<pubnumber>601R99009</pubnumber>
<title>Technology Demonstration Plan Evaluation of Explosives Field Analytical Techniques</title>
<pages>50</pages>
<pubyear>1999</pubyear>
<provider>NEPIS</provider>
<access>online</access>
<origin>PDF</origin>
<author></author>
<publisher></publisher>
<subject></subject>
<abstract></abstract>
<operator>mja</operator>
<scandate>11/28/23</scandate>
<type>single page tiff</type>
<keyword></keyword>
Environmental Security
Technology Certification
Program
August 1999
Technology Demonstration Plan
Evaluation of Explosives Field Analytical Techniques
Sponsored by:
U. S. Environmental Protection Agency
National Exposure Research Laboratory
Las Vegas, NV 89193-3478
and
U.S. Department of Defense
Office of the Deputy under Secretary of Defense for Environmental Security
Environmental Security Technology Certification Program
Washington, DC 20301-3400
Prepared by:
Oak Ridge National Laboratory
Lockheed Martin Energy Research Corporation
Oak Ridge, TN 37831-6120
US Army Corps
of Engineers*
Cold Regions Research &
Engineering Lfcbur^tury
oml
image:
APPROVAL SIGNATURES
This document is intended to ensure that all aspects of the demonstration are documented, scientifically sound,
and that operational procedures are conducted within quality assurance/quality control specifications and health
and safety regulations.
The signatures of the individuals below indicate concurrence with, and agreement to operate compliance with,
procedures specified in this document.
U. S. ENVIRONMENTAL PROTECTION AGENCY, ETV Program
Project Manager:
Eric Koglin
ESD Quality Manager:
George Brilis
U. S. DEPARTMENT OF DEFENSE, ESTCP Program
Program Manager:
Cathy Vogel Date
U. S. DEPARTMENT OF ENERGY, Oak Ridge Operations Office
Program Manager:
Regina Chung Date
OAK RIDGE NATIONAL LABORATORY
Program Manager:
Roger Jenkins, Ph.D. Date
Technical Expert:
Michael Maskarinec, Ph.D. Date
Technical Lead:
Amy Dindal Date
QA Specialist:
Janet Wagner Date
Date
Date
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Statistician:
Charles Bayne, Ph.D.
SITE APPROVAL
ES&H Officer:
Fred Smith
TECHNOLOGY DEVELOPERS
Barringer Instruments:
John Avolio
Research International Inc.:
Elric Saaski
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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 Department of Defense (DoD) Environmental Security Technology Certification Program's
(ESTCP) goal is to demonstrate and validate promising, innovative technologies that target DoD's most urgent
environmental needs. The ETV and ESTCP can meet their common goal by working with technology
developers in planning and conducting demonstrations, evaluating the data generated, and promoting acceptance
of the technology. In addition to a detailed technical report, ETV provides the developers with a verification
statement, which summarizes the performance of the technology under the conditions of the demonstration.
ESTCP provides a cost and summary report and aids in the dissemination of the results across the DoD.
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.
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TABLE OF CONTENTS
FOREWORD iii
EXECUTIVE SUMMARY \ iii
ABBREVIATIONS AND ACRONYMS ix
1.0 INTRODUCTION 1
1.1 Demonstration Objectives 1
1.2 What is the Environmental Technology Verification Program? 1
1.3 Technology Verification Process 2
1.3.1 Needs Identification and Technology Selection 2
1.3.2 Demonstration Planning and Implementation 2
1.3.3 Report Preparation 3
1.3.4 Information Distribution 3
1.4 Purpose of this Demonstration Plan 3
2.0 DEMONSTRATION RESPONSIBILITIES AND COMMUNICATION 3
2.1 Demonstration Organization and Participants 3
2.2 Organization 4
3.0 TECHNOLOGY DESCRIPTION 6
3.1 Barringer Instruments'GC-IONSCAN 6
3.1.1 Technology Overview 6
3.1.2 Sample Preparation and Analysis Procedure 7
3.1.3 Instrument Calibration 7
3.2 Research International/Naval Research Laboratory's FAST 2000 7
3.2.1 General Technology Description 7
3.2.2 Instrument Calibration 8
3.2.3 Sample Analysis 8
3.2.3.1 Groundwater Samples 8
3.3 Performance Characteristics 8
4.0 CONFIRMATORY PROCESS 9
4.1 Method Selection 9
4.2 Reference Laboratory Selection 9
4.3 Laboratory Audit 9
4.4 Validation and Evaluation of Reference Laboratory Data 9
4.4.1 Data Validation 10
4.4.1.1 Completeness of Laboratory Records 10
4.4.1.2 Holding Times 10
4.4.1.3 Correctness of Data 10
4.4.1.4 Correlation Between Replicates 10
4.4.1.5 Evaluation of QC Results 10
4.4.1.6 Evaluation of Spiked Sample Data 10
4.4.2 Data Analysis 11
5.0 DEMONSTRATION SITE AND SAMPLE DESCRIPTIONS 11
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5.1 Demonstration Testing Location 11
5.2 Soil Sample 11
5.2.1 Iowa Army Ammunition Plant 11
5.2.2 Louisiana Army Ammunition Plant 12
5.2.3 Milan Army Ammunition Plant 13
5.2.4 Volunteer Army Ammunition Plant 13
5.2.5 Fort Ord Military Base 13
5.3 Water Sample Descriptions 13
5.3.1 Louisiana Army Ammunition Plant 13
5.3.2 Milan Army Ammunition Plant 13
5.3.3 Umatilla Chemical Depot 14
5.3.4 Volunteer Army Ammunition Plant 14
5.4 Sample Preparation 14
5.4.1 Sample Collection Procedures 14
5.4.2 Sample Preparation for Demonstration 14
5.4.2.1 Soil Samples 14
5.4.2.2 Water Samples 14
5.4.3 Sample Labeling 15
5.4.4 Sample Storage 15
6.0 PREDEMON STRATI ON STUDY 15
6.1 Predemonstration Sample Distribution 15
6.2 Predemonstration Results 15
7.0 EXPERIMENTAL DESIGN 16
7.1 Objectives 16
7.2 Experimental Performance Measures 16
7.2.1 Qualitative Performance measures 16
7.2.2 Quantitative Performance measures 16
7.3 Summary of Demonstration Design 16
7.4 Field Data 17
7.5 Demonstration Schedule 17
7.6 Field Operations 17
7.6.1 Communication and Documentation 17
7.6.2 Sample Distribution 18
7.6.3 Archive Samples 18
7.7 Evaluation of Performance Factors 18
7.7.1 Precision 18
7.7.2 Accuracy 19
7.7.3 Representativeness 19
7.7.4 Completeness 19
7.7.5 Comparability 19
7.7.6 False Positive/Negative Results 20
7.7.7 Detection Limits 20
7.7.8 Sample Throughput 20
7.7.9 Ease of Use 20
7.7.10 Miscellaneous Factors 21
8.0 QUALITY ASSURANCE PROJECT PLAN (QAPP) 21
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8.1 Quality Assurance Responsibilities 21
8.2 Data Validation 21
8.3 Data Quality Indicators 21
8.4 Calibration Procedures and Quality Control Checks 21
8.4.1 Initial Calibration Procedures 21
8.4.2 Continuing Calibration Procedures 22
8.4.3 Method Blanks 22
8.4.4 Matrix Spike Samples 22
8.4.5 Laboratory Control Samples 22
8.4.6 Surrogate Recovery 22
8.4.7 Spiked Samples 22
8.4.8 Replicate Samples 23
8.5 Data Reduction, Review, and Reporting 23
8.5.1 Data Reduction 23
8.5.1.1 Quantitative (Continuous) Data 23
8.5.1.2 Semi-quantitative (Interval) Data 23
8.5.2 Data Review 23
8.6 Audits 25
8.6.1 Technical Systems Audit 25
8.6.2 Performance Audit 25
8.6.3 On-Site System Audits 25
8.7 Quality Assurance Reports 25
8.7.1 Status Reports 25
8.7.2 Audit Reports 25
8.8 Corrective Actions 25
9.0 HEALTH AND SAFETY PLAN 26
9.1 Introduction 26
9.2 Contact Information 26
9.3 Health and Safety Plan Enforcement 26
9.4 Site Location 26
9.5 Site Access 26
9.6 Training Requirements 26
9.7 Technology-Specific Hazards 26
9.8 Demonstration Site Hazards 27
9.8.1 Chemical Hazards 27
9.8.2 Physical Hazards 27
9.8.3 Mechanical, Electrical, Noise Hazards 27
9.8.4 Inclement Weather 27
9.8.5 Heat Stress 27
9.8.6 Insect and Other Animal Stings and Bites 27
9.8.7 Fire 28
9.8.8 Radiological Hazards 28
9.9 Personal Protection 28
9.10 Emergency Support 28
9.11 Environmental Surveillance 28
9.12 Hazardous Waste Disposal 28
9.13 Site Control 28
9.14 Safe Work Practices 28
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9.15 Complaints 29
REFERENCES 30
APPENDIX A 32
LIST OF FIGURES
2-1. Organizational Chart 4
5-la. Overview of Oak Ridge Reservation 12
5-lb. Close-up of Freels Bend Area 12
LIST OF TABLES
2-1. Participants in Explosives Detection Technology Demonstration 5
7-1. Experimental Design Features 17
8-1. Specialized Assays Inc. Acceptance Criteria for MS/MSD 24
8-2. Example of reporting intervals 24
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EXECUTIVE SUMMARY
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 the EPA's National Exposure Research Laboratory in Las Vegas, Nevada. For the verification of explosives
field analytical technologies, ETV is working in partnership with the Department of Defense (DoD)
Environmental Security Technology Certification Program (ESTCP). ESTCP's goal is to demonstrate and
validate promising, innovative technologies that target DoD's most urgent environmental needs. ETV and
ESTCP can meet their common goal by working with technology developers in planning and conducting
demonstrations, evaluating the data generated, and promoting acceptance of the technology.
This technology demonstration plan has been developed to describe the verification of field analytical
technologies for the determination of explosives compounds in contaminated soil and groundwater.
Technologies from Barringer Instruments (GC-IONSCAN) and Research International Inc. (FAST 2000) will
be evaluated. The Oak Ridge National Laboratory (ORNL) will serve as the verification organization for the
demonstration, with the U.S. Army Cold Regions Research and Engineering Laboratory providing technical
guidance and support. ORNL's role is to provide technical and administrative leadership in conducting the
demonstration.
The purpose of this demonstration is to obtain performance information regarding the technologies, to
compare the results to conventional fixed-laboratory results, and to provide supplemental information (e.g., cost,
sample throughput, and training requirements) regarding the operation of the technology. Multiple soil types,
collected from sites in California, Louisiana, Iowa, and Tennessee, will be used in this study. In addition,
explosives-contaminated water samples from Tennessee, Oregon, and Louisiana will also be evaluated. The
concentrations will range from 0 to approximately 90,000 mg/kg . Water samples will range in concentration
from 0 to 25,000 |ig/L. The primary constituents in the samples are expected to be 1,3,5-trinitrotoluene (TNT),
isomeric dinitrotoluene (DNT),hexahydro-l,3,5-trinitro-l,3,5-triazine (RDX), andoctahydro-l,3,5,7-tetranitro-
1,3,5,7-tetrazocine (HMX).
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ABBREVIATIONS AND ACRONYMS
AAP
Army Ammunition Plant
2-Am-DNT
2-amino-4,6-dinitrotoluene, CAS # 35572-78-2
4-Am-DNT
4-amino-2,6-dinitrotoluene, CAS # 1946-51-0
ANOVA
Analysis of Variance
Cy5
cyano-based fluorescent dye
CASD
Chemical and Analytical Sciences Division
CFI
Continuous Flow Immunosensor
CRREL
U. S. Army Cold Regions Research and Engineering Laboratory
DL
detection limits
2,4-DNT
2,4-dinitrotoluene, CAS # 121-14-2
2,6-DNT
2,6-dinitrotoluene, CAS # 606-20-2
DNT
isomeric dinitrotoluene (includes both 2,4-DNT and 2,6-DNT)
DoD
U. S. Department of Defense
ELISA
enzyme linked immunosorbent assay
EPA
U. S. Environmental Protection Agency
ERA
Environmental Resource Associates
ESD-LV
Environmental Science Division-Las Vegas
ESH&Q
Environmental Safety, Health, and Quality
ESTCP
Environmental Security Technology Certification Program
ETV
Environmental Technology Verification Program
ETVR
Environmental Technology Verification Report
fn
false negative result
fp
false positive result
GC
gas chromatography
HASP
Health and Safety Plan
HMX
Octahydro-l,3,5,7-tetranitro-l,3,5,7-tetrazocine, CAS # 2691-41-0
HPLC
High performance liquid chromatography
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IMS
ion mobility spectrometry
LAAAP
Louisiana Army Ammunition Plant
LCS
Laboratory Control Sample
LMER
Lockheed Martin Energy Research
MLAAP
Milan Army Ammunition Plant
MS/MSD
matrix spike/matrix spike duplicate
MSDS
Material Safety Data Sheets
NRL
Naval Research Laboratory
ORNL
Oak Ridge National Laboratory
PARCC
precision, accuracy, representativeness, completeness, comparability
PE
performance evaluation
PPE
personal protective equipment
ppm
parts per million, mg/kg for soil
ppb
parts per billion, |ig/L for water
QA
quality assurance
QAPP
Quality Assurance Project Plan
QAS
Quality Assurance Specialist
QC
quality control
RDX
Hexahydro-l,3,5-trinitro-l,3,5-triazine, CAS # 121-82-4
RPD
relative percent difference
RSD
percent relative standard deviation
SAI
Specialized Assays Inc.
SCMT
Site Characterization and Monitoring Technologies Pilot of ETV
SD
standard deviation
SITE
Superfond Innovative Technology Evaluation program
SVOCs
semivolatile organic compounds
TNB
1,3,5-trinitrobenzene, CAS # 99-35-4
TNT
2,4,6-trinitrotoluene, CAS # 118-96-7
X
image:
USACE
U.S. Army Corp of Engineers
VOCs
volatile organic compounds
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1.0 INTRODUCTION
This chapter discusses the purpose of the demonstration and the demonstration plan, describes the
elements of the demonstration plan, and provides an overview of the Environmental Technology Verification
(ETV) Program and the technology verification process.
1.1 Demonstration Objectives
The purpose of this demonstration is to evaluate the performance of commercially available field
analytical technologies for performing explosives analyses in water and/or soil samples. Specifically, this plan
defines the following elements of the demonstration:
Roles and responsibilities of demonstration participants;
Procedures governing demonstration activities such as sample collection, preparation,
analysis, data collection, and interpretation;
Experimental design of the demonstration;
Quality assurance (QA) and quality control (QC) procedures for conducting the
demonstration and for assessing the quality of the data generated from the
demonstration; and,
Health and safety requirements for performing work at hazardous waste sites.
1.2 What is the Environmental Technology Verification Program?
The U.S. Environmental Protection Agency (EPA) has created the Environmental Technology
Verification Program (ETV) to facilitate the deployment of innovative or improved environmental technologies
through performance verification and dissemination of information. The goal of the ETV Program is to further
environmental protection by substantially accelerating the acceptance and use of improved and cost-effective
technologies. ETV seeks to achieve this goal by providing high quality, peer reviewed data on technology
performance to those involved in the design, distribution, financing, permitting, purchase, and use of
environmental technologies.
ETV works in partnership with recognized standards and testing organizations, stakeholder groups
which consist of regulators, buyers, and vendor organizations, and with the full participation of individual
technology developers. The Program evaluates the performance of innovative technologies by developing test
plans that are responsive to the needs of stakeholders, conducting field or laboratory tests (as appropriate),
collecting and analyzing data, and preparing peer reviewed reports. All evaluations are conducted in accordance
with rigorous quality assurance protocols to ensure that data of known and adequate quality are generated and
that the results are defensible.
ETV is a voluntary program that seeks to make objective performance information available to all of
the actors in the environmental marketplace for their consideration and to assist them in making informed
technology decisions. ETV does not rank technologies nor compare their performance, label or list technologies
as acceptable or unacceptable, nor seek to determine "best available technology", nor approve or disapprove
technologies. The program does not evaluate technologies at the bench- or pilot-scale and does not conduct or
support research.
The program now operates twelve pilots covering a broad range of environmental areas. ETV has
begun with a 5-year pilot phase (1995-2000) to test a wide range of partner and procedural alternatives in
various pilot areas, as well as the true market demand for and response to such a program. In these pilots, EPA
utilizes the expertise of partner "verification organizations" to design efficient processes for conducting
performance tests of innovative technologies. EPA has selected its partners from both the public and private
sectors including Federal laboratories, states, industry consortia, and private sector facilities. 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.. This
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demonstration will be administered by the Site Characterization and Monitoring Technology (SCMT) Pilot
[Note: To learn more about ETV, go to ETV's Internet Web site at the following address:
http ://www. epa. gov/etv].
1.3 Technology Verification Process
The technology verification process is intended to serve as a template for conducting technology
demonstrations that will generate high quality data which can be used 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
1.3.1 Needs Identification and Technology Selection
The first step in the technology verification process is to determine technology needs of the user-
community (typically state and Federal regulators and the regulated community). Each Pilot utilizes stakeholder
groups. Members of the stakeholder groups come from EPA, the Departments of Energy and Defense, industry,
and state regulatory agencies. The stakeholders are invited to identify technology needs and to assist in finding
technology developers with commercially available technologies that meet the needs. Once a technology need
is established, a search is conducted to identify suitable technologies. 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. The following
criteria are used to determine whether a technology is a good candidate for the verification:
Meets user needs
May be used in the field or in a mobile laboratory
Applicable to a variety of environmentally impacted sites
High potential for resolving problems for which current methods are unsatisfactory
Costs are competitive with current methods
Performance is better than current methods in areas such as data quality, sample preparation, or
analytical turnaround
Uses techniques that are easier and safer than current methods
Is commercially available and field-ready.
1.3.2 Demonstration Planning and Implementation
After a developer agrees to participate, EPA, the Verification Organization, and the developer meet to
discuss each participants responsibilities in the demonstration process. In addition, the following issues are
addressed:
Site selection. Identifying sites that will provide the appropriate physical or chemical environment,
including contaminated media
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, QA/QC, health and safety considerations, scheduling of field and laboratory operations, data
analysis procedures, and reporting requirements
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1.3.3 Report Preparation
Innovative technologies are evaluated independently and, when possible, against conventional
technologies. The technologies being verified are operated by the developers in the presence of independent
observers. The observers are EPA staff, state staff or from a independent third-party organization. The data
generated during the demonstration are used to evaluate the capabilities, limitations, and field applications of
each technology. A data summary and detailed evaluation of each technology are published in an Environmental
Technology Verification Report (ETVR). The original complete data set is available upon request.
An important component of the ETVR is the Verification Statement. Verification
Statements of three to five pages, using the performance data contained in the report, are issued by EPA and
appear on the ETV Internet Web page. The Verification Statement is signed by representatives of EPA and the
Verification Organization.
1.3.4 Information Distribution
Producing the ETVR and the Verification Statement represents a first step in the ETV outreach efforts.
ETV gets involved in many activities to showcase the technologies that have gone through the verification
process. The Program is represented at many environmentally-related technical conferences and exhibitions.
ETV representatives also participate in panel sessions at major technical conferences. ETV maintains a traveling
exhibit that describes the program, displays the names of the companies that have had technologies verified, and
provides literature and reports.
We have been taking advantage of the Web by making the ETVRs available for downloading to anyone
interested. The ETVRs and the Verification Statements are available in Portable Document Format (.pdf) on
the ETV Web site (http://www.epa.gov/etv).
1.4 Purpose of this Demonstration Plan
The purpose of the demonstration plan is to describe the procedures that will be used to verify the
performance goals of the technologies participating in this demonstration. This document incorporates the
QA/QC elements needed to provide data of appropriate quality sufficient to reach a credible position regarding
performance. This is not a method validation study, nor does it represent every environmental situation which
may be appropriate for these technologies. But it will provide data of sufficient quality to make a judgement
about the application of the technology under conditions similar to those encountered in the field under normal
conditions.
2.0 DEMONSTRATION RESPONSIBILITIES AND COMMUNICATION
This section identifies the organizations involved in this demonstration and describes the primary
responsibilities of each organization. It also describes the methods and frequency of communication that will
be used in coordinating the demonstration activities.
2.1 Demonstration Organization and Participants
Participants in this demonstration are listed in Table 2-1. The specific responsibilities of each
demonstration participant are discussed in Section 2.3 This demonstration is being coordinated by Oak Ridge
National Laboratory (ORNL) under the direction ofthe U.S. Environmental Protection Agency's (EPA) Office
of Research and Development, National Exposure Research Laboratory, Environmental Sciences Division - Las
Vegas, Nevada (ESD-LV) and the U. S. Department of Defense's Environmental Security Technology
Certification Program (ESTCP), Washington, DC. The U.S. Army Cold Regions Research and Engineering
Laboratory (CRREL) is assisting ESTCP by providing technical guidance and support to ORNL. ESD-LV and
ESTCP's roles are to administer the demonstration program. ORNL's role is to provide technical and
administrative leadership and support in conducting the demonstration. Barringer Instruments and Research
International Inc. are the technology developers participating in this demonstration. Note that the Naval
Research Laboratory, which developed the FAST 2000 technology that was licensed to Research International,
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will be performing the on-site analysis.
2.2 Organization
In Figure 2-1 is presented an organizational chart depicting the lines of communication for the
demonstration. Note that the double-arrow lines signify that each participant is encouraged to openly
communicate with other members of the demonstration team.
US Army
CRREL
Hanover. NH
Technology
Developer
EPA Project
Management
Team
Las Vegas, NV
ORNL
Verification
Organization
Oak Ridge, TN
DoD ESTCP
Office
Washington,
DC
Reference
Laboratory
(SAI)
1
Site Personnel
Figure 2-1. Organizational chart.
2.3 Responsibilities
The following is a delineation of each participant's responsibilities for the demonstration. Henceforward,
the term "developer" applies to Barringer Instruments and Research International, Inc./Naval Research
Laboratory.
The Developer, in consultation with ORNL, ESTCP, and EPA, is responsible for the following elements of this
demonstration:
Contribute to the design and preparation of the demonstration plan;
Provide detailed procedures for using the technology;
Prepare the technology for demonstration;
Operating the technology during the demonstration;
Documenting the methodology and operation of the technology during the
demonstration;
Furnishing data in a format that can be compared to reference values;
Logistical and other support, as required.
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Table 2-1. Participants in Explosives Detection Technology Demonstration
Organization
Point(s) of Contact
Role
Oak Ridge National Laboratory
P.O. Box 2008
Bethel Valley Road
Bldg. 4500S, MS-6120
Oak Ridge, TN 37831-6120
Program Manager: Roger Jenkins
phone: (423) 576-8594
fax: (423) 576-7956
email: jenkinsra@ornl.gov
verification
organization
U.S. Army
Cold Regions Research and Engineering Laboratory
72 Lyme Road
Hanover, NH 03755
Technical Lead: Tom Jenkins
phone: (603) 6464385
fax: (603) 646-4785
email: tjenkins@crrel.usace.army.mil
technical advisor
U. S. EPA
National Exposure Research Laboratory
Environmental Science Division
P.O. Box 93478
Las Vegas, NV 89193-3478
Program Manager: Eric Koglin
phone: (702) 798-2432
fax: (702) 798-2261
email: Koglin.Eric@epa.gov
EPA project
management
U. S. DOE
ORNL Site Office
P.O. Box 2008
Bldg. 4500N, MS-6269
Oak Ridge, TN 37831-6269
Program Manager: Regina Chung
phone: (423) 576-9902
fax: (423) 574-9275
email: chungr@ornl.gov
DOE/ORO
project
management
U.S. DoD
Office of the Deputy under Secretary of Defense
for Environmental Security
Environmental Security Technology Certification
Program
Washington, DC 20301-3400
Program Manager: Cathy Vogel
phone: (703)696-2118
fax: (703) 696-2114
email: vogelc@acq.osd.mil
DoD project
management
Barringer Instruments
30 Technology Drive
Warren, NJ 07059
(see Section 3.1)
Contact: JohnAvolio
phone: (908) 222-9100, ext 3003
fax: (908) 222-1557
email: javolio@bii.barringer.com
technology
developer
Naval Research Laboratory
4555 Overlook Avenue, S. W.
Washington, DC 20375
Contact: Anne Kusterbeck
phone: (202) 404-6042
fax: (202) 404-8897
email:akusterbeck@cbmse.nrl.navy.mil
technology
developer
Research International Inc.
18706 142nd Avenue, NE
Woodinville, WA 98072-8523
(see Section 3.4)
Contact: Elric Saaski
phone: (425) 486-7831
email: resrchintl@aol.com
technology
developer
Specialized Assays Incorporated (SAI)
2960 Foster Creighton Drive
Nashville, TN 37204
(see Section 4.0)
Contact: Mike Dunn
phone: (615) 726-0177
fax: (615) 726-3404
reference
laboratory
ORNL has responsibilities for:
Preparing the demonstration plan;
Developing a quality assurance project plan (QAPP) (Section 8 of the demonstration
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plan);
Preparing a health and safety plan (HASP) (Section 9 of the demonstration plan) for
the demonstration activities;
Acquiring the necessary reference analysis data;
Performing sampling activities (including collecting, homogenizing, dividing into
replicates, bottling, labeling, and distributing);
Conducting the demonstration.
ORNL, ESTCP, and EPA have coordination and oversight responsibilities for:
Providing needed logistical support, establishing a communication network, and
scheduling and coordinating the activities of all demonstration participants;
Auditing the on-site sampling activities;
Managing, evaluating, interpreting, and reporting on data generated by the
demonstration; and,
Evaluating and reporting on the performance of the technologies.
Site access;
Characterization information for the site;
Other logistical information and support needed to coordinate access to the site for the
field portion of the demonstration, such as waste disposal.
3.0 TECHNOLOGY DESCRIPTION
This section provides a description of the technologies participating in the verification. The descriptions
were provided by the technology developers, with minimal editing by ORNL. This section also describes the
performance factors of the technology that will be assessed based on the data generated during the
demonstration. Note that TNT is 2,4,6-trinitrotoluene, RDX is hexahydro-l,3,5-trinitro-l,3,5-triazine, HMX
is octahydro-l,3,5,7-tetranitro-l,3,5,7-tetrazocine, and DNT is isomeric dinitrotoluene, including both 2,4-
dinitrotoluene and 2,6-dinitrotoluene.
3.1 Barringer Instruments' GC-IONSCAN
3.1.1 Technology Overview
The GC-IONS CAN ® is a fully transportable field screening instrument combining the rapid analysis time
of ion mobility spectrometry (IMS) with the separation ability of gas chromatography. The unit can be used
to detect and quantify explosives based on their retention time, ion mobility, characteristic chemical ionization
peaks, and amplitude of the response. The instrument can be operated in IONSCAN® mode or in GC-
IONSCAN® mode. The user can switch between the two modes in less than 30 seconds.
In the IONSCAN® mode, samples are thermally desorbed from a substrate and the GC column is
bypassed permitting the direct and fast analysis of residue or particulate material in 6 to 8 seconds. In GC-
IONSCAN® mode liquid samples or extracts are directly injected onto the GC column and analysis occurs
within 1 to 5 minutes, depending on the type of explosive. The operating conditions of the IONSCAN® mode
permits rapid prescreening of samples, identifying the major constituents of the sample and semi-quantitative
analysis, while the GC-IONSCAN® mode permits full characterization and quantitative analysis of the sample.
The GC-IONSCAN® is fully controlled by the front panel or through an external computer with the GC-
IONSCAN® software. The injector port can be set in split or splitless modes, providing a means for quantitative
analysis within the linear dynamic range of the detector. One to five microliter samples are directly injected onto
the heated injector. For explosive analysis, a 15 m DB-1 column, (internal diameter of 0.53 mm and film
thickness of 0.1 fim) is used. Other types of columns can be used, provided that the coil diameter of the column
does not exceed 4". The oven temperature can be operated under isothermal conditions or multi-stage
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temperature ramping conditions. Maximum allowable oven temperature is 300°C and maximum temperature
ramping rate is 40 °C/min. The transfer line from the column to the detector is heated at a control temperature
(usually 150 °C , adjustable range from 30 to 300 °C) and consists of an extension of the column to the heated
inlet of the IONSCAN®. Eluent from the GC column enters the IONSCAN® inlet combining with a makeup
gas doped with reactant and proceeds into the ionization region. This occurs only during the analysis cycle.
When the analysis is finished, the drift gas of the IONSCAN® is vented through the heated inlet acting like a
purge gas and ensuring that the ionization region and inlet are free of any contaminants or carry over from the
sample.
3.1.2 Sample Preparation and Analysis Procedure
In both solid and liquid matrices, minimal sample preparations are required. Soil sample preparation
involves a one-step solvent extraction with acetone. Ten mL of acetone is added to a 2 g of soil sample in a 20
mL vial. The mixture is shaken and allowed to settle to extract the explosives into the acetone fraction. For
rapid field screening protocol, up to 50 |il of the acetone solution can be deposited on the Teflon filter and, once
the solvent has evaporated, analyzed by thermal desorption in the IONSCAN®mode. If explosives are detected,
quantitative analysis and peak confirmation are performed by injecting l to 5 |iL of the same acetone sample
onto the heated injector after selecting the GC-IONSCAN® mode of operation. Serial dilution of the extracted
solution may be performed for highly contaminated samples.
For the analysis of aqueous samples, 10jj.L of water sample are deposited onto the Teflon filter and
analyzed as described previously. If explosives are detected, l to 4 |iL is directly injected into the heated injector
for GC separation and analysis.
Quantitative assessment of explosives in the sample is done by either integration of GC peaks or from
peak maximum amplitude of target explosive signals. Barringer states that both methods are extremely reliable
within standard laboratory practices. Amounts of explosives in the soil (mg explosive/kg soil) will be determined
from the quantitative analysis of the GC peaks and knowing the ratio of solvent extraction to liquid injection
volumes. Barringer indicates that, in the IONSCAN® mode, larger aliquots can be analyzed (up to 100 uL),
permitting a 30 to 100 fold increase in sensitivity.
3.1.3 Instrument Calibration
Barringer states that the GC-IONSCAN® system is very stable and daily response variation is small.
System calibration once prior to the field screening is sufficient to provide the required response factors for
quantitative analysis of the sample. Four to five point calibration curves for each explosive analyte will be first
established using pre-mixed standard solutions of explosive mixtures in acetone. Repeatability of the
measurements will be established by performing 3 to 5 injections of the same standard solution. The
concentration of the explosive of interest in the standard solution will cover the linear dynamic range of the
detection system. Linear regression of calibration points, as well as standard deviation in each measurement,
will be plotted.
3.2 Research International/Naval Research Laboratory's FAST 2000
3.2.1 General Technology Description
The Continuous Flow Immunosensor (CFI) is based on a displacement assay that utilizes antibodies
as a means of detection. The key elements of the sensor are: 1) antibodies specific for the analyte, 2) signal
molecules which are similar to the analyte but labeled with a fluorophore (usually a cyano-based fluorescent dye
(Cy5)) so they are highly visible to a fluorescence detector, and 3) a fluorescence detector. For analysis, the
antibodies which specifically recognize the contaminants are immobilized onto a solid support and the
fluorescently labeled signal molecule is bound, creating an antibody/signal molecule complex. If the sample
contains the target analyte, a proportional amount of the labeled signal molecule is displaced from the antibody
and detected by the fluorimeter downstream.
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The technology was originally developed by the Naval Research Laboratory. The manufacturable,
field-portable version of the CFI, the FAST 2000, has been engineered by Research International. The
optically-based signal gathering capabilities are combined with precise fluidics control in a computer application.
The software provides a simple menu driven interactive user interface to lead users through the steps required
to successfully determine if a trace amount of analyte is present in a given sample. The software also allows
the more advanced user complete control of the operational parameters for running nonstandard procedures.
Data analysis is made easy with the use of real time plotting of the data, data logging, and custom calibration.
The Windows-based software allows for both ease of use and complex system manipulation, keeping all skill
levels in mind.
The FAST 2000 unit can be easily carried into the field (2.8 lbs, dimensions: 6 cm x 15.5 cm x 16 cm))
and plugged directly into a portable PC for on-site data acquisition and analysis. The assay chemistry for TNT
and RDX detection has been developed to be a functional and robust system that can be successfully used in
the field without the need for excessive environmental controls. Analysis time for each sample is approximately
2 minutes. The coupon and membrane can be used for repeated assays. The life of the membrane is
dependent upon the number and concentration of positive assays that were run.
3.2.2 Instrument Calibration
Calibration of the FAST 2000 immunosensor is performed with an initial injection (150 |iL) of a
prepared explosive standard (100 or 1000 |ig/L). Subsequent injections of the explosive standard during sample
analysis occur every 3rd sample injection. The explosive standards are prepared by drying down 20 |iL from
the stock explosive vial (1,000,000 |ig/L stored in acetonitrile) with a nitrogen air stream. Using a micropipettor
2.0 mL of system flow buffer (10 mM sodium monophosphate, 2.5% ethanol and 0.01% Tween, pH 7.4) is
added to the tube to dissolve the explosive residue, forming the 10 ppm explosive standard. Serial dilutions of
the 10,000 |ig/L standard are made in flow buffer to obtain the 10, 100 and 1000 |ig/L standards. Signals from
the samples (peak unit area) are compared to the peak unit area of the closest standard for quantitation.
3.2.3 Sample Analysis
The CFI is based on a displacement immunoassay in which the explosive molecules in the sample
selectively "displace" a fluorescently labeled signal molecule from an immobilized antibody. The Naval
Research Laboratory's 11B3 TNT and Strategic Diagnostics RDX monoclonal antibodies are immobilized onto
porous membrane supports and saturated with the fluorescent analog using the detailed protocols outlined in
draft U.S. EPA Method 4656. The membrane is inserted into a disposable coupon, placed in the FAST 2000,
and the buffer flow is started by a computer command. Once the fluorescence background signal due to
unbound Cy5 has stabilized (generally 15-20 minutes), the biosensor is ready for sample injection.
3.2.3.1 Groundwater Samples
For analysis of groundwater, 40 |iL 0.5 M sodium phosphate/0.5% Tween 20 and 50 |iL ethanol are
added to 1.91 mL of a 20 mL test water sample. Test samples (150 |iL) are injected using a 1 cc tuberculin
syringe in the following order: standard (10-1000 |ig/L). three test samples, standard. Additional standards can
be assayed to optimize the quantitation.
For all samples, the computer calculates the Peak Area (integral) that are designated by the operator
corresponding to the start of the peak and the end of the peak. From the standards that are co-injected with
the samples, a sample value is calculated. Ideally, the concentrations of the standards give signals that are close
to the signals that are obtained from the samples being analyzed. This value is then used to derive a
concentration/unit signal value (ng/mL/Peak Area Unit). This averaged value is then applied to the peak area
from each sample injection to acquire a concentration for that injection of the sample.
3.3 Performance Characteristics
For each of the technologies, the following performance characteristics will be evaluated during the
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demonstration. Specific calculations (where applicable) are described in Section 7.7
• Precision
Accuracy
Representativeness
Completeness
Comparability
False positive/false negative results
• Detection limits
Sample throughput
Ease of use
4.0 CONFIRMATORY PROCESS
The verification process is based on the presence of a statistically validated data set against which the
performance goals of the technology may be compared. The choice of an appropriate reference method and
reference laboratory are critical to the success of the demonstration.
4.1 Method Selection
The reference analytical method will be EPA SW-846 Method 8330 [1],
4.2 Reference Laboratory Selection
To assess the performance of the explosives field analytical technologies, the data obtained will be
compared to data obtained using conventional analytical methods. This decision is based on the experience of
prospective laboratories with QA procedures, reporting requirements, and data quality parameters consistent
with the goals of the Program.
In selecting a reference laboratory, Specialized Assays Inc. (SAI), Nashville, Tennessee, was chosen
as the leading candidate to perform the analyses based on ORNL's experience with laboratories capable of
performing explosives analyses. ORNL reviewed SAI's record of laboratory validation which was performed
by the U.S. Army Corp of Engineers (USACE, Omaha, Nebraska). EPA and ORNL decided that, based on
the credibility of USACE program and ORNL's prior experience with the laboratory, SAI would be selected to
perform the reference analyses. Selection was finalized with the successful analyses of the predemonstration
samples. In Appendix A is presented SAI's standard operating procedures for preparation and analysis.
A contingency laboratory has been selected, in case SAI is incapable of analyzing the samples, or if
there is some question concerning the sample results. Severn Trent Laboratories (Colchester, Vermont) was
selected as the contingency laboratory based on successful analysis of predemonstration samples.
4.3 Laboratory Audit
ORNL's technical expert and statistician conducted an audit of laboratory operations on May 4, 1999.
This evaluation focused specifically on the procedures that will be used for the analysis of the demonstration
samples. Results from this audit indicated that SAI was proficient in several areas, including quality
management, document/record control, sample control, and information management. SAI was found to be
compliant with Method 8330 analytical procedure implementation. SAI provided a copy of its QA plan, which
details all of the QA/QC procedures for all laboratory operations [2], Additionally, the audit team noted that
SAI had excellent procedures in place for data back-up, retrievability, and long-term storage. The audit report
was reviewed and approved by ORNL's Quality Assurance Specialist.
4.4 Validation and Evaluation of Reference Laboratory Data
The demonstration samples will be sent to the reference laboratory at the start of the demonstration
activities (August 23). The full data package of results for a given analytical batch of 40 samples will be due
to ORNL in 21 working days (per SAI project/quote # 120998A199) after the start of analysis.
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4.4.1 Data Validation
ORNL will be responsible for validating the reference laboratory data. Validation determines the quality
of the results relative to the end use of the data. (Note that the developer is responsible for validating its own
data prior to final submission.) Several aspects of the data (listed below) will be reviewed. The findings of the
review will be documented in the validation records. As appropriate, the ETVR will describe instances of failure
to meet quality objectives and the potential impact on data quality.
4.4.1.1 Completeness of Laboratory Records
This qualitative review ensures that all of the samples that were sent to the laboratory were analyzed,
and that all of the applicable records and relevant results are included in the data package.
4.4.1.2 Holding Times
For soil, the method requirement is that the samples be extracted within 14 days of receipt and analyzed
within 40 days of extraction. For water, the analysis requirement is the same, but the samples must be prepared
within 7 days of receipt. ORNL has requested that SAI analyze the water samples as soon after receipt as
possible.
4.4.1.3 Correctness of Data
So as not to bias the assessment of the technology's performance, errors in the reference laboratory
data will be corrected as necessary. Corrections may be made to data that has transcription errors, calculation
errors, and interpretation errors. These changes will be made conservatively, and will be based on the guidelines
provided in the method used. The changes will be justified and documented in the validation records.
4.4.1.4 Correlation Between Replicates
Normally, one would not know if a single sample result was "suspect" unless (a) the sample was a
spiked sample, where the concentration is known or (b) a result was reported and flagged by the reference
laboratory as suspect for some obvious reason (e.g., no quantitative result was determined). The experimental
design implemented in this verification study will provide an additional indication of the abnormality of data
through the inspection of the replicate results from homogenous sample sets. Criteria may be established to
determine if data is suspect. For example, data sets could be considered suspect if the percent relative standard
deviation for replicate samples was greater than 50%, because this criteria would indicate imprecision. These
data would be flagged so as not to bias the assessment of the technology's performance. Precision and accuracy
evaluations may be made with and without these suspect values to represent the best and worst case scenarios.
If both the reference laboratory and the developer(s) report erratic results, the data may be discarded if it is
suspected that the erratic results are due to a sampling error.
4.4.1.5 Evaluation of QC Results
QC samples will be analyzed by the reference laboratory with every batch of samples to indicate
whether or not the samples were analyzed properly. Acceptable QC results are specified in the reference
laboratory's procedure and in Section 8.4 of this demonstration plan. The QC samples will include, but are not
limited to: initial calibration, continuing calibration verification, laboratory control samples, matrix spike and
matrix spike duplicates, surrogate recoveries, and blank results. See Section 8.4 of the Quality Assurance Project
Plan for a more detailed description of the QC results evaluation.
4.4.1.6 Evaluation of Spiked Sample Data
Spiked samples are homogenous samples containing known concentrations of analyte(s). The
performance of the reference laboratory will be evaluated relative to the spiked samples. Results for these
samples represent the best estimate of accuracy and precision for verification testing.
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4.4.2 Data Analysis
Where possible, the reference laboratory data will be analyzed identically to the technologies that
perform quantitative analyses (see Section 7.7 for specific calculations). For example, precision and accuracy
will be evaluated.
5.0 DEMONSTRATION SITE AND SAMPLE DESCRIPTIONS
This section discusses the demonstration site, and the history and characteristics of the sites where the
explosives-contaminated soil and water samples were collected. This information was gathered from the Internet
[3, 4] and published reports [5],
5.1 Demonstration Testing Location and Conditions
The demonstration of explosives field analytical technologies will be conducted at the Oak Ridge
National Laboratory, Freels Bend Cabin site, in Oak Ridge, Tennessee. A map of the site is presented in Figures
5-la and 5-lb. The samples used in this study will be brought to the demonstration testing location for
evaluation by the vendors. Explosives-contaminated soils from several Army Ammunition Plants (AAP) in
Iowa, Louisiana, and Tennessee will be used in this demonstration. Soils from a former Army base in California
(Fort Ord) will also be evaluated. Additionally, explosives-contaminated water samples from Oregon, Louisiana,
and Tennessee will be evaluated.
T o test the capabilities of the technologies under actual field conditions, the demonstration activities will
occur outdoors. While studies are being conducted, the temperature and relative humidity will be monitored
regularly by ORNL so that the working conditions will be documented. Generally, the average August
temperature for eastern Tennessee is 77°F.
5.2 Soil Sample Descriptions
Multiple soil types, collected from sites in California, Louisiana, Iowa, and Tennessee, will be used in
this study. The primary constituents in the samples are expected to be 1,3,5-trinitrotoluene (TNT), isomeric
dinitrotoluene (DNT) including both 2,4-dinitrotoluene and 2,6-dinitrotoluene, hexahydro-l,3,5-trinitro-l,3,5-
triazine (RDX), octahydro-l,3,5,7-tetranitro-l,3,5,7-tetrazocine (HMX), 2-amino-4,6-dinitrotoluene (2-Am-
DNT), and 4-amino-2,6-dinitrotoluene (4-Am-DNT), with concentrations ranging from 0 to approximately
90,000 mg/kg.
5.2.1 Iowa Army Ammunition Plant
Currently still an active site, the Iowa Army Ammunition Plant was constructed to load, assemble, and
pack various conventional ammunition and fusing systems. Current production includes 120 mm tank rounds,
warheads for missiles, and mine systems. Disposal of industrial wastes containing explosives through the early
years primarily consisted of disposing the wastes into surface impoundments, landfills, and sumps on the
installation. These operations caused contamination of both the soil and groundwater. The major contaminants
in these samples will be TNT, RDX, and HMX.
11
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5.2.2 Louisiana Army Ammunition Plant
Louisiana Army Ammunition Plant (LAAAP), near Shreveport, Louisiana, is a government-owned
facility where production began in 1942. The facility is currently an Army Reserve Plant. Production items at
LAAAP have included artillery shell metal parts, and load, assemble, and pack of artillery shells, mines, rockets,
mortar rounds, and demolition blocks. As a result of these activities and the resulting soil and groundwater
contamination, the EPA placed LAAAP on the National Priorities List in 1989. The major constituents in the
samples are expected to be TNT, RDX, and HMX, with trace levels of 1,3,5-trinitrobenzene (TNB), DNT, 2-
Am-DNT, and 4-Am-DNT.
5.2.3 Milan Army Ammunition Plant
Currently still active, Milan Army Ammunition Plant (MLAAP) in Milan, Tennessee was established
in late 1940 as part of the pre-World War II buildup. The facility still has ten ammunition load, assemble, and
package lines. Munitions-related wastes have resulted in soil contamination. Primary contaminants in the soils
are expected to be RDX and TNT.
5.2.4 Volunteer Army Ammunition Plant
Volunteer Army Ammunition Plant, in Chattanooga, Tennessee, was built beginning in 1941 to
manufacture TNT and DNT. All production ceased in 1977. Past production practices resulted in significant
soil and groundwater contamination. Concentrations of TNT and DNT are expected to range from 10 to
90,000 mg/kg in the samples from this site, with significantly less contributions from the Am-DNT isomers.
5.2.5 Fort Ord Military Base
Fort Ord, located near Marina, California, is a military base that was closed as a military installation in
1993. Currently, the California State University at Monterey Bay opened its doors on former Fort Ord
property, the University of California at Santa Cruz has based a new research center there, and the Monterey
Institute of International Studies will take over the officer's club and several other buildings. The post's airfield
was turned over to the city of Marina. The Army still occupies several buildings. Since its opening in 1917, Fort
Ord primarily served as a training and staging facility for infantry troops. A study conducted in 1994 by the
Army revealed that the impact areas at the inland firing ranges of Fort Ord were contaminated with residues of
high explosives [5], Fort Ord is on the National Priorities List of contaminated sites (Superfund) that requires
the installation to be characterized and remediated to a condition that does not pose unacceptable risks to public
health or the environment. The contaminant present at the highest concentration (as much as 300 mg/kg) is
expected to be HMX, with much lower concentrations of RDX, TNT, 2-Am-DNT, and 4-Am-DNT.
5.3 Water Sample Descriptions
Explosives-contaminated water samples from Tennessee, Oregon, and Louisiana will be evaluated.
Primary contaminants are expected to be RDX, TNT, and DNT. Water samples will range in concentration
from 0 to 25,000 (ig/L.
5.3.1 Louisiana Army Ammunition Plant
See Section 5.2.2 for site description. Major contaminants in the water samples are expected to be
RDX, TNT, TNB, and HMX.
5.3.2 Milan Army Ammunition Plant
See Section 5.2.3. MLAAP has two sewage treatment plants. In the past, wastewater from various
production activities was discharged to open ditches that drained from sumps or surface impoundments into both
intermittent and perennial steams and rivers. Currently, MLAAP treats all process water from the lines that
generate explosives-contaminated wastewater. The EPA placed MLAAP on the National Priorities List in 1987.
These water samples are expected to contain RDX, as well as TNT and DNT.
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5.3.3 Umatilla Chemical Depot
Umatilla Chemical Depot is located in northeastern Oregon. The mission of the facility recently changed
to static storage of chemical warfare ammunition. Once the chemicals are destroyed, the installation is scheduled
to close. Several environmental sites have been identified for cleanup prior to base closure. One site has
explosives-contaminated groundwater; the cleanup identified for this site is to pump and treat the water with
granulated activated carbon. The major contaminants in these samples are expected to be TNT, RDX, HMX,
and TNB. According to a remedial investigation conducted at the site, these groundwater
samples will not be contaminated with any chemical warfare agents.
5.3.4 Volunteer Army Ammunition Plant
See Section 5.2.4. The major contaminants in the groundwater samples are expected to be TNT, 2,4-
DNT, and 2,6-DNT, with lower levels of TNB and 1,3-dinitrobenzene.
5.4 Sample Preparation
5.4.1 Sample Collection Procedures
All of the soil samples will be shipped at ambient temperature to ORNL for use in the demonstration.
This effort will be coordinated by CRREL. The soil samples will be from the various sites described in Section
5.2. The soil samples will be shipped in double-bagged plastic Ziplock™ bags and stored frozen (< 0 °C) prior
to splitting.
The water samples will be shipped to ORNL for use in the demonstration. Again, these efforts will be
coordinated by CRREL. The water samples will be collected approximately 7 days prior to the demonstration
start date (August 23) and shipped immediately to ORNL. The samples will be collected in 2.5-gallon carboy
containers and stored under refrigeration (~4 °C).
5.4.2 Sample Preparation for Demonstration
5.4.2.1 Soil Samples
In order to ensure that the developers and the reference laboratory analyze comparable samples, the
soils will be homogenized prior to sample splitting. The process is as follows. The sample will be kneaded in
the Ziplock™ bag to break up large clumps. Approximately 1500 g of soil will be poured into a Pyrex™ pan.
Debris will be removed. The sample will be air-dried overnight (or longer, as necessary). The sample will be
sieved using a 9 mesh (2 mm particle size) screen and placed in a 1-L wide-mouth jar. After thorough mixing
with a metal spatula, the sample will be quartered. After mixing each quarter, approximately 250 g from each
quarter will be placed in the 1-L wide-mouth jar, for a total sample amount of approximately 1000 g.
After analysis by an in-house method (modified Method 8330) to confirm homogeneity, the sample will
be split into jars for distribution. Each 4-oz sample jar will contain approximately 20 g of soil. The sample will
be remixed after every five 20-g subsamples have been removed. Four replicate splits of each soil sample will
be prepared for each participant. The samples will be randomized in two stages. First, the order in which the
filled jars will be distributed will be randomized so that the same developer does not always receive the first jar
filled for a given sample set. Second, the order of analysis will be randomized so that each developer analyzes
the same set of samples, but in a different order.
5.4.2.2 Water Samples
To prepare the water sample, the 2.5-gallon carboy will be gently shaken to stir the contents. A spout
will be attached to the carboy. The water sample will be split by filling 250-mL amber glass bottles. Due to
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holding time issues, sample splitting will be performed at the last possible moment. The water samples will be
sent immediately to the reference laboratory for analysis and will also be analyzed in-house.
5.4.3 Sample Labeling
Each jar will be labeled with a sample number. Replicate samples will be assigned unique (but not
sequential) sample numbers. Spike materials and blanks will be labeled in the same manner, such that these QC
samples are indistinguishable from other samples. The order of analysis will be randomized and set for each
developer. A separate label will be used to identify the developer analysis order.
5.4.4 Sample Storage
To ensure that degradation will not occur, the soil samples will be frozen (< 0 °C)prior to analysis. The
water samples will be kept refrigerated (~4 °C). Additionally, the samples will be shipped to the reference
laboratory under these conditions. These precautions will be taken per the guidance outlined in, "Stability of
Explosives in Environmental Water and Soil Samples [6]."
6.0 PREDEMONSTRATION STUDY
A predemonstration study is required by this demonstration program to allow the technology developers
to refine their technologies and revise their operating instructions, if necessary. This analysis also allows an
evaluation of matrix effects or interferences that may affect performance. A failure to meet the performance
goals at this point could indicate a lack of maturity of the technology and the demonstration would be canceled
for that developer.
This requirement has the following objectives:
To allow the developers to analyze samples that will be included in the demonstration and, if
necessary, refine and calibrate their technologies and revise their operating instructions;
To allow an evaluation of any unanticipated matrix effects or interferences that may occur
during the demonstration
For the predemonstration study, the developers analyzed six explosives-contaminated soils (including
one spiked sample) from LAAAP (see site information in Section 5.2.2) and/or six explosives-contaminated
water samples (including two spiked samples) from Volunteer (see site information in Section 5.3.4). The
spiked soil sample was obtained from Environmental Resource Associates (ERA, Arvada, CO). The soil was
prepared using ERA's semivolatile blank soil matrix. This matrix was a top soil that had been dried, sieved, and
homogenized. Particle size was approximately 60 mesh. The soil was approximately 40% clay. Some of the
groundwater samples were fortified with RDX and TNT to represent the type of sample that may be obtained
from other AAPs, such as a load, assemble, and pack facility. The spiked water samples were prepared by
CRREL.
6.1 Predemonstration Sample Distribution
The predemonstration samples were sent to the developers and the reference laboratory on June 9,
1999. The developer results for the predemonstration sample analyses were provided to ORNL two weeks after
the receipt of the samples.
6.2 Predemonstration Results
The developers' predemonstration results were compared to the reference laboratory results.
Additionally, the results were compared to performance acceptance ranges generated from analytical verification
data. The acceptance ranges were guidelines established by ORNL's statistician to gauge acceptable analytical
results. The results indicated the technologies described in this demonstration plan are mature and ready for
field testing.
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7.0 EXPERIMENTAL DESIGN
This section discusses the objectives of the demonstration, factors that must be considered to meet the
performance objectives, and the information that ORNL, ESTCP, and EPA will use to evaluate the results of
the demonstration.
7.1 Objectives
The primary objectives of this demonstration are to evaluate the explosives field analytical technologies
in the following areas: (1) comparability relative to Method 8330, (2) variability of replicate samples, (3) the
effect of different soil and/or water matrices, (4) accuracy for spiked samples, and (5) the logistical and
economic resources necessary to operate the technology. Secondary objectives for this demonstration are to
evaluate the technologies in terms of portability, cost, sample throughput, and ease of operation. Where
possible, the performance will be compared to the performance of the conventional analytical method that would
be used in similar site characterization activities. The verification process will also evaluate the performance
of the technology against the performance goals as stated in Section 3.3.
7.2 Experimental Performance Measures
This section discusses performance measures that will be considered in the design and implementation
of the demonstration. These performance measures include accuracy, precision, portability, ease of operation,
health and safety issues, sample throughput, and sample matrix effects.
7.2.1 Qualitative Performance measures
Some performance measures, while important, are difficult or impossible to quantify. These are
considered qualitative performance measures: ease of operation, operator training requirements, portability, and
special requirements.
7.2.2 Quantitative Performance measures
Many performance measures in this demonstration can be quantified by various means, including the
following: accuracy, precision, detection limits, number of false positive (fp) results, number of false negative
(fn) results, waste generation, sample throughput, and operating costs. These quantitative performance
measures will be used to assess the technology performance by comparison to reference laboratory data, where
possible.
7.3 Summary of Demonstration Design
The demonstration will be held at ORNL's Freels Bend Cabin site from August 23 through September
5, 1999. The samples to be evaluated during the demonstration consist of (1) naturally-contaminated samples
from DoD sites, (2) spiked samples, and (3) blank samples. The demonstration samples will be homogenized
and split such that the developer and the reference laboratory will be supplied with comparable samples. Some
features of the approach are presented in Table 7-1. The developer will analyze a total of 108 soil samples
and/or 176 water samples. Note that Barringer will analyze both soil and water samples, and Rf/NRL will
analyze only water samples.
The concentrations of the samples will range from 0 to 90,000 mg/kg for soil, and 0 to 25,000 |ig/L
for water. This large dynamic range is necessary to thoroughly evaluate the capability of the technology.
Additionally, a significant issue when evaluating field technologies for explosives is whether the technology is
capable of indicating if the concentrations are above levels that will sustain a detonation. This level has been
established for soil by the U.S. Army Environmental Center to be 10% by weight (100,000 mg/kg) [7],
Equally as important is evaluating if the technology can accurately determine if a sample meets a specified
cleanup level, such as 0.5 mg/kg for RDX [6], or if it exceeds the EPA's health advisory limit of 2 |ig/L for
TNT [8],
In order to provide site characterization information that would normally be supplied during site
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remediation activities, the developer will be provided with a list which designates which samples came from
which sites (Sections 5.2 and 5.3). This will allow the developer to consider possible interferents or cross-
reactive compounds, and which samples are suspected to contain extremely high levels of a particular
contaminant.
Table 7-1. Experimental Design Features
Properties: 23 unique samples for soil and 41 unique samples for water; acquire more data on fewer
samples; statistically rich approach
Replicates: equal number (quadruplicate) for all sample types and concentration levels
Accuracy: equal number of comparisons with certified and spike concentrations for the PE soils and
extract samples, respectively, at all concentration levels
Precision: estimated for all sample types and concentration levels
Data Analysis: simplified statistics due to consistency with number of replicates
7.4 Field Data
The technology will be operated by the developer, who will provide the results to ORNL. The
developer will be responsible for reducing the raw data into a presentation format consistent with the evaluation
requirements. ORNL will provide a sample results form to the developers. Before leaving the demonstration
site, the developers will submit all final results and raw data to ORNL.
7.5 Demonstration Schedule
Demonstration activities will occur from August 23 through September 5, 1999. Visitors will be
scheduled to talk with the vendors and view technology demonstrations as necessary.
7.6 Field Operations
This demonstration requires close communication between the developer, ORNL, and EPA.
Preliminary site training (on August 23) will be required before initiation of the field study. Successful field
operations require detailed planning and extensive communication. The implementation of the demonstration
must be consistent with the requirements of the study and routine operation of the technology.
7.6.1 Communication and Documentation
ORNL will communicate regularly with the demonstration participants to coordinate all field activities
associated with this demonstration and to resolve any logistical, technical, or QA issues that may arise as the
demonstration progresses. The successful implementation of the demonstration will require detailed coordination
and constant communication between all demonstration participants. All developer/ORNL field activities will
be thoroughly documented. Field documentation will include field logbooks, photographs, field data sheets, and
chain-of-custody forms.
The ORNL technical lead will be responsible for maintaining all field documentation. Field notes will
be kept in a bound logbook. Each page will be sequentially numbered. Completed pages will be signed and
dated by the individual responsible for the entries. Errors will have one line drawn through them, and this line
will be initialed and dated. Any deviations from the approved final demonstration plan will be thoroughly
documented in the field logbook and provided to ORNL. Photographs will be taken with a digital camera.
The developers will obtain all equipment needed for field work associated with this demonstration. Prior
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to the demonstration, the developers will work with ORNL to secure any equipment requirements (such as
tables, chairs, etc.) that the developers will need for the demonstration.
7.6.2 Sample Distribution
ORNL will be responsible for sample distribution. Soil samples will be packaged in 4 ounce (120 mL)
jars. Water samples will be packaged in 250-mL amber bottles. All samples will be prepared for distribution
at the start of the demonstration. The developers will go to a sample distribution table to pick-up the samples.
The samples will be distributed in batches of 12. Completion of chains-of-custody will document sample
transfer.
7.6.3 Archive Samples
Archive samples which are replicates of the developer samples will be retained by ORNL. An archive
sample will be used during the demonstration if the integrity of a developer's sample has been compromised.
Additional unhomogenized material and unused archive samples will also be retained at ORNL at the completion
of the demonstration, in case any questions arise where reanalysis is necessary.
7.7 Evaluation of Performance Factors
This section describes the performance factors that will be evaluated from the data generated during
the demonstration. It also discusses the characteristics of the technologies which will be reported in the ETVR
and verification statement.
Technology performance will be evaluated in terms of precision, accuracy, representativeness,
completeness, and comparability (PARCC) parameters [9], which are indicators of data quality. Additionally,
false positive and negative results, sample throughput, and ease of use will also be evaluated. Results will be
evaluated from the analysis of naturally-contaminated, spiked, and blank samples.
During any experiment, unusual measurements may occur either as random events or from
determinable causes. It is important that the developer note and record any problems with each measurement.
Identification of unusual measurements does not mean that they will be automatically set aside. The statistical
analysis can be performed with or without the suspected measurements to see if there are any changes in the
conclusions of the demonstration experiment.
7.7.1 Precision
Precision is the reproducibility of measurements under a given set of conditions. For those technologies
which report quantitative (i.e., continuous) data, standard deviation (SD) and relative standard deviation (RSD)
for replicate results will be used to assess precision. The following equation will be used:
standard deviation .m0/
KoL) - x lUU/o (7-1)
average concentration
The overall RSD will be characterized by three summary values:
mean—i.e., average;
median—i.e., 50th percentile value, at which 50% of all individual RSD values are below and
50% are above; and
95th percentile—i.e., the value at which 95% of all individual RSD values are below and 5%
are above.
The mean RSD of the developer's technology will be compared with the mean RSD of the reference laboratory.
For those technologies which report interval data, precision will be quantified by the frequency with
which the same interval is reported for sample replicates. Reporting a higher number of replicates in the same
interval will indicate higher precision. The highest possible precision is reporting all four replicate results as the
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same interval.
7.7.2 Accuracy
Accuracy represents the closeness of the technology's measured concentrations to known values. For
those technologies which report quantitative data, accuracy will be assessed in terms of percent recovery, which
is
measured concentration inn0/ —
percent recovery = x 100% (7-2)
known concentration
As with precision, the overall percent recovery will be characterized by three summary values: mean, median,
and 95th percentile. The mean percent recovery of the developer's technology will be compared with the mean
percent recovery of the reference laboratory.
For those technologies which produce interval results, accuracy will be evaluated in terms of the
percentage of samples which agree with, are above (i.e., biased high), and are below the known value (i.e.,
biased low). For example, if a technology reports a result as 10 to 50 mg/kg, and the known amount is 40
mg/kg, the results would agree because 40 mg/kg falls into the interval from 10 to 50 mg/kg. If the known
amount is 100 mg/kg and the technology reported 10 to 50 mg/kg, the technology would be biased low. If the
known amount was 5 mg/kg and the technology reported 10 to 50 mg/kg, the technology would be biased high.
7.7.3 Representativeness
Representativeness expresses the degree to which the sample data accurately and precisely represent
the capability of the technology. Representative samples, in general, are samples that contain a reasonable
cross-section of the "population" over which they are to be used to make inferences. The population for
demonstrations analyzed as part of this project includes a variety of media and contaminants that the innovative
technologies are developed to accommodate. The performance data will be accepted as representative of the
technology if the technology is capable of analyzing diverse samples types (i.e., performance is not affected
based on the matrix).
7.7.4 Completeness
Completeness is defined as the percentage of measurements that are judged to be useable (i.e., the
result is not rejected). The optimum completeness is 95% or greater.
7.7.5 Comparability
Comparability refers to the confidence with which one data set can be compared to another. A one-to-
one sample comparison of the technology results and the reference laboratory results will be performed for all
samples. For the quantitative technologies, coefficients of determination (R2) [10] will computed for the plot
of the field technology's concentrations versus the reference laboratory concentrations. Perfect correlation
between the reference laboratory and field technology will be indicated by an R2 value of 1.0.
Additional examinations of the data using multiple comparison tests will indicate the similarities and
differences between the field technology and the reference laboratory measurements. Statistical tests (such as
Analysis of Variance (ANOVA) [11, 12] and the Wilcoxon signed rank test [13]) may be performed to assess
if there is a significant difference between the technology and the reference laboratory results. Nonparametric
statistical methods will be used if the approximating data distributional assumptions are not supported. The
nonparametric Wilcoxon signed rank test is particularly useful because of the pairing of developer's and
reference laboratory's samples. The Wilcoxon test is designed to test whether the developer's and reference
laboratory's measurements have the same median.
Additionally, a direct comparison between the field technologies and reference laboratory data will be
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performed by evaluating the percent difference (%D) between the measured concentrations, defined as
0/o D = Wield Technology] - [Ref Lab] ^ 10QO/o
[Ref Lab\
The range of %D values will be summarized and reported.
The ANOVA and Wilcoxon statistical tests are useful for analyzing continuous (i.e., quantitative)
measurements, but several of the technologies will give interval or qualitative measurements. Similar to
accuracy, the technologies which report interval results will be evaluated in terms of the percentage of samples
which agree with, are above (i.e., biased high), and are below (i.e., biased low) relative to the results generated
by the reference laboratory.
7.7.6 False Positive/Negative Results
A false positive (fp) result [14] is one in which the technology detects explosives in the sample when
there actually are none. A false negative (fii) result [14] is one in which the technology indicates that there are
no explosives present in the sample, when there actually are. Both fp and fn results are influenced by the
method detection limit of the technology. False positive and false negative results will be assessed using all of
the samples, based on the reference laboratory results, and will be reported as a percentage. Those technologies
reporting interval data will be given the benefit of the doubt when reporting the lowest reporting interval. For
example, if the reference laboratory indicates that no explosives were detected in a sample, and the technology
reports the result as 0 to 1 mg/kg, the technology's result will be considered correct, and not a false positive
result. Similarly, if the reference laboratory reports a result as 0.9 mg/kg, and the technology's paired result is
0 to 1 mg/kg, the technology's result will be considered correct, and not a false negative result.
7.7.7 Detection Limits
Detection limits (DLs) are often defined as the minimum concentration of a substance that can be
measured and reported. DLs are determined from repeated analyses of a sample in a given matrix containing
the analyte. The DL for quantitative technologies will be calculated, most likely from the results for spiked
samples, using regression methods to calculate DL [15], Where possible, the DL calculated from the
demonstration analyses will be compared to that which is reported in the developer's literature.
7.7.8 Sample Throughput
Sample throughput is a measure of the number of samples that can be processed and reported by a
technology in an hour. ORNL will record the total number of hours required to analyze the total sample suite
and report an estimated sample throughput rate. In addition, each sample will be logged in and out using chain-
of-custody documentation. A sample will be considered completed when the final result is submitted to ORNL.
This data will be considered when calculating the sample throughput rate. Sample throughput will be affected
by the number of analysts operating the technology and the skill of those operators.
7.7.9 Ease of Use
A significant factor in purchasing an instrument or a test kit is how easy the technology is to use.
Several factors will be considered when assessing this parameter:
What is the operator skill level (e.g., technician, BS, MS, or Ph.D.)?
How many operators were used during the demonstration? Could the technology be run by
a single person?
How much training would be required in order to run this technology?
Is the technology portable and easy to set-up?
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7.7.10 Miscellaneous Factors
Any information that might be useful to a person who is considering purchasing the technology will be
documented in the ETVR. ORNL will be looking for this type of information during field activities. Examples
of information that might be useful to a prospective purchaser are: the amount of hazardous waste generated
during the analyses, the ruggedness of the technology, the amount of electrical or battery power necessary to
operate the technology, and aspects of the technology or method which makes it easy to use (for example,
"Reagent handling was minimized by the use of premeasured, breakable glass ampules.").
An important factor in the consideration of whether to purchase a technology is cost. ORNL will
estimate the cost involved with operating the technology and the standard reference analyses. To account for
the variability in cost data and assumptions, the economic analysis will be presented as a list of cost elements
and a range of costs for sample analysis. Several factors affect the cost of analysis. Where possible, these
factors will be addressed so that decision-makers can independently complete a site-specific economic analysis
to suit their needs.
8.0 QUALITY ASSURANCE PROJECT PLAN (QAPP)
The QAPP for this demonstration specifies procedures that will be used to ensure data quality and
integrity. Careful adherence to these procedures will ensure that data generated from the demonstration will
meet the desired performance objectives and will provide sound analytical results. EPA considers the
demonstration to be classified as a Category II project. This section of the demonstration plan addresses the key
elements that are required for Category II projects prepared according to guidelines in EPA guidance documents
[16, 17],
8.1 Quality Assurance Responsibilities
Each developer is responsible for adhering to this QAPP and ensuring the quality of data submitted
to ORNL for evaluation. ORNL will be responsible for evaluating the reference laboratory's performance on
the various QA/QC factors outlined in this QAPP.
8.2 Data Validation
The developer is responsible for supplying final results that have been validated. ORNL is responsible
for validating the reference laboratory's results (see Section 4.4).
8.3 Data Quality Indicators
The data obtained during the demonstration must be of sufficient quality for conclusions to be drawn
on the explosives field analytical technology. For all measurement and monitoring activities conducted for EPA,
the Agency requires that data quality parameters be established based on the proposed end uses of the data.
Data quality parameters include five indicators of data quality: representativeness, completeness, comparability,
accuracy, and precision. These are discussed in detail in Section 7.7.
8.4 Calibration Procedures and Quality Control Checks
This section describes the calibration procedures and method-specific QC requirements that apply to
the reference analyses. Some may also apply to the field technology. It also contains a discussion of the
corrective action to be taken if the QC parameters fall outside of the evaluation criteria. Note that a batch
includes no more than 20 samples. SAI's analytical procedures and QC acceptance criteria are described in
Appendix A of this document and in their QA plan [2],
8.4.1 Initial Calibration Procedures
The reference laboratory's initial calibration procedure includes analysis of five standards at 100,250,
500, 1000, and 2000 |ig/L. A successful calibration using response factors must have RSD less than 20% or
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a linear fit greater than 0.99. The initial calibration must also be verified with a mid-point standard prepared
from a different source or lot of stock standard. The RSD must be less than 15% or the instrument must be
recalibrated.
8.4.2 Continuing Calibration Procedures
The initial calibration is verified daily with a mid-level standard. It must be within 15% of the initial
calibration or the initial calibration procedure must be repeated. Additionally, mid-level check standards must
be run with every 10 samples and at the end of a batch. The same acceptance criteria applies.
8.4.3 Method Blanks
A method blank is an analyte-free matrix to which all reagents are added in the same volumes or
proportions as used in sample processing, and is carried through the complete sample preparation and analytical
procedures. One method blank will be included with each batch. To be acceptable, no analytes must be
detected above the practical quantitation limits (0.5 |ig/L for water and 0.5 mg/kg for soil).
8.4.4 Matrix Spike Samples
Matrix spikes are prepared by fortifying a sample chosen from the sample batch with known amounts
of the method analytes (5 |ig/L for water and 5 mg/kg for soil). The sample is analyzed with and without
spiking. The percent relative difference between the known concentration (spike + original sample
concentration) and the analyzed value is termed the percent recovery. SAI will prepare and analyze a matrix
spike and a matrix spike duplicate (MS/MSD) with every batch. The relative percent difference (RPD) between
the MS and MSD results will be evaluated. The equation for determining RPD is:
RPD = lMA " MSI) x 100% (8-1)
1/2 * (MS + MSD)
SAI's
acceptance criteria for MS/MSD accuracy and precision, which are documented in their QA plan [2], are
presented in Table 8-1. If the acceptance criteria for the MS/MSD are not met, the acceptance of the analytical
batch is determined by the validity of the Laboratory Control Sample (Section 8.4.5). A MS analyte may not
be reported in the QC report if the level of contamination in the sample is exceedingly high.
8.4.5 Laboratory Control Samples
Laboratory control samples (LCS) are samples of known composition that are analyzed periodically
to assure that the analytical system is in control. One LCS will be analyzed per batch. The concentration level
for the LCS will be 5 |ig/L in water and 5 mg/kg in soil. SAI's acceptance criteria will be 60 -140% recovery
for both soil and water. The LCS criteria must be met in order for the batch results to be acceptable.
8.4.6 Surrogate Recovery
Compounds having similar chemical characteristics to those being analyzed but which are not generally
found in environmental samples are used as surrogate compounds. SAI will use 3,4-dinitrotoluene as the
surrogate compound for these analyses. Known concentrations of this compound will be added to all samples
in the batch prior to sample preparation. The performance acceptance ranges for surrogate recovery will be 65-
153% for soil and 35-125% for water. If the surrogate is out of limits, the individual sample must be repeated.
8.4.7 Spiked Samples
Soil and water samples will be spiked with known concentrations of explosives and included in the suite
of samples for evaluation. These will be blind to the developer and the reference laboratory. The matrix will be
interference-free, so that accuracy can be assessed on relatively "clean" samples. The samples will be obtained
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from Environmental Resource Associates or prepared by ORNL.
8.4.8 Replicate Samples
As part of the experimental design, all of the samples (naturally-contaminated, spike, and blank) will
be analyzed in quadruplicate (i.e., four separate subsamples), so that precision can be determined for every
sample type.
8.5 Data Reduction, Review, and Reporting
To maintain good data quality, specific procedures will be followed during data reduction, review, and
reporting. These procedures are detailed below.
8.5.1 Data Reduction
Data reduction refers to the process of converting the raw results from the technology into a
concentration or other data format which will be used in the comparison. The reference laboratory and the
developer will be responsible for reducing the data to final results. The procedures to be used will be technology
dependent. The following is required for data reduction:
8.5.1.1 Quantitative (Continuous) Data
For quantitative technologies (including the reference laboratory), the reported concentrations will be
in mg/kg for soil samples and |ig/L for water samples.
8.5.1.2 Semi-quantitative (Interval) Data
For technologies reporting interval data, the data will be reported using a "[" and ")" notation. The
brackets indicate that the end-points are included, while the parentheses indicate that the end-points of the
concentration range are excluded. Additionally, the range of intervals used will be inclusive for all possible
results. Each developer will provide a list of all possible interval reporting ranges to ORNL at the start of the
demonstration activities. Table 8-2 is an example of how the intervals would be reported.
8.5.1.3 Nondetect Concentrations for Quantitative Data
If no explosives are detected in a sample, the concentration should be reported as less than the reporting
limit. For example, the reference laboratory should report a blank soil as "< 0.5 mg/kg" for each analyte.
8.5.2 Data Review
The developer will verify the completeness and correctness of data acquisition and reduction. The
ORNL technical lead may review calculations and inspect laboratory logbooks and data sheets to verify
accuracy, completeness, and adherence to the specific analytical method protocols. Calibration and QC data
may also be examined by ORNL. The developer will verify that all instrument systems are in control and that
QA objectives for accuracy, completeness, and method detection limits have been met.
The reference laboratory will be responsible for providing a complete data package to ORNL per their
QA procedures [2], In addition, ORNL will validate the reference laboratory data as described in Section 4.4.
8.5.3 Data Reporting
This section contains a list of the data to be reported by both the technology and the reference method.
At a minimum, the data tabulation will list the results for each sample and include reporting units, sample
numbers, results, and data qualifiers. (A sample results form will be provided for completion by the developers.)
Where applicable, all QC information such as calibrations, blanks and reference samples will also be included
with the raw analytical data. All data should be reported in hardcopy.
Developer results will be due to ORNL at the conclusion of the field activities. For sample throughput
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Table 8-1. Specialized Assays Inc. Acceptance Criteria for MS/MSD
Analyte
Matrix Precision
(percent RPD)
Matrix Accuracy
(percent recovery)
soil
water
soil
water
HMX
30
29
55-147
40-128
RDX
27
9
66-142
49-112
1,3,5 -trinitrobenzene
31
16
55-149
42-127
1,3 -dinitrobenzene
23
6
67-140
29-120
Tetryl
48
32
24-146
47-129
Nitrobenzene
30
21
64-145
12-117
2,4,6-Trinitrotoluene
41
27
51-129
34-121
4-Amino-2,6-dinitrotoluene
23
15
43-156
51-105
2-Amino-4,6-dinitrotoluene
28
13
60-142
60-122
2,6-Dinitrotoluene
29
12
62-147
59-117
2,4-Dinitrotoluene
30
13
60-143
24-110
2-Nitrotoluene
25
26
63-138
39-109
4-Nitrotoluene
24
41
68-132
38-107
3-Nitrotoluene
26
46
58-143
35-111
Table 8-2. Example of reporting intervals
Interval
Soil concentration range for TNT
[0, 1)
0< TNT mg/kg< 1
[1, 10)
1< TNT mg/kg < 10
[10, 50)
10 <TNT mg/kg < 50
[50,°°)
TNT mg/kg > 50
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calculations, a sample will not be considered completed until the final result is submitted to ORNL. The
developer's final report will be due to ORNL one week after the conclusion of the demonstration. Any
discrepancies between the originally reported result and the final result must be described.
For the reference laboratory, the full data package of results for a given analytical batch of 40 samples
will be due to ORNL in 21 working days (per SAI project/quote # 120998A199) after the start of analysis.
8.6 Audits
The following audits will be performed during this demonstration. These audits will determine if this
demonstration plan is being implemented as intended.
8.6.1 Technical Systems A udit
ORNL's Quality Assurance Specialist (QAS) will perform a surveillance during the field demonstration
activities to assess compliance with the demonstration plan. After the surveillance, the QAS will prepare a
report which will be signed by the ORNL program manager. Corrective actions for noncompliance will be taken
either on-the-spot, or a plan will be devised.
8.6.2 Performance Audit
Both the field technology and the reference laboratory will evaluate spiked samples, which will be of
known concentration. The results will be compared to the range of acceptable results for the spiked samples,
as determined by the provider of the spiked material and verified by the statistician. This evaluation will serve
as a measure of accuracy and precision, and will be reported in the ETVR. During the field activities, ORNL
may choose to inform a developer if their results on spiked samples are significantly different from the expected
concentrations. Spiked samples will be obtained from Environmental Resource Associates or prepared by
ORNL.
8.6.3 On-Site System A udits
During the field demonstration activities, ORNL will observe the operation of the field technology, such
as observing the vendor operations, photo-documenting the demonstration activities, surveying calibration
procedures, and reviewing sample data. The observations will be documented in a laboratory notebook or by
completing a field audit form. The reference laboratory was audited by ORNL on May 4.
8.7 Quality Assurance Reports
QA reports provide the necessary information to monitor data quality effectively. It is anticipated that
the following types of QA reports will be prepared as part of this demonstration.
8.7.1 Status Reports
When problems occur, the developer will discuss them with ORNL, estimate the type and degree of
impact, and describe the corrective actions taken to mitigate the impact and to prevent a recurrence of the
problems. ORNL will regularly inform the EPA project manager of the status of the project. ORNL should
discuss project progress, problems and associated corrective actions, and future scheduled activities associated
with the demonstration.
8.7.2 Audit Reports
A copy of the technical systems audit report will be provided to the EPA project manager. Informal
reporting of audit results will be reported immediately to EPA.
8.8 Corrective Actions
Routine corrective action may result from common monitoring activities, such as:
Performance evaluation audits
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Technical systems audits
Calibration procedures
If the problem identified is technical in nature, the individual developers will be responsible for seeing that the
problem is resolved. If the issue is one that is identified by ORNL or EPA, the identifying party will be
responsible for seeing that the issue is properly resolved. All corrective actions will be documented. Any event
that causes discrepancies from the demonstration plan will be noted in the technology verification report. Section
8.4 describes the reference laboratory's corrective action plan for not meeting minimum QC requirements.
9.0 HEALTH AND SAFETY PLAN
9.1 Introduction
This chapter describes the specific health and safety procedures that will be used during the field work
at the Oak Ridge National Laboratory's Freels Bend Cabin site.
9.2 Contact Information
The ORNL program manager is Roger Jenkins, (423) 576-8594.
The ORNL technical lead is Amy Dindal, (423) 574-4863.
The environmental, safety, and health officer is Fred Smith, (423) 574-4945.
The environmental protection officer is Kim Jeskie, (423) 574-4947.
The laboratory shift superintendent phone number is (423) 574-6606.
9.3 Health and Safety Plan Enforcement
ORNL program manager and technical lead will be responsible for enforcing the health and safety plan.
ORNL program manager will ultimately be responsible for ensuring that all demonstration participants abide by
the requirements of this HASP. ORNL technical lead will oversee and direct field activities compliant with this
HASP.
9.4 Site Location
The demonstration of explosives field analytical techniques will be conducted at the Oak Ridge National
Laboratory, which is managed by Lockheed Martin Energy Research Corporation, Oak Ridge, Tennessee. The
demonstration will be held at the Freels Bend Cabin site, which is located on the Oak Ridge Reservation, a short
distance (5-6 miles) from ORNL. The site consists of a cabin that is primarily used as an educational facility.
The cabin has electrical power, but no running water.
9.5 Site Access
Developers and any other visitors will be escorted at all times by ORNL personnel. Visitors will follow
standard ORNL safety and health policies and practices. Visitors will not be allowed to physically operate the
developers' equipment.
9.6 Training Requirements
Site-specific training will be provided by the ORNL program manager or designated representative on
the first day of testing to ensure that the developers are familiar with the requirements of the HASP.
9.7 Technology-Specific Hazards
The hazards associated with this demonstration include the specific physical and chemical hazards
associated with operating the technology. Potentially, each developer will be exposed to different hazards. Each
developer is responsible for identifying these hazards and taking the appropriate precautions. In addition, all
participants should be aware of the demonstration site hazards listed in Section 9.8.
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9.8 Demonstration Site Hazards
Because the developers will be operating their technologies in the field for several consecutive days,
there are a number of site hazards that the participants should be aware of.
9.8.1 Chemical Hazards
Prior to the start of the demonstration activities, all developers will evaluate the potential chemical
hazards associated with the technology and report it to ORNL. ORNL will have Material Safety Data Sheets
(MSDS) available at the site for all chemicals. If hazardous chemicals are used, a portable eye wash station will
be located at the site. The developers will label all chemicals.
ORNL will provide all compressed gas cylinders. After hours, each cylinder will be strapped to a
cylinder cart and stored in the cabin or on the cabin porch.
9.8.2 Physical Hazards
Physical hazards associated with field activities present a potential threat to on-site personnel. Dangers
are posed by unseen obstacles, noise, heat, and poor illumination. Injuries may results from the following:
Accidents due to slipping, tripping, or falling
Improper lifting techniques
Moving or rotating equipment
Improperly maintained equipment
Injuries resulting from physical hazards can be avoided by adopting safe work practices and by using caution
when working with machinery.
9.8.3 Mechanical, Electrical, Noise Hazards
Some technology-specific hazards may be identified once the developers set-up their equipment.
Proper hazards controls (i.e., guarding or markings) or personal protective equipment (PPE) (i.e., ear plugs for
noise hazards) will be implemented as necessary.
Electrical cables represent a potential tripping hazards. When practical, cables will be placed in areas
of low pedestrian travel. If necessary, in high pedestrian travel areas, covers and/or markings will be installed
over cables.
9.8.4 Inclement Weather
The demonstration will occur the latter part of August. The possibility of inclement weather
(particularly rain and thundershowers) exists. The developers should be prepared to deal with a possible
inclement weather situation. No work shall be performed if there is an electrical storm.
9.8.5 Heat Stress
Since the demonstration will occur in August, the possibility of a heat-related injury during field work
is possible. All demonstration participants are encouraged to be attentive and responsive to signs of heat-induced
illness. Heat stress symptoms include heat cramps, heat exhaustion, and heat stroke. Heat stroke is the most
serious condition and can be life-threatening. Some symptoms of heat-related injuries are pale clammy skin,
sweating, headache, weakness, dizziness, and nausea. Signs of heat stroke include dry, hot, red skin, chills, and
confusion. In the case of a suspected heat-related injury, try to cool the person down and contact medical help.
ORNL will provide drinking water to the participants to help avoid heat stress. Also, the participants will be
encouraged to take several breaks during the day.
9.8.6 Insect and Other Animal Stings and Bites
A potential for insect (e.g., honey bees, wasps, yellow jackets), snake (e.g., rattlesnake, copperhead),
arachnid (e.g., black widow, brown recluse, scorpions), and other animal (such as reptiles) stings or bites exists
during the technology demonstration. Insect repellent may be used to minimize insect bite hazards. In the event
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of snake or other large animal bite, the injury should be immobilized and immediately reported to medical
personnel. The number for medical personnel will be posted at the demonstration site.
9.8.7 Fire
The following specific actions will be taken to reduce the potential for fire during site activities:
No smoking within 100 feet of any operating technology or the staging area.
Fire extinguishers will be maintained on-site.
All personnel will be trained on the location of the portable fire extinguishers.
The number for the fire department will be posted.
9.8.8 Radiological Hazards
The proposed demonstration activities have been evaluated by ORNL radiation protection personnel.
No radiation protection hazards have been identified.
9.9 Personal Protection
Based on the specific hazards associated with their technology, the technology developers will determine
and provide the appropriate PPE. Appropriate work clothes (no shorts or open-toed shoes) shall be worn at
all times. ORNL will provide visitors with PPE if necessary. If site conditions indicate that additional hazards
are present, PPE levels will be reconsidered.
9.10 Emergency Support
In case of a medical or fire, emergency phone numbers will be posted at the demonstration site. A
cellular phone will be available for use at all times.
9.11 Environmental Surveillance
The environmental protection officer will be responsible for surveying the site before, during, and after
the demonstration. Appropriate personnel will be on-hand to assist all demonstration participants to deal with
any health or safety concerns. All concerns will be reported to the environmental, safety, and health officer.
9.12 Hazardous Waste Disposal
All hazardous waste generated by the technology developers will be properly disposed of by the
environmental protection officer. The technology developers will assist with this process by providing accurate
records of the waste contents and approximate concentrations.
9.13 Site Control
Access to the demonstration site will be controlled. Any visitors to the site must be accompanied by
ORNL personnel. The technology developers should be aware that there is unlimited access to the site from
Melton Lake. As a result, vandalism can occur after hours. The developers should be prepared to secure their
equipment while they are not at the site.
9.14 Safe Work Practices
Each company shall provide the required training and equipment for their personnel to meet safe
operating practice and procedures. The individual technology developer and their company are ultimately
responsible for the safety of their workers. The following safe work practices will be implemented at the site
for worker safety:
Eating, drinking, chewing tobacco, and smoking will be permitted only in designated areas;
PPE requirements (See Section 9.9) will be followed.
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9.15 Complaints
All complaints should be filed with the ORNL technical lead. All complaints will be treated on an
individual basis and be dealt with accordingly.
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REFERENCES
[1] U. S. Environmental Protection Agency. "Method 8330: Nitroaromatics and Nitramines by High
Performance Liquid Chromatography (HPLC)," 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.
[2] Specialized Assays Incorporated. "Comprehensive Quality Assurance Plan." SAL-QC-Rec 5.0.
January 6, 1999.
[3] Industrial Operations Command of the U.S. Army home page, http://www.ioc.army.mil/
home/elements.htm (accessed May 1999).
[4] Fort Ord Remembered home page, http://www.mbay.net/~crswann/ftord.htm (accessed June 1999).
[5] Jenkins, Thomas F., Walsh, Marianne E., Thorne, Philip G. "Site Characterization for Explosives
Contamination at a Military Firing Range Impact Area." Special Report 98-9, 1998.
[6] Maskarinec, M.P., Bayne, C.K., Johnson, L.H., Holladay, S.K., Jenkins, R.A., and Tomkins, B.A.
"Stability of Explosives in Environmental Water and Soil Samples." ORNL/TM-11770, Oak Ridge
National Laboratory, Oak Ridge, TN, January 1991.
[7] Jenkins, Thomas F., Schumacher, Patricia W., Mason, Jane G., and Thorne, Philip G. "On-Site
Analysis for High Concentrations of Explosives in Soil: Extraction Kinetics and Dilution Procedures."
Special Report 96-10, 1996.
[8] U. S. Environmental Protection Agency. "Trinitrotoluene Health Advisory." Office of Drinking Water,
Washington, D.C., 1989.
[9] U. S. Environmental Protection Agency. "Data Quality Objectives for Remedial Response Activities."
EPA 540/G-87/003, EPA, Washington, D.C., March 1987.
[10] Draper, N.R. and Smith, H. "Applied Regression Analysis." 2nd ed., John Wiley & Sons Inc., New
York, 1981.
[11] Snedecor, G.W. and Cochran, W.G. "Statistical Methods." The Iowa State University Press, Ames,
Iowa, 1967.
[12] Sachs, Lothar. "Applied Statistics: A Handbook of Techniques." 2nd ed., Springer-Verlag, New York,
1984.
[13] Conover, W.J. "Practical Nonparametric Statistics." John Wiley & Sons Inc., New York, 1971.
[14] Berger, Walter, Harry McCarty, and Roy-Keith Smith, "Environmental Laboratory Data Evaluation."
Genium Publishing Corporation, Schenectady, New York, 1996.
[15] Gibbons, Robert D. "Statistical Methods for Groundwater Monitoring." John Wiley & Sons, Inc.,
NewYork, 1994.
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[16] U.S. Environmental Protection Agency. "Preparation Aids for the Development of Category II Quality
Assurance Project Plans." EPA/600/8-91/004, February 1991.
[17] U. S. Environmental Protection Agency. "Preparing Perfect Project Plans." EPA/600/9-89/087,
October 1989.
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APPENDIX A
Reference Laboratory Standard Operating Procedures
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S.O.P, No 26
REV. DATE: 7/2B/98
PAGE 1 of 2
EXTRACTION, EXPLOSIVES
10 SCOPE
LI Method 8330 is intended for the trace level extraction of tiitroaromatics
from water, soil and sediment- Method 1332 is intended for the extraction of
nitroglycerine,
2.& SUMMARY
2.1 Fur nltroaroraatics, method 8330, samples arc prepared by salting-out and
extracting for water and solvent extracting with aeelonitrite for soils and
sediments. For NG water samples are diluted, for soils samples are extracted with
acetonilrile.
3.0 INTERFERENCE S
3.1 Use reagent grade chemicals and cleaned glassware to minimise interferences.
3.2 Organic? may interfere with suhsquent analysis.
4.0 INSTRUMENTATION
4.1 Ultrasonic Bath
4.2 Refrigeration system, hold temperature to 4 C,
4.3 Balance, analytical, 0.0001 g accuracy.
5.0 REAGENTS
5,1 Acctoriitnk (MeCN) and Methanol (MeOHl, HPLC grade, commeicial.
5,22.2 Sodium Chloride (NaCl) and Calcium Chloride fCaC 13), reagent gnjde4
commercial, ftrepare a 5 % CaQ2 solution by adding 5 g to 1 I, DJ water.
6 0 SAMPLE COLLECTION, PRESERVATION AND HANDLING
6.1 Samples and extracts must be stored in the dark at 4 C.
6.2 Extraction must be within 14 days from dale of collection.
1.0 PROCEDURE
7.1 Water
7.1.1 For tiisroaromatics transfer 400 ml of sample into a 500 ml separatoiy
furrncl, add 130 g NaCl, shake until all salt is dissolved. Add 1.0 ml
explosives spike standard, if needed
7.1.2 Add 100 ml of MeCN, shake well for 5 minutes, allow phases to separate for at
least 30 minutes. Discard lower water layer, collect top organic layer,
rinse funnel with 10 ml MeCN and add to organic extract
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PAGB 2 of 2
7.1.3 Reduce MeCN volume lo 10 ml using warm-water tath not to exceed
40 C and niirogen blow down, Dilute with 2 0 ml DI water Cor a final
volume of 4.0 ml. Sample is ready for HPLC analysis,
7.1.4 for nitroglycerine., dilute 5.0 ml of sample with 5.0 ml McCN ecraminiiig
the surrogate at 1,0 ug/ml, Filter through a 0,45 um teflon filter Store in
dark al 4 +/- 2 C.
7.2 Soil/Sediment
7.2.1 Homogenize in a mortar and air dry about 5 g of sample. Place 2.0 g io a
15 ml glass vial and add 10 ml MeCN, cap and shake or 8,0 ml if spike is
to be added. For spike add 2.0 ml of spike standard. For riitroatomaties,
place in cfcuUed ultrasonic bath and sonicate for IS +/-1 hour. For NO
sonicate for 1 hour +/- IS minutes. The bath must not exceed 4 C,
7.2.2 Allow sonicated sample to settle for 30 minutes. Take 5.0ml aliquot and
add 5-0 ml of a 5 g/L CaCl 2 solution- Sliake and let. stand 15 miitutes.
Filler through a 0 45 um Teflon filter into a 15 ml vial. This filtrate is
ready for HPT. jC analysis,
8.0 QA/QC
8.1 Eveiy batch or eveiy 20 sample must have a blank, spike and spike duplicate
Spike recovery should be 70-130%. %RPD 20.
9-0 REFERENCES
9.3 SW-S4fj, Third Ed, Method 8330, Rev 0 1994
10.0 SAFETY
10-1 Grinding of soils could result in detonation, presc reen by grinding a
small sample of about 0.2 g.
10-2 A distinct pay color may suggest high levels of explosives. Contact
Safety Officer prior to initial grinding operation,
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S.Q.P.No 21
REV DATE 7/28/98
PAGE 1 OP 3
EXPLOSIVES BY OPIX
1,0 SCOPE:
1.1 Method 8330 is used to determine the concentration of nilroaromatic explosives
in soil and water, The following compounds may be determined: 1,3 -
Dinitrobenzere, 2,4 - Dimtrotoluene. 2,6 Dinilrotoluene, HMX, RDX,
Nitrobenzene, 2 - Nitrotoluene, 3- Nitrotoluene, 4 - Nilrotoluenk Tetryl, TNT,
1,3,5 - Trinitrobenzene, 2 - Amino - 4,6 - Dinitrolofuene, and 4 - Amino - 2,6 -
Dirutra toluene Practical quantitation limit for ««tcr is 0.0QQ5 mg'L and 0.5
mgflcg for soils, This method witfi modifications is suilable for nitroglycerine
PQL/RL =1,0 mgrt. or 5 mglcg.
2,0 SUMMARY:
2,1 Method 8330 provides liquid chromatographic conditions for the analysis of
mtroaromaiics, Samples are introduced by liquid injection and delected by IIV
Primai}1 analytical column is a C-18 reverse-phase with confirmation by a cyano
column,
3.0 INTERFERENCES:
3,1 TetryI decomposes in MeOHMjO and when exposed to heat. Degradation
appears as a shoulder on TOT, use peak height for quantitation if both ire
present. Nitroglycerine is detected at 214 nin. which is prone to interference from
other non-target organics
4.0 INSTRUMENTATION
4.1 HPLC (SJiimadzu) with pulse-free pump (LC-600) and U, V detector set to 254
nnt far nitroaromades and 214 am for NG, Data system is by Ezehrome,
4.2 Primary analytical column is a 25 cm x 4,6 mm RP-C18 (Phenomenex Ultncaxb
5- ODS). Flow rale of 0J ml/mili, is ysed,
4.3 Confirmation column is a 25 cm x 4,6 nn CN column, Mobile phase is
70 % MeOEOQ % Water at a flow rate of 1.5 mVmintiLc.
4.4 Optional: 10 cm x 4.6 mm RP-C18 ODS Hypersil, 3 nm (Keystune Scientific):
modify mobile phase as follows:
38 % MeOH/62 % Waler with 2 % Tetrahydrofuran added to the water phase,
Flow rate of 1,0 ml/mioute.
5.0 REAGENTS
5.1 Acelonitrile (MeCN) 8rld Methanol (MeOH), HPLC grade, commercial source,
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PAGE 2 OF 3
5.2 Calcium Chloride and Sodium Chloride, Reagent Grade, comminerclal
Calcium Chloride solution; Add 5.0 g to 1 L Dt water,
5.3 Slock standards: Aecustandard or Ultra, 1000 (i&'ml ea,s certified, commercial..
5.4 Intermediate standards: dilute 0.1 m( stock to 10.0 ml in MeCN for a 10.0 ug/ml
solution- Refrigerate. Usable for 30 days."
5.5 Prepare five calibration standards immediately before use by diluting the
intermediate standard as follows:
ill added final vol. fml'i cone, std. ffmaD
10 1.0 0.1 jjig/ml
25 1.0 0.25pg/ml
50 1.0 0.5 lig/ml
100 1.0 1.0 ml
200 1,0 2.0 jig/ml
AH Calibration standards should be prepared in a 50:50 solution of MeCN: 5%
CaCl;_ For NG the low standard is 0.5 ugrtnl up to 10 ug/ml.
5.6 Prepare matrix spike solution by adding 0,1 ml of slock solution (1000 (lg^ml) to
9.9 ml MeCN. Add 1.0 ml of the 10 (xg-'mI spike solution to i 1, water sample for
a 0.010 mg/L solution and 2,0 ml to 2 g soil for a 10 m^/kg standard.
NOTE: air dry soil to remove solvent poor to extraction
6,0 SAMPLE COLLECTION, PRESERVATION AND HANDLING
6.1 Collection / preservation - N,A,
6.2 Sample and extracts must be stored in dark at 4 C. Holding curies are 14 days
for extortion and 40 days for analysis.
7.0 PROCEDURE
7.1 For extraction see SOF #26.
7 2 Instail primary LC column, prepare mobile phase by adding 560 ml MeOH to
440 ml DI water. Load File 2 In system controller. Set flow to 0,8 ml/min,, turn
onlJV and set wavelength to 254 ran Allow to stabilize For at least 15
minutes. Injection volume is 25 |il.
7.3 Initially calibrate by loading Die five calibration standards, highest to lowest, in
the autosampler. Load "Explosiv" method. Stall auiosampler and
calibrate using area. Successful calibration using RF must have a % RSD of less
than 20 or a linear tit greater than 0.99. Verify calibration with a mid-point
standard prepared from a different source or lot of stock standard, % RSD roust
be less than 15 or recalibrate,
7.4 Verify calibration daily using a mid-level standard. It must be within 15%
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PAGE 3 OF 3
of initiai calibration or repeal initial calibration poroedore.
7.5 Run samples using same procedure as standards, include a oiid-level check
siajidard every 10 samples and at end of batch. % RSD should be less lhan IS or
renin samples, All positive results must be confirmed using the CN column,
7.6 Concentrations are calculated using integrated results or manually as follows:
(area ca: Iil &k) (vol. of extract)
oom, {mpL Qt nlpfty) *" H—X cOae.sLl, x dllyliiwix —
(area cef hL sui) (voL os wt exiraoed}
7 7 Calculate spike recovery as follow; (conc.in extract)/1.0 x 100
SO QA/QC
8.1 Every batch or every 25 samples must have a Wank, spike and spike duplicate.
Acceptable Spike recovery for water is 70-130% and soils 50-150%. If not, re-
extracl, if still outside range flag results.
8.2 Ho iiitroaromatic target compounds in blank shall be greater than 0.05 |ig/ml. For
NO the blank must be tess than 0 5 ug/ml.
90 REFERENCES
9,1 SW * 8*16. ThirdF.d., Method 8330 Rev, 0, 1994
9 2 S W - 846, Third Ed. Method 8332 Rev 0,1996
10.0 SAFETY - Solvents are flammable. Avoid breathing,
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