Shipment, Preservation, and Analysis of Chemical Warfare Agents (CWAs) in Environmental Matrices


E
PA
www.epa.gov/research ^
technical BRIEF
BUILDING A SCIENTIFIC FOUNDATION FOR SOUND ENVIRONMENTAL DECISIONS
Shipment, Preservation,
Warfare Agents (CWAs)
Matrices
INTRODUCTION
Recent uses of chemical warfare agents (CWA) in the Middle East1
and United Kingdom2 have highlighted the need for methods to
characterize the nature and extent of CWA contamination in the
environment. CWA blister agents of concern include sulfur mustard (HD)
Lewisite (L), while nerve agents of concern include cyclohexyl sarin (GF),
sarin (GB), soman (GD), and 0-ethyl-S-(2-diisopropylamino-ethyl)-
methyl-phosphonothiolate (VX). The lethality of these agents requires
verified and sensitive sampling and analysis methods.
The U.S. Environmental Protection Agency (EPA) is responsible for
remediating civilian areas contaminated with CWAs. Historically there
were a lack of available environmental CWA methods, making sample
collection, preservation, and analysis challenging. Furthermore, the
number of anticipated samples collected during remediation would
have undoubtedly overwhelmed laboratory capacity and capability
and delayed results needed to support decision-making during
decontamination and clearance,
To address the challenge of a timely response and remediation effort,
the EPA has developed the capability and capacity to handle these
agents. Over twenty gas-chromatography mass spectrometry (GC-MS)
analysis methods, liquid-chromatography mass spectrometry (LC-MS)
analysis methods, and study reports were developed for use by EPA's
national network of laboratories specifically dedicated to
environmental samples, the Environmental Response Laboratory
Network (ERLN) and the Water Laboratory Alliance (WLA). Study
reports discuss the advantages and disadvantages of the available
methods and other available resources for CWA analysis. All of the
work, described herein, addresses the gap for improving laboratory capacity and capability to collect,
preserve, handle, process, and analyze CWA samples in environmental matrices. Furthermore, these
U.S. EPA's Homeland Security
Research Program (HSRP) develops
products based on scientific research
and technology evaluations. Our
products and expertise are widely
used in preventing, preparing for,
and recovering from public health
and environmental emergencies that
arise from terrorist attacks,
accidents, or natural disasters. Our
research and products address
biological, radiological, or chemical
contaminants that could affect
indoor areas, outdoor areas, or
water infrastructure. HSRP provides
these products, technical assistance,
and expertise to support EPA's roles
and responsibilities under the
National Response Framework,
statutory requirements, and
Presidential Directives,
1	Washington Post, https://www.wasliingtonpost.coin/world/niiddle_east/global-watchdog-sarin-was-used-in-deadly-
syria-attack/2017/04/19/be6cf350-2528-lle7-836b-e91bll3bfi)60_story.htnil?noredirect=on&utm_terin=.d98ee77f99cd
(accessed September 2018))
2	Novichok nerve agent use in Salisbury: UK government response, March to April 2018.
https://www.gov.uk/government/news/novichok-nerve-agent-use-in-salisbury-uk-goveriiment-response (accessed
September 2018)
and Analysis of Chemical
in Environmental
U.S. Environmental Protection Agency
Office of Research and Development, Homeland Security Research Program
EPA/600/S-18/332
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methods and reports increase ERLN's capability and capacity to analyze environmental samples and ensure
that analytical results generated by the various labs conducting analysis are comparable.
CHEMICAL WARFARE AGENT (CWA) ANALYTICAL METHOD DEVELOPMENT
HSRP initially developed CWA analytical methods for HD, GF, GB, and VX in various environmental matrix
types (e.g., water, soil, surfaces). The CWA methods were multi-laboratory evaluated to verify their use for
an environmental response. Method data are listed in Table 1. HSRP also established an ultra-dilute
standards program for these CWAs. These standards are required for ERLN laboratories across the country
to have the capability to store and analyze CWA contaminated samples. Ultra-dilute standards were
evaluated, including the procedures for preservation, shipping, handling, and storage of the standards.
These studies showed that ERLN laboratories can use the ultra-dilute standards up to six months, if
preservation and storage requirements are followed.
These methods can be found within the EPA Homeland Security Research Program's (HSRP) Environmental
Sampling and Analytical Methods Program (ESAM). ESAM is composed of documents and information
supporting field and laboratory efforts for site characterization, remediation and release, including the
Selected Analytical Methods for Environmental Remediation and Recovery (SAM) 2017 document. SAM
provides the single best method for an analyte- environmental matrix pair, which for many of the CWAs is
the HSRP-developed method. ESAM also contains Sample Collection Information Documents (SCIDs), which
provide general sample collection, handling and shipping information for collection of samples analyzed
using the specific methods listed in EPA's SAM document. These methods will improve data comparability
and confidence, permit sharing of the sample load between laboratories, and simplify the task of
outsourcing analytical support to the commercial laboratory sector, if required. In addition, use of these
methods will help improve the follow-up activities of validating results, evaluating data, and creating and
communicating risk-management decisions. Overall, ESAM facilitates a coordinated response to a chemical
contamination incident.
ADDITIONAL CWA METHOD DEVELOPMENT AND STUDY REPORTS
HSRP developed additional CWA methods for Lewisite (L) and hazardous CWA degradation products [e.g., S-
[2-(diisopropylamino)ethyl] hydrogen methylphosphonothioate (EA2192), 2-chlorovinylarsonous acid
(CVAA), and (2-chlorovinyl)arsonic acid (CVAOA)] in various environmental matrices. Although these
methods are not multi-laboratory verified, the method evaluation reports are available on EPA's Homeland
Security webpage. ESAM. or in EPA's Science Inventory. These methods (and additional CWA degradation
methods) are also available in SAM for the EPA and ERLN to use during characterization activities. Method
data for these select agents and degradation products are listed in Table 1.
Table 1: Select CWA and CWA Degradation Methods*
Analyte
Method Detection Limit
Reporting Limit
(mg/L)
Analytical Run Time
(minutes)
water
(Hg/L)
soil
(Hg/kg)
wipes
(Hg/wipe)
GB
0.1
0.16
0.002
0.01
12.75
GD
0.08
0.12
0.003
0.005
12.75
GF
0.1
0.17
0.003
0.01
12.75
HD
0.08
0.09
0.003
0.005
12.75
VX
0.1
0.33
0.006
0.01
12.75
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EA2192
0.013
-
-
0.000125
30
L
41
28
0.38
0.02
38
CVAA
41
28
0.38
0.02
38
CVAOA
41
28
0.38
0.02
38
* Information in table taken from the referenced methods. These methods were not developed for compliance monitoring and they
should not be considered as having EPA approval for compliance monitoring or any other regulatory program.
LINKS TO CHEMICAL METHODS
• ASTM. 2016. "Method D7597-16: Standard Test Method for Determination of Diisopropyl
Methylphosphonate, Ethyl Hydrogen Dimethylamidophosphate, Ethyl Methylphosphonic Acid, Isopropyl
Methylphosphonic Acid, Methylphosphonic Acid and Pinacolyl Methylphosphonic Acid in Water by
Liquid Chromatography/Tandem Mass Spectrometry." West Conshohocken, PA: ASTM International.
http://www.astm.org/Standards/D7597.htm
• ASTM. 2016. "Method D7598-16: Standard Test Method for Determination of Thiodiglycol in Water by
Single Reaction Monitoring Liquid Chromatography/Tandem Mass Spectrometry." West Conshohocken,
PA: ASTM International. http://www.astm.org/Standards/D7598.htm
• ASTM. 2016. "Method D7599-16: Standard Test Method for Determination of Diethanolamine,
Triethanolamine, A/-Methyldiethanolamine and A/-Ethyldiethanolamine in Water by Single Reaction
Monitoring Liquid Chromatography/Tandem Mass Spectrometry (LC/MS/MS)." West Conshohocken, PA:
ASTM International. http://www.astm.org/Standards/D7599.htm
• ASTM. 2016. "Method E2787-11: Standard Test Method for Determination of Thiodiglycol in Soil Using
Pressurized Fluid Extraction Followed by Single Reaction Monitoring Liquid Chromatography/Tandem
Mass Spectrometry." West Conshohocken, PA: ASTM International.
http://www.astm.org/Standards/E2787.htm
• ASTM. 2016. "Method E2838-11: Standard Test Method for Determination of Thiodiglycol on Wipes by
Solvent Extraction Followed by Liquid Chromatography/Tandem Mass Spectrometry." West
Conshohocken, PA: ASTM International. http://www.astm.org/Standards/E2838.htm
• ASTM. 2016. "Method E2866-12: Standard Test Method for Determination of Diisopropyl
Methylphosphonate, Ethyl Methylphosphonic Acid, Isopropyl Methylphosphonic Acid,
Methylphosphonic Acid and Pinacolyl Methylphosphonic Acid in Soil by Pressurized Fluid Extraction and
Analyzed by Liquid Chromatography/Tandem Mass Spectrometry." West Conshohocken, PA: ASTM
International. http://www.astm.org/Standards/E2866.htm
• Dynamac Corporation. 2012. "Standard Operating Procedure for the Determination of Ethanolamines,"
Dynamac SOP L-A-303 Rev. 2. Copies of this analytical protocol may be requested from NHSRC at
https://www.epa.gov/homeland-securitv-research/forms/contact-us-about-homeland-securitv-research
• Sample Collection Information Document for Chemicals. Radiochemicals & Biotoxins (SCID) (EPA/600/R-
17/389)
• Selected Analytical Methods for Environmental Remediation and Recovery (SAM)-2017 [(EPA/600/R-
17/356) (accessed August 2018)]
• Shoemaker, J.A. 2009. "Method 538: Determination of Selected Organic Contaminants in Drinking Water
by Direct Aqueous Injection-Liquid Chromatography/Tandem Mass Spectrometry (DAI-LC/MS/MS)."
Revision 1.0. Cincinnati, OH: U.S. EPA. EPA/600/R-09/149U.S. EPA and CDC. 2011. "Surface Analysis
Using Wipes for the Determination of Nitrogen Mustard Degradation Products by Liquid
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Chromatography/Tandem Mass Spectrometry (LC/MS/MS)." Cincinnati, OH: U.S. EPA. EPA/600/R-
11/143. http://www2.epa.gov/sites/production/files/2015-07/documents/epa-60Q-r-ll-143.pclf
•	U.S. EPA and CDC. 2013. "Surface Analysis of Nerve Agent Degradation Products by Liquid
Chromatography/Tandem Mass Spectrometry (LC/MS/MS)." Cincinnati, OH: U.S. EPA. EPA/600/R-
13/224. https://www.hsdl.org/?abstract&did=74648
•	U.S. EPA. 2013. "Verification of Methods for Selected Chemical Warfare Agents (CWAs)." Washington,
DC: U.S. EPA. EPA/600/R-12/653.
https://cfpub.epa.gov/si/si public record report.cfm?dirEntrvld=248575
•	U.S. EPA. 2015. "Extraction and Analysis of Lewisite 1, by its Degradation Products, Using Liquid
Chromatography Tandem Mass Spectrometry (LC/MS/MS)," Revision 1. Washington, DC: U.S. EPA.
EPA/600/R-15/258. https://cfpub.epa.gov/si/si public record report.cfm?dirEntrvId=310272
•	U.S. EPA. 2016. "Analytical Protocol for VX Using Gas Chromatography/Mass Spectrometry (GC/MS)."
Cincinnati, OH: U.S. EPA. EPA/600/R-16/116.
https://cfpub.epa.gov/si/si public record report.cfm?dirEntrvId=337633
•	U.S. EPA. 2016. "Analytical Protocol for Cyclohexyl Sarin, Sarin, Soman and Sulfur Mustard Using Gas
Chromatography/Mass Spectrometry." Cincinnati, OH: U.S. EPA. EPA/600/R-16/115.
https://cfpub.epa.gov/si/si lab search results.cfm?fed org id=1253&subiect=Homeland%20Securitv%
20Research&view=desc&sortBv=pubDateYear&showCriteria=l&count=25&searchall=%22SAM%20QR%
20%27analvtical%20methods%27%200R%20%27analvtical%20method%27%200R%20analvsis%22%27
•	U.S. EPA. 2016. "Adaptation of the Conditions of U.S. EPA Method 538 for the Analysis of a Toxic
Degradation Product of Nerve Agent VX (EA2192) in Water by Direct Aqueous Injection- Liquid
Chromatography/Tandem Mass Spectrometry." Cincinnati, OH: U.S. EPA. EPA/600/R-15/097.
https://cfpub.epa.gov/si/si public record report.cfm?dirEntrvld=311259
•	U.S. EPA. 2016. "Analytical Protocol for Measurement of Extractable Semivolatile Organic Compounds
Using Gas Chromatography/Mass Spectrometry." Cincinnati, OH: U.S. EPA. EPA/600/R-16/114.
https://cfpub.epa.gov/si/si lab search results.cfm?fed org id=1253&subject=Homeland%20Securitv%
20Research&view=desc&sortBy=pubDateYear&showCriteria=l&count=25&searchall=%22SAM%20OR%
20%27analvtical%20methods%27%200R%20%27analvtical%20method%27%200R%20analysis%22%27
CONTACT INFORMATION
For more information, visit the EPA Web site at www.epa.gov/nhsrc.
Technical Contacts: Stuart Willison (willison.stuart@epa.gov); Romy Campisano (campisano.romy@epa.gov)
General Feedback/Questions: Kathy Nickel (nickel.kathy@epa.gov)
If you have difficulty accessing this PDF document, please contact Kathy Nickel (nickel.kathy@epa.gov) or
Amelia McCall (mccall.amelia@epa.gov) for assistance.
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September 2018
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