporting
interval, which included zero; therefore, the percentage of false positive results was 0%. The kit reported no false negative
results for extracts, and 4% (7 of 192 samples) for soils.
Precision: The overall precision—based on the percentage of combined sample sets where all four replicates were
reported as the same interval—was 56% for the PE soils, 68% for the environmental soils, and 75% for the extracts.
Accuracy: Accuracy was assessed using PE soil and extract samples. Accuracy, defined as the percentage of the PCB
in Soil Tube Assay results that agreed with the accepted concentration, was 78% for PE soils and 92% for extracts. In
general, the fraction of samples that was biased high was comparable (10% for PE soils and 0% for extracts) to the
fraction that was biased low (13% for PE soils and 8% for extracts).
Comparability: Comparability, like accuracy, was defined as the percentage of results that agreed with, was above (i.e.,
biased high), or was below (i.e., biased low) the reference laboratory result. The percentage of samples that agreed with
the reference laboratory results was 82% for all soils (PE and environmental). The fraction of samples that was biased
EPA-VS-SCM-29 The accompanying notice is an integral part of this verification statement. December 1998
iv
-------
high was again comparable (12%) to the fraction that was biased low (7%). Extract results could not be compared
because no reference laboratory data was generated for these samples.
Regulatory Decision-making: One objective of this demonstration was to assess the technology's ability to perform at
regulatory decision-making levels for PCBs, specifically 50 ppm for soils. For PE and environmental soil samples in the
range of 40 to 60 ppm, 66% of the PCB in Soil Tube Assay results agreed with the reference laboratory, 32% were
biased high, and 2% were biased low. The test kit results for this concentration range were different from what was
observed for the entire data set in that the fraction of samples that were biased high was significantly higher (32% versus
12%).
Data quality levels: The performance of the test kit was characterized as unbiased, because most (78%) of the PCB in
Soil Tube Assay results agreed with the certified PE values, but imprecise, because nearly half (44%) of the PE replicate
results were not reported as the same interval. It should be noted that almost all of the imprecision occurred when the
concentration of the sample was near one of the test kit's threshold values (i.e., 1, 10, or 50 ppm).
The results of the demonstration show that the PCB in Soil Tube Assay can provide useful, cost-effective data for
environmental problem-solving and decision-making. Undoubtedly, it will be employed in a variety of applications,
ranging from serving as a complement to data generated in a fixed analytical laboratory to generating data that will stand
alone in the decision-making process. As with any technology selection, the user must determine if this technology is
appropriate for the application and the project data quality objectives. For more information on this and other verified
technologies, visit the ETV web site at http://www.epa.gov/etv.
Gary J. Foley, Ph.D.
Director
National Exposure Research Laboratory
Office of Research and Development
NOTICE: EPA verifications are based on an evaluation of technology performance under specific, predetermined criteria and the
appropriate quality assurance procedures. EPA makes no expressed or implied warranties as to the performance of the technology and
does not certify that a technology will always, under circumstances other than those tested, operate at the levels verified. The end user
is solely responsible for complying with any and all applicable Federal, State, and Local requirements.
EPA-VS-SCM-29 The accompanying notice is an integral part of this verification statement. December 1998
V
-------
VI
-------
Foreword
The U.S. Environmental Protection Agency (EPA) is charged by Congress with protecting the nation's natural
resources. The National Exposure Research Laboratory (NERL) is EPA's center for the investigation of
technical and management approaches for identifying and quantifying risks to human health and the
environment. NERL's research goals are to (1) develop and evaluate technologies for the characterization and
monitoring of air, soil, and water; (2) support regulatory and policy decisions; and (3) provide the science
support needed to ensure effective implementation of environmental regulations and strategies.
EPA created the Environmental Technology Verification (ETV) Program to facilitate the deployment of
innovative technologies through performance verification and information dissemination. The goal of the ETV
Program is to further environmental protection by substantially accelerating the acceptance and use of
improved and cost-effective technologies. The ETV Program is intended to assist and inform those involved
in the design, distribution, permitting, and purchase of environmental technologies. This program is
administered by NERL's Environmental Sciences Division in Las Vegas, Nevada.
The U.S. Department of Energy's (DOE's) Environmental Management (EM) program has entered into active
partnership with EPA, providing cooperative technical management and funding support. DOE EM realizes
that its goals for rapid and cost-effective cleanup hinge on the deployment of innovative environmental
characterization and monitoring technologies. To this end, DOE EM shares the goals and objectives of the
ETV.
Candidate technologies for these programs originate from the private sector and must be commercially ready.
Through the ETV Program, developers are given the opportunity to conduct rigorous demonstrations of their
technologies under realistic field conditions. By completing the evaluation and distributing the results, EPA
establishes a baseline for acceptance and use of these technologies.
Gary J. Foley, Ph.D.
Director
National Exposure Research Laboratory
Office of Research and Development
VII
-------
-------
Abstract
In July 1997, the U.S. Environmental Protection Agency (EPA) conducted a demonstration of poly chlorinated
biphenyl (PCB) field analytical techniques. The purpose of this demonstration was to evaluate field analytical
technologies capable of detecting and quantifying PCBs in soils and solvent extracts. The fundamental
objectives of this demonstration were (1) to obtain technology performance information using environmental
and quality control samples, (2) to determine how comparable the developer field analytical results were with
conventional reference laboratory results, and (3) to report on the logistical operation of the technology. The
demonstration design was subjected to extensive review and comment by EPA's National Exposure Research
Laboratory (NERL) Environmental Sciences Division in Las Vegas, Nevada; Oak Ridge National Laboratory
(ORNL); EPA Regional Offices; the U.S. Department of Energy (DOE); and the technology developers.
The demonstration study was conducted at ORNL under two sets of environmental conditions. The first site
was outdoors, with naturally variable temperature and relative humidity conditions typical of eastern Tennessee
in the summer. A second site was located inside a controlled environmental chamber having lower, and
relatively stable, temperature and relative humidity conditions. The test samples analyzed during this
demonstration were performance evaluation (PE) soil, environmental soil, and extract samples. Actual
environmental soil samples, collected from sites in Ohio, Kentucky, and Tennessee, were analyzed and ranged
in concentration from 0.1 to 700 parts per million (ppm). Extract samples were used to simulate surface wipe
samples, and were evaluated at concentrations of 0, 10, and 100 pg/mL. The reference laboratory method used
to evaluate the comparability of data was EPA SW-846 Method 8081.
In September 1998, EnviroLogix's PCB in Soil Tube Assay was evaluated. Six other field analytical
technologies were tested in July 1997: the L2000 PCB/Chloride Analyzer (Dexsil Corporation), the PCB
Immunoassay Kit (Hach Company), the 4100 Vapor Detector (Electronic Sensor Technology), and three
immunoassay kits—D TECH, EnviroGard, and RaPID Assay System (Strategic Diagnostics Inc.). The
purpose of an Environmental Technology Verification Report (ETVR) is to document the demonstration
activities, present demonstration data, and verify the performance of the technology. This ETVR presents
information regarding the performance of EnviroLogix's PCB in Soil Tube Assay. Separate ETVRs have been
published for the other technologies demonstrated.
The PCB in Soil Tube Assay is an immunoassay kit used to determine PCB concentrations as interval results.
The test kit uses a competitive binding enzyme immunoassay to perform rapid testing for PCBs in soils and
solutions at specified threshold values of 1, 10, and 50 ppm. The test kit is standardized using Aroclor 1254.
The presence of PCBs is detected by a photometer based on a colored reaction in which the color development
is inversely proportional to the concentration of PCB in the sample (e.g., the darker the color, the less analyte
PCB is present in the sample). The kit provides no information on Aroclor identification.
The kit's quantitative results were based on the analysis of calibration standards with every batch of 12 to 17
samples. Because the test kit is an interval technique, method detection limits are not applicable. Precision,
defined as the percentage of the sample sets where all four replicates were reported as the same interval range,
ix
-------
was 56% for PE soils, 68% for environmental soils, and 75% for extracts. Accuracy, defined as the percentage
of PCB in Soil Tube Assay results that agreed with the accepted concentration, was 78% for PE soils and 92%
for extracts. In general, the percentage of samples that was biased high was comparable (10% for PE soils and
0% for extracts) to the percentage that was biased low (13% for PE soils and 8% for extracts). Comparability
was defined similarly to accuracy, but the test kit result was compared with the reference laboratory result
rather than with the accepted concentration to determine comparability. For all soil samples (PE and
environmental), the percentage of samples that agreed with the reference laboratory results was 82%. The
percentage of samples that was biased high was again comparable (12%) to the percentage that was biased
low (7%). Comparability could not be assessed for extract samples because no reference laboratory data were
generated for these samples.
The demonstration found that the PCB in Soil Tube Assay was simple to operate in the field, requiring about
an hour for initial setup and preparation for sample analysis. Once the kit was operational, the sample
throughput of the kit by a single analyst was 8 samples/hour under outdoor conditions and 7 samples/hour
under chamber conditions. Minimal training (4 hours) is required to operate the test kit, provided the user has
a fundamental understanding of basic chemical and field analytical techniques. The performance of the test kit
was characterized as unbiased, because most (78%) of the PCB in Soil Tube Assay results agreed with the
certified PE values, but imprecise, because nearly half (44%) of the PE replicate results were not reported as
the same interval. It should be noted that almost all of the imprecision occurred when the concentration of the
sample was near one of the test kit's threshold values (i.e., 1, 10, or 50 ppm). The test kit had no false positive
results (i.e., a result in which the technology detects PCBs in the sample above the detection limit when there
actually are no PCBs present), and 4% of the soil sample results were false negatives (i.e., the technology
indicates that there are no PCBs present in the sample, when there actually are). For extract samples, the test
kit had no false positive or false negative results.
-------
Table of Contents
Notice ii
Verification Statement iii
Foreword vii
Abstract ix
List of Figures xv
List of Tables xvii
List of Abbreviations and Acronyms xix
Acknowledgments xxi
Section 1 — Introduction 1
Technology Verification Process 2
Needs Identification and Technology Selection 2
Demonstration Planning and Implementation 3
Report Preparation 3
Information Distribution 3
Demonstration Purpose 4
Section 2 — Technology Description 5
Objective 5
Principle 5
Applications and Advantages 5
Procedure 6
Materials 6
Extraction 6
Assay 6
Interpreting Results 7
Precautions and Notes 8
Sensitivity and Cross-Reactivity 8
XI
-------
Section 3 — Site Description and Demonstration Design 9
Objective 9
Demonstration Site Description 9
Site Name and Location 9
Site History 9
Site Characteristics 10
Experimental Design 10
Environmental Conditions during Demonstration 13
Sample Descriptions 13
Performance Evaluation Materials 13
Environmental Soil Samples 13
Extract Samples 14
Sampling Plan 14
Sample Collection 14
Sample Preparation, Labeling, and Distribution 14
Predemonstration Study and Results 16
Deviations from the Demonstration Plan 16
Section 4 — Reference Laboratory Analytical Results and Evaluation 19
Objective and Approach 19
Reference Laboratory Selection 19
Reference Laboratory Method 20
Calibration 20
Sample Quantification 20
Sample Receipt, Handling, and Holding Times 21
Quality Control Results 21
Objective 21
Continuing Calibration Verification Standard Results 22
Instrument and Method Blank Results 22
Surrogate Spike Results 22
Laboratory Control Sample Results 23
Matrix Spike Results 23
Conclusions of the Quality Control Results 23
Data Review and Validation 24
Objective 24
Corrected Results 24
Suspect Results 24
Data Assessment 25
Objective 25
Precision 26
Performance Evaluation Samples 26
Environmental Soil Samples 27
Extract Samples 27
xn
-------
Accuracy 27
Representativeness 29
Completeness 30
Comparability 30
Summary of Observations 30
Section 5 — Technology Performance and Evaluation 33
Objective and Approach 33
Interval Reporting 33
Data Assessment 33
Objective 33
Precision 34
Performance Evaluation Samples 34
Environmental Soil Samples 35
Extract Samples 37
Precision Summary 37
Accuracy 37
Performance Evaluation Soil Samples 38
Extract Samples 39
False Positive/False Negative Results 40
Representativeness 41
Completeness 41
Comparability 41
Summary of PARCC Parameters 42
Regulatory Decision-Making Applicability 42
Additional Performance Factors 44
Sample Throughput 44
Cost Assessment 44
PCB in Soil Tube Assay Costs 45
Reference Laboratory Costs 46
Cost Assessment Summary 47
General Observations 47
Performance Summary 48
Section 6 — Technology Update and Representative Applications 51
Objective 51
Technology Update 51
Representative Applications 51
Data Quality Objective Example 51
Section 7 — References 53
Xlll
-------
Appendix A — Description of Environmental Soil Samples 55
Appendix B — Characterization of Environmental Soil Samples 59
Appendix C — Temperature and Relative Humidity Conditions 63
Appendix D — PCB in Soil Tube Assay PCB Technology Demonstration Sample Data 67
Appendix E — Data Quality Objective Example 77
Disclaimer 79
Background and Problem Statement 79
DQO Goals 79
Use of Technology Performance Information to Implement the Decision Rule 80
Determining the Number of Samples 80
Alternative FP Parameter 83
xiv
-------
List of Figures
3-1 Schematic map of ORNL, indicating the demonstration area 11
C-l Summary of temperature conditions for outside site 65
C-2 Summary of relative humidity conditions for outdoor site 65
C-3 Summary of temperature conditions for chamber site 66
C-4 Summary of relative humidity conditions for chamber site 66
xv
-------
-------
List of Tables
2-1 Interpretation of photometer readings for undiluted samples 7
2-2 Interpretation of photometer readings for diluted samples 7
2-3 Sensitivity of PCB in Soil Tube Kit to various Aroclors 8
3-1 Summary of experimental design by sample type 12
3-2 Summary of PCB in Soil Tube Assay predemonstration results 16
4-1 Suspect measurements within the reference laboratory data 25
4-2 Precision of the reference laboratory for PE soil samples 26
4-3 Precision of the reference laboratory for environmental soil samples 28
4-4 Accuracy of the reference laboratory for PE soil samples 29
4-5 Summary of the reference laboratory performance 31
5-1 PCB in Soil Tube Assay reporting intervals 33
5-2 Classification of precision results 34
5-3 Precision of the PCB in Soil Tube Assay for PE soil samples 35
5-4 Precision of the PCB in Soil Tube Assay for environmental soil samples 36
5-5 Precision of the PCB in Soil Tube Assay for extract samples 37
5-6 Overall precision of the PCB in Soil Tube Assay for all sample types 38
5-7 PCB in Soil Tube Assay accuracy data for PE soil samples 39
5-8 Evaluation of agreement between PCB in Soil Tube Assay's PE sample results
and the certified PE values as a measure of accuracy 40
5-9 Accuracy of the PCB in Soil Tube Assay for extract samples 40
5-10 Evaluation of agreement between PCB in Soil Tube Assay's extract results and the spike concentration
as a measure of accuracy 40
5-11 Evaluation of agreement between PCB in Soil Tube Assay's soil results and the reference laboratory's
results as a measure of comparability 42
5-12 Comparison of the PCB in Soil Tube Assay results with the reference laboratory's suspect measurements
43
5-13 PCB in Soil Tube Assay performance for precision, accuracy, and comparability 43
5-14 Estimated analytical costs for PCB soil samples 45
5-15 Performance summary for the PCB in Soil Tube Assay 49
A-l Summary of soil sample descriptions 57
B-l Summary of environmental soil characterization 61
C-l Average temperature and relative humidity conditions during testing periods 64
D-l PCB in Soil Tube Assay technology demonstration soil sample data 69
D-2 PCB in Soil Tube Assay technology demonstration extract sample data 74
D-3 Corrected reference laboratory data 75
E-l Comparison of PCB in Soil Tube Assay Results with the reference laboratory at 50 ppm level . . 81
xvii
-------
-------
List of Abbreviations and Acronyms
ASTM American Society for Testing and Materials
BHC benzenehexachloride
CCV continuing calibration verification standard
CSCT Consortium for Site Characterization Technology
DCB decachlorobiphenyl
DOE U.S. Department of Energy
DQO data quality objective
ELISA enzyme-linked immunosorbent assay
EM Environmental Management (DOE)
EPA U.S. Environmental Protection Agency
ERA Environmental Resource Associates
ETTP East Tennessee Technology Park
ETV Environmental Technology Verification Program
ETVR Environmental Technology Verification Report
EvTEC Environmental Technology Evaluation Center
fn false negative result
FN false negative decision error rate
fp false positive result
FP false positive decision error rate
HEPA high-efficiency particulate air
ID identifier
LCS laboratory control sample
LV Las Vegas
MS matrix spike
xix
-------
MSB matrix spike duplicate
n number of samples
NRC Nuclear Regulatory Commission
OD optical density
ORNL Oak Ridge National Laboratory
ORO Oak Ridge Operations (DOE)
PARCC precision, accuracy, representativeness, completeness, comparability
PCB polychlorinated biphenyl
PE performance evaluation
ppm parts per million (equivalent units: mg/kg for soils and (jg/mL for extracts)
Pr probability
QA quality assurance
QC quality control
R2 coefficient of determination
RDL reporting detection limit
RH relative humidity
RFD request for disposal
RPD relative percentage difference
RSD relative standard deviation (percent)
SARA Superfund Amendments and Reauthorization Act of 1986
SD standard deviation
SITE Superfund Innovative Technology Evaluation
SMO Sample Management Office
SOP standard operating procedure
SSM synthetic soil matrix
TCMX tetrachloro-ra-xylene
xx
-------
Acknowledgments
The authors wish to acknowledge the support of all those who helped plan and conduct the demonstration,
analyze the data, and prepare this report. In particular, we recognize the technical expertise of Mitchell
Erickson (Environmental Measurements Laboratory), Viorica Lopez-Avila (Midwest Research Institute), and
Robert F. O'Brien (Pacific Northwest National Laboratory), who were peer reviewers of this report. For
internal peer review, we thank Stacy Barshick (ORNL); for technical support during the demonstration, Todd
Skeen and Ralph Ilgner (ORNL); for site safety and health support, Kim Thomas, Marilyn Hanner, and Fred
Smith (ORNL); for administrative support, Betty Maestas and Linda Plemmons (ORNL); for sample collection
support, Wade Hollinger, Charlotte Schaefer, and Arlin Yeager (LMES), and Mike Rudacille and W. T.
Wright (EET Corporation); for preliminary soil characterization support, Frank Gardner, John Zutman, and
Bob Schlosser (ORNL, Grand Junction, Colo.); for sample management support, Angie McGee, Suzanne
Johnson, and Mary Lane Moore (LMES); for providing performance evaluations samples, Michael Wilson
(EPA's Office of Solid Waste and Emergency Response's Analytical Operations and Data Quality Center);
and for technical guidance and project management of the demonstration, David Garden, Marty Atkins, and
Regina Chung (DOE's Oak Ridge Operations Office), David Bottrell (DOE, Headquarters), Deana Crumbling
(EPA's Technology Innovation Office), and Stephen Billets, Gary Robertson, and Eric Koglin (EPA's National
Exposure Research Laboratory, Las Vegas, Nevada). The authors also acknowledge the participation of
EnviroLogix, Inc., in particular, Jonathan Matt, who performed the analyses during the demonstration.
For more information on the PCB Field Analytical Technology Demonstration, contact
Eric N. Koglin
Project Technical Leader
Environmental Protection Agency
Characterization and Research Division
National Exposure Research Laboratory
P. O. Box 93478
Las Vegas, Nevada 89193-3478
(702) 798-2432
For more information on the PCB in Soil Tube Assay, contact
Jonathan Matt
EnviroLogix Inc.
55 Industrial Way
Portland, ME 04103
(207) 797-0300
xxi
-------
Section 1
Introduction
The performance evaluation of innovative and alternative environmental technologies is an integral part of the
U.S. Environmental Protection Agency's (EPA's) mission. Early efforts focused on evaluating technologies
that supported the implementation of the Clean Air and Clean Water Acts. In 1987, the Agency began to
evaluate the cost and performance of remediation and monitoring technologies under the Superfund Innovative
Technology Evaluation (SITE) program. This was in response to the mandate in the Superfund Amendments
and Reauthorization Act (SARA) of 1986. In 1990, the U.S. Technology Policy was announced. This policy
placed a renewed emphasis on "making the best use of technology in achieving the national goals of improved
quality of life for all Americans, continued economic growth, and national security." In the spirit of the
Technology Policy, the Agency began to direct a portion of its resources toward the promotion, recognition,
acceptance, and use of U.S.-developed innovative environmental technologies both domestically and abroad.
The Environmental Technology Verification (ETV) Program was created by the Agency to facilitate the
deployment of innovative technologies through performance verification and information dissemination. The
goal of the ETV Program is to further environmental protection by substantially accelerating the acceptance
and use of improved and cost-effective technologies. The ETV Program is intended to assist and inform those
involved in the design, distribution, permitting, and purchase of environmental technologies. The ETV Program
capitalizes upon and applies the lessons that were learned in the implementation of the SITE Program to the
verification of twelve categories of environmental technology: Drinking Water Systems, Pollution
Prevention/Waste Treatment, Pollution Prevention/ Innovative Coatings and Coatings Equipment, Indoor Air
Products, Air Pollution Control, Advanced Monitoring Systems, EvTEC (an independent, private-sector
approach), Wet Weather Flow Technologies, Pollution Prevention/Metal Finishing, Source Water Protection
Technologies, Site Characterization and Monitoring Technology [also referred to as the Consortium for Site
Characterization Technology (CSCT)], and Climate Change Technologies. The performance verification
contained in this report was based on the data collected during a demonstration of polychlorinated biphenyl
(PCB) field analytical technologies. The demonstration was administered by CSCT.
For each pilot, EPA utilizes the expertise of partner "verification organizations" to design efficient procedures
for conducting performance tests of environmental technologies. To date, EPA has partnered with federal
laboratories and state, university, and private sector entities. Verification organizations oversee and report
verification activities based on testing and quality assurance protocols developed with input from all major
stakeholder/customer groups associated with the technology area.
In July 1997, CSCT, in cooperation with the U.S. Department of Energy's (DOE's) Environmental
Management (EM) Program, conducted a demonstration to verify the performance of six field analytical
technologies for PCBs: the L2000 PCB/Chloride Analyzer (Dexsil Corporation), the PCB Immunoassay Kit
1
-------
(Hach Company), the 4100 Vapor Detector (Electronic Sensor Technology), and three immunoassay kits from
Strategic Diagnostics, Inc.: D TECH, EnviroGard, and RaPID Assay System. Another technology, the
EnviroLogix, Inc., PCB in Soil Tube Assay, was evaluated in September 1998. This environmental technology
verification report (ETVR) presents the results of the demonstration study for
the PCB in Soil Tube Assay. Separate ETVRs have been published for the other six technologies.
Technology Verification Process
The technology verification process is intended to serve as a template for conducting technology demonstrations
that will generate high-quality data that EPA can use to verify technology performance. Four key steps are
inherent in the process:
Needs identification and technology selection
Demonstration planning and implementation
Report preparation
• Information distribution
Needs Identification and Technology Selection
The first aspect of the technology verification process is to determine technology needs of EPA and the
regulated community. EPA, DOE, the U.S. Department of Defense, industry, and state agencies are asked to
identify technology needs and interest in a technology. Once a technology need is established, a search is
conducted to identify suitable technologies that will address this need. The technology search and identification
process consists of reviewing responses to Commerce Business Daily announcements, searches of industry and
trade publications, attendance at related conferences, and leads from technology developers. Characterization
and monitoring technologies are evaluated against the following criteria:
• meets user needs;
• may be used in the field or in a mobile laboratory;
• is applicable to a variety of environmentally impacted sites;
• has high potential for resolving problems for which current methods are unsatisfactory;
• is cost competitive with current methods;
• performs better than current methods in areas such as data quality, sample preparation, or analytical
turnaround time;
-------
• uses techniques that are easier and safer than current methods;
• is a commercially available, field-ready technology.
Demonstration Planning and Implementation
After a technology has been selected, EPA, the verification organization, and the developer agree to the
responsibilities for conducting the demonstration and evaluating the technology. The following tasks are
undertaken at this time:
• identifying demonstration sites that will provide the appropriate physical or chemical environment,
including contaminated media;
• identifying and defining the roles of demonstration participants, observers, and reviewers;
• determining logistical and support requirements (for example, field equipment, power and water
sources, mobile laboratory, communications network);
• arranging analytical and sampling support;
• preparing and implementing a demonstration plan that addresses the experimental design, sampling
design, quality assurance/quality control (QA/QC), health and safety considerations, scheduling of
field and laboratory operations, data analysis procedures, and reporting requirements.
Report Preparation
Innovative technologies are evaluated independently and, when possible, against conventional technologies. The
field technologies are operated by the developers in the presence of independent technology observers. The
technology observers are provided by EPA or a third-party group. Demonstration data are used to evaluate the
capabilities, limitations, and field applications of each technology. Following the demonstration, all raw and
reduced data used to evaluate each technology are compiled into a technology evaluation report, which is
mandated by EPA as a record of the demonstration. A data summary and detailed evaluation of each
technology are published in an ETVR.
Information Distribution
The goal of the information distribution strategy is to ensure that ETVRs are readily available to interested
parties through traditional data distribution pathways, such as printed documents. Documents are also available
on the World Wide Web through the ETV Web site (http://www.epa.gov/etv) and through a Web site supported
by the EPA Office of Solid Waste and Emergency Response's Technology Innovation Office (http://CLU-
in.com).
-------
Demonstration Purpose
The purpose of this demonstration was to obtain performance information for PCB field analytical
technologies, to compare the results with conventional fixed-laboratory results, and to provide supplemental
information (e.g., cost, sample throughput, and training requirements) regarding the operation of the
technology. The demonstration was conducted under two climatic conditions. One set of activities was
conducted outdoors, with naturally fluctuating temperatures and relative humidity conditions. A second set was
conducted in a controlled environmental facility, with lower, relatively stable temperatures and relative
humidities. Multiple soil types, collected from sites in Ohio, Kentucky, and Tennessee, were used in this study.
PCB soil concentrations ranged from approximately 0.1 to 700 parts per million (ppm). The developer also
analyzed 24 solutions of known PCB concentration that were used to simulate extracted wipe samples. The
extract samples ranged in concentration from 0 to 100 (jg/mL.
-------
Section 2
Technology Description
Objective
The objective of this section is to describe the technology being demonstrated, including the operating principles
underlying the technology and the overall approach to its use. The information provided here is excerpted from
that provided by the developer. Performance characteristics described in this section are specified by the
developer; they may or may not be substantiated by the data presented in Section 5.
Principle
The EnviroLogix PCB in Soil Tube Assay applies the principles of enzyme-linked immunosorbent assay
(ELISA) to determine PCB concentration. In such an assay, an enzyme has been chemically linked to a PCB
molecule or a PCB analog to create a labeled PCB reagent. The labeled PCB reagent (called a conjugate) is
mixed with an extract of native sample containing the PCB contaminant. A portion of the mixture is applied
to a surface (i.e., the inside of a test tube) to which an antibody specific for PCB has been affixed. The native
PCB and PCB-enzyme conjugate compete for a limited number of antibody sites. After a period of time, the
solution is washed away, and what remain are either PCB-antibody complexes or enzyme-PCB-antibody
complexes attached to the test surface. The proportion of the two complexes on the test surface is determined
by the amount of native PCB in the original sample. The enzyme present on the test surface is used to catalyze
a color change reaction in a solution added to the test surface. Because the amount of enzyme present is
inversely proportional to the concentration of native PCB contaminant, the amount of color development is
inversely proportional to the concentration of PCB contaminant. The color development is quantified through
the use of a hand-held photometer.
The EnviroLogix PCB in Soil Tube Kit is designed for semi-quantitative field-screening for PCBs in soil. The
kit is supplied with calibrators equivalent to 1 part per million (ppm) and 10 ppm PCB (Aroclor 1254) in soil.
These calibrators are used to evaluate threshold levels of 1 and 10 ppm. A threshold level of 50 ppm can also
be evaluated using the 10-ppm calibrator by preparing a 1:5 sample extract dilution into methanol. For the
extract samples, the threshold levels are 0.4, 4, and 20 (jg/mL.
Applications and Advantages
The EnviroLogix PCB test kit can be used in a number of applications, including initial site characterization
and mapping, real-time testing during remediation, and screening of negatives prior to gas chromatography
confirmation. The test kit has a number of advantages:
• real-time progress monitoring while crews and equipment are on-site;
clear, accurate pass/fail determinations at meaningful threshold values;
• meets site-specific calibration needs without a special kit;
reduces wastes and costs.
-------
Procedure
Materials
The EnviroLogix PCB in Soil Tube Kit contains the following items:
• 40 antibody-coated test tubes
1 vial negative control
• 1 vial 1 ppm calibrator
1 vial 10 ppm calibrator
• 1 bottle of PCB-enzyme (horseradish peroxidase) conjugate
1 bottle of substrate
• 1 bottle of stop solution
The following items will need to be provided:
• EnviroLogix Soil Extraction Kit
methanol (10 mL per sample)
• repeater pipettes
• (3) 12.5 mL combos-syringes
• positive displacement pipette
• marking pen
• timer
distilled water
• portable photometer (Ariel Differential Photometer or equivalent)
test tube rack
Extraction
Five grams of soil are weighed into a soil extraction bottle containing two ball bearings. (The ball bearings are
used to agitate the soil and may not be necessary for dry, sandy soils.) Then 10 mL of methanol are added to
the bottle, and the bottle is capped tightly and shaken vigorously by hand for 2 min. After the contents are
allowed to settle for 1 min, the extract is poured into the base of the Uniprep™ and the filter plunger is slowly
pushed into the base until it stops at the bottom. To evaluate the samples relative to the 1 and 10 ppm
calibrators, the filtered extract is poured into labeled 4-mL glass amber vials and capped tightly. To evaluate
a 50 ppm threshold value, 800 ^L of methanol are added to a 4-mL amber glass vial and then 200 yL of the
sample extract are added. This is a 1:5 dilution.
Assay
All reagents should be at room temperature before assay begins. The number of antibody-coated test tubes
needed (up to 20) are removed from the kit and placed in the test tube rack; the tester should label one each for
the negative control, for the two calibrators, and for each of the samples. After dispensing 500 (iL of conjugate
into each tube, dispensing down the side of the tubes with the syringe tip at an angle to prevent splashback, the
tester adds 50 (iL of sample to the tube(s) labeled for samples and 50 (iL of negative control and calibrators
to the appropriate tubes. The contents of the tubes are thoroughly mixed by moving the rack in a rapid circular
motion for 20 to 30 seconds. After the tubes have been allowed to incubate for 10 min, the tube contents are
-------
emptied into a suitable container. The tubes are then filled with distilled water, emptied, and shaken to remove
any remaining drops. This wash process is repeated three times, after which the tubes are inverted and tapped
on paper towels to remove excess water. Next, 500 i\L of substrate is added to each tube and the contents
mixed thoroughly by moving the rack in a rapid circular motion for 20 to 30 seconds. The tubes are left to
incubate for 10 min. If blue color does not develop in the negative control tube, the assay is invalid and
should be repeated. Now, 500 ^L of stop solution is added to each tube. The tubes are read within 30 min
of addition of the stop solution.
Interpreting Results
An Ariel Differential Photometer (or an equivalent) is used to measure the optical density of each tube's
contents. The wavelength on the photometer should be set to 450 nanometers (nm). If the photometer has dual
wavelength capability, 600, 630, or 650 nm should be used as the reference wavelength. If the photometer does
not auto-zero on air, the instrument should be zeroed against 1 mL water in a blank tube. The optical density
(OD) of each tube's contents is then measured and recorded. The information shown in Tables 2-1 and 2-2
is used to interpret the results.
The test kit results are reported as concentration ranges designated as intervals incorporating
parenthesis/bracket notation. The parentheses indicate that the end-points of the concentration range are
excluded, while brackets indicate that the end-points are included. As shown in Table 2-1, the interval [0, 1)
indicates that the PCB concentration range is >0 and <1. If the sample is >10 ppm, a 1:5 dilution of the sample
can be prepared and assayed to determine if the concentration is >50 ppm. This diluted sample can be evaluated
using the 10-ppm calibrator, as shown in Table 2-2.
Table 2-1. Interpretation of photometer readings for undiluted samples
Samples with OD values . . .
> OD of 1-ppm calibrator
Between OD of 1-ppm and OD of
10-ppm calibrators
10 ppm PCB
And are reported as . .
[0,1)
[1,10)
[10, co)
Table 2-2. Interpretation of photometer readings for diluted samples
Diluted (1:5) samples with OD
values . . .
>OD of 10 ppm calibrator
50 ppm PCB
And are reported
as ...
[10,50)
[50, co)
-------
Precautions and Notes
The following items should be noted about the test kit:
• All components should be stored at 4° to 8 °C when not in use. Reagents must be allowed to come
to ambient temperature before use. The components should not be used after the expiration date. It
is important that the substrate solution not be exposed to direct sunlight during pipetting or while
incubating in the test tubes.
The stop solution is 1.0 N hydrochloric acid and should be handled with caution.
It is recommended that positive results be confirmed by an alternate method (such as gas
chromatography).
Sensitivity and Cross-Reactivity
The test kit can be calibrated with other Aroclors. Table 2-3 shows the degree of sensitivity with the other
Aroclors. It should also be noted that at 1000 ppm, the following compounds had low cross-reactivity (i.e., did
not result in a positive response) at the 1-ppm interpretation level: 1,2-dichlorobenzene, 1,3-dichlorobenzene,
1,4-dichlorobenzene, 3,4-dichlorophenol, 2,5-dichlorophenol, biphenyl, pentachlorophenol, and humic acid.
Table 2-3. Sensitivity of PCB in Soil Tube Kit to various Aroclors
Aroclor
1242
1248
1254
1260
Limit of Detection in Soil
(ppm)
1.7
0.6
0.3
0.3
-------
Section 3
Site Description and Demonstration Design
Objective
This section describes the demonstration site, the experimental design for the verification test, and the sampling
plan (sample types analyzed and the collection and preparation strategies). Included in this section are the
results from the predemonstration study and a description of the deviations made from the original
demonstration design.
Demonstration Site Description
Site Name and Location
The demonstration of PCB field analytical technologies was conducted at Oak Ridge National Laboratory
(ORNL) in Oak Ridge, Tennessee. PCB-contaminated soils from three DOE sites (Oak Ridge; Paducah,
Kentucky; and Piketon, Ohio) were used in this demonstration. The soil samples used in this study were
brought to the demonstration testing location for evaluation of the field analytical technologies.
Site History
Oak Ridge is located in the Tennessee River Valley, 25 miles northwest of Knoxville. Three DOE facilities are
located in Oak Ridge: ORNL, the Oak Ridge Y-12 Plant, and East Tennessee Technology Park (ETTP).
Chemical processing and warhead component production have occurred at the Y-12 Plant, and ETTP is a
former gaseous diffusion uranium enrichment plant. At both facilities, industrial processing associated with
nuclear weapons production has resulted in the production of millions of kilograms of PCB-contaminated soils.
Two other DOE facilities—the Paducah plant in Paducah, Kentucky, and the Portsmouth plant in Piketon,
Ohio—are also gaseous diffusion facilities with a history of PCB contamination. During the remediation of the
PCB-contaminated areas at the three DOE sites, soils were excavated from the ground where the PCB
contamination occurred, packaged in containers ranging in size from 55-gal to 110-gal drums, and stored as
PCB waste. Samples from these repositories (referred to as "Oak Ridge," "Portsmouth," and "Paducah"
samples in this report) were used in this demonstration.
In Oak Ridge, excavation activities occurred between 1991 and 1995. The Oak Ridge samples comprised PCB-
contaminated soils from both Y-12 and ETTP. Five different sources of PCB contamination resulted in soil
excavations from various dikes, drainage ditches, and catch basins. Some of the soils are EPA-listed hazardous
waste due to the presence of other contaminants (e.g., diesel fuels).
A population of more than 5000 drums containing PCB-contaminated soils was generated from 1986 to 1987
during the remediation of the East Drainage Ditch at the Portsmouth Gaseous Diffusion Plant. The ditch was
reported to have three primary sources of potential contamination: (1) treated effluent from a radioactive liquid
treatment facility, (2) runoff from a biodegradation plot where waste oil and sludge were disposed of, and (3)
storm sewer discharges. In addition, waste oil was reportedly used for weed control in the ditch. Aside from
-------
PCB contamination, no other major hazardous contaminants were detected in these soils. Therefore, no EPA
hazardous waste codes are assigned to this waste.
Twenty-nine drums of PCB-contaminated soils from the Paducah plant were generated as part of a spill
cleanup activity at an organic waste storage area (C-746-R). The waste is considered a listed hazardous waste
for spent solvents (EPA hazardous waste code F001) because it is known to contain trichloroethylene. Other
volatile organic compounds, such as xylene, dichlorobenzene, and cresol, were also detected in the preliminary
analyses of some of the Paducah samples.
Site Characteristics
PCB-contaminated environmental soil samples from Oak Ridge, Portsmouth, and Paducah were collected from
waste containers at storage repositories at ETTP and Paducah. Many of the soils contained interfering
compounds such as oils, fuels, and other chlorinated compounds (e.g., trichloroethylene). Specific sample
descriptions of the environmental soils used in this demonstration are given in Appendix A. In addition, each
sample was characterized in terms of its soil composition, pH, and total organic carbon content. Those results
are summarized in Appendix B.
Field demonstration activities occurred at two sites at ORNL: a natural outdoor environment (the outdoor site)
and inside a controlled environmental atmosphere chamber (the chamber site). Figure 3-1 shows a schematic
map of a section of ORNL indicating the demonstration area where the outdoor field activities occurred.
Generally, the average September temperature for eastern Tennessee is 71 °F. Average temperatures during
the testing periods ranged from 74 to 82°F, as shown in Appendix C. Studies were also conducted inside a
controlled environmental atmosphere chamber, hereafter referred to as the "chamber," located in Building 5507
at ORNL. Demonstration studies inside the chamber were used to evaluate performance under environmental
conditions that were markedly different from the ambient outdoor conditions at the time of the test. Average
temperatures in the chamber during the testing periods ranged from 56 to 57°F. The controlled experimental
atmosphere facility consists of a room-size walk-in chamber 10 ft wide and 12 ft long with air processing
equipment to control temperature and humidity. The chamber is equipped with an environmental control
system, including reverse-osmosis water purification that supplies the chamber humidity control system. High-
efficiency particulate air (HEPA) and activated charcoal filters are installed for recirculation and building
exhaust filtration.
Experimental Design
The analytical challenge with PCB analysis is to quantify a complex mixture that may or may not resemble the
original commercial product (i.e., Aroclor) because of environmental aging, and to report the result as a single
number [1]. The primary objective of the verification test was to compare the performance of the field
technology with laboratory-based measurements. Often, verification tests involve a direct one-to-one
comparison of results from field-acquired samples. However, because sample heterogeneity can preclude
replicate field or laboratory comparison, accuracy and precision data must often be derived from the analysis
of QC and performance evaluation (PE) samples. In this study, replicates of all three sample types (QC, PE,
and environmental soil) were analyzed. The ability to use environmental soils in the verification test was made
10
-------
Figure 3-1. Schematic map of ORNL, indicating the demonstration area.
possible because the samples, collected from drums containing PCB-contaminated soils, could be thoroughly
homogenized and characterized prior to the demonstration. This facet of the design, allowing additional
precision data to be obtained on actual field-acquired samples, provided an added performance factor in the
verification test.
Another objective of this demonstration was to evaluate the field technology's capability to support regulatory
compliance decisions. For field methods to be used in these decisions, the technology must be capable of
informing the user, with known precision and accuracy, that concentrations are greater than or less than an
action level, such as 50 ppm for soil samples and 100 (jg/100 cm2 for wipe samples [2]. The samples selected
for analysis in the demonstration study were chosen with this objective in mind.
The experimental design is summarized in Table 3-1. This design was approved by the developer prior to the
start of the demonstration study. In total, the developer analyzed 208 soil samples, 104 each at both locations
(outdoors and chamber). The 104 soil samples comprised 68 environmental samples (17 unique environmental
samples prepared in quadruplicate) ranging in PCB concentration from 0.1 to 700 ppm and 36 PE soils (9
unique PE samples in quadruplicate) ranging in PCB concentration from 0 to 50 ppm. To determine the impact
of different environmental conditions on the technology's performance, each batch of 104 samples contained
five sets of quadruplicate soil samples from DOE's Paducah site. These were analyzed under both sets of
environmental conditions (i.e., outdoor and chamber conditions). In addition, 12 extracts ranging in
concentration from 0 to 100 pg/mL were analyzed in each location (chamber and outdoors). All samples were
analyzed without prior knowledge of sample type or concentration and were analyzed in a randomized order.
11
-------
Table 3-1. Summary of experimental design by sample type
Concentration
range
Sample ID "
Outdoor site
Chamber site
Total #
samples
analyzed
PE materials
0
2.0 ppm
2.0 ppm
5.0 ppm
10.9 ppm
20.0 ppm
49.8 ppm
50.0 ppm
50.0 ppm
126
118
124
120
122
119
125
121
123
226
218
224
220
222
219
225
221
223
8
8
8
8
8
8
8
8
8
Environmental soils
0.1-2.0 ppm
2. 1-20.0 ppm
20. 1-50.0 ppm
50. 1-700.0 ppm
101, 107, 108, 109, 113, 114
102, 103, 104, 115
111, 116
105, 106, 110, 112, 117
201,202,206
203,207,212,213
204,208,209,214,215
205,210,211,216,217
36
32
28
40
Extracts
0
10 ug/mL
100 ug/mL
Grand total
132
130
131
116
232
230
231
116
8
8
8
232 b
" Each sample was analyzed in quadruplicate.
6 All samples were analyzed in random order.
Environmental Conditions during Demonstration
As mentioned earlier, field activities were conducted both outdoors under natural environmental conditions and
indoors in a controlled environmental atmosphere chamber to evaluate the effect of environmental conditions
on technology performance. The weather outside during the September demonstration consisted of highs
approaching 90°F and 90% relative humidity (RH). Daily average temperatures were around 78°F with 50%
12
-------
RH. While outside, the developer set up a canopy to provide shade and protection from late afternoon
thundershowers. In the indoor chamber tests, conditions were set to 55 °F and 50% RH. An independent check
of the conditions inside the chamber indicated that the temperature ranged from 54 to 58°F, while relative
humidities ranged from 44 to 55%. Appendix C contains a summary of the environmental conditions
(temperature and relative humidity) during the demonstration.
Sample Descriptions
PCBs (C^Hjo^Cy are a class of compounds that are chlorine-substituted linked benzene rings. There are 209
possible PCB compounds (also known as congeners). PCBs were commercially produced as complex mixtures
beginning in 1929 for use in transformers, capacitors, paints, pesticides, and inks [1]. Monsanto Corporation
marketed products that were mixtures of 20 to 60 PCB congeners under the trade name Aroclor. Aroclor
mixtures are identified by a number (e.g., Aroclor 1260) that represents the mixture's chlorine composition as
a percentage (e.g., 60%).
Performance Evaluation Materials
Samples of Tennessee reference soil [3] served as the blanks. Pre-prepared certified PE samples were obtained
from Environmental Resource Associates (ERA) of Arvada, Colorado, and the Analytical Operations and Data
Quality Center of EPA's Office of Solid Waste and Emergency Response. The soils purchased from ERA had
been prepared using ERA's semivolatile blank soil matrix. This matrix was a topsoil that had been dried,
sieved, and homogenized. Particle size was approximately 60 mesh. The soil was approximately 40% clay. The
samples acquired from EPA's Analytical Operations and Data Quality Center had been prepared using
contaminated soils from various sites around the country in the following manner: The original soils had been
homogenized and diluted with a synthetic soil matrix (SSM). The SSM had a known matrix of 6% gravel, 31%
sand, and 43% silt/clay; the remaining 20% was topsoil. The dilution of the original soils was performed by
mixing known amounts of contaminated soil with the SSM in a blender for no less than 12 h. The samples were
also spiked with target pesticides (a, P, A, and A-BHC, methoxychlor, and endrin ketone) to introduce some
compounds that were likely to be present in an actual environmental soil. The hydrocarbon background from
the original sample and the spiked pesticides produced a challenging matrix. The PE soils required no additional
preparation by ORNL.
Environmental Soil Samples
As noted in the site description, PCB-contaminated environmental soil samples from Oak Ridge, Portsmouth,
and Paducah were used in this demonstration. The soils were contaminated with PCBs as the result of spills
and industrial processing activities at the various DOE facilities. Originally, the contaminated soils were
excavated from dikes, drainage ditches, catch basins, and organic waste storage areas. The excavated soils were
then packaged into waste containers and stored at the repositories in ETTP and Paducah in anticipation of
disposal by incineration. The environmental soil samples used in this study were collected from these waste
containers. Many of the soils contained interfering compounds such as oils, fuels, and other chlorinated
compounds, while some contained multiple Aroclors. For more information on sampling locations and sample
characteristics (soil composition, pH, and total organic carbon content), refer to Appendices A and B,
respectively.
13
-------
Extract Samples
Traditionally, the amount of PCBs on a contaminated surface is determined by wiping the surface with a cotton
pad saturated with hexane. The pad is then taken to the laboratory, extracted with additional hexane, and
analyzed by gas chromatography. Unlike soil samples, which can be more readily homogenized and divided,
equivalent wipe samples (i.e., contaminated surfaces or post-wipe pads) were not easily obtainable. Therefore,
interference-free methanolic solutions of PCBs were analyzed to simulate an extracted surface wipe pad.
Extract sample analyses provided evaluation data that relied primarily on the technology's performance rather
than on elements critical to the entire method (i.e., sample collection and preparation). A total of 12 methanolic
solutions were analyzed per site; these consisted of four replicates each of a blank and two concentration levels
(10 and 100 (jg/mL).
Sampling Plan
Sample Collection
Environmental soil samples were collected from April 17 through May 7, 1997. Portsmouth and Oak Ridge
Reservation soils were collected from either storage boxes or 55-gal drums stored at ETTP. Briefly, the
following procedure was used to collect the soil samples. Approximately 30 Ib of soil were collected from the
top of the drum or B-25 box using a scoop and placed in a plastic bag. The soil was sifted to remove rocks and
other large debris, then poured into a plastic-lined 5-gal container. All samples were subjected to radiological
screening and were determined to be nonradioactive. Similarly, soil samples were collected from 55-gal drums
stored at Paducah and shipped to ORNL in lined 5-gal containers.
Sample Preparation, Labeling, and Distribution
Aliquots of several of the environmental soils were analyzed and determined to be heterogeneous in PCB
concentration. Because this is unsatisfactory for accurately comparing the performance of the field technology
with the laboratory-based method, the environmental soils had to be homogenized prior to sample distribution.
Each Portsmouth and Oak Ridge environmental soil sample was homogenized by first placing approximately
1500 g of soil in a glass Pyrex dish. The dish was then placed in a large oven set at 35 °C, with the exhaust and
blower fans turned on to circulate the air. After drying overnight, the soil was pulverized using a conventional
blender and sieved using a 9-mesh screen (2 mm particle size). Last, the soil was thoroughly mixed using a
spatula. A comparison of dried and undried soils showed that a minimal amount of PCBs (< 20%) was lost as
the result of sample drying, making this procedure suitable for use in the preparation of the soil samples. The
Paducah samples, because of their sandy characteristics, required only the sieving and mixing preparation
steps. Extract sample preparation involved making solutions of PCBs in methanol at two concentration levels
(10 and 100 pg/mL). Multiple aliquots of each sample were analyzed using the analytical procedure described
below to confirm the homogeneity of the samples with respect to PCB concentration.
To provide the developer with soils contaminated at higher concentrations of PCBs, some of the environmental
soils (those labeled with an "S" in Appendix B) were spiked with additional PCBs. Spiked soils samples were
prepared after the soil was first dried in an oven set at 35°C overnight. The dry soil was ground using a
conventional blender and sieved through a 9-mesh screen (2 mm particle size). Approximately 1500 g of the
sieved soil were spiked with a diethyl ether solution of PCBs at the desired concentration. The fortified soil was
agitated using a mechanical shaker and then allowed to air-dry in a laboratory hood overnight. A minimum of
four aliquots were analyzed using the analytical procedure described below to confirm the homogeneity of the
soil with regard to the PCB concentration.
14
-------
The environmental soils were characterized at ORNL prior to the demonstration study. The procedure used to
confirm the homogeneity of the soil samples entailed the extraction of 3 to 5 g of soil in a mixture of solvents
(1 mL water, 4 mL methanol, and 5 mL hexane). After the soil/solvent mixture was agitated by a mechanical
shaker, the hexane layer was removed and an aliquot was diluted for analysis. The hexane extract was analyzed
on a Hewlett Packard 6890 gas chromatograph equipped with an electron capture detector and autosampler.
The method used was a slightly modified version of EPA's SW-846 dual-column Method 8081 [4].
After analysis confirming homogeneity, the samples were split into jars for distribution. Each 4-oz sample jar
contained approximately 20 g of soil. Four replicate splits of each soil sample were prepared for each
developer. The samples were randomized in two fashions. First, the order in which the filled jars were
distributed was randomized so that the same developer did not always receive the first jar filled for a given
sample set. Second, the order of analysis was randomized so that each developer analyzed the same set of
samples, but in a different order. The extract samples were split into 10-mL aliquots and placed into 2-oz jars.
The extracts were stored in the refrigerator (at <4°C) until released to the developers. Each sample jar had
three labels: (1) developer order number, (2) sample identifier number, and (3) a PCB warning label. The
developer order number corresponded to the order in which the developer was required to analyze the samples
(e.g., 1001 through 1116). The sample identifier number was in the format of "xxxyzz," where "xxx" was the
three-digit sample ID (e.g., 101) listed in Table 3-1, "y" was the replicate (e.g., 1 to 4), and "zz" was the
aliquot order of each replicate (e.g., 01 to 11). For example, sample identifier 101101 corresponded to sample
ID "101" (an Oak Ridge soil from RFD 40022, drum 02), "1" corresponded to the first replicate from that
sample, and "01" corresponded to the first jar filled in that series.
Once the samples were prepared, they were stored at a central sample distribution center. During the
demonstration study, the developer was sent to the distribution center to pick up his samples. Samples were
distributed sequentially in batches of 12 to ensure that samples were analyzed in the order specified.
Completion of chain-of-custody forms and scanning of bar code labels documented sample transfer activities.
Some of the developers received information regarding the samples prior to analysis. This was provided at the
request of the developer to simulate the type of information that would be available during actual field testing.
EnviroLogix elected not to receive sample information prior to analysis. The developer returned the unused
portions of the samples with the analytical results to the distribution center when testing was completed. The
sample bar codes were scanned upon return to document sample throughput time.
Three complete sets of extra samples, called archive samples, were available for distribution in case the
integrity of a sample was compromised. No archive samples were utilized over the course of the EnviroLogix
demonstration.
Predemonstration Study and Results
Ideally, environmental soil samples are sent to the developers prior to the demonstration study to allow them
the opportunity to analyze representative samples in advance of the verification test. This gives developers the
opportunity to refine and calibrate their technologies and revise their operating procedures on the basis of the
predemonstration study results. The predemonstration study results can also be used as an indication that the
selected technologies are of the appropriate level of maturity to participate in the demonstration study.
15
-------
According to ORNL regulations, however, one of two conditions must exist in order to ship environmental soils
that were once classified as mixed hazardous waste: either the recipient—in this case, the developer's
facilities—must have proper Nuclear Regulatory Commission (NRC) licensing to receive and analyze
radiological materials; or the soils must be certified as entirely free of radioactivity, beyond the no-rad
certification issued from radiological screening tests based on ORNL standards. Because the developer did not
have proper NRC licensing, and proving that the soils were entirely free of radioactivity was prohibitive, PE
soils were used for the predemonstration study. The developer also analyzed a solvent extract.
The predemonstration samples were sent to the developer on August 17, 1998. Predemonstration results were
received by August 19, 1998. Table 3-2 summarizes the test kit's results for the predemonstration samples.
Results indicated that EnviroLogix's PCB in Soil Tube Assay was ready for field evaluation.
Table 3-2. Summary of PCB in Soil Tube Assay predemonstration results
Sample
1
2
3
4
5
Certified
concentration
0
5.0 ppm
49.8 ppm
20.0 ppm
10 |ig/mL
Aroclor
n/a
1254
1254, 1260
1248
1254
Acceptance range a
n/a
2.1-6.2 ppm
23.0-60.8 ppm
11.4-32.4 ppm
n/a
Total PCB concentration (ppm)
Result #1
[0,1)"
[1,10)
[SO.co)
[10,50)
[4,20)
Result #2
[0,1)
[1,10)
[SO.co)
[10,50)
[4,20)
" Acceptance ranges were provided by the supplier of the performance evaluation material.
b The notation [0,1) indicates that the sample concentration was > 0 and < 1. See Sections 2 and 5 for more information
on interval reporting.
Deviations from the Demonstration Plan
A few deviations from the demonstration plan occurred. In Appendix B of the technology demonstration plan
[5], the reference laboratory's procedure states that no more than 10 samples will be analyzed with each
analytical batch (excluding blanks, standards, QC samples, and dilutions). The analytical batch is also stated
as 10 samples in the Quality Assurance Project Plan of the demonstration plan. The reference laboratory
actually analyzed 20 samples per analytical batch. Because a 20-sample batch is recommended in SW-846
Method 8081, this deviation was deemed acceptable. In addition, the parentheses and bracket notations in
Tables 3-1 and 3-2 are slightly different than what was used in the demonstration. See Tables 2-1 and 2-2 of
this report for the correction notation.
During the demonstration study, EnviroLogix noted the following deviations from the procedure described in
the technology demonstration plan [5] for the PCB in Soil Tube Assay:
16
-------
Instead of two, one or no ball bearings were used for extraction. The purpose of the ball bearings is to aid
in the extraction by agitating the soil. Since the soils were sandy and dry, the ball bearings were not
necessary.
Multiple filtrations (usually 12 tubes at a time) were performed by pushing the plungers down on the
UniPrep tubes simultaneously using a small board. The procedure in the demonstration plan describes the
filtration as being performed individually.
Three washes of the coated tubes were performed instead of four.
17
-------
-------
Section 4
Reference Laboratory Analytical Results and Evaluation
Objective and Approach
This section presents the evaluation of the PCB data generated by the reference laboratory. Evaluation of the
results from the analysis of PE, environmental soil, and extract samples was based on precision, accuracy,
representativeness, completeness, and comparability (PARCC) parameters [6]. This section describes how the
analytical data generated by the reference laboratory were used to establish a baseline performance for PCB
analysis.
EnviroLogix demonstrated the PCB in Soil Tube Assay kit using the same samples that were used in the July
1997 demonstration of six PCB technologies. Soil samples were available for the EnviroLogix demonstration
because extra samples were prepared and stored since 1997. ORNL performed chemical analyses of
representative samples to verify that significant amounts of PCBs had not been lost due to storage for one year.
Duplicate analyses from each unique soil sample were performed. It was confirmed that no considerable losses
in PCB concentration had occurred. Therefore, all soil samples were utilized in the EnviroLogix demonstration,
and the reference laboratory data described in this section was used for comparison with the PCB in Soil Tube
Assay results. Because the original extract samples were prepared in methanol, new extract samples were
prepared by ORNL. Therefore, no reference laboratory results are presented for these samples. Instead of a
reference laboratory result, the EnviroLogix's result was compared to the nominal concentration value only.
Confirmational analyses at ORNL indicated that the extracts were prepared to the nominal concentrations.
Reference Laboratory Selection
The Oak Ridge Sample Management Office (SMO) has been tasked by DOE Oak Ridge Operations (DOE-
ORO) with maintaining a list of qualified laboratories to provide analytical services. The technology
demonstration plan [5] contains the SMO's standard operating procedures (SOPs) for identifying, qualifying,
and selecting analytical laboratories. Laboratories are qualified as acceptable analytical service providers for
the SMO by meeting specific requirements. These requirements include providing pertinent documentation
(such as QA and chemical hygiene plans), acceptance of the documents by the SMO, and satisfactory
performance on an on-site prequalification audit of laboratory operations. All laboratory qualifications are
approved by a laboratory selection board, composed of the SMO operations manager and appointees from all
prime contractors that conduct business with the SMO.
All of the qualified laboratories were invited to bid on the demonstration study sample analysis. The lowest-cost
bidder was LAS Laboratories, in Las Vegas, Nevada. A readiness review conducted by ORNL and the SMO
confirmed the selection of LAS as the reference laboratory. Acceptance of the reference laboratory was
finalized by satisfactory performance in the predemonstration study. The SMO contracted LAS to provide full
data packages for the demonstration study sample analyses within 30 days of sample shipment.
19
-------
The SMO conducts on-site audits of LAS annually as part of the laboratory qualification program. At the time
of selection, the most recent audit of LAS had occurred in February 1997. Results from this audit indicated
that LAS was proficient in several areas, including program management, quality management, and training
programs. No findings regarding PCB analytical procedure implementation were noted. A second on-site audit
of LAS occurred August 11-12, 1997, during the analysis of the demonstration study samples. This
surveillance focused specifically on the procedures that were currently in use for the analysis of the
demonstration samples. The audit, jointly conducted by the SMO, DOE-ORO, and EPA-Las Vegas (LV),
verified that LAS was procedurally compliant. The audit team noted that LAS had excellent adherence to the
analytical protocols and that the staff were knowledgeable of the requirements of the method. No findings
impacting data quality were noted in the audit report.
Reference Laboratory Method
The reference laboratory's analytical method, also presented in the technology demonstration plan [5], followed
the guidelines established in EPA SW-846 Method 8081 [4]. According to LAS's SOP, PCBs were extracted
from 30-g samples of soil by sonication in hexane. Each extract was then concentrated to a final volume that
was further subjected to a sulfuric acid cleanup to remove potential interferences. The analytes were identified
and quantified using a gas chromatograph equipped with dual electron-capture detectors. Each extract was
analyzed on two different chromatographic columns with slightly different separation characteristics (primary
column: RTX-1701, 30 m x 0.53 mm ID x 0.5 (jm; confirmatory column: RTX-5, 30 m x 0.53 mm ID x 0.5
(jm). PCBs were identified when peak patterns from a sample extract matched the patterns of standards for
both columns. PCBs were quantified based on the initial calibration of the primary column.
Calibration
Method 8081 states that, because Aroclors 1016 and 1260 include many of the peaks represented in the other
five Aroclor mixtures, it is only necessary to analyze two multilevel standards for these Aroclors to demonstrate
the linearity of the detector response for PCBs. However, per LAS SOPs, five-point (0.1 to 4 ppm) initial
calibration curves were generated for Aroclors 1016, 1248, 1254, and 1260 and the surrogate compounds
[decachlorobiphenyl (DCB) and tetrachloro-ra-xylene (TCMX)]. Single mid-level standards were analyzed for
the other Aroclors (1221, 1232, and 1242) to aid in pattern recognition. All of the multi-point calibration data,
fitted to quadratic models, met the QC requirement of having a coefficient of determination (R2) of 0.99 or
better over the calibration range specified. The detection limits for soil samples were 0.033 ppm (ng/g) for all
Aroclors except Aroclor 1221, which was 0.067 ppm. For extract samples, the detection limits were 0.010 ppm
((ig/mL) for all Aroclors except Aroclor 1221, which was 0.020 ppm. Reporting detection limits were
calculated based on the above detection limits, the actual sample weight, and the dilution factor.
Sample Quantification
For sample quantification, Aroclors were identified by comparing the samples' peak patterns and retention
times with those of the respective standards. Peak height ratios, peak shapes, sample weathering, and general
similarity in detector response were also considered in the identification. Aroclor quantifications were
performed by selecting three to five representative peaks, confirming that the peaks were within the established
retention time windows, integrating the selected peaks, quantifying the peaks based on the calibrations, and
averaging the results to obtain a single concentration value for the multicomponent Aroclor. If mixtures of
Aroclors were suspected to be present, the sample was typically quantified in terms of the most representative
Aroclor pattern. If the identification of multiple Aroclors was definitive, total PCBs in the sample were
20
-------
calculated by summing the concentrations of both Aroclors. Aroclor concentrations were quantified within the
concentration range of the calibration curve. If PCBs were detected and the concentrations were outside of the
calibration range, the sample was diluted and reanalyzed until the concentration was within the calibration
range. If no PCBs were detected, the result was reported as a non-detect (i.e., "< reporting detection limit").
Sample Receipt, Handling, and Holding Times
The reference laboratory was scheduled to analyze a total of 256 PCB samples (208 soil samples, 24 iso-octane
extract samples, and 24 methanol extract samples). Of these same samples, the developer was scheduled to
analyze a total of 232 PCB samples (208 soil samples and 24 extract samples in solvent of choice). The
samples were shipped to LAS at the start of the technology demonstration activities (July 22). Shipment was
coordinated through the SMO. Completion of chain-of-custody forms documented sample transfer. The
samples were shipped on ice in coolers to maintain <6°C temperatures during shipment. Samples were shipped
with custody seals to ensure sample integrity and to prevent tampering during transport.
Upon receipt of the samples, the reference laboratory checked the receipt temperature and conditions of the
sample containers, assigned each sample a unique number, and logged each into its laboratory tracking system.
All samples were received at the proper temperature and in good condition. Demonstration samples were
divided into 11 analytical batches (with no more than 20 samples per batch). The samples were analyzed in an
order specified by ORNL to ensure that the analysis of sample types was randomized. Analyses of QC samples,
supplied by the reference laboratory to indicate method performance, were performed with each analytical
batch of soils.
Prior to analysis, samples were stored in refrigerators kept at 4 to 6° C to maintain analyte integrity. The
reference laboratory was required to analyze the extract samples and to extract the soil samples within 14 days
of shipment from ORNL. Once the soils were extracted, the reference laboratory had an additional 40 days to
analyze the soil extracts. Maximum holding times were not exceeded for any of the demonstration samples. The
final reference laboratory data package for all samples was received at ORNL in 72 days, on October 1, 1997.
The contractual obligation was 30 days.
The remainder of this section is devoted to summarizing the data generated by the reference laboratory and to
assessing the analytical performance.
Quality Control Results
Objective
The purpose of this section is to provide an assessment of the data generated by the reference laboratory's QC
procedures. The QC samples included continuing calibration verification standards (CCVs), instrument blanks,
method blanks, surrogate spikes, laboratory control samples (LCSs), and matrix spike (MS) /duplicate matrix
spike (MSB) samples. Each control type is described in more detail in the following text and in the technology
demonstration plan [5]. Because extraction of these liquid samples was not required, calibration check
standards and instrument blanks were the only control samples implemented for the extract samples. The
reference laboratory's implementation of QC procedures was consistent with SW-846 guidance.
21
-------
Continuing Calibration Verification Standard Results
A CCV is a single calibration standard of known concentration, usually at the midpoint of the calibration range.
This standard is evaluated as an unknown and is quantified against the initial calibration. The calculated
concentration is then compared with the nominal concentration of the standard to determine whether the initial
calibration is still valid. CCVs were analyzed with every 10 samples or at least every 12. The requirement for
acceptance was a percentage difference of less than 15% for the CCV relative to the initial calibration. This
QC requirement was met for all Aroclors and surrogates, except for one standard that had a 16% difference
for DCB. These results indicated that the reference laboratory maintained instrument calibrations during the
course of sample analysis.
Instrument and Method Blank Results
Instrument blanks (hexane) were analyzed prior to each CCV. The QC requirement was that instrument blanks
must contain less than the reporting detection limit for any analyte. All instrument blanks were acceptable.
A method blank is an analyte-free soil matrix sample that is taken through the extraction process to verify that
there are no laboratory sources of contamination. One method blank was analyzed for each analytical batch.
The QC requirement was that method blanks must contain less than the reporting detection limit for any
Aroclor. No PCBs were detected in any of the eleven method blanks that were analyzed. These results
demonstrated that the reference laboratory was capable of maintaining sample integrity, and that it did not
introduce PCB contamination to the samples during preparation.
Surrogate Spike Results
A surrogate is a compound that is chemically similar to the analyte group but is not expected to be present in
the environmental sample. A surrogate is added to test the extraction and analysis methods to verify the ability
to isolate, identify, and quantify a compound similar to the analyte(s) of interest without interfering with the
determination. Two different surrogate compounds, DCB and TCMX, were used to bracket the retention time
window anticipated in the Aroclor chromatograms. All soil samples, including QC samples, were spiked with
surrogates at 0.030 ppm prior to extraction. Surrogate recoveries were deemed to be within QC requirements
if the measured concentration fell within the QC acceptance limits that were established by past method
performance. (For LAS this was 39 to 117% for DCB, and 66 to 128% for TCMX). The results were
calculated using the following equation:
measured amount ,™n/
percent recovery = x 100%
actual amount (4-1)
In all undiluted samples, both of the surrogates had percentage recoveries that were inside the acceptance limits.
Surrogate recoveries in diluted samples were uninformative because the spike concentration (0.030 ppm, as
specified by the method) was diluted below the instrument detection limits. The surrogate recovery results for
undiluted samples indicated that there were no unusual matrix interferences or batch-processing errors for these
samples.
22
-------
Laboratory Control Sample Results
An LCS is an aliquot of a clean soil that is spiked with known quantities of target analytes. The LCS is spiked
with the same analytes and at the same concentrations as the MS. (MSs are described in the next section.) If
the results of the MS analyses are questionable (i.e., indicating a potential matrix effect), the LCS results are
used to verify that the laboratory can perform the analysis in a clean, representative matrix.
Aroclors 1016 and 1260 were spiked into the clean soil matrix at approximately 0.300 ppm, according to the
reference laboratory's SOP. The QC requirements (defined as percent recovery) for the LCS analyses were
performance-based acceptance limits that ranged from 50 to 158%. In all but 1 of the 1 1 LCSs analyzed, both
Aroclor percent recoveries fell within the acceptance limits. Satisfactory recoveries for LCS verified that the
reference laboratory performed the analyses properly in a clean matrix.
Matrix Spike Results
In contrast to an LCS, a MS sample is an actual environmental soil sample into which target analytes are
spiked at known concentrations. MS samples are used to assess the efficiency of the extraction and analytical
methods for real samples. This is accomplished by determining the amount of spiked analyte that is
quantitatively recovered from the environmental soil. An MSB sample is spiked and analyzed to provide a
measure of method precision. Ideally, to evaluate the MS/MSD results, the environmental soil is analyzed
unspiked so that the background concentrations of the analyte in the sample are considered in the recovery
calculation.
For the demonstration study samples, one MS and MSB pair was analyzed with each analytical batch. The MS
samples were spiked under the same conditions and QC requirements as the LCS (50 to 158% acceptance
limits), so that MS/MSD and LCS results could be readily compared. The QC requirement for MS and MSB
samples was a relative percentage difference (RPD) of less than 30% between the MS/MSD pair. RFD is
defined as
RPD = MS reCOVery ~ MSD r£COVery x 100%
average recovery
A total of 11 MS/MSD pairs were analyzed. Because the MS/MSD spiking technique was not always properly
applied (e.g., a sample which contained 100 ppm of Aroclor 1254 was spiked ineffectively with 0.300 ppm of
Aroclor 1260), many of the MS/MSD results were uninformative. For the samples that were spiked
appropriately, all MS/MSD QC criteria were met.
Conclusions of the Quality Control Results
The reference laboratory results met performance acceptance requirements for all of the samples where proper
QC procedures were implemented. Acceptable performance on QC samples indicated that the reference
laboratory was capable of performing analyses properly.
23
-------
Data Review and Validation
Objective
The purpose of validating the reference laboratory data was to ensure usability for the purposes of comparison
with the demonstration technologies. The data generated by the reference laboratory were used as a baseline
to assess the performance of the technologies for PCB analysis. The reference laboratory data were
independently validated by ORNL and SMO personnel, who conducted a thorough quality check and reviewed
all sample data for technical completeness and correctness.
Corrected Results
Approximately 8% of the results provided by the reference laboratory (20 of 256) were found to have
correctable errors. So as not to bias the assessment of the technology's performance, errors in the reference
laboratory data were corrected. These changes were made conservatively, based on the guidelines provided in
the SW-846 Method 8081 for interpreting and calculating Aroclor results. The errors (see Appendix D, Table
D-3) were categorized as transcription errors, calculation errors, and interpretation errors. The corrections
listed in Table D-3 were made in the final data set that was used for comparison with the demonstration
technologies.
Suspect Results
Normally, one would not know if a single sample result was "suspect" unless (1) the sample was a PE sample,
where the concentration is known, or (2) a result was reported and flagged as suspect for some obvious reason
(e.g., no quantitative result was determined). The experimental design implemented in this demonstration study
provided an additional indication of the abnormality of data through the inspection of the replicate results from
a homogenous soil sample set (i.e., four replicates were analyzed for each sample ID).
Data sets were considered suspect if the standard deviation (SD) of the four replicates was greater than 30 ppm
and the percent relative standard deviation (RSD) was greater than 50%. Five data sets (sample IDs 106, 205,
216,217, 225) contained measurements that were considered suspect using this criteria, and the suspect data
are summarized in Table 4-1. A number of procedural errors may have caused the suspect measurements (e.g.,
spiking heterogeneity, extraction efficiencies, dilution, etc.). In the following subsections for precision and
accuracy, the data were evaluated with and without these suspect values to represent the best- and worst-case
scenarios.
24
-------
Table 4-1. Suspect measurements within the reference laboratory data
Criteria
SD > 30 ppm
RSD > 50%
Qualitative result
Sample ID
106
205
216
217
225
110
112
PCB concentration (ppm)
Replicate results
(ppm)
255.9,269.9,317.6
457.0,483.3,538.7
47.0, 54.3, 64.0
542.8, 549.8, 886.7
32.1,36.5,56.4
< reporting detection
limits
Suspect result(s)
(ppm)
649.6
3305.0
151.6
1913.3
146.0
<66, <98, <99, <490
<66, <130, <200,
<200
Data usability
Performed data analysis with
and without this value
Used as special case for
comparison with developer
results
Samples that did not fall into the above criteria, but were also considered suspect, were non-blank samples that
could not be quantified and were reported as "< the reporting detection limit." This was the case for
environmental soil sample IDs 110 and 112. It is believed that the reference laboratory had trouble quantifying
these soil samples because of the abundance of chemical interferences. These samples were diluted by orders
of magnitude to reduce interferences, thereby diluting the PCB concentrations to levels that were lower than
the instrument detection limits. With each dilution, the reporting detection limits values were adjusted for
sample weight and dilution, which accounts for the higher reporting detection limits (up to 490 ppm). It is
believed that these samples should have been subjected to additional pre-analytical cleanup to remove these
interferences before quantification was attempted. Sample IDs 110 and 112 were collected from the same
cleanup site (see Appendix B), so it is not surprising that similar difficulties were encountered with both sample
sets. Because the results for sample IDs 110 and 112 were not quantitative, these data were compared with the
technology data only on a special case basis.
Data Assessment
Objective
The purpose of this section is to provide an evaluation of the performance of the reference laboratory results
through statistical analysis of the data. The reference laboratory analyzed 72 PE, 136 environmental soil, and
48 extract samples. All reference laboratory analyses were performed under the same environmental conditions.
Therefore, site differentiation was not a factor in data assessment for the reference laboratory. For comparison
with the technology data, however, the reference laboratory data are delineated into "outdoor site" and
"chamber site" in the following subsections. For consistency with the technology review, results from both sites
were also combined to determine the reference laboratory's overall performance for precision and accuracy.
This performance assessment was based on the raw data compiled in Appendix D. All statistical tests were
performed at a 5% significance level.
25
-------
Precision
The term "precision" describes the reproducibility of measurements under a given set of conditions. The SD
of four replicate PCB measurements was used to quantify the precision for each sample ID. SD is an absolute
measurement of precision, regardless of the PCB concentration. To express the reproducibility relative to the
average PCB concentration, RSD is used to quantify precision, according to the following equation:
RSD =
Standard Deviation
Average Concentration
100%
(4-3)
Performance Evaluation Samples
The PE samples were homogenous soils containing certified concentrations of PCBs. Results for these samples
represent the best estimate of precision for soil samples analyzed in the demonstration study. Table 4-2
summarizes the precision of the reference laboratory for the analysis of PE samples. One suspect measurement
(sample ID 225, 146.0 ppm) was reported for the PE soil samples. The RSDs for the combined data ranged
from 9 to 33% when the suspect measurement was excluded, and from 9 to 79% including the suspect
measurement. The overall precision, determined by the mean RSD for all PE samples, was 21% for the worst
case (including the suspect result) and 18% for the best case (excluding the suspect result).
Table 4-2. Precision of the reference laboratory for PE soil samples
Outdoor site
Sample
ID
126"
118
124
120
122
119
125
121
123
Average
concentration
(ppm)
0
1.6
1.7
5.0
11.1
20.1
37.9
54.6
60.1
SD
(ppm)
n/a
0.6
0.2
1.0
0.9
3.4
6.9
3.4
4.6
RSD
(%)
n/a
39
13
20
8
17
18
6
8
Chamber site
Sample
ID
226
218
224
220
222
219
225
221
223
Average
concentration
(ppm)
0
2.6
1.7
5.8
12.8
23.3
41.7"
44.9
55.8
SD
(ppm)
n/a
0.2
0.5
1.8
0.3
6.1
12.9"
11.3
7.7
RSD
(%)
n/a
6
29
31
3
26
31"
25
14
Combined sites
Average
concentration
(ppm)
0
2.1
1.7
5.4
11.9
21.7
39. 5C
49.8
58.0
SD
(ppm)
n/a
0.7
0.4
1.4
1.1
4.9
9.2 c
9.3
6.3
RSD
(%)
n/a
33
21
26
9
23
23 c
19
11
* All PCB concentrations were reported as non-detects.
^Results excluding the suspect value (results including the suspect value: mean = 67.8 ppm, SD = 53.2 ppm, RSD = 79%).
c Results excluding the suspect value (results including the suspect value: mean = 52.8 ppm, SD = 38.6 ppm, RSD = 73%).
26
-------
Environmental Soil Samples
The precision of the reference laboratory for the analysis of environmental soil samples is reported in Table 4-
3. In this table, results including suspect measurements are presented in parentheses. Average concentrations
were reported by the reference laboratory as ranging from 0.5 to 1196 ppm with RSDs that ranged from 7 to
118% when the suspect results were included. Excluding the suspect results, the highest average concentration
decreased to 660 ppm, and the largest RSD decreased to 71%. Because the majority of the samples fell below
125 ppm, precision was also assessed by partitioning the results into two ranges: low concentrations (< 125
ppm) and high concentrations (> 125 ppm). For the low concentrations, the average RSD was 23% excluding
the suspect value and 26% including the suspect value. These average RSDs were only slightly larger than the
RSDs for the PE soil samples of comparable concentration (18% for best case and 21% for worst case). Five
soil sample sets (sample IDs: 106, 117, 205, 211 and 217) were in the high-concentration category. The
average precision for high concentrations was 56% for the worst case and 19% for the best case. The precision
estimates for the low and high concentration ranges were comparable when the suspect values were excluded.
This indicated that the reference laboratory's precision for the environmental soils was consistent
(approximately 21% RSD) and was comparable to the PE soil samples when the suspect values were excluded.
The Paducah soils (indicated as bold sample IDs in Table 4-3) were analyzed by the technologies under both
outdoor and chamber conditions to provide a measure of the effect that two different environmental conditions
had on the technology's performance. Although this was not an issue for the reference laboratory (because all
the samples were analyzed under laboratory conditions), the reference laboratory's results were delineated into
the different site categories for comparison with the technologies. Sample IDs 113 and 201, 114 and 202, 115
and 203, 116 and 204, and 117 and 205 each represent a set of eight replicate samples of the same Paducah
soil. The RSDs for four of the five Paducah pairs (excluding the suspect value for sample ID 205) ranged from
11 to 17%. The result from one pair (sample IDs 113 and 201) had an RSD of 42%, but the reported average
concentration was near the reporting limits.
Extract Samples
The extract samples, which were used to simulate surface wipe samples, were the simplest of all the
demonstration samples to analyze because they required no extraction and were interference-free. Three types
of extract samples were analyzed: solvent blanks, spikes of Aroclor 1248 at 10 (jg/mL, and spikes of Aroclor
1016 at 100 (jg/mL. The reference laboratory did not analyze the extract samples for the EnviroLogix
demonstration.
Accuracy
Accuracy represents the closeness of the reference laboratory's measured PCB concentrations to the accepted
values. Accuracy was examined by comparing the measured PCB concentrations in the PE soils with the
certified PE values and known spiked extract concentrations. Percent recovery was used to quantify the
accuracy of the results. The optimum percent recovery value is 100%. Percent recovery values greater than
100% indicate results that are biased high, and values less than 100% indicate results that are biased low.
27
-------
Table 4-3. Precision of the reference laboratory for environmental soil samples
Outdoor site
Sample
ID
101
102
103
104
105
106
107
108
109
110
111
112
113 c
114
115
116
117
Average
concentration
(ppm)
0.5
2.0
2.3
9.4
59.4
281.0
(373.2)"
1.3
1.8
2.0
n/a6
38.7
n/a
1.1
1.3
14.8
41.3
383.9
Standard
deviation
(ppm)
0.1
0.3
0.6
4.0
16.5
32.4
(186.2)
0.3
0.1
0.4
n/a
4.3
n/a
0.6
0.3
1.8
5.9
55.2
RSD
(%)
16
16
27
43
28
12
(50)
20
8
20
n/a
11
n/a
55
20
12
14
14
Chamber site
Sample
ID
206
207
208
209
210
211
212
213
214
215
216
217
201
202
203
204
205
Average
concentration
(ppm)
1.9
18.8
30.5
40.2
88.6
404.5
3.2
8.1
25.2
26.7
55.1
(79.2)
659.8
(973.2)
0.9
1.4
13.9
44.3
493.0
(1196.0)
Standard
deviation
(ppm)
0.9
3.5
7.9
28.5
25.6
121.8
1.6
1.6
3.7
3.2
8.5
(48.7)
196.6
(647.0)
0.2
0.2
1.7
2.9
41.7
(1406.4)
RSD
(%)
49
19
26
71
29
30
50
20
15
12
15
(62)
30
(66)
24
12
12
7
8
(118)
" Data in parentheses include suspect values.
6 N/a indicates that qualitative results only were reported for this sample.
c Bold sample IDs were matching Paducah sample pairs (i.e., 113/201, 114/202, 115/203, 116/204, 117/205).
The reference laboratory's performance for the PE samples is summarized in Table 4-4. Included in this table
are the performance acceptance ranges and the certified PCB concentration values. The acceptance ranges,
based on the analytical verification data, are guidelines established by the provider of the PE materials to gauge
acceptable analytical results. As shown in Table 4-4, all of the average concentrations were within the
acceptance ranges, with the exception of sample ID 218. The average result of sample ID 225 was outside of
28
-------
the acceptance range only when the suspect result was included. All of the replicate measurements in sample
ID 225 were biased slightly high. Average percent recoveries for the PE samples (excluding suspect values)
ranged from 76 to 130%. Overall accuracy was estimated as the average recovery for all PE samples. The
overall percent recovery was 105% as a worst case when the suspect value was included. Excluding the suspect
value as a best case slightly lowered the overall percent recovery to 101%. A regression analysis [7] indicated
that the reference laboratory's results overall were unbiased estimates of the PE sample concentrations.
Table 4-4. Accuracy of the reference laboratory for PE soil samples
Certified
concentration
(ppm)
(acceptance
range, ppm)
0°
(n/a)
2.0
(0.7-2.2)
2.0
(0.9-2.5)
5.0
(2.1-6.2)
10.9
(4.0-12.8)
20.0
(11.4-32.4)
49.8
(23.0-60.8)
50.0
(19.7-63.0)
50.0
(11.9-75.9)
Outdoor site
Sample
ID
126
118
124
120
122
119
125
121
123
Average
cone
(ppm)
0
1.6
1.7
5.0
11.1
20.1
37.9
54.6
60.1
Recovery
(%)
n/a
79
85
99
102
100
76
109
120
Chamber site
Sample
ID
226
218
224
220
222
219
225
221
223
Average
cone
(ppm)
0
2.6
1.7
5.8
12.8
23.3
41. lb
44.9
55.8
Recovery
(%)
n/a
130
85
117
117
116
84"
90
112
Combined sites
Average
cone
(ppm)
0
2.1
1.7
5.4
11.9
21.7
39.5 c
49.8
58.0
Recovery
(%)
n/a
105
85
108
109
109
79"
100
116
"All PCB concentrations reported as non-detects by the laboratory.
'Results excluding the suspect value (results including the suspect value:
'Results excluding the suspect value (results including the suspect value:
average = 67.8 ppm and recovery = 136%).
average = 52.8 ppm and recovery = 106%).
Representativeness
Representativeness expresses the degree to which sample data accurately and precisely represent the capability
of the method. Representativeness of the method was assessed based on the data generated for clean-QC
samples (i.e., method blanks and laboratory control samples) and PE samples. Based on the data assessment
discussed in detail in various parts of this section, it was determined that the representativeness of the reference
laboratory data was acceptable. In addition, acceptable performance on laboratory audits substantiated that
29
-------
the data set was representative of the capabilities of the method. In all cases, the performance of the reference
laboratory met all requirements for both audits and QC analyses.
Completeness
Completeness is defined as the percentage of measurements that are judged to be usable (i.e., the result was
not rejected). Usable results were obtained for 248 of the 256 samples submitted for analysis by the reference
laboratory. Eight results (for sample IDs 110 and 112) were deemed incomplete and therefore not valid because
the measurements were not quantitative. To calculate completeness, the total number of complete results were
divided by the total number of samples submitted for analysis, and then multiplied by 100 to express as a
percentage. The completeness of the reference laboratory was 97%, where a completeness of 95% or better is
typically considered acceptable.
Comparability
Comparability refers to the confidence with which one data set can be compared with another. The
demonstration study was designed to have a one-to-one, sample-by-sample comparison of the PCB results
obtained by the reference laboratory and the PCB results obtained by the technology being evaluated. Based
on thorough examination of the data and acceptable results on the PE samples, it was concluded that the
reference laboratory's SOPs for extraction and analysis, and the data generated using these procedures, were
of acceptable quality for comparison with the field technology results. Additional information on comparability
was available because the experimental design incorporated randomized analysis of blind, replicate samples.
Evaluation of the replicate data implicated some of the individual data points as suspect (see Table D-2). The
reference laboratory's suspect data were compared with the technology data on a special-case basis, and
exceptions were noted.
Summary of Observations
Table 4-5 provides a summary of the performance of the reference laboratory for the analysis of all sample
types used in the technology demonstration study. As shown in the table, the precision of the PE soils was
comparable to that of the environmental soils. A weighted average, based on the number of samples, gave a
best-case precision of 21% and a worst-case precision of 28% for all the soil data (PE and environmental).
Evaluation of overall accuracy was based on samples with certified concentrations. The overall accuracy, based
on percent recovery, for the PE samples (which ranged from 0 to 50 ppm) was 105% for the worst case (which
included the suspect value) and 101% for the best case (which excluded the suspect value). These results
indicated that the reference laboratory results were unbiased estimates of the certified PE concentrations. The
reference laboratory correctly reported all blank samples as non-detects but had difficulty with two soil samples
(IDs 110 and 112) that contained chemical interferences. Overall, it was concluded that the reference laboratory
results were acceptable for comparison with the developer's technology.
30
-------
Table 4-5. Summary of the reference laboratory performance
Sample matrix
Blank
Environmental soil with
interferences
Soil — Best case
(excluding suspect data)
Soil — Worst case
(including suspect data)
Sample type
Soil
Sample ID 110
Sample ID 112
PE
Environmental
< 125 ppm
> 125 ppm
Overall
PE
Environmental
< 125 ppm
> 125 ppm
Overall
Number of
samples
8
4
4
63
107
17
187
64
108
20
192
Precision
(average % RSD)
n/a"
n/a"
18
23
19
21
21
26
56
28
Accuracy
(average % recovery)
All samples reported as
non-detects
All samples reported as
non-detects
101
n/a6
n/a6
101
105
n/a6
n/a6
105
* Because the results were reported as non-detects, precision assessment is not applicable.
6 Accuracy assessment calculated for samples of known concentration only.
31
-------
32
-------
Section 5
Technology Performance and Evaluation
Objective and Approach
This section presents the evaluation of the data generated by EnviroLogix's PCB in Soil Tube Assay. The
technology's precision and accuracy are presented for the data generated in the demonstration study. In
addition, an evaluation of comparability, through a one-to-one comparison with the reference laboratory data,
is presented. An evaluation of other aspects of the technology (such as cost, sample throughput, hazardous
waste generation, and logistical operation) is also presented in this section.
Interval Reporting
The PCB in Soil Tube Assay results were reported as concentration ranges that were designated as intervals
incorporating parenthesis/bracket notation. The parentheses indicated that the end-points of the concentration
range were excluded, while brackets indicated that the end-points were included. The reporting intervals for
soils and extracts are presented in Table 5-1. Note that the intervals are different for the soils and extracts
because the soils incorporate an extraction step into the procedure. As shown in the table, the interval [1, 10)
indicates that the PCB concentration range is > 1 and <10.
Table 5-1. PCB in Soil Tube Assay reporting intervals
Interval
[0,1)
[1,10)
[10,50)
[SO.co)
Soil concentration
range
0< PCBppm< 1
1< PCBppm< 10
10 < PCBppm<50
PCB ppm > 50
Interval
[0, 0.4)
[0.4,4)
[4,20)
[20, co)
Extract concentration
range
0< PCB ppm < 0.4
0.4< PCB ppm < 4
4 < PCB ppm < 20
PCB ppm > 20
Data Assessment
Objective
The purpose of the data assessment section is to present the evaluation of the performance of EnviroLogix's
PCB in Soil Tube Assay through a statistical analysis of the data. PARCC parameters were used to evaluate
the test kit's ability to measure PCBs in PE soil, environmental soil, and extract samples. The developer
analyzed splits of replicate samples that were also analyzed by the reference laboratory (72 PE soil samples
and 136 environmental soil samples). See Section 4 for a more detailed analysis of the reference laboratory's
results. Replicate samples were analyzed by the developer at two different sites (under outdoor conditions and
inside an environmentally controlled chamber) to evaluate the effect of environmental conditions on the test
33
-------
kit's performance; see Section 3 for further details on the different sites. Evaluation of the measurements made
at each site indicated that there were no significant differences between the two data sets. Because
environmental conditions did not appear to affect the results significantly, data from both sites were also
combined for each parameter—precision and accuracy—to determine the test kit's overall performance. All
statistical tests were performed at the 5% significance level. Appendix D contains the raw data that were used
to assess the performance of the kit.
Precision
Precision is the reproducibility of measurements under a given set of conditions. The frequency with which the
same interval was reported within a set of replicates was used to quantify precision. Examples of how the
precision was classified are presented in Table 5-2. Reporting a higher number of replicates in the same interval
for a given replicate set indicates higher precision. In other words, reporting all four replicate results as the
same interval indicates the highest possible precision.
Table 5-2. Classification of precision results
If the replicate results are . . .
[1, 10), [1, 10), [1, 10), [1, 10)
[0, 1), [1, 10), [1, 10), [1, 10)
[0,1), [1,10), [1,10), [10, 50)
[0,1), [1, 10), [10, 50), [50, oo )
. . . then the number reported
in identical intervals are . . .
4
3
2
0
. . . and the precision
classification is ...
high
medium
low
none
Performance Evaluation Samples
Table 5-3 summarizes the precision information for the test kit's analysis of the PE samples. The PCB in Soil
Tube Assay reported all four replicates as the same interval (i.e., high precision) for five of the eight PE sample
sets under outdoor conditions, and four of the eight PE sample sets under the chamber conditions. Operating
under the outdoor conditions, all eight replicate sets were classified as having either medium or high precision.
Under the chamber conditions, medium to high precision was achieved for five of eight replicate sets, with the
remaining three replicate sets classified as having low precision. A more detailed analysis of the data showed
that the replicates classified as having medium to low precision were never more than one interval away from
the most frequently reported interval. None of the replicate sets were classified with the lowest precision (i.e.,
none) under either set of environmental conditions. With the exception of sample ID 119, the sample sets with
low to medium precision had concentrations that were near threshold values (i.e., 10 and 50 ppm), which
caused the results to be split into two intervals. For example, for sample ID 222, which had a nominal
concentration of 10.9 ppm, the technology reported two results in the [1, 10) interval and two results in the
[10, 50) interval.
34
-------
Table 5-3. Precision of the PCB in Soil Tube Assay for PE soil samples
Certified
PE Cone.
(ppm)
0
2.0
2.0
5.0
10.9
20.0
49.8
50.0
50.0
Outdoor site
Sample
ID
126"
118
124
120
122
119
125
121
123
No. in each preci-
sion classification
precision
none high
Number of replicates reported in
identical intervals
0"
0
2
0
3
X
X
X
3
4
X
X
X
X
X
X
5
Chamber site
Sample
ID
226"
218
224
220
222
219
225
221
223
precision
none high
Number of replicates reported in
identical intervals
0"
0
2
X
X
X
3
3
X
1
4
X
X
X
X
X
4
" Indicates that all four replicates were reported as different intervals.
b Blank data were not included in the determination of the overall precision.
Environmental Soil Samples
The PCB in Soil Tube Assay results for the replicate environmental soil sample measurements are presented
in Table 5-4. Under the outdoor conditions, the highest precision classification (i.e., the same interval reported
for all four replicates) was achieved for 12 of 17 replicate sets. Under the chamber conditions, 11 of 17 sample
sets were classified as high-precision. None of the replicate sets were classified with the lowest precision (i.e.,
none) under either set of environmental conditions. Of the sample sets for which precision was classified as
medium to low, only sample ID 203 had one replicate result that differed by more than one interval range.
Because most of the measurements fell below 125 ppm, precision was also assessed by partitioning the results
into two ranges: low concentration (reference laboratory values < 125 ppm) and high concentration (reference
laboratory values > 125 ppm). See Section 4 for the delineation of which sample IDs were in the low and high
categories. For the low concentrations, 62% of the sample sets (18 of 29) were reported with
35
-------
Table 5-4. Precision of the PCB in Soil Tube Assay for environmental soil samples
Outdoor site
Sample
ID
101
102
103
104
105
106
107
108
109
110
111
112
113"
114
115
116
117
No. in each
precision
classification
precision
none high
Number of replicates reported in
identical intervals
0"
0
2
X
X
2
3
X
X
X
3
4
X
X
X
X
X
X
X
X
X
X
X
X
12
Chamber site
Sample
ID
206
207
208
209
210
211
212
213
214
215
216
217
201
202
203
204
205
precision
none high
Number of replicates reported in
identical intervals
0"
0
2
X
X
2
3
X
X
X
X
4
4
X
X
X
X
X
X
X
X
X
X
X
11
" Indicates that all four replicates were reported as different intervals.
6 Bold sample IDs were matching Paducah sample pairs (i.e., 113/201, 114/202, 115/203, 116/204, 117/205).
all four replicates in the same interval (i.e., highest possible precision). For the high concentration category,
100% of the sample sets (five of five) were reported with the highest possible precision.
The Paducah soils (indicated by bold sample IDs in Table 5-4) were analyzed at both sites to provide an
assessment of the test kit's performance under different environmental conditions. For these samples, the data
generated under both environmental conditions were also combined to provide an overall assessment of
precision. Sample IDs 113 and 201, 114 and 202, 115 and 203, 116 and 204, and 117 and 205 represented
replicate Paducah soil sample sets; the 100 series were samples analyzed under the outdoor conditions, and the
200 series were samples analyzed inside the chamber. Additional statistical analysis was used to compare the
effect of the two environmental conditions on the measurements. Results from this analysis showed that there
were no significant differences in the data generated at each site. This indicated that these different
environmental conditions did not affect the performance of the test kit.
36
-------
Extract Samples
The PCB in Soil Tube Assay results for the replicate extract measurements are presented in Table 5-5. All
three sample sets analyzed under the chamber conditions were reported with the highest possible precision (i.e.,
all four replicates were within the same interval). Two sample sets analyzed under the outdoor conditions
achieved the highest precision, and the remaining sample set (sample ID 132) was reported with low precision
(i.e., two replicates were reported in the same interval).
Table 5-5. Precision of the PCB in Soil Tube Assay for extract samples
Outdoor site
Sample ID
130"
131
132
No. in each
precision
classification
precision
none high
Number of replicates reported in
identical intervals
0"
0
2
X
1
3
0
4
X
X
1
Chamber site
Sample ID
230"
231
232
precision
none high
Number of replicates reported in
identical intervals
0"
0
2
0
3
0
4
X
X
X
2
" Indicates that all four replicates were reported as different intervals.
6 Blank data were not included in the determination of the overall precision
Precision Summary
A summary of the test kit's overall precision is presented by sample type (PE, environmental soil, and extract
samples) in Table 5-6. For PE and environmental soil samples, 56% and 68% of the samples, respectively,
achieved the highest possible precision (i.e., all four sample replicates were reported as the same interval). For
the extract samples, 75% of the samples achieved the highest precision.
Accuracy
Accuracy represents the closeness of the PCB in Soil Tube Assay's measured PCB concentrations to the
certified values. Because the test kit produced interval results, accuracy was evaluated in terms of the
percentage of samples that agreed with, were above (i.e., biased high), and were below (i.e., biased low) the
certified value.
37
-------
Table 5-6. Overall precision of the PCB in Soil Tube Assay for all sample types
Environmental
site
Outdoor site
Chamber site
Combined sites
Percentage of samples classified in each precision category
PE samples
None
0
0
0
Low
0
38
19
Med
38
13
25
High
63
50
56
Environmental soil samples
None
0
0
0
Low
12
12
12
Med
18
24
21
High
71
65
68
Extract samples
None
0
0
0
Low
50
0
25
Med
0
0
0
High
50
100
75
Performance Evaluation Soil Samples
Table 5-7 contains a comparison between the PCB in Soil Tube Assay's interval result and the corresponding
certified PE value. The interval(s) listed under a particular column indicate how many of the four replicates
were reported as that interval. For example, for sample ID 222, two replicates were reported as [1, 10), and
two were reported as [10, 50). For sample ID 119, three are reported as [10, 50), and one is reported as [1, 10).
The table also presents performance acceptance ranges for the PE results, which are the guidelines established
by the provider of the PE materials to gauge acceptable analytical results. These ranges were not used to
evaluate the test kit results because the acceptance ranges overlap several reporting intervals. However, in all
but two individual analyses of PE samples, the reported interval result included a value within the range of
acceptable results.
The data in Table 5-7 were used to derive the accuracy results that are presented in Table 5-8. Accuracy was
based on a comparison of the certified PE value with the interval reported by the test kit. If the interval
encompassed the certified PE value, the PCB in Soil Tube Assay result "agreed" with the certified value. If
the test kit result was above the certified value, the result was classified as "biased high." If the test kit result
was below the certified value, the result was classified as "biased low." For example, for sample ID 222, the
certified value was 10.9 ppm (for Aroclor 1260). The comparison would be classified as "agreed" for the PCB
in Soil Tube Assay interval result [10, 50) and as "biased low" for the interval result [1, 10).
Separate comparisons were made for the two environmental conditions to determine if ambient temperature and
humidity had an effect on the technology performance. Statistical analysis showed that there was no significant
difference between the results obtained by the test kit under the two different environmental conditions
evaluated in this demonstration. Therefore, all PE sample results were combined to determine the overall
percentage of agreement between the PCB in Soil Tube Assay results and the certified PE value. The overall
percentage of agreement was 78%. A comparable number of results were biased high (10%) and biased low
(13%). For most of the samples which did not agree with the certified value, the result was near a test kit
threshold value. For example, six of the eight test kit results for sample IDs 125 and 225 were [50, <=°); the other
two results were [10, 50). The nominal concentration forthese PE sample was 49.8 ppm, so those reported [10,
50) would be in agreement with the certified value, while the results reported as [50, <=°) were biased high. It
appears that the test kit generally reports the more conservative (i.e., higher)
38
-------
Table 5-7. PCB in Soil Tube Assay accuracy data for PE soil samples
Certified
cone, (ppm)
(Acceptance
range, ppm)
0
(n/a)
2.0
(0.7-2.2)
2.0
(0.9-2.5)
5.0
(2.1-6.2)
10.9
(4.0-12.8)
20.0
(11.4-32.4)
49.8
(23.0-60.8)
50.0
(19.7-63.0)
50.0
(11.9-75.9)
Outdoor site
Sample
ID
126
118
124
120
122
119
125
121
123
# of replicates reported at each interval
1
[1,10)
[50, »)<•
[1,10)"
2
3
[0,1)
[10,50)
[10,50)
4
[0,1)
[1,10)
[1,10)
[SO.co)
[50,0=)
[SO.oo)
Chamber site
Sample
ID
226
218
224
220
222
219
225
221
223
# of replicates reported at each interval
1
[10,50)
2
[1,10)
[10,50)
[10,50)
[50,°°)
[10,50)
[SO.oo)
3
[50, oo)
4
[0,1)
[1,10)
[1,10)
[1,10)
[10,50)
" Result not included in the acceptance range.
interval when the result is near the threshold value of 50 ppm (see Regulatory Decision-Making Applicability
section for more information). Note that in a situation where the sample concentration is near the threshold
value, the operator of the test kit can compare the optical density of the sample assay to that of the calibration
assay and recognize that the sample concentration is near the threshold value.
Extract Samples
Table 5-9 contains a comparison between the PCB in Soil Tube Assay interval result and the corresponding
spike concentration for the extract samples. The test kit's percentage of agreement with the spike concentration
of the extract samples is summarized in Table 5-10. Statistical analysis showed that environmental conditions
had no significant effect upon the performance of the test kit. Therefore, the data sets generated under the
outdoor and chamber conditions were combined. Overall, 22 of 24 extract samples (92%) agreed with the spike
concentration. Two 100-ppm spiked samples (8%) were biased low relative to the spike concentration. None
were biased high.
39
-------
Table 5-8. Evaluation of agreement between PCB in Soil Tube Assay's PE sample results and the
certified PE values as a measure of accuracy
Environmental
site
Outdoor site
Chamber site
Combined sites
Relative to certified values for performance
evaluation samples
Biased
low
11%
14%
13%
Agree
75%
81%
78%
Biased
high
14%
6%
10%
Number of
samples
36
36
72
Table 5-9. Accuracy of the PCB in Soil Tube Assay for extract samples
Spike cone.
(ug/mL)
0
10
100
Outdoor site
Sample
ID
132
130
131
# of replicates reported at each interval
1
2
[20, oo )
[4,20)
3
4
[0, 0.4)
[4,20)
Chamber site
Sample
ID
232
230
231
# of replicates reported at each interval
1
2
3
4
[0, 0.4)
[4, 20]
[20, co)
Table 5-10. Evaluation of agreement between PCB in Soil Tube Assay's extract results and the spike
concentration as a measure of accuracy
Environmental
site
Outdoor site
Chamber site
Combined sites
Relative to spike concentration for extract
samples
Biased
low
17%
0%
8%
Agree
83%
100%
92%
Biased
high
0%
0%
0%
Number of
samples
12
12
24
False Positive/False Negative Results
A false positive (fp) result [10] is one in which the technology detects PCBs in the sample above the detection
limit when there actually are no PCBs present. A false negative (fn) result [8] is one in which the technology
indicates that there are no PCBs present in the sample, when there actually are. Both fp and fn results are
influenced by the method detection limit of the technology. All of the eight blank soil samples were reported
as the lowest reporting interval, which included zero, so the fp result was 0%. Of the 192 non-blank soil
samples analyzed, the PCB in Soil Tube Assay reported twelve in the lowest reporting interval (0 to 1 ppm ).
40
-------
Five of the corresponding reference laboratory results fell into the test kit's reporting interval (0.5 ppm), and
were therefore reported correctly. Seven results were false negatives. Therefore, 4% of the soil sample results
were false negatives. For the eight extract samples, the kit reported all blanks as [0, 1), indicating no fp results.
All other extract samples were reported as non-blanks; therefore, the fn result was 0%.
Representativeness
Representativeness expresses the degree to which the sample data accurately and precisely represent the
capability of the technology. The performance data were accepted as being representative of the technology
because the PCB in Soil Tube Assay was capable of analyzing diverse sample types (PE samples, simulated
wipe extract samples, and actual field environmental samples) under multiple environmental conditions. When
this technology is used, QC samples should be analyzed to assess the performance of the test kit under the
testing conditions.
Completeness
Completeness is defined as the percentage of measurements that are judged to be useable (i.e., the result was
not rejected). Valid results were obtained by the technology for all 232 samples. Therefore, completeness was
100%.
Comparability
Comparability refers to the confidence with which one data set can be compared to another. A one-to-one
sample comparison of the PCB in Soil Tube Assay results and the reference laboratory results was performed
for all soil samples. Accuracy was evaluated in terms of the percentage of samples that agreed with, were above
(i.e., biased high), and were below (i.e., biased low) the certified value. For comparability, the test kit results
were compared with the results generated by the reference laboratory, including both environmental soils and
PE samples. Sample IDs 110 and 112 were excluded because the reference laboratory did not generate
quantitative results for these samples. The results are summarized in Table 5-11. The percentage of PCB in
Soil Tube Assay results that agreed with the reference laboratory results was 81%. Approximately 12% were
biased high, and approximately 7% were biased low relative to the results reported by the reference laboratory.
For the extract samples, the test kit's results could not be compared with the reference laboratory's results
because no reference laboratory data were generated for these samples.
The soil data not included in previous comparability evaluations (because the replicate data for the reference
laboratory were considered suspect) are shown in Table 5-12. Refer to Section 4, especially Table 4-1, for
more information on the reference laboratory's suspect measurements. The reference laboratory's suspect data
were compared with the PCB in Soil Tube Assay's matching results. For sample IDs 110 and 112, the
reference laboratory obtained qualitative results only. The test kit appeared to have little difficulty with these
samples, as all four replicates were reported as the same interval. For the other five suspect values for the
reference laboratory data, the test kit generated results that agreed with the replicate means of the reference
laboratory. The only exceptions were sample IDs 216 and 225, where the
41
-------
Table 5-11. Evaluation of agreement between PCB in Soil Tube Assay's soil results and the reference
laboratory's results as a measure of comparability
Environmental
site
Outdoor site
Chamber site
Combined sites
Relative to reference laboratory results for
soil samples
Biased
low
7%
6%
7%
Agree
78%
85%
81%
Biased
high
15%
10%
12%
Number of
samples
96
104
200
reference laboratory results were near the kit's threshold value of 50 ppm. These comparisons demonstrated
that the PCB in Soil Tube Assay did not have difficulty with most of the samples that were troublesome for
the reference laboratory.
Summary of PARCC Parameters
Table 5-13 summarizes the test kit's performance for precision, accuracy, and comparability. Precision was
assessed by the percentage of replicate samples where the highest precision was achieved (i.e., all four
replicates were reported as the same interval), which was 56% for the PE samples, 62% for the environmental
soils, and 75% for the extract samples. The test kit's performance was based on agreement and disagreement
with the certified PE values (accuracy) and the reference laboratory results (comparability). Overall, the test
kit's performance was similar for all samples because the percentages of agreement and disagreement were not
significantly different for each sample type. The percentage in agreement ranged from 78 to 92, the percentage
biased high was 10 to 13, and the percentage biased low was 6 to 13.
Regulatory Decision-Making Applicability
One objective of this demonstration was to assess the technology's ability to perform at regulatory decision-
making levels for PCBs, specifically 50 ppm for soils. To assess this ability, the test kit's performance for PE
and environmental soil samples ranging in concentration from 40 to 60 ppm (as determined by the paired
reference laboratory analyses) can be used. For this concentration range, the test kit's results agreed with the
reference laboratory's results 66% of the time. Results were biased high 32% of the time, and 2% of the results
were biased low. No false negatives were observed. The test kit results for this concentration range were
different from what was observed for the entire data set, in that the percentage of samples that were biased high
was significantly higher (32% versus 12%). This indicates that the test kit results appear to have a higher
percentage of results that are reported more conservatively (i.e., reported in a higher interval range than the
actual result) for this concentration range than for the entire concentration range of the samples analyzed (0
to 700 ppm).
42
-------
Table 5-12. Comparison of the PCB in Soil Tube Assay results with the reference laboratory's suspect measurements
Sample ID
110
112
106
205
216
217
225
Reference laboratory
Suspect measurement
(ppm)
-------
Additional Performance Factors
Sample Throughput
Sample throughput is representative of the estimated amount of time required to extract the PCBs, to perform
appropriate reactions, and to analyze the sample. Operating under the outdoor conditions, one analyst from
EnviroLogix had a sample throughput rate of about eight samples per hour. Working in the chamber, the
analyst obtained a lower rate, around seven samples per hour. This increased sample throughput under the
outdoor conditions may be attributed to the analysis order: because the EnviroLogix analyst performed sample
analyses under the chamber conditions first, he may have gained valuable experience that was applied during
the analysis of the outdoor samples. Alternatively, EnviroLogix may have had more difficulty with the sample
matrices that were analyzed only under the indoor conditions.
Cost Assessment
The purpose of this economic analysis is to provide an estimation of the range of costs for an analysis of PCB-
contaminated soil samples using the PCB in Soil Tube Assay and a conventional analytical reference laboratory
method. The analysis was based on the results and experience gained from this demonstration, costs provided
by EnviroLogix, and representative costs provided by the reference analytical laboratories that offered to
analyze these samples. To account for the variability in cost data and assumptions, the economic analysis was
presented as a list of cost elements and a range of costs for sample analysis using the test kit and by the
reference laboratory.
Several factors affected the cost of analysis. Where possible, these factors were addressed so that decision-
makers can independently complete a site-specific economic analysis to suit their needs. The following
categories are considered in the estimate:
sample shipment costs,
labor costs,
equipment costs, and
waste disposal costs.
Each of these cost factors is defined and discussed and serves as the basis for the estimated cost ranges
presented in Table 5-14. Costs for sample acquisition and pre-analytical sample preparation, which are tasks
common to both methods, were not included here. This analysis assumed that the individuals performing the
analyses were fully trained to operate the technology. EnviroLogix provides free assistance, on an as-needed
basis, through its technical service department. It also offers a free one-day training session on the kit at its
facility in Portland, Maine. Training at the user's facility is handled on a case-by-case basis.
44
-------
Table 5-14. Estimated analytical costs for PCB soil samples
PCB in Soil Tube Assay
EnviroLogix Inc.
Sample throughput rate: 8 samples/hour (outdoors)
7 samples/hour (chamber)
Cost category Cost (S)
Sample shipment 0
Labor
Mobilization/demobilization 25CMOO
Travel 15-1000 per analyst
Per diem 0-150 per day per analyst
Rate 30-75 per hour per analyst
Equipment
Mobilization/demobilization 0-150
Purchase field lab kit 965-1 975
Reagents/supplies 1 8 per sample
Waste disposal 135-1790
EPA SW-846 Method 8081
Reference laboratory
Typical turnaround time: 14-30 days
Actual turnaround time: 72 days
Cost category Cost (S)
Sample shipment
Labor 100-200
Overnight shipping charges 50-150
Labor
Mobilization/demobilization Included"
Travel Included
Per diem Included
Rate 44-239 per sample
Equipment
Mobilization/demobilization Included
Purchase field lab kit Included
Reagents/supplies Included
Waste disposal Included
""Included" indicates that the cost is included in the labor rate.
PCB in Soil Tube Assay Costs
• Sample shipment costs. Because the samples were analyzed on site, no sample shipment charges were
associated with the cost of operating the test kit.
• Labor costs. Labor costs included mobilization/demobilization, travel, per diem, and on-site labor.
— Labor mobilization/demobilization: This cost element included the time for one person to
prepare for and travel to each site. The estimate ranged from 5 to 8 hours, at a rate of $50 per
hour.
— Travel: This element was the cost for the analyst(s) to travel to the site. If the analyst is
located near the site, the cost of commuting to the site (estimated to be 50 miles at $0.30 per
mile) would be minimal ($15). The estimated cost of an analyst traveling to the site for this
demonstration ($1000) included the cost of airline travel and rental car fees.
— Per diem: This cost element included food, lodging, and incidental expenses and was estimated
ranging from zero (for a local site) to $150 per day per analyst
— Rate: The cost of the on-site labor was estimated at a rate of $30 to $75 per hour, depending
on the required expertise level of the analyst. This cost element included the labor involved
with the entire analytical process comprising sample preparation, sample management,
analysis, and reporting.
45
-------
• Equipment costs. Equipment costs included mobilization/demobilization, purchase of equipment, and
the reagents and other consumable supplies necessary to complete the analysis.
— Equipment mobilization/demobilization: This included the cost of shipping the equipment to
the test site. If the site is local, the cost would be zero. For this demonstration, the cost of
shipping equipment and supplies was estimated at $150.
— Purchase of field test lab: At the time of the demonstration, EnviroLogix offered a field
laboratory that would include all of the equipment necessary to complete the analyses for a
cost of $1975. The field laboratory includes a Microman M-25 positive displacement pipettor,
an Eppendorf Repeater pipettor, Acculab pocket balance, Artel Differential Photometer, wash
bottle, and black suitcase. The field lab can also be purchased without the photometer for
$965 (photometer alone is $1250).
— Reagents/supplies: These items are consumable and are purchased on a per-sample basis. At
the time of the demonstration, the cost of the reagents and supplies needed to prepare and
analyze PCB soil samples using the test kit was $18 per sample. This cost included the sample
preparation/extraction supplies (including solvent), assay supplies, and consumable reagents.
Waste disposal costs. Waste disposal costs are estimated based on the 1997 regulations for disposal
of PCB-contaminated waste. The test kit generated approximately 43 Ib of vials containing soils and
liquid solvents (classified as solid PCB waste suitable for disposal by incineration) and approximately
43 Ib of other solid PCB waste (used and unused soil, gloves, paper towels, ampules, etc.). The cost
of disposing of PCB solid waste by incineration at a commercial facility was estimated at $1.50 per
pound. The cost for solid PCB waste disposal at ETTP was estimated at $18/lb. The test kit also
generated approximately 21 Ib of liquid waste. The cost for liquid PCB waste disposal at a commercial
facility was estimated at $0.25/lb, while the cost at ETTP was estimated at $11/lb.
Reference Laboratory Costs
• Sample shipment costs. Sample shipment costs to the reference laboratory included overnight
shipping charges, as well as labor charges associated with the various organizations involved in the
shipping process.
— Overnight shipping: The overnight express shipping service cost was estimated to be $50 for
one 50-lb cooler of samples.
— Labor: This cost element included all of the tasks associated with the shipment of the samples
to the reference laboratory. Tasks included packing the shipping coolers, completing the chain-
of-custody documentation, and completing the shipping forms. Because the samples contained
PCBs, the coolers were inspected by qualified personnel to ensure acceptance with the U.S.
Department of Transportation's shipping regulations for PCBs. The estimate to complete this
task ranged from 2 to 4 hours at $50 per hour.
Labor, equipment, and waste disposal costs. The labor bids from commercial analytical reference
laboratories who offered to perform the PCB analysis for this demonstration ranged from $44 per
sample to $239 per sample. The bid was dependent on many factors, including the perceived difficulty
of the sample matrix, the current workload of the laboratory, and the competitiveness of the market.
In this case, the wide variation in bids may also be related to the cost of PCB waste disposal in a
particular laboratory's state. LAS Laboratories was awarded the contract to complete the analysis as
46
-------
the lowest qualified bidder ($44 per sample). This rate was a fully loaded analytical cost that included
labor, equipment, waste disposal, and report preparation.
Cost Assessment Summary
An overall cost estimate for the PCB in Soil Tube Assay vs the reference laboratory was not made because of
the extent of variation in the different cost factors, as outlined in Table 5-14. The overall costs for the
application of each technology will be based on the number of samples requiring analysis, the sample type, and
the site location and characteristics. Decision-making factors, such as turnaround time for results, must also
be weighed against the cost estimate to determine the value of the field technology vs the reference laboratory.
General Observations
The following are general observations regarding the field operation and performance of the test kit:
• The system was light, easily transportable, and rugged. It took less than an hour for the
EnviroLogix analyst to prepare to analyze samples on the first day of testing. While working
at the outdoor site, the analyst completely disassembled his work station, bringing everything
inside at the close of each day. It took the analyst less than an hour each morning to prepare
for sample analyses.
• The technology was operated by a single person.
• Operators generally require 4 hours of training. They should have a basic knowledge of field
analytical techniques.
Each batch of samples was analyzed with 1 and 10 ppm standards and a negative control. (A
batch generally consisted of 12 to 17 samples). This controlled for changing environmental
conditions (i.e., temperature and humidity), and other causes of batch-to-batch variation.
Data processing and interpretation was minimal. The results were quantified relative to the
two calibration standards and reported in terms of intervals. The photometer's optical density
readings were recorded in a laboratory notebook.
All reagents were allowed to come to ambient temperature before use. It is recommended that
all of the reagents in the test kit be stored under refrigerated conditions. When work was being
done outdoors, the analyst returned the reagents and calibrators to the refrigerator at the end
of the day. During the chamber work, the reagents were stored in the chamber overnight
because of the low temperature (around 57 °F). New reagents and calibrators were used for
each site (i.e., outdoor and chamber conditions).
• The measurement system (photometer) was recharged nightly. The analyst used the
photometer for up to 10 hours without recharging. The manufacturer specifies that 500
measurements can be made on a single battery charge.
• The test kit generated approximately 43 Ib of vials containing soils and liquid solvents
(classified as solid PCB waste suitable for disposal by incineration) and approximately 43 Ib
47
-------
of other solid PCB waste (used and unused soil, gloves, paper towels, ampules, etc.). The test
kit also generated approximately 21 Ib of liquid waste (aqueous with trace methanol).
Performance Summary
A summary of the performance characteristics of EnviroLogix's PCB in Soil Tube Assay, presented previously
in this section, is shown in Table 5-15. The performance of the test kit was characterized as unbiased, because
most (78%) of the PCB in Soil Tube Assay results agreed with the certified PE values, but imprecise, because
nearly half (44%) of the PE replicate results were not reported as the same interval. It should also be noted that
almost all of the imprecision occurred when the concentration of the sample was near one of the test kit's
threshold values (i.e., 1, 10, or 50 ppm). The test kit had no fp and 4% of the soil sample results were fn. For
extract samples, the test kit had no fp or fn results.
48
-------
Table 5-15. Performance summary for the PCB in Soil Tube Assay
Feature/parameter
Blank results
Precision
Accuracy
False positive results
False negative results
Comparison with reference laboratory
results
Regulatory decision-making applicability
Sample throughput
Power requirements
Operator requirements
Cost
Hazardous waste generation
Performance summary
Soils: Correctly reported all 8 samples as [0,1) ppm
Extracts: Correctly reported all 8 samples as [0,1) ppm
Percentage of combined sample sets where all four replicates were
reported as the same interval
PE soils: 56%
Environmental soils: 68%
Extracts: 75%
PE soils Extracts
agreed = 78% agreed = 92%
biased high =10% biased high = 0%
biased low = 13% biased low = 8%
Blank soils: 0% (0 of 8 samples)
Blank extracts: 0% (0 of 8 samples)
PE and environmental soils: 4% (7 of 192 samples)
Spiked extracts: 0% (0 of 16 samples)
PE and environmental soils
agreed = 82%
biased high = 12%
biased low = 7%
PE and environmental soils
(40 to 60 ppm)
agreed = 66%
biased high = 32%
biased low =2%
7 samples/hour (chamber)
8 samples/hour (outdoors)
Photometer with rechargeable battery
Basic knowledge of chemical techniques; 4 hours technology-specific
training
Incremental: $18 per sample
Field lab: $1975 ($965 without photometer); $1250 photometer alone
40 Ib of solid/liquid (classified as solid PCB waste suitable for disposal by
incineration)
40 Ib of solid (used gloves, pipettes, paper towels, etc.)
20 Ib of liquid waste (aqueous with trace methanol)
49
-------
50
-------
Section 6
Technology Update and Representative Applications
Objective
The purpose of this section is to allow the developer to provide information regarding new developments with
its technology since the demonstration activities. In addition, the developer has provided a list of representative
applications in which its technology has been or is currently being used.
Technology Update
At the time of the demonstration, the PCB in Soil Tube Assay was just beginning commercialization, so no
changes to the technology were anticipated by EnviroLogix in the near future.
Representative Applications
A typical application of the PCB in Soil Tube Assay would be at a Superfund site where EPA and the site
contractor were mapping the site for PCB contamination. The PCB immunoassay kit would be used to
determine where the samples should be taken and which samples should be sent off-site to the fixed analytical
laboratory for evaluation. In October 1998, EnviroLogix participated in such a study at a small Superfund
site in Kingston, New Hampshire. Other customers of the PCB immunoassay kit are the U.S. Army Corp of
Engineers, General Electric, Metcalf and Eddy, and the Roy F. Weston Corporation.
Data Quality Objective Example
This application of EnviroLogix's PCB in Soil Tube Assay is based on data quality objective (DQO) methods
for project planning advocated by the American Society for Testing and Materials [9, 10] and EPA [11].
ORNL derived a DQO example from the performance results in Section 5. This example, which is presented
in Appendix E, illustrates the use of the performance data for the test kit from the ETV demonstration in the
DQO process to select the number of samples to characterize the FP and FN error rates for the decision rule.
51
-------
-------
Section 7
References
[1] Erickson, M. D. Analytical Chemistry ofPCBs, 2nd ed., CRC Press/Lewis Publishers, Boca Raton,
Fla., 1997.
[2] "Polychlorinated Biphenyls (PCBs) Manufacturing, Processing, Distribution in Commerce, and Use
Prohibitions," Code of Federal Regulations, 40 CFR, pt. 761, rev. 7, December 1994.
[3] Maskarinec, M.P., et al. Stability of Volatile Organics in Environmental Soil Samples, ORNL/TM-
12128, Oak Ridge National Laboratory, Oak Ridge, Tenn., November 1992.
[4] U.S. Environmental Protection Agency. "Method 8081: Organochlorine Pesticides and PCBs as
Aroclors by Gas Chromatography: Capillary Column Technique," in Test Methods for Evaluating
Solid Waste: Physical/Chemical Methods (SW-846), 3rd ed., Final Update II, Office of Solid Waste
and Emergency Response, Washington, D.C., September 1994.
[5] Oak Ridge National Laboratory. Technology Demonstration Plan: Evaluation of Polychlorinated
Biphenyl (PCB) Field Analytical Techniques, Chemical and Analytical Sciences Division, Oak
Ridge National Laboratory, Oak Ridge, Tenn., September 1998.
[6] U.S. Environmental Protection Agency. Data Quality Objectives for Remedial Response Activities,
EPA 540/G-87/003, EPA, Washington, D.C., March 1987.
[7] Draper, N. R., and H. Smith. Applied Regression Analysis, 2nd ed., John Wiley & Sons, New York,
1981.
[8] Berger, Walter, Harry McCarty, and Roy-Keith Smith. Environmental Laboratory Data Evaluation,
Genium Publishing Corp., Schenectady, N.Y., 1996.
[9] American Society for Testing and Materials (ASTM). Standard Practice for Generation of
Environmental Data Related to Waste Management Activities Quality Assurance and Quality
Control Planning and Implementation, D5283-92, 1997.
[10] American Society for Testing and Materials (ASTM), Standard Practice for Generation of
Environmental Data Related to Waste Management Activities Development of Data Quality
Objectives, D5 792-95, 1997.
[11] U.S. Environmental Protection Agency. Guidance for Data Quality Assessment, EPA QA/G-9;
EPA/600/R-96/084, EPA, Washington, D.C., July 1996.
53
-------
Appendix A
Description of Environmental Soil Samples
55
-------
-------
Table A-l. Summary of soil sample descriptions
Location
Oak Ridge
Oak Ridge
Oak Ridge
Oak Ridge
Oak Ridge
Paducah
Portsmouth
Tennessee
Reference Soil
Request for
Disposal
(RFD)#
40022
40267
24375
43275
134555
97002
7515
n/a
Drum #
02
01
02
03
04
01
02
03
01
02
03
01
02
03
04
858
1069
1096
1898
2143
2528
3281
538
940
4096
n/a
Description
Soil from spill cleanup at the Y-12 Plant in Oak Ridge, Tennessee.
This soil is PCB-contaminated soil excavated in 1992.
Soil from the Elza Gate area, a DOE Formerly Utilized Sites Remedial
Action Program site in Oak Ridge, Tennessee. This soil is PCB-
contaminated soil that was excavated in 1992.
Catch-basin sediment from the K-71 1 area (old Powerhouse Area) at
the DOE East Tennessee Technology Park (formerly known as Oak
Ridge Gaseous Diffusion Plant) in Oak Ridge, Tennessee. This soil is
PCB-contaminated storm drain sediment that was excavated in 1991.
Soil from the K-25 Building area at the DOE East Tennessee
Technology Park (formerly known as Oak Ridge Gaseous Diffusion
Plant) in Oak Ridge, Tennessee. This soil is PCB-contaminated soil
that was excavated in 1993.
Soil from the K-707 area at the DOE East Tennessee Technology Park
(formerly known as Oak Ridge Gaseous Diffusion Plant) in Oak Ridge,
Tennessee. This soil is PCB-contaminated soil from a dike spillage that
was excavated in 1995.
Soil from the DOE Paducah Gaseous Diffusion Plant in Kentucky. This
soil is PCB-contaminated soil from a spill cleanup at the C-746-R
(Organic Waste Storage Area) that was excavated in 1989.
Soil from the DOE Portsmouth Gaseous Diffusion Plant in Ohio. This
soil is PCB-contaminated soil from a probable PCB oil spill into the
East Drainage Ditch that was excavated in 1986.
Captina silt loam from Roane County, Tennessee; used as a blank in
this study (i.e., not contaminated with PCBs)
57
-------
-------
Appendix B
Characterization of Environmental Soil Samples
59
-------
-------
Table B-l. Summary of environmental soil characterization
Location
Oak Ridge
Paducah
Portsmouth
Sample
ID
101
102
103
104
105
106
107
108
109
110
111
112
126, 226
113,201
114,202
115,203
116,204
117,205
206
207
208
209
210
216
211
217
212
213
214
215
RFD
Drum # "
40022-02
40267-03
40267-01
40267-04
40267-01 S6
24375-03
24375-01
40267-02
24375-02
43275-01
134555-03S6
43275-02
non-PCB soil
97002-04
97002-01
97002-03
97002-02
97002-02S b
7515-4096
7515-1898
7515-1096
7515-2143
7515-0940
7515-0538
7515-0538S6
7515-0538S6
7515-2528
7515-3281
7515-0858
7515-1069
Composition
% gravel
0
0.5
0.2
0.6
0.5
0.5
2.5
0.4
0.3
0
0.5
0.1
0
0
0.2
0.1
0.4
0
0.2
0.4
0
0.3
0.5
0.5
0.5
0
1.3
% sand
91.8
99.3
96.7
98.2
94.8
87.8
92.5
94.2
93.1
89.2
88.1
91.4
85.6
92.4
87.6
83.6
93.7
87.1
78.0
74.4
74.3
73.0
73.3
70.4
72.6
65.8
75.0
% silt + clay
8.2
0.2
3.1
1.2
4.7
11.7
5.0
5.4
6.6
10.8
11.4
8.5
14.4
7.6
12.2
16.3
5.8
12.9
21.8
25.2
25.7
26.7
26.3
29.1
26.8
34.2
23.7
Total Organic
Carbon
(mg/kg)
5384
13170
13503
15723
14533
19643
1196
9007
1116
14250
10422
38907
9249
1296
6097
3649
4075
3465
3721
3856
10687
7345
1328
5231
5862
6776
4875
PH
7.12
7.30
7.21
7.07
7.28
7.36
7.26
7.30
7.48
7.57
7.41
7.66
7.33
7.71
7.64
7.59
7.43
7.72
7.66
7.77
7.71
7.78
7.78
7.92
7.67
7.85
7.56
a Request for disposal drum number (see Table A-l).
b "S" indicates that the environmental soil was spiked with additional PCBs.
61
-------
-------
Appendix C
Temperature and Relative Humidity Conditions
63
-------
Table C-l. Average temperature and relative humidity conditions during testing periods
Date
9/21/98
9/22/98
9/23/98
9/24/98
9/25/98
Outdoor site
Average
temperature
(°F)
a
a
82
78
74
Average
relative humidity
(%)
a
a
43
56
59
Chamber site
Average
temperature
(°F)
57
57
56
a
a
Average
relative humidity
(%)
46
46
52
a
a
a The developer was working at the other site on this day.
64
-------
90
~, 80
LL
d> 70
5. 60
1 5°
2 40
-------
9/21/98
9/22/98
9/23/98
Figure C-3. Summary of temperature conditions for chamber site.
JD
E
'•5
jD
0)
9/21/98
9/22/98
9/23/98
Figure C-4. Summary of relative humidity conditions for chamber site.
66
-------
Appendix D
PCB in Soil Tube Assay
PCB Technology Demonstration Sample Data
-------
Legend for Appendix D Tables
Table Heading
Obs
Sample ID
Rep
EnviroLogix Result
Ref Lab Result
Reference Aroclor
Type
Spike
Order
Definition
Observation
Sample identification
101 to 126 = outdoor site soil samples
127 to 130 = outdoor site extract samples
201 to 226 = chamber site soil samples
227 to 230 = chamber site extract samples
Replicate of sample ID (1 through 4)
PCB in Soil Tube Assay's measured PCB concentration (ppm)
LAS reference laboratory measured PCB concentration (ppm)
Values with "<" are samples that the reference laboratory
reported as "< reporting detection limit"
Aroclor(s) identified by the reference laboratory
Sample = environmental soil
1016, 1248, 1254, 1260 = Aroclor in PE soil samples or
extract spiking solutions
Blank = non-PCB-contaminated sample
Nominal spike concentrations ((jg/mL) of extract solutions
prepared by ORNL
Order of sample analysis by EnviroLogix (started with
200 1-2 11 6, then 1001-1116)
68
-------
Table D-l. PCB in Soil Tube Assay technology demonstration soil sample data
Sample EnviroLogix Ref Lab Reference
Obs ID Rep Result Result Aroclor Type Order
(ppm) (ppm)
1 101 1 [0,1)
69
-------
Sample EnviroLogix
Obs ID Rep Result
(ppm)
Ref Lab Reference
Result Aroclor
(ppm)
Non-Detect
Non-Detect
Non-Detect
Non-Detect
Type
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
1248
1248
1248
1248
Order
1248
1248
1248
1248
81
82
83
84
88
70
-------
Sample EnviroLogix
Obs ID Rep Result
(ppm)
Ref Lab Reference
Result Aroclor
(ppm)
Type
Order
Non-Detect
Non-Detect
Non-Detect
Non-Detect
Blank
Blank
Blank
Blank
1248
1248
1248
1248
1248
1248
1248
1248
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
71
-------
Obs
Sample
ID
Rep
EnviroLogix
Result
(ppm)
Ref Lab Reference
Result Aroclor
(ppm)
1248
1248
1248
1248
Type
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
Sample
1248
1248
1248
1248
Order
72
-------
Sample EnviroLogix
Obs ID Rep Result
(ppm)
Ref Lab Reference
Result Aroclor
(ppm)
Type
1248
1248
1248
1248
Order
Non-Detect
Non-Detect
Non-Detect
Non-Detect
Blank
Blank
Blank
Blank
73
-------
Table D-2. PCB in Soil Tube Assay technology demonstration extract sample data
Obs
Sample
ID
Rep
EnviroLogix
Result
(ppm)
Spike "
(ug/mL)
Type
1248
1248
1248
1248
Order
Blank
Blank
Blank
Blank
1248
1248
1248
1248
Blank
Blank
Blank
Blank
2 Nominal spike concentration of the extract sample prepared by ORNL.
74
-------
Table D-3. Corrected reference laboratory data
Error
Transcription
Calculation
Interpretation
Sample ID
106
130
205
207
210
118
119
209
214
219
101 a
101 a
107
109
1136
1136
119
127
201
219
Reported Result
(ppm)
<490
5.6
32,000
180
160
3.6
4.3
2.3
43.0
29.0
<0.7
<0.7
<1.3
18.0
<0.9
<1.0
18.0
7.2
< 1.0
21.0
Corrected Result
(ppm)
255.9
10.3
3,305.0
17.8
123.2
2.1
17.4
37.9
26.0
22.4
0.5
0.6
1.2
1.5
0.6
0.7
21.2
10.9
0.6
26.0
a Two of four measurements in sample ID 101 were corrected.
Two of four measurements in sample ID 113 were corrected.
75
-------
-------
Appendix E
Data Quality Objective Example
77
-------
-------
Disclaimer
The following hypothetical example serves to demonstrate how the information provided in this report may be
used in the data quality objectives (DQO) process. This example serves to illustrate the application of
quantitative DQOs to a decision process, but it cannot attempt to provide a thorough education in this topic.
Please refer to other educational or technical resources for further details. In addition, since the focus of this
report is on the analytical technology, this example makes the simplifying assumption that the contents of these
drums is homogeneous. In the real world, this assumption is seldom valid, and matrix heterogeneity constitutes
a source of considerable uncertainty that must be adequately evaluated if the overall certainty of a site decision
is to be quantified.
Background and Problem Statement
An industrial company discovered a land area contaminated with PCBs from an unknown source. The
contaminated soil was excavated into waste drums. The drums are to be treated as Resources Conservation and
Recovery Act (RCRA) waste if the PCB concentration of their contents is <50 ppm and as Toxic Substances
Control Act (TSCA) waste if their PCB concentration is >50 ppm. The company's DQO team was considering
the use of EnviroLogix's PCB in Soil Tube Assay kit to measure the PCB concentration in each drum. The
plan was to randomly collect soil samples from each drum and test them with the kit to determine if the
measured concentrations fell within one of four intervals: [0, 1), [1, 10), [10, 50), or [50, °°). (Recall that this
notation describes the concentration ranges 0 ppm < PCB < 1 ppm, 1 ppm < PCB < 10 ppm, 10 ppm < PCB
< 50 ppm and PCB > 50 ppm, as used in Section 5.) The DQO team decided that a drum would be processed
as TSCA waste if any of the test kit results indicated a concentration in the intervals [50, °°); otherwise, the
drum would be processed as RCRA waste. In agreement with the regulator, the DQO team determined that a
decision rule for processing the waste would be based on the number of samples with PCB concentrations in
the intervals [50, °°).
General Decision Rule
If all of the PCB sample results show concentrations < [50, °°), then process the soil drum by RCRA
methods.
If any of the PCB sample results are in the intervals [50, °°) then process the soil drum by TSCA
methods.
DQO Goals
Section 1.2 of EPA's Guidance for Data Quality Assessment states: "The true condition that occurs with the
more severe decision error... should be defined as the null hypothesis."1 The DQO team decided that the more
severe decision error would be for a drum to be erroneously processed as RCRA waste if the drum's PCB
concentration actually exceeded the 50 ppm limit. Therefore, the null hypothesis is constructed to assume that
a drum's true PCB concentration exceeds the 50 ppm limit; as a "hot" drum, it would be processed as TSCA
1. U.S. Environmental Protection Agency, Guidance for Data Quality Assessment, EPA QA/G-9; EPA/600/R-96/084, EPA,
Washington, B.C., July 1996.
79
-------
waste. Drums would be processed as RCRA waste only if the null hypothesis is rejected and it is concluded
that the "true" average PCB concentration is less than 50 ppm.
With the null hypothesis defined in this way, a false positive decision is made when it is concluded that a drum
contains <50 ppm PCBs (i.e., the null hypothesis is rejected), when actually the drum is hot (i.e., the null
hypothesis is true). The team required that the error rate for processing a hot drum as RCRA waste (i.e., FP
= the false positive error rate for the decision) should be 5% or less. This error rate is expressed either as a
percentage or as a probability. Therefore, a sufficient number of samples must be taken from each drum so that
the false positive decision error rate (FP) is 0.05 (or less) if the true drum concentration is >0 ppm. This
scenario represents a maximum risk of 5% for processing a drum containing 50 ppm or more of PCBs as
RCRA waste.
The DQO team did not want to process an excessive number of drums as TSCA waste if the average PCB
concentration was <50 ppm because of the expense. In this situation, a false negative decision is made when
it is concluded that a drum is hot (i.e., the null hypothesis is not rejected), when in actuality, the drum contains
soil with <50 ppm PCBs (i.e., the null hypothesis is actually false). After considering the guidelines presented
in Section 1.1 of EPA's Guidance for Data Quality Assessment, the DQO team recommended that the false
negative decision error rate (FN) be 0.10 if the true drum concentration was <50 ppm. That is, there would be
a 10% chance of processing a drum as TSCA waste (e.g., FN = Pr[Falsely Processing a Drum as TSCA
waste]) if the true PCB concentration for a drum was <50 ppm.
Permissible FP and FN Error Rates and Critical Decision Point
FP: Pr[Drum is RCRA waste] < 0.05 when true PCB concentration > 50 ppm
FN: Pr[Drum is TSCA waste] < 0.10 when true PCB concentration < 50 ppm
Use of Technology Performance Information to Implement the Decision Rule
Technology performance information is used to evaluate whether a particular analytical technology can produce
data of sufficient quality to support the site decision. Because the DQO team is considering the use of the
EnviroLogix PCB kit, the performance of this technology [as reported in this Environmental Technology
Verification (ETV) report] was used to assess its applicability to this project. The question arises: How many
samples are needed from a single drum to permit a statistically valid decision at the specified certainty? Recall
that the simplifying assumption was made that the PCB distribution throughout the soil within a single drum
is homogeneous, and thus, matrix heterogeneity will not contribute to overall variability. The only variability
to be considered in this example, therefore, is the variability in performance of the EnviroLogix test kit's
analytical method, which is determined by precision and accuracy studies.
Determining the Number of Samples
The number of samples needed to satisfy the FP and FN requirements depends on the misclassification error
rates of the PCB test kit. Two types of misclassifications have to be considered:
80
-------
1. underestimating the PCB concentration—i.e., classifying a sample concentration to be <50 ppm when the
true PCB concentration is >50 ppm
2. overestimating the PCB concentration—i.e., classifying a sample concentration to be >50 ppm when the
PCB concentration is <50 ppm.
The DQO team compared the experimental conditions for the EnviroLogix ETV demonstration with their
expected project conditions for variables such as soil type and ambient conditions. The team determined that
the relevant variables would be sufficiently similar so that misclassification rates determined from the ETV
demonstration would be adequately predictive of rates for their project. The DQO team then used the ETV data
to prepare Table E-l to assess the misclassification rates around the 50 ppm action level using all performance
evaluation (PE) and environmental soil samples. Table E-l summarizes a sample-by-sample comparison of
the reference lab results with the results generated by the EnviroLogix kit (see Appendix D).
Table E-l. Comparison of PCB in Soil Tube Assay results with the reference laboratory at 50 ppm level
Reference laboratory
results
Greater or equal to 50 ppm
Less than 50 ppm
PCB in Soil Tube Assay results
[0, 1) or [1, 10) or [10, 50)
2
139
[50, co)
43
16
Number of samples
(PE + environmental soils)
45
155
Table E-l can be used to estimate the two types of misclassifications as
PJJ = Pr [Underestimating the PCB concentration] = 2/45 = 0.044 when reference values > 50 ppm,
P0 = Pr [Overestimating the PCB concentration] = 16/155 = 0.103 when reference values < 50 ppm.
The probability distribution of classifying the number of soil samples in different concentration intervals
follows a binomial probability distribution.2 This probability distribution and the requirements for FP and FN
can be used to determine the number of samples to meet the DQO goals. The FP for the decision rule is related
to 7^ by
FP = Pr[All EnviroLogix results < 50ppm for PCB > 50ppm] =
(E-l)
The FP error rate decreases as the sample size increases. The sample size is solved as
2 Lothar Sachs, Applied Statistics: A Handbook of Techniques, 2nd ed., Springer-Verlag, New York, 1984.
81
-------
Log(FP)
n = —£i L
Log(Pu}
where
n = number of samples from a drum to be measured
FP = false positive decision error rate (e.g., FP = 0.05)
Pv = probability of underestimating the PCB concentration
n = Log(0.05) = -1.301 = Q %
Zog(0.044) -1.357
The sample size was rounded up to the next integer, an operation that will decrease the FP for the decision rule.
The DQO team would have to analyze only one sample from each drum to meet the decision rule's FP
requirement. The FN for the decision rule is related to P0 by
FN = Pr[Some of EnviroLogix results > 50ppm for PCB < 50ppm] = 1 - (1 - Po)n . (E-3)
The error rate of a false negative decision actually increases with increasing sample size because the chance
that the kit will overestimate a concentration increases with continued testing. The sample size required to meet
the FN requirement is
Log( 1 - FN)
-
where
n = number of samples from a drum to be measured
FN = false negative decision error rate (e.g., FN = 0.10)
P0 = probability of overestimating a PCB concentration
Log(l - 0.10) = -0.046 = Q
Log(l - 0.103) -0.047
82
-------
The sample size must be rounded up to n = 1 (fractions of a sample analysis are not possible). When n = 1,
the value of FN = 10.3% which is only slightly higher than the DQO team's goal of 10% FN. This situation
occurs because the 10.3% overestimation error rate of the kit is nearly equal to 10%. If additional samples were
taken, FN would increase (e.g., for n = 2, FN = 19.5%) and might not meet the DQO team's goal. The only
way to reduce the FN in this scenario is to use an analytical technology with a lower overestimation error rate.
The DQO team in this example decided that the sampling procedure would be to randomly select one soil
sample from each drum and test the sample with the EnviroLogix's PCB in Soil Tube Assay kit. (Recall that
for the purposes of this example, the soil in the drum has been assumed to be homogeneous.) The DQO team
would process the drum as RCRA waste if the EnviroLogix result was less than 50 ppm, and process the drum
as TSCA waste if the EnviroLogix result was greater than 50 ppm. The DQO team's goals of a 5% FP and
a 10% FN would be closely met by this sampling plan.
Decision Rule for 5% FP and 10% FN
If one randomly selected soil sample has a PCB test result reported in an interval less than [50, °°), then
process the soil drum as RCRA waste.
If one randomly selected soil sample has a PCB test result in the interval [50, °°), then process the soil
drum as TSCA waste.
Alternative FP Parameter
The following statement describes how changing the FP requirement from 5% to 0.1 % would affect the decision
rule. Using FP = 0.001, the calculated sample sizes would be n = 2.2, which is rounded up to 3. The FN would
be 28%. The higher FN occurs because any of the three samples have a 10.3% chance of being overestimated,
and if only one is overestimated, the drum is processed as TSCA waste. The decision rule for the lower FP
requirement would be as shown.
Decision Rule for FP = 0.1% and FN = 28%
If all three randomly selected soil samples have PCB test results reported in intervals less than 50 ppm,
then process the soil as RCRA waste.
If any of the three randomly selected soil samples have a PCB test result in the interval [50, °°), then
process the soil drum TSCA waste.
83
------- |