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CWA and Degradation Product
Analysis for Matrix-Specific
Environmental Samples
Stuart A. Willison
U.S. EPA, National Homeland Security Research Center
National Environmental Monitoring Conference, San Antonio, TX
8/9/2013 1
U.S. Environmental Protection Agency
Outline
National Homeland Security Research
Program
• Drivers/Priorities
• Research Supporting EPA’s Response to Contamination
• Analytical Capability for CWAs in Target Matrices
(Sampling and Analysis)
• Analytical Capability for CWA Degradation Products in
Target Matrices (Sampling and Analysis)
2
EPA Homeland Security Drivers
and Responsibilities
3
Drivers
Bioterrorism Act (2002)
Homeland Security Presidential Directives (2003-2008)
National Response Framework (revised 2008)
Elements of:
– Comprehensive Environmental Response, Compensation and Liability Act
– Emergency Planning and Community Right-to-Know Act
– Clean Water Act
– Safe Drinking Water Act
– Oil Pollution Act
– Clean Air Act
Responsibilities • Protect water systems from attacks and
for detecting and recovering from successful attacks affecting water systems by leading efforts to provide States and water utilities guidance, tools and strategies. EPA is the federal government Sector Specific Agency (SSA) lead for water infrastructure.
• Decontaminate buildings and outdoor areas impacted by a terrorist attack by leading efforts to establish clearance goals and clean up.
• Develop a nationwide laboratory network
with the capability and capacity to analyze
for chemical, biological and radiological
agents for routine monitoring and in
response to a terrorist attack.
Food Safety
Modernization Act of 2010 “provide support for, and technical assistance to, State,
local, and tribal governments in preparing for, assessing,
decontaminating, and recovering from an agriculture or
food emergency”
Partner/Stakeholder Priorities
4
Research for Chemical Warfare Agents (CWAs)
and their degradation products in
environmental matrices to include:
• Analytical protocols
• Sampling different matrices (surfaces, soils, water)
• Stability studies for CWA and degradate standards
Increased laboratory capability and capacity
for CWA and degradate sampling/analysis.
5
Potential approaches
• Methods which can be applied to multiple labs for
workload distribution by the Environmental Response
Laboratory Network (ERLN) www.epa.gov/oemerln1
• High throughput sampling techniques and laboratory
analysis techniques, including automated or rapid
method capabilities
Meeting Lab Throughput
Requirements
Sampling and Analysis • To detect contaminants
• To determine extent of
contamination
Research to Support EPA’s Response to
Contamination Events and Site-Specific
Risk-Based Decisions
Informs Risk
Management Decisions
Risk assessment • To assess potential risk of
exposure, at harmful doses,
and identify exposure
pathways
7
• Analytes
– Tabun (GA), sarin (GB), soman (GD), cyclosarin (GF), sulfur
mustard (HD), nitrogen mustards (HN-1 & HN-3), lewisite (L), VX
and Russian VX (R-VX)
– Nitrogen mustard degradates
– Nerve agent degradates
Research Focused Towards
Chemical Warfare Agents
• Analytical Techniques
– Gas Chromatography/Time-of-Flight Mass Spectrometry
(GC/TOF-MS)
– Liquid Chromatography/Tandem Mass Spectrometry
(LC/MS/MS)
• Sample Types
– Soil
– Water
– Surface Analysis via Wipes
8
Residential Soil
(µg/kg)
Water
(µg/L)
Wipe
(ng/kg)
Agent MDL MDL MDL
GB 0.22 0.14 0.0030
GD 0.67 0.11 0.0017
GF 0.12 0.14 0.0047
HD 0.12 0.10 0.0015
VX 0.41 0.23 0.0080
Method Detection Levels (MDL) for G-series, HD and VX
by GC/TOF-MS
9
Residential Soil
(mg/kg)
Water
(µg/L)
Wipe
(ng/kg)
Agent MDL MDL MDL
GA 0.00033 0.13 11
HN1 0.00057 0.084 2.3
HN3 0.0016 0.72 35
R-VX 0.015 22 440
Method Detection Levels (MDL)
for GA, HN-1, HN-3 and R-VX by
GC/TOF-MS
Stability Study for Ultra-Dilute
CWA Standards
10
• One year stability study for 10 ppm standards of
GB, GD, GF, HD and VX • Flame-sealed ampoules - one year shelf-life
• Opened ampoules ~ 2-6 months depending on analyte
IMPACT:
• Dilute concentrations allow for shipment to ERLN labs
without special requirements.
• Provides stability of analyte standards over time in
order to ensure availability of standard and reduce
costs.
• Additional preservation study with only VX
Japan Subway Attack by Use of a Nerve
Agent
11
Kasumigaseki station was one of the many subway stations
affected during the attack
12
Sample Collection During an
Incident
13
31P NMR results: (a) 0.1 days, (b) 6 days, (c) 10 days,
(d) 14 days, (e) 17 days, (f) 20 days, and (g) 24 days
after the contamination.
Persistence of VX and Degradation
Product on Asphalt
Degradation profile of VX on ground asphalt.
Columbus et. al., Environ. Sci. Technol., 2012, 46, 3921−3927
Importance of Degradate Analysis
IMPACT:
• Identifies potentially toxic degradates, which may
persist
• Degradate analysis allows samplers to identify
potentially concentrated areas of concern for parent
compound
• Ensure remediation efforts can be completed
14
15
Challenges of Analysis Procedure
for Degradation Products
• Most CWA degradation products are not amenable to
gas-chromatography/mass spectrometry (GC-MS)
analysis without a derivatization step
• Step can be time-consuming with often times
incomplete conversion to the derivatized product
• Liquid chromatography/mass spectrometry (LC-MS)
offers advantages over GC-MS because polar analytes
can be directly analyzed
16
Optimization of Analysis Procedure
for Degradation Products
• Optimal eluents, chromatography separation, mass
spectrometric parameters were characterized with
low (ppb) detection limits*
• Optimal wipe investigated: cotton gauze, non-woven
polyester fiber cloth, pre-cleaned textile wipe, glass
fiber filter, and filter paper
• Surface evaluation included the following surfaces:
galvanized steel, glass, laminate, vinyl tile, treated
wood, painted drywall
* EPA Reports: EPA 600/R-11/143 and EPA/600/R-12/581
Hydrolysis Pathway of Nitrogen
Mustards in the Environment
17
18
LC-MS/MS Chromatogram of Wipe
Blanks*
* EPA Reports: EPA 600/R-11/143 and EPA/600/R-12/581
8/9/2013 19
Analyte TEA EDEA MDEA DEA
Wipe % Recovery
(n=7)
% Recovery
(n=7)
% Recovery
(n=7)
% Recovery
(n=7)
Approximate Spike
Concentration
(ng/mL)
10 50 10 50 10 50 10 50
Cotton Gauze 680 150 35 28 49 30 1600 430
Non-woven
polyester cloth 510 480 130 82 120 75 370 190
Alphawipe™ 9 23 18 22 17 21 10 18
Filter Paper 74 82 87 100 76 83 62 77
LC-MS/MS Chromatogram of Spiked
Wipe Samples
20
LC-MS/MS Chromatogram of Nitrogen
Mustard Degradation Products
Wipe 2 Wipe 1
Analyte Recoveries from Surface
Wiping*
21
Analyte TEA1 EDEA MDEA DEA1
Surface % Recovery
(n=7)
% Recovery
(n=7)
% Recovery
(n=7)
% Recovery
(n=7)
Laminate 81-99 47-71 66-80 71-81
Metal 20-46 49-56 54-74 62-79
Glass 91-150 31-36 52-61 59-81
Vinyl Tile 41-79 7-22 51-61 25-39
Painted
Drywall2 19 8 17 13
Wood2 2 1 2 1
1 Recoveries were subtracted from surface blanks for a
representative recovery of target analytes 2 Recoveries were only possible at highest spike concentration
* Results from surface wiping were performed using filter paper
22
LC-MS/MS Chromatogram of Nitrogen
Mustard Degradation Products*
* S.A. Willison, J. Chromatogr. A, 1270 (2012) 72–79
23
Hydrolysis Pathway of VX
in the Environment
24
Wipe Cotton
Gauze
Non-woven
Polyester
Cloth
Alphawipe™ Glass Fiber
Filter
Filter
Paper
Analyte %
Recovery
%
Recovery
%
Recovery
%
Recovery
%
Recovery
MPA 65 50 57 88 87
EMPA 67 54 57 89 89
IMPA 42 34 44 75 81
EHDMAP 56 59 74 75 78
PMPA 72 65 83 90 88
LC-MS/MS Chromatogram of Spiked
Wipe Samples
25
Laminate Surface
Filter Paper Cotton Gauze
Analyte %
Recovery
%
Recovery
%
Recovery
%
Recovery
Ionization
Mode ESI + ESI - ESI + ESI -
IMPA 67 98 72 79
MPA 102 55 122 35
EMPA 84 96 74 88
EHDMAP 57 67 53 71
PMPA - 85 - 79
LC-MS/MS Chromatogram of Spiked
Surface Samples
26 * manuscript in preparation
Enhancing Throughput for LC-MS/MS
Analytical Methods*
27
Summary
• Wipe selection may impact analysis capabilities due to
the presence of native contaminants/interferences
• Sampling and analysis capabilities for CWA and their
degradation products have been developed and tested
for a variety of target matrices
• Rapid analysis methods will enhance laboratory
throughput capability and capacity, improve detection
levels, and generate less waste
• CWA ultra-dilute stability studies ensure quality and
availability of standards during an incident
Acknowledgements
28
Co-authors/Collaborators: Romy Campisano1
Tonya Nichols1
Terry Smith2
Carolyn Koester3
Bob Streicher4
1U.S. EPA, National Homeland Security Research Center 2U.S. EPA, Office of Emergency Management 3Lawrence Livermore National Laboratory 4National Institute for Occupational Safety and Health
Website: www.epa.gov/sam
SAM 2012 Published: July 2012
DISCLAIMER: The U.S. EPA through its Office of Research and
Development partially funded the research described in this
presentation. It has been reviewed by the Agency but does not
necessarily reflect the Agency’s views. No official endorsement
should be inferred. EPA does not endorse the purchase or sale
of any commercial products or services.
Stuart Willison, Ph.D.
Research Chemist, Threat and
Consequence Assessment Division
[email protected]; 513-569-7253