EPA/600/R-20/436 | December 2020
www.epa.gov/homeland-security-research
United States
Environmental Protection
Agency
oEPA
Literature Search and Review for
Sampling, Analysis, and
Decontamination of Chemical
Warfare Agent - Contaminated
Maritime Vessels
Office of Research and Development
Homeland Security Research Program
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EPA/600/R-20/436
December 2020
LITERATURE SEARCH AND REVIEW FOR SAMPLING, ANALYSIS,
AND DECONTAMINATION OF CHEMICAL WARFARE AGENT-
CONTAMINATED MARITIME VESSELS
Lukas Oudejans
and
David See
Homeland Security and Materials Management Division (HSMMD)
Center for Environmental Solutions and Emergency Response (CESER)
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, NC 27711
ii
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DISCLAIMER
The U.S. Environmental Protection Agency (EPA) through its Office of Research and
Development funded and managed the research described herein under Contract Number EP-C-
15-002, Task Orders 68HE0C18F0807 and 68HERC20F0074 with Battelle. This study was
funded through the Vessel Detection USCG Project by the U.S. Department of Homeland
Security Science and Technology Directorate under EPA-DHS interagency agreement No.
7095923201 (DHS IAA No: HSHQM-17-X-00245). This report has been subjected to the
Agency's review and has been approved for publication. Note that approval does not signify that
the contents necessarily reflect the views of the Agency. Any mention of trade names, products,
or services does not imply an endorsement by the U.S. Government or EPA. The EPA does not
endorse any commercial products, services, or enterprises. The contractor role did not include
establishing Agency policy.
Questions concerning this document, or its application should be addressed to:
Lukas Oudejans, Ph.D.
U.S. Environmental Protection Agency
Center for Environmental Solutions and Emergency Response
Homeland Security and Materials Management Division
109 T.W. Alexander Drive
Research Triangle Park, NC 27711
Phone: 919-541-2973
Fax:919-541-0496
E-mail: Oudeians.Lukas@epa.gov
in
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FOREWORD
The U.S. Environmental Protection Agency (EPA) is charged by Congress with
protecting the Nation's land, air, and water resources. Under a mandate of national environmental
laws, the Agency strives to formulate and implement actions leading to a compatible balance
between human activities and the ability of natural systems to support and nurture life. To meet
this mandate, EPA's research program is providing data and technical support for solving
environmental problems today and building a science knowledge base necessary to manage our
ecological resources wisely, understand how pollutants affect our health, and prevent or reduce
environmental risks in the future.
The Center for Environmental Solutions and Emergency Response (CESER) within the
Office of Research and Development (ORD) conducts applied, stakeholder-driven research and
provides responsive technical support to help solve the Nation's environmental challenges. The
Center's research focuses on innovative approaches to address environmental challenges
associated with the built environment. We develop technologies and decision-support tools to
help safeguard public water systems and groundwater, guide sustainable materials management,
remediate sites from traditional contamination sources and emerging environmental stressors,
and address potential threats from terrorism and natural disasters. CESER collaborates with both
public and private sector partners to foster technologies that improve the effectiveness and
reduce the cost of compliance, while anticipating emerging problems. We provide technical
support to EPA regions and programs, states, tribal nations, and federal partners, and serve as the
interagency liaison for EPA in homeland security research and technology. The Center is a
leader in providing scientific solutions to protect human health and the environment.
This report summarizes the current scientific literature on remediation-related activities
associated with US Coast Guard vessels and other assets. It also provides descriptions of
research gaps and needs for consideration by US Coast Guard and other federal agencies to
improve on sampling and decontamination of vessels following a chemical warfare agent release
scenario.
Gregory Sales, Director
Center for Environmental Solutions and Emergency Response
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ACKNOWLEDGMENTS
This effort was directed by the principal investigator (PI) from the Office of Research and
Development's (ORD's) Homeland Security and Materials Management Division (HSMMD)
within the Center for Environmental Solutions and Emergency Response (CESER). The
contributions of the following individuals have been a valued asset throughout this effort.
EPA Project Team
Lukas Oudejans, ORD/CESER/HSMMD (PI)
Shannon Serre, OLEM/OEM/CMAD
Worth Calfee, ORD/CESER/HSMMD
Sandip Chattopadhyay, current OCSPP/OPPT/RAD
Battelle Memorial Institute
David See
Ryan James
U.S. EPA Technical Reviewers of Report
Mace Barron, ORD/CESER/HSMMD (Detail)
Stuart Willison, ORD/CESER/HSMMD
U.S. EPA Quality Assurance
Eletha Brady-Roberts, ORD/CESER
Ramona Sherman, ORD/CESER/HSMMD
U.S. EPA Editorial Review
Joan Bursey
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TABLE OF CONTENTS
DISCLAIMER Ill
FOREWORD IV
ACKNOWLEDGMENTS V
LIST OF ACRONYMS VIII
1. INTRODUCTION 1
1.1. Background 1
1.2. Scope and Purpose 1
1.3. Objectives 2
1.4. Use of Secondary Data 4
1.5. Organization of Report 4
2. LITERATURE SEARCH 6
2.1. Literature Search Approach 6
2.1.1. USCG Vessels 6
2.1.2. Target CWAs 8
2.2. Literature Search Resources 8
2.3. Literature Search Criteria and Strategy 9
2.4. Literature Source Quality Assessment 11
2.4.1. Qualitative Quality Assessment 11
2.4.2. Quantitative Quality Assessment 12
2.5. Literature Search Results 13
2.6. Source Compilation Document 13
3. KNOWLEDGE REVIEW 14
3.1. CWA Fate and Transport 14
3.2. CWA Contamination Management and Response 16
3.3. CWA Decontamination Efficacy 21
3.4. CWA Decontaminant Material Compatibility 30
3.5. CWA Sampling and Analysis 32
3.6. Comprehensive Summary Tables 36
4. KNOWLEDGE/CAPABILITY GAP ASSESSMENT AND RESULTS 39
4.1. Knowledge/Capability Gaps 39
4.2. Additional Information, Discussion, and Notes 41
4.3. Gap Table 42
5. REFERENCES 43
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ATTACHMENTS
Attachment A - Literature Assessment Factor Rating 52
Attachment B - Source Quality Evaluations 53
LIST OF TABLES
Table 1. Focus Materials 7
Table 2. Source Document Types 12
Table 3. Research Focus Areas and Sources Collected 13
Table 4. CWA Decontamination and Sampling Summary (USCG Materials) 37
Table 5. CWA Decontamination and Sampling Summary (Additional Materials) 38
Table 6. Gap Table 42
LIST OF FIGURES
Figure 1. Project Overview and Progression 3
Figure 2. 1st Search Run 10
Figure 3. 2nd Search Run 10
Figure 4. 3rd Search Run 11
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LIST OF ACRONYMS
ฐc
Degree(s) Celsius
ฐF
Degree(s) Fahrenheit
a-Fe203
Iron oxide
Hg
Microgram(s)
|iL
Microliter(s)
|im
Micrometer(s)
|imol
Micromole(s)
2-PAM
Pralidoxime
ACES
Advanced Catalytic Enzyme System
AED
Atomic emission detector
AP-AI2O3
Aero-gel produced alumina
APC
Advanced Performance Coating
b-NPP
Bis(4-nitrophenyl) phosphate
BIS
Bis-(2-ethylhexyl) phosphite
BTEX
Benzene, toluene, ethylbenzene, /^-xylene
BWA
Biological warfare agent
CAFTA
Computer-aided fault tree analysis
CaO
Calcium oxide
Ca(OCl)2
Calcium hypochlorite
Ca(OH)2
Calcium hydroxide
CARC
Chemical agent resistant coating
CASCAD
Canadian Aqueous System for Chemical/Biological Agent Decontamination
CaS04
Calcium sulfate
CBRN
Chemical, biological, radiological, nuclear
CD
Compact disk
CE
Capillary electrophoresis
CEES
2-chloroethyl ethyl sulfide
CEPS
2-chloroethyl phenyl sulfide
CESER
Center for Environmental Solutions and Emergency Response
ChE
cholinesterase
CIO2
Chlorine dioxide
cm
Centimeter(s)
CREATIVE
Contact hazard Residual hazard Efficacy Agent T&E Integrated Variable
Environment
CT
Concentration time
CWA
Chemical warfare agent
DEA
Diethanolamine
DEM
Diethyl malonate
DES
Diethyl sulfide
DESI-MS
Desorption electrospray ionization mass spectrometry
DETA
Di ethyl enetri amine
DFP
Dii sopropylfluorophosphate
DFPase
Dii sopropylfluorophosphatase
DHS
U.S. Department of Homeland Security
DIMP
Diisopropyl methyl phosphonate
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DMCP Dimethyl chlorophosphate
DMMP Dimethyl methyl phosphonate
DS2 Decontamination Solution 2
DTIC Defense Technical Information Center
DVD Digital video disk
EDEA N-ethyl diethanolamine
EGME Ethylene glycol monomethyl ether
EHDMAP Ethylhydrogen dimethylphosphonate
EMPA Ethyl methylphosphonic acid
EPA U.S. Environmental Protection Agency
ESAM Environmental Sampling and Analysis Methods
ESI Electrospray ionization
FGA Fourth generation agent
FGAC Fiberglass-supported activated carbon
FOUO For Official Use Only
g Gram(s)
GA Tabun
GB Sarin
GC/MS Gas chromatography/mass spectrometry
GD Soman
GF Cyclosarin
h Hour(s)
H2O2 Hydrogen peroxide
HAD Hot air decontamination
HCO4- Peroxymonocarbonate
HD Sulfur mustard
HL Agent Yellow
HMRC Hazardous Materials Research Center
HN1,HN2, HN3 Nitrogen mustard
HPLC High performance liquid chromatography
HSMMD Homeland Security and Materials Management Division
HSRP Homeland Security Research Program
HTH High test hypochlorite
HVAC Heating, ventilation, and air conditioning
IMPA Isopropyl methylphosphonate
in Inch
kg kilogram
KOH Potassium hydroxide
L Lewisite, liter
LOD Limit of detection
m Meter(s)
M Molar
MDEA N-methyl diethanolamine
MDSPE Magnetic dispersive solid phase extraction
MEM S Mi cro-el ectro-mechani cal - sy stem
MeS Methyl salicylate
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mg
Milligram(s)
MIL
Military
min
Minute(s)
mL
Milliliter(s)
mm
Millimeter(s)
MnO
Manganese oxide
MOF
Metal organic framework
MPA
Methylphosphonate
in VHP
Modified vaporous hydrogen peroxide
NA
Not applicable
NaCl
Sodium chloride
NaHC03
Sodium bicarbonate
NaOCl
Sodium hypochlorite
NaOH
Sodium hydroxide
ND:YAG
Neodymium-doped yttrium aluminum garnet (Nd:Y3AI5O12)
ng
Nanogram(s)
nh3
Ammonia
nm
Nanometer
NMR
Nuclear magnetic resonance
OP
Organophosphorus
OPAA
Organophosphorus acid anhydrolase
OPAB
N-octylpyridinium 4-aldoxime bromide
OPH
Organophosphorus hydrolase
ORD
Office of Research and Development
pAB
pH-adjusted bleach
PC
Personal computer
PDA
Personal digital assistant
PI
Principal investigator
PMPA
Pinacolyl methylphosphonate
ppb
Part(s) per billion
PPE
Personal protective equipment
ppm
Part(s) per million
ppmv
Part(s) per million by volume
PTE
Phosphotriesterase
QCM
Quartz crystal microbalance
(Q)SAR
Quantitative structure activity relationship
RAC
Risk assessment code
RB-M
Response Boat - Medium
RB-S
Response Boat - Small
RH
Relative humidity
RSD
Relative standard deviation
RSDL
Reactive Skin Decontamination Lotion
SAM
Selected Analytical Methods
SAW
Surface acoustic wave
SCID
Sample Collection Information Document
SDF
Surface decontamination foam
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slpm
Standard liter(s) per minute
SPME
Solid phase microextraction
SSMAS NMR
Solid state magic angle spinning nuclear magnetic resonance spectroscopy
STB
Super tropical bleach
SWCNT
Single-walled carbon nanotube
TBP
Tributyl phosphate
TDI
Tolyl diisocyanate
TEA
Triethanolamine
TEP
Triethyl phosphate
TGD
Thickened Soman
TiCh/Au/Mg
Titanium dioxide/gold/magnesium
UPLC-MS/MS
Ultrahigh performance liquid chromatography - tandem mass spectrometry
US
United States
USCG
United States Coast Guard
UV
Ultraviolet
VHP
Vaporous hydrogen peroxide
VOC
Volatile organic compound
VX
O-ethyl S-[2-(diisopropylamino)-ethyl] methylphosphonothioate
w/v
Weight/volume
Zr
Zirconium
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1. INTRODUCTION
1.1. Background
The U.S. Environmental Protection Agency (EPA) is responsible for preparing for, responding
to, and recovering from threats to public health, welfare, or the environment caused by actual or
potential hazardous materials incidents. Hazardous materials include chemical, biological, and
radiological substances, whether accidentally or intentionally released.
In 2002, Congress passed the Public Health Security and Bioterrorism Preparedness and
Response Act (Bioterrorism Act). The Office of the President issued a series of Homeland
Security Presidential Directives to specify the responsibilities of federal agencies as related to the
Bioterrorism Act. EPA's roles and responsibilities include protecting human health and the
environment from bioterrorism. Included within the scope of these responsibilities are the
personnel and assets of the U.S. Coast Guard (USCG), the principal federal agency responsible
for maritime safety, security, and environmental stewardship in U.S. ports and waterways.
The USCG protects and defends more than 100,000 miles of U.S. coastline and inland
waterways. To this end, the USCG may be responsible for countering and responding to
incidents involving weapons of mass destruction, including biological warfare agents (BWAs)
and chemical warfare agents (CWAs). To carry out their mission, the USCG maintains a fleet of
small boats, larger cutters and aircraft, as well as a network of fixed infrastructure. Such assets
are likely to be utilized in the event of a USCG response to an incident involving BWAs and/or
CWAs and would likely become contaminated as a result.
Following a contamination incident, decontamination is necessary so that assets may be returned
to service and USCG capability can be maintained. Efficacious decontamination strategies are
thus necessary. Further, effective sampling is necessary to determine the extent and magnitude of
contamination, inform responders on selection of decontamination strategies, determine the
success of decontamination strategies, and determine the presence/absence of residual
contaminants to clear assets for return to service. USCG vessel usage scenarios, operating
environments, and materials of construction present unique challenges to BWA and CWA
decontamination and sampling that have not been previously addressed.
1.2. Scope and Purpose
The purpose of this project was to (1) conduct a review of existing BWA and CWA
contamination response and management, decontamination, and sampling strategies, (2) assess
their applicability to USCG vessels and the associated materials of construction, and (3) identify
knowledge/capability gaps associated with decontamination and sampling of USCG vessel
materials. The review of existing BWA and CWA contamination response and management,
decontamination, and sampling strategies was accomplished through completion of a systematic
search of the open literature, focused primarily on representative USCG vessels and contaminant
groups (refer to Sections 2.1.1 and 2.1.2, respectively).
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1.3. Objectives
Specific objectives to support the purpose of this project included the following:
Conduct a search of the open literature (including existing guidance documentation,
information, scientific literature, secondary data, etc.) for BWA and CWA contamination
response and management, decontamination, and sampling strategies that are potentially
applicable to USCG vessels and associated materials of construction.
Develop summaries of the guidance documentation, information sources, scientific
literature, secondary data sources, etc. that were identified and collected during the search
and develop a source compilation document to collate the findings from the literature
search according to primary research focus.
Based on review of the search results and the secondary data and information collected
related to BWA and CWA contamination response and management, decontamination,
and sampling strategies, identify knowledge/capability gaps associated with
decontamination and sampling of USCG vessel materials due to the unique vessel usage
scenarios, operating environments, and materials of construction.
Develop reports to summarize and discuss:
o The approach and resources used to conduct the literature search and results of the
search.
o The approaches, procedures, and methodologies for BWA and CWA
contamination response and management, decontamination, sampling and
analysis that were identified during the search and that may have relevance to
USCG vessels and associated materials of construction.
o The knowledge/capability gaps identified that relate to the unique challenges
presented by USCG vessel operations and materials that must be overcome for
development of effective decontamination and sampling strategies for BWA-
and/or CWA-contaminated USCG vessels that allow for prompt and safe return to
service.
Figure 1 provides an overview of the steps taken during the project to accomplish the above
project objectives to conduct the literature search, summarize the search results and collate the
summaries into the source compilation document, identify knowledge/capability gaps based on
the search results, and develop reports to present the search results, information and data
collected, and gaps identified.
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Definition of Project
Scope and Objectives
Defined by EPA in
consultation with project
stakeholders
Pre-Search Activities
Selection of focus
USCG vessels materials
Selection of focus
BWAs/CWAs
Development of the
search strategy
(including selection of
search terms and
resources)
Literature Search
Application of the
search terms to the
search resources to
collect information and
secondary data
Refinement of the search
terms and re application
to the search resources
to elicit identification
and collection of
additional data and
increase data relevancy
to the project objectives
Summary of Sources
and Development of
Source Compilation
Document
Summary of
information secondary
data sources using a
standardized template
As s e s sment of s ource
quality
Collation of source
summaries into the
source compilation
document based on
primary re search focus
Identification and
Discussion of
Kno wle dge/C ap ability
Gaps
Presentation of the
information and
secondary data collected
during the search to
project stakeholders
Identification of
kno wle dge capability
gap s. bas e d on the
search results
Reporting
Presentation of the
project objectives and
search strategy
Presentation of the
information and
secondary data collected
Presentation of
kno wle dge cap ability
gaps identified
Separate reports for
BWAs and CWAs
Figure 1. Project Overview and Progression
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1.4. Use of Secondary Data
Secondary data are defined as existing data, also termed non-direct measurements, that were not
developed originally through the project to which they are being applied 1. For this project,
secondary data that was gathered consisted of information and data related to BWA and CWA
contamination response and management, decontamination, and sampling strategies that are
potentially applicable to USCG vessels and associated materials of construction. These data were
collected from various sources including government reports and publications in the open
literature.
1.5. Organization of Report
This report is organized by section to (1) describe how the literature search was conducted to
review existing BWA and CWA contamination response and management, decontamination, and
sampling strategies, and how the quality of the secondary data and information that were
collected were assessed, (2) present and review the secondary data and information collected,
and (3) describe the approach for identification of knowledge/capability gaps associated with
decontamination and sampling of USCG vessel materials and present the outcomes of the gap
discussions. The three primary sections of the report are outlined and described as follows:
Literature Search
The approach for conducting the literature search is described (Section 2.1). To focus the
literature search efforts, specific USCG vessels and their associated materials of
construction and specific CWAs were selected as focus materials/contaminants (Sections
2.1.1 and 2.1.2). Search criteria including lists of strategic keywords (i.e., search terms)
and the arrangements of the keywords with Boolean operators to execute the searches
were developed (Section 2.3) and the criteria were applied to a variety of
repositories/resources (Section 2.2) to identify and collect information and secondary
data. Quality of the information and secondary data sources that were collected was
assessed qualitatively and quantitatively (Section 2.4). Following completion of the
search but prior to development of this report, the articles, reports, guidance documents,
and other information and secondary data sources of sufficient quality that were collected
during the literature search were summarized using a standardized summary structure,
categorized according to content and primary research focus, and the summaries were
collated into a source compilation document (Section 2.6).
Knowledge Review
The information and secondary data collected during the literature search are presented,
categorized according to content and primary research focus, and bibliographic citations
are provided for the literature sources from which the information and secondary data
were collected. The research focus areas include (1) CWA fate and transport, (2) CWA
contamination management and response, (3) CWA decontamination efficacy studies, (4)
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CWA decontaminant material compatibility studies, and (5) CWA sampling and analysis
methodologies (Sections 3.1 through 3.5).
Knowledge/Capability Gap Assessment
Based on the results of the literature search, gaps in information/secondary data related to
methodologies, procedures, and technologies for decontamination and sampling of CWA
contamination on USCG assets were identified. Project stakeholders met to discuss the
literature search and the identified gaps. The knowledge/capability gaps identified and
other information, discussions, and notes from the meeting are presented (Section 4).
As discussed in Section 1.2, the scope of this project included (1) review of existing
contamination response and management, decontamination, and sampling strategies, (2)
assessment of the applicability of the strategies to USCG vessels and their associated materials of
construction, and (3) identification of knowledge/capability gaps associated with
decontamination and sampling of USCG vessel materials for both BWA and CWA
contaminants. Discussion of BWAs and the approach for conducting the literature search to
include both BWAs and CWAs is included in Section 2 of this report, but the results of the
literature search and discussions of knowledge/capability gaps provided in Sections 3 and 4,
respectively, are focused only on CWAs in this report. Literature search results and discussion of
knowledge/capability gaps related to methodologies, procedures, and technologies for
decontamination and sampling of BWA contamination on USCG assets is provided in a separate
report.
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2. LITERATURE SEARCH
2.1. Literature Search Approach
The literature search was conducted using the resources described in Section 2.2 and the search
criteria and strategy described in Section 2.3. The secondary data gathered during this effort
includes information on BWA and CWA contamination response and management,
decontamination, and sampling strategies that are potentially applicable to USCG vessels and
associated materials of construction. For the purpose of this search, BWA and CWA
contamination response and management, decontamination, and sampling are defined as:
Contamination response and management - Initial action(s) taken in response to an
incident involving creation or spread of contamination by BWA, CWA, or similar, as
well as ongoing actions taken to assess the initial response and to direct and modify
subsequent response steps. Such actions may include: initial steps to stop the spread of
contamination and contain existing contamination (in the case of USCG vessels, such
actions may include storing/staging of contaminated vessels that cannot be
decontaminated immediately); procedures and guidance for development of response
plans and for continuous assessment and modification of plans, as necessary; guidance
and considerations regarding response safety and personal protective equipment (PPE)
requirements; and information, considerations, and guidance related to disposition and
disposal of contaminated and decontaminated wastes.
Decontamination - General guidance and procedures for decontamination/neutralization
of contamination by BWA, CWA, or similar. Information and secondary data related to
use and efficacy of specific methodologies and technologies for decontamination of
BWA, CWA, or similar.
Sampling - General guidance and procedures for qualitative and/or quantitative detection
of BWA and/or CWA (or similar) contamination, either prior to or following
decontamination. Information and secondary data related to use, resolution, precision,
and accuracy of specific methodologies and technologies for decontamination of BWA,
CWA, or similar contamination.
To focus search efforts, information and data related to specific USCG vessels and associated
materials of construction and specific CWAs were sought primarily.
2.1.1. USCG Vessels
2.1.1.1. Vessels and Vessel Missions
Four (4) USCG vessels were selected as focus assets for directing the literature search efforts.
The vessels and their primary missions are provided and summarized below:
Response Boat - Medium (RB-M) - The RB-M is a 45-foot multi-mission capable, all-
aluminum utility boat. The RB-M includes wireless crew communication systems and is
powered by twin diesel engines and water jet propulsion. RB-M missions include search
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and rescue, living marine resources, recreational boating safety, enforcement of laws and
treaties, and port, waterways, and coastal security 2
Response Boat - Small (RB-S) - The RB-S (also referred to as the Defender-class boat)
is a 25-foot boat introduced by the USCG in 2003 to replace shore-based non-standard
boats. RB-S assets serve a variety of law enforcement, security, and vessel safety
missions 2
RB-S II - The RB-S II is a 29-foot boat designed as an upgrade and replacement to the
25-foot RB-S. It is a high-speed deployable asset designed to operate year-round in
shallow waters along coastal borders. The RB-S II supports search and rescue,
recreational boating safety, law and treaty enforcement, marine environmental protection,
defense, and port, waterways, and coastal security missions 2
Marine Protector-class Patrol Boat - The 87-foot Marine Protector-class patrol boat is a
multi-mission vessel capable of supporting search and rescue, law enforcement, fishery
patrol, drug interdiction, illegal immigrant interdiction, and homeland security missions
up to 200 miles offshore. The vessel includes improved seakeeping abilities and
enhanced habitability compared to other vessels, capability to interface with surface
search radars used by U.S. warships, and is designed to maintain compliance with current
and projected environmental protection laws 3.
2.1.1.2. Vessel Materials of Construction
Specific materials used in construction of the vessels described in Section 2.1.1.1 were selected
as focus materials for the purpose of further directing search efforts. The focus materials
selected, categorized by vessel, are provided in Table 1.
Table 1. Focus Materials
Vessel
Component
45-foot RB-M
Vessel Type
25-foot RB-S 29-foot RB-S II
87-foot Patrol Boat
Hull material
Aluminum
Aluminum
Aluminum
Coated steel
Decking material
Non-skid coatings
Non-skid coatings
Non-skid coatings
Non-skid coatings
Sensitive
equipment/
components
Propulsion (air and
seawater intakes)
Other electronic
systems
Propulsion (air and
seawater intakes)
Other electronic
systems
Propulsion (air and
seawater intakes)
Other electronic
systems
Ventilation
Propulsion (air and
seawater intakes)
Other electronic and
internal systems
Additional
relevant
materials
Foam
Glass
Glazing materials
Insulation and other
bulkhead coverings
Foam
Glass
Glazing materials
Insulation and other
bulkhead coverings
Foam
Glass
Glazing materials
Insulation and other
bulkhead coverings
Glass
Glazing materials
Insulation and other
bulkhead coverings
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2.1.2. Target CWAs
Three (3) CWAs were selected as focus contaminants for the purpose of directing the literature
search efforts. The three CWAs include:
Distilled sulfur mustard (HD) - Blister (vesicant)-type CWA that causes severe, delayed
burns to the eyes, skin, and respiratory tract. Damages cells within minutes, though onset
of pain and other health effects is delayed. Alkylating agent and known carcinogen 4
Sarin (GB) - Organophosphorus nerve CWA that inhibits acetylcholinesterase. Higher
volatility than other G-series organophosphate nerve CWAs, thus generally considered to
pose a significant vapor/inhalation hazard 5.
O-ethyl S-[2-(diisopropylamino)-ethyl] methylphosphonothioate (VX) -
Organophosphorus nerve CWA that inhibits acetylcholinesterase. Lower volatility than
other nerve CWAs, thus generally considered to pose a long-term/persistent threat6.
2.2. Literature Search Resources
The following resources were utilized to identify information and secondary data related to
BWA and CWA contamination response and management, decontamination, and sampling
strategies that are potentially applicable to USCG vessels and associated materials of
construction:
SciTech Premium (also or formerly known as ProQuest Science & Technology)
Multidisciplinary content collection of scholarly material in the natural sciences,
technology, engineering and related disciplines. Includes a number of databases,
including a military database that indexes over 700 scholarly journal articles, trade and
industry journals, magazines, technical reports, conference proceedings, government
publications, etc. Included as part of the military database is the National Technical
Information Service which provides summaries of U.S. government research,
development, and engineering, plus analyses prepared by federal agencies or their
contractors.
Scopus
An abstract and citation database of peer-reviewed literature, with bibliometrics tools to
track, analyze and visualize research. Scopus contains over 22,000 titles from more than
5,000 publishers around the world, covering the fields of science, technology, medicine,
social sciences, and others. Scopus has 55 million records dating back to 1823, and 84%
of these contain references dating from 1996.
Battelle Library
The Battelle library holds over 20,000 volumes and subscribes to over 10,000 print and e-
journal titles in a range of scientific and technical disciplines, both foreign and domestic.
In addition, the library manages access to more than 150 foreign and domestic databases,
including, eBrary, Hooversฎ, Applied Science & Technology, EBSCOhostฎ, and
National Technical Reports Library.
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Internet
Internet searches (e.g. - EPA website, Google, Google Scholar, etc.) were used to
identify available information on studies conducted using BWAs and CWAs focused on
vessel response, decontamination, and sampling.
2.3. Literature Search Criteria and Strategy
Prior to initiation of the literature search, the criteria used to perform the search were developed.
The criteria included lists of strategic keywords anticipated to elicit identification of relevant
secondary data and information, and the arrangement of the keywords with Boolean operators to
execute the searches. Following each iteration of the search and subsequent review of the results,
the arrangement of keywords and Boolean operators were revised in order to further focus the
search and attempt to identify additional relevant secondary data and information.
To ensure identification of a wide breadth of response and management, decontamination, and
sampling strategies potentially applicable to BWA and CWA-contamination on USCG vessels,
initial search criteria were comprehensive, including provisions for identification of procedures,
methodologies, techniques, and technologies for contamination response and management,
decontamination, and sampling for any type of contaminant (toxic chemicals, biological
contaminants, radionuclides, etc., beyond the focus CWAs discussed in Section 2.1.2) from any
maritime vessel or environment-related material (beyond the focus materials provided in Table 1
in Section 2.1.1.2). Information regarding fate and transport of persistent BWAs and CWAs on
and across various materials were sought as well. Furthermore, the search criteria were
developed to elicit collection of information related to all relevant aspects of BWA and CWA
contamination on USCG vessel materials and impacts of use of the contamination response and
management, decontamination, and sampling strategies identified.
Boolean searches were performed using strategically-selected keywords with the operators AND
and OR. After each search run (with a run defined as application of a particular arrangement of
the keywords with the operators to the sources provided in Section 2.2) the resulting identified
literature was reviewed to determine the effectiveness of the search and the relevancy of the
results. Based on the search run results, the Boolean search strategy was revised, and another run
was performed. Three runs were performed in this manner using the keywords and operators in
different arrangements to refine and focus the searches to maximize the potential of identifying
meaningful and relevant results. Figures 2, 3, and 4 below provide the search strategies used.
9
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Related to response Related to Related to , . , . ... Related to materials,
. . ..... .. Related to contaminants . ,
and management decontamination sampling systems, and environments
ResporT
Decontaminat*
Surface
Chemical agent
Marine
OR
Manag*
OR
Detoxif*
OR
Sam pi*
OR
Chemical warfare agent
OR
Maritime
OR
Mitigat*
OR
Disinfect*
OR
Analy*
OR
CWA
OR
Vessel
OR
Hazard*
OR
Clean*
OR
Wip*
OR
Distilled Mustard
OR
Boat
OR
Incident*
OR
Remov*
OR
Headspace
OR
HD
OR
Seawater
OR
Remediat*
OR
Attenuat*
OR
Vapor
OR
Sarin
OR
Foul*
AND
OR
Steriliz*
AMD
OR
Qualitative
OR
GB
OR
Hull
OR
Neutraliz*
OR
Quantitative
OR
VX
OR
Bulkhead
OR
Oxidiz*
OR
Detect*
OR
Biological agent
OR
Sensitive equipment
OR
Hydroly*
OR
Inhibit*
OR
Biological warfare agent
OR
Propulsion
OR
Degrad*
OR
Interfer*
OR
BWA
AND
OR
Electronic
OR
Efficac*
OR
Sorbent
OR
Bacillus anthracis
OR
Ventilation
OR
Da mag*
OR
Fate
OR
Anthrax
OR
Intake
OR
Compatib*
OR
Transport
AND
OR
Ebola
OR
Deck*
OR
Radiological agent
OR
Aluminum
OR
Radionuclide
OR
Non-skid
OR
Radioactive
OR
Glazing
OR
Radioisotope
OR
Steel
OR
Cesium*
OR
Insulation
OR
Cs-137
OR
Foam
OR
Radiological dispersal device
OR
Glass
OR
Improvised nuclear device
OR
Fallout
OR
Nuclear
OR
Chlorinated biphenyl
OR
PCB
OR
Contamina*
Figure 2. 1st Search Run
Related to response Related to Related to ... Related to materials,
..... Related to contaminants . ,
and management decontamination sampling systems, and environments
Mitigat*
Decontaminat*
Surface
Chemical agent
Marine
OR
Hazard*
OR
Detoxif*
OR
Sampl*
OR
Chemical warfare agent
OR
Maritime
OR
Incident*
OR
Disinfect*
OR
Analy*
OR
CWA
OR
Vessel
OR
Remediat*
OR
Clean*
OR
Wip*
OR
Distilled Mustard
OR
Boat
OR
Remov*
OR
Headspace
OR
HD
OR
Seawater
OR
Attenuat*
OR
Vapor
OR
Sarin
OR
Foul*
OR
Steriliz*"
AND
OR
Qualitative
AND
OR
GB
OR
Hull
AND
OR
Neutraliz*
OR
Quantitative
OR
VX
OR
Bulkhead
OR
Oxidiz*
OR
Detect*
OR
Biological agent
OR
Sensitive equipment
OR
Hydroly*
OR
Inhibit*
OR
Biological warfare agent
OR
Propulsion
OR
Degrad*
OR
Interfer*
OR
BWA
AND
OR
Electronic
OR
Efficac*
OR
Sorbent
OR
Bacillus anthracis
OR
Ventilation
OR
Damag*
OR
Fate
OR
Anthrax
OR
Intake
OR
Compatib*
OR
Transport
OR
Ebola
OR
Deck*
OR
JnajQMt*
OR
Aluminum
OR
Non-skid
OR
Glazing
OR
Steel
OR
Insulation
OR
Foam
OR
Glass
Figure 3. 2nd Search Run
10
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Related to response Related to Related to , . .. ... Related to materials, systems.
. .. Related to contaminants .
and management decontamination sampling and environments
Mitigat*
AND
Decontaminat*
AND
Sampl"
AND
Chemical warfare agent
AND
Marine
OR
Hazard*
OR
Detoxif*
OR
Analy*
OR
Distilled Mustard
OR
Maritime
OR
Incident*"
OR
Disinfect*
OR
Wip*
OR
HD
OR
Boat
OR
Remediat*
OR
Remov"
OR
Headspace
OR
Sarin
OR
Seawater
OR
Emergency
OR
Steriliz*
OR
Vapor
OR
GB
OR
Foul*
OR
Attack
OR
Neutraliz*
OR
Detect4,
OR
VX
OR
Hull
OR
Rescue
OR
Oxidiz*
OR
Interfer*
OR
Biological warfare agent
OR
Bulkhead
OR
Contain4"
OR
Hydroly*
OR
Sorbent
OR
BWA
OR
Sensitive equipment
OR
Risk
OR
Degrad*
OR
Fate
OR
Bacillus anthracis
OR
Ventilation
OR
Cleanup
OR
OR
Transport
OR
Anthrax
OR
Deck*
OR
Ebola
OR
Aluminum
OR
Vesicant
OR
Non-skid
OR
Nerve agent
OR
Steel
OR
Foam
OR
Glass
OR
Sea
OR
Military
OR
Coast Guard (coast + guard)
Figure 4. 3rd Search Run
2.4. Literature Source Quality Assessment
2.4.1. Qualitative Quality Assessment
During the literature search, information and secondary data sources were qualitatively assessed
according to the source document type. Table 2 provides the source document type list used
during the literature search (not all source document types were accumulated during the search).
Knowledge of the document type provided an indication of trustworthiness of the
information/secondary data contained therein, based on general professional judgment of each
document type.
11
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Table 2. Source Document Types
Designation
Description
A
Technical Report, U.S. Government
B
Technical Report, Contractor for U.S. Government
C
Translated Foreign-Language Document
D
Translated Foreign-Language Abstract
E
Untranslated Foreign-Language Document
F
Untranslated Foreign-Language Abstract
G
Peer-Reviewed English Language Literature, post-1975
H
Peer-Reviewed English Language Literature, 1925-1975
I
Peer-Reviewed English Language Literature, pre-1925
J
Government Website, with citations
K
Government Website, without citations
L
Non-Government Website, with citations
M
Non-Government Website, without citations
N
Book Chapter or Book, with peer-review and/or editorial oversight
0
Book Chapter or Book, no peer-review nor editorial oversight
P
Book Chapter or Book, peer review and editorial oversight unknown
Q
Patent (United States)
R
Patent (International)
S
Thesis/Dissertation
T
News Article
U
Manufacturer-Supplied Literature
V
Other
W
Analysis Pending
The majority of the sources collected were of type A (Technical Report, U.S. Government), type
B (Technical Report, Contractor for U.S. Government), or type G (Peer-Reviewed English
Language Literature, post-1975).
2.4.2. Quantitative Quality Assessment
Each source of information and/or secondary data was evaluated according to the following
categories: focus, verity, integrity, rigor, utility, clarity, soundness, uncertainty and variability,
and evaluation and review. A description of each attribute is provided in the Literature
Assessment Factor Rating (Attachment A). Information sources were evaluated against the
Literature Assessment Factor Rating and assigned an overall rating to accomplish a semi-
quantitative assessment of the quality of the source. For the quality of a source to be deemed
sufficient, it was required that the source receive an overall Literature Assessment Factor Rating
score of 15 or greater.
Source quality evaluations (document type designations and Literature Assessment Factor Rating
scores) for all sources of sufficient quality that were collected during the literature search,
included in the source compilation document (refer to Section 2.6), and discussed in Section 3
are included as Attachment B.
12
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2.5. Literature Search Results
During the literature search, 94 sources of information and secondary data related to CWA
contamination response and management, decontamination, and sampling strategies that are
potentially applicable to USCG vessels and the associated materials of construction (the focus
materials provided in Table 1 in Section 2.1.1.2) were collected. All articles, reports, guidance
documents, and other pertinent information sources of sufficient quality that were collected
during the literature search were summarized using a standardized summary structure and
categorized according to content and primary research focus. Table 3 provides a list of the
research focus areas and the number of information/secondary data sources collected for each
category during the literature search.
Table 3. Research Focus Areas and Sources Collected
Research Focus Area
Number of
Sources Collected
CWA Fate and Transport
6
CWA Contamination Management and Response
21
CWA Decontamination Efficacy Studies
28
CWA Decontaminant Material Compatibility Studies
12
CWA Sampling and Analysis Methodologies
27
Total 94
2.6. Source Compilation Document
Following the literature search and summarization of the information/secondary data sources that
were collected, the summaries were collated into a source compilation document according to the
primary research foci listed in Table 3. The source compilation document also provided
descriptions of the literature search approach, strategy, criteria, and resources (as described in
Sections 2.1, 2.2, and 2.3) and provisions for assessment of the quality of information/secondary
data sources that were collected during the search (as described in Section 2.4).
13
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3. KNOWLEDGE REVIEW
Any interpretations or conclusions presented in the knowledge review are those of the authors of
the articles/publications from which the information is taken.
3.1. CWA Fate and Transport
Fate and transport of CWA contamination on USCG vessel construction materials will impact
the efficacy of decontamination and sampling strategies and thus drive contamination response
and management decisions. The information and secondary data related to CWA fate and
transport described below were collected during the search and should be assessed, as applicable,
alongside the information and data on decontamination strategies (described in Section 3.3) and
sampling strategies (described in Section 3.5) when decisions are made and strategies are
developed for response to incidents that involve CWA contamination of USCG vessels.
Data on persistence and evaporation characteristics of HD, HD simulants, and VX on various
materials are described below:
Mechanisms and rates for evaporation of HD from stainless steel and aluminum were
determined for a variety of temperatures and droplet sizes7. HD droplets of 1 microliter
(|iL), 6 |iL, or 9 |iL (> 95% purity) were evaluated. Temperature was controlled to 15,
25, or 35 degrees Celsius (ฐC), and relative humidity (RH) was controlled to 10%. Air
flow across the droplets was controlled to 175 standard liters per minute (slpm).
Evaporation rates from stainless steel of 9 microgram (|ig)/minute (min) at 15ฐC, 12
|ig/min at 25ฐC, and 19 |ig/min at 35ฐC were measured. Evaporation rates from
aluminum of 10 |ig/min at 15ฐC, 14 |ig/min at 25ฐC, and 22 |ig/min at 35ฐC were
measured. Previous studies measured HD evaporation rates from glass of 9 |ig/min at
15ฐC, 16 |ig/min at 25ฐC, and 29 |ig/min at 35ฐC. Evaporation rates were observed to be
linearly proportional to droplet size, regardless of substrate.
Vapor concentrations downwind of evaporating droplets were evaluated for HD and HD
simulants to compare vapor phase mass transport and assess representativeness of the
simulants for HD in terms of the associated chemical properties8. Single l-|iL droplets of
HD and the simulants methyl salicylate (MeS), 2-chloroethyl ethyl sulfide (CEES),
diethyl malonate (DEM), and 2-chloroethyl phenyl sulfide (CEPS) were deposited onto
an impermeable material in a dynamic contact angle analyzer environmental chamber
with a stagnant air environment at 20ฐC to 40ฐC. Based on the results, the use of a one-
to-one correspondence between simulant-to-agent vapor pressure ratio and concentration
ratio is valid if certain conditions are met.
Degradation of VX on crushed glass, air-dried sand, and oven-dried sand at a variety of
temperatures and evaporation of VX from glass and sand were investigated9.31P solid
state magic angle spinning nuclear magnetic resonance (SSMAS NMR) spectroscopy
showed that the final VX degradation product was nontoxic ethyl methylphosphonic acid
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(EMPA), though an intermediate was toxic EA-2192. The degradation process was
autocatalytic (EMPA was both the catalyst and product for VX degradation). Degradation
rate was approximately 5 to 9 times slower on moist sand than on air-dried sand. Relative
to evaporation of VX, approximately 9% of an initial 6-|iL droplet of VX on sand and
approximately 60% of an initial 6-|iL droplet of VX on glass had been recovered as VX
vapor after four days.
Data related to fate and transport of CWAs and CWA simulants in various coatings and coating
systems and in porous materials (concrete) as described below:
Uptake and distribution of CEES and dimethyl methyl phosphonate (DMMP) into
polyurethane and alkyd coatings applied to aluminum and silicone substrates were
evaluated10. Air Force Advanced Performance Coating (APC), water-dispersible
chemical agent resistant coating (CARC), and Navy ship coat samples were produced
according to military (MIL) standards for use during evaluations. APC and Navy ship
coat samples were each contaminated with single 20-|iL droplets of CEES (to simulate
HD) and DMMP (to simulate VX), and CARC samples were contaminated with 40-|iL
droplets of each simulant. Droplet spreading, evaporation, and sorption
characteristics/behaviors varied with the contaminant and coating type. Contamination on
both APC and Navy ship coat by CEES and DMMP was largely isolated to the topcoat
layer regardless of residence time. Widespread distribution of contaminants in CARC
was observed.
Mass transport parameters of the CWAs HD and VX in different paint and coating
systems were determined experimentally11. Two coating types were evaluated: a solvent-
dispersible aliphatic polyurethane coating system and a water-dispersible aliphatic
polyurethane coating system. Coatings were applied to 1-square inch (in2) stainless steel
shim stock with a coating thickness of approximately 100 micrometers (|im). Each
sample was contaminated with a single l-|iL droplet of either neat HD or VX and aged
for 60 minutes at 20ฐC. Experimental results for HD and VX demonstrated that HD and
VX formed a macroscopic thin film across the substrates within a few minutes following
contamination.
Liquid and vapor HD sorption onto, diffusion into, and degradation on/within concrete
was assessed12. HD vapor began to adsorb onto concrete as relative vapor pressure (P/Ps)
increased above 0.1. Sorption of HD at over 30 milligrams per gram (mg/g) could be
measured as the HD vapor concentration reached saturation. An 80-|iL droplet of HD in
concrete was degraded into less toxic byproducts (likely due to basic sites within the
concrete matrix) but at a very low rate (k = 4.8 x 10"5/min and ti/2 = 16 x 104 minutes at
room temperature). HD droplets of 80 |iL were able to break through the 3-millimeter
(mm)-thick concrete wafers in 12 minutes. Diffusion coefficient of HD molecules in
concrete was determined to be approximately 1.3 x 10"4 square centimeters (cm2)/min.
15
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The following additional data and findings (beyond the six sources indicated in Table 3 related to
CWA fate and transport that were collected during the search) on CWA fate and transport in
marine waters may be relevant to USCG CWA contamination response strategies given the
operational settings of USCG vessels. The following data highlight the need for adequate
decontamination of CWA and careful consideration and planning related to waste handling and
conscientious waste disposal strategies following a contamination incident and response
operations.
Until the 1970s, disposal of unexploded ordnance and munitions was accomplished by
dumping into oceans. After many decades, these unexploded munitions (many likely
containing CWAs) are now facing a high-corrosion stage and could leak toxic, even
mutagenic, products into the marine ecosystem13.
Risk assessments to determine human and/or environmental risks posed by ocean-
dumped CWAs from World War I and World War II have been performed14. In lieu of
reliably measured property data, the dissipation of CWA at deep sea levels (>100 meters
[m]) may be modeled. Assessments have also included evaluations of the environmental
threat posed by dumped CWA and CWA munitions to benthic species15.
Sediments have been sampled at sites adjacent to chemical and conventional discarded
military munitions at depths of 400 to 650 m. Results have demonstrated that HD and its
degradation products can persist in the deep-marine environment for decades following
disposal of munitions by ocean-dumping16. Similarly, results of geophysical and
chemical investigations carried out at a chemical munition dumpsite in the Baltic Sea
indicated a widespread contamination that reached far beyond the dumpsite boundary17.
Literature searches have been performed to identify locations, quantity, and types of sea-
dumped chemical weapons, related environmental concerns, and human encounters with
sea-dumped chemical weapons18. Findings were discussed in the context of risk due to
increasing deep-sea accessibility and threats to the benthic habitat.
3.2. CWA Contamination Management and Response
USCG vessel materials and operational settings present unique challenges to the development of
effective, efficient, and safe strategies for management of and response to CWA contamination
incidents. Despite these challenges, the objectives of USCG vessel CWA contamination incident
management, response, and remediation operations must remain unchanged from those of any
other CWA contamination incident - (1) Personnel safety must be ensured, (2) CWA
contamination must be identified, contained, and adequately decontaminated, and (3) deleterious
environmental, equipment/infrastructure, and financial impacts must be avoided or minimized to
the greatest extent possible.
CWAs are highly toxic, and exposure (as a direct result of a CWA attack, during incident
response and remediation actions, after an incident due to residual contact hazard, etc.) can often
16
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be lethal. Numerous literature assessments19'20'21 and data analyses have been conducted to
collate available information and summarize and describe CWA types/classes, toxicological
characteristics and mechanisms of toxicity, delivery/exposure routes, exposure symptoms and
medical diagnosis guidance, treatments/interventions, etc. Studies have evaluated the effects of
various decontamination regimens on levels of VX in the skin, VX plasma levels, and blood
cholinesterase following exposure22. The impacts of various decontamination regimens on
hairless guinea pig survival rates following VX exposure were also evaluated, with the survival
rate measured for control groups (no decontamination, no clinical treatment) being the lowest,
followed by decontamination alone, then clinical treatment alone, and the highest survival rate
(100%) observed from the group that received a combination of decontamination and treatment.
Highly volatile CWAs such as GB pose significant vapor hazards, while persistent CWAs such
as VX can leave lasting contact hazards (VX is approximately 2,000 times less volatile than
GB)23. As highlighted in Section 4.1, studies and data demonstrate that CWA contamination can
volatilize and transport hazards via vapor to previously unaffected areas, persist in the
environment in porous materials and surface coatings, and persist in marine environments. These
data and considerations highlight the need for effective, comprehensive, and rapidly mobilized
contamination management, response, and remediation strategies following incidents involving
USCG vessels/assets and CWA.
Assessment of the effectiveness of response and management strategies used during prior CWA
contamination incidents (whether accidental or terrorism-related), the associated outcomes, and
the successes and failures that were experienced can provide invaluable insight during post-
incident refinement and improvement of procedures and development of new and/or modified
procedures and/or capabilities based on any knowledge/capability gaps that were exposed.
During a period of time spanning from 1994 to 1995, terrorism-related incidents resulted in
exposure of Japanese citizens to GB and VX on eleven (11) different occasions19, including the
Tokyo subway GB incident that occurred in March of 1995 that left at least 640 victims
immediately hospitalized24, over 5,500 injured, and 13 dead23. Several analyses of the response
strategies used during the 1995 Tokyo subway GB attacks, as well as other incidents involving
GB, have been conducted, including:
Discussions of the various incident response areas that were identified as requiring
improvement based on response assessments made in the aftermath of the Tokyo subway
incident, including PPE considerations, methods for detection and analysis of GB,
decontamination procedures, antidote administration, and management systems and
preparations24.
Various other chemical attacks/disasters that occurred in Japan were summarized25, and
the changes in chemical terrorism countermeasures that were developed and enacted after
these attacks are described. Focus surrounds two GB attacks from the 1990s (the
Matsumoto incident in 1994, and the Tokyo subway attack in 1995) and the measures
taken in response.
17
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A focused analysis of the GB attack in the Tokyo subway system was performed to
review toxicology and management of GB poisoning26. Recommendations for a mass
casualty management strategy were summarized, including considerations for incident
response, treatment, infrastructure, and post-incident patient monitoring.
YouTube videos which documented the near-real-time consequences of GB gas
poisonings from the 2013 GB attacks that occurred on the outskirts of Damascus in Syria
were analyzed to delineate the clinical presentations observed and treatments
administered during the mass causality event27. Findings were also compared against the
current paradigm for such an event.
While, as discussed, review, assessment, and consideration of past incidents and the associated
response actions utilized (both successful and unsuccessful) can be valuable for directing the
development of new and improvement of existing strategies for management and response
during CWA incidents, as mentioned previously, the environmental settings in which the USCG
operates and the assets requiring decontamination are likely to be very different from those
involved during incidents in civilian/urban/etc. settings. Nonetheless, various basic principles for
contamination management and response strategies may still be translatable.
Quantitative risk analysis systems, computer simulations, and mathematical models have also
been developed as valuable tools used to assist with contamination management and response
operation planning, such as in the following examples:
Correlations from literature were used to assign hazard severity levels to various
postulated VX contamination/release incidents that could occur at the U.S. Army
Newport Chemical Agent Disposal Facility. Computer-Aided Fault Tree Analysis
(CAFTA) was then used to quantitatively determine hazard occurrence frequency. Based
on the severity and frequency, risk assessment codes (RACs) were assigned to the
potential hazard incidents, and possible mitigations were identified28.
A suite of regression-based models (Quantitative Structure-Activity Relationship
[(Q)SAR]) was used to estimate acute aquatic toxicity of CWAs29. A compilation of
predicted environmental toxicity data of parent and hydrolysis products of CWAs was
provided. The persistence and bioconcentration potential of some CWAs were presented.
A semi-empirical, deterministic model (Contact hazard Residual hazard Efficacy Agent
T&E Integrated Variable Environment [CREATIVE]) has been developed to characterize
and predict laboratory-scale decontaminant efficacy and hazards for a range of CWAs
(current focus on HD), operational surfaces common to ground vehicle, aircraft, and
equipment construction (e.g., aluminum, glass, CARC, silicone), realistic threat
challenges (0.5-10 g/m2), environmental conditions (10-40ฐC) and decontamination
process parameters (decon, residence time, etc.)30. The model is intended to enable faster
characterization of decontaminant performance and provide the capability to predict
performance and hazards under untested conditions. An example application of the model
18
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was provided involving HD contamination on aluminum, glass, and silicone.
Decontamination approaches included use of DF200 and bleach as well as no
decontaminant. Output data included contact hazard, vapor hazard, and residual HD
contamination.
Existing plans governing operations for sampling and detection of CWAs, contamination
management, and infrastructure at other sites/facilities/installations/etc. can be used as templates
for development of effective similar plans and guidance documents tailored to specific USCG
sites, vessels, and/or assets. Existing plans may often also provide insight into strategies for
selection of adequate PPE and development of emergency response and exposure
control/response plans. Examples from the literature include the following:
A site safety plan was developed to describe procedures for: (1) sampling for the
presence of HD in the south plant of the Rocky Mountain Arsenal at Aberdeen Proving
Ground in Maryland, (2) protection of workers during HD sampling operations, and (3)
procedures for decontamination should HD be detected31.
The current standard protocol for nerve agent exposure treatment (post-exposure
administration of atropine and oxime) was discussed32, as well as drawbacks associated
with the protocol. Alternatives are then presented, including competitive
acetylcholinesterase inhibitors and nerve agent scavengers (administered as
pretreatments/preventive measures).
Summaries of some of the regulations concerning designation and safety in a CWA
analysis and research laboratory and medical countermeasures in case of an accidental
exposure are provided33. Discussion of decontamination and protection means against
CWAs is also presented.
Limitations, challenges, and procedures associated with treatment of acute CWA
poisoning are reviewed34. Data and discussions focus on nerve agents and HD.
Background on the physical nature of CWAs and BWAs is provided along with brief
overviews of the basic principles of particle and vapor filtration, and information and
sample calculations are presented to illustrate the viability of retrofitting heating,
ventilation, and air conditioning (HVAC) systems with filtration to remove
CWAs/BWAs from air35.
In a report submitted to the Office of Naval Research, a conceptual design for a scalable
emergency response system to manage at-sea response and decontamination of a chemical,
biological, radiological, nuclear (CBRN) event is presented36. Information presented and
discussed includes:
Description of a three-phased scalable emergency response system to address at-sea
CBRN events. Phases include: (1) detailing current on-vessel and local response that
19
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could be expected if a CBRN event were to occur, (2) actions to lay the groundwork for
thorough decontamination, and (3) options for additional decontamination, if necessary.
Capability concepts for decontamination and recovery of affected vessels.
Required reach-back, operational, research and development (including decontamination,
PPE, waste processing and treatment, and sensitive equipment-related efforts), and
maintenance functions.
As part of the development of effective, efficient, and risk-based strategies for management of
and response to CWA contamination incidents involving USCG vessels, procedures for
conscientious, risk-based, and effective processing of wastes (including secondary wastes37), use
of PPE38 (as well as decontamination of PPE; refer to Section 3.3), and administrative and
engineering controls39'40 (as applicable) are critical. Additionally, during contamination
management and response operations, USCG personnel may be inadvertently exposed
to/contaminated by CWAs and require decontamination and treatment. Thus, methods and
technologies for personnel treatment and decontamination following CWA exposure must also
be considered as part of contamination management and response planning. Secondary
information and data collected during the literature search from studies focused on
decontamination and treatment of personnel exposed to CWA include the following:
Skin samples (dermatomed human skin) were exposed to neat and dilute VX, and then
decontaminated using four commercially available products (Reactive Skin
Decontamination Lotion [RSDLฎ; oxime-based technology], Fuller's Earth [dry
absorbent without degradative properties], PS 104 [decontaminant with both absorptive
and reactive properties], and alldecontMED [liquid hypochlorite-based decontaminant])
and plain water41. All decontamination procedures resulted in a statistically significantly
decreased VX penetration rate when decontamination was initiated five (5) minutes post-
exposure to neat VX. RSDL lotion was superior for skin decontamination.
Enzymes (cholinesterase [ChE]) and oximes immobilized in a polyurethane foam sponge
were evaluated as a skin decontamination system42. The system was tested on guinea pig
skin to decontaminate Soman (GD) and compared to the M291 decon kit. Tolyl
diisocyanate (TDI; 5%) polymer was used as the sponge material. Mechanistically, the
sponge soaks up organophosphorus (OP) on skin, then the immobilized ChE and oxime
detoxify the OP in the sponge. Triacetin and tetraglyme provided additional ability to
remove GD from the skin, protecting guinea pigs approximately four to five-fold better
than the M291 kit. Sponges containing pralidoxime (2-PAM) also showed increased
protection against GD skin toxicity compared to the M291 kit (at least fourfold).
Two skin decontamination systems were evaluated against HD and VX using hairless
mice43. CWA was delivered to the backs of mice (2 |iL HD or 50 |ig/kilogram [kg] VX),
and decontamination was performed five (5) minutes after exposure. Fuller's Earth (75
mg) was deposited followed by a 30-second rub with a glove 30 seconds after deposition.
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RSDL was applied at decontaminant/toxicant ratios of 10, 20, and 50. RSDL was applied
for 30 seconds followed by a 30-second sponge rub. RSDL was more effective in
reducing epidermal necrosis and erosion. Only Fuller's Earth demonstrated significant
efficiency in preventing ChE inhibition.
Real hair locks were exposed to MeS or CEES vapor and then decontaminated by RSDL
and rinsing, RSDL and showering, Fuller's Earth and showering, or showering alone44.
MeS decontamination efficacy reached 67% with RSDL and rinsing. For CEES,
decontamination efficacy reached 85% with Fuller's Earth and showering.
Various foam-making blends and alkalized hydrogen peroxide (H2O2) removed CWAs
(GD, VX) from skin and transformed them into nontoxic compounds45.
The efficacies of skin decontamination products were evaluated against a 10-|iL droplet
of 14C-MeS applied to the surface of porcine skin46. Further work is necessary to fully
evaluate the five most effective products, which include the military product Fuller's
Earth, Fast Act, and three novel polymers against HD, GD, and VX.
An evidence-based guidance document is focused on providing flexible and scalable
recommendations for practices for planning for and responding to mass chemical
exposure incidents47. The subject matter is limited to external decontamination of living
people with hazardous chemicals (including CWAs) but also attempts to address the full
spectrum of the response operation (from initial assessment through evaluation of
decontamination effectiveness).
Skin decontamination efficacy of Pickering emulsions (solid-stabilized emulsions
containing silica or Fuller's Earth) was evaluated 45 minutes after an exposure to VX48.
The Pickering emulsion formulations resulted in removal of greater than 90% of VX
contamination.
3.3. CWA Decontamination Efficacy
CWA decontamination is most often accomplished via: (1) physical removal of CWA through
natural attenuation, wiping, or through use of rinsing/washing procedures, surfactants, sorbents,
etc., (2) chemical neutralization by one or more of a variety of active species that have been
evaluated for efficacy, or (3) a combination of both mechanisms49. Technologies for chemical
decontamination of CWAs should, ideally: (1) be broad-spectrum in nature (i.e.,
reactive/effective against a variety of CWA classes), (2) be material-compatible, (3) not interfere
with contamination monitoring or measurement equipment and methodologies, (4) be easy to
transport, prepare, and apply, as applicable, (5) be of low toxicity, flammability, and
environmental impact, and (6) minimize waste products and avoid generation of hazardous
wastes (i.e., avoid formation of hazardous or toxic decontamination byproducts)49.
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CWA decontamination approaches and technologies based on a wide range of neutralization and
removal mechanisms have been evaluated for efficacy. Mechanisms and active chemistries for
CWA decontamination that are commonly used and evaluated include (but are not limited to):
Natural attenuation and weathering, which can be applicable to all CWAs and most
surfaces if sufficient time is available for complete evaporation and/or degradation of
contaminants50'51. Attenuative decontamination can be enhanced using hot air (hot air
decontamination [HAD]). The effectiveness of HAD varies with respect to evaporative
characteristics of the contaminant CWA, the extent of distribution, and the characteristics
of the contaminated material (i.e., higher efficacy against higher volatility CWAs on
nonporous materials)51.
Water rinsing, which can be applicable to all CWAs and most surfaces and is often
utilized and recommended in immediate-response situations in the absence of more
specific/targeted decontamination formulations and when decontamination of personnel
is required. Efficacy of water washing/rinsing can be improved with addition of
soap/surfactants and/or heat (including use of steam)50'51.
Oxidative chlorine and hypochlorite-based formulations, including bleach (sodium
hypochlorite [NaOCl]), diluted bleach, pH-adjusted bleach (pAB) high test hypochlorite
(HTH; calcium hypochlorite [Ca(OCl)2]), super tropical bleach (STB),
dichloroisocyanurate (e.g., Fichlor and Canadian Aqueous System for
Chemical/Biological Agent Decontamination [CASCAD]) and trichloroisocyanurate-
based formulations, chlorine dioxide (CIO2; liquid or vapor application), Chloramine-B,
and others. Hypochlorite-based technologies such as bleach are well established as
efficacious decontaminants for neutralization of a wide range of CWAs, though they are
corrosive on many materials and not recommended for use on sensitive equipment and
surfaces or on personnel (i.e., skin, unless extremely dilute)49'50'51.
Strong bases such as calcium oxide (CaO), calcium hydroxide (Ca(OH)2), potassium
hydroxide (KOH), and sodium hydroxide (NaOH), which demonstrate efficacy in
hydrolysis of CWAs, particularly against organophosphate nerve CWAs (e.g., GB, GD,
Tabun [GA])50'51. Decontamination Solution 2 (DS2) is comprised of 2% NaOH, 70%
diethylenetriamine (DETA), and 28% ethylene glycol monomethylether (EGME),
forming a very strong basic solution51 demonstrating high efficacy against HD, VX, GA,
and GB49, although EGME is corrosive and destructive to many materials and also
flammable50.
H2O2 and H202-based decontamination systems (including Sandia foam formulations,
e.g., DF200), and vaporous H2O2 (VHP). VHP has demonstrated efficacy against HD and
VX, and addition of ammonia (NH3) gas to H2O2 vapor imparts efficacy against GD
(resultant vaporous decontaminant is referred to as modified VHP [mVHP])49'50.
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Various other technologies and methodologies including nonreactive and reactive
sorbents (e.g., Fuller's Earth, metal oxides and metal organic frameworks [MOFs]),
oximes, microemulsions, enzyme-based technologies, and plasma-based
technologies49'50'51.
Furthermore, decontaminant evaluations have measured the efficacies of decontamination
technologies on a variety of material types, including the materials listed in Table 1 as USCG
vessel materials of construction. Also, in some cases, decontamination data for a specific
material may be translatable to one or more similar materials (e.g., high efficacy on aluminum
may suggest high efficacy on stainless steel).
Several secondary information and data sources were collected during the literature search from
studies focused on evaluation of decontaminants based on a variety of active species applied as
liquids, including hypochlorite-based decontaminants (bleach, diluted bleach, and pAB), H2O2
and FhCh-based decontaminants (including DF200 and Steriplexฎ Ultra), CASCAD Surface
Decontamination Foam (SDF), soap and water, RSDL, and other decontamination
technologies. The CWA decontamination efficacy data collected include the following:
Decon Green is a peroxide-based decontaminant designed to be more environmentally
benign and material-compatible and less corrosive than other more commonly used CWA
decontaminants (i.e., bleach and other hypochlorite-based decontaminants). A cold-
weather variant of Decon Green, CA2WT, has also been developed for use in subfreezing
temperatures. The efficacies of the two Decon Green formulations (the standard
formulation, referred to as New Decon Green, and the CA2WT cold weather variant)
were evaluated against CWA simulants at temperatures of 4ฐC, -5ฐC, and -15ฐC52'53.
CARC-coated aluminum coupons were contaminated with CEPS (HD simulant) or bis-
(2-ethylhexyl) phosphite (BIS, a VX simulant) at 10 g/m2 A volume of 1 milliliter (mL)
of either CA2WT Decon Green (for the -5ฐC or -15ฐC tests) or New Decon Green (for the
4ฐC tests) was applied for various contact times (10, 20, 30, 40 or 120 min). Contact-
hazard assessments were then conducted to simulate the transfer of CWA simulants to
skin. Generally, the first of two contact hazard transfer measurements collected post-
decontamination resulted in approximately twice the hazard of the second of the two
measurements. Decontamination with Decon Green significantly reduced contact hazards
for both CEPS and BIS. At -5ฐC and -15ฐC, CA2WT was found to be 87% and 93%
effective against CEPS and 73% and 86% effective against BIS, respectively.
The efficacies of a 0.5% hypochlorite bleach solution containing trisodium phosphate and
the decontaminants Decon Green, Allen Vanguard CASCAD SDF, and Modec
Inc. Sandia Decontamination Foam (DF200) were evaluated against the CWAs GB, GD,
HD, and VX on the surface of materials including stainless steel, latex-painted drywall,
glass, vinyl floor tile, and concrete54. Decontamination efficacies of greater than or equal
to 98%) from the surface of stainless steel and glass were demonstrated for all four
decontaminant technologies after a contact period of 24 hours against VX and HD, with
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the exception of bleach/VX (67% efficacy on stainless steel, 60% efficacy on glass).
Decontamination efficacies of greater than or equal to 98% from the surface of glass were
demonstrated for all four technologies after 24 hours against GD. Decontamination
efficacies for other combinations of decontaminant, material, and CWA ranged from 20%
to greater than 99%.
Bleach (5.65% to 6% sodium hypochlorite), dilute bleach (0.5% to 0.6% sodium
hypochlorite), H2O2 (3%), and DF200 were evaluated for efficacy against the vesicant
CWAs HD, Agent Yellow (HL), and Lewisite (L) on wood, glass, and galvanized
metal55. Decontaminant contact periods of 30 to 60 min were evaluated. Dilute bleach
reduced L contamination by greater than 92% after 30 minutes but had limited efficacy
against HD. Full strength bleach was the most efficacious, reducing HD and L below
sampling and analysis method detection limits (solvent extraction and gas
chromatography/mass spectrometry [GC/MS]) after 30 minutes on metal and glass
(although lower efficacy was demonstrated by full strength bleach on wood). H2O2
exhibited generally high efficacies (i.e., below detection limit after 30 minutes) against
both HD and L on all materials, except HD on glass. DF200 showed limited efficacy
against HD but higher efficacy against L (generally 80% or greater).
Decontamination of PPE-related materials (including butyl rubber, neoprene, Vitonฎ,
and nitrile) and laboratory equipment-related materials (polyethylene, acrylic, and
stainless steel) by detergent (Tideฎ Original) and water, bleach (Cloroxฎ Concentrated
Germicidal Bleach; 8% sodium hypochlorite), diluted bleach (1:10 dilution of the full
strength bleach decontaminant), pH-amended bleach (diluted bleach acidified to an
average pH of 6.8), EasyDeconฎ DF200, RSDLฎ, and Steriplexฎ Ultra (a peroxide-
based sporicidal decontaminant) was evaluated56. Material coupons were contaminated
with 20 |iL of malathion (VX simulant), CEES (HD simulant), nitrobenzene (toxic
industrial chemical), phenol (toxic industrial chemical), or chlordane (pesticide), or 40
|iL of carbaryl (insecticide). Full strength bleach and RSDLฎ demonstrated
approximately 60% efficacy against malathion (other decontaminants ranged from just 5
to 15% efficacy). DF200 demonstrated 47% average efficacy (when applied as a liquid)
or 64% average efficacy (when applied as a foam) against carbaryl. Against CEES, no
decontaminant showed greater than 50% decontamination efficacy. DF200 and RSDLฎ
efficacies were generally low (17% or less).
Hot gases (hot combustion exhaust gases), steam, FREONฎ vapor circulation, flashblast
(high intensity xenon-quartz strobe light that thermally decomposes surface
contaminants), monoethanolamine (rapidly alkylated by HD), ammonia, ammonia/steam,
and an aqueous solution of iV-octylpyridinium 4-aldoxime bromide (OPAB; oxime-based
decontaminant) were experimentally evaluated for their effectiveness in decontaminating
HD, GB and VX from painted and unpainted mild and stainless steels and unpainted
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porous materials57. Data demonstrated destruction efficacies of up to 99.8% for steam
and OPAB across all CWA/material combinations that were evaluated.
Enzyme-based decontaminants carry benefits such as being generally non-toxic, non-corrosive,
and environmentally benign. Efficacies of currently studied enzyme-based decontamination
options are still being definitively determined. However, further investigation and development
of technologies is likely required before enzyme-based systems can be reliably fielded.
Secondary information and data collected during the literature search from studies focused on
evaluation of enzyme-based CWA decontamination technologies include the following:
Efficacy of a decontaminant consisting of "First Defense" firefighting foam surfactant
solution (4%) added to a solution of organophosphorus hydrolase (OPH; a nerve agent
hydrolyzing enzyme) was evaluated against paraoxon (simulant of the nerve CWA VX)
on the surface of glass (contamination load ranging from 0.26 micromoles (|imol)/cm2 to
1.51 |imol/cm2)58. Depending on the initial paraoxon load and the strength of OPH
solution (i.e., concentration of OPH enzyme), conversion of paraoxon to />nitrophenol
ranged from complete conversion to 69.7% conversion after a decontaminant contact
period of 60 minutes.
Recombinant enzymes used for decontamination of CWAs often show limited activity
under nonideal environmental conditions (e.g., salinity, pH, etc.). To mitigate
environmental impacts to enzymatic decontaminant activity, phosphotriesterase was
encapsulated in a bacterial outer membrane vesicle. Efficacy of the encapsulated enzyme
decontaminant was then evaluated against paraoxon (VX simulant)59. Coupons of
nylon/cotton fabric, polyurethane paint-coated aluminum, and borosilicate glass were
contaminated with paraoxon at 10 g/square meters (m2). Spiked materials were then
treated with 2 mL of the encapsulated phosphotriesterase decontaminant. Average
removal from painted aluminum was 76%, and little to no paraoxon was detected from
glass. The nylon/cotton fabric surface retained significantly more paraoxon.
Advanced Catalytic Enzyme System (ACES) is an enzymatic CWA decontamination
technology designed to be non-corrosive, non-toxic, environmentally safe and user-
friendly. ACES incorporates three enzymes that hydrolyze OP-based CWAs - OPH,
organophosphorus acid anhydrolase (OPAA), and diisopropylfluorophosphatase
(DFPase). Retention of catalytic activity of ACES in the presence of various firefighting
foams, degreasers, detergents, and commercial disinfectants has been evaluated. To
produce a decontaminant that is efficacious against both CWAs and BWAs, retention of
ACES activity was evaluated in the presence of two broad-range
disinfectants/antimicrobials - Biocidal ZFฎ (a commercial disinfectant based on
quaternary ammonium compounds) and EcoTruฎ (chloroxylenol-based)60. In the
presence of Biocidal ZFฎ alone, OPAA, OPH, and DFPase retained 94, 52, and 75%
enzymatic activity, respectively. A reduction of over 85% enzymatic activity of these
enzymes was measured in the presence of EcoTruฎ disinfectant.
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Decontamination of three CWA simulants by OPH and OPAA was evaluated to assess
the relative efficacies of the enzymes in degradation of three different organophosphate
bond substrates61. The simulants included paraoxon (P-0 bond), demeton-S (P-S bond),
and diisopropyl fluorophosphate (DFP; P-F bond). OPH outperformed OPAA in
degradation of all three simulants. Both enzymes demonstrated the lowest catalytic
efficiency against demeton-S (the P-S bond substrate; simulant for the CWA VX).
The mechanism of hydrolyzation of GA, GB, GD, and VX by the enzyme
phosphodiesterase (PTE) was elucidated 62. Modifications of the enzyme (specifically,
substitution of Zn2+ ions for Al3+ ions in the enzyme active site structure) resulted in
reduced activation energies and faster hydrolysis rates.
As a vaporous/volumetric decontamination technology, VHP and mVHP provide
decontamination approaches that can be used on accessible surfaces, across larger areas, and in
confined or "hard to reach" areas. VHP breaks down safely into water and oxygen so hazardous
residues from application and use of the decontaminant are avoided, though hazardous/toxic
byproducts from decontamination of the target CWAs must still be considered, and compatibility
of the decontaminated items/surfaces/structures must also be considered (e.g., condensation in
electronic equipment). Secondary information and data from studies focused on evaluation of
VHP/mVHP include the following:
Decontamination efficacy of mVHP was evaluated against CWAs on glass63. Glass
microfiber disks (24 mm) were contaminated with VX, GD, or HD in amounts of either 1
g/m2 (the anticipated interior surface/sensitive equipment contamination level) or 10 g/m2
(the anticipated exterior vehicle/terrain contamination level). Following contamination,
the disks were treated with mVHP. H2O2 and NH3 at concentrations of 160 to 200 parts
per million (ppm) and 10 ppm, respectively, reduced HD contamination to undetectable
levels within 20 min. H2O2 and NH3 at concentrations of 50 to 100 ppm and 100 ppm,
respectively, reduced VX contamination to undetectable levels within 60 min
(additionally, no EA-2192, a toxic VX decontamination byproduct, was formed). H2O2
and NH3 at concentrations of 20 to 40 ppm and 100 ppm, respectively, reduced GD
contamination to undetectable levels in under 5 min.
mVHP (using H2O2 and NH3 concentrations of 600 ppm and 100 ppm, respectively) was
used to decontaminate glass wool microfiber disks contaminated with VX at 10 g/m2 64.
Decontamination efficacy of 85% was achieved after 30 minutes. Efficacy increased to
98% after 60 minutes. No trace of VX was detected after two hours of mVHP treatment.
Furthermore, no toxic EA-2192 was detected, though another toxic VX byproduct was
detected (O-ethyl S-vinyl methylphosphonothioate).
mVHP decontamination of VX, GD, and HD on stainless steel, glass, CARC-painted
steel, aluminum, Air Force topcoat-coated aluminum, butyl rubber-covered cloth, Kapton
(polyimide; wiring insulation), nylon webbing, and concrete was evaluated65. CWA or
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simulant was applied to samples (2 to 4 |iL), and samples were subsequently treated with
mVHP (250 ppm H2O2, 20 ppm NH3) for 3, 8, or 24 hours. Decontamination using
mVHP for 24 hours reduced contact hazard of HD, GD, and VX to below limits of
detection. 24-hour mVHP decontamination reduced the GD and VX vapor hazard from
decontaminated materials to limits of detection, but detectable amounts of HD vapor
from materials remained, especially from porous surfaces.
Decontamination of HD, GD, thickened Soman (TGD), and VX on bare aluminum,
CARC-painted aluminum, Air Force topcoat-painted aluminum, glass polycarbonate,
Vitonฎ, Kaptonฎ, and silicone by mVHP was evaluated66. Results demonstrated that
mVHP (target 500 ppm H2O2 and 30 ppm ammonia) can decontaminate CWAs on the
materials to below target levels (0.00087 mg/m3 for GD, TGD, 0.000036 mg/m3 for VX,
and 0.0058 mg/m3 for HD).
As discussed, technologies and methodologies for physical removal of CWA contamination
include application of sorbent materials, surface wiping (with solvent-wetted or sorbent-
impregnated wipes, etc.), contaminated coating removal, etc. Secondary information and data
that were collected during the literature search from studies focused on physical removal of
CWA contamination include the following:
PPE material (chemically protective suit; butyl rubber-based protective layer) and painted
steel (gloss exterior alky-based paint) were contaminated with VX at 2.1 g/m2, HD at 10
g/m2, o-cresol at 50 g/m2, or acrylonitrile at 50 g/m2. Surfaces were then decontaminated
with Desprach sorbent (commercial version of Fuller's earth), FAST-ACT nano-sorbent,
wiping with a FAST-ACT-impregnated glove, RSDL sponge (reactive oximes), Hvezda
foam applicator (surfactant and H2O2), or using the INDEHA kit (ethanol wipe for
physical removal of contaminants from a surface)67. The only procedure that reduced
contamination levels of all substances on both surfaces to below permissible residual
contamination levels was wiping with ethanol (INDEHA). The high efficacy of ethanol
wiping was attributed to the INDEHA application procedure that used multiple wipes.
In ongoing efforts to identify efficacious decontamination technologies for CWA
contamination on sensitive equipment, a variety of dry and solvent-moistened wipes were
evaluated for CWA removal efficacy on a range of sensitive equipment-related surface
types that were contaminated with droplets of neat HD, TGD, and VX (i.e., physical
removal of CWAs, to avoid material compatibility issues related to chemical
decontaminants)68. Test surfaces evaluated included stainless steel, aluminum, CARC-
painted panels, alkyd-painted panels, polyethylene, polycarbonate, and nylon webbing.
The most effective wipe system was a woven activated carbon fabric wipe pre-moistened
with a commercial ethoxy-nonafluorobutane solvent (3M NoveeTM HFE-7200). This
wipe system effectively removed from 90% (by weight) to greater than 99% of HD,
TGD, and VX contamination on non-absorptive and low-absorptive test surfaces.
Furthermore, HFE-7200 is nonflammable, essentially nontoxic, generally non-hazardous
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to personnel, has a low environmental impact, and is compatible with a wide range of
plastics, metals, and elastomers.
Decontamination of coated surfaces (coated hull steel, non-skid-coated decking, etc.)
may require removal of the coating layers to achieve adequate levels of decontamination
(e.g., aqueous-based decontaminants may not be capable of sufficient penetration to reach
and decontaminate deeply permeated contaminants). Blast processes (e.g., dry media
blasting), chemical processes (e.g., strippers), and applied light energy processes
(FlashJet and neodymium-doped yttrium aluminum garnet [Nd:Y3AI5O12; Nd:YAG]
lasers) have been evaluated and used previously for removal of a variety of coating
systems. Removal of CARC from aluminum, steel, and composite materials by media
blasting (using a variety of media including walnut hull, zirconia alumina, plastic media,
garnet abrasive, stainless steel shot, and wheat starch), chemical stripping (using a variety
of strippers, including formulations that both include and exclude dichloromethane),
FlashJet, and neodymium-doped yttrium aluminum garnet (Nd: YAG) lasers was
evaluated69. Stripping technology application parameters and stripping test results
(including strip rates) for all technologies on all tested substrates were determined.
Numerous proof-of-concept and reactor studies have been performed to evaluate a wide variety
of emerging chemistries and technologies for decontamination and/or removal of CWAs,
including MOFs, nanoparticles, micromotors, etc. Many of these technologies are still in
developmental and investigatory phases and are not yet incorporated into field ready systems for
application and use, but demonstration of generally high CWA decontamination/removal
efficacies, anticipated high material compatibility, and low environmental threat are attractive
features that continue to drive research.
Bicarbonate (NaHC03)-activated H2O2 efficiently degraded CWAs into nontoxic
products70. Peroxymonocarbonate (HCO4-) was observed in the NaHC03-activated H2O2
solution, and pH was a key factor in its production (optimal pH of 8.5 for activation of
the decontaminant). Two (2) mL of NaHCCb-activated H2O2 was used to decontaminate
10 |iL of HD and GD during reactor studies.
Reaction half-lives of 1 minute for hydrolysis of GD, 1.8 minutes for hydrolysis of VX,
and 33 minutes for hydrolysis of HD have been measured using zirconium (Zr)-based
MOFs71. With the exception of VX, rapid hydrolysis rates require fixing pH at 8.5 or
above.
Silica nanoparticles impregnated with reactive chemicals were evaluated for efficacy as
reactive adsorbents to remove CWAs and CWA simulants from solutions72. A reactive
sorbent system based on trichloroisocyanuric acid impregnated (10%, w/w) silica
nanoparticles was found to be the best-performing among prepared systems to remove
and detoxify CWAs into non-toxic products effectively in less time. HD, GB, and CWA
simulants were mixed with octane, and the prepared nanoparticles added to the mixture.
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Upon demonstration of adequate efficacy, reactive sorbent systems can be incorporated
into decontamination devices or filtration systems.
Zinc-iron and copper-iron mixed hydroxides were evaluated as reactive adsorbents for
decontamination of CWA simulants73. The mixed metal oxides were exposed to vapors
of CEES and dimethyl chlorophosphate (DMCP), a vesicant and nerve CWA surrogate,
respectively. CEES was observed to be degraded mainly via dehydrochlorination and
DMCP by hydrolysis. The mixed hydroxides showed activity for the decomposition of
both surrogates.
A half-life of 30 min was measured for hydrolysis of GB by aero-gel produced alumina
(AP-AI2O3) nanoparticles during decontamination kinetics reactor studies74.
Reactor studies were performed to evaluate decontamination of GD, VX, and CWA
simulants in aqueous solutions by aluminum sulfate (alum), sodium aluminate, or
mixtures of the two75. Saturated alum solution alone degraded approximately 10%, 20%,
and 94% of DMMP, tributylphosphate (TBP), and triethylphosphate (TEP), respectively.
Malathion was decomposed within 4 days. VX was unaffected. GD was eliminated
within 18 hours. Efficacies were pH-dependent.
Titanium dioxide/gold/magnesium (TiCh/Au/Mg) micromotors were evaluated during
reactor studies for efficacy against CWA simulants76. The micromotors (described as
Janus sphere micromotors consisting of a highly-photoactive TiC>2 outer shell [containing
gold nanoparticles] and a Mg-based inner core) were immersed in 600 |iL of 0.08 molar
(M) sodium chloride (NaCl) solution spiked with methyl paraoxon and bis(4-
nitrophenyl)phosphate (b-NPP) and irradiated with ultraviolet (UV) light. Using a 10-
minute reaction time, approximately 95% degradation of methyl paraoxon and b-NPP
was achieved.
Catalytic degradation of vapor-phase diethyl sulfide (DES; simulant of HD) at higher
concentration (approximately 1200 ppm) using a fixed bed flow reactor over manganese
oxide (MnO)/zeolite-13X catalysts of different Mn content was evaluated77. Degradation
studies were carried out at temperatures ranging from 100ฐC to 400ฐC using air as the
oxidizing agent. A Mn content of 7% (by weight) MnO/zeolite-13X exhibited the highest
catalytic performance.
As an alternative to the use of chemical or biological means or the use of granular
activated carbon for purification of drinking water, a low-cost fiber glass supported
activated carbon (FGAC) filter technology has been prepared that displays enhanced
adsorption characteristics for the removal of benzene, toluene, ethylbenzene, and p-
xylene (BTEX) to below EPA maximum contaminant levels and two CWA simulants
(diisopropylmethyl phosphonate [DIMP] and CEES) to barely detectable levels78.
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Decontamination approaches selected for remediation of CWA contamination on USCG vessels
must be simultaneously efficacious and material compatible to ensure CWA surface and vapor
hazards are sufficiently neutralized while not compromising the integrity and function of vessel
materials, construction, and mechanical and electrical systems, allowing for unlimited return of
vessels to service. It may also be critically important that decontamination approaches avoid: (1)
substantial logistical burden related to application and/or use of technologies (i.e., high utility
requirements, bulky equipment, high raw material or reagent needs, etc.) and (2) production of
large amounts of wastes and/or hazardous wastes, given the operational settings of USCG
vessels.
3.4. CWA Decontaminant Material Compatibility
Reactive CWA decontaminants are largely designed to oxidize or hydrolyze CWAs, as most
CWAs are susceptible to breakdown via these two mechanisms, and an important category of
decontaminant reactions is oxidative chlorination using hypochlorite in alkaline solution50.
Oxidative technologies may be unsuitable for use, however, in certain circumstances given the
corrosive nature of the reaction chemistries toward the surface(s) to be decontaminated49,
especially critical for sensitive equipment and related surface materials, as such equipment and
materials are often associated with high procurement costs and long lead times. Sensitive
equipment and surfaces are incorporated extensively into the construction of USCG vessels.
Consideration of the compatibility of decontamination systems with the materials incorporated
into the construction of USCG vessels, including sensitive equipment and related materials, is
critical to ensure a prompt and unlimited return to service of the assets following
decontamination.
Secondary information and data collected during the literature search from studies focused on
evaluation of the compatibility of decontamination technologies with a variety of materials
(including sensitive equipment and sensitive equipment-related materials). Most of the data were
related to BWA contamination-related material compatibility studies. Material compatibility
studies that use decontaminants that are not suitable for CWA remediation are excluded here.
Described test conditions are based on biological agent remediation and may not yield high
efficacy against CWAs.
The compatibilities of unpainted concrete cinder block, standard stud lumber (fir), latex-
painted gypsum wallboard, ceiling suspension tile, painted structural steel, carpet, and
electrical circuit breakers with VHP (application conditions of < 30% RH and > 30ฐC)
were evaluated79. Materials were exposed to either 250 ppm VHP for four (4) hours for a
total concentration time (CT) of 1000 ppm-hour (h), or 125 ppm VHP for eight (8) h also
for a total CT of 1000 ppm-h. Generally, VHP-exposed building materials showed no
change in appearance or integrity compared to non-exposed samples.
Compatibilities of CIO2 gas (CTs ranging from 900 ppm by volume [ppmv]-hours to
9,000 ppmv-hours) and VHP with sensitive equipment (including functioning personal
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computers [PCs]) were evaluated80. CIO2 treatment caused material degradation, but PCs
remained functional. No changes in visual appearance or functionality due to exposure to
VHP were observed.
Fumigation technologies that have been used to decontaminate sensitive equipment
materials were reviewed81. VHP treatment is effective and material-compatible, but the
application process must be closely monitored and controlled to prevent damage (due to
condensation). CIO2 gas is generally a more efficacious decontaminant than VHP but
demonstrates decreased material compatibility in comparison to VHP.
Compatibility of CIO2 fumigation with sensitive electronic components and materials was
evaluated using multiple conditions, including: (1) 3,000 ppmv CIO2 with 75% RH, (2)
75 ppmv CIO2 with 75% RH, (3) 75 ppmv CIO2 with 40% RH, and (4) 3,000 ppmv CIO2
with 90% RH82. No visual or functional changes for stainless steel, laser-printed paper, or
gaskets were observed. Circuit breaker screws and inkjet-printed paper were affected
under every condition (including tests using only high RH [i.e., no CIO2]). RH at 75%
severely affected low carbon steel, copper, photographs, and drywall nails and screws.
CIO2 fumigation at high temperature and RH led to intermittent light switch failures. No
impacts to personal digital assistant (PDA) devices under any fumigation condition were
observed. Mild discoloration and fading of cell phone screens were noted under certain
conditions. CIO2 and condensing humidity caused severe corrosion of fax machine printer
bars, compact disks (CDs), and digital video disks (DVDs). At lower RH, these impacts
were not observed. Power state of PCs affected material/decontaminant compatibility.
Use of CIO2 and RH resulted in corrosion of computer components at least 75% of the
time. CD/DVD drives were damaged by 3,000 ppmv CIO2 and RH greater than 75%.
Unpainted concrete cinder block, standard stud lumber (2-in by 4-in fir), latex-painted
0.5-in gypsum wallboard, ceiling suspension tile, painted structural steel, carpet, and
electrical (circuit) breakers were exposed to CIO2 vapor83. Fumigation conditions were
2,000 ppm CIO2 for six (6) h for a total CT of 12,000 ppm-h, or 1,000 ppm CIO2 for
twelve (12) h also for a total CT of 12,000 ppm-h. RH target was 75% and temperature
target was 75 degrees Fahrenheit (ฐF). No visual differences were observed for any of the
materials following CIO2 exposure. Tensile strength of standard stud lumber furring strips
was reduced by exposure to high concentrations of CIO2 for short durations. Under a 30-
amp load, C102-exposed circuit breakers tripped more slowly than the control units.
Otherwise, no functional impacts were observed.
The material demand (mass flux) of selected materials for CIO2 under select fumigation
conditions (specifically, CIO2 concentrations of 1,000 ppmv or 2,000 ppmv to achieve a
total CT of 12,000 ppmv-h) was determined84. The materials included concrete, painted
steel, wood, gypsum wallboard, ceiling tile, and carpet. Required feed concentration and
the time required to reach the target CIO2 fumigant concentration were found to be
functions of building material. Rank of CIO2 demand for the building materials over the 0
31
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to 12,000 CT range was (from highest demand to lowest) ceiling tile > wood > gypsum
wallboard > carpet > concrete = steel = baseline for the 1,000 ppmv tests, and ceiling tile
> gypsum wallboard > carpet > wood > concrete = steel = baseline for the 2,000 ppmv
tests.
Compatibility of H2O2 (3% liquid), and bleach (0.58% hypochlorite) were evaluated on
metals (copper, brass, silver, tin, titanium, iron, and gold), inks, cellulose from new and
aged paper and cotton fabrics, collagen, keratin, and fibroin (silk)85. Results
demonstrated that the decontaminants damaged the materials, but the degree of damage
varied with the specific decontaminant and the material. Damage can be minimized with
the appropriate choice of decontaminant. H2O2 was generally the least aggressive on
metals. Bleach decontamination affected a higher percentage of inks.
The material demands of unpainted concrete cinder block, standard stud lumber, latex
painted gypsum wallboard, acoustical ceiling suspension tile, primer-painted structural
steel, and carpet for VHP was evaluated86. Concrete cinder block coupon had the greatest
impact on maintaining the VHP concentration, while carpet and steel had a low impact on
the VHP concentration.
3.5. CWA Sampling and Analysis
To identify specific CWA contaminants, accurately and precisely determine the extent of CWA
contamination, and assess the effectiveness of CWA decontamination efforts, effective sampling
procedures, methodologies, and technologies for qualitative and/or quantitative measurement of
CWA concentrations/amounts in a variety of environmental matrices are necessary (including
measurement of surface concentration levels, concentrations in liquid matrices, and vapor
concentrations). As with approaches for decontamination, the unique operational settings and
construction materials associated with USCG vessels can create challenging sampling scenarios.
Effective surface sampling can be challenged by the materials themselves (which, at times,
incorporate complex coating systems) and/or by various contaminants and foulants introduced by
USCG vessel operational settings (e.g., seawater, grime, etc.).
Summaries and overviews of common sample collection and analysis techniques for detection
and quantitation of CWAs in various matrices are available in the literature87. Sampling of
vapor-phase CWAs present in gas matrices such as air is often accomplished by sorption onto
solid-phase extraction media (either passive sorption or by drawing a sample via vacuum onto
the sorption media) followed by extraction of the collected CWA from the media via solvent
extraction or thermal desorption and subsequent analysis of the extracted CWA by GC/MS,
liquid chromatography-tandem mass spectrometry (LC-MS/MS), or other analytical approach.
Solid phase microextraction (SPME) is an increasingly common method of sample collection
which involves immersion of a specially coated fiber into a sample matrix (which can be solid,
liquid, or gas/vapor) to allow for adsorption of target analytes onto the fiber88. The adsorbed
target analytes are then thermally desorbed for analysis via, e.g., GC/MS, LC-MS/MS, etc.
32
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Derivatization of target CWA analytes can also be performed to facilitate and/or enhance
detection capabilities.
The EPA Homeland Security Research Program's (HSRP) Environmental Sampling and
Analytical Methods (ESAM) program includes Sample Collection Information Documents
(SCIDs) which provide general sample collection, handling, and shipping information for
collection of samples analyzed using methods described in the Selected Analytical Methods for
Environmental Remediation and Recovery (SAM) 2017 document89. Methods for sampling and
analysis described in Environmental Sampling and Analysis Methods (ESAM/SAM) may be
applicable, translatable, and/or adaptable for use on USCG vessel-related materials.
Wipe sampling is often used to identify the types and amounts of contaminants on the surface of
materials. Secondary information and data collected during the literature search from studies
focused on collection of CWA samples via surface wiping methodologies include the following:
Commercially-available wipe materials were evaluated to determine the optimal wipe
sampling method parameters for recovery of nerve CWA degradation products (including
EMPA, isopropyl methylphosphonate [IMPA], pinacolyl methylphosphonate [PMPA],
methyl phosphonate [MPA], and ethylhydrogen dimethylphosphonate [EHDMAP]) from
surfaces that are largely porous/permeable (vinyl tile, painted drywall, and wood) and
nonporous/impermeable (laminate, galvanized steel, and glass)90. The selected wipe
sampling method involved use of a cotton gauze wipe wetted with 1 mL of water and two
successive "S" wipe patterns. Following collection, wipes were extracted in 5 mL of high
performance liquid chromatography (HPLC)-grade water and extracts were analyzed via
ultrahigh performance liquid chromatography - tandem mass spectrometry (UPLC-
MS/MS). Recoveries were 60% to 98% for PMPA, 60% to 103% for IMP A, and 61% to
91% for EMPA. MP A and EHDMAP recoveries were lower. Data indicated that wipe
samples may be held for up to 30 days prior to analysis, and target analytes can persist on
the tested surfaces for at least six (6) weeks.
Cotton gauze, glass fiber filter, non-woven polyester fiber, and filter paper wipes were
evaluated for efficacy in collection of degradants of nitrogen mustards (HN1, HN2, and
HN3) from the surface of porous (vinyl tile, painted drywall, wood) and mostly
nonporous (laminate, galvanized steel, glass) materials91. Filter paper wipes were
selected over the other wipe types that were tested. Detection limits achieved were 0.2
nanogram (ng)/cm2 for triethanolamine (TEA), 0.03 ng/cm2 for N-ethyldiethanolamine
(EDEA), 0.1 ng/cm2 for N-methyldiethanolamine (MDEA), and 0.1 ng/cm2 for
diethanolamine (DEA).
Efficacy of wipe methods has been compared to strippable coatings for sampling CWAs
on the surface of materials92. Surfaces that were tested include glazed ceramic tile, grade
304 stainless steel, painted drywall, ceiling tile, smooth cement, upholstery fabric,
finished and unfinished wood flooring, and escalator handrail. Average percent
33
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recoveries using solvent-wetted gauze wipes and body paint, respectively, were: (1)
finished wood, 30.2%, 2.97%; (2) escalator handrail, 4.40%, 4.09%; (3) stainless steel,
21.2%, 3.30%; (4) glazed ceramic tile, 49.7%, 16.7%; (5) ceiling tile, 0.33%, 11.1%; (6)
painted drywall 2.05%>, 10.6%; (7) cement, 1.20%, 35.2%; (8) upholstery fabric, 7.63%,
6.03%; and (9) unfinished wood, 0.90%, 1.74%.
Given that: (1) identification and quantitation of CWA contamination during incident
management and response as well as following decontamination efforts is critical to operational
success, and (2) collection of samples and transport offsite for ex-situ analysis can be
prohibitively time-consuming, portable on-site CWA detection equipment is being evaluated and
used by a variety of first responder teams and military forces (including the USCG). A variety of
CWA sensing and detection technologies have been developed and evaluated including mass
sensitive sensors, surface acoustic wave (SAW) sensors, quartz crystal microbalance (QCM)
sensors, micro-electro-mechanical-system (MEMS) sensors, chemicapacitors, chemiresistive
sensors, carbon nanotubes, field-effect transistors93, and bioassays94. Secondary information and
data collected during the literature search from studies focused on evaluation of various detector
and sensor technologies for identification and measurement of CWA contamination include the
following:
Raman spectroscopy is being evaluated for standoff detection of CWAs. Raman spectra
of 22 CWAs were measured using 785 nanometer (nm) and 1064 nm excitation95.
Generally, for pure CWA detection, 785-nm excitation is preferred, but for crude samples
(e.g., identification of CWAs in a gasoline mixture), 1064-nm excitation yields better
detection performance. A prototype system that couples a Raman spectrometer with a
reflective telescope using fiber optics has also been developed and evaluated96. The
system was capable of detection of CWA simulants including DMMP and CEES at
standoff distances of up to 6.6 m. Quantification studies using the prototype Raman
system demonstrated a DMMP limit of detection (LOD) value of 3% weight/volume
(w/v) at a distance of 6.6 m.
The ability of the OPAA enzyme to selectively hydrolyze the P-F bond of fluorine-
containing OP CWAs (e.g., GB and GD) has been studied to investigate the possibility of
using the enzyme to create a discriminative detection capability97. The CWA simulants
DFP (P-F bond), paraoxon (P-0 bond), and demeton-S (P-S bond) were used. No sensor
response was observed for paraoxon or demeton-S, but DFP concentrations down to 20
micromolar (|iM) were readily detected.
A single-walled carbon nanotube (SWCNT)-polyaniline composite sensor was evaluated
using DMMP gas98. A response of 27.1% was achieved within 5.5 seconds of exposure to
10 ppm DMMP gas (better than pure SWCNT network sensors). Response increased
linearly with increasing DMMP gas concentration.
34
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A nanocomposite gas sensor comprised of iron oxide (a-Fe203), graphite, and calcium
sulfate (CaSC>4) achieved a detection limit of 1 part per billion (ppb) for DMMP vapor 99
Results demonstrated that the presence of CaSC>4 in the nanocomposite allowed for the
observed sensor performance at room temperature (avoiding the need for operation at
high temperature, which is a known drawback to the use of metal oxide gas sensors).
Flexible epidermal tattoo- and textile-based electrochemical sensors incorporating
stretchable OPH enzyme electrodes have been developed for continuous vapor-phase
detection of OP threats100. A detection limit of 12 mg/L was achieved for methyl
paraoxon (nerve CWA simulant).
SAW sensors can be used for detection of CWA vapors101. Real time detection
capabilities, high specificity (when sensor arrays are utilized), and selectively tuned
detection algorithms are benefits to the use of SAW sensor-based detection systems.
Other secondary information and data collected during the literature search from studies focused
on CWA sampling and analysis methodologies include the following:
A novel method for extraction of CWAs from liquid matrices has been developed that
uses iron oxide microspheres as a sorbent, coupled with magnetic dispersive solid phase
extraction (MDSPE) followed by GC/MS analysis102. Parameters affecting the efficiency
of the method were evaluated and optimized. Recoveries of the CWAs GA, GD, and
cyclosarin (GF) were in the range of 72 to 90% (3.9 to 5.5% relative standard deviation
[RSD]) from dodecane, 84 to 95% (3.3 to 6.2% RSD) from silicon oil, and 70 to 82%
(5.3 to 8.2% RSD) for the CWAs in ซ-hexane.
Studies have been conducted to evaluate the sampling efficiency of different
combinations of SPME fibers and analysis methods to quantify numerous CWAs in a
variety of sample matrices (e.g., air, water, soil, etc.). For collection and quantitation of
HD and associated byproducts, a butyl acrylate SPME fiber was found to be most
efficient, whereas for organoarsenic compounds, a methyl acrylate/methyl methacrylate
copolymer fiber was found to be the best-performing fiber103. Using a
polydimethylsiloxane/divinylbenzene fiber, detection limits for nerve CWAs in water
matrices were 0.05 |ig/L for GB, GD, and GA, and as low as 0.05 |ag/m L for VX
depending on the sample analysis method88.
Agentase Disclosure Spray is an enzyme-based CWA-detection system in a spray
formulation that changes color when sprayed on contaminated surfaces. Detection of
CWA at sub-microgram levels within five minutes has been reported104.
A rapid, sensitive, and robust method for identification of Lewisite(s) and hydrolysis
products in aqueous and multiphase sample matrices has been developed that
incorporates in-sorbent-tube butylthiolation derivatization105. Experiments were designed
to determine the optimal injection sequence of sample and derivatization agent into a
35
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thermal desorption tube, the sequence of derivatization and water removal steps, the best
solvent for the derivatization reagent, the optimal volume of the derivatization reagent
solution, and the optimal sample pH.
Analysis of CWA degradation products (including MP A, EMPA, IMP A, and PMPA) in
environmental samples was performed by capillary electrophoresis (CE) using
electrokinetic injection106. Detection limits for CWA degradants were as low as 1 to 2
|ig/L for water samples and 25 to 50 |ig/L for aqueous leachates of soil samples (10 mL
of leachate/1.5 g of soil).
An evacuated canister method was validated for sampling specific volatile organic
compounds (VOCs) that can be used as simulants for CWAs107. The method was found
to be suitable for sampling VOCs (including cyclohexane, chloroform, methylene
chloride, methyl ethyl ketone, hexane, and carbon tetrachloride) in the range of 2.3 to 50
ppb.
OP-active enzymes have been immobilized onto porous polyurethane foam to produce
CWA detection sponges/badges108. The technology can be used to sample OPs in
anything from soil to water to air and is CWA-selective through use of a variety of
enzymes including OPH (hydrolyzed GB more readily than other G-series CWAs) and
laccase (preferentially hydrolyzes VX over G-series CWAs).
A "dip and shoot" method has been developed for rapid sampling and analysis of CWAs
and hydrolysis products (by desorption electrospray ionization mass spectrometry [DESI-
MS]) in liquid and soil samples109. Sampling was performed by dipping a fused silica,
stainless steel, or SPME tip into organic or aqueous samples. The tip was then
immediately introduced through the septum port on the electrospray ionization (ESI)
housing during DESI-MS analysis.
A variety of analytical methodologies were used to characterize bulk-CWA waste to
screen for presence of CWAs and CWA degradants110. The study provides a summary of
the techniques used as well as degradants of interest for each CWA. Techniques included
GC/MS, GC/atomic emission detection (AED), LC/MS, CE, and nuclear magnetic
resonance spectroscopy (NMR).
A multilayered extraction membrane disk system was developed and used to recover
DIMP and DMMP (CWA simulants) from aqueous samples, achieving detection limits as
low as 0.20 |ig/Lm.
3.6. Comprehensive Summary Tables
Table 4 provides a summary of techniques, technologies, and methodologies for decontamination
and sampling of the target CWAs (or simulants of the target CWAs) indicated in Section 2.1.2
from the USCG vessel-relevant materials listed in Table 1 in Section 2.1.1.2, based on the
information and secondary data collected during the literature search.
36
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Table 4. CWA Decontamination and Sampling Summary (USCG Materials)
Vessels
Material
Information/Data
Area
HD
GB
VX
Aluminum
(hull)
Decontamination
mVHP 65 66
Wiping 68
NA
ni VHP 6566
Wiping 68
Sampling
NA
NA
NA
Coated steel
(hull)
Decontamination
ni VHP 65
RSDL 61
Reactive sorbents/materials 61
Physical removal methods 69
Thermal decontamination 57
Physical removal methods 69
Thermal decontamination 57
ni VHP 65
RSDL 61
Reactive sorbents/materials 61
Physical removal methods 69
Thermal decontamination 57
Sampling
NA
NA
NA
C3
HH O
a w
^ ฉ
Foam
Decontamination
NA
NA
NA
Sampling
NA
NA
NA
CQ 5-1
2 ^
2 Ph
o *-
2
Non-skid coatings
Decontamination
NA
NA
NA
(decking)
Sampling
NA
NA
NA
*7 <ฉ
OS i
r-
r. CO
1 l
>n sS
"T
Glass
Decontamination
Bleach, diluted bleach 54'55
Liquid H202 55
DF200 54 55
Decon Green 54
CASCAD. SDF 54
ni VHP 65'66
Bleach, diluted bleach 54
DF200 54
Decon Green 54
CASCAD. SDF 54
Enzyme-based 5& 59
ni VHP 61 6-66
Bleach, diluted bleach 54
DF200 54
Decon Green 54
CASCAD. SDF 54
Enzyme-based 58 59
Sampling
Wipe sampling 91
Wipe sampling 90
Wipe sampling 90
Insulation, other
Decontamination
ni VHP 65
NA
ni VHP 65
bulkhead coverings
Sampling
NA
NA
NA
Glazing materials
Decontamination
NA
NA
NA
Sampling
NA
NA
NA
Sensitive equipment
Decontamination
NA
NA
NA
and components
Sampling
NA
NA
NA
NA - Not applicable; no related information o secondary data were collected during the literature search
Table 5 provides a summary of techniques, technologies, and methodologies identified during
the search for decontamination and sampling of CWAs (including the target CWAs provided in
Section 2.1.2 [VX, HD, and GB] as well as other G-series [e.g., GD] and vesicant [e.g., L, HL]
CWAs) from various other materials (apart from the USCG vessel-relevant materials identified
in Table 1 of Section 2.1.1.2).
37
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Table 5. CWA Decontamination and Sampling Summary (A dditional Materials)
Material
Decontamination
Sampling
Noncoated metals
(excl. aluminum;
e.g., stainless steel,
galvanized metal,
etc.)
Bleach, diluted bleach 54 55-56
pAB 56
Liquid H202 55
DF200 5455-56
Decon Green 54
CASCAD. SDF 54
m VHP 65
Soap and water 56
RSDL 56
Steriplex56
Wiping 68
Thermal
decontamination 57
Wipe sampling 91191 92
Bioassays 94
Strippable coating 92
Tile (e.g., glazed
ceramic, vinyl,
acoustic ceiling, etc.)
Bleach, diluted bleach 54
DF200 54
Decon Green 54
CASCAD SDF 54
Wipe sampling 9119192
Strippable coating 92
Plastics (e.g., LDPE,
HDPE, acrylic,
laminate, etc.)
Bleach, diluted bleach 56
pAB 56
DF200 56
niVHP 65'66
Soap and water 56
RSDL 56
Steriplex56
Wiping 68
Wipe sampling 91191
Coated porous
materials (e.g.,
drywall, concrete,
wood, etc.)
Bleach, diluted bleach 54
DF200 54
Decon Green 54
CASCAD SDF 54
Wipe sampling 9119192
Strippable coating 92
Coated nonporous
(e.g., coated metals
excl. steel, CARC-
coated aluminum,
etc.)
Enzyme-based 59
Decon Green 5153
ni VHP 65'66
Physical removal
methods 69
Wiping 68
NA
Noncoated porous
materials (e.g.,
drywall, concrete,
wood, etc.)
Bleach, diluted bleach 54 55
Liquid H202 55
DF20 0 54 55
Decon Green 54
CASCAD SDF 54
ni VHP 65
Wipe sampling 9119192
Strippable coating 92
Fabric
Enzyme-based 59
ni VHP 65
Wipe sampling 92
Strippable coating 92
Rubber
Bleach, diluted bleach 56
pAB 56
DF200 56
ni VHP 65
Soap and water 56
RSDL 56
Steriplex56
Wipe sampling 92
Strippable coating 92
Liquid or solid
matrices
NA
Raman 96
Enzyme-based detectors
Solid sorbent105
Extraction disks/filters 111
108 Capillary electrophoresis 106
"Dip and shoot" DESI-MS 109
Vapor-phase CWA
NA
Enzyme-based detectors
Reactive material-based
sensors 98 99
SPME 103
100. 108
Raman 95
SAW sensors 101
Evacuated canister 107
Developmental,
reactor studies, or
similar
Enzyme-based 60-6L 62
NaHC03-activated H202 70
Reactive sorbents/materials 7L 49-
72. 73. 74. 75. 76. 77. 78
DS2 49
C8 49
Plasma 49
Liquid H202 49
Wipe sampling 89
MDSPE 102
Enzyme-based detectors
Reactive material-based
sensors 93
97.1M -SPME 8887
Solid sorbent87
PPE materials
Bleach, diluted bleach 56
pAB 56
DF200 56
Soap and water 56
RSDL5467
Steriplex56
Reactive
sorbents/materials 67
NA
Skin, hair
Liquid H202 45
Enzyme-based 42
Soap and water 44
RSDL41'4344
Reactive sorbents/materials 46
PS 104 41
Fuller's Earth41'43'44
46.48
alldecontMED 41
Oxime 42
NA
NA - Not applicable; no related information or secondary data were collected during the literature search
38
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4. KNOWLEDGE/CAPABILITY GAP ASSESSMENT AND RESULTS
As described in Section 2.6, information/secondary data source summaries were collated into the
source compilation document according to the content and primary research focus of the sources.
This arrangement of the literature summaries in the source compilation document served to
illustrate the distribution of the information and secondary data that were collected during the
search across the research focus areas and support identification of gaps in
information/secondary data related to methodologies, procedures, and technologies for
decontamination and sampling of CWA contamination on USCG assets.
On 27 April 2020, project stakeholders from the USCG and the U.S. Department of Homeland
Security (DHS) joined with the EPA and Battelle in a meeting to review and discuss the
information and secondary data collected during the literature search and to identify
data/information/capability gaps related to decontamination and sampling capabilities for CWA
contamination on USCG assets. Prior to the discussion, EPA and Battelle provided expected
attendees with the complete results of the literature search for review (specifically, the source
compilation document was provided, which, as described in Section 2.6, included summaries of
all secondary data and information sources collected during the literature search categorized by
research focus). Meeting discussions focused on identification of knowledge/capability gaps
related to the unique challenges imposed on CWA contamination response and management,
decontamination, and sampling and analysis strategies due to USCG vessel operations and
operational environments and/or vessel construction materials (based on the
information/secondary data collected during the literature search).
The knowledge/capability gaps that were identified and discussed, as well as additional
discussion topics, are provided in Sections 4. 1 and 4.2, respectively.
4.1. Knowledge/Capability Gaps
Although outside the scope of the current work, data on efficacy of decontamination and
sampling technologies and methodologies in/on other matrices (not just the select
material surfaces) would be valuable.
o This may be especially true for air and liquid matrices (i.e., seawater, bilge water,
oil, lubricants, fluids, other vessel areas that may require liquid sampling, HVAC,
and exhaust systems, etc.).
o Liquid matrices can become contaminated during decontamination and/or
sampling efforts, spread contamination or re-contaminate surfaces, and/or cause
further penetration into other contaminated materials, areas, and/or surfaces,
o This may be especially important for CWAs, as some (e.g., VX and Fourth
Generation Agents [FGAs]/Novichok Agents) can be persistent.
While some data were collected, collection of additional data (and thorough evaluation of
collected data) related to sampling from porous materials would be valuable.
39
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The generally smaller amount of data related to decontamination and sampling of CWAs
on coated steel that was collected is notable.
o Some coated steel-related CWA decontamination and material compatibility data
source summaries were presented, but none that were focused on
evaluation/efficacy of sampling technologies or methodologies,
o Likely more data have been generated, but such data may be For Official Use
Only [FOUO] and/or unpublished.
No data that appear (initially, at least) to be related to decontamination (or any other
focus area, actually) on bumper foam were collected.
o The term "bumper foam" may have been too restrictive ("elastomeric foam" or
just "foam" may have been a better approach for the literature search),
o Decontamination and/or sampling data related to bumper foam may have been
collected, though the report/article/data source/etc. does not refer to the material
as "bumper foam".
o Need to consider what the bumper foam material is comprised of to determine if
data related to CWA decontamination and/or sampling from the specific
composition material(s) have already been collected.
ฆ Determined that the bumper foam material is comprised of a polyurethane
fabric wrapped around a (rounded) interior foam,
o Data related to decontamination and/or sampling of CWAs on other types of
plastic and/or rubber may be applicable/translatable to bumper foam.
Additional data on and consideration of the impacts to decontamination and/or sampling
by fouling of/on a surface (i.e., salt/seawater, grime, etc.) would be valuable.
o Need data related to realistic surfaces (most of the collected studies used clean
[i.e., unused, pristine] materials/surfaces),
o A few search terms were included to attempt to collect some data related to
fouling/foulants, and some data related to BWA decontamination and sampling in
the presence of heavy/light organic load were collected112, but more emphasis
should be placed on this topic/focus,
o Sea/saltwater was discussed as an "interferent" and/or "foulant" impacting
decontamination and sampling efficacy. Other specific foulants of interest should
be identified.
In addition to vessels, an area of focus to consider would be areas/locations within USCG
bases or stations (and the specific/associated construction materials) that are more
susceptible to frequent contamination and/or re-contamination/cross-contamination.
o Analogous to subway trains/stations,
o Surfaces/items that are frequently touched/interacted with.
Collection and inclusion of additional data/information from CWA decontamination
efficacy studies conducted by other government agencies would be valuable.
40
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Additional data/information related to compatibility of hot/humid air decontamination
with the materials of interest would be valuable.
o Reports/articles on studies performed by other government agencies on efficacy
of hot/humid air decontamination of CWAs may also include data/information on
compatibility of the tested materials with the decontamination process,
o It was discussed that studies have been conducted/data have been generated
related to the operability of CI30 aircraft after hot/humid air decontamination.
Other characteristics of CWA decontamination and sampling technologies and
approaches must be considered also, beyond just efficacy of the technologies/approaches.
Such considerations include "scale-up" requirements (for larger areas and/or multiple
assets/vessels, etc.), supply-chain, availability limitations, surge capacities, etc.
Although outside the scope for this effort, data related to decontamination and sampling
of CWAs on soil and vegetation (foliage, grass, etc.) would be valuable.
4.2. Additional Information, Discussion, and Notes
Scientific articles, reports, guidance documents, etc. that are publicly available
from/through the Defense Technical Information Center (DTIC) were collected and
summarized during the literature search and included in the source compilation
document. Anything not publicly available from/through DTIC (i.e., classified,
controlled, limited distribution, etc.) was not collected or included.
Quality of the scientific articles, reports, guidance documents, etc. collected during the
literature search was assessed both qualitatively through use of source document type
designations (refer to Section 2.4.1) and quantitatively through use of the Literature
Assessment Factor Rating (refer to Section 2.4.2).
The absence of data in the open literature related to decontamination and/or sampling of a
particular contaminant on the surface of a particular material does not necessarily indicate
that such knowledge/data/capabilities do not exist. Similarly, the presence/existence of
data related to decontamination and sampling of specific contaminants on specific
materials in the literature does not indicate that the decontamination and/or sampling
technologies/methodologies are efficacious.
Although there do appear to be gaps in the data/information that were collected and/or
that exist related to decontamination and sampling of CWAs on the specified USCG
materials, sampling plans and future research can be directed at filling these gaps.
In addition to specific technologies for decontamination and sampling of CWAs, the
methods/procedures for use/application of technologies must be considered (i.e.,
decontamination and sampling tactics/strategies in addition to technologies).
CWA sampling and analysis technologies/methodologies may carry inherent
susceptibilities to various interferents that may cause false positive/negative results
and/or impact quantification of the level/concentration of CWA contaminants.
Knowledge of such susceptibilities is critical during selection of CWA sampling and
41
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analysis technologies/methodologies, and susceptibilities must be considered in light of
specific target analytes, sample matrices, sampling/analysis conditions, etc.
4.3. Gap Table
The knowledge/capability gaps described in Section 4.1 and the additional information,
discussion topics, and notes described in Section 4.2 are summarized in Table 6.
Table 6. Gap Table
Knowledge/Capability Gaps
Data on efficacy of decontamination approaches in/on other
matrices (besides the target USCG vessel-related materials).
Limited data were collected related to decontamination of
CWAs on coated steel.
No data were collected related to decontamination of CWAs
on bumper foam.
Additional data on the impacts of foulants to the efficacy of
decontamination technologies/approaches would be
valuable.
In addition to vessels, consider areas/locations within USCG
bases or stations that are susceptible to contamination.
Additional data on the efficacy of hot, humid air
decontamination would be valuable.
Consider other characteristics of CWA decontamination
technologies/approaches (e.g., "scale-up" requirements,
supply-chain, availability, surge capacities, etc.).
Data related to decontamination of CWAs on soil and/or
vegetation would be valuable.
Additional Information, Discussion, Notes
Literature and data publicly available through DTIC
were collected. Anything not publicly available through
DTIC was not collected.
Literature and data source quality was assessed both
qualitatively and quantitatively (refer to Section 2.4).
The absence of data in the open literature related to
decontamination of CWA on a particular material does
not necessarily indicate that such knowledge/capability
does not exist. Similarly, the presence/existence of such
data does not indicate that the described
decontamination technology/method is efficacious.
Future research can be directed at filling the
knowledge/capability gaps identified during this effort.
In addition to specific technologies for decontamination
of CWA, methods/procedures for use/application of
decontaminants must be considered.
Data on efficacy of sampling approaches in/on other
matrices (besides the target USCG vessel-related materials).
Need additional data related to sampling from porous
materials.
Limited data were collected related to sampling of CWAs
on coated steel.
No data were collected related to sampling of CWAs on
bumper foam.
Additional data on the impacts of foulants to the efficacy of
sampling technologies/approaches would be valuable.
In addition to vessels, consider areas/locations within USCG
bases or stations that are susceptible to contamination.
Consider other characteristics of CWA sampling
technologies/approaches (e.g., "scale-up" requirements,
supply-chain, availability, surge capacities, etc.).
Data related to sampling of CWAs on soil and/or vegetation
would be valuable.
Literature and data publicly available through DTIC
were collected. Anything not publicly available through
DTIC was not collected.
Literature and data source quality was assessed both
qualitatively and quantitatively (refer to Section 2.4).
The absence of data in the open literature related to
sampling of CWA on a particular material does not
necessarily indicate that such knowledge/capability does
not exist. Similarly, the presence/existence of such data
does not indicate that the described sampling
technology/method is efficacious.
Future research can be directed at filling the
knowledge/capability gaps identified during this effort.
In addition to specific technologies for CWA sampling,
methods/procedures for use/application of sampling
technologies must be considered.
CWA sampling and analysis
technologies/methodologies may carry inherent
susceptibilities to interferents that must be considered.
42
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95 Kondo, T.; Hashimoto, R.; Ohrui, Y.; Sekioka, R.; Nogami, T.; Muta, F.; Seto, Y. Analysis of
chemical warfare agents by portable Raman spectrometer with both 785 nm and 1064 nm
excitation. Forensic Science International. 2018, 291, pp 23-38.
96 Ortiz-Rivera, W.; Pacheco-Londono, L.C.; Hernandez-Rivera, S.P. Remote continuous wave
and pulsed laser Raman detection of chemical warfare agents simulants and toxic industrial
compounds. Sensing and Imaging. 2010, 11, pp 131-145.
97 Simonian, A.L.; Grimsely, J.K.; Flounders, A.W.; Schoeniger, J.S.; Cheng, T.-C.; DeFrank,
J.J.; Wild, J.R. Enzyme-based biosensor for the direct detection of fluorine-containing
organophosphates. Analytica Chimica. 2001, 442, pp 15-23.
98 Yoo, R.; Kim, J.; Song, M.-J.; Lee, W.; Noh, J. S. Nano-composite sensors composed of
single-walled carbon nanotubes and polyaniline for the detection of a nerve agent simulant
gas. Sensors and Actuators B: Chemical. 2015, 209, pp 444-448.
99 Alizadeh, T.; Jahani, R. A new strategy for low temperature gas sensing by nano-sized metal
oxides: Development of a new nerve agent simulant sensor. Materials Chemistry and
Physics. 2015, 168, pp 180-186.
100 Mishra, R.K.; Martin, A.; Nakagawa, T.; Barfidokht, A.; Lu, X.; Sempionatto, J.R.; Lyu,
K.M.; Karajic, A.; Musameh, M.M.; Kyratzis, I.L.; Wang, J. Detection of vapor-phase
organophosphate threats using wearable conformable integrated epidermal and textile
wireless biosensor systems. Biosensors andBioelectronics. 101, 2018, pp 227-234.
101 McGill, R.A.; Antevil, J.; Anderson, M.R.; Venezky, D.L. Fire Detection by Surface Acoustic
Wave Chemical Sensor Systems', NRL/MR/617093-7421; Office of Naval Research,
Technology Directorate, Arlington, VA, December 1993.
102 Singh, V.; Purohit, A.K.; Chinthakindi, S.; Raghavender, D. G.; Tak, V.; Pardasani, D.;
Shrivastava, A.R.; Dubey, D.K. Analysis of chemical warfare agents in organic liquid
samples with magnetic dispersive solid phase extraction and gas chromatography mass
spectrometry for verification of the chemical weapons convention. Journal of
Chromatography A. 2016, 1448, pp 32-41.
103 Nawala, J.; Czuprynski, K.; Popiel, S.; Dziedzic, D.; Beldowski, J. Development of the HS-
SPME-GC-MS/MS method for analysis of chemical warfare agent and their degradation
products in environmental samples. Analytica Chimica Acta. 2016, 933, pp 103-116.
104 Anonymous. Enzyme-Based Chemical Agent Detection Spray. Security, 2008, 45, 3, pp 25.
105 Terzic, O.; Bartenbach, S.; de Voogt, P. Determination of Lewisites and their hydrolysis
products in aqueous and multiphase samples by in-sorbent tube butyl thiolation followed by
thermal desorption-gas chromatography-full scan mass spectrometry. Journal of
Chromatography A. 2013, 1304, pp 34-41.
106 Nassar, A.F.; Lucas, S.V.; Hoffland, L.D. Determination of chemical warfare agent
degradation products at low-part-per-billion levels in aqueous samples and sub-part-per-
million levels in soils using capillary electrophoresis. Analytical Chemistry. 1999, 71 pp
1285-1292.
107 Coffey, C.C.; LeBouf, R.F.; Calvert, C.A.; Slaven, J.E. Validation of an evacuated canister
method for measuring part-per-billion levels of chemical warfare agent simulants. Journal of
the Air & Waste Management Association. 2011, 61, pp 826-833,
50
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108 Gordon, R.K.; Gunduz, A.T.; Feaster, S.R.; Doctor, B.P.; Cronin, T. Selective, Specific, and
Versatile Personal Biosensors to Organophosphate Chemical Toxins Composed of
Polyurethane Immobilized Enzymes. ADA409494, 2001 ECBC Scientific Conference on
Chemical and Biological Defense Research, Hunt Valley, MD, January 2002.
109 D'Agostine, P. A.; Chenier, C.L. Rapid Analysis of Chemical Warfare Agents and their
Hydrolysis Products by Desorption Electrospray Ionization Mass Spectrometry (DESI-MS).
Defence R&D Canada, Technical Memorandum, DRDC Suffield TM 2009-027, October
2009.
110 Creasy, W. R.; Brickhouse, M. D.; Morrissey, K. M.; Stuff, J. R.; Cheicante, Jr., R. L.; Ruth,
J.; Mays, J.; Williams, B. R. Analysis of chemical weapons decontamination waste from old
ton containers from Johnston Atoll using multiple analytical methods. Environmental Science
& Technology. 33, 1999, pp. 2157-2162.
111 Tomkins, B.A.; Griest, W.H.; Hearle, D.R. Determination of Small Dialkyl
Organophosphonates at Microgram/L Concentrations in Contaminated Groundwaters Using
Multiple Extraction Membrane Disks. CONF-9608262. Rocky Mountain Arsenal, U.S.
Dept. of Energy, 1996.
112 Guan, J.; Chan, M.; Brooks, B.W.; Rohonczy, L. Influence of temperature and organic load
on chemical disinfection of Geobacillus stearothermophilus spores, a surrogate for Bacillus
anthracis. The Canadian Journal of Veterinary Research. 77, 2013, pp 100-104.
51
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Attachment A - Literature Assessment Factor Rating
Rate each factor from 0 (not applicable) to 5 (strongly applicable) and total for the overall rating.
Title of Secondary Data Source:
Reviewer:
Rating (1-5)
Focus
The work not only addresses the area of inquiry under consideration but also
contributes to its understanding; it is germane to the issue at hand.
Verity
The data are consistent with accepted knowledge in the field or, if not, the new
or varying data are explained within the work. The data fit within the context
of the literature and are intellectually honest and authentic.
Integrity
The data are structurally sound and present a cohesive story. The design or
research rationale is logical and appropriate.
Rigor
The work is important, meaningful, and non-trivial relative to the field. It
exhibits sufficient depth of intellect rather than superficial or simplistic
reasoning.
Utility
The work is useful and professionally relevant. It makes a contribution to the
field in terms of the practitioners' understanding or decision-making on the
topic.
Clarity
The work is written clearly, not dependent on jargon. The writing style is
appropriate to the nature of the study.
Soundness
The extent to which the scientific and technical procedures, measures,
methods, or models employed to generate the information is well documented
and reasonable for, and consistent with, the intended application.
Uncertainty and
Variability
The extent to which the variability and uncertainty (quantitative and
qualitative) in the information or in the procedures, measures, methods, or
models are evaluated and characterized.
Evaluation and
Review
The extent of independent verification, validation, and peer review of the
information or of the procedures, measures, methods, or models.
Total:
Overall Rating:
3545 Source and secondary data are deemed to be high quality
2534 Source and secondary data are deemed to be moderately high quality
1524 Source and secondary data are deemed to be lower quality article but with
some useful information
<15 Unacceptable/Do not use
52
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Attachment B - Source Quality Evaluations
Source quality evaluations (document type designations and Literature Assessment Factor Rating
scores) for all sources of sufficient quality that were collected during the literature search,
included in the source compilation document (refer to Section 2.6), and discussed in Section 3,
are provided below. Refer to Section 5 for bibliographic citations (according to the reference
number) for each source.
Refere
Source
Literature Assessment Factor Rating Score
nee
Numbe
r*
nt Type
Designat
ion
Foe
us
Veri
ty
Integri
ty
Rig
or
Utili
ty
Clari
ty
Soundn
ess
nty and
Variabili
ty
Evaluati
on and
Review
Tot
al
7
G
5
5
4
4
4
5
4
4
4
39
8
G
5
4
4
4
4
2
4
4
4
35
9
G
4
4
4
4
4
3
4
3
3
33
10
G
4
4
4
5
5
4
4
4
4
38
11
G
5
5
4
5
4
5
4
4
4
40
12
G
3
4
3
3
3
1
2
2
3
24
13
G
4
4
3
3
4
4
3
3
3
31
14
G
4
5
4
5
4
4
3
4
4
37
15
G
4
4
3
4
4
3
3
3
2
30
16
G
3
4
4
2
3
4
3
3
4
30
17
G
4
4
4
3
4
4
3
4
4
34
18
G
5
5
5
4
4
4
4
3
4
38
19
G
3
4
4
2
3
4
4
3
4
31
20
G
4
5
5
5
5
5
5
4
5
43
21
G
3
3
3
4
4
3
3
3
4
30
22
G
5
4
4
5
5
4
5
5
4
41
23
G
4
4
4
3
3
4
4
2
3
31
24
G
5
5
5
5
4
5
5
5
3
42
25
G
4
4
4
4
4
5
4
3
3
35
26
G
4
4
3
4
4
4
4
3
3
33
27
G
2
4
4
4
3
5
3
1
4
30
28
G
3
4
2
3
4
4
3
0
3
26
29
G
4
4
4
4
4
3
3
3
4
33
30
A
5
3
5
5
5
4
5
3
3
38
31
V
4
3
4
3
1
3
3
0
0
21
32
V
3
3
4
4
3
4
0
3
3
27
33
G
3
4
3
3
3
3
2
0
3
24
34
G
4
4
4
3
4
3
3
3
4
32
35
B
2
5
5
3
3
5
4
2
4
33
36
A
5
4
4
5
5
2
3
3
3
34
37
V
5
3
3
4
4
5
4
3
3
34
38
G
5
4
4
5
5
4
4
4
4
39
39
A
4
3
4
4
4
3
3
3
3
31
40
G
5
4
4
4
4
5
4
4
4
38
41
G
5
5
5
4
5
4
5
5
4
42
42
A
4
4
4
3
4
3
4
3
4
33
43
G
3
4
4
3
4
4
3
2
4
31
44
G
4
4
4
3
5
5
3
3
3
34
45
G
4
5
4
4
5
3
4
4
4
37
53
-------
Literature Assessment Factor Rating Score
Uncertai _ . .
Foe Veri Integri Rig Utili Clari Soundn nty and vaua i j()t
us ty ty or ty ty ess Variabili al
, Review
ty
46
G
4
5
5
4
4
5
4
4
4
39
47
V
4
4
4
4
4
3
3
3
3
32
48
G
4
4
4
4
4
4
4
3
4
35
49
G
4
3
3
3
4
4
3
3
4
31
52
G
4
5
5
4
4
5
4
4
4
39
53
A
4
5
4
5
4
4
4
4
4
38
54
G
5
5
5
5
5
5
4
5
4
43
55
G
4
3
4
4
4
4
4
4
4
35
56
G
4
5
4
4
5
5
4
4
4
39
57
B
5
4
5
5
5
4
5
4
5
42
58
G
5
4
5
5
4
4
4
5
4
40
59
G
4
4
4
4
4
3
4
4
4
35
60
V
4
4
4
3
4
4
4
3
4
34
61
s
4
4
4
5
4
2
4
4
4
35
62
G
5
4
4
4
4
4
4
3
3
35
63
G
5
5
4
5
5
3
4
4
4
39
64
G
4
5
4
4
4
4
4
4
4
37
65
A
5
5
5
5
5
4
4
5
4
42
66
A
5
5
4
5
5
4
5
4
4
41
67
G
5
4
4
4
5
4
4
4
4
38
68
A
5
4
5
4
4
5
4
4
3
38
69
A
5
4
4
5
4
3
4
4
4
37
70
G
4
5
4
5
4
3
3
5
4
37
71
G
5
4
4
5
4
4
4
4
4
38
72
G
4
5
4
4
5
4
4
4
4
38
73
G
5
5
4
4
5
4
4
5
5
41
74
G
5
5
4
4
5
3
5
4
5
40
75
A
3
3
3
4
5
3
2
2
1
26
76
G
4
4
4
4
4
4
3
3
3
33
77
G
5
4
5
4
4
4
4
4
3
37
78
G
4
3
4
4
4
4
4
3
3
33
79
A
5
5
5
5
5
5
4
5
5
44
80
V
4
4
4
5
4
5
3
3
4
36
81
V
3
4
4
3
3
4
3
3
3
30
82
B
4
4
4
4
4
3
3
3
3
32
83
A
4
4
4
4
4
4
3
3
3
33
84
A
4
4
4
4
3
3
3
4
3
32
85
G
3
4
4
3
3
4
3
2
3
29
86
A
5
5
4
5
4
4
5
4
4
40
87
G
4
5
5
4
4
5
4
4
4
39
88
G
5
4
4
5
4
3
4
4
4
37
89
V
4
4
4
4
3
3
3
3
3
31
90
G
5
5
5
4
4
5
4
4
4
40
91
G
5
3
5
4
4
4
4
4
4
37
92
G
4
4
4
3
5
4
4
2
4
34
93
G
4
4
4
4
3
3
3
3
4
32
94
G
3
4
5
3
4
5
5
3
4
36
95
G
5
4
4
5
4
3
4
4
4
37
96
G
4
3
3
3
4
3
4
3
4
31
Refere
nee
Numbe
Source
Docume
nt Type
Designat
54
-------
Refere
nee
Source
Docume
nt Type
Foe Veri Integri Rig
Literature Assessment Factor Rating Score
Uncertai
i Rig Utili Clari Soundn nty and
Evaluati
mimue
r*
Designat
ion
us
ty
ty
or
ty
ty
ess
Variabili
ty
on anu
Review
al
97
G
4
4
5
5
4
2
3
4
4
35
98
G
4
4
4
4
4
4
3
4
4
35
99
G
4
4
4
4
4
4
3
4
4
35
100
G
4
4
4
4
3
3
4
4
4
34
101
A
4
4
4
3
4
2
2
3
3
29
102
G
4
4
4
4
4
4
4
4
4
36
103
G
4
4
4
4
4
4
4
4
4
36
104
V
4
0
3
3
3
4
0
0
0
17
105
G
5
4
4
4
5
4
3
5
4
38
106
G
4
4
4
5
4
2
5
3
4
35
107
G
4
4
4
4
5
4
4
4
4
37
108
V
4
2
3
3
3
3
2
2
2
24
109
V
3
3
4
3
3
4
3
3
3
29
110
G
4
4
5
3
4
3
3
3
4
33
111
B
3
3
4
3
3
4
3
2
2
27
*: Reference IDs 1-6 and 50,51 are report references and not literature review references and are therefore not
assessed
55
-------
vvEPA
United States
Environmental Protection
Agency
PRESORTED STANDARD
POSTAGE & FEES PAID
EPA
PERMIT NO. G-35
Office of Research and Development (8101R)
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