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Fate of the chemical warfare agent O-ethyl S-2-diisopropylaminoethyl methylphosphonothiolate (VX) on soil following accelerant-based fire and liquid decontamination

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Abstract

In the event of alleged use of organophosphorus nerve agents, all kinds of environmental samples can be received for analysis. These might include decontaminated and charred matter collected from the site of a suspected chemical attack. In other scenarios, such matter might be sampled to confirm the site of a chemical weapon test or clandestine laboratory decontaminated and burned to prevent discovery. To provide an analytical capability for these contingencies, we present a preliminary investigation of the effect of accelerant-based fire and liquid decontamination on soil contaminated with the nerve agent O-ethyl S-2-diisopropylaminoethyl methylphosphonothiolate (VX). The objectives were (a) to determine if VX or its degradation products were detectable in soil after an accelerant-based fire promoted by aviation fuel, including following decontamination with Decontamination Solution 2 (DS2) or aqueous sodium hypochlorite, (b) to develop analytical methods to support forensic analysis of accelerant-soaked, decontaminated and charred soil and (c) to inform the design of future experiments of this type to improve analytical fidelity. Our results show for the first time that modern analytical techniques can be used to identify residual VX and its degradation products in contaminated soil after an accelerant-based fire and after chemical decontamination and then fire. Comparison of the gas chromatography–mass spectrometry (GC-MS) profiles of VX and its impurities/degradation products from contaminated burnt soil, and burnt soil spiked with VX, indicated that the fire resulted in the production of diethyl methylphosphonate and O,S-diethyl methylphosphonothiolate (by an unknown mechanism). Other products identified were indicative of chemical decontamination, and some of these provided evidence of the decontaminant used, for example, ethyl 2-methoxyethyl methylphosphonate and bis(2-methoxyethyl) methylphosphonate following decontamination with DS2. Sample preparation procedures and analytical methods suitable for investigating accelerant and decontaminant-soaked soil samples are presented. VX and its degradation products and/or impurities were detected under all the conditions studied, demonstrating that accelerant-based fire and liquid-based decontamination and then fire are unlikely to prevent the retrieval of evidence of chemical warfare agent (CWA) testing. This is the first published study of the effects of an accelerant-based fire on a CWA in environmental samples. The results will inform defence and security-based organisations worldwide and support the verification activities of the Organisation for the Prohibition of Chemical Weapons (OPCW), winner of the 2013 Nobel Peace Prize for its extensive efforts to eliminate chemical weapons.

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Abbreviations

CI:

Chemical ionisation

CWA:

Chemical warfare agent

CWC:

Chemical Weapons Convention

DS2:

Decontamination Solution 2

EI:

Electron ionisation

GC×GC-ToFMS:

Two-dimensional gas chromatography–time of flight mass spectrometry

GC-MS:

Gas chromatography–mass spectrometry

GC-MS-dFPD:

Simultaneous gas chromatography–mass spectrometry and dual flame photometric detection

LC-HRMS:

Liquid chromatography–high-resolution mass spectrometry

LC-MS:

Liquid chromatography–mass spectrometry

LLE:

Liquid–liquid extraction

OPCW:

Organisation for the Prohibition of Chemical Weapons

SPE:

Solid-phase extraction

UHP:

Ultra-high purity

VX:

O-Ethyl S-2-diisopropylaminoethyl methylphosphonothiolate

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Acknowledgments

We are grateful to the UK Ministry of Defence (MoD) for funding this study and to Professor Vernon Gibson FRS, Chief Scientist of the MoD, for his interest in the research work of our laboratory. © Crown Copyright 2014 Published with permission of the Defence Science and Technology Laboratory on behalf of the Controller of Her Majesty’s Stationery Office.

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Authors and Affiliations

  1. Detection Department, Defence Science and Technology Laboratory (Dstl), G12, Building 383B Porton Down, Salisbury, Wiltshire, SP4 0JQ, UK

    M. R. Gravett, F. B. Hopkins, A. J. Self, A. J. Webb, C. M. Timperley & J. R. Riches

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  1. M. R. Gravett
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  2. F. B. Hopkins
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  3. A. J. Self
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  4. A. J. Webb
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  5. C. M. Timperley
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  6. J. R. Riches
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Correspondence to J. R. Riches.

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Published in the topical collection Analysis of Chemicals Relevant to the Chemical Weapons Convention with guest editors Marc-Michael Blum and R. V. S. Murty Mamidanna.

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Gravett, M.R., Hopkins, F.B., Self, A.J. et al. Fate of the chemical warfare agent O-ethyl S-2-diisopropylaminoethyl methylphosphonothiolate (VX) on soil following accelerant-based fire and liquid decontamination. Anal Bioanal Chem 406, 5121–5135 (2014). https://doi.org/10.1007/s00216-014-7963-9

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  • DOI: https://doi.org/10.1007/s00216-014-7963-9

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