EPA/600/R-18/254 | September 2018
www.epa.gov/homeland-security-research
United States
Environmental Protection
Agency
oEPA
Best Practices to Minimize
Laboratory Resources for Waste
Characterization During a Wide-
Area Release of Chemical Warfare
Agents
Office of Research and Development
Homeland Security Research Program
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EPA/600/R-18/254
September 2018
Best Practices to Minimize Laboratory Resources for
Waste Characterization During a Wide-Area Release
of Chemical Warfare Agents
by
Stuart Willison
Matthew Magnuson
Erin Silvestri
National Homeland Security Research Center
Cincinnati, OH 45268
Paul Lemieux
Timothy Boe
National Homeland Security Research Center
Research Triangle Park, NC
Stephanie Hines
Ryan James
Battelle Memorial Institute
Columbus, OH
Contract No. EP-C-15-002 Task Orders 0003 and 0010
U.S. Environmental Protection Agency Project Officer
Homeland Security Research Program
Cincinnati, OH 45268
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Disclaimers
The U.S. Environmental Protection Agency (EPA) through its Office of Research and
Development participated in and managed the research described here. This work was performed
by Battelle under Contract No. EP-C-15-002 Task Orders 0003 and 0010.
This text is a draft that has not been reviewed for technical accuracy or adherence to EPA policy;
do not quote or cite.
The processes described in this document do not rely on and do not affect authority under the
Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA), 42
U.S.C. 9601 et seq., and the National Contingency Plan (NCP), 40 Code of Federal Regulations
(CFR) Part 300. This document is intended to provide information and suggestions that might be
helpful for waste characterization efforts after a chemical incident and should be considered
advisory. The best practices in this document are not required elements of any rule. Therefore,
this document does not substitute for any statutory provisions or regulations, nor is it a regulation
itself, so it does not impose legally binding requirements on EPA, states, or the regulated
community. The lessons and recommendations herein might not be applicable to each and every
situation.
Questions concerning this document or its application should be addressed to:
Stuart Willison
National Homeland Security Research Center
Office of Research and Development
U.S. Environmental Protection Agency
26 W. Martin Luther King Drive, MS NG16
Cincinnati, OH 45220
513-569-7253
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Table of Contents
Disclaimers vii
Acronyms and Abbreviations v
Executive Summary vii
1 Introduction 1
1.1 Purpose of this Best Practices Document 2
1.2 Intended AudienceO 2
2 Scope 3
2.1 Quality Assurance 3
3 Data Gathering Processes for Waste Characterization 4
3.1 Considerations of Waste Characterization Process 4
3.2 Sources and Amounts of Waste: Relationship to Sampling Needs 5
4 Operational Assumptions 6
4.1 Regulatory Context 6
4.2 Pre-Incident Waste Management Planning 7
4.3 Known Laboratory Resources and Capabilities 9
4.4 Generalized DQOs Identified 10
5 Planning Assumptions 10
5.1 Limited Laboratory Capacity Relative to Analysis Needs 10
5.2 Lack of Universal Sampling Approaches for Wide-Area Incidents 11
6 Waste Characterization Process 12
6.1 General Characteristics of Waste Materials 12
6.2 Summary of Waste Characterization Process 14
6.3 Segregation of Waste into Homogeneous Groups 17
6.4 Determine Waste Acceptance Criteria and DQOs 18
6.5 Determine Waste Characterization Strategy 19
6.6 Determining Sample Collection Technique 287
6.7 Determine Analytical Technique and Available Laboratories 32
7 Conclusions 35
8 References 36
Appendix A. Glossary A-l
Appendix B. Background on Chemical Warfare Agents B-l
Appendix C. DQO Process Case Study for Characterizing Waste for Proper Management Using the
Hypothetical Denver WARRP Scenario C-l
Appendix D. Features of Various Sampling Designs D-l
Appendix E. Features of Various Sample Collection Techniques E-l
Appendix F. Findings and Recommendations from the Table-top Exercise and Computer Simulation
Assessments F-l
Appendix G. Best Practices Guide (BPG) G-l
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FIGURES
Figure ES-1. Waste characterization flow chart x
Figure 1. Interaction of data gathering strategy, collection, and analysis 5
Figure 2. Pre-incident all-hazards waste management planning process 8
Figure 3. Waste characterization process 16
Figure C- 1. Chemical attack scenario. Source:(DHS, 2012b) C-l
Figure F-l. Screenshot of computer simulation (a) office and (b) warehouse locations F-2
Figure F-2. Computer simulation sample capture for two waste group samples during
exercise F-3
Figure F-3. Computer simulation sample capture in Excel format F-4
Figure G-l. Waste characterization process flow chart G-5
TABLES
Table 1. Features of Sampling Designs for Waste Characterization 243
Table 2. Features of Various Sample Collection Approaches for Waste Characterization 29
Table B-l. Review of Chemical Warfare Agents, Persistence, and Breakdown Products B-3
Table G-l. Features of Sampling Design for Waste Characterization G-5
Table G-2. Features of Sample Collection for Waste Characterization G-l
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Acronyms ai viations
AEGL
Acute Exposure Guideline Level
ASTM
American Society for Testing Materials, now ASTM International
BOTE
Bio-Response Operational Testing and Evaluation
BPD
Best Practices to Minimize Laboratory Resources for Waste Characterization
During a Wide-Area Release of Chemical Warfare Agents Document
BPG
Best Practices Guide as a quick reference tool to the BPD
GA
Tabun, CAS Number 77-81-6
GB
Sarin, CAS Number 107-44-8
GD
Soman, CAS Number 96-64-0
GF
Cyclosarin, CAS Number 329-99-7
CDC
United States Centers for Disease Control and Prevention
CERCLA
Comprehensive Environmental Response, Compensation, and Liability Act
CFR
Code of Federal Regulations
CI
Critical Infrastructure
CK
Cyanogen Chloride, CAS Number 506-77-4
CI
Chlorine
CMAD
Consequence Management Advisory Division
CMPA
Cyclohexyl Methylphosphonic Acid, CAS Number 1932-60-1
COLIWASA
Composite Liquid Waste Sampler
CVAA
2-chlorovinyl arsenous acid, CAS Number 85090-33-1
CVAOA
2-chlorovinylarsonic acid, CAS Number 64038-44-4
CWA
Chemical Warfare Agent
DIMP
Diisopropyl methylphosphonate, CAS Number 1445-75-6
DoD
U.S. Department of Defense
DOE
U.S. Department of Energy
DQO
Data Quality Objective
DU
Decision Unit
EA-2192
S-(2-diisopropylaminoethyl) methylphosphonothioic acid, CAS Number
73207-98-4
EHDAP
Ethyl Hydrogen Dimethylamidophosphate, CAS Number 2632-86-2
EMPA
Ethyl Methylphosphonic Acid, CAS Number 1832-53-7
EPA
U.S. Environmental Protection Agency
ERLN
Environmental Response Laboratory Network
FR
Federal Register
GC/MS
Gas Chromatography/Mass Spectrometry
H
Undistilled Sulfur Mustard, di-2 chloroethyl sulfide, bis(2-chloroethyl)
sulfide, same CAS Number (505-60-2) as HD
HD
Distilled Sulfur Mustard, bis(2-chloroethyl) sulfide, CAS Number 505-60-2
HVAC
Heating, Ventilation, and Air Conditioning
ICS
Incident Command System
IC/UC
Incident Command/Unified Command
IMPA
isopropyl methylphosphonic acid, CAS Number 1832-54-8
ISM
Incremental Sampling Methodology
V
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L
Lewisite, collective abbreviation for L-l (CAS Number 541-25-3), L-2
(40334-69-8), and L-3 (CAS Number 40334-70-1)
LC/MS
Liquid Chromatography/Mass Spectrometry
MPA
Methylphosphonic Acid, CAS Number 993-13-5
NCP
National Contingency Plan
NPDES
National Pollution Discharge Elimination System
Mil
National Response Framework
NRT
U.S. National Response Team
OSC
On-Scene Coordinator
PATS
Prioritized Area Targeted Sampling
PMPA
Pinacolyl Methylphosphonic Acid, CAS Number 616-52-4
POTW
Publicly Owned Treatment Works
PPE
Personal Protective Equipment
QA
Quality Assurance
QC
Quality Control
QRG
Quick Reference Guide
RAP
Remediation Action Plan
RCRA
Resource Conservation and Recovery Act
SAM
Standardized Analytical Methods
SAP
Sampling and Analysis Plan
SME
Subject Matter Expert
START
Superfund Technical Assessment & Response Team
TCLP
Toxicity Characteristic Leaching Procedure
TDG
thiodiglycol, CAS Number 111-48-8
TSDF
Treatment, Storage, and Disposal Facility
TTX
Table-top Exercise
TWG
Technical Working Group
UASI
Urban Area Security Initiative
UCL
Upper Confidence Limit
VSP
Visual Sample Plan
VX
0-ethyl-S-(2-diisopropylaminoethyl) methylphosphonothioate, CAS Number
50782-69-9
WARRP
Wide-Area Recovery and Resiliency Program
WMP
Waste Management Plan
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Executive Summary
The executive summary is intended to be used as a "quick reference" to the
Best Practices to Minimize Laboratory Resources for Waste Characterization
During a Wide-Area Release of Chemical Warfare Agents (Best Practices
Document, (BPD) document. For the convenience of the reader, Appendix G
is formatted as a standalone document that is intended to be used as a reference
to the main BPD.
The BPD will assist users in minimizing the number of samples sent for
laboratory analysis for waste characterization tasks while still meeting the data
needs of waste regulators and receivers. The executive summary is also
reproduced as Appendix G of this document and formatted as a Best Practices
Guide (BPG) with the intention that it be used as a stand-alone document,
serving as a quick reference tool to the BPD, particularly for use during
tabletop/simulation/training events. This executive summary and the BPG
include the central flow chart for the waste characterization process, along
with identification and a brief description that should enable the participant in such events to locate relevant
sections of the BPD as quickly as possible. The quick reference is not intended to replace the full BPD in
terms of information or strategy.
A wide-area release of a chemical warfare agent may result in the contamination of several square miles of
an urban area, potentially affecting hundreds of buildings. The response and recovery activities from this
type of incident could generate several tons of solid waste and millions of gallons of liquid waste. Materials
that are not going to be reused or recycled from the incident will become waste when they are identified for
disposal. All generated waste from the wide-area incident must be appropriately characterized. However,
laboratory demand during a wide-area incident will likely be greater than the available capacity due to the
need for sampling and analysis during site characterization, assessment of decontamination efficacy, waste
characterization, and clinical or medical testing. As a result, laboratory analysis could become a chokepoint
and limit overall progress in incident management.
Important concepts to reduce the number of laboratory samples include:
Waste characterization is a legal requirement for all generated wastes, but sampling might not be
necessary if acceptable to regulators and waste receivers;
Appropriate waste segregation is critical for efficient waste characterization;
Waste
characterization is a
process that uses
knowledge of the
waste and/or
sampling results to
document that the
waste meets
regulatory
requirements and any
additional
requirements of waste
receivers.
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Waste characterization strategies should leverage the use of lines of evidence to the extent possible
as a primary means to reduce sample numbers for laboratory analysis;
Field screening can be combined with lines of evidence or the use of a
limited number of confirmatory laboratory samples to reduce the number
of laboratory samples analyzed; and
Waste characterization strategies must be acceptable to regulators and
waste receivers, and these entities should be involved throughout the
process, especially in the beginning where many decisions are made that
drive characterization and decontamination waste streams.
Waste Characterization Process
Figure 1, as detailed in the BPD, provides a description of the overall waste
characterization process. For clarity, progression through Figure 1 is intended
to be a stepwise process. However, there are multiple factors within the process
that may be optimized to reduce the number of laboratory samples and may
result in the simultaneous determination of several process decisions or dictate
an iterative nature to waste characterization decisions. Site- or incident-specific
conditions may also dictate the sequence of decision-making.
Lines of Evidence are
information or data
from various sources
that can be used to
support waste
characterization
decisions. Lines of
Evidence can include
technical data on agent
fate and transport,
persistence in defined
environmental
conditions, and
efficacy of
decontamination
technologies.
viii
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Step 1: Segregate waste into homogeneous groups (Section 6.3). Identify waste acceptance criteria
and associated data quality objectives (DQOs) for each waste group (Section 6.4). and Identify
laboratories with analysis capabilities for desired analyses that will accept material (Section 6.7)
Waste materials are segregated to facilitate reduced sampling requirements by grouping materials
assumed to have similar characteristics. Waste group characteristics that might be relevant for segregation
are described in further detail in the BPD. Individual waste groups might be targeted for different waste
management options, with varying waste acceptance criteria and DQOs based on the waste receiver(s),
i.e., utilities that will be receiving the waste. Waste acceptance criteria are specific to each waste receiver
that will accept the waste. There might also be unique acceptance criteria for locations that hold or stage
waste prior to its final management, particularly with hazardous chemical warfare agent (CWA) waste. It
will be helpful to identify contractor and waste receiver resources that will be present on-scene during an
incident who can provide region-specific knowledge for waste characterization and available waste
receivers. The criteria can be concentration-based or performance-based standards (i.e., decontamination
technology) and include the volume of waste that will be accepted (Section 6.4). It is important to
recognize that degradation products (Table B-l) and non-CWA constituents of the waste should also be
considered in the waste characterization process. If laboratory analysis of samples will be performed,
laboratories that can perform the analysis and that will accept the waste material must be confirmed
(Section 6.7).
Step 2: Determine the waste characterization strategy (Section 6,5). The waste characterization
strategy is developed to demonstrate if the waste material meets the identified waste acceptance criteria
and DQOs. The strategy might consist of application of lines of evidence, field and/or laboratory
sampling, or a combination of the two approaches. Lines of evidence should be considered as a first
approach. Software tools are available to assist with the development of sampling strategies (Section
6.5.3.1).
Step 3: Gather Data. Lines of evidence data can be gathered from the published literature, subject matter
experts, waste receivers, regulators, and previously gathered site data (Section 6.5.1). In the case of
sampling, decisions to gather data are made for the overall sampling strategy (i.e., non-probabilistic,
probabilistic, combination), (Sections 6.5.2 and 6.5.3, Table ES-1), sample collection (Section 6.6, Table
ES-2), and analysis (Section 6.7).
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START:
Collection of
Waste of
Materials
\
Please note that waste characterization
process may be affected by factors that
are not identified in the flow chart.
Examples of these factors may include:
cost, political considerations, public
concern, volume of waste accepted by
waste receiver, and selection of
decontamination technology.
Segregate Potential
Waste Materials into
Homogeneous
Groups (e.g., porous,
nonporous)
(Section 6.3)
Identify Waste
Acceptance Criteria
and DQOs for Waste
Receivers that Will
Accept Each
Segregated Waste
Group
(Section 6,4)
Identify Laboratories with
Analysis Capabilities for
Desired Analyses that will
Accept Material
(Section 6.7)
Waste Characterization Strategy Determination
(Section 6.5)
Determine Use of Lines of Evidence (Section 6.5.1)
Determine Use of Sampling (Section 6.5.2)
Data Gathering Step
If Lines of
Evidence are
Used:
(Section 6.5.1)
If Sampling is Used, Determine:
What Sampling Strategies can be Used -
Nonprobabilistic, Probabilistic, or Combination?
[Sections 6 5.2. and 6.5.3}
Should Waste be Further Segregated Prior to
Sampling?
Will Field Screening and/or Laboratory Analysis will be
Used? (Section 6.7)
Can Composite Sampling be Performed? (Section
6.5.3.2)
Can Split Samples be Used? (Section 6.6.2)
wedge f
Literature, Subject
Matter Experts, and
Previously Gathered Site
Data
(Section 6.5.1)
Identify Field
Analysis Method
(Section 6.7)
Identify
Laboratory
Analysis Method
(Section 6.7)
Identify Collection
Technique
(Section 6.6)
Identify
Collection
Technique
(Section 6.6)
Figure ES-1. Waste characterization process flow chart
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1 Introduction
The U.S. Environmental Protection Agency (EPA) is designated as a coordinating agency, under
the National Response Framework (NRF), to prepare for, respond to, and recover from a threat to
public health, welfare, or the environment caused by actual or potential hazardous materials
incidents. Hazardous materials can include chemical, biological, and radiological substances. A
wide-area incident may result in large-scale contamination because of its geographical size (e.g.,
tens to hundreds of square miles) and the potential for additional transport after the release due to
urban conditions (e.g., complexity of environment, magnitude of contamination, and spread of
contamination). Environmental remediation might be driven by the desire to return contaminated
areas to their original use and by compressing the timeline for the associated environmental
remediation activities. Urban wide-area contamination might result in items or materials that
require characterization before decontamination, after decontamination, and prior to waste
management decisions. Waste characterization is a necessary task in making waste management
decisions. Waste characterization is a process that uses knowledge of the waste and/or sampling
results to document that the waste meets regulatory requirements and any additional
requirements of waste receivers. Developing and implementing sampling plans to address wide-
area contamination and associated waste characterization is complex. Laboratory resources will
be limited during an incident, yet samples will need to be collected and assessed in such a
manner that the resulting data are useful for the overall, site-specific recovery process. There will
likely be a variety of types of materials within an urban environment, each requiring distinct
sampling and analysis procedures during waste characterization, creating a potential bottleneck
that could limit the overall recovery effort.
The potential size of an urban wide-area incident will add to the complexity of developing a
sampling plan. Sufficient samples will need to be collected without overwhelming the available
laboratory capacity and capability. Because chemical warfare agent (CWA) incidents are
infrequent and direct practical knowledge is limited, approaches for performing the appropriate
sampling techniques are inherently novel with unpredictable technical needs and complexities.
Further increasing the complexity of developing a sampling plan are the multitude of phases and
activities surrounding an urban CWA release, each of which will have its own sampling needs.
The phases and activities that follow a chemical contamination incident start with the initial
notification of an incident/first response, continue with remediation of the site, and end with the
clearance decisions and restoration/re-occupancy of the contaminated site. Considerations for
appropriate waste management, including waste characterization, should be incorporated into all
activities from the earliest stage of the incident. As a result, waste receivers (e.g., treatment,
storage, and disposal facility [TSDF] personnel) and regulators should be involved from the start
of the incident to provide information on waste characterization requirements. States may have
more stringent regulations on CWA-generated waste, which will require further input from waste
receivers and regulators. In general, efforts to remediate a site might include characterization of
the site, decontamination of the site, and sampling following decontamination to ensure
decontamination efforts were successful. Information about treatment, decontamination, and
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other topics related to sampling are not discussed in detail in this document, but can be found
elsewhere (EPA, 2012c; EPA, 2015d; NRT, 2015b).
As waste management is a common feature of all these phases and activities, towards addressing
these complex issues, a literature review was conducted that focused on comparing and
contrasting multiple approaches to address the challenges in sample planning, sample collection,
and analysis for waste samples during an urban wide-area release of chemical warfare agents
(CWAs). Three acutely toxic CWAs were targeted in the literature review: nerve agent VX (O-
ethyl-S-(2-diisopropylaminoethyl) methylphosphonothioate), blister agent distilled sulfur
mustard (HD), and blister agent Lewisite (L). Each agent has properties that may extend its
persistence in an urban environment. The literature review was limited to published information
from peer-reviewed journals, EPA, and other state and federal agencies. The information
obtained from the literature review, as well as with input from response professionals, was used
to help identify best practices to assist users in reducing the analytical laboratory sampling load
for activities associated with the waste characterization process. The best practices were
identified based on waste characterization considerations for the three identified CWAs in an
urban wide-area release scenario. However, the material presented might also be appropriate for
an all-hazards evaluation of non-CWA waste that because of volume or toxicity presents a
similar waste characterization challenge relative to significant limits on available laboratory
analysis capacity.
irposc of this Best Practices Document
The purpose of this document, the Best Practices to Minimize Laboratory Resources for Waste
Characterization During a Wide-Area Release of Chemical Warfare Agents (Best Practices
document or BPD), is to present best practices to minimize resources needed for determination
of waste characterization strategies, sample collection techniques, and analytical approaches for
characterization of waste materials contaminated by an urban wide-area release of CWAs. The
best practices discussed in this document might be applicable to consequence management
activities that EPA will be involved with and will require waste characterization. This document
is intended to be general and all-hazards in nature, applicable to a multitude of settings, and to
provide information on techniques and approaches that efficiently optimize sampling and
analytical resources associated with the response to a wide-area incident. The material presented
has value for pre-incident planning and use during an incident. The processes described in this
document do not rely on and do not affect authority under the Comprehensive Environmental
Response, Compensation, and Liability Act (CERCLA), the Resource Conservation and
Recovery Act (RCRA), the NRF, the National Contingency Plan (NCP), or any other statute.
1.2 Intended Audience
This document is intended for personnel involved in the waste characterization process,
specifically: On-Scene Coordinators (OSCs), local, state, tribal, and Regional Response Teams;
Superfund Technical Assessment & Response Team (START) contractors; waste regulators,
waste receivers including TSDF personnel, and subject matter experts (SMEs) who might be
called upon by the Incident Command or Unified Command (IC/UC) or the Technical Working
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Group (TWG) that might convene under the IC/UC as part of a wide-area incident. The
document might also be useful for the individuals identified above when they are working in a
Superfund setting and wish to consider waste characterization practices that minimize the use of
laboratory analysis.
2 Scope
The following best practice objectives are included to reduce the number of samples sent to
laboratories for analysis: data gathering strategies, analysis approaches and methods, and
collection techniques. Other potential approaches may be available, but were not evaluated.
While the document discusses three CWAs (nerve agent VX [i.e., 0-ethyl-S-(2-
diisopropylaminoethyl) methylphosphonothioate], blister agent sulfur mustard [HD], and blister
agent Lewisite [L]), other agents of interest may have unique properties that affect the sampling
and analysis procedures. This document specifically deals with the waste characterization
component of response and recovery. Other components such as site characterization,
decontamination, and clearance are beyond the scope of this BPD and could be the subject of
follow-on efforts.
To assist users of the document, several appendices have been developed to provide additional
resources for waste characterization. Given the diversity of users who may have varying levels of
background knowledge for terminology associated with sampling and waste characterization, a
glossary is provided in Appendix A for important terms that are used in the BPD. Background
information on CWA agents, including potential degradation products and markers, can be found
in Appendix B. Appendix C provides a data quality objectives (DQO) case study specific to
waste characterization of CWAs. Appendices D and E provide summaries of sampling designs
and collection techniques, respectively. Appendix F reports on the findings and
recommendations from a table-top exercise (TTX) held to evaluate an earlier draft version of the
best practices identified herein and from which final revisions to the best practices were
identified. Appendix G provides a Best Practices Guide (BPG) that summarizes important
concepts associated with the waste characterization best practices described in this document.
2,1 Quality Assurance
This report was generated using references (secondary data) identified as having relevant content
for the purpose of this study. Some of the literature was derived from sources other than US
EPA and used for other purposes. Therefore, it might not necessarily be ideal in terms of
accuracy, precision, representativeness, completeness, and/or comparability. However, the
selected literature was considered to be the best sources of available information. If additional
sources of information become available, they should be considered during use of this document.
Secondary data were limited to peer-reviewed documents and evaluated based on content
relevance for each source. The literature review identified and assessed the secondary data for
intended use(s). After the literature searches were conducted and the results subsequently
reviewed, the quality of the secondary data was examined against the overall needs and was
deemed either appropriate or inappropriate for inclusion in the results. Professional judgment
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was used to assess each article qualitatively according to the document evaluation categories
listed below.
An extensive literature review was performed using several sources of secondary data related to
assessing the extent of contamination, verification of decontamination efficacy, and waste
disposal characterization of chemical agents embedded on surfaces, solid materials and waters
contaminated by an urban wide area release of chemical agent. The key chemical agents that
were the focus of this review were sulfur mustard (HD), Lewisite (L), and nerve agent VX along
with their various degradation products. The information sources were collected from existing
data primarily in peer-reviewed documents, including journal articles; books; and government
and industry reports. The literature search included databases, such as, Energy Science &
Technology and the National Technical Information Service (NTIS), the Homeland Defense and
Security Information Analysis Center (HDIAC) managed by the Defense Technical Information
Center (DTIC) [formerly CBRNIAC], Google Scholar, and active identification of EPA
research reports that are in varying stages of completion.
3 Dal ; -fhering Processes imi *< aste C haracterization
Waste will be generated during each phase of the response and recovery process. Therefore,
waste management begins from the moment the incident occurs until the very end. All phases
need to be considered together for effective incident pre-planning. Waste management activities
should be identified within a waste management plan (WMP) and incorporated into the
remediation action plan (RAP). The information provided within the document contains
valuable resources and material that can be used even if a pre-incident waste management plan
has not been developed. This document focuses on the waste characterization efforts during
remediation of a contaminated wide area; other aspects of response and recovery will not be
discussed in detail. Further information about other phases can be found in additional planning
documents (DHS 2011 and EPA, 2005).
3.1 Considerations of Waste Characterization Process
The following best practices are focused on waste characterization prior to treatment and proper
management. Figure 1 illustrates the interactions of data gathering strategy, collection, and
analysis that the best practices coalesce during waste characterization. The waste characterization
process should consider both the site-specific circumstances (e.g., agent, environment) and
desired downstream applications of the data to ensure the validity of the data generated from the
process. The DQO process should be integrated throughout all waste characterization decisions.
While first response activities will have been completed at this point, additional hazards might
remain. Therefore, all planning activities should be coordinated with health and safety planners
to ensure that the number and types of planned samples are compatible with available sampling
resources and the constraints of the health and safety plan.
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Agent specifics
Conceptual site model
Characterization requirements
(i.e., statistical power)
Resources (i.e., time, funds, personnel)
Use of process knowledge and/or
sampling
Sampling approaches: Judgmental or
probabilistic sampling, composite or
singular sampling
Data Quality Objectives (DQOs)
Process
1. Describe the problem
2. Identify the goal of the study
3. Identify information inputs
4. Define the boundaries of the
study
5. Develop the analytic approach
6. Performance or acceptance
criteria
7. Develop the detailed plan for
obtaining data
d
Appropriate
Data
Gathering
Strategy
Available
Sample
Collection
Techniques
- DQOs
- Health and
Safety Plans
Implement
Sample and
Analysis
Plan
Assess
Resulting
Data
Suitable
Analytical
Method
Decision
Makers
Reassess
DQOs
Agent specifics
Available laboratory analyses
Transportation considerations
(i.e..time, temperature, holding)
Sample size
Resources (i.e.. time, funds, personnel)
Agent specifics
Laboratory capabilities
Resources (i.e..time, funds, personnel)
Generated wastes
Specificity
Figure 1. Interaction of data gathering strategy, collection, and analysis.
3.2 Sources and Amounts of Waste: Relationship to Sampling Needs
Waste is generated throughout all phases of the response and recovery process, and the
associated waste management activities will likely be an important factor in the duration and cost
of the response and remediation (EPA, 2015d; Lemieux et aL, 2016). Urban wide-area incidents
may generate large quantities and wide varieties of waste such as waste generated from
residential homes, businesses, industry, infrastructure, and hospitals (EPA, 2012d). Waste
streams might include (EPA, 2012d):
Personal protective equipment (PPE) such as disposable gloves, suits, and boot covers;
Decontaminated items from characterization and post-decontamination phases destined
for disposal or further management; and
Decontamination water (rinsate).
Federal and state requirements for waste management identify that all waste should be
appropriately characterized as part of proper management practices. For purposes of this
document, waste characterization is defined as information, gathered through situationally-
appropriate means, about the composition of waste that can be used by decision makers to
properly direct waste management.
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As illustrated in Figure 1, sampling is a key element of waste characterization. As a result, the
waste characterization process has the potential to contribute significantly to the overall sampling
demand during a wide-area incident. Waste items will likely be packaged in bags, barrels, or
other containers that inhibit access for sampling. Given that an urban wide-area incident might
produce millions of tons of waste, sampling every bag or waste container might be logistically
impossible. A pre-incident WMP should not only identify the waste management facilities
available for use but also identify their individual waste characterization requirements, as
individual establishments might have additional requirements beyond what is required in their
state-issued permit(s). Given the volume of waste and potential limits on the capacity of
individual waste receivers, multiple waste facilities should be identified and relevant WMP data
gathered to ensure sufficient options to manage the total volume of waste that may be generated.
It is also important to note that after environmental samples have been analyzed by the
laboratory and are stored for further management, they will also be treated as regulated waste
(EPA, 2010).
e rational Assumptions
The best practices identified in this document are not designed to be regulatory or formal
guidance. Given that the best practices will be implemented within a larger framework for
response and recovery after a wide-area incident, it is acknowledged that additional or varying
operational assumptions may better describe an individual wide-area incident.
There are six main operational elements that have been assumed:
(1) Regulatory requirements at the federal, state, and local level must be met in the waste
characterization process;
(2) Pre-incident waste management planning has been performed (NOTE: The material
within this document may be valuable towards developing a WMP and should be
considered);
(3) Laboratory resources and capabilities are known;
(4) Generalized DQOs have been identified;
(5) The chemical contaminant(s) of concern (including potential breakdown products or
impurities) have been identified; and
(6) Waste receivers are known.
The first four assumed operational elements are described in more detail below.
4,1 Regulatory Context
All materials that will be disposed of as waste must be characterized to meet the requirements of
regulators and waste receivers. Waste characterization must, at a minimum, meet the regulatory
requirements associated with the waste and the identified management action. Communication
with treatment, storage, and disposal facility (TSDF) personnel is necessary to determine if
emergency RCRA permits will apply to assess alternative options for waste disposal. Land
disposal of solid and hazardous waste is primarily regulated by federal laws such as the RCRA of
1976 and the Hazardous and Solid Waste Amendments of 1984 (DHS, 2012a; EPA, 2012a).
Under RCRA, "solid waste" is broadly defined and includes discarded materials such as solids,
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liquids, semi-solids, and contained gaseous materials. However, RCRA Subtitle C hazardous
waste landfills (CFR Title 40 Part 264ง264.314) and RCRA Subtitle D solid waste landfills
(CFR Title 40 Part 258 ง258.28) have restrictions on the disposal of waste containing "free"
liquids that must be accommodated. In addition, surface runoff or other discharges to surface
water bodies from decontamination wastewater might fall under the purview of the National
Pollution Discharge Elimination System (NPDES) in the Clean Water Act (Campbell et al.,
2012). Certain waste treatment technologies (e.g., incineration) are also regulated under the
Clean Air Act Amendments of 1990 (e.g., Kilgroe (1996)). The management of liquid waste as
wastewater by Publicly Owned Treatment Works (POTW) is related to the Clean Water Act, but
is also subject to any additional requirements of state and local managers of the POTWs
(Campbell et al., 2012; DHS, 2012a), introducing many complexities, with no universal solutions
regarding the role of POTWs in the management of liquid wastes such as decontamination
rinsates. Liquids may need to be collected and held in secure storage until a designated disposal
facility is identified.
In most states, the authority for these federal laws is delegated (i.e., implemented and enforced)
by the states, and thus state and possibly local regulatory agencies determine the waste testing
requirements associated with various waste management practices. The states could impose more
stringent requirements than the Federal Government. However, it is ultimately the waste
management facilities that accept the waste, and these facilities might have waste acceptance
criteria of their own in addition to the state requirements (EPA, 2015d; Lemieux et al., 2016).
4,2 Pre-Incident Waste Management Planning
A pre-incident WMP is assumed to be available to support development of an incident-specific
waste management plan, so is not described extensively in this section. It is useful, however, to
briefly discuss this topic to see how it integrates with the overall goal of this document Figure 2
shows the waste management planning process, including the presence of multiple steps that
might occur prior to an incident. Pre-incident planning may help to reduce potential chokepoints
in the recovery process that may delay the overall rate of recovery (DHS, 2012a). During the
initial stages of an incident, a pre-incident WMP will be developed by a team to address waste
management issues. Development of the plan will require coordination and approvals with
regional response teams, state officials and agencies for each state expected to receive waste, and
waste treatment, and disposal facilities. As part of pre-incident waste management planning, the
process and outputs should be communicated to politicians, state and local regulators, and waste
receivers. Factual communication, technical translation, and the viability of a proposed solution
will provide valuable information for the planning process. These groups will be critically
important to implementation of the waste management plan during an incident.
These pre-incident plans should be incorporated into area contingency plans for each region in
accordance with the National Contingency Plan (NCP). In instances of a chemical release, the
pre-incident WMP would ideally be quickly adapted for the specific incident (i.e., the incident-
specific RAP and the associated WMP). Such adaptations are critical for successful responses to
wide-area incidents and especially for those involving chemical agents because of the limited
experience involved in handling these wastes and the difficulties that might arise in finding
facilities willing to accept such waste (EPA, 2015d).
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The pre-incident WMP should provide guidance on the options and preferences for waste
management as well as potential preferred options for waste management for identified waste
streams. In the context of wide-area incidents for biological agents, Lemieux (2016) observed
that waste management tasks were simplified when aqueous wastes (i.e., wastewaters) can be
managed at a POTW facility and non-aqueous wastes can be managed as solid waste in a RCRA
Subtitle D facility. This simplification is also likely true for wide-area incidents involving
chemical agents, and as mentioned above, it cannot be taken for granted "if' managing wastes in
this manner is possible for a specific site. It is important for response managers, regulatory
authorities, and utility managers to meet, and pre-plan if possible, to prevent, assess, and respond
to the potential impacts of decontamination wastewater (EPA, 2015d; National Association of
Clean Water Agencies, 2005), solid waste, and hazardous waste generated during the response to
a wide-area urban chemical agent release. EPA (2016a) provides an excellent example of a pre-
planning activity in the form of a collaborative workshop held with the wastewater sector, SMEs,
and regulatory representatives. EPA (2016a) reports on the findings of the workshop and
includes relevant references that might assist in future pre-planning activities for the
management of chemically contaminated wastewater. EPA is developing an online tool to aid
communities, states, tribes, and facilities in preparing a pre-incident WMP (2018).
Step 1:
Pre-Planning
Activities
Step 4:
incident-
Specific
WMP
Step 2:
Pre-incident
WMP
Step 3:
WMP Review,
Maintenance,
Exercise, and Training
Conduct the following:
Develop the pre-incident
WMP
Use available tools for
assistance
Coordinate with stakeholders
Consult with WM facilities'
owners and operators
Establish acceptance criteria
for reuse and recycling
Perform the following:
Meet with stakeholders to review and update
the pre-incident WMP regularly
Schedule and perform WMP exercises
Develop training plan
Incorporate WM lessons learned, after action
reports, and improvement plans
Plan/Do the following:
Form planning team with federal, state,
local, tribal, and territorial WM officials
Assume worst case scenario
Identify key resources for the development
of the pre-incident WMP
Determine regulatory issues/considerations
Review existing plans
Assess WM mitigation measures
Implement the following:
Tailor the pre-incident WMP to
incident-specific conditions
Present the incident-specific WMP
to the Unified Command
Notify WM facilities of needs and
exercise contract support where
necessary
Implement the community outreach
plan
Track WM operations and report
progress
Figure 2. Pre-incident all-hazards waste management planning process. Source: (EPA, 2016b).
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Elements of a WMP, based on the process described in Figure 2, can include:
Waste management requirements (federal, state, and local)
Waste types and quantities
Waste facilities and resources needed
Waste acceptance criteria of waste management facilities
Waste facility personnel contact information
Waste characterization requirements
Waste sampling and analysis plan
Waste management strategies (e.g., collection, segregation, staging/storage,
transportation, treatment and disposal)
Waste tracking and reporting
Waste management oversight activities
Community outreach and communication plan
Waste management health and safety.
4,3 Known Laboratory Resources and Capabilities
The basic tasks of determining the extent of contamination, determining the efficacy of
decontamination, and characterizing waste for proper management are key sampling decisions
that place demands on laboratory resources. As a result, pre-incident planning, including the
development of sampling plans, should identify known laboratory resources to ensure that such
information is readily available during an incident. Planning can also identify gaps in coverage
that could be addressed as resources become available. Available laboratory resources with
capabilities to analyze CWAs should be identified prior to an incident so that individuals
developing sampling plans are aware of analytical capabilities (e.g., specific analyses and
equipment, matrices, detection limits) and laboratory quality capabilities (e.g., data quality
programs). EPA established the Environmental Response Laboratory Network (ERLN) as a
national network of laboratories that can be ramped up as needed to support large scale
environmental responses (EPA, 2017). The ERLN provides consistent analytical capabilities,
capacities, and quality data in a systematic, coordinated response. The ERLN integrates
capabilities of existing public-sector laboratories with accredited private sector laboratories to
support environmental responses.
Given the probable large number of samples requiring analysis, knowledge of laboratory
capacity and capability would assist distribution of samples to multiple laboratories to facilitate
timely analyses. Depending upon individual laboratory capabilities, this knowledge might also
assist in covering the diverse types of materials being sampled.
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r
4.4 Generalized DQOs Identified
The DQO process (see inset) is an
iterative seven-step process that
generates performance criteria for the
collection of new data that guide waste
management decisions. It is important
to recognize that the DQO process
might need to be repeated multiple
times as the incident unfolds and new
information becomes available.
Pre-incident planning might involve
identifying the data quality process
necessary to make decisions using data
of defined quality in the response and
recovery process following a wide-area incident. While decision-making will be performed in an
agent- and incident-specific manner during a wide-area incident, pre-incident knowledge of the
generalized DQOs and processes that are in place will facilitate the decision-making process.
1.
2.
3.
4.
5.
6.
7.
DQO Process
State the Problem
Identify the Goal of the Study
Identify Information Inputs
Define the Boundaries of the Study
Develop the Analytical Approach
Specify Performance or Acceptance Criteria
Develop the Detailed Sampling and Analysis
Plan for Obtaining Data
Note that the Process Should be Repeated as
New Data or Data Needs Are Identified
Six crucial inputs are necessary before developing the overall Sampling and Analysis Plan (SAP)
in step seven (EPA, 2006). The optimized SAP would outline the desired quality assurance (QA)
and quality control (QC) parameters to achieve the overall project goal. The SAP should outline
agent activity, agent formulation, toxicological properties, persistence, and other physical
properties of the agent at hand.
Knowledge of the types of decisions to be made and the desired data quality will assist in the
development of a range of potential sampling strategies for consideration prior to a specific
incident. For each activity detailed herein, DQO examples for a Decision Problem and an
Estimation Problem have been hypothesized (Appendix C) for a specific scenario. Note that the
DQO examples included in Appendix Care hypothetical and should be appropriately modified
for an actual incident but show the importance of having adequate DQOs during these types of
incidents.
5 Planning Assumptions
Three planning assumptions were identified during the development of this document and are
described in in the following subsections.
5.1 Limited Laboratory Capacity Relative to Analysis Needs
Laboratory resources are limited relative to the anticipated demand caused by a wide-area CWA
incident. The reasons for the lack of necessary laboratory capacity are twofold. The first reason
is that the laboratory capacity to analyze CWA agents is limited to existing ERLN laboratories.
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Using HD analysis as an example, there are only 10 ERLN laboratories in the United States
where samples can be sent for analysis.
The second reason is the potential for an extremely large number of samples that could be
collected and sent for laboratory analysis throughout a wide-area incident. Sampling is used
extensively in a wide-area incident for site characterization, decontamination efficacy, waste
characterization, and evaluation of clinical/medical samples. As result, there is the potential that
sample analyses could become a limiting pathway and greatly reduce progress on the overall
response and recovery. Evaluations were not identified that described the potential number of
samples associated with response to a wide-area CWA incident. However, one evaluation
reported the potential number of samples that may be collected to evaluate extent of
contamination in a wide-area release for a biological agent. France et al. (2015) evaluated
potential sampling needs for an airport area of approximately 140 square kilometers (km2) with
different rates for sample collection by material type (e.g., every 5,000 square meters [m2] of
open ground, every 500 m2 on asphalt, and every 100 m2 on buildings) and estimated that
approximately 85,000 samples would need to be collected. Laboratory analysis and timely
reporting of results cannot be performed on this scale of sample numbers.
While field analysis techniques represent a potential factor to limit demands on laboratory
resources, they might lack sufficient sensitivity to accurately determine the presence or
concentration of an agent across the material types in an urban environment (DHS, 2012a). As a
result, increased use of field analysis techniques alone is insufficient to fully address the issue of
limited laboratory capacity.
5,2 Lack of Universal Sampling Approaches for Wide-Area Incidents
A wide-area release of CWAs has the potential to impact square-kilometer areas of significant
size (e.g., tens of square kilometers) depending upon the agent released, the site-specific
definition of contamination by the responsible authorities (e.g., loading concentration, presence
or absence), weather conditions, and numerous other factors (DHS, 2012b). However, no
specific open-source guidance or peer-reviewed publications provide detailed sampling strategies
for such an incident. The agent-specific Quick Reference Guides (QRGs) developed by the U.S.
National Response Team (NRT) provide general agent information relevant to sampling and site
selection, waste management, and sample shipping considerations
(https://www.nrt.org/Main/Resources.aspx?ResourceTvpe=Hazards&ResourceSection=2Y
A primary challenge in determining sampling strategies is the development of sampling plans
that can be scaled for a broad geographic area while not exceeding the finite capacity of
laboratory resources. Based on the scale of the area for assessment, there might be resulting
tradeoffs that might affect overall data precision, accuracy, or generalizability. Knowledge of
traditional sampling approaches used at Superfund or other hazardous material remediation sites
might help to inform the identification of potential sampling approaches for consideration. These
approaches will likely have to be modified in a wide-area incident to stay within bounds of the
current laboratory capacity. As a result, it might be appropriate to consider potential
modifications when applying traditional sampling approaches in a wide-area incident. However,
data are scarce describing potential advantages and disadvantages for traditional sampling
approaches (with or without potential modification) when applied to a wide-area incident.
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6 Waste Characterization Process
6.1 General Characteristics of Waste Materials
Prior to characterization of waste for proper management, it must be determined which materials
or items will be treated as waste and which materials or items will be decontaminated and reused
(EPA, 2015a). The determination of materials as waste or items that will be re-used is likely to
be determined on an incident-by-incident basis (EPA, 2015a). However, there are some general
types of materials that are more likely to be waste than others. For example, waste materials from
a wide-area incident might include, but not be limited to (EPA, 2012d):
Personal protective equipment such as disposable gloves, suits, and boot covers;
Decontaminated items destined for treatment and disposal (e.g., carpet, furniture,
computers);
Spent decontamination reagents; and
Decontamination water (rinsate).
In the hypothetical Denver Wide Area Recovery and Resiliency Program (WARRP) chemical
agent scenario (Appendix C), an analysis of the waste generated noted that the greatest
contributors of items to be decontaminated and disposed were ceiling tile, carpet, electronics,
furniture, paper, and other office supplies (EPA, 2012d).
Items that are more likely to be considered for decontamination and reuse include:
Structural components of building spaces; and
High-value or irreplaceable materials (e.g., large computer servers, heavy equipment,
artwork, elements of subway cars).
After delineation of the waste and non-waste items in the sampling environment, waste
characterization must be performed on all waste items to ensure proper management. The waste
characterization process might not require sampling. Other characterization approaches (i.e.,
lines of evidence) may be used if acceptable to regulators and waste receivers. Materials will be
decontaminated, using appropriate approaches, prior to transportation off-site. When the
materials are aqueous wastes that may potentially be discharged to a wastewater system,
decontamination of such waste may include appropriate treatment prior to discharge. It is
important to identify whether owner/operators of the wastewater system have specific treatment
requirements for acceptance of the waste prior to initiating treatment (National Association of
Clean Water Agencies, 2005). The requirement for approval of the selected treatment by
owner/operators may be especially important if the wastewater system is not already
contaminated by uncontrolled discharges of contaminated water as may occur for wide-area
incidents.
One purpose of waste characterization is to determine if the waste meets the acceptance criteria
for a specified treatment or disposal facility or if subsequent decontamination/treatment is
required. The presence of multiple surface types in the urban environment may affect the ability
to decontaminate all materials to meet re-use criteria and may lead to re-designation of these
materials to waste when decontamination cannot be performed (DHS, 2012a). Furthermore,
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liquid waste designated for disposal may be complicated by the unknown factors determining
how chemical agents may behave in wastewater systems.
The significant volume of waste material generated from an urban wide-area incident will
require unique data gathering approaches for waste characterization. An urban wide-area incident
might produce millions of tons of waste. Sampling every bag or container of waste would be
logistically impossible based on the anticipated load placed on field teams to collect data and
laboratories for sample analysis. For example, waste analysis of the hypothetical Denver
WARRP chemical agent scenario (described more fully in Appendix C) estimated that there
could be 15 to 36 million gallons of aqueous waste and approximately 3 to 8 million tons of solid
waste generated due to the decontamination of personnel, materials to be reused, and materials
that will be disposed (EPA, 2012d).
The analysis of waste characterization samples will be competing with all other collection and
analytical resources (e.g., characterization, clearance, clinical) during consequence management.
Therefore, it is critical that waste sampling requirements be considered along with all other
analytical needs as part of the prioritization of available analysis capacity for various uses (EPA,
2015d). However, it is possible that waste characterization samples identified for laboratory
analysis may have a lower priority than other sampling tasks. As a result, care must be taken to
minimize the analytical samples needed to perform waste characterization while still meeting the
data requirements set forth by facility managers, transporters, and regulators. Ultimately, the goal
is to minimize the number of analytical samples sent to the laboratories and ensure that all
necessary sampling and analysis needs are met for consequence management.
The following best practices are applicable for waste characterization and apply during all phases
of response and recovery after an urban wide-area incident. The purpose of these best practices is
to optimize the collection and analysis of data to characterize waste in a manner that meets the
data quality needs of regulators and waste receivers. Waste characterization is a legal
requirement of federal, state, and local regulators (Lemieux et al., 2016) and is a condition of
acceptance of waste by waste receivers (e.g., landfills, incinerators, POTWs). Waste
characterization also provides necessary data for proper handling, labeling, transportation, and
treatment (Lemieux et al., 2016).
The identified best practices utilize available (EPA, 2015d) guidance on waste characterization
and the development of waste analysis plans. The best practices also provide additional
information specific to waste characterization of chemical agents and the wide-area incident
environment. The best practices incorporate the following three starting assumptions:
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Starting Assumptions:
Extent of the urban wide-area release is confirmed and the release is no longer
ongoing
Contaminating agent has been identified and the extent of contamination is well
characterized
Pre-Incident Waste Management Plan is in place
V
These best practices could also be used to help prepare pre-incident waste management planning
documents, particularly to initiate a dialog with the relevant regulatory authorities so that waste
management strategies could appropriately incorporate required analytical laboratory capacity
and capabilities. Pre-planning could identify applicable regulations, key decision-makers, and
potential waste management facility compliance requirements that are necessary to develop
sampling requirements and assess analytical laboratory capabilities (EPA, 2012d). Ideally, many
relevant technical decisions needed to perform waste characterization could be addressed via pre-
planning for various hypothetical scenarios. The waste characterization best practices were
developed for use by sampling professionals, especially those personnel who will be developing
the waste characterization sampling plan, as well as incident decision-makers such as those
experts serving on technical working groups. When developing a sampling plan for
characterizing waste for proper management, it is important to work closely with a wide range of
personnel to ensure that the sampling effort results are adequate to characterize the waste
including representatives from the following perspectives (EPA, 2003):
End user of data or decision-maker (e.g., waste receiver and federal, state or local
regulators);
Project Team (Manager or project chemist);
Health and Safety Officer;
Sampling Team (Lead);
Analytical Laboratory (Director or analytical project coordinator);
Quality Assurance;
Risk Assessment; and
Statistics.
6,2 Summary of Waste Characterization Process
Figure 3 reflects the overall waste characterization process. When presented with a collection of
waste materials, the first step is to segregate waste into homogeneous groups (e.g., porous,
nonporous) to facilitate identification of materials with similar properties to aid in the assessment
of residual agent levels. After the waste has been segregated, the waste acceptance criteria and
associated DQOs must be determined for each waste group. The waste acceptance criteria
include a concentration- or performance-based criterion and the volume of waste that will be
accepted. Individual waste groups might be targeted for different waste management options, and
individual waste management options might have unique waste acceptance criteria and DQOs. If
laboratory sampling is necessary to demonstrate that the waste acceptance criteria have been met,
15
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the laboratories with the desired analysis capabilities should be identified, and they should be
consulted for confirmation that they can perform the identified analysis at the requested sampling
load and that they will accept the waste material for analysis. After the waste acceptance criteria
and DQOs are known and laboratories identified if needed, the next step is to determine the
waste characterization strategy for each waste group. The waste characterization strategy can
consist of the use of lines of evidence, field and/or laboratory sampling, or a combination of the
two approaches. The next step is to collect the data. In the case of sampling, decisions must be
made on the overall sampling strategy, analytical approach (i.e., laboratory, field analysis, or
combination), analytical method, and collection method for the sample. Lines of evidence data
can be gathered from the literature, SMEs, waste receivers, regulators, and previously gathered
site data.
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START:
Collection of
Waste of
Materials
Please note that waste characterization
process may be affected by factors that
are not identified in the flow chart.
Examples of these factors may include:
cost, political considerations, public
concern, volume of waste accepted by
waste receiver, and selection of
decontamination technology.
Segregate Potential
Waste Materials into
Homogeneous
Groups (e.g., porous,
nonporous)
(Section 6.3)
Identify Waste
Acceptance Criteria
and DQOs for Waste
Receivers that Will
Accept Each
Segregated Waste
Group
(,Section 6.4)
Identify Laboratories with
Analysis Capabilities for
Desired Analyses that will
Accept Material
(Section 6.7)
Waste Characterization Strategy Determination
(Section 6.5)
Determine Use of Lines of Evidence (Section 6.5.1)
Determine Use of Sampling (Section 6.5.2)
Data Gathering Step
If Lines of
Evidence are
Used:
(Section 6.5.1)
If Sampling is Used, Determine:
What Sampling Strategies can be Used -
Nonprobabilistic, Probabilistic, or Combination?
(Sections 6.5.2. and 6.5.3)
Should Waste be Further Segregated Prior to
Sampling?
Will Field Screening and/or Laboratory Analysis will be
Used? (Section 6.7)
Can Composite Sampling be Performed? (Section
6.5.3.2)
Can Split Samples be Used? (Section 6.6.2)
Gather Knowledge from
Literature, Subject
Matter Experts, and
Previously Gathered Site
Data
(Section 6.5.1)
Identify Field
Analysis Method
(Section 6.7)
Identify
Laboratory
Analysis Method
(Section 6.7)
Identify Collection
Technique
(Section 6.6)
Identify
Collection
Technique
(Section 6.6)
Figure 3. Waste characterization process
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For clarity, progression through Figure 3 is intended to be a stepwise process. However, there are
multiple factors within the process that may be optimized to reduce the number of laboratory
samples and may result in the simultaneous determination of several process decisions or dictate
an iterative nature to waste characterization decisions. Agent- or incident-specific conditions
may also dictate the sequence and relevant considerations necessary for decision-making. It is
important to note that there may be additional outside factors that may affect the ability to
perform waste management, but that are not explicitly considered in the waste characterization
process. These factors might include, but are not limited to: cost, political consideration (e.g.,
stigma of waste), public concerns, volume of waste that can accepted by waste receivers,
acceptance of waste by potential waste receivers, and selected decontamination technology. Each
of the following sections describes the individual elements in the flow chart in greater detail.
Similarly, the information presented in each of the sections should be evaluated for its relevance
based on agent- or incident-specific conditions.
6,3 Segregation of Waste into Homogeneous Groups
After a collection of waste materials has been identified for characterization, the first step in the
waste characterization process may be to segregate waste into homogeneous groups. Segregation
of waste materials is necessary for collection of representative samples and might facilitate
reduced sampling requirements by waste receivers with prior approval. Materials that are
designated for re-use or recycling are not waste. However, these materials might re-enter the
waste stream if they cannot be decontaminated or are no longer able to be re-used or recycled.
Relevant areas of consideration to segregate waste include:
Material characteristics - e.g., porous, nonporous, material susceptibility to
contamination during the incident and decontamination technology in use;
Distribution of material characteristics - e.g., homogeneous or heterogeneous collection
of material characteristics to be sampled;
Agent characteristics - e.g., agent affinity for materials and surfaces, persistence under
defined environmental conditions; and
Environmental conditions - e.g., temperature, relative humidity, time since agent release.
To demonstrate how these considerations can be implemented in an environment likely to be
encountered in an urban wide-area incident, a typical office environment contaminated with
Agent Yellow will be reviewed using the areas of consideration identified above. A typical office
setting environment is a heterogeneous mixture of materials and surface types that exhibit
diversity in their likelihood to capture and retain released agent. In the office environment, the
presence of porous and nonporous materials may be a common contributor to heterogeneity in
waste materials. Porous material may include cubicle dividers, ceiling tiles, vinyl floor tiles,
fabric-covered chairs, carpeting, wallboard, or grout between tiles whereas nonporous material
may include stainless steel surfaces, desks, porcelain sinks, toilets, or glass. Materials that are
porous, permeable, organic or polymeric (e.g., carpet, floor tile) should be considered to
preferentially capture, retain, and release agents such as Agent Yellow (Mustard - Lewisite
Mixture, HL) (NRT, 2015h) when compared to nonporous materials.
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The presence of a heterogeneous mixture of materials in a sampling environment is a signal that
either waste segregation should be performed or a restricted set of sampling strategies should be
considered. EPA (2002b) reported that heterogeneous waste (such as demolition debris, drums)
can be challenging to sample representatively due to the variability in size, shape, and
composition. In the context of waste characterization, heterogeneous materials may exhibit
differing potential to capture and/or retain agent. The representativeness of the sample is a key
contributor to the accuracy of the sampling results to answer the sampling questions of interest
(EPA, 2003; EPA, 2015d).
As a result, the chemical concentrations may not be consistent across the mixture of
heterogeneous materials, affecting the ability to use sampling strategies and calculate statistical
measures that assume a relatively homogeneous waste source. In situations with a heterogeneous
mixture of materials, segregation of materials could be performed to group materials with similar
characteristics, and then random sampling could then be conducted within the segregated
populations of materials (i.e., stratified random sampling). Absent segregation of waste into
similar groupings, strategies must be selected that do not rely on identification and collection
from an individual population (e.g., simple random, systematic grid or transect, judgmental).
In addition to concerns regarding the chemical agent contamination levels of waste, waste items
might be packaged in bags, barrels, or other containers that inhibit access for sampling and could
affect collection of representative samples. The specific types of indoor waste materials
identified for the biological agent decontamination study might be useful for an indoor chemical
agent contamination incident.
6,4 Determine Waste Acceptance Criteria a
Prior to selection of appropriate data gathering strategies for waste characterization, the waste
characterization criteria and associated DQOs must be determined for each waste group and
waste receiver(s) identified that will accept the waste. The waste acceptance criteria define the
standards that must be met and the volume of waste that will be accepted. The DQOs define the
process to generate the data to document that the waste materials meet the waste acceptance
criteria. If a pre-incident WMP is not available, the relevant NRT QRG might be consulted as a
first step to identify general waste characterization information for an individual agent. For more
specific waste characterization and disposition information, consult other sources such the
Incident Waste Decision Support Tool [(i-WASTE DST) (2018)] and appropriate authorities
within the locality of the incident. It will also be helpful to identify contractor and waste receiver
resources that will be present on-scene during an incident who can provide region-specific
knowledge for waste characterization and available waste receivers.
Waste acceptance criteria identify the standards that must be met for an individual waste
management facility to accept the waste and the volume of waste that will be accepted. Waste
acceptance criteria can take the form of a concentration-based criterion or performance-based
criterion. Concentration-based criteria, also termed numerical-based criteria, identify chemical-
specific concentrations that must be must achieved. Concentration-based criteria are typically
associated with the presentation of analytical results and sampling plans to document attainment
19
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of the standard. Appendix C provides additional information on the types of comparisons that
might be associated with a waste acceptance criterion (e.g., comparison of average waste
concentration including upper confidence limit with concentration-based criterion).
The second type of waste acceptance criteria, performance-based criteria, identify the
technologies or treatment processes that can be used to treat the waste as a demonstration of
meeting identified clearance levels. With the prior approval of regulators and waste receivers,
performance-based criteria might take the form of lines of evidence data as detailed in Section
6.5.1. As part of a lines of evidence demonstration, technical documentation is then provided to
substantiate the effectiveness of the process and its effective implementation in the wide-area
incident during which the waste was generated. The use of performance-based criteria might still
be associated with sampling, either field screening or laboratory analysis, to verify anticipated
agent concentration levels in the waste. However, the number of samples required is likely to be
considerably reduced. The most current available waste management plan (i.e., pre-incident
WMP, incident-specific WMP) should be consulted for information on waste acceptance criteria
for the wide-area incident. If a pre-incident WMP is used, waste receivers and regulators should
also be re-contacted to ensure that the waste acceptance criteria are still valid and to confirm that
appropriate data collection strategies are identified.
To ensure that the process to achieve the waste acceptance standards meets the data quality needs
identified by decision-makers, EPA (1992b; 2002b) recommends following a systematic
planning process such as the DQO Process to define the quality control requirements for
sampling, analysis, and data assessment for environmental data collection. The DQO process can
be used to help clarify study objectives, define appropriate data types, and specify tolerable
levels of decision errors that will form the basis of establishing the quality and quantity of data
required (EPA, 2006). As described by EPA (2006), the DQO process is not specific for
chemical agents, so consideration must be give on how to apply the DQO process to the
contaminant at hand. In this manner, the optimized sampling plan would predetermine the QA
and QC parameters desired for achieving the overall project goal.
If lines of evidence are used to reduce or replace sampling, the DQO process will identify
indicators of data quality that must be met prior to use of these data in waste characterization.
For example, data quality indicators can identify quality requirements for data sources (e.g.,
peer-reviewed publication, federal agency report) that are deemed to provide acceptable data. If
sampling is conducted, an explicit evaluation of the characteristics of the waste materials (e.g.,
concentration distribution based on waste characteristics) should be performed relative to the
statistical requirements of the sampling strategies and associated statistical measurements as part
of the DQO process. An example application of the DQO process for waste characterization is
given in Appendix C.
6.5 Determine Waste Characterization Strategy
A waste characterization strategy must be developed to determine if the waste material meets the
identified waste acceptance criteria and DQOs. Figure 3 identifies the data gathering options
available during the waste characterization process. The purpose of the waste characterization is
to generate an accurate assessment of the residual contamination levels of an identified waste
20
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group. Data can be generated using lines of evidence, chemical analysis, or a mixture of both
data gathering approaches. Each approach will be discussed more fully in the following sections.
6.5.1 Lines of Evidence
The first element of consideration when collecting data for waste characterization is lines of
evidence. Lines of evidence are defined as information or data from various sources that can be
used to support waste characterization decisions and reduce the number of laboratory samples
required for analysis. Lines of evidence can include, but are not limited to, technical data on
agent fate and transport, persistence in defined environmental conditions, and efficacy of
decontamination technologies when properly deployed. Lines of evidence is analogous to the use
of acceptable knowledge for hazardous waste characterization that is "obtained from existing
published or documented waste analysis data or studies conducted on hazardous waste generated
by processes similar to that which generated the waste" (EPA, 2015d). Alternative names for
lines of evidence include process knowledge or generator knowledge (EPA, 2015d). Knowledge
of waste is an acceptable means of waste characterization for typical hazardous waste streams
(e.g., generation from a known industrial process) to determine whether a waste is likely to be a
solid or hazardous waste per federal and state regulations (EPA, 2015d) or if wastewater has
been sufficiently pre-treated prior to discharge to a POTW or surface water body. As a result,
lines of evidence might also have utility in the management of less typical waste streams such as
those generated from management of a wide-area incident. However, the use of lines of evidence
approaches might be more difficult for a CWA for which the level of knowledge is low relative
to the more studied CWAs such as HD or Lewisite. As a result, the effectiveness of lines of
evidence in reducing the number of laboratory samples may be limited.
Lines of evidence can dramatically reduce sampling and analytical demands associated with
waste characterization. For example, a demonstration of the efficacy of a decontamination
approach prior to a release incident could be used to reduce the number of waste characterization
samples (EPA, 2014c). However, the regulators and waste receivers must be involved in the
development of the lines of evidence demonstration and agree to its use to replace sampling data.
The availability of sufficient technical data is key to successful use of lines of evidence claims
(EPA, 2015d).
In the context of a wide-area incident, there are no prior published analytical studies that describe
the waste generated from such an incident. However, a broad definition of lines of evidence can
be employed with prior approval by the regulators and waste receivers. As a result, lines of
evidence data can be used to generate a weight of evidence determination that the waste items
will meet waste acceptance criteria. Relevant lines of evidence data will vary based on the
consequence management stage, management approach (e.g., active or passive decontamination
technologies), agent, and environmental conditions. For example, a weight of evidence
determination could be used to characterize residual contamination of waste after
implementation of a monitored natural attenuation process. The determination would document
available persistence data for the agent when associated with similar waste materials and
environmental conditions (e.g., temperature, relative humidity, operation of heating, ventilation
and air conditioning (HVAC) or other fans) during and after the incident. The identification of
conditions necessary for successful deployment of decontamination technologies followed by
21
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thorough documentation that these conditions were achieved might meet waste acceptance
criteria based on certification that the decontamination process was followed (DHS, 2012c).
General elements that could be relevant to characterize the residual contamination of waste
materials generated during a wide-area incident may include:
(1) Loading of chemical agent in or on waste material based on prior sampling results,
distance from release, and expected transport of contaminants (e.g., environmental fate
and transport, movement via contaminated persons and material),
(2) Fate and transport characteristics of chemical agent (e.g., affinity for porous
materials/surfaces, persistence),
(3) Environmental conditions (e.g., characteristics of waste material in contact with chemical
agent including porous or nonporous composition, temperature, relative humidity, time
since release), and
(4) Expected interaction of the chemical agent, material, and decontamination technology if
assessing waste after decontamination (e.g., time after monitored attenuation initiated,
loading of decontamination agent if applied, contact time, access of decontamination
technology to material in environment).
A second effective means of reducing sampling load is selection of waste management options
based on the reduced sampling requirements associated with them. For example, sulfur mustard,
which was sometimes disposed of at sea in the early 1900s, has recently resulted in human
exposure during clam harvesting by commercial fisherman (Coast Guard, 2010). In June 2010, a
commercial fishing vessel inadvertently harvested unexploded ordnance projectiles containing
sulfur mustard (Lagan, 2010). The projectiles leaked, requiring decontamination of the fishing
vessel and disposal of approximately 500,000 pounds of clams. The clams were shipped in lined
containers for incineration. Off-site incineration was selected over landfilling as the disposal
option in part because the clams were not required to be sampled and analyzed for sulfur mustard
prior to disposal (Coast Guard, 2010). Understanding and applying such processes in sampling
plans could reduce many of the waste sampling and analytical demands, which could greatly
reduce the time and expense associated with the overall response when there is available
incinerator capacity. This type of option may be most useful for selected waste materials that are
difficult to sample reliably or have some other characteristics that make management at a solid or
hazardous waste landfill infeasible.
6.5.2 Sampling Strategies
Samples must be collected and analyzed when non-sampling options cannot be used as the sole
determinant of residual contamination. In this context, the best practices define "sampling
strategy" as the study plan or design by which sample locations, numbers, and types are collected
for measurement to collectively reach an appropriate conclusion regarding the incident at hand
(EPA, 2015d). However, in the context of an urban wide-area release, the amount of waste
generated could overwhelm the laboratory analysis capacity with waste characterization efforts
alone. Sampling strategies for characterizing waste must incorporate approaches to streamline
the sampling process. Applicable sampling strategies to characterize waste for proper
management are summarized in an EPA report entitled "Waste Management Benefits, Planning
and Mitigation Activities for Homeland Security Incidents" (EPA, 2016b). The sampling
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strategy for waste will likely be dictated by federal regulations (e.g., RCRA) as implemented by
the states, and individual waste management facilities. Many states have delegated authority for
waste management and might have more stringent requirements than federal regulations. Since it
is most likely that a wide-area incident will require waste management facilities in multiple
states and/or regions, a pre-incident WMP should identify available facilities ahead of an
incident to ensure that waste management does not impede the response activities (EPA, 2015d).
Table 1 identifies the three most likely sampling strategies
for use in waste characterization. Appendix D provides a
more detailed table identifying sampling strategies that
might be used across all sampling tasks in a wide-area
incident, and might have utility for unique waste sampling
situations in the wide-area incident.
Waste Characterization
Sampling Strategies
Judgmental
Simple Random
Stratified Random
In more typical waste characterization scenarios, a random sampling approach is typically
identified as a strategy of choice for obtaining the most "representative sample" from waste
piles, which might include powdered, granular, or block materials of various size and structure
(EPA, 2002c).1 However, the complex mixtures of waste materials in an urban wide-area
incident and associated surfaces will require segregation to develop waste groups with similar
characteristics prior to the ability to generate a representative sample.
Non-probabilistic judgmental sampling, also termed biased sampling, is intended to collect
samples with the highest amounts of contamination (EPA, 2002b). Biased sampling might be
used when taking multiple samples from heterogeneous waste contained within a discrete item
(such as a barrel). The biased sampling conservatively estimates high-end contamination levels
and can be useful when there is insufficient sampling capacity for use of other strategies. This
strategy can be very efficient and cost-effective if the site is well known (Table 1). The strategy
also has advantages for screening to determine the presence or absence of agent.
With simple random sampling, each sample location/item has an equal chance of being sampled
(EPA, 2002c). Sample location selection is not haphazard, but is based on equiprobable
selection, often relying on the use of randomly generated numbers (EPA, 2002c). Simple random
sampling can be used only with uniform or homogeneous populations. Using prior knowledge
and professional judgment, stratified random sampling divides heterogeneous wastes into groups
that are relatively homogeneous (EPA, 2002c). The homogeneous groups are then randomly
sampled. The primary advantage of simple random sampling is that it allows for estimates of
uncertainty and statistics to be developed (Table 1). Simple random sampling can also be easy to
understand and implement after appropriate segregation has been implemented.
1 Note that regulatory programs or analytical methodologies may have specific definitions for
representative that should take precedence over other definitions of the term, as appropriate.
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Table 1. Features of Sampling Designs for Waste Characterization.
Sampling
Strategy
Non-Probabilistic
Judgmental
Probabilistic
Simple Random
Stratified Random
Definition Selection of samples based on professional
judgment alone without randomization. Biased
sampling (a type of judgmental sampling) is
intended to collect samples with the highest
amounts of contamination.
A set of sampling units is independently selected
at random from a population.
Prior information is used to determine groups (lots) that
are sampled independently.
Application Small-scale conditions are under investigation
Screening for presence/absence of a contaminant
Might be used in conjunction with simple random
sampling of containerized waste (i.e., samples
collected from within the container might be
judgmentally sampled to maximize the collection
of biological agen, such as collecting samples
from porous materials)
Relatively uniform or homogeneous
populations
Selecting a sample aliquot from a composite
sample
Used to produce estimates with pre-specified
precision for important subpopulations
Monitoring of trends
Used to gain specific information (i.e., mean)
regarding each group Potentially more efficient
approach for sampling heterogeneous wastes, if the
wastes can be segregated
Required
Laboratory
Resources
Low: site information used to minimize laboratory
resources
Medium: sample number is predetermined
Medium: sample number is predetermined
Wide-Area Can be very efficient and cost effective if site is
Pros well known
Ideal for presence/ absence screening
Quick implementation to achieve time and
funding constraints
Enables uncertainty and statistical inferences
to be calculated
Protects against sampling bias
Easy to understand and implement
Sample size formulas are available for
determining sample numbers (EPA, 2002a)
Provides an estimate of the population to effectively
define groups and specify sample sizes
Sample size formulas are available to aid in
determining adequate sample numbers (EPA, 2002a)
Wide-Area Dependent upon expert knowledge
Cons Cannot reliably evaluate precision
Personal judgment is needed to interpret data
Confidence statements regarding absence of
contamination difficult to make
Random locations might be difficult to specify
Sampling design depends upon the accuracy of
the conceptual model
All prior information regarding the site is
ignored
Sampling can be costly if there are difficulties
in obtaining samples due to location
Random locations might be difficult to specify
Sampling design depends upon the accuracy of the
conceptual model
All prior information regarding the site is ignored
Sampling can be costly if there are difficulties in
obtaining samples due to location
Cautions or *Does not ensure that unsampled items are free of
Additional contamination
Critical "Degradation by-products might be of concern
Information depending upon the parent agent and create a
hazardous environment incident after the parent (or
tested agent) is no longer present
Simple random sampling is often used as the
last stage of sampling when multiple iterations
are conducted - selecting an aliquot from a
composite sample
All populations should be relatively uniform
Degradation by-products might be of concern,
depending upon the parent agent, and create a
hazardous environment incident after the parent
(or tested agent) is no longer present
Each group should be homogeneous within itself
Groups should be defined before determining sample
sizes
Degradation by-products might be of concern,
depending upon the parent agent, and create a
hazardous environment incident after the parent (or
tested agent) is no longer present
Potentially more efficient approach for sampling
heterogeneous wastes, if it can be segregated
Reference(s) EPA (2006); EPA (2002a); EPA (1998); EPA
(2015c); EPA (2013a)
EPA (2002b); EPA (2002c); ITRC (2012); EPA
(2006)
EPA (2002b); EPA (2006)
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6.5.3 Sampling Strategy Tools
6.5.3.1 Visual Sample Plan - VSP
The Visual Sampling Plan (VSP) is a software tool that follows the DQO process and aids the
user in determining the number and location of samples that will be collected (PNNL, 2014).
Data collected per VSP and the associated sampling plan have the statistical confidence needed
for decision-making and typically involve a planning team with statistical expertise to guide a
statistical approach (PNNL, 2014). The development of VSP, which is public domain software,
was sponsored by several U.S. government agencies, including EPA (PNNL, 2014).
Within VSP, there are several applications (or sampling goals)
that are intended to address the rationale for why data are being
collected. One sampling goal, "Item Sampling", is especially
applicable to waste characterization. This module, which might
also be referred to as acceptance or compliance sampling, is
applicable for the sampling of discrete items (such as barrels).
The intent is to determine a limited number of discrete items that must be sampled from a larger
number of distinct items, so that an X % confidence statement can be made about Y % of the
population being acceptable. An example of VSP output for item sampling is: "If 51 of the 200
items are selected using random sampling and all 51 are acceptable, then you will be 95%
confident that at least 95% of the items in the population are acceptable" (PNNL, 2014). In the
instance of characterizing waste for proper management, the acceptability criteria could be, for
example, the absence of detectable chemical agent. EPA (2002b) acknowledged that a
straightforward approach to determine whether a specific proportion of waste achieves
acceptability is to use the simple exceedance rule, which requires zero or a few analysis results to
exceed an applicable standard for a set of samples. The statistical expertise of the planning team
should be utilized to ensure that the underlying statistical assumptions are met before proceeding
with a statistical approach. In addition, the planning team will need to ensure that the sampling
strategy includes all site-specific circumstances and established DQOs.
A similar approach to VSP item sampling was proposed by Sexton (1993) for sampling nearly
38,000 drums of solid heterogeneous mixed waste, containing hazardous and radioactive waste.
The drums were grouped and processed based, in part, on the procedure that produced the waste.
Random samples from approximately 25 drums for lot sizes of 100 or more would be used to
draw X %/Y % confidence statements such as X % confident Y % (or fewer) drums containing
hazardous waste will be accepted. A lines of evidence approach to characterize waste streams
can help optimize waste characterization strategies, if applied appropriately and planned in
advance. EPA (2015d) recognizes that there are rare cases where it is dangerous, impractical, or
unnecessary to use direct sampling and analysis to characterize waste feed streams. In these
instances, the use of lines of evidence approaches to characterize waste should be maximized to
document that: (1) the waste can be protectively handled at the specific treatment facility, and (2)
the treatment facility is complying with all federal, state, and local regulations (EPA, 2015d).
The advantages of the statistical sampling approaches that generate X %/Y % confidence
statements using the simple exceedance rule are that they are relatively easy (assumptions about
25
VSP includes functions
for developing sampling
plans with specific
sampling goals.
-------
the underlying data distributions are not required), and they can be used when many of the
analytical results are non-detections (EPA, 2002b). Statistical sampling designs for waste
characterization involve establishing an assumption of whether a waste is or is not hazardous,
designing a data collection program that will test that assumption, evaluating the resulting data,
and drawing a conclusion about whether the data are sufficiently strong to support or reject the
assumption, given the uncertainties in the data. Selection of an appropriate statistical approach to
sampling and data evaluation will depend upon the waste generation and management scenario,
the type of test data generated, the ability to apply statistical assumptions to the site-specific
conditions associated with the incident, and limitations on laboratory capacity to fulfill statistical
requirements. Depending on the desired level of confidence that will be assumed in the statistical
sampling design, statistical sampling might identify a specific number of samples to be collected
that does not effectively facilitate a reduction in the number of samples sent to laboratories for
analysis.
Efforts to segregate the waste to make the waste more homogeneous might allow decision-
makers to accept lower levels of confidence, which would likely result in fewer samples needed
(e.g., the use of stratified random sampling rather than simple random sampling of waste). As
noted by EPA (2002b), if stratified sampling is applied, one of the following types of
stratification will likely be used:
Spatial boundaries/physical area to be sampled (e.g., in an urban wide-area incident, this
might be all waste generated from the same floor of a decontaminated building);
Temporal boundaries/time interval to be sampled (e.g., this might be all materials
decontaminated on the same day); and
Component (items/materials) (e.g., waste items will likely be segregated to improve the
homogeneity of the population such as grouping carpet and ceiling tile waste separately).
Stratification by component type is applicable for wastes that are difficult to characterize such as
wastes originating from buildings (EPA, 2002b). Use of the item sampling approach in VSP (or
similar approaches) to generate X %/Y % confidence statements about a population based on
limited sampling might be enhanced or supplemented with judgment (biased) sampling to focus
on materials most likely to harbor chemical agent and/or composite sampling to further reduce
sampling and analytical efforts.
6.5.3.2 Composite Sampling
Composite sampling is a strategy in which multiple individual or "grab" samples (from different
locations or times) are physically combined and mixed into a single sample so that a physical,
rather than a mathematical, averaging takes place. Combining samples from multiple locations
into one sample might help reduce the resource demands on the analytical and sampling efforts.
Additional advantages of composite sampling are:
Improved precision (i.e., reduction of between-sample variance) of the estimate of the
mean concentration of a constituent in a waste or medium.
Reduced cost of estimating a mean concentration, especially in cases in which analytical
costs greatly exceed sampling costs or in which analytical capacity is limited
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Increased sample support and reduced grouping and segregation errors through the use
of "local" composite samples, formed from several increments obtained from a localized
area
Finding "hot spots" or determining whether the concentration of a constituent in one or
more individual samples used to form the composite exceeds a fixed standard.
Composite sampling is not a statistically based sampling strategy per se. However, composite
sampling can be used in conjunction with the strategies listed in Table 1 to maximize the
area/items sampled while minimizing analytical costs. For example, if three to four samples are
to be collected from each discrete item sampled, a single composite sample (i.e., a single wipe
used to sample all three or four surfaces) would still result in only one sample to analyze rather
than three or four. There are multiple ways to composite samples. For example, one approach
simply uses the same sampling device (e.g., a wipe) to sample multiple locations. Another
approach might combine multiple sample extracts into one sample for analysis. Composite
samples can improve sampling precision while reducing the number of samples analyzed (EPA,
2002b). Composite sampling might be especially beneficial when the prevalence of
contamination is low (EPA, 1995).
EPA (2002b) gave an example where systematic composite sampling was used to make
remediation decisions for tetrachlorodibenzo-p-dioxin-contaminated soil. EPA (2005) also
provided examples of how composite sampling has been used with chemical contamination
including the characterization of polyaromatic hydrocarbon soil contamination at a Superfund
site, assessing contamination in fish tissue, and ground water monitoring programs.
Potential limitations associated with composite sampling might be:
When a regulation specifies otherwise;
When sampling costs are much greater than analytical costs;
When analytical imprecision outweighs sampling imprecision and population
heterogeneity;
When individual samples are incompatible and may react when mixed;
When properties of discrete samples such as pH or flash point may change qualitatively
upon mixing;
When analytical holding times are too short to allow for analysis of individual samples if
testing of individual samples is required later (e.g., identify a "hot" sample);
When the sample matrix impedes correct homogenization and/or subsampling;
When there is a need to evaluate whether the concentrations of different contaminants
are correlated in time or space;
When samples contain volatile chemicals;
When the integrity of the sample may be compromised by physically combining samples
(e.g., samples that contain volatile chemicals) (EPA, 2002b).
The integrity of individual sample values could be affected by chemical precipitation,
exsolvation, or volatilization during the pooling and mixing of samples. For example, volatile
constituents can be lost upon mixing of samples or interactions can occur among sample
constituents. In some cases, compositing of individual sample extracts (e.g., volatile constituents)
27
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within a laboratory environment might be a reasonable alternative to mixing individual samples
as they are collected.
6.6 Determining Sample Collectk unique
Sample collection techniques have not been standardized for characterizing waste for disposal
following an urban wide-area incident (EPA, 2014c). Waste associated with these incidents is
often porous in nature and might be wet following decontamination with liquid decontaminants,
which tends to decrease the efficiency of many sample collection techniques. The sampling of
wastes might further be complicated by limited accessibility issues as waste being stored in bags,
barrels, or dumpsters, or the waste might be bundled.
The most likely sample collection approaches for use are documented in Table 2. This table
summarizes the collection approaches and their applications, pros and cons, and additional
cautions. Selected collection approaches will depend upon the type of waste (e.g., porous or
nonporous, wet or dry) and the physical state of the wastes (i.e., liquid or solid). A
comprehensive table describing sample collection approaches is provided in Appendix E.
The NRT (https://www.nrt.org) produces and regularly updates QRGs that are specific to various
chemical hazards. In a similar manner, the EPA has developed the Environmental Sampling and
Analytical Methods Program (ESAM) (https://www.epa.gov/homeland-security-
research/environmental-sampling-analytical-methods-esam-program-home) to facilitate a
coordinated response to a chemical contamination incident. The program is comprised of
documents and information supporting field and laboratory efforts for site characterization,
remediation and release, including the Selected Analytical Methods for Environmental
Remediation and Recovery (SAM) (https://www.epa.gov/homeland-securitv-research/sam). The
analytical approaches included in SAM are not specified for waste samples (except post-
decontamination wastewater), but the protocols are intended more generally for soil/powders,
particulates (swab, wipe, and dust socks), liquid/water, and aerosols. Additionally, coordination
with qualified laboratory personnel or chemical analysis SMEs is necessary when selecting
incident-specific sampling and analysis approaches. While every effort has been made to prepare
for a CWA incident, verified or validated sample collection methods might not be available for
the chemical agent and sample type of interest (see the SAM document for several sample types
such as soil, surfaces, water, etc.). Therefore, protocols might need to be adapted from similar
chemicals and/or sample types in the scientific literature. Collection approaches should be
evaluated relative to the site-specific circumstances and DQOs. Note that QRGs and SAM
documentation do not detail CWA detection methods but rather direct the user to the ERLN. To
control DQOs, QA/QC, and data comparability, only laboratories approved by ERLN are
authorized to handle and analyze CWAs (https://www.epa.gov/emergencv-
response/environmental-response-laboratory-network).
Regardless of the sample collection approach or the determined purpose of the sampling effort,
sampling kits would ideally be available to aid in the organization and ease of use of the
collectors. Each sampling kit should be comprised of the sample container, materials, supplies
and appropriate forms needed to collect the field samples, decontaminate the exterior, and field-
pack the samples for transport to the specified analytical laboratory. Sampling kits might need to
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be built for the specific incident as each agent and collection technique might require specific
materials (EPA, 2014b). Guidance is available to assist in constructing the appropriate field
sampling equipment, supplies, and field documentation that should be included in each sampling
kit (EPA, 2014b).
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Table 2. Features of Various Sample Collection Approaches for Waste Characterization
Extractive (Solid Material)
Sampling
Wipe (Surface)
Sampling
Liquid (Surface)
Sampling
Liquid (Drum) Sampling -
Discrete Depth Samplers
Liquid (Drum)
Sampling -
Profile Samplers
Air
Sampling
Description Extractive sampling refers to
whole objective sampling or
the cutting/removal of a
portion of the material
sampled. Might also be
referred to as bulk sampling or
direct extraction.
Surface sampling
techniques using wipes,
cotton-balls/wipes, or
gauze sponges.
The collection of liquid
samples from the
surface (or shallow
depths) might be
obtained with various
devices including a
bailer, dipper, liquid
grab sampler, swing
sampler, or solid phase
microextraction fibers.
Liquid samples might be
obtained from discrete
depths with a variety of
devices include a syringe
sampler, discrete level
sampler, lidded
sludge/water sampler, or
solid phase
microextraction fibers.
Liquid samples might be
obtained from
throughout a vertical
column of liquid or
sludge with a variety of
devices including a
composite liquid waste
sampler (COLIWASA),
drum thief, valved drum
sampler, plunger type
sampler or solid phase
microextraction fibers.
Air sampling devices
such as those that
might be used to
sample the headspace
of waste containers for
volatile compounds
could include solid
phase adsorbent media
(tubes), solid phase
microextraction fibers,
or air samplers (e.g.,
SUMMAฎ canisters).
Application Applicable for the sampling
of targeted areas (sink
materials) where liquid
agent might remain,
especially porous surfaces
or collection of spilled
powder
Applicable for sampling
materials that are not
amenable to wipe sampling
such as materials that are
wet, irregularly shaped,
and/or porous
Might be applicable for
sampling heterogeneous
waste; cutting, chipping, or
drilling of waste samples
(and subsequent
grinding/mixing together)
can make the samples more
homogeneous and amenable
to being sampled simply
with a spoon or scoop
Generally used for
sampling smooth,
nonporous surfaces
but might also be
used on porous
surfaces (EPA,
2012b)
Applicable to
relatively small
sample areas
Although designed for
groundwater
sampling, bailers can
be used to collect
liquid samples from
tanks and surface
impoundments; bailers
collect samples of 0.5
to 2 liters
The dipper, liquid
grab sampler, and
swing sampler
generally collect 0.5-
to 1.0-liter samples
from the surface of
drums, tanks, and
surface impoundments
The syringe sampler and
discrete level sampler
can collect 0.2- to 0.5-
liter samples from
drums, tanks, and surface
impoundments
A lidded sludge/water
sampler can collect 1.0-
liter volumes from tanks
and ponds
Profile sampling devices
typically collect between
0.1- to 3-liter samples
from tanks and drums, as
well as surface
impoundments
Air sampling,
especially of the
headspace of waste
containers might be
helpful in confirming
that adequate
decontamination of
wastes materials has
occurred
Wide-Area Extractive-based sampling
Pros minimizes the loses of agent
that might arise with
Can be an easy and
quick way of assessing
surface contamination
levels
The bailer, dipper,
liquid grab sampler,
and swing sampler are
A syringe sampler is
easy to use and
decontaminate; it can
also be used to sample
The COLIWASA, Analysis of samples
drum thief, and valved from some sampling
drum sampler are devices can be
inexpensive, easy to
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Extractive (Solid Material)
Sampling
Wipe (Surface)
Sampling
Liquid (Surface)
Sampling
Liquid (Drum) Sampling -
Discrete Depth Samplers
Liquid (Drum)
Sampling -
Profile Samplers
Air
Sampling
collection inefficiencies of
other sampling protocols
generally easy to use
and inexpensive
Analysis of samples
from some sampling
devices can be
performed in the field
for some analytes.
discrete depths, including
the bottom
The jar in the lidded
sludge/water sampling
device serves as the
sample container
reducing the chance of
cross-contamination
Solid phase
microextraction fibers
can be taken into the
field to sample. These
samples might be
returned to the laboratory
for analysis or the fibers
can be analyzed in the
field using portable
GC/MS systems
use, and available as
reusable or single-use
models
The plunger type
sampler is easy to
operate, relatively
inexpensive, and is
available in various
lengths
Solid phase
microextraction fibers
can be taken into the
field to sample. These
samples might be
returned to the
laboratory for analysis
or the fibers can be
analyzed in the field
using portable GC/MS
systems
performed in the field
for some analytes
Wide-Area Extractive-based sampling
Cons might be difficult for
personnel working in
personal protective
equipment.
Extractive-based sampling
techniques are not well
defined/established
Extracted samples might
require more extraction
solvent and more time to
process than other surface
sampling approaches
Small concentrations of a
contaminant might be
diluted within a larger bulk
sample
Wipe sampling might These sampling devices
not result in high agent are not intended to
recoveries from
porous materials such
as wood
Wipe sampling
procedures can vary
based on the agent of
interest and the
material sampled
Limited in area that
can be sampled (100
cm2)
collect samples from
specific/deep subsurface
depths (unless a point-
source bailer is used)
The maximum depth that
can be reached with a
syringe sampler is
approximately 1.8 meters
The lidded sludge/water
sampling device is rather
heavy and limited to one
jar size
The COLIWASA,
drum thief, and valved
drum sampler can be
difficult to
decontaminate, and it
might be difficult to
collect samples from
the bottom of the
container
The drum thief cannot
sample depths longer
than the drum thief
itself
Might be difficult to
implement, depending
upon the accessibility
of the containerized
waste to be sampled
Cautions or Extraction efficiencies and
Additional agent recoveries will vary
Critical with material and extraction
Information approach
Agent recovery will
vary depending upon
the area sampled,
material type, wipe
> Liquid samples should
be collected with the
appropriate
Liquid samples should
be collected with the
appropriate neutralizers
and stabilizers added
Liquid samples should For sampling vapors
be collected with the that are heavier than air
appropriate (e.g., sulfur mustard
and Lewisite), include
31
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Extractive (Solid Material)
Sampling
Wipe (Surface)
Sampling
Liquid (Surface)
Sampling
Liquid (Drum) Sampling -
Discrete Depth Samplers
Liquid (Drum)
Sampling -
Profile Samplers
Air
Sampling
Constituents within some
materials might interfere
with detection technologies
Extractive-based sampling
techniques are not well
defined/established
Neutralization might be
needed to inhibit any
residual decontamination
solution that could possibly
bias/lower the agent
recoveries
Evidence collection
sampling might have been
conducted in this manner
material, amount and
type of wetting
solution, wipe pattern,
etc.
Recovery might be
affected by the
presence of dirt and
other residues as well
as background
chemical constituents.
neutralizers and
stabilizers added
> Larger sample
volumes or multiple
samples might be
required such that
filtration can be used
to detect low levels of
contamination
Larger sample volumes
or multiple samples
might be required such
that filtration can be
used to detect low levels
of contamination
neutralizers and
stabilizers added
Larger sample
volumes or multiple
samples might be
required so that
filtration can be used
to detect low levels of
contamination
low lying areas where
vapors might
accumulate
Reference(s)
EPA (2012d); Nassar et al.
(1998); NRT (2015a)
EPA (2008); EPA
(2014a); Koester and
Hoppes (2010); Nassar
et al. (1998); NRT
(2015a); Qi etal. (2013)
EPA (2002b); NRT
(2015a); Popiel and
Sankowska (2011)
EPA (2002b); NRT
(2015a); Popiel and
Sankowska (2011)
EPA (2002b); NRT
(2015a); Popiel and
Sankowska (2011)
Kimm et al. (2002);
NRT (2015a); Popiel
and Sankowska (2011);
Smith etal. (2011)
* SAM (which guides the ERLN laboratories) focuses on environmental sample types that are most prevalently used to fulfill EPA's homeland security
responsibilities following an incident involving chemical agents (e.g., aerosols, surface wipes or swabs, drinking water, and post-decontamination wastewater).
Other sample types (e.g., soil and vacuum samples) might have to be analyzed, and for those sample types, specific requests should be sent to the SAM technical
contacts.
32
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6.6.1 Decontamination Rinsate Sample Neutralization
Waste that will be placed in a landfill may require decontamination prior to disposal.
Neutralization of the decontaminant is a potentially important consideration. Decontaminant in
the rinsate or extraction liquid of waste-associated samples could bias the analytical results. This
bias could result from analytical interferences or simply by allowing additional reaction time
between the decontaminant and the contaminant. To determine contaminant
concentration/viability at the time of sampling, decontaminant neutralizers should be added
immediately after sample collection to inhibit the decontaminant activity (EPA, 2014c). Prior to
characterizing waste, neutralization tests might need to be conducted to determine the amount
and type of neutralizer required to inhibit the activity of any residual decontaminant. For
example, Qi et al. (2013) used a sodium thiosulfate solution to neutralize the oxidants associated
with CWA testing with sodium percarbonate and tetraacetylethylenediamine. Note that the waste
acceptance criteria at waste treatment or disposal facilities frequently limits or prohibits standing
liquids in the bags or containers of waste. It is critically important that the appropriate regulatory
authorities be consulted when planning any on-site waste treatment operations (including
additional decontamination and/or neutralization), so that decisions meant to expedite the waste
management process do not inadvertently complicate and/or paralyze the waste management
(Ierardi, 2013).
6.6.2 Split Samples
The potential use of split samples should be considered to collect samples more efficiently. If
appropriate, it should be incorporated in the initial stages of planning for sample collection. A
split sample is a sample that is collected from a single location but will be analyzed in two or
more analyses. For example, one sample could be collected from decontamination rinsate that
would be split for individual organic and inorganic analyses. Care must be taken that an
appropriate sample volume is collected to perform each desired analysis and that necessary
sample treatment or preparation is appropriately identified for each sample analysis to be
performed.
6.7 Determine Analytic (unique and Available Laboratories
Numerous analytical techniques might be used to determine the concentration of a particular
target analyte within a collected environmental sample. Target analytes should include CWAs,
non-CWA constituent chemicals (i.e., arsenic in Lewisite) but also degradation products and any
chemicals that may remain from the decontamination process that may pose a human health,
safety, or ecological hazard. Regardless of the contaminants that may or may not remain in the
waste, waste characterization requirements might be imposed (e.g., Toxicity Characteristic
Leaching Procedure [TCLP]) due to other potentially hazardous components. Therefore, it is
important to check with the relevant authorities to determine the waste acceptance criteria and
associated regulatory requirements. However, these best practices are focused on minimizing the
laboratory requirements when characterizing waste for management following an urban wide-
area incident. For target agents where no natural concentrations are found within the typical
urban area (e.g., VX or HD), field tests and/or quick-response laboratory analyses that determine
presence or absence might be appropriate with prior planning and approval from waste
authorities.
-------
After the determination of the appropriate analytical technique for samples that will require
laboratory analysis, laboratories should be identified that have the capability to perform the
requested analyses. It is important to then confirm with the laboratories that they will accept the
waste material and that they can perform the requested analyses within the required DQOs (e.g.,
method detection limit) for the identified type(s) of waste (e.g., decontamination rinsate,
contaminated bulk solids). Specifically, coordination with the laboratories should take place
prior to collection of samples to ensure that the laboratory will accept samples with potential
contamination by CWAs and that they have the capacity to perform the number of requested
analyses.
Analytical methods are not available specifically for waste materials. However, there might be a
number of possible analytical approaches that could be used to detect a CWA or its degradation
by-products within a generated waste stream. However, the technique used for waste
characterization must have a quantitation limit below the waste facility acceptance criteria
outlined in the DQOs (EPA, 2013c). Ideally, the selected analytical protocol would be able to
detect the agent of interest to the lowest available quantitation detection limit as decontaminated
waste will likely have low or negative results. Often, the more sensitive techniques that provide
the greatest level of confidence for chemical identification and quantification will require a
laboratory with well-trained operators rather than a rapid, field-based protocol, and therefore
sample results might not be available immediately
(EPA, 2013c). Possible laboratory techniques for
low concentration CWA testing include, but are not
limited to, gas chromatography coupled with flame
photometric detection, mass spectrometry, and
tandem mass spectrometry.
QRGs that are specific to various chemical hazards are available from the NRT
(https://www.nrt.org). Agent-specific SAM sampling documents that outline rapid screening
protocols are available from EPA for Environmental Remediation and Recovery
(https://www.epa.gov/homeland-security-research/sam). The most current SAM document and
the product website should be consulted to determine whether an EPA-validated method exists
for the specified agent and sample type under consideration. In addition, the SAM website has
several companion documents related to sample disposal, rapid screening and preliminary
identification techniques, and sample collection procedures. The analytical approaches included
in SAM are not specified for waste samples (except post-decontamination wastewater), but the
protocols are intended more generally for soil/powders, particulates (swab, wipe, and dust
socks), liquid/water, and aerosols.
The chemical techniques included within SAM have been assigned tiers to indicate the level of
usability for a specific analyte and sample type, although in interpreting these tiers, it will be
necessary to match the waste type most closely to the sample type listed in SAM. If a validated
method is not available, the best available protocol adapted from the chemical literature might
need to be conducted. The analysis of atypical samples/materials (i.e., not described in SAM)
will require coordination with the SAM technical contacts and the ERLN. The analysis of
atypical samples/materials may increase analytical cost and the analysis time. For all the
EPA's SAM document should be
consulted to determine whether a
validated method exists for the
specified agent and sample type under
consideration.
34
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analytical approaches used, careful documentation of the accuracy and limits of detection and
quantitation must be available to meet all predefined QA/QC measures. For many CWAs, most
laboratories will not have access to ultra-dilute analytical standards for calibration and QC.
Access to the CWA agents is controlled by numerous statutes and regulations. The ERLN is
supplied with ultra-dilute chemical warfare agent standards (EPA, 2013b). These ultra-dilute
standards contain approximately 5-10 parts per million of select CWAs that serve as authentic
standards and aid in analytical protocol development by the ERLN (EPA, 2013b). Contact the
ERLN directly at https://www.epa.gov/emergencv-response/environmental-response-laboratory-
network for information regarding laboratory requirements to possess and use ultra-dilute agent
standards.
If analytical challenges/gaps arise with SAM and analytical techniques for quantifying CWAs on
waste materials, approaches potentially applied more often in Department of Defense-related
settings could be discussed, such as:
Tenting of waste followed by the monitoring of headspace vapor concentrations with gas
chromatography (National Academy of Sciences, 2012).
Ionization mass spectrometric technologies to directly measure (semi-quantitatively) the
chemical composition of material surfaces, including porous surfaces (National Academy
of Sciences, 2012).
However, these techniques have not yet been proven for environmental remediation scenarios.
Limitations include the inability to directly measure the waste materials during the tenting
approach and the potential to increase the spread of contamination during the ionization mass
spectrometric approach. Additional testing is needed prior to use in an environmental
investigation.
6.7.1 Degradation Products
For post-decontaminated waste associated with CWAs, it is important to analyze for dangerous
degradation products, some of which (e.g., EA-2192 - S-(2-diisopropylaminoethyl)
methylphosphonothioic acid) could be as hazardous as the parent CWA (e.g., VX) (Munro et al.,
1999). Capoun and Krykorkova (2014) and Qi et al. (2013) each conducted separate studies that
documented degradation products of multiple CWAs following various decontamination
technologies. In each study, the decontamination products found were dependent upon the initial
chemical agent(s), the environmental conditions, and the decontamination process used. Munro
et al. (1999) identified important degradation products from the standpoint of environmental
persistence and toxicity. Because Lewisite is an arsenical, inorganic arsenic will likely remain
following decontamination and will need to be considered during all waste management plans
(EPA, 2014a). Similarly, a VX decontamination study using a hydrogen peroxide-based solution
found that EA-2192 persists for at least one week in rinsate-effluents (Wagner and Xega, 2012).
A review of degradation products and markers of contamination for selected CWAs is provided
in Table B-l.
Many chemical warfare agent decontamination technologies include strong alkaline chemicals
that make it difficult to detect trace levels of degradation products in the decontamination
35
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solution (Koskela et al., 2007). Nerve agent degradation products on select surfaces have also
been detected via wipe sampling (Willison, 2015). Careful attention should therefore be given to
degradation by-products when selecting the appropriate analytical approach for characterizing
waste for proper waste management.
7 Conclusions
A wide-area incident that releases a CWA in an urban area will require a significant response
effort and involve complex management activities. Wide-area contamination incidents can
generate large numbers of samples with the potential to overwhelm existing laboratory analysis
capacity. Sample analysis has the potential to become a bottleneck that may impede a timely
recovery.
A literature search found few documents that addressed sampling approaches specific to CWA
wide-area incidents. No resources were identified that evaluated CWA wide-area sampling
approaches relative to their demand on laboratory resources. Thus, best practices identified in
this report are reflective of traditional sampling approaches for a wide-area incident (e.g.,
sampling strategies at a Superfund site). Although the incident- and agent-specific considerations
are intended for the selection of sampling approaches during a CWA wide-area incident, the best
practices may also be used for a variety of chemical scenarios and pre-planning activities.
Numerous data gaps and uncertainties were identified during the evaluation of potential sampling
approaches to minimize laboratory demand during management of a CWA wide-area incident.
Significant data gaps included:
The lack of available data on the impact of sampling strategies and collection techniques
that will affect sample analysis numbers and the resulting laboratory demand;
Applicability of a composite sampling approach during various stages of consequence
management;
Verified and validated sample collection techniques for materials commonly found in the
urban environment; and
How to handle mixtures of contaminants during the characterization process.
Potential research studies that may bridge these data gaps were also identified and include:
Statistical evaluation of resampling when using compositing systems at various stages of
consequence management;
Statistical evaluation of resampling when identified rates of residual contamination are
present;
Testing of various sample collection techniques for commonly identified materials (e.g.,
cement, marble); and
Appropriateness of various field screening techniques.
36
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PNNL (2010). Acceptance Sampling Using Judgemental and Randomly Selected
Samples. Oak Ridge, TN: U.S. Department of Energy, Pacific Northwest National
Laboratory. PNNL-19315;
http://www.pnl.gov/main/publications/external/technical_reports/PNNL-19315.pdf.
PNNL (2014). Visual Sample Plan Version 7.0 User's Guide. Richland, WA: U.S.
Department of Energy, Pacific Northwest National Laboratory. PNNL-23211;
http://vsp.pnnl.gov/documentation.stm.
Popiel, S. and M. Sankowska (2011). Determination of Chemical Warfare Agents and
Related Compounds in Environmental Samples by Solid-Phase Microextraction with Gas
Chromatography. Journal of Chromatography A. 1218(47): 8457-8479.
Qi, L., G. Zuo, Z. Cheng, L. Wang, and C. Zhou (2013). Treatment of Chemical Warfare
Agents by Combined Sodium Percarbonate with Tetraacetylethylenediamine Solution.
Chemical Engineering Journal. 229: 197-205.
Sexton, R.A. (1993). An Approach for Sampling Solid Heterogeneous Wastes at the
Hanford Site Waste Receiving and Processing and Solid Waste Projects. Prepared for the
U.S. Department of Energy Office of Environmental Restoration and Waste Management
by Westinghouse Hanford Company, Presented at Second International Mixed Waste
Symposium, Baltimore, Maryland.
Smith, J.N., R.J. Noll, and R.G. Cooks (2011). Facility Monitoring of Chemical Warfare
Agent Simulants in Air using an Automated, Field-Deployable, Miniature Mass
Spectrometer. Rapid Communications in Mass Spectrometry. 25(10): 1437-1444.
Wagner, G.W. and R. Xega (2012). Mitigation of VX Effluents in Thorough
Decontamination Operations. Industrial & Engineering Chemistry Research. 51(49):
16146-16150.
Willison, S.A. (2015). Investigation of the Persistence of Nerve Agent Degradation
Analytes on Surfaces through Wipe Sampling and Detection with Ultrahigh Performance
Liquid Chromatography-Tandem Mass Spectrometry. Analytical Chemistry. 87(2): 1034-
1041.
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Appent ossary
Agency - A division of government with a specific function, or a non-governmental organization
(e.g., private contractor, business, etc.) that offers a specific kind of assistance. In the incident
command system (ICS), agencies are defined as jurisdictional (having a statutory role in incident
mitigation) or assisting and/or cooperating (providing resources and/or assistance).
Agent Yellow - a mixture of the CWAs sulfur mustard (HD) and Lewisite (L) that was
evaluated as part of the Wide-Area Recovery and Resiliency Program (WARRP) chemical attack
scenario in Denver
All-Hazards - The spectrum of all types of hazards, including accidents, technological incidents,
natural disasters, terrorist attacks, warfare, and chemical, biological (e.g., pandemic influenza),
radiological, nuclear, or explosive incidents.
Bias - Sampling, analytical or statistical inaccuracies that result in an incorrect estimate of a true
concentration estimate (EPA, 2002b).
Clearance - The process of determining that a cleanup goal has been met for a specific
contaminant in or on a specific site or item. Generally, occurs after decontamination and before
re-occupancy.
Cleanup Goal - For the purposes of this document, a level that has been determined by
decision-makers determining that decontamination was effective and/or a specific contamination
no longer poses a concern.
Code of Federal Regulations (CFR) - The codification of the Federal regulations published in
the Federal Register by the executive departments and agencies of the Federal government. Each
volume of the CFR is updated once each calendar year and is issued on a quarterly basis. See
http ://www. gpo. gov.
Critical Infrastructure (CI) - Systems and assets, whether physical or virtual, so vital that the
incapacity or destruction of such might have a debilitating impact on the security, economy,
public health or safety, environment, or any combination of these matters, across any Federal,
state, regional, territorial, or local jurisdiction (DHS, 2011).
Decision Unit (DU) - Subdivisions of a larger population of waste or media about which
decisions can be made (EPA, 2002b).
Decontamination- Processes used to reduce, remove, inactivate, or neutralize chemical or
biological contamination. Decontamination might include physical, chemical, or other processes
to meet a cleanup goal.
Data Quality Objectives (DQOs) Process - A series of logical steps that guides managers or
staff to plan for the resource-effective acquisition of environmental data to ensure that the quality
of the data are sufficient for the intended use (EPA, 2006).
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Emergency - Any incident, whether natural or man-made, that requires responsive action within
hours to protect life or property. As defined in the Stafford Act, any occasion or instance for
which, in the determination of the President, Federal assistance is needed to supplement state and
local efforts and capabilities to save lives and to protect property and public health and safety, or
to lessen or avert the threat of a catastrophe in any part of the United States (42 U.S.C. 5122).
Federal On-Scene Coordinator (OSC) - The Federal official responsible for coordinating and
directing Federal responses under subpart D, or the government official designated by the lead
agency to coordinate and direct removal actions under subpart E, of the National Contingency
Plan (NCP) (per 40 CFR 300.5). The specific duties of the OSC are provided in 40 CFR 300.120.
The Federal OSC is predesignated by the U.S. Environmental Protection Agency (EPA), U.S.
Coast Guard, U.S. Department of Energy (DOE), or U.S. Department of Defense (DoD)
depending upon the location and/or source of the release and might be designated by other
Federal agencies under certain circumstances.
Federal Register (FR) - The official weekday publication for rules, proposed rules, and notices
of Federal agencies and organizations, as well as executive orders and other presidential
documents. See http://www.gpo.gov/fdsvs/browse/collection.action?collectionCode=FR.
Hazardous Waste - Waste that, because of its quantity, concentration, physical, or chemical
characteristics, might: (1) cause or contribute to increased mortality or illness or (2) pose a
potential hazard to human health or the environment when improperly treated, stored,
transported, or disposed of, or otherwise managed (EPA, 2015b). Hazardous wastes are a subset
of solid wastes. See Solid Waste for the definition of a solid waste for the purposes of this
document.
Incident - An occurrence, caused by either human action or natural phenomena, that might
cause harm and might require action. Incidents can include major disasters, emergencies,
terrorist attacks, terrorist threats, wild and urban fires, floods, hazardous material spills, nuclear
accidents, aircraft accidents, earthquakes, hurricanes, tornadoes, tropical storms, war-related
disasters, public health and medical emergencies, and other occurrences requiring an emergency
response.
Initial Response - Actions taken immediately following notification of a contamination incident
or release. In addition to search and rescue, scene control, and law enforcement activities, initial
response might include initial site containment, environmental sampling and analysis, and public
health activities such as treatment of potentially exposed persons.
Key Resources - As defined in the Homeland Security Act, publicly or privately controlled
resources essential to the minimal operations of the economy and government.
Laboratory - A permanent/semi-permanent facility with capabilities for processing and
assessing environmental samples with predetermined detection limits.
Lines of Evidence - Information or data from various sources that can be used to support waste
characterization decisions. Lines of evidence can include technical data on agent fate and
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transport, persistence under defined environmental conditions, and efficacy of decontamination
technologies.
Method - For the purposes of this document, a method is a multi-laboratory, verified procedure
that outlines sample collection through laboratory processing including relevant details such as
holding times, holding temperatures, quality assurance, quality control, etc.
Mobile Laboratory - A laboratory space that can be transported onto an incident site. The unit
may have the rapid processing capabilities for select chemical agents. However, the detection
limit may be higher than laboratory protocols.
National Contingency Plan (NCP) - Also called the National Oil and Hazardous Substances
Pollution Contingency Plan, this plan (40 CFR Part 300) generally provides a blueprint for
carrying out response actions under the Comprehensive Environmental Response,
Compensation, and Liability Act (CERCLA) and section 311 of the Clean Water Act. The NCP
is designed to provide for efficient, coordinated, and effective response to discharges of oil and
releases of hazardous substances, pollutants, and contaminants. The NCP describes the
organizational structure and procedures for preparing for and responding to discharges of oil and
releases of hazardous substances, pollutants, and contaminants.
Population - All waste, or media, of interest located within a target study area (EPA, 2002b).
Recovery - Those capabilities necessary to assist communities affected by an incident to recover
effectively, including, but not limited to, rebuilding infrastructure systems; providing adequate
interim and long-term housing for survivors; restoring health, social, and community services;
promoting economic development; and restoring natural and cultural resources (DHS, 2011).
Recycling - The process of converting waste items into reusable materials.
Remediation - For the purposes of this document, the actions taken and techniques used to
implement cleanup of hazardous waste, all solid and hazardous wastes, and all media (including
groundwater, surface water, soils, and sediments) and debris that are managed for implementing
cleanup. The cleanup process described in this document does not rely on and does not affect
authority under CERCLA, 42 U.S.C. 9601 et seq., and the NCP, 40 CFR Part 300.
Resource Conservation and Recovery Act (RCRA) - A 1976 Federal law (42 U.S.C. ง6901 et
seq.) that gives the U.S. Environmental Protection Agency (EPA) the authority to control
hazardous waste from the "cradle to grave." This authority includes the generation,
transportation, treatment, storage, and disposal of hazardous waste. RCRA also set forth a
framework for the management of nonhazardous solid wastes. The 1986 amendments to RCRA
enabled EPA to address environmental problems that could result from underground tanks
storing petroleum and other hazardous substances.
Response - Those capabilities necessary to save lives, protect property and the environment, and
meet basic human needs after an incident has occurred (DHS, 2011).
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Sample - A portion of material collected from a larger quantity for estimating the properties
and/or composition of the larger quantity (EPA, 2002b).
Site Characterization - For the purposes of this document, site characterization refers to all
available information regarding the incident site- maps, building layouts, weather patterns,
population distributions, traffic patterns, agent distribution, etc.
Solid Waste - For the purposes of this document, any garbage, refuse, sludge, and other
discarded material resulting from industrial, commercial, mining, agricultural, or community
activities. Solid waste includes materials that are destined for final, permanent treatment and
placement in disposal units, as well as certain materials that are destined for recycling (EPA,
2015b). It is important to note that under RCRA, "solid waste" is broadly defined and includes
discarded materials such as solids, liquids, semi-solids, and contained gaseous materials.
Source Reduction - For the purposes of this document, source reduction refers to removal of
contaminated items for off-site treatment and reuse or off-site disposal.
Treatment, Storage, and Disposal Facility (TSDF) - A facility where hazardous wastes are
stored, treated, and/or placed in or on land or water (EPA, 2015d).
Treatment Technology - For the purposes of this document, any unit operation or series of unit
operations that alters the composition of a hazardous substance or pollutant or contaminant
through chemical, biological, or physical means to reduce toxicity, mobility, or volume of the
contaminated materials being treated. Treatment technologies are an alternative to land disposal
of hazardous wastes without treatment. (See 55 FR 8819, March 8, 1990.) The definition of
treatment technology as defined in the NCP can be found at 40 CFR 300.5.
Validation - For the purposes of this document, the term is to be used as described by the EPA
Policy Directive FEM-2010-01 "Ensuring the Validity of Agency Methods Validated and Peer
Review Guidelines: Methods of Analysis Developed for Emergency Response Situations" (EPA,
2010). More specifically, ".. .validation is the confirmation by examination and provision of
objective evidence that the particular requirements for a specific intended use are fulfilled"
(EPA, 2010).
Verification - For the purposes of this document, a synonym for "confirmation" (e.g.,
decontamination verification or verification that key process variables were controlled).
Waste - For the purposes of this document, waste is defined as any material that is intended for
disposal and will not be re-used or recycled. This is a general definition of waste and the
applicable legal definition of waste should also be considered when identifying, characterizing,
storing, or otherwise managing presumed waste materials.
Waste Characterization - A process that uses knowledge of the waste and/or sampling results
to document that the waste meets regulatory requirements and any additional requirements of
waste receivers.
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Waste Disposal - The placement of waste materials in permanently contained areas (e.g., a
landfill, where wastes are disposed of in carefully constructed units designed to protect
groundwater and surface water resources).
Waste Management - For the purposes of this document, the administration of activities that
include, but are not limited to, source reduction, waste minimization, waste segregation,
decontamination, recycling, transport, staging, storage, treatment, and disposal.
Waste Minimization - Actions that reduce the amount of waste generated and/or reduce the
amount of waste that is considered hazardous.
Waste Segregation - Sorting and separating waste into more homogeneous waste streams.
Waste Staging - The interim/temporary storage of waste (e.g., waste collected from various
buildings may be taken to a staging area prior to being transported to a solid waste disposal
facility).
Waste Storage - The holding of wastes until they are treated or disposed. Hazardous waste must
be stored in containers, tanks, containment buildings, drip pads, waste piles, or surface
impoundments that comply with RCRA regulations.
Waste Transport - For the purposes of this document, waste transport refers to the
transportation of waste (e.g., by truck or railroad).
Waste Treatment - Processes such as neutralization or incineration that change the physical,
chemical, or biological character of a waste, making it safer for transport, storage, or disposal.
Wide-area - For the purposes of this document, an incident with the potential to generate
numerous environmental samples associated with site characterization, clearance determination,
and waste management taxing man-power, analytical, and financial resources. A wide-area
incident might arise due to the large geographic area affected and/or intensity of the incident
relative to critical infrastructure requiring especially robust sampling requirements.
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Appeni ickground on Chemical Warfare Agents
Chemical warfare agents (CWAs) are acutely toxic and capable of causing serious and lethal
health effects at very low exposure doses (Table B-l). The CWAs are categorized based on their
toxicological actions: vesicants (also called blister agents), nerve agents, blood agents, and
incapacitating agents. Vesicant agents are the sulfur mustard agents: the undistilled form of
sulfur mustard (H), the distilled form of sulfur mustard (HD), Lewisite (an organic arsenical
agent), and Agent Yellow, a combination of HD and Lewisite. The toxicological effects of
vesicant agents are blistering and tissue damage of the skin, eyes, and respiratory tract (Munro et
al., 1999; NRT, 2015f; NRT, 2015a; NRT, 2015c). Nerve agents, derived from organophosphate
chemical compounds, are GA (tabun), GB (sarin), GD (soman), and VX (Munro et al., 1999).
Blood agents include cyanogen chloride (CK) (Munro et al., 1999). The toxicological effects of
nerve agents might vary depending upon the route of exposure and dose, but can include
difficulty in breathing, nausea, vomiting, convulsions, loss of consciousness, coma, and death
(NRT, 2015i; NRT, 2015d; NRT, 2015h; NRT, 2015e).
The CWAs can cause both immediate acute effects at the initial site of direct contact with tissues
and delayed systemic effects after exposure. For example, sulfur mustard can cause toxicity to
the skin, eyes, and respiratory tract within hours to a day of initial direct contact as well as
chronic effects, including cancer (Munro et al., 1999). Degradation products of CWAs can be as
toxic as the parent compounds themselves, so care must be taken to manage these hazards along
with the CWAs during a wide-area incident (Munro et al., 1999).
The CWAs are unique in that they can exhibit lethal toxicity at very low exposure
concentrations, with exposure routes of concern in an urban environment most often inhalation,
ingestion, or dermal contact. An acute exposure guideline level (AEGL) for a one time 10-
minute exposure to an airborne concentration of sarin (GB) is 0.38 milligrams per cubic meter
(mg/m3); this value represents a threshold for severe human health effects and increasing
potential for lethality (AEGL Effect Level 3) (NRT, 2015i). Because CWAs are highly toxic at
low exposure concentrations, the development of sampling plans to delineate very low levels of
contamination can pose a challenge due to variable persistence in the release environment. The
development of sampling plans to delineate very low levels of contamination might require
modification from the sampling plans typically used at traditional remedial sites. The presence of
undetected hotspots (i.e., conditions of elevated concentrations relative to the surrounding area)
could lead to unacceptable exposures and/or provide an ongoing source for exposure in the
population. Novel exposure pathways might direct sampling of materials that would not be
typically addressed in traditional sampling approaches. For example, the off-gassing of low
concentrations of CWA from porous materials to which the CWA has sorbed could become the
primary route of human health exposure as the duration of an incident extends.
The CWAs are known to exhibit diversity in fate and transport characteristics (DHS, 2012a),
even within the same toxicological category (Table B-l). From a sampling perspective,
knowledge of these fate and transport characteristics can inform determination of sample
location, environmental media to be sampled, or potentially impacted indoor or outdoor materials
to target for sample collection. Judgmental sampling uses expert judgment of known chemical
behavior to target areas most likely to retain persistent CWAs, as well as areas with the greatest
B-l
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potential for ongoing, frequent human contact. For example, liquid VX is relatively persistent,
with a possible range of persistence lasting from hours to months depending upon environmental
conditions (NRT, 2015h). In contrast, liquid sarin exhibits the greatest volatility among the nerve
agents, and therefore exhibits very low persistence (NRT, 2015i). However, volatility is also
predictive of sorption and penetration behavior of the released agent in porous or permeable
materials (DHS, 2012a). Targets for sampling might also be selected based on the identification
of materials that might function as sinks through prolonged persistence relative to other
environmental matrices that might represent an attractive target for sampling (NRT, 2015i).
Depending upon the environmental conditions present at the time of the incident, CWAs may
break down into a variety of detectable breakdown products. The rate of formation, structure of
formation, and overall persistence is dependent upon environmental conditions (e.g., pH,
temperature, relative humidity). In some situations, the breakdown products may serve as a
"marker" for determining the extent of contamination. The "marker" agents are intended to act as
an indicator of presence, and not as means of identifying which agent is present as some marker
compounds can come from multiple parent CWAs.
B-2
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Table B-l. Review of Chemical Warfare Agents, Persistence, and Breakdown Products
Chemical Abbreviation Common
Name; Chemical Formula
AEGL3
1 hour
(mq/m3)
General Persistence
Common Environmental Breakdown Products
Potential Marker
Compounds for Extent
of Contamination
Determination *
References
Nerve Agents
GA
Tabun; C5H11N2O2P
GB
Sarin; C4H10FO2P
GD
Soman; C7H16FO2P
GF
Cyclosarin; C7H14FO2P
VX
O-Ethyl S-(2-
diisopropylaminoethyl)
methylphosphonothiolate;
C11H26NO2PS
0.0028
Moderately low
persistence
0.13 Very low persistence
0.013 Low persistence
0.013
Moderately low
persistence
0.010 Persistent
Cyanide compounds including: ethylphosphoryl cyanidate,
dimethylamine, ethyl N,N-dimethylamidophosphoric acid,
hydrogen cyanide, dimethylphosphoramidate, and
phosphoric acid
Relatively non-toxic methylphosphonic acid (MPA),
isopropyl methylphosphonic acid (IMPA), diisopropyl
methylphosphonic acid (DIMP), and fluoride ion
Relatively non-toxic MPA, pinacolylmethylphosphonic acid
(PMPA), and fluoride ion, which might exist as hydrofluoric
acid
Relatively non-toxic fluoride ion,
cyclohexylmethylphosphonic acid (CMPA), cyclohexanol,
MPA, and combustible hydrofluoric acid
Relatively non-toxic MPA and ethyl methylphosphonic acid
(EMPA), and S-(2-diisopropylaminoethyl)
methylphosphonothioic acid (EA-2192), which is
considered almost as toxic as VX by some routes of
exposure
Cyanide compounds;
EH DAP
Fluoride ion, MPA, IMPA,
DIMP
PMPA, fluoride ion, MPA
Fluoride ion, MPA; CMPA
EA-2192, MPA, EMPA
NRT (2015d)
Kroening et al.
(2011)
NRT (2015i)
Kroening et al.
(2011)
NRT (2015e)
Kroening et al.
(2011)
NRT (2015g)
Kroening et al.
(2011)
NRT (2015h)
Kroening et al.
(2011)
Vesicant Agents
HD
Distilled Sulfur Mustard; C4H8SC12
Lewisite; C2H2AsCh
HL
Agent Yellow; Mustard-Lewisite
Mixture
2.1
0.74
HD: 2.1
L: 0.74
Semi-persistent
Low to moderately
persistent; however,
vesicant and toxic
breakdown products
are persistent for
decades
Semi-persistent; could
persist in water as
globules for decades
Relatively nontoxic thiodiglycol (TDG) and hydrochloric
acid, and potentially toxic sulfones
Highly toxic arsenic (III) compounds such as arsenites,
Lewisite oxide, and 2-chlorovinyl arsenous acid (CVAA),
which have vesicant properties. Decontamination by-
products include: arsenic (V) compounds, which are less
toxic but might be hazardous
Relatively nontoxic TDG and highly toxic arsenic (III)
compounds, such as arsenites, Lewisite oxide, and CVAA,
which have vesicant properties
TDG
Lewisite oxide, CVAA, 2-
chlorovinylarsonic acid
(CVAOA), total arsenic
TDG, CVAA, CVAOA, total
arsenic
NRT (2015c)
NRT (2015f)
NRT (2015a)
*Forsome agents, environmental conditions [e.g., pH, temperature, relative humidity) determine the individual markers that may be formed, their rate of formation, and persistence.
CVAA - 2-chlorovinyl arsenous acid; CVAOA - 2-chlorovinylarsonic acid; EMPA - ethyl methylphosphonic acid; EA-2192 - S-(2-diisopropyIaminoethyI] methylphosphonothioic acid-,
MPA - methylphosphonic acid; IMPA - isopropyl methylphosphonic acid; PMPA - pinacolylmethylphosphonic acid; TDG - thiodiglycol; DIMP - diisopropyl methylphosphonic acid;
CMPA - cyclohexylmethylphosphonic acid; EHDAP - ethyl hydrogen dimethylamidophosphate sodium salt
B-3
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Appendix C. DQO Process Case Study for Characterizing Waste for Proper
Management Using the Hypothetical Denver WARRP Scenario
The Denver Urban Area Security Initiative (UASI) developed a hypothetical chemical incident
for Agent Yellow (DHS, 2012b). This pre-established Denver Wide-Area Recovery and
Resiliency Program (WARRP) scenario will be used as a basis for generating hypothetical
examples throughout this appendix (hereinafter: Denver WARRP chemical scenario). Details
regarding this scenario are shown in Figure C-l.
WARRP Chemical Attack Scenario
Terrorist agents acquire 175 gallons of Agent YELLOW, equip a small
airplane with sprayers and fly the plane at low altitude over Denver's
Coors Field during a Rockies baseball game. At his closest approach
to the stadium, the pilot veers directly towards the target. Ignoring
frantic air traffic control calls and an approaching police helicopter, he
cuts his speed and drops over the stadium, simultaneously hitting the
spray release button. A coarse spray of Agent YELLOW is released. In
the stadium, surprise at the appearance of the aircraft turns to panic
when the spray is observed coming out of the rear of the plane. In total,
53,000 people have been either hit by, or breathe vapors of, the Agent
YELLOW spray. Thousands are injured and many are killed in the rush
to exit the stadium. People hit in the eyes experience immediate pain,
and the first ones out of the stadium are trying to get away as soon and
as far as possible. Numerous auto accidents occur in the parking lot
and access roads. Some people track contamination into nearby
residences, onto public transportation and into hospitals.
Figure C-1. Chemical attack scenario. Source: DHS (2012b).
The hypothetical Denver WARRP chemical scenario describes hundreds of facilities that would
be contaminated over a five-mile area surrounding the open-air baseball stadium and the
downtown Denver infrastructure (DHS, 2012b). Off-gassing of Agent Yellow and the
transportation of individuals and materials from or through the contaminated area could increase
the extent of contamination and subsequent generation of waste. EPA (2012d) estimated that this
incident could generate 15 million to 36 million gallons of aqueous waste and 3 million to 8
million tons of solid waste; these estimates excluded the waste associated with outdoor
remediation. Estimates were based on waste generation from hospital and sampling personal
protective equipment (PPE), personnel decontamination operations, and building
decontamination. Most aqueous waste was estimated to be generated from personnel
decontamination operations, and most solid waste was estimated to consist of ceiling tile, carpet,
electronics, furniture, and paper (EPA, 2012d).
The WARRP Denver scenario will be used as a basis for demonstrating a hypothetical example
of a decision problem data quality objective (DQO) process and an estimation problem DQO
process for characterizing waste for proper management following the wide-area release of
Agent Yellow over Denver's Coors Field during a baseball game (DFtS, 2012b). Pre-Incident
WMPs should be compiled prior to any incident to aid all planning efforts after an incident.
0.03 mg/mA2 Area
Length: 18 km
Width: 1.5 km
30 mg/mA2 ฆ
3 mg/mA2 ฆ
0.3 mg/mA2 ฆ
0.03 mg/mA2 M
C-l
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The DQO process is an iterative seven-step process that generates performance criteria for the
collection of new data. Six crucial inputs are necessary before developing the overall sampling
and analysis plan (SAP) in step seven (EPA, 2006). The DQOs identified for an incident will
define the indicators of acceptable sampling and analysis data that can be used to answer the
question being assessed. The DQO process supports two intended uses of the data: decision-
making and estimation (EPA, 2006). Decision-making uses the DQO process to decide between
alternative conditions, while estimation evaluates the magnitude of an environmental parameter
(EPA, 2006). More detailed direction for utilizing the DQO process can be found within U.S.
Environmental Protection Agency (EPA) documentation (EPA, 2006).
To provide a working scenario for the hypothetical DQO process and estimation problems, a
conceptual site model was developed based on the conditions expected to be present during
Denver WARRP scenario.
Agent: Agent Yellow, a mixture of the CWAs HD and Lewisite, is a liquid blistering
agent with a garlic-like odor. Agent Yellow is persistent for several hours in the
environment depending upon the temperature and type of surface (DHS, 2012a). Overall,
Agent Yellow has low volatility, low water solubility, and may sorb strongly to materials
(DHS, 2012a). Additionally, Lewisite contains arsenic, which will not be addressed by
Agent Yellow decontamination technologies that rely on chemical oxidation and could
require separate remediation strategies (DHS, 2012a).
Degradation by-products: Under certain environmental conditions, HD breaks down in
the environment to relatively non-toxic thiodiglycol (TDG), while Lewisite breaks down
into highly toxic arsenic (III) compounds, including Lewisite oxide and 2-chlorovinyl
arsenous acid (CVAA), can cause blistering like Lewisite (NRT, 2015a).
Release Scenario: Agent Yellow is released from a small agricultural aircraft over a
populated baseball stadium in Denver, Colorado. The Agent Yellow deposition plume
covers an area over five miles, which includes the open-air baseball stadium, the
surrounding area, and infrastructure of downtown Denver (DHS, 2012a). Hundreds of
facilities and areas are contaminated.
Potential Transport Mechanisms: After the initial wind dispersal, Agent Yellow
dispersal might continue by off-gassing after deposition and transport from contaminated
victims who have been moved for medical attention and cross contamination from other
material goods transported through the contaminated area (DHS, 2012a).
Potentially Affected Waste Materials: Excluding considerations for outdoor
remediation, this scenario was estimated to generate a substantial amount of waste:
liquid waste (15 million to 36 million gallons) and other solid waste (3 million to 8
million tons) (EPA, 2012d). Waste estimation included hospital and sampling PPE,
personnel decontamination waste, and building decontamination or demolition. Most
aqueous waste was estimated to come from personnel decontamination operations, and
most solid waste was estimated to consist of ceiling tile, carpet, electronics, furniture, and
C-2
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paper (EPA, 2012d). Depending upon the chemical agent in question, concrete and brick
might also constitute a significant fraction of the waste.
Waste Management Options: The National Response Team (NRT) Quick Reference
Guide should be consulted as a first step to identify waste management options. A waste
can become hazardous waste under Resource Conservation and Recovery Act (RCRA)
when it is identified as a listed waste, exhibits specified characteristics, or is generated
from discarded commercial chemical product or off-specification chemical product,
container residues, or spilled residues. Chemical warfare agents are not categorically
regulated under federal RCRA requirements.
In the context of the WARRP scenario, the Agent Yellow waste components are
identified as listed hazardous waste by the state of Colorado. As a result, waste
management officials from Colorado would require mustard agent waste materials to be
handled as hazardous waste (DHS, 2012). These wastes will be regulated by RCRA
requirements and Clean Water Act requirements if discharges to a Publicly Owned
Treatment Works (POTW) or surface water body occur (DHS, 2012a). Waste could be
incinerated in hazardous waste combustors or disposed of in RCRA Subtitle C (hazardous
waste) or possibly Subtitle D (non-hazardous waste) landfills (EPA, 2012d). The waste
produced would preferably qualify for disposal as municipal solid waste, but waste
sampling would likely be needed to confirm acceptability as some states/locations might
have more stringent requirements than the Federal government (EPA, 2012d; EPA,
2015d). Since it is likely that a wide-area incident will require waste management
facilities in multiple states and/or regions, it becomes critical to have these facilities
identified before an incident.
Decision Problem DQO Example
1. State the Problem
a. Describing the problem^ A timely process is needed to efficiently manage the
sampling and analytical level of effort required to determine how waste incurred
during the incident should properly be managed.
b. Establishing the planning team. The planning team includes representatives
from the incident command, EPA remediation oversite, the sampling team,
federal and state waste management programs, the owners/operators of potential
waste management facilities, health and safety personnel, analytical laboratory,
statistical expert, quality assurance representative, and risk assessment.
c. Describing the conceptual model of the potential hazard. For this example, up
to 8 million tons of solid waste will be generated from this incident. Waste
management officials from Colorado require Agent Yellow-related waste
materials to be handled as hazardous waste. This hypothetical case study assumes
that "Pre-Incident Waste Management Plans" were prepared prior to the incident
with potential Subtitle C landfills and hazardous waste incinerators. It is also
assumed that waste acceptance criteria are more restrictive for the Subtitle C
landfills than the hazardous waste incinerators, but the Subtitle C landfills are less
expensive than the hazardous waste incinerators.
C-3
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d. Identifying available resources, constraints, and deadlines: Sampling team and
analytical capabilities are being stretched by the demands associated with other
sampling activities (e.g., defining the extent of contamination, verifying the
decontamination efficacy).
2. Identify the Goal of the Study
a. Specifying the primary question. Is waste associated with the Denver WARRP
scenario adequately decontaminated (as pre-determined in the "Pre-Incident
Waste Management Plan") to be accepted by the Subtitle C landfills?
b. Determining alternative actions. Possible alternative actions include:
Dispose of waste in Subtitle C landfill
Treat the associated waste using an on-site decontamination operation and
re-assess
Treatment of the waste in a hazardous waste incinerator.
c. Specifying the decision statement. Determine whether each lot of
decontaminated waste can be disposed of in the Subtitle C landfills.
3. Identify Information Inputs
a. Identify the type of information that is needed to resolve the decision
statement. This is a new data collection effort, with analyses being performed on
waste samples collected as part of the Denver WARRP scenario. The planning
team has decided to collect wipe samples for the sulfur mustard component of
Agent Yellow from the decontaminated waste items.
b. Identifying the source of information. Data will be collected from lots of
similar waste containers (e.g., those of the same types of materials and/or those
waste materials originating from the same location and/or undergoing the same
decontamination incident).
c. Identifying how the Action Level will be determined. The Action Level will be
determined per direction from the owners/operators of the Subtitle C landfills and
the Colorado solid waste regulator.
d. Identifying appropriate sampling and analysis approaches. For this
hypothetical example only: wipe samples of containerized waste will be sampled
for sulfur mustard (an analytical technique for Agent Yellow is not available).
Table 2 should be used to identify an appropriate sampling method if this
approach is not suitable. The surface concentrations of sulfur mustard will be
measured, as directed in the latest on-line version of EPA's Selected Analytical
Methods for Environmental Remediation and Recovery (SAM). However,
specific methods for CWAs are available only via the Environmental Response
Laboratory Network (ERLN).
the Boundaries of the Study
Specifying the target population. The target populations consist of all possible
samples of waste that comprise the total volume of a given lot of waste
containers. Samples collected from this target population will consist of wipe
samples.
Specifying spatial and temporal boundaries and other practical constraints.
The lot of physical containers holding the waste will serve as the spatial boundary
4. Define
a.
b.
C-4
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of the waste to be sampled. Each lot will be comprised of several waste
containers. Lots will be established by the possible approaches:
Spatially and temporally, for example, waste originating from the same area
(e.g., the same building or same city block) that underwent the same
application of decontamination technology (e.g., liquid bleach application
from the same vendor) at the same time (e.g., all waste generated during that
day of decontamination).
Lots of waste might further be created by considering the types of waste and
performing waste segregation (e.g., decontaminated carpet might comprise a
lot and ceiling tile might comprise another lot).
The sampling of each lot will be conducted within the same time frame (e.g., all
lot samples will be collected on the same day).
c. Specifying the scale of inference for decision-making. A decision unit
corresponds to a specific lot of waste containers. The boundaries of the study (as
well as other aspects of characterizing waste for proper management) should be
determined as part of the "Pre-Incident Waste Management Plan". The
assumptions used in this hypothetical case study should ideally be studied before
an actual incident to provide lines of evidence (i.e., acceptable knowledge) in
accordance with federal (RCRA) and state regulations to assist decision makers
should the incident occur. Waiting until an actual incident will prove costly and
delay the remediation. If data are needed to inform decision makers, an
investigation should be conducted prior to the incident and documented with the
"Pre-Incident Waste Management Plan" so that the incident can be an execution
of the lines of evidence already documented Table 2 should be used to identify an
appropriate sampling method if this approach is not suitable.
5. Develop the Analytical Approach
a. Specifying the Action Level. For this hypothetical example only: An agreement
with the owners/operators of the Subtitle C landfills and the Colorado solid waste
regulator, waste will not be accepted by the Subtitle D landfills if any of the waste
container wipe samples have a sulfur mustard concentration >0.1 |ig/cm2 (the
upper calibration range for sulfur mustard from wipe samples). Note: the >0.1
|ig/cm2 concentration is ONLY for illustration purposes. The actual value would
be determined on a site-specific basis.
Please note that this assumption is simplified. Agent Yellow is a mixture of sulfur
mustard and Lewisite, and Lewisite contains arsenic. Arsenic will remain even if
the sulfur mustard and Lewisite are appropriately degraded. Action levels might
also be needed for air/headspace, extraction-based samples of decontaminated
items, and water/decontamination solution, and action levels will likely be needed
for sulfur mustard, Lewisite, and degradation products including arsenic for these
media.
b. Specifying the theoretical decision rule. The theoretical decision rule is as
follows: If any concentrations of sulfur mustard >0.1 |ig/cm2 are detected in the
wipes of the sampled containers from a waste lot, then the waste in that lot will
not be disposed of in the Subtitle C landfills without further decontamination and
reassessment or the waste might dictate that the waste be sent to hazardous waste
C-5
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incinerators. Otherwise, the lot of waste will be considered acceptable for disposal
in the Subtitle C landfills. Note: the >0.1 |ig/cm2 concentration is ONLY for
illustration purposes. The actual value would be determined on a site-specific
basis.
6. Specify Performance or Acceptance Criteria: Specify Probability Limits for False
Rejection and False Acceptance Decision Errors
a. Setting baseline and alternative conditions. The planning team determined that
any decision on the disposal of waste in Subtitle C landfills must be made with
the safeguard of the public health being of paramount importance. Following the
ERLN protocol for measuring the concentration of sulfur mustard in wipe
samples, the collected data from a given lot of waste must result in detections
<0.1 |ig/cm2. The associated baseline condition has been established as "the waste
is not acceptable for the Subtitle C landfills" (i.e., a sulfur mustard concentration
>0.1 |ig/cm2 was detected), while the alternative condition is "the waste is
acceptable for the Subtitle C landfills" (i.e., all measured sulfur mustard
concentrations were <0.1 |ig/cm2). The statistical hypotheses are then:
H0: a sulfur mustard concentration >0.1 |ig/cm2 was detected in the waste lot
Ha: a sulfur mustard concentration >0.1 |ig/cm2 was not detected in the waste lot
Note: the >0.1 |ig/cm2 concentration is ONLY for illustration purposes. The actual
value would be determined on a site-specific basis.
Unless there is conclusive information from the collected data to reject the null
hypothesis (i.e., H0, the baseline condition) for the alternative hypothesis (i.e., Ha,
the alternative condition), we therefore assume that the baseline condition is true.
b. Determining the impact of decision errors. A "false acceptance decision error"
corresponds to deciding that the waste contains sulfur mustard at >0.1 |ig/cm2
(i.e., Ho is not rejected) when (in reality) the waste is not (i.e., Ha is false). In
contrast, a "false rejection decision error" corresponds to deciding that the waste
is not hazardous (i.e., Ha is rejected in favor of Ha) when (in reality) it is
hazardous (H0 is true). The planning team identified the following consequences
for each decision error:
The primary consequence of making a false acceptance decision error is the
considerable expense (in both time and cost) required to treat the associated
waste again for potential disposal in a Subtitle C landfill or the increased
expense of taking the waste to a hazardous waste incinerator.
The consequences of making a false rejection decision error is waste would be
sent to a Subtitle C landfill containing Agent Yellow at concentrations
possibly endangering human health. Additionally, making a false rejection
decision error could compromise public confidence in the remediation.
As the risk to human health outweighs the consequences of having to pay more
for waste disposal and associated delays, the planning team has concluded that
making a false rejection decision error would lead to more severe consequences
than making a false acceptance decision error.
c. Specifying the confidence statement about the waste lot based on limited
samples. Because all waste containers will not be sampled, the goal will be to
take limited samples and based on those samples, make statements (with an
C-6
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associated confidence statement) about unsampled areas. The planning team's
desire is to be 95% confident that 95% of the waste containers are sufficiently
decontaminated (i.e., sulfur mustard concentrations >0.1 |ig/cm2 were not detected
in any of the associated lot samples).
7. Develop the Plan for Obtaining Data
a. Selecting a sampling design. The planning team's statistician determined that for
each lot of containerized wastes (e.g., barrels), random samples will be collected
from a sufficient number of barrels so that if no sulfur mustard is detected at
concentrations >0.1 |ig/cm2, the planning team can be 95% confident that 95% of
the waste containers are not contaminated with sulfur mustard concentrations >0.1
|ig/cm2. The number of waste containers to be sampled for each lot will be
determined statistically (e.g., using the Visual Sample Plan [VSP] software) based
on the required confidence statement and the total number of waste containers.
For each waste container sampled, one wipe sample will be collected from an
item within the drum.
b. Specifying key assumptions supporting the selected design. The sampling
design assumes that the containerized waste has undergone complete immersion
in a liquid decontaminant and the liquid was then drained/removed.
Estimation Problem DQO Example
1. State the Problem
a. Describing the problem^ A timely process is needed to efficiently manage the
sampling and analytical level of efforts required to determine how waste incurred
during the incident should properly be managed.
b. Establishing the planning team. The planning team includes representatives
from the incident command, EPA remediation oversite, the sampling team,
federal and state waste management programs, the owners/operators of potential
Subtitle C landfills and hazardous waste incinerators, health and safety personnel,
analytical laboratory, statistical expert, quality assurance representative, and risk
assessment.
c. Describing the conceptual model of the potential hazard. For this example, up
to 8 million tons of solid waste will be generated from this incident. Waste
management officials from Colorado require Agent Yellow-related waste
materials to be handled as hazardous waste. This hypothetical case study assumes
that "Pre-Incident Waste Management Plans" were prepared prior to the incident
with potential Subtitle C landfills and hazardous waste incinerators. It is also
assumed that waste acceptance criteria are more restrictive for the Subtitle C
landfills than the hazardous waste incinerators, but the Subtitle C landfills are less
expensive than the hazardous waste incinerators.
e. Identifying available resources, constraints, and deadlines: Sampling team and
analytical capabilities are being stretched by the demands associated with other
sampling activities (e.g., defining the extent of contamination, verifying the
decontamination efficacy).
2. Identify the Goal of the Study
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a. Specifying the primary question. Is waste associated with the Denver WARRP
scenario adequately decontaminated (as pre-determined in the "Pre-Incident
Waste Management Plan") to be accepted by the Subtitle C landfills?
b. Specifying the estimation statement. The principal estimation measure will be
an average concentration of sulfur mustard sampled from randomized lots of
containerized wastes. Upper confidence limits (UCLs) calculated on this
measurement are needed to reflect uncertainty. The UCL provides additional
assurance that the magnitude of the chemical contaminant levels is properly
attained. The process used to estimate these parameters should account for the
underlying distribution of measurements and the handling of non-detected
measures.
Please note that this is a simplified assumption. Agent Yellow is a mixture of
sulfur mustard and Lewisite, and Lewisite contains arsenic. The estimation
statement for the study could also include estimates for Lewisite, arsenic, or other
degradation products/markers.
Identify Information Inputs
a. Identify the type of information that is needed to resolve the decision
statement. This data collection effort is new, with analyses being performed on
waste samples collected as part of the Denver WARRP scenario. The planning
team has decided to collect wipe samples for the sulfur mustard component of
Agent Yellow from the decontaminated waste items.
b. Identifying the source of information. Data will be collected from lots of
similar waste containers (e.g., those of the same types of materials and/or those
waste materials originating from the same location and/or undergoing the same
decontamination incident).
c. Identifying how the Action Level will be determined. The Action Level will be
determined per direction from the owners/operators of the Subtitle C landfills and
the Colorado solid waste regulator.
d. Identifying appropriate sampling and analysis approaches. For this
hypothetical example only: wipe samples of containerized waste will be collected
for sulfur mustard (an analytical technique for Agent Yellow is not available).
The surface concentrations of sulfur mustard will be measured, as directed in the
latest on-line version of EPA's SAM. However, specific methods for CWAs are
available only via the ERLN.
Define the Boundaries of the Study
a. Specifying the target population. The target populations consist of all possible
samples of waste that comprise the total volume of a given lot of waste
containers. Samples collected from this target population will consist of wipe
samples.
b. Specifying spatial and temporal boundaries and other practical constraints.
The lot of physical containers holding the waste will serve as the spatial boundary
of the waste to be sampled. Each lot will be comprised of several waste
containers. Lots will be established by the possible approaches:
C-8
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Spatially and temporally, for example, waste originating from the same area
(e.g., the same building or same city block) that underwent the same
application of decontamination technology (e.g., liquid bleach application
from the same vendor) at the same time (e.g., all waste generated during that
day of decontamination).
Lots of waste might further be created by considering the types of waste and
performing waste segregation (e.g., decontaminated carpet might comprise a
lot and ceiling tile might comprise another lot).
The sampling of each lot will be conducted within the same time frame (e.g., all
lot samples will be collected on the same day).
c. Specifying the scale of inference for decision-making. A decision unit
corresponds to a specific lot of waste containers. The boundaries of the study (as
well as other aspects of characterizing waste for proper management) should be
determined as part of the "Pre-Incident Waste Management Plan". The
assumptions used in this hypothetical case study should ideally be studied before
an actual incident to provide lines of evidence (i.e., acceptable knowledge) in
accordance with federal (RCRA) and state regulations to assist decision makers
should the incident occur. Waiting until an actual incident will prove costly and
delay the remediation. If data are needed to inform decision makers, an
investigation should be conducted prior to the incident and documented within the
"Pre-Incident Waste Management Plan" so that the incident can be an execution
of the lines of evidence already documented.
5. Develop the Analytical Approach
Determining the key study parameter and a specification of the estimator.
The planning team determined that for sulfur mustard, the parameter that will be
estimated is the average surface concentration of sulfur mustard (|ig/cm2) from
waste items within the containerized waste.
6. Specify Performance or Acceptance Criteria: Specify Performance Metrics and
Acceptable Levels of Uncertainty
a. Specifying how uncertainty will be accounted for in the estimate. The upper
confidence limit (UCL) represents a density level that falls above the true level
(unobservable) with a given degree of confidence (with the confidence level
specified as a percentage). Use of the UCL in this context places the burden of
proof on demonstrating that the sulfur mustard surface concentration is neither
moderate nor high. By calculating the UCL on the average, uncertainty associated
with the estimate can be accounted for in estimating the sulfur mustard surface
concentration.
b. Specifying the confidence level associated with the UCL. The planning team
selected 75% as the confidence level associated with the UCL on the average.
These values will be used to identify lots of containerized waste to be at or above
specific concentrations.
c. Specifying performance or acceptance criteria. The planning team determined
that a sufficient number of samples should be collected to allow for the 75% UCL
to be no more than 20% higher than the average concentration.
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7. Develop the Plan for Obtaining Data
a. Selecting a sampling design. The planning team's statistician determined that for
each lot of containerized wastes (e.g., barrels) random samples will be collected
from a sufficient number of barrels to meet the performance/acceptance criteria
described in Step 6. The number of waste containers to be sampled for each lot
will be determined statistically (e.g., using the VSP software) based on the
required confidence level and the total number of waste containers. For each
waste container sampled, three wipe samples will be collected from waste items
within the drum.
b. Specifying key assumptions supporting the selected design. The sampling
design assumes that the containerized waste has undergone complete immersion
in a liquid decontaminant and then drained/removed.
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Appendix D. Features of Various Sampling Designs
Sampling Strategy
Non-Probabilistic
Judgmental
Probabilistic
Simple Random
Stratified Random
Systematic: Grid or
Transect
Ranked Set
Adaptive or
Response/Adaptive
Hybrid
Combined Targeted
and Random Sampling
Composite
Definition
Selection of sample locations
based on professional judgment
targeting locations most likely to
be contaminated.
A set of sampling units
is independently
selected at random
from an area to protect
against bias.
Prior information is used
to determine groups
(strata) that are sampled
independently.
Collecting samples at
locations in a specified
pre-determined grid
pattern or transecting
paths to ensure target
area is fully and
uniformly represented in
the collected samples.
Combines simple random
sampling with the
professional knowledge
and judgment of the field
investigator to rank the
selected locations that are
subsequently selected for
more accurate
measurement.
Sampling design where
additional samples are
collected based upon initial
sample results. Particularly
useful when a
characteristic of interest is
sparsely distributed, but
highly aggregated.
Combines results from
judgment and
probabilistic samples to
cover most likely and
less likely areas of
contamination.
A composite sampling and
processing protocol that reduces
data variability and provides an
estimate of mean contaminant
concentrations in a composite
sample collected from a defined
area. Can be collected through
either a judgment or probabilistic
sampling scheme or a
combination thereof.
Application Small-scale conditions are under
Relatively uniform or
Used to produce
Practical and
Ideal when laboratory
Ideal for lines of
All negative judgment
Estimating a mean
investigation
homogeneous
estimates with pre-
convenient
measurement costs are
contamination or hot spot
results can be combined
concentration
Screening for presence/absence
populations
specified precision for
implementation for
high relative to field
investigations
with probabilistic
Efficiently estimating the
of a contaminant
Selecting a sample
important
field sampling with
screening (hand-held or
Simultaneous
samples to determine
proportion of a population with
Might be used in conjunction
aliquot from a
subpopulations
more complete
professional judgment)
determination of mean
extent of contamination
a contaminant without needing
with simple random sampling of
composite sample
Monitoring of trends
coverage of an area
A cost-effective
concentrations and extent
lines or
to know which units have the
containerized samples (i.e.,
Used to gain specific
than random sampling
approach for estimating
of contamination -
decontamination
contaminant (i.e., how many
samples collected from within
information (i.e.,
Appropriate if no prior
the mean for a specified
particularly when a field
assessment
waste containers are
the container might be
mean) regarding each
information is known
precision
screening technique is
contaminated, but not which
judgmentally sampled to
group
about a location, if a
A Bayesian model has
available
ones)
maximize the collection of the
distribution pattern is
been developed for use
chemical agent such as
suspected, or if looking
in areas where
collecting samples from porous
for a "hot spot"
contamination is deemed
materials)
Site characterization or
evaluating cleanup
standards within
contaminated soils
unlikely either when
determining the extent of
contamination or
following
decontamination
Required Laboratory
Resources
Low: site information used to
minimize laboratory resources
Medium: sample
number is
predetermined
Medium: sample
number is predetermined
Medium: sample number
is predetermined using a
gridded scale, with the
grid scale determining
the intensity of sampling
Low: site information used
to minimize laboratory
resources
Unknown/High: no site
information is used to limit
the number of samples that
might be required
Low: site information
used to minimize
laboratory resources
Low: site information used to
minimize laboratory resources
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Non-Probabilistic
Probabilistic
Hybrid
Sampling Strategy
Judgmental
Simple Random
Stratified Random
Systematic: Grid or
Transect
Ranked Set
Adaptive or
Response/Adaptive
Combined Targeted
and Random Sampling
Composite
Wide-Area Pros
Can be very efficient and cost
effective if site is well known
Ideal for presence/ absence
screening
Quick implementation to achieve
time and funding constraints
Provides the ability
to calculate
uncertainty limits and
statistical inferences
Protects against
sampling bias
Easy to understand
and implement
Sample size formulas
are available to aid in
determining adequate
sample numbers
(EPA, 2002a)
Provides an estimate
of overall population
parameters equal to or
better than simple
random sampling
Sample size formulas
are available to aid in
determining adequate
sample numbers
(EPA, 2002a)
Provides uniform,
known, complete
spatial/temporal
coverage of an area
Design and field
implementation is
intuitive
Little to no prior
information of the site
might decrease sample
numbers (EPA, 2002a)
Increases the chance that
the collected samples
will yield representative
measurements
Can be more cost-
efficient than simple
random sampling
because fewer samples
need to be collected and
measured
Simultaneously estimates
mean concentrations and
extent of contamination
Sampling resources are
concentrated to the areas
of greatest interest
Leverages all
available information
Allows calculation of
statistical confidence
statements
Combines the
advantages of
probabilistic and
judgmental sampling
approaches
Significant reduction in
analysis costs potentially equal
to better representation
Some sources of sampling
error are addressed by
increasing sample
representativeness
Wide-Area Cons
Dependent upon expert
knowledge
Cannot reliably evaluate
precision
Personal judgment is needed to
interpret data
Confidence statements
concerning the absence of
contamination are difficult to
make
Random locations
might be difficult to
identify
Sampling design
depends upon the
accuracy of the
conceptual model
All prior information
regarding the site is
ignored
Sampling can be
costly if there are
difficulties in
obtaining samples due
to location
Random locations
might be difficult to
identify
Sampling design
depends upon the
accuracy of the
conceptual model
All prior information
regarding the site is
ignored
Sampling can be
costly if there are
difficulties in
obtaining samples due
to location
Sample locations are
fixed and might not
work in an urban
environment
If the scale of the grid
sampling pattern is
larger than the pattern
for the agent of interest,
the target agent might
be missed entirely
Not using any available
prior knowledge
regarding the site might
decrease sample
efficiency
Dependent upon expert
knowledge
More complex
implementation
Iterative nature of the
design might increase the
overall time
requirements
The final overall sample
size is an unknown
quantity
Dependent upon
expert knowledge
Negative perception
of inferring
confidence when
compared to
statistically based
designs
Compositing cannot be applied
to all sample types or detection
technologies
Does not provide information
on the spatial distribution of
contaminants within a given
sampling unit
Error might be introduced
during the compositing
process, i.e., weighing or
homogenizing heterogeneous
sample Confidence Limits
(CLs)
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Sampling Strategy
Non-Probabilistic
Judgmental
Probabilistic
Simple Random
Stratified Random
Systematic: Grid or
Transect
Ranked Set
Adaptive or
Response/Adaptive
Hybrid
Combined Targeted
and Random Sampling
Composite
Cautions or
Additional Critical
Information
Does not ensure that unsampled
items are free of contamination
Degradation by-products might be
of concern depending upon the
parent agent and create a
hazardous environment incident
after the parent (or tested agent) is
no longer present
Simple random
sampling is often used
as the last stage of
sampling when
multiple iterations are
conducted - selecting
an aliquot from a
composite sample
All populations should
be relatively uniform
Degradation by-
products might be of
concern depending
upon the parent agent
and create a hazardous
environment incident
after the parent (or
tested agent) is no
longer present
Each group should be
homogeneous within
itself
Groups should be
defined before
determining sample
sizes
Potentially more
efficient approach for
sampling
heterogeneous wastes,
if the wastes can be
segregated
Degradation by-
products might be of
concern depending
upon the parent agent
and create a hazardous
environment incident
after the parent (or
tested agent) is no
longer present
A random starting
location must be
identified from which all
other sampling locations
are based
Degradation by-products
might be of concern
depending upon the
parent agent and create a
hazardous environment
incident after the parent
(or tested agent) is no
longer present
> Statistical SME input is
recommended
Degradation by-products
might be of concern
depending upon the
parent agent and create a
hazardous environment
incident after the parent
(or tested agent) is no
longer present
Field screening or rapid
laboratory protocols are
ideal
Degradation by-products
might be of concern
depending upon the parent
agent and create a
hazardous environment
incident after the parent
(or tested agent) is no
longer present
Especially useful for
determining when an
area is not
contaminated
Degradation by-
products might be of
concern depending
upon the parent agent
and create a hazardous
environment incident
after the parent (or
tested agent) is no
longer present
Area of interest is divided into
decision units from which
multiple samples are collected
and combined, processed, and
subsampled before analytical
detection
Generally, a minimum of 20-30
[equally sized] discrete samples
are needed for an adequate
characterization of a defined
decision unit area with
Incremental Sampling
Methodology (ISM)
Degradation by-products might
be of concern depending upon
the parent agent, and create a
hazardous environment incident
after the parent (or tested agent)
is no longer present
Previous Use(s) Brownfield land assessments
(EPA, 1998); Capitol Hill
Anthrax Response (EPA, 2015c);
Bio-response Operational Testing
and Evaluation (BOTE) (EPA,
2013a)
Proposed by Sexton (1993) to
sample within randomly selected
drums. Three to four samples
were proposed from each drum
(soft items were to be sampled via
extractive-based approaches and
hard items were to be sampled via
wiping). The waste items most
likely to contain hazardous
materials were to be sampled
Recommended by
Sexton (1993) for drum
sampling.
Proposed by Sexton
(1993) for random drum
sampling within "lots"
of drums with similar
characteristics
Attainment of cleanup
standards (EPA, 1992a)
Reference(s) EPA (2006); EPA (1998); EPA
(2015c); EPA (2013a); Sexton
(1993)
EPA (2002b); EPA
(2006); ITRC (2012);
Sexton (1993); EPA
(2002c)
EPA (2002b); EPA
(2006); Sexton (1993)
EPA (2006); EPA
(1998); EPA (1992a)
EPA (2006)
EPA (2006); Hardwick and
Stout (2016); EPA (2015b)
EPA (2015c); PNNL
(2010)
EPA (2006); ITRC (2012)
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Appendix E. Features of Various Sample Co I lectio hniques
Extractive (Solid Material)
Bulk Sampling
Soil
Sampling
Wipe (Surface)
Sampling
Vacuum (Surface)
Sampling
Liquid (Surface)
Sampling
Liquid (Drum)
Sampling -
Discrete Depth
Samplers
Liquid (Drum)
Sampling -
Profile Samplers
Air
Sampling
Description Extractive sampling refers to
the cutting/removal of a portion
of the material sampled. Might
also be referred to as bulk
sampling or direct extraction.
Soil samples might be
collected from the surface
or from lower depths
depending upon the
conditions. Might also be
referred to as bulk
sampling.
Surface sampling
techniques using wipes,
cotton-balls/wipes, filter
paper wipes, or gauze
sponges.
Surface collection of dust and
or particulates.
The collection of liquid samples
from the surface (or shallow
depths) might be obtained with
various devices including a
bailer, dipper, liquid grab
sampler, swing sampler, or solid
phase microextraction fibers.
Liquid samples might
be obtained from
discrete depths with a
variety of devices
include a syringe
sampler, discrete level
sampler, lidded
sludge/water sampler,
or solid phase
microextraction fibers.
Liquid samples might be
obtained from
throughout a vertical
column of liquid or
sludge with a variety of
devices include a
composite liquid waste
sampler (COLIWASA),
drum thief, valved drum
sampler, plunger type
sampler or solid phase
microextraction fibers.
Air sampling devices
could include high-
volume air samplers,
solid phase adsorbent
media (tubes), solid phase
microextraction fibers, or
other air samplers (e.g.,
SUMMAฎ canisters).
Application Applicable for the sampling
of targeted areas (sink
materials) where liquid agent
might remain, especially
porous surfaces
Applicable for sampling
materials that are not
amenable to wipe sampling
such as materials that are wet,
irregularly shaped, and/or
porous
Might be applicable for
sampling heterogeneous
waste; cutting, chipping, or
drilling of waste samples
(and subsequent
grinding/mixing together) can
make the samples more
homogeneous and amenable
to being sampled simply with
a spoon or scoop
Soils might be sampled to
assess surface
contamination or
contaminant permeation
Generally used for
sampling smooth,
nonporous surfaces, but
might also be used on
porous surfaces (EPA,
2012b)
Applicable to relatively
small sample areas
Suitable for porous or
nonporous surfaces
Might allow for larger surface
areas to be assessed in a
single sample than wipe
sampling techniques
Although designed for
groundwater sampling, bailers
can be used to collect liquid
samples from tanks and
surface impoundments;
bailers collect samples of 0.5
to 2 liters
The dipper, liquid grab
sampler, and swing sampler
generally collect 0.5- to 1.0-
liter samples from the surface
of drums, tanks, and surface
impoundments
The syringe sampler
and discrete level
sampler can collect
0.2- to 0.5-liter
samples from drums,
tanks, and surface
impoundments
A lidded sludge/water
sampler can collect
1.0-liter volumes
from tanks and ponds
These sampling devices
typically collect between
0.1- to 3-liter samples
from tanks and drums, as
well as surface
impoundments
Air sampling might be
helpful in confirming the
presence of an agent over
a wide area
E-l
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Extractive (Solid Material)
Bulk Sampling
Soil
Sampling
Wipe (Surface)
Sampling
Vacuum (Surface)
Sampling
Liquid (Surface)
Sampling
Liquid (Drum)
Sampling -
Discrete Depth
Samplers
Liquid (Drum)
Sampling -
Profile Samplers
Air
Sampling
Wide-Area Extractive-based sampling
Pros minimizes the losses of agent
than might arise with collection
inefficiencies of other sampling
protocols
Grab samples are simple
and can be easily
composited across a wide
area
Can be an easy and quick
way of assessing surface
contamination levels
Large surface areas can be
sampled relatively quickly, even
for personnel working in PPE
The bailer, dipper, liquid grab
sampler, and swing sampler
are generally easy to use and
inexpensive
Analysis of some sampling
devices can be performed in
the field for some analytes.
A syringe sampler is
easy to use and
decontaminate; it can
also be used to
sample discrete
depths, including the
bottom
The jar in the lidded
sludge/water
sampling device
serves as the sample
container reducing
the chance of cross-
contamination
Solid phase
microextraction
fibers can be taken
into the field to
sample. These
samples might be
returned to the
laboratory for
analysis or the fibers
can be analyzed in
the field using
portable GC/MS
systems
The COLIWASA,
drum thief, and valved
drum sampler are
inexpensive, easy to
use, and available as
reusable or single-use
models
The plunger type
sampler is easy to
operate, relatively
inexpensive, and is
available in various
lengths
Solid phase
microextraction fibers
can be taken into the
field to sample. These
samples might be
returned to the
laboratory for analysis
or the fibers can be
analyzed in the field
using portable GC/MS
systems
Analysis of some
sampling devices can be
performed in the field for
some analytes
E-2
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Extractive (Solid Material)
Bulk Sampling
Soil
Sampling
Wipe (Surface)
Sampling
Vacuum (Surface)
Sampling
Liquid (Surface)
Sampling
Liquid (Drum)
Sampling -
Discrete Depth
Samplers
Liquid (Drum)
Sampling -
Profile Samplers
Air
Sampling
Wide-Area Extractive-based sampling
Cons might be difficult for
personnel working in PPE
Extractive-based sampling
techniques are not well-
defined/established
Extracted samples might
require more extraction
solvent and more time to
process than other surface
sampling approaches
Small concentrations of a
contaminant might be diluted
within a larger bulk sample
Soil protocols that
require extraction might
require more extraction
solvent and time to
process than other
surface sampling
approaches
Extractive-based
sampling techniques are
not well-
defmed/established and
might be difficult for
personnel working in
PPE
Small concentrations of
a contaminant might be
diluted within a larger
bulk sample
Wipe sampling might
not result in high agent
recoveries from porous
materials such as wood
Wipe sampling
procedures can vary
based on the wipe
material, agent of
interest, and the material
sampled
Limited in sample area
(100 cm2)
1 Low levels of agent might be
diluted within a large sample
Might not be applicable for
wet surfaces (surfaces
remaining wet after being
soaked in liquid
decontaminant)
These sampling devices are not
intended to collect samples
from specific/deep subsurface
depths (unless a point-source
bailer is used)
The maximum depth
that can be reached
with a syringe
sampler is
approximately 1.8
meters
The lidded
sludge/water
sampling devise is
rather heavy and
limited to one jar size
The COLIWASA,
drum thief, and valved
drum sampler can be
difficult to
decontaminate, and it
might be difficult to
collect samples from
the bottom of the
container
The drum thief cannot
sample depths longer
than the drum thief
itself
Might be difficult to
implement depending
upon the accessibility of
the sample area
Cautions or Extraction efficiencies and
Additional agent recoveries will vary
Critical with material and extraction
Information approach
Constituents within some
materials might interfere with
detection technologies
Extractive-based sampling
techniques are not well-
defined/established
Neutralization might be
needed to inhibit any residual
decontamination solution that
could possibly bias/lower the
agent recoveries
Evidence collection sampling
might have been conducted in
this manner
Extraction efficiencies
and agent recoveries
will vary with material
and extraction approach
Constituents within
some soils might
interfere with detection
technologies
Extractive-based
sampling techniques are
not well
defined/established
Neutralization might be
needed to inhibit any
residual
decontamination
solution that could
possibly bias/lower the
agent recoveries
Small concentrations of
a contaminant might be
diluted within a larger
bulk sample
Agent recovery will vary
depending upon the area
sampled, material type,
wipe material, amount
and type of wetting
solution, wipe pattern,
etc.
ฆ Recovery might be
affected by the presence
of dirt and other residues
as well as background
chemical constituents
Extraction efficiencies and
agent recoveries will vary
with material and extraction
approach
Recovery might be affected
by the presence of dirt and
other residues as well as
background chemical
constituents
1 Liquid samples should be
collected with the appropriate
neutralizers and stabilizers
added
1 Larger sample volumes or
multiple samples might be
required so that filtration can
be used to detect low levels of
contamination
Liquid samples
should be collected
with the appropriate
neutralizers and
stabilizers added
Larger sample
volumes or multiple
samples might be
required so that
filtration can be used
to detect low levels
of contamination
> Liquid samples should
be collected with the
appropriate neutralizers
and stabilizers added
> Larger sample volumes
or multiple samples
might be required so
that filtration can be
used to detect low
levels of contamination
For sampling vapors that
are heavier than air (e.g.,
sulfur mustard and
Lewisite), include low
lying areas where vapors
might accumulate
E-3
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Extractive (Solid Material)
Bulk Sampling
Soil
Sampling
Wipe (Surface)
Sampling
Vacuum (Surface)
Sampling
Liquid (Surface)
Sampling
Liquid (Drum)
Sampling -
Discrete Depth
Samplers
Liquid (Drum)
Sampling -
Profile Samplers
Air
Sampling
Previous Nassaretal. (1998) collected
Use(s) bulk vegetation samples from a
military area exposed to nerve
agent and subsequently
remediated. Nassar et al. (1998)
collected bulk vegetation
samples from a military area
exposed to nerve agent and
subsequently remediated.
Kimm et al. (2002)
studied the application
of headspace solid-
phase microextraction of
sulfur mustard from soil
and subsequent GC/MS
analysis
Solid phase
microextraction fibers
can sample CWAs in
air, headspaces above
solutions, water, or soil
(Popiel and Sankowska,
2011)
EPA (2014a) used
wetted gauze sponges in
a Lewisite
decontamination study
using glass and wood
coupons
Nassar et al. (1998) used
cotton wipes to sample
painted surfaces from a
military area exposed to
nerve agent and
subsequently remediated
Solid phase microextraction
fibers can sample CWAs in air,
headspaces above solutions,
water, or soil (Popiel and
Sankowska, 2011)
Solid phase
microextraction fibers
can sample CWAs in
air, headspaces above
solutions, water, or soil
(Popiel and Sankowska,
2011)
Solid phase
microextraction fibers
can sample CWAs in air,
headspaces above
solutions, water, or soil
(Popiel and Sankowska,
2011)
Kimm et al. (2002)
studied the application
of headspace solid-
phase microextraction
of sulfur mustard from
soil and subsequent
GC/MS analysis
Smith et al. (2011 could
detect and quantify
gaseous samples of
CWA simulants with a
fully automated, field-
deployable, miniature
MS equipped with a
glow discharge electron
ionization source and a
cylindrical ion trap
mass analyzer
Solid phase
microextraction fibers
can sample CWAs in
air, headspaces above
solutions, water, or soil
(Popiel and Sankowska,
2011)
Reference(s)
EPA (2012d); Nassar et al.
(1998); NRT (2015a)
EPA (2002b); Nassar et
al. (1998); NRT (2015a);
EPA (2002b); Kimm et al.
(2002); Popiel and
Sankowska (2011)
EPA (2008); EPA (2014a); ASTM(2006)
Koester and Hoppes
(2010); Nassar et al.
(1998); NRT (2015a); Qi
et al. (2013)
EPA (2002b); NRT (2015a);
Popiel and Sankowska (2011)
EPA (2002b); NRT
(2015a); Popiel and
Sankowska (2011)
EPA (2002b); NRT
(2015a); Popiel and
Sankowska (2011)
Kimm et al. (2002); NRT
(2015a); Popiel and
Sankowska (2011); Smith
et al. (2011)
* Standardized Analytical Methods (SAM) (which guides the Emergency Response Laboratory Network [ERLN] laboratories) focuses on environmental sample types that are most prevalently used to fulfill EPA's homeland security
responsibilities following an incident involving chemical agents (e.g., aerosols, surface wipes or swabs, drinking water, and post-decontamination wastewater). Other sample types (e.g., soil and vacuum samples) may have to be
analyzed, and for those sample types, specific requests should be sent to the SAM technical contacts.
E-4
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Appendix F. Findings and Recommendations from the Tab cise
ami Computer Simulation Assessments
Introduction
To evaluate the waste characterization process and the proposed best practices for waste
characterization, a table-top exercise (TTX) was held on October 19, 2017 at the EPA facility in
Edison, New Jersey. This report documents the exercise process and reports on the
recommendations and findings from the players and attendees that were reported during the
TTX.
Table-Top Exercise
The purpose of the exercise was two-fold: (1) obtain feedback on the "Best Practices to
Minimize Laboratory Resources for Waste Characterization During a Wide-Area Release of
Chemical Warfare Agents (October 9, 2017)" (BPD), a draft version of the Best Practices Guide
(BPG), and the associated waste characterization process, and (2) evaluate the use of a simulated
three-dimensional sampling environment computer simulation as a tool to review the BPD and
waste characterization process. For the exercise, a scenario was developed, and waste
characterization tasks were identified for players to perform. The overall scenario was designed
to be generally consistent with the Denver WARRP scenario for chemical warfare agents. In the
scenario, Agent Yellow (a mixture of Lewisite and distilled sulfur mustard [HD]) was released in
the air over an urban environment.
Players in the exercise were identified from two main target groups at EPA, subject matter
experts who would be able to provide technical feedback on elements of the BPD or individuals
who might be expected to use the document as part of their duties during a wide-area CWA
incident. Examples of individuals from EPA who were included based on the expectation that
they might develop or implement waste characterization strategies during a wide-area incident
include On-Scene Coordinators (OSCs) or Consequence Management Advisory Division
(CMAD) staff. A list of players and attendees is provided in Attachment F1 to this appendix.
Exercise materials, including the agenda, PowerPoint slide presentation, scenarios and associated
player tasks, an identification of reference materials, and the player evaluation form are included
in Attachments F2 through F10.
The TTX was performed in two parts: a traditional format and a computer simulation format.
The sequence of exercise formats in the table-top was designed to increase in complexity from a
set of drums containing waste materials to a simulated three-dimensional environment with a
mixture of different waste and non-waste materials. For the traditional format, players were split
into groups and given a waste characterization task to complete and report back on their selected
approach. A simple scenario was provided where players were asked to make waste
characterization decisions for a set of drums containing decontamination rinsate, decontaminated
PPE, and office materials that had been decontaminated. Sampling results were provided for the
areas where sampling was performed by the personnel who went through the decontamination
process where the decontamination rinsate was generated.
For the computer simulation, players were to perform the assigned waste characterization task in
three computer-generated locations (Figure F-l). The locations were: furnished office,
warehouse, and outdoor area with decontamination material present. The computer simulation
F-l
-------
software provided a unique opportunity for interaction with a realistic, three-dimensional
environment to perform waste characterization tasks. Interactive videos were also generated and
served as an interaction tool for the user and the software. The contents of the locati ons were
carefully selected to include materials for which waste characterization would be performed
during an urban wide-area incident. Materials included office equipment, indoor materials (e.g.,
carpet, ceiling tile), mixture of low- and potentially high-value materials, porous and nonporous
materials, materials that would be hazardous waste without presence of CWA-contaminated
materials, and waste products generated from the decontamination of personnel. To encourage
players to incorporate composite sampling, materials were selected for inclusion in the
warehouse and outdoor setting that presented good opportunities for the appropriate use of
composite sampling (e.g., rock salt, decontamination rinsate drums). The use of the simulation
also provided a unique opportunity to capture the sampling behavior of players. Each collected
sample was documented for player review during the performance of their sampling plan as well
as for review after the exercise to evaluate sampling decisions made by players (Figure F-2a and
b).
Figure F-l. Screen shot of computer simulation (a) office and (b) warehouse locations.
F-2
-------
(a)
Waste Group:
metal
Lines of Evidence?
Yes
Use Sampling?
Yes
Strategy:
Non-Probabitistic - Judgmental
Collection Technique:
Wipe (Surface) Sampling
Analysis Type:
Field Analysis
SAM
Notes:
t ^ >>
b)
Waste Group:
wood
Lines of Evidence?
Yes
Use Sampling?
Yes
Strategy:
Composite
Collection Technique:
Extractive (Solid Material) Sampling
Analysis Type:
Laboratory Analysis
SAM
Notes:
composite 2
Figure F-2. Computer simulation sample capture for two waste group samples during exercise.
F-3
-------
For each waste characterization task, players were encouraged to use the waste characterization
process flow chart provided in the draft BPD and BPG. A Waste Characterization Worksheet
(Attachment F.6) was also provided to assist users in the implementation of the waste
characterization process. Additionally, the computer simulation software queried users regarding
sampling choices using the same terminology and question sequencing as the waste
characterization process presented in the BPD and BPG.
Figure F-3 illustrates the summary available for each sampling group that can be exported to
Excel software to facilitate further analysis of these data. The capture of sampling data allows for
the assessment of the identified waste groups that were determined to have homogenous
characteristics, and the waste characterization strategy (i.e., lines of evidence, sampling).
Group
Name
Image Name
Line of Evidence Use Sampling
Strategy
Collection
Technique
AnalysisType
Analysis
Method
carpet
IndoorOffi ce
carpetO
Yes Yes
Non-
P ro babi listi c -
Judgmental
Extractive (Solid
Material) Sampling
Laboratory
Analysis
SAM
wood
IndoorOffi ce
wood 0
Yes Yes
Non-
P ro babi listi c -
Judgmental
Extractive (Solid
Material) Sampling
Laboratory
Analysis
SAM
metal
IndoorOffice
metalO
Yes Yes
Non-
P ro babi listi c -
Judgmental
Wipe (Surface)
Sampling
Field Analysis
SAM
Figure F-3. Computer simulation sample capture in Excel format.
Findings and Recommendations from Exercise
The players provided valuable feedback that will be used to improve the waste characterization
process and associated documents. Feedback was provided verbally during hot wash discussions
after the traditional TTX and computer simulation. A written player evaluation form was given
to players for completion (Attachment F10). Players were not asked to achieve consensus on
feedback elements or recommendations. As a result, the summary of feedback and
recommendations is reflective of individual opinions with varying levels of concurrence from the
group. For ease in reviewing, the material is categorized into the following: waste
characterization process, material and content in the BPD and BPG, simulation software,
suggestions for next reviewers, and format and content of the exercise. Note that some of the
feedback and recommendations refer to the materials in this document that are contained in
Appendices F and G. Therefore, the reader should evaluate these appendices in context with the
summary below.
(1) Waste Characterization Process
(a) The waste characterization flow chart and process should identify that earlier
upstream decisions could affect how waste characterization might be performed.
F-4
-------
The waste characterization process might be affected by upstream decisions made in the
response and recovery process. Examples of these decisions should be identified in the BPD and
it should be noted that they might limit the ability to fully implement the proposed waste
characterization strategy. Examples of upstream decisions that may affect waste characterization
identified during the exercise are provided below. The BPD andBPG were updated to identify
the upstream decisions and the addition of waste volume to the waste acceptance criteria.
The waste receiver that stores or manages the waste might dictate which
decontamination technologies can be used (e.g., landfill that will not take waste
unless specific type of treatment used). If waste characterization is not evaluated
until the end of the decontamination and clearance processes, the use of the proposed
waste characterization process might be significantly limited. Waste management
planning, specifically including waste characterization considerations, should be an
explicit element of earlier planning activities (e.g., Remedial Action Plans).
Process needs to identify that waste receivers will have limits to the volume of
waste that they will accept. The potential for waste receivers to identify a limit on
the volume of waste that they will accept is an additional element to balance in the
optimization of laboratory samples for analysis. It is possible that the total number of
samples for laboratory analysis could be reduced through evaluation of the sampling
requirements associated with waste acceptance criteria in combination with the
volume of waste that can be managed by each individual receiver. The volume of
waste that can be accepted by each waste receiver should be identified as an explicit
element of the waste acceptance criteria.
(b) Education/communication and acceptance by politicians, state and local regulators,
and potential waste receivers will be critically important to implementation of the
process. The lines of evidence concept in the waste characterization process must be
demonstrated to have acceptance by regulators and waste receivers. Players noted the
concern that absent input from regulators and waste receivers regarding the acceptability
of lines of evidence, there may be concerns about use of the proposed process during an
incident. Ideally, communication with these stakeholders should begin prior to an
incident and continue throughout the incident. Target areas for education should
specifically include the lines of evidence approach. It was also noted that the waste might
be placed in staging areas for an extended period while the waste receivers and regulators
determine whether they will accept the waste. The BPD was revised to identify the
importance of early involvement by politicians, state and local regulators, and potential
waste receivers. The potential for long-term storage or staging of the waste was also
identified.
(c) The ability to effectively use the waste characterization process to reduce the
laboratory analysis resources might be limited by CWAs for which there are scarce
data or limited familiarity with expected agent behavior. In contrast to level of
knowledge associated with Agent Yellow constituents (i.e., HD, Lewisite), CWAs for
which less is known might require more laboratory analysis of samples due to the lack of
technical data that could be used to inform lines of evidence determinations. This concept
was added to the BPD.
F-5
-------
(d) The waste characterization process should be presented as an all-hazards approach.
A player noted that an all-hazards approach for the waste characterization process could
be evaluated to maximize its use. Overall strategies associated with waste
characterization can be appropriately applied to all-hazards scenarios (e.g., biological
agent, chemical agent, natural disasters) regardless of the agent, release environment, and
other specifics of a wide-area incident. The tactics or specific decision-making
considerations including lines of evidence could then be developed by waste and/or agent
type (e.g., biological agents, chemical agents, storm debris) in document appendices. The
comment suggested that the focus should be on a process that can be applied universally
and not the development of an individual plan for each specific agent or group.
The document authors recommend that the BPD document continue to emphasize its
development for CWAs, but note its potential utility for all-hazards application. The BPD
was revised to note that the process could be implemented as an all-hazards approach in
the general sense that it could be evaluatedfor implementation across chemical
incidents, whether the release involved CWAs in a wide-area incident or other
catastrophic release of industrial chemicals that exhibited high acute toxicity or
contaminated a significant volume of materials.
(e) The BPD must better communicate the importance of using the lines of evidence
approach to perform waste characterization to most effectively reduce the number
of samples analyzed at laboratories. The players commented that the waste acceptance
criteria have been determined for a set of CWAs in states that were associated with
chemical demilitarization activities through the Department of Defense. However, these
specific waste streams are well characterized and lack the sheer volume of waste
materials likely to be generated during a wide-area incident.
The BPD needs to communicate clearly that waste characterization processes must meet
all regulatory requirements, but the laboratory resources are not available to utilize
sampling as it is typically conducted in waste characterization. The BPD should also
continue to emphasize that the final determinations on whether a waste receiver will
accept the proposed waste acceptance criteria are jointly decided by the waste receiver
and regulator. However, it is still possible that these entities might choose to require
extensive sampling as part of their waste acceptance criteria. The BPD has been revised
to more clearly emphasize the lines of evidence as a critical tool in the waste
characterization process.
(2) Material/Content in BPD and BPG
(a) Identify the elements outside the scope of the waste characterization process in the
BPD and BPG that will impact waste characterization decision-making. The
elements outside the process include a variety of potential considerations (e.g., politics,
stigma, public concerns, cost, selection of decontamination technology). These elements
were recommended to be explicitly identified in the document and their importance to the
overall waste management process noted. The comment that cost should be included
within the waste characterization process was also provided.
F-6
-------
The BPD was revised to include an identification of the considerations that were deemed
to be outside the waste characterization process. However, the decision to exclude cost
as an explicit consideration within the BPD was maintained. The primary reason for this
is the complexity of introducing cost within the process and the difficulty of identifying
data to aid in implementing the process.
(b) Tables 1 and 2 should be added to the BPG. The requested change was made to the
BPG. The change was also made in the Executive Summary of the BPD.
(c) The BPD should incorporate additional content on the sample collection volumes to
facilitate the use of split samples. Given the limited number of samples that were
allowed in the TTX and likely during an actual incident, the BPD should note the
potential challenges of sufficient sample volume for splitting of samples for multiple
analyses (e.g., inorganic and organic to capture arsenic from Lewisite and HD or
degradation products in Agent Yellow scenario). A new section has been added to the
BPD to provide additional detail on split samples..
(d) The DQO appendix in the BPD is useful to assist in the waste characterization
process. The focused examples that are used to walk through the DQO should be helpful
to users because of the difficulty in the development of this information. Concerns were
noted that DQOs may not be necessary, while others identified the importance of DQOs
as the basis to determine the necessary type and quality of data for waste characterization
decisions. As an example, the DQOs will describe the type and quality of data necessary
to make the lines of evidence "assumptions." No change was made in response to this
comment.
(e) Consider identifying waste characterization resources that will be associated with
the response to a wide-area incident. The BPD and BPG should identify contractor and
waste receiver resources who will provide region-specific knowledge necessary for waste
management during a wide-area incident. The resources will include contractors with a
defined role in the remedial process (e.g., START) and representatives from facilities that
will be the waste receivers (e.g., on-site treatment, storage, and disposal facilities [TSDF]
representatives). A TSDF is a facility where hazardous wastes are stored, treated, and/or
placed in or on land or water (EPA, 2015d). Waste receivers, including owner/operators
of TSDFs, have region-specific knowledge of waste characterization, the TSDFs that
might accept the waste, and associated waste acceptance criteria. These resources will be
available throughout the duration of a wide-area incident to provide assistance and
maintain current information on TSDF facilities. This concept was added to the BPD and
the BPG.
Add more content to emphasize evaluation of degradation compounds in BPD.
Given the importance of degradation compounds, more information should be included in
the BPD for users that highlights their importance and provides additional background
information. The draft BPD includes degradation compound information, but may not be
easily found by players. The Executive Summary of the BPD and the BPG were revised to
note the availability of a summary table that included data on degradation compounds
(Table B-l) and additional cross-references to the text were added to the BPD.
F-7
-------
(f) Clarify in the BPD that non-Environmental Response Laboratory Network (ERLN)
laboratories might not accept samples if there is the potential for CWA-
contamination to be present. In the context of sampling for arsenic from Lewisite
breakdown or residual after decontamination, it was noted that laboratories that are not
members of the ERLN group might not accept samples for analysis for non-CWA
constituents due to the concern for potential CWA contamination. The BPD was updated
to note that the laboratories should be consulted prior to collection of samples to confirm
that they will accept samples with potential CWA contamination and have capacity to
perform the desired analyses.
(g) BPD may need to have greater emphasis that waste characterization is necessary
prior to disposal of all materials from the incident. It was noted several times during
the meeting that sampling might not be warranted when the cost of material or sampling
(e.g., labor, analysis) was greater than the cost of disposal (e.g., disposal of ceiling tile
instead of sampling). While the statement regarding the cost of sampling relative to
disposal may be true, waste characterization regulatory requirements must be met prior to
disposal of all waste materials. It is possible that lines of evidence (e.g., decontamination
efficacy) are implicitly being considered to assume that waste meets waste acceptance
criteria for solid waste. It may be helpful if the BPD more clearly identifies the
requirement for waste characterization and reaffirms that the process does not require
sampling if proposed waste acceptance criteria are satisfactory to both regulators and
waste receivers. An example or case study that illustrates this concept may help to clarify
this point for the BPD user. The clam shell study described in the BPD is noted as a case
study that incorporates this concept. The BPD andBPG were revised to include earlier
and more frequent mention that waste characterization is required for all wastes, but that
sampling might not be required if acceptable to regulators and waste receivers.
(h) The BPD provides a valuable summary of multiple documents. It was identified that the
BPD should be very helpful because it combines materials from a several sources and
provides a good resource for use. No changes were made in response to this comment.
(3) Simulation Software
The simulation software was outside the scope of the BPD and BPG, but was included as an
evaluation tool for the waste characterization process. The exercise format was also used to
evaluate potential uses of the simulation software for training or incident response. No
changes were made in the BPD and BPG in response to these comments. However, the
comments were compiledfor future consideration.
(a) The simulation software has utility for the training of OSCs and contractors who
are involved in sampling planning and collection. The simulation software will have
utility for OSCs during initial sampling training to develop an understanding of sample
strategies and sampling methods. There is also the potential for application in just-in-time
training to highlight known sampling issues in a specific situation or to refresh
knowledge. Because contractors are expected to do most of the actual sampling, there is
value in including contractors as another group that could benefit from use of the
software in training.
F-8
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(b) Refinements for simulation software for training. The simulation software could
be improved by the creation of more sampling locations. Identified sampling locations,
also termed scenarios in the discussion, include transit hubs, subways, and stadiums. It
may also be helpful to incorporate statistical sampling and the Visual Sampling Plan
(VSP) directly within the simulation. The ability of the simulation software to generate a
two-dimensional map of sampling locations that could be reviewed during or after the
sampling session was identified as desirable. Players noted that it was cumbersome not to
be able to "remove" or "change" a sample in the simulation after it had been collected. It
was also suggested that the ability to click on flags to edit within the simulation or to
make direct edits on the .csv summary Excel file would be useful refinements for the
software.
(c) Simulation software may have limited utility for response activities. For use in
response, it would be necessary to rapidly upload a three-dimensional representation of
the impacted building structures and interior contents. It was assumed that these
environments could not be built fast enough to use in the response unless they were
already generated. It was noted that the NYC Prioritized Area Targeted Sampling (PATS)
has pre-determined sampling locations in high-value locations. This situation where the
simulation software could include these data as an environment for training may be a
very good idea.
(4) Suggestions for Next Groups for Future Reviews of Process
The suggestions for groups for future reviews of the process was outside the scope of the
BPD and BPG.
(a) The next overall review of the process should include the EPA regions,
contractors, and a set of potential waste receivers. The next set of reviewers for the
overall process should include the EPA regions and their contractors (e.g., START
and TSDF representatives that have extensive experience in waste characterization).
The group would be able to provide feedback on the acceptability of proposed waste
characterization approaches. These representatives maintain ongoing contact with
waste facilities. As noted earlier, they should be asked to review the utility of the
lines of evidence concept (i.e., acceptable or generator knowledge) during a wide-area
incident. Some players noted that POTWs were unlikely to accept waste regardless of
the incident, but others disagreed because the POTW might recognize its system was
already contaminated by uncontrolled discharges as might occur during a wide-area
incident. For the future, groups representing POTWs may be an appropriate contact to
begin the education process and determine if they would find the lines of evidence
approach acceptable. Some wording changes were made to the BPD to emphasize the
complexity of POTW issues. Other waste-related comments were compiledfor future
consideration.
F-9
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(5) Format and Content of Exercise
The suggestions for improvements in the format and content of the exercise were outside the
scope of the BPD and BPG. No changes were made in the BPD and BPG in response to
these comments. However, the comments were compiledfor future consideration.
(a) To ensure a review of the actual BPD, a facilitator could be assigned to each group
as they work through the exercise tasks to ensure that they are able to utilize the
document. Given that players only had access to the quick reference BPG prior to the
exercise, players did not have time to acquaint themselves more fully with the full-size
BPD for maximum use during the exercise. As a result, the waste characterization
process was a greater focus of the review than the BPD. Another suggestion to allow for
a more comprehensive review of the BPD was to provide training on the BPD prior to the
exercise or include more training within the exercise.
(b) The reversal of the exercise questions may be helpful for players to work through
the scenario tasks easier. As an example, the exercise could have started with a review
of the DQO process supplied in an appendix in the BPD. This review would have
provided the players with a more solid grasp of the waste acceptance criteria and desired
sampling approaches. This sequencing of the presentation of exercise material would also
reinforce the idea that the exercises, although focused on small areas, were actually part
of a wide-area incident and therefore had unique waste management challenges.
(c) Additional assumptions were needed to complete the tasks in the exercise. Players
felt that more complete assumptions were needed for them to efficiently complete the
table-top tasks. Necessary data might include the volume of waste that each identified
facility would accept or if the facility would accept the waste at all. Specifically, players
wondered if a wastewater system would accept water treated on-site, especially if the
system was already contaminated from uncontrolled discharge, as might occur during a
wide-area incident. A control cell was included in the exercise, but players did not use
that as an opportunity to ask questions. Future exercises should emphasize the importance
of asking questions if players feel that they need additional information or are having
difficulty with a specific assigned task.
F-10
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Attachment Fl. Player and Attendee List
The following is a list of the exercise players and attendees for the exercise.
Players
Consequence Management and Assessment Division
U.S. Environmental Protection Agency
David Bright
Elise Jakabhazy
Paul Kudarauskas
Michael Nalipinski
Shannon Serre
National Homeland Security Research Center
U.S. Environmental Protection Agency
Sarah Taft
Environmental Response Team,
U.S. Environmental Protection Agency
Lawrence Kaelin
Christopher Gallo
Office of Resource Conservation and Recovery
U.S. Environmental Protection Agency
Christina Langlois-Miller
Region 3
U.S. Environmental Protection Agency
Jessica Duffy
Charlie Fitzsimmons
Attendees
U.S. Environmental Protection Agency, National Homeland Security Research Center
Timothy Boe
Paul Lemieux
Matthew Magnuson
Erin Silvestri
Stuart Willison
Battelle
Stephanie Hines
Ryan James
Spectral Laboratories
John Rolando
Rhett Barnes
F-ll
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Attachment F2. Agenda for Exercise
Agenda
Date: October 19, 2017
Location: U.S. EPA Region 2
2890 Woodbridge Ave, BIdg 238
Edison, NJ 08837
Room 801
Best Practices to Minimize Laboratory Resources for Waste Characterization During a
Wide-Area Release of Chemical Warfare Agents
8:00 Introduction
8:15 Begin Table-top exercise
Scenario introduction and objectives
TTX Worksheet
9:15 Discussion from Table-top
9:45 Wrap-up and Lessons Learned
10:00 Break
10:15 Begin Simulation exercise
New Player Tutorial, Sample Collection Review Discussion, Player Use of
Software (Note: Players can walk through all locations and then collect samples in
one or two locations to test out simulation software)
10:30 Participants walkthrough simulation and perform simulation exercises
11:30 Discussion from Simulation
12:00 Wrap-up and Lessons Learned from Simulation and additional comments from TTX
12:30-12:45 Adjourn
F-12
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F3. Presentation Provided to Players
11/1/2017
oEPA
Best Practices to Minimize
Laboratory Resources for Waste
Characterization During a Wide-Area
Release of Chemical Warfare Agents
TTX Exercise
US EPA Region 2
Edison, New Jersey
October 19 2017
Disclaimer: This document is distributed solely for the purpose of pre-
dissemination peer review under applicable information quality guidelines. It has
not been formally disseminated by the U.S. Environmental Protection Agency. It
does not represent and should not be construed to represent any agency
determination or policy.
&EPA Agenda for Exercise
Exercise Scenario Overview
Review of Waste Characterization
Table-top Exercise with Hotwash
Break
Simulation Exercise with Hotwash
Review of Best Practices for Waste Characterization Document
and Exercise Format
1
F-13
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Exercise Scenario Overview
Urban wide-area release of chemical blister
agent
* Agent Yellow 55 gallons of 50/50 mixture
of Mustard and Lewisite, agent is relatively
persistent, low volatility and water
solubility, rapid hydrolysis, potentially
strong sorption to some materials
Released to air in an urban area, with
transport through air and movement of
contaminated vehicles and individuals
Hundreds of buildings impacted over 5-mile
area from release
Waste is generated during all phases of the
incident
We're excited to be able to add a 3-D simulation element to this
review process and are interested in your feedback on this
element of the exercise.
0.03 mg/mA2 Area
Length: 18 km
Width: 1.5 km
30 mg/mA2 ฆ
3 mg/mA2 J
0.3 mg/mA2 ^
0.03 mg/mA2 _
Agent Yellow surface concentrations
\>EPA Waste Characterization Exercise
* Table-top
ฆ Set of waste-containing barrels to characterize
Contents include decontamination rinsate, used PPE, and other materials
Apply best practices to characterize with limited number of samples
Computer Simulation
Increased complexity in waste characterization task
- Office
- Warehouse
- Industrial Park
Apply best practices to characterize with limited number of samples
We need your help to review the Best Practices process!
F-14
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SERA What is Waste Characterization?
Waste Characterization is the use of sampling and/or
knowledge of the waste (i.e., lines of evidence) to document
waste meets regulatory requirements and any additional
requirements of waste receivers
Type of data
Lines of Evidence
Information or data from various sources that can be used to support
waste characterization decisions.
Lines of evidence can include technical data on agent fate and
transport, persistence in defined environmental conditions, and
efficacy of decontamination technologies.
Sampling
Who determines the standards for waste characterization?
Must meet Federal/state/local regulatory requirements
Must meet any meet any other identified requirements of waste
receivers (e.g., Landfill or POTW operators)
SERA Waste in Wide-Area Incident
Waste is any material that is intended for disposal and will not
be re-used or recycled
Waste streams will be generated throughout the incident
Personal Protective Equipment (PPE) - gloves, suits, boot covers
Decontaminated items for disposal or further management
Office materials, dry wall, carpet, ceiling tiles, cubicles, furniture, paper
Decontamination rinsate
Volume of waste material prevents from use of typical sampling
approaches used for industrial processes or typical Superfund
remedial setting
F-15
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SERA
Wide-area Waste Volumes
Generated from
WEST simulations
of the WARRP
Scenario
Chem Scenario - Waste Distribution
10,000,000
1,000,000
1U.UUU
X
LTD
1 1
Estimated total liquid
waste of 15 to 36
million gallons and 3
to 8 million tons of
solid waste
ฆ Volumetric Decon
Surface Decon
ปcp/v Wide-area Incident Waste Characterization
-*" Challenges
Why do we need to limit the number of analysis samples?
Capacity for laboratory analysis of samples cannot meet the sampling
demand in chemical agent wide-area event
Sampling is used extensively in wide-area incident for site
characterization, decontamination efficacy, waste characterization, and
clinical or medical samples
Waste will likely be a low priority for analysis
Potential for sampling to be a chokepoint in response and recovery
process
Best practices designed to reduce the number of samples sent
to laboratories for analysis for waste characterization
F-16
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vvERA Development of Best Practices Document
Process to generate Best
Practices Document
Targeted literature search to
identify published, open-
source data available
Wide-area event sampling
considerations and waste
characterization
General waste characterization
approaches that may be applied
or customized for use
Important pre-planning
activity to identify and
address data gaps
Continuing technical peer
review
SERA Waste Management Resources
Pre-incident Waste Management Plan
Describes planning activities that have been conducted for
incident
Identifies anticipated waste streams, volume of materials,
potential management locations/entities and associated waste
acceptance criteria
Tool to develop the pre-incident waste management plan are
available and will be discussed in more detail later today
Additional information in binders
Four-step Waste Management Planning Process
All-hazard Waste Management Decision Diagram
Tซblc of Content)
toAjulr%aK*afc
32 Lick ofUmmul Appro&cbK &ป Wui-Am lack
Wul* QufKteuihoe Guufcluป;
AppvodctS Bxlsnaiad oc Chmscal Wnฃnซ AfcaC:
Aj*ซฃx C DOO tn
-------
SERA Waste Characterization Flow Chart
Figure 5 in Best
Practices
Document
r-pft Best Practices for Waste Characterization
CrR t0 Minimize Sample Numbers
Segregate wastes
Group similar wastes to consolidate sampling tasks
Identify Waste Acceptance Criteria and DQOs for
segregated waste groups
Determine Waste Characterization Strategy for
segregated waste groups
Strategy: Lines of Evidence and/or Sampling
Identify Analysis Method (if sampling)
Determine Laboratory Method or Field Screening
Identify Sampling Collection Technique (if sampling)
F-18
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vvEPA
13
Table-top
\>EPA Table-top Scenario
7 days after the release of Agent Yellow
Temperatures have been approximately 70F in the daytime and
50F at night
Building HVAC systems have not run since the evening of the
release
Waste was generated during sampling to determine the extent
of contamination in an office suite of one building
Average concentration levels derived from wipe samples from nonporous
surfaces
First floor office7 ng/cm' for Sulfur Mustard and 7 ng/m' for Lewisite
Second floor office -0.01 ng/cm2 for Sulfur Mustard and 0.001 ng/cm2for Lewisite
F-19
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vvERA Table-top Scenario Task
The exercise task is to perform waste characterization for the following
collection of waste materials:
Eight 55-gallon drums containing decontamination rinsate that used a bleach and water
mixture to decontaminate material
Two labeled 55 gallon drums with an assortment of used PPE
Two labeled 55-gallon drums of mixed soaked porous materials treated with bleach and
water
You have 2 samples that can be sent to laboratory analysis
Hint 1: Remember Available Sampling Data
Average concentration levels derived from wipe samples from nonporous surfaces
First floor office - 7 |ig/cm2 for Sulfur Mustard and 7 |ig/m2 for Lewisite
* Second floor office - 0.01 |^g/cm2 for Sulfur Mustard and 0.001 ng/cm2 for
Lewisite
Hint 2: Many Ways to Segregate Waste
Consider ways that best reduce or eliminate laboratory sampling
We acknowledge that there may be some elements of the scenario
that may not be true to all elements of wide-area incident
Please refrain from fighting the scenario
SERA Table-top Drum Detail
8 Decontamination Rinsate Drums
Labels identify that waste was
generated from decontamination of
personnel, equipment, and other
materials and identify the office floor
materials removed from (First or
Second Floor)
2 drums labeled to contain
decontaminated office
materials and removed
from second floor, office
materials are contained in a
bag in each drum
2 drums labeled to contain assorted
used PPE, the PPE in each drum is
contained in a bag
i
F-20
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vvERA Table-top Resources
Review Binder Contents
Best Practices Document (Full length)
Best Practices Guide (3 pager brief)
NRT Quick Reference Guide (QRG) for Mustard-Lewisite Mixture
Pre-incident Waste Management Plan and Waste References
~ Identifies est. waste quantities, regulatory requirements, management strategies,
waste acceptance criteria, waste management facilities
Scenario and table-top tasks
Summary Table Handout (Exercise Use Only)
Waste acceptance criteria, method detection limits, generalized DQOs
Control Cell - Available to ask questions, copies of selected
NHSRC SAM documents
We will distribute Waste Characterization Worksheets to the
group for use.
SERA
Overview of Waste Characterization
Worksheet
Best Practices for Waste Characterization Worksheet
(1) Segregate the waste into homogeneous groups relevant.for waste characterization
and complete this worksheet, for each segregated waste group that, was identified.
(Section 63)
Segregated Waste Group Name:
(2) Please consider the following questions collectively before identifying your final
response to each.
(a) Identify Waste Acceptance Criteria for the segregated waste group (Section
6.4 and Pre-incident. Waste Management Plan).
Waste Acceptance Qiteria;
(b) Identify relevant DQOs for the segregated waste group (Section 6.4 and
Summary Table).
For exercise purposes, consider using these example DQOs:
~ Acceptable waste characterization strategies can take the form of
coiiceiiiralioii-based or performance-based u ila'ia,
~ The detection limits must be at or lower than the identified waste
acceptance criteria, and
~ For acceptance of the waste, none of the samples from a segregated waste
group can exceed the waste acceptance criteria.
18
DQOs:
F-21
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Overview of Waste Characterization
Worksheet
(a) Determine Wasle Characterization Strategy (Section6.2 including Figure 3,
Section 6.5)
(Note: More than one strategy can be used)
WiU Lines of Evidence be Used? Yes No
(Section 6.5.1)
Will Samplingbe Used? Yes No
(Section 6.5.2)
If Ilines of Evidence will he used, describe the basis for the determination:
If sampling will be used, determtae the sampling strategy. (Section 6.5.2, Table 1)
(b) Which sampling strategy will beused?
Nonprobabilistic Probabilistic Combination of Both
Further define sampling strategy (e.g., judgmentai, simple random)
(c) Will composite sampling be performed? (Section 6.5.3.2) Yes No
(d) If sampling will be used, describe sample number(s) and location/material
19
Overview of Waste Characterization
Worksheet
(g) Identify the sample collection method(s). (Section 6.6 andTable2)
(Nole: More than one slrateyy can be used)
Field Analysis Collection Method:
Laboratory Analysis Collection Method:
Identify type of samp liny; and the analysis method. (Section 6.7)
(Note: More than one strategy can beused)
Field Analysis Yes Wo Method:
Laboratory Anafysls Yes No Method:
Waste CbaractB~ization Summary Box
Segregated Wasle Group Name:
Describe Approach to Segregation:
Waste Characterization Strategy
(Identity Lines of Evidence; Sampling or Combination)
Total Sample Number Sent to Laboratory for Analysis
Total Number of Field Samples Collected
SEPA
F-22
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vvERA Table-top Scenario Task
The exercise task is to perform waste characterization for the following
collection of waste materials:
Eight 55-gallon drums containing decontamination rinsate that used a bleach and water
mixture to decontaminate material
Two labeled 55 gallon drums with an assortment of used PPE
Two labeled 55-gallon drums of mixed soaked porous materials treated with bleach and
water
You have 2 samples that can be sent to laboratory analysis
Hint 1: Remember Available Sampling Data
Average concentration levels derived from wipe samples from nonporous surfaces
First floor office - 7 |ig/cm2 for Sulfur Mustard and 7 |ig/m2 for Lewisite
* Second floor office - 0.01 |^g/cm2 for Sulfur Mustard and 0.001 ng/cm2 for
Lewisite
Hint 2: Many Ways to Segregate Waste
Consider ways that best reduce or eliminate laboratory sampling
We acknowledge that there may be some elements of the scenario
that may not be true to all elements of wide-area incident
Please refrain from fighting the scenario
\>EPA Table-top Exercise - Hotwash
How did you approach the waste characterization task?
How much prior knowledge (defined as knowledge you walked in to
exercise with and prior to use of the Best Practices document) did you
utilize in performing the waste characterization task?
What elements of the Best Practices document were most helpful to
perform this task? What elements can be improved? How?
Where there any concepts or ideas that were not in the BPD that you
feel should be added? Any references missing?
What available resources provided the most assistance?
F-23
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vvEPA
23
Simulation
&EPA Simulation Scenario and Task
It is now 10 days after the release of Agent Yellow in the same scenario
Temperature and relative humidity have stayed the same
The office floor, warehouse, and outdoor locations have been
decontaminated with a bleach and water solution
You are to identify and characterize the waste present in each location
Segregate, Identify Waste Acceptance Criteria and DQOs, Waste Characterization
Strategy, and Collect Data
You have a total of 24 samples for the three locations
You will complete sampling at one location before entering the next
location
21
F-24
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SERA
Simulation Resources
1 Same resources in binder as used in the table-top
Please remember
Complete the Notes section in software thoroughly to document your sampling
choices
Control Cell - Available to ask questions
We will distribute Waste Characterization Worksheets to the group for use.
\>EPA Sample Capture Process
Simulation mirrors waste characterization
flow chart
.BP Section6.3
When you choose sampling, follow flow
downs
Segregate Homogeneous Waste1
Segregate Homogeneous Waste
Materials into Named Groups:
Determine Data Gathering Strategy:
Use Lines of Evidence?
Sampling?
BP
Section
6.5.2
3n5 Strilte
Use Lines of Evidence?
Usa Sampling?
Section
Simple Hamlom
SliMhfmd Random
Grid or T
6.5.1
Sections
6.6 and
6.5.2
Emmcttvn | Soซ0 Untmnjl) Samptmg
Strategy: p.obMhm*
Ffl
Please complete notes to
document thought process
wnt your decision making below
F-25
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Simulation Scenario and Task
It is now 10 days after the release of Agent Yellow in the same scenario
Temperature and relative humidity have stayed the same
The office floor, warehouse, and outdoor locations have been
decontaminated with a bleach and water solution
You are to identify and characterize the waste present in each location
Segregate, Identify Waste Acceptance Criteria and DQOs, Waste Characterization
Strategy, and Collect Data
You have a total of 24 samples for the three locations
You will complete sampling at one location before entering the next
location
SB
27
\>EPA Simulation - Hotwash
How did you approach this waste characterization task?
Review selected player sample captures
The simulation introduced a more challenging waste characterization
task in a more complex environment. Did that affect your data gathering
strategy? How was your strategy affected?
Did the Best practices document provide sufficient information to help
you reduce sample numbers? What was most useful? Least useful?
28
F-26
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Wrap-up Discussion
After using the Best Practices document for table-top and
simulation tasks, what did you find most useful about the Best
Practices document?
What are suggested improvements to the Best Practices
document to improve effectiveness to reduce sampling
number or increase ease of use?
Was there sufficient description in the Best Practices
document to select an appropriate data gathering strategy?
Did the waste characterization document sufficiently describe
the available data gathering strategies to aid in decision-
making?
X?EI
SERA Wrap-up Discussion
Did you have sufficient technical information to reduce
samples sent to the laboratory for waste characterization?
Did you find listing the pros/cons of the sampling strategies
useful in the Best Practices document ?
Is the exercise format (table-top, simulation) used for today's
meeting a useful approach to review the Best Practices
document ?
Could this simulation be used for a wide-area incident? Are
there other simulations that you would like to see?
Do you think the simulation format would be a useful training
tool?
F-27
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vvEPA Next Steps
Thank your for your help!
We will use your feedback to revise and the strengthen Best
Practices for Waste Characterization document and associated
waste characterization processes.
Thank you for your assistance and safe travels home!
F-28
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Attachment F4. Overall Scenario Provided to Players
The scenario is based on the Wide-Area Recovery & Resiliency Program (WARRP)
scenario for a hypothetical wide-area incident involving chemical blister agent. However, it is
modified to facilitate its use for the tabletop and simulation environment evaluation of the
Standard Operating Guideline (SOG) draft documents.
The chemical Agent Yellow is released in an urban environment. Agent Yellow is a
50/50 mixture of the blister agents Mustard and Lewisite, and approximately 55 gallons are
released from an airplane in a coarse spray over the Denver urban area. Agent Yellow is
relatively persistent and expected to present a hazard for 24 hours or more. Mustard and Lewisite
have low volatility, low water solubility, but potentially strong sorption to specific material
types. Mustard may exhibit a delayed toxic response, whereas Lewisite may cause immediate
and significant health effects.
The agent release by air directly contacts and contaminates exposed individuals, building
exteriors, streets, vehicles, and other urban infrastructure. Agent is then further transported from
the immediate release area through vapors that travel downwind and movement of contaminated
individuals and/or vehicles traveling away from the contaminated area. If they enter buildings to
take cover, individuals may track contamination into buildings. Agent Yellow vapor may also be
taken up by building HVAC systems and serve as a pathway for the contaminated outdoor air to
be transported into building interiors.
This same scenario will be used for the tabletop and simulation exercises. The exercises
will focus on decision-making associated with sampling and characterization of waste and
subsequent steps needed to properly manage wastes generated from the interior of a
contaminated building during response and recovery activities. Waste management decisions are
made throughout the response and recovery effort. Collectively, hundreds of facilities could be
contaminated over a five-mile area from the release location (DHS, 2012), with an estimated 15
to 36 million gallons of aqueous waste and 3 to 8 million tons of solid waste associated with the
incident (EPA, 2012). Federal and state requirements for waste management note that all waste
must be appropriately characterized as part of a proper management plan. Waste streams might
include PPE, items decontaminated for disposal or further management, and decontamination
wastewater.
References
EPA, 2012. WARRP Waste Management Workshop, U.S. Environmental Protection Agency,
Office of Homeland Security: Denver, CO, March 15-16.
DHS, 2012. Wide Area Recovery and Resiliency Program (WARRP) Key Planning Factors for
Recovery from a Chemical Warfare Agent Incident. U.S. Department of Homeland Security.
Summer 2012. https://www.fema.gov/media-library/assets/documents/31719.
F-29
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Attachment F5. Traditional Table-top Scenario and Task
Table-top Scenario
7 days after the release of Agent Yellow
Temperatures have been approximately 70 ฐF in the daytime and 50 ฐF at night
Building HVAC systems have not run since the evening of the release
Waste was generated during sampling to determine the extent of contamination in an
office suite of one building
Average concentration levels derived from wipe samples from nonporous surfaces
First floor office - 7 |ig/cm2 for Sulfur Mustard and 7 |ig/m2 for Lewisite
Second floor office - 0.01 |ig/cm2 for Sulfur Mustard and 0.001 |ig/cm2for
Lewisite
Table-top Task
The exercise task is to perform waste characterization for the following collection of
waste materials:
Eight 55-gallon drums containing decontamination rinsate that used a bleach and water
mixture to decontaminate material
Two labeled 55-gallon drums with an assortment of used PPE
Two labeled 55-gallon drums of mixed soaked porous materials treated with bleach and
water
You have two samples that can be sent to laboratory analysis
Hints Provided
Hint 1: Remember Available Sampling Data
Average concentration levels derived from wipe samples from nonporous surfaces
First floor office - 7 |ig/cm2 for Sulfur Mustard and 7 |ig/m2 for Lewisite
Second floor office - 0.01 |ig/cm2 for Sulfur Mustard and 0.001 |ig/cm2for
Lewisite
Hint 2: Many Ways to Segregate Waste
Consider ways that best reduce or eliminate laboratory sampling
We acknowledge that there may be some elements of the scenario that may not be true to
all elements of wide-area incident, please refrain from fighting the scenario
F-30
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Attachment F6. Waste Characterization Worksheet
Best Practices for Waste Characterization Worksheet
(1) Segregate the waste into homogeneous groups relevant for waste characterization and
complete this worksheet for each segregated waste group that was identified. (Section
6.3)
Segregated Waste Group Name:
(2) Please consider the following questions collectively before identifying your final
response to each.
(a) Identify Waste Acceptance Criteria for the segregated waste group (Section 6.4
and Pre-incident Waste Management Plan).
Waste Acceptance Criteria:
(b) Identify relevant DQOs for the segregated waste group (Section 6.4 and Summary
Table).
For exercise purposes, consider using these example DQOs:
Acceptable waste characterization strategies can take the form of concentration-
based or performance-based criteria,
The detection limits must be at or lower than the identified waste acceptance
criteria, and
For acceptance of the waste, none of the samples from a segregated waste group
can exceed the waste acceptance criteria, (e.g., If/Then Statement: If any
concentrations of sulfur mustard >0.1 [j,g/cm2 are detected in the wipes of the
sampled containers from a waste lot, then the waste in that lot will not be disposed
of in the Subtitle C landfills without further decontamination and reassessment or
the waste might be sent to hazardous waste incinerators.)
DQOs:
F-31
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(c) Determine Waste Characterization Strategy (Section 6.2 including Figure 3,
Section 6.5)
(Note: More than one strategy can be used)
Will Lines of Evidence be Used? Yes No
(Section 6.5.1)
Will Sampling be Used? Yes No
(Section 6.5.2)
If Lines of Evidence will be used, describe the basis for the determination. (Section
6.5.1)
If sampling will be used, determine the sampling strategy (Section 6.5.2 and
Table 1)
(d) Which sampling strategy will be used?
Nonprobabilistic Probabilistic Combination of Both
Further define sampling strategy (e.g., judgmental, simple random)
(e) Will composite sampling be performed? (Section 6.5.3.2) Yes No
(f) If sampling will be used, describe sample number(s) and location/material
(g) Identify the sample collection method(s). (Section 6.6 and Table 2)
(Note: More than one strategy can be used)
Field Analysis Collection Method:
Laboratory Analysis Collection Method:
F-32
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Identify type of sampling and the analysis method. (Section 6.7 and Summary
Table)
(Note: More than one strategy can be used)
Field Analysis Yes No Method:
Laboratory Analysis Yes No Method:
Waste Characterization Summary Box
Segregated Waste Group Name:
Describe Approach to Segregation:
Waste Characterization Strategy:
(Identify Lines of Evidence, Sampling or Combination)
Total Sample Number Sent to Laboratory for Analysis:
Total Number of Field Samples Collected:
F-33
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Attachment F7. Computer Simulation Scenario and Tasks
It is now 10 days after the release of Agent Yellow in the same scenario
Temperature and relative humidity have stayed the same
The office floor, warehouse, and outdoor locations have been decontaminated with a
bleach and water solution
You are to identify and characterize the waste present in each location
Segregate, Identify Waste Acceptance Criteria and DQOs, Waste Characterization
Strategy, and Collect Data
You have a total of 24 samples for the three locations
You will complete sampling at one location before entering the next location
F-34
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Attachment F8. Summary Table Identifying Potential Waste Acceptance Criteria for Water, Soils, and Surface Wipes for
Mustard and Lewisite. (For Exercise Use Only- The table was used for the purposes of this exercise and this inherent approach
should not necessarily be used for a specific incident)
Water
Soils
Surface Wipes
Mustard
Lewisite
Mustard
Lewisite
Mustard
Lewisite
Potential Waste Acceptance Criteria for POTW (Water), Soi
and Surface Wipes (Subtitle C Solid Waste Landfill)
Quick Reference
Guide (QRG)
Exposure Guidelines
(NRT, 2015b)
140 |ig/La
80 (ig/Lb
Residential Exposure
Scenario
0.01 mg/kg
(10"5 cancer risk)
Residential
Exposure Scenario
0.3 mg/kg
No Data
No Data
Condensed Chemical
Agent Field
Guidebook for
Consequence
Management (NRT,
2015b)
140 ng/La
28 (ig/Lb
Residential Exposure
Scenario
0.01 mg/kg
(10"5 cancer risk)
Residential
Exposure Scenario
0.3 mg/kg
8.1 x 10-5 jig/cm2
6.0 x 10-2 jig/cm2c
Method Detection Limits
QRG Real-time Field
Screening Equipment
Identified Detection
Limits3
M272 (water)
2.0 mg/L
(2000 ng/L)
M272 (water)
0.1-2 mg/L
(100 to 2000 ng/L)
No Data
No Data
No Data
No Data
SAM Rapid Screening
and Preliminary
Identification
Techniques and
Methods (EPA, 2012)
Photoionization mass
spectrometry
0.07 to 0.7 mg/L
(70 to 700 ng/L)
Spectrophotometry
(fieldable)
Detection range
0.02 to 0.20 mg/L,
(20 to 200 ng/L)
Measures total
arsenic
GC-MS-EI,EPA
Method 3571/3572 with
8271 (EPA SW-846
Compendium)
No detection limit
identified. Recovery levels
for direct injection soil
recovery, 103 to 112(+/-
19)%
X-ray Fluorescence
(fieldable), EPA
Method 6200/SW-
846 (EPA SW-846
Compendium)
Interference free
detection limit 40
mg/kg, Measures
total arsenic
GC-MS-EI, EPA
Method 3571/3572 with
8271 (EPA SW-846
Compendium)
No detection limit
identified. Recovery
levels for direct injection
soil recovery, 103 to
112(+/-19)%
X-ray Fluorescence
(fieldable), EPA
Method 6200/SW-846
(EPA SW-846
Compendium)
Interference free
detection limit 40
mg/kg,
Measures total arsenic
F-35
-------
Water
Soils
Surface Wipes
Mustard
Lewisite
Mustard
Lewisite
Mustard
Lewisite
Standardized
Analytical Methods for
Environmental
Restoration Following
Homeland Security
Events (SAM)
(EPA, 2012)
CWA Protocol (EPA
NHSRC)
Calibration range in full
scan mode for water,
5.7 to 57 ng/L
Analyze for total
arsenic
CWA Protocol (EPA
NHSRC)
Calibration range in full
scan mode for soils 10 to
100 ng/kg
(0.01 mg/kg to 0.1 mg/kg)
Analyze for total
arsenic
ICP-AES, EPA
SW-846 Method
3050B
Instrument
detection limit, 30
jug/L for extraction
CWA Protocol (EPA
NHSRC)
Calibration range in full
scan mode for wipes 0.01
to 0.1 |ig/cm2
Analyze for total
arsenic
NIOSH Method 9102
Instrument detection
limit, 30 ng/L for
extraction
F-36
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Attachment F8 Table Notes:
Generalized Data Quality Objectives (DQOs) for Waste Characterization
1 Acceptable waste characterization strategies can take the form of concentration-based criteria or performance-based criteria.
Concentration-based, also termed numerical-based criteria, identify chemical-specific concentrations that must be met and will include
the presentation of analytical results to document attainment. The second type of waste acceptance criteria, performance-based criteria,
identify the technologies or treatment processes that must be used and the necessary information to document that the processes were
effectively implemented (i.e., lines of evidence).
2 All waste must be appropriately segregated prior to sampling. Segregation must be performed to account for potential variability in
contaminant concentrations that may affect ability to gather representative samples. Examples of considerations include: material type
(e.g., porous, nonporous), expected contamination levels, and application of similar decontamination technologies.
3 The detection limits must be at or lower than the identified waste acceptance criteria when sampling is performed.
4 For acceptance of the waste, none of the samples from a segregated waste group can exceed the waste acceptance criteria. Further
decontamination or reassessment of the waste will be necessary. An example of an acceptable decision statement for type of decision
statement this DQO is: Determine whether each lot of decontaminated waste can be disposed of in a Subtitle C landfills. The theoretical
decision rule in the form of an if/then statement is as follows: If any concentrations of sulfur mustard >0.1 (ig/cm2 are detected in the
wipes of the sampled containers from a waste lot, then the waste in that lot will not be disposed of in the Subtitle C landfills without
further decontamination and reassessment or the waste might be sent to hazardous waste incinerators. Otherwise the lot of waste will be
considered acceptable for disposal in the Subtitle C landfills.
Summary Table Notes:
aThe U.S. Army's Military Exposure Guidelines (MEGs) were used due to the absence of public health values; the MEG at 5 L/day,
for 7 days = 140 ug/L (NRT, 2015).
bThe U.S. Army's Military Exposure Guidelines (MEGs) were used due to the absence of public health values; the MEG at 5 L/day, for
7 days = 80 ug/L (NRT, 2015).
^Preliminary Remediation Goals (PRG), risk based goals for surfaces calculated via EPA's Risk Assessment Guide for Superfund
(RAGS) methodologies (available at http://www.epa.gov/oswer/riskassessment/ragse/).
F-37
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Attachment F9. Reference Materials Provided to Players
(1) Draft Best Practices Guide to Minimize Laboratory Resources for Waste Characterization
During a Wide-Area Release of Chemical Warfare Agents (BPG) (See revised BPG in Appendix
G)
(2) Draft Best Practices Document to Minimize Laboratory Resources for Waste
Characterization During a Wide-Area Release of Chemical Warfare Agents (BPD)
(3) National Response Team Reference Guide (QRG). Mustard - Lewisite Mixture (HL). July
2015 Update.
(5) Waste Management Resources including: Pre-incident All Hazards Waste Management Plan
Guidelines: Four-step Waste Management Planning Process.
(6) All-hazards Waste Management Decision Diagram
(7) Summary Table Identifying Potential Waste Acceptance Criteria for Water, Soils, and
Surface Wipes for Mustard and Lewisite (Marked "For Exercise Use Only")
F-38
-------
Attachment F10. Player Evaluation Form
Player Evaluation
Draft Chemical Agent Waste Management Review Exercise
October 19,2017
Please provide input for each of the following statements provided below:
(1) What did you find useful about the waste characterization best practices document?
2) Please identity suggested improvements for the Waste Characterization document that
would increase its effectiveness to reduce sample number or increase its ease of use.
3) Did the waste characterization document provide the necessary technical information to
reduce the number of samples sent to the laboratory for waste characterization tasks
during a wide area incident?
4) Did the waste characterization document sufficiently describe the different sampling
strategies that are available to allow for a decision to be made regarding the type of
sampling strategy needed for waste characterization?
5) Did you find listing the sampling strategies and their respective advantages and
tradeoffs useful within the waste characterization document?
6) Are there any waste characterization resources that you currently using that are
missing within the waste characterization document?
1
F-39
-------
7) What sampling strategy (sampling, process knowledge, and combination of sampling
and process knowledge) did you use in the T ablet op and simulation for waste
characterization and why?
8) Did you find the Table Top exercise and Simulation useful for applying the Waste
Characterization document to a scenario?
9) Could the simulation be used for a wide area incident? If useful, what other simulations
would you like to see developed?
10) Did you find the format used for today's meeting a useful approach to review the waste
characterization best practices document and its content? What would you have preferred
to see if something was not adequately covered?
11) Were you able to easily use the simulation software after the initial training?
Strongly Disagree Neutral Agree Strongly
Disagree Agree
2
F-40
-------
Appent 'st Practices Glide (BPG)
G-l
-------
United States
iKHHu Environmental Protection
IbbiI M ^Agency
QUICK REFERENCE
Best Practices Guide (BPG) to Minimize Laboratory Resources for Waste Characterization
During a Wide-Area Release of Chemical Warfare Agents
This quick reference document summarizes the waste characterization process described in Best
Practices to Minimize Laboratory Resources for Waste Characterization During a Wide-Area
Release of Chemical Warfare Agents (Best Practices Guide, BPD). The full BPD will assist users
in minimizing the number of samples sent for laboratory analysis for waste characterization tasks
while still meeting the data needs of regulators and receivers of the waste. The purpose of this
document is to provide a quick reference to the BPD, particularly for use during
tabletop/simulation/training events. This document includes the central flow chart to the waste
characterization process, along with identification and brief description that should enable the
participant in such events to locate relevant sections of the BPD as quickly as possible. The
quick reference is not intended to replace the full BPD in terms of information or strategy.
A wide-area release of chemical warfare agent may result in the contamination of several square
miles of urban area, potentially affecting hundreds of buildings. The response and recovery
activities from this type of incident could generate several tons of solid waste and millions of
gallons of liquid waste.
Materials that are not going to be reused or recycled from the
incident area will become waste when they are identified for
disposal. All waste generated during management of the wide-
area incident must be appropriately characterized. However,
laboratory demand during a wide-area incident will likely be
greater than the available capacity due to the need for
sampling and analysis during site characterization, assessment
of decontamination efficacy, waste characterization, and
clinical or medical testing. As a result, laboratory analysis
could become a chokepoint and limit overall progress in
incident management.
Important concepts to reduce the number of laboratory samples include:
Waste characterization is a legal requirement for all generated wastes, but sampling
might not be necessary if acceptable to regulators and waste receivers.
Appropriate waste segregation is critical for efficient waste characterization.
Waste characterization strategies should leverage the use of lines of evidence to the
extent possible as a primary means to reduce sample numbers for laboratory analysis.
Waste characterization is a
process that uses knowledge
of the waste and/or
sampling results to
document that the waste
meets regulatory
requirements and any
additional requirements of
waste receivers
G-2
-------
Field screening can be combined with lines of evidence or the use
of a limited number of confirmatory laboratory samples to reduce
the number of laboratory samples analyzed.
Waste characterization strategies must be acceptable to regulators
and waste receivers, and these entities should be involved
throughout the process especially in the beginning where many
decisions are made that drive characterization and
decontamination waste stream.
Waste Characterization Process
Figure 1, detailed and referring to sections in the BPD, provides a
description of the overall waste characterization process. For clarity,
progression through the Figure 1 is intended to be a stepwise process.
However, there are multiple factors within the process that might be
optimized to reduce the number of laboratory samples and may result in
the simultaneous determination of several process decisions or dictate an
iterative nature to waste characterization decisions. Site- or incident-
specific conditions might also dictate the sequence of decision-making.
Step 1: Segregate waste into homogeneous groups (Section 6.3), Identify waste acceptance
criteria and associated data quality objectives (DQOs) for each waste group (Section 6.4).
Identify laboratories with analysis capabilities for desired analyses that will accept material
(Section 6.7)
Waste materials are segregated to facilitate reduced sampling requirements by grouping
materials assumed to have similar characteristics. Waste group characteristics that might be
relevant for segregation are described in further detail in the BPD. Individual waste groups might
be targeted for different waste management options, with varying waste acceptance criteria and
DQOs based on the waste receiver(s). Waste acceptance criteria are specific to each waste
receiver that will accept the waste. There might also be unique acceptance criteria for locations
that hold or stage waste prior to its final management. It will be helpful to identify contractor and
waste receiver resources that will be present on-scene during an incident who can provide
region-specific knowledge for waste characterization and available waste receivers. The criteria
can be concentration-based or performance-based standards (i.e., decontamination technology)
and include the volume of waste that will be accepted (Section 6.4). It is important to recognize
that degradation products (Table B-l) and non-CWA constituents of the waste should also be
considered in the waste characterization process. If laboratory analysis of samples will be
performed, laboratories that can perform the analysis and that will accept the waste material must
be confirmed (Section 6.7).
Step 2: Determine the waste characterization strategy (Section 6.5). The waste
characterization strategy is developed to demonstrate if the waste material meets the identified
waste acceptance criteria and DQOs. The strategy might consist of application of lines of
evidence, field and/or laboratory sampling, or a combination of the two approaches. Lines of
Lines of Evidence are
information or data
from various sources
that can be used to
support waste
characterization
decisions. Lines of
evidence can include
technical data on agent
fate and transport,
persistence in defined
environmental
conditions, and
efficacy of
decontamination
technologies.
G-3
-------
evidence should be considered as a first approach. Software tools are available to assist with the
development of sampling strategies (Section 6.5.3.1).
Step 3: Gather Data. Lines of evidence data can be gathered from the published literature,
subject matter experts, waste receivers, regulators, and previously gathered site data (Section
6.5.1). In the case of sampling, decisions to gather data are made for the overall sampling
strategy (i.e., non-probabilistic, probabilistic, combination), (Sections 6.5.2 and 6.5.3, Table 1),
sample collection (Section 6.6, Table 2), and analysis (Section 6.7).
G-4
-------
START:
Collection of
Waste of
Materials
Please note that waste characterization
process may be affected by factors that
are not identified in the flow chart
Examples of these factors may include:
cost, political considerations, public
concern, volume of waste accepted by
waste receiver, and selection of
decontamination technology.
Segregate Potential
Waste Materials into
Homogeneous
Groups (e.g., porous,
nonporous)
(Section 6.3)
Identify Waste
Acceptance Criteria
and DQOs for Waste
Receivers that Will
Accept Each
Segregated Waste
Group
(Section 6.4)
Identify Laboratories with
Analysis Capabilities for
Desired Analyses that will
Accept Material
(Section 6.7)
Waste Characterization Strategy Determination
(Section 6.5)
Determine Use of Lines of Evidence /Section 6.5.1)
Determine Use of Sampling (Section 6.5.2)
Data Gathering Step
If Sampling is Used, Determine:
le Used -
or Combination?
What Sampling Strategies can be Used
Nonprobabilistic, Probabilistic,
(f Lines of
Evidence are
Used:
(Section 6.5.1)
s 6.5.2. and 6.5.3)
Should Waste be Further Segregated Prior to
Sampling?
Will Field Screening and/or Laboratory Analysis will be
Used 1 (Section 6.7)
Can Composite Sampling be Performed? (Section
6.5.3.2
Can Split Samples be Used? (Section 6.6.2)
Gather Know edge from
edge
Literature, Subject
Matter Experts, and
Previously Gathered Site
Data
(Section 6.5.1)
Identify
Identify Field
isM
Laboratory
thod
Analysis Method
(Section 6.7)
Analysis Me
(Section 6.7)
Identify
Collection
Technique
(Section 6.6)
Identify Collection
Technique
(Section 6.6)
Figure G-l. Waste characterization process flow chart
G-5
-------
Table G-l. Features of Sampling Design for Waste Characterization
Sampling
Non-Probabilistic
Probabilistic
Strategy
Judgmental
Simple Random
Stratified Random
Definition
Selection of samples based on professional
judgement without randomization. Biased sampling
(a type of judgmental sampling) is intended to
collect samples with the highest contamination.
A set of sampling units are independently
selected at random from a population.
Prior information is used to determine groups (lots) that
are sampled independently.
Application
Small-scale conditions are under investigation
Screening for presence/absence of a contaminant
Might be used in conjunction with simple random
sampling of containerized waste (i.e., samples
collected from within the container might be
judgmentally sampled in an attempt to maximize
the collection of biological agent)
Relatively uniform or homogeneous
populations
Selecting a sample aliquot from a composite
sample
Used to produce estimates with pre-specified
precision for important subpopulations
Monitoring of trends
Used to gain specific information (i.e., mean)
regarding each group; potentially more efficient
approach for sampling heterogeneous wastes if waste
can be segregated
Laboratory
Resources
Low: site information used to minimize laboratory
resources
Medium: sample number is predetermined
Medium: sample number is predetermined
Wide-Area
Pros
Can be very efficient and cost effective if site is
well known
Enables uncertainty and statistical inferences
to be calculated
Provides an estimate of the population to effectively
define groups and specify sample sizes
Ideal for presence/ absence screening
Quick implementation to achieve time and
funding constraints
Protects against sampling bias
Easy to understand and implement
Sample size formulas are available for
determining sample numbers (EPA, 2002a)
Sample size formulas are available to aid in
determining adequate sample numbers (EPA, 2002)
Wide-Area
Cons
Dependent upon expert knowledge
Cannot reliably evaluate precision
Personal judgement is needed to interpret data
Confidence statements regarding absence of
Random locations might be difficult to locate
Sampling design depends upon the accuracy of
the conceptual model
All prior site information site is ignored
Random locations might be difficult to locate
Sampling design depends upon the accuracy of the
conceptual model
All prior information regarding the site is ignored
contamination difficult to make
Sampling can be costly if there are difficulties
in obtaining samples due to location
Sampling can be costly if there are difficulties in
obtaining samples due to location
Cautions or ปDoes not ensure that unsampled items are free of
Additional contamination
Critical "Degradation by-products might be of concern
Information depending upon the parent agent, and create a
hazardous environment incident after the parent (or
tested agent) is no longer present
Simple random sampling is often used as the
last stage of sampling when multiple iterations
are conducted - selecting an aliquot from a
composite sample
All populations should be relatively uniform
Degradation by-products might be of concern
depending upon the parent agent, and create a
hazardous environment incident after the parent
(or tested agent) is no longer present
Each group should be homogeneous within itself
Groups should be defined before determining sample
sizes
Degradation by-products might be of concern
depending upon the parent agent, and create a
hazardous environment incident after the parent (or
tested agent) is no longer present
Potentially more efficient approach for sampling
heterogeneous wastes, if it can be segregated
Reference(s) EPA (2006); EPA (2002a); EPA (1998); EPA
(2015c); EPA (2013a)
EPA (2002b); EPA (2002c); ITRC (2012); EPA
(2006)
EPA (2002b); EPA (2006)
G-6
-------
Table G-2. Features of Sample Collection for Waste Characterization
Extractive (Solid Material)
Sampling
Wipe (Surface)
Sampling
Liquid (Surface)
Sampling
Liquid (Drum) Sampling -
Discrete Depth Samplers
Liquid (Drum) Sampling - Air
Profile Samplers Sampling
Description Extractive sampling refers to
whole objective sampling or
the cutting/removal of a
portion of the material
sampled. Might also be
referred to as bulk sampling or
direct extraction.
Surface sampling
techniques using wipes,
cotton-balls/wipes, or
gauze sponge.
The collection of liquid
samples from the
surface (or shallow
depths) might be
obtained with various
devices including a
bailer, dipper, liquid
grab sampler, swing
sampler, or solid phase
microextraction fibers.
Liquid samples might be
obtained from discrete
depths with a variety of
devices include a syringe
sampler, discrete level
sampler, lidded
sludge/water sampler, or
solid phase
microextraction fibers.
Liquid samples might be
obtained from throughout
a vertical column of liquid
or sludge with a variety of
devices include a
composite liquid waste
sampler (COLIWASA),
drum thief, valved drum
sampler, plunger type
sampler or solid phase
microextraction fibers.
Air sampling devices,
such as those that might
be used to sample the
headspace of waste
containers for volatile
compounds could
include solid phase
adsorbent media
(tubes), solid phase
microextraction fibers,
or air samplers (e.g.,
SUMMAฎ canisters).
Application Applicable for the sampling
of targeted areas (sink
materials) where liquid
agent might remain,
especially porous surfaces
or collection of spilled
powder
Applicable for sampling
materials that are not
amenable to wipe sampling
such as materials that are
wet, irregularly shaped,
and/or porous
Might be applicable for
sampling heterogeneous
waste; cutting, chipping, or
drilling of waste samples
(and subsequent
grinding/mixing together)
can make the samples more
homogeneous and amenable
to being sampled simply
with a spoon or scoop
Generally used for
sampling smooth,
non-porous surfaces,
but might also be
used on porous
surfaces (EPA,
2012b)
Applicable for
relatively small
sample areas
Although designed for
groundwater
sampling, bailers can
be used to collect
liquid samples from
tanks and surface
impoundments; bailers
collect samples of 0.5
to 2 liters
The dipper, liquid
grab sampler, and
swing sampler
generally collect 0.5 to
1.0 liter samples from
the surface of drums,
tanks, and surface
impoundments
The syringe sampler and
discrete level sampler
These sampling devices
typically collect between
can collect 0.2 to 0.5 liter 0.1 to 3 liter samples from
samples from drums,
tanks, and surface
impoundments
A lidded sludge/water
sampler can collect 1.0
liter volumes from tanks
and ponds
tanks and drums, as well as
surface impoundments
Air sampling,
especially of the
headspace of waste
containers might be
helpful in confirming
that adequate
decontamination of
wastes materials has
occurred
Wide-Area Extractive-based sampling
Pros minimizes the loses of agent
that might arise with other
sampling protocols' collection
inefficiencies
Can be an easy and
quick way of assessing
surface contamination
levels
The bailer, dipper,
liquid grab sampler,
and swing sampler are
generally easy to use
and inexpensive
A syringe sampler is
easy to use and
decontaminate; it can
also be used to sample
The COLIWASA, drum Analysis of some
thief, and valved drum sampling devices can be
sampler are inexpensive, performed in the field
easy to use, and for some analytes
G-7
-------
Table G-2 (continued). Features of Sample Collection for Waste Characterization
Extractive (Solid Material)
Sampling
Wipe (Surface)
Sampling
Liquid (Surface)
Sampling
Liquid (Drum) Sampling -
Discrete Depth Samplers
Liquid (Drum) Sampling - Air
Profile Samplers Sampling
Analysis of some
sampling devices can
be performed in the
field for some
analytes.
Wide-Area Extractive-based sampling
Cons might be difficult for
personnel working in
personal protective
equipment.
Extractive-based sampling
techniques are not well
defined/established
Extracted samples might
require more extraction
solvent and more time to
process than other surface
sampling approaches
Small concentrations of a
contaminant might be
diluted within a larger bulk
sample
Wipe sampling might These sampling devices
not result in high agent are not intended to
recoveries from
porous materials, such
as wood
Wipe sampling
procedures can vary
based on the agent of
interest and the
material sampled
Limited in sample area
(100 cm2)
collect samples from
specific/deep subsurface
depths (unless a point-
source bailer is used)
discrete depths, including
the bottom
The jar in the lidded
sludge/water sampling
device serves as the
sample container
reducing the chance ot
cross-contamination
Solid phase
microextraction fibers
can be taken into the
field to sample. These
samples might be
returned to the laboratory
for analysis or the fibers
can be analyzed in the
field using portable
GC/MS systems
The maximum depth that
can be reached with a
syringe sampler is about
1.8 meters
The lidded sludge/water
sampling devise is rather
heavy and limited to one
jar size
available as reusable or
single-use models
The plunger type
sampler is easy to
operate, relatively
inexpensive, and is
available in various
lengths
Solid phase
microextraction fibers
can be taken into the
field to sample. These
samples might be
returned to the
laboratory for analysis
or the fibers can be
analyzed in the field
using portable GC/MS
systems
The COLIWASA, drum
thief, and valved drum
sampler can be difficult
to decontaminate, and it
might be difficult to
collect samples from the
bottom of the container
The drum thief cannot
sample depths longer
than the drum thief itself
Might be difficult to
implement depending
upon the accessibility of
the containerized waste
to be sampled
Cautions or Extraction efficiencies and
Additional agent recoveries will vary
Critical with material and extraction
Information approach
Agent recovery will
vary depending upon
the area sampled,
material type, wipe
material, amount and
type of wetting
1 Liquid samples should
be collected with the
appropriate
neutralizers and
stabilizers added
Liquid samples should
be collected with the
appropriate neutralizers
and stabilizers added
Larger sample volumes
or multiple samples
Liquid samples should
be collected with the
appropriate neutralizers
and stabilizers added
Larger sample volumes
or multiple samples
For sampling vapors
that are heavier than air
(e.g., sulfur mustard and
Lewisite), include low
lying areas where
G-8
-------
Table G-2 (continued). Features of Sample Collection for Waste Characterization
Extractive (Solid Material)
Wipe (Surface)
Liquid (Surface)
Liquid (Drum) Sampling -
Liquid (Drum) Sampling -
Air
Sampling
Sampling
Sampling
Discrete Depth Samplers
Profile Samplers
Sampling
Constituents within some
solution, wipe pattern,
Larger sample
might be required such
might be required such
vapors might
materials might interfere
etc.
volumes or multiple
that filtration can be
that filtration can be
accumulate
with detection technologies
Recovery might be
samples might be
used to detect low levels
used to detect low levels
Extractive-based sampling
affected by the
required such that
of contamination
of contamination
techniques are not well
presence of dirt and
filtration can be used
defined/established
other residues as well
to detect low levels of
Neutralization might be
as background
contamination
needed to inhibit any
chemical constituents.
residual decontamination
solution that could possibly
bias/lower the agent
recoveries
Evidence collection
sampling might have been
conducted in this manner
Reference(s) EPA (2012d); Nassar et al.
EPA (2008); EPA
EPA (2002b); NRT
EPA (2002b); NRT
EPA (2002b); NRT
Kimm et al. (2002);
(1998); NRT (2015a)
(2014a); Koester and
(2015a); Popiel and
(2015a); Popiel and
(2015a); Popiel and
NRT (2015a); Popiel
Hoppes (2010); Nassar
Sankowska (2011)
Sankowska (2011)
Sankowska (2011)
and Sankowska (2011);
et al. (1998); NRT
Smith etal. (2011)
(2015a); Qietal. (2013)
G-9
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vvEPA
United States
Environmental Protection
Agency
PRESORTED STANDARD
POSTAGE & FEES PAID
EPA
PERMIT NO. G-35
Office of Research and Development (8101R)
Washington, DC 20460
Official Business
Penalty for Private Use
$300
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