Gravett M R, Hopkins F B, Self A J, Webb A J, Timperley C M, Riches J R
Detection Department, Defence Science and Technology Laboratory (Dstl), G12, Building 383B Porton Down, Salisbury, Wiltshire, SP4 0JQ, UK.
Anal Bioanal Chem. 2014 Aug;406(21):5121-35. doi: 10.1007/s00216-014-7963-9. Epub 2014 Jun 28.
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.
如果涉嫌使用有机磷神经毒剂,各类环境样本均可接收用于分析。这些样本可能包括从疑似化学袭击现场收集的已去污和烧焦的物质。在其他情况下,可能会采集此类物质样本以确认化学武器试验地点或秘密实验室,这些实验室已进行去污和焚烧以防止被发现。为具备应对这些突发情况的分析能力,我们对基于助燃剂的火灾及液体去污对被神经毒剂O - 乙基 - S - 2 - 二异丙氨基乙基甲基硫代磷酸酯(VX)污染的土壤的影响进行了初步调查。目标如下:(a)确定在航空燃料引发的基于助燃剂的火灾后,包括在用去污溶液2(DS2)或次氯酸钠水溶液去污后,土壤中是否可检测到VX或其降解产物;(b)开发分析方法以支持对浸有助燃剂、已去污和烧焦的土壤进行法医分析;(c)为今后此类实验的设计提供参考,以提高分析的准确性。我们的结果首次表明,现代分析技术可用于识别在基于助燃剂的火灾后以及化学去污再火灾后的受污染土壤中的残留VX及其降解产物。对受污染烧焦土壤以及添加VX的烧焦土壤中VX及其杂质/降解产物的气相色谱 - 质谱(GC - MS)图谱进行比较,结果表明火灾导致了甲基膦酸二乙酯和O,S - 二乙基甲基硫代磷酸酯的产生(通过未知机制)。鉴定出的其他产物表明存在化学去污,其中一些提供了所使用去污剂种类的证据,例如在用DS2去污后出现的2 - 甲氧基乙基甲基膦酸乙酯和双(2 - 甲氧基乙基)甲基膦酸酯。本文介绍了适用于调查浸有助燃剂和去污剂的土壤样本制备程序和分析方法。在所研究的所有条件下均检测到了VX及其降解产物和/或杂质,这表明基于助燃剂的火灾以及基于液体的去污再火灾不太可能阻止获取化学战剂(CWA)试验的证据。这是首次发表的关于基于助燃剂的火灾对环境样本中化学战剂影响的研究。研究结果将为全球国防和安全相关组织提供参考,并支持禁止化学武器组织(OPCW)的核查活动,该组织因在消除化学武器方面的广泛努力而荣获2013年诺贝尔和平奖。