Robert W. Read

Analysis of clothing and urine from moscow theatre siege casualties reveals carfentanil and remifentanil use

On October 26, 2002, Russian Special Forces deployed a chemical aerosol against Chechen terrorists to rescue hostages in the Dubrovka theatre. Its use confirmed Russian military interest in chemicals with effects on personnel and caused 125 deaths through a combination of the aerosol and inadequate medical care. This study provides evidence from liquid chromatography-tandem mass spectrometry analysis of extracts of clothing from two British survivors, and urine from a third survivor, that the aerosol comprised a mixture of two anaesthetics--carfentanil and remifentanil--whose relative proportions this study was unable to identify. Carfentanil and remifentanil were found on a shirt sample and a metabolite called norcarfentanil was found in a urine sample. This metabolite probably originated from carfentanil.

ENVIRONMENTAL AND BIOMEDICAL SAMPLE ANALYSIS IN SUPPORT OF ALLEGATIONS OF USE OF CHEMICAL WARFARE AGENTS

In cases of allegations of use of chemical weapons, supporting evidence may be obtained from the analysis of environmental samples for chemical agents and their degradation products, and from the analysis of biomedical samples for metabolites and covalent adducts of agents with proteins and DNA. The concentrations of analytes may vary from parts per million or higher, down to sub-parts per billion, requiring a number of different mass spectral techniques. This paper provides an overview of the analysis of environmental and biomedical samples associated with the use of chemical warfare agents in the Iraq-Iran conflict, and against the Kurdish population in Iraq. It is based, in part, on a presentation to the International Symposium on NBC Terrorism Defence, held in the 10th anniversary year of the terrorist dissemination of sarin in the Tokyo subway, 20 March 1995.

Hydrolysis and Oxidation Products of the Chemical Warfare Agents 1,2-Bis[(2-chloroethyl)thio]ethane Q and 2,2′-Bis(2-chloroethylthio)diethyl Ether T

Syntheses of diols of structure [HOCH2CH2S]2(CH2)n in 86–95% yield from the sodium salt of 2-mercaptoethanol and Br(CH2)nBr (n = 1 to 5) or in 60–90% yield from 2-chloroethanol and NaS(CH2)nSNa (n = 2 to 5) are described. The diol [HOCH2CH2SCH2CH2]2O was prepared in 82% yield from the sodium salt of 2-mercaptoethanol and [ClCH2CH2]2O, and in 88% yield from 2-chloroethanol and [HSCH2CH2]2O. Mono- and bis-sulfoxides and bis-sulfones of these species were prepared in generally high yield by treatment with an equivalent of KIO4 in aqueous methanol, two equivalents of NaIO4 in aqueous methanol, or four equivalents of H2O2 in trifluoroacetic acid respectively. The compounds are important analytical standards for investigating the fate of the chemical warfare agents sesquimustard Q and oxygen mustard T in environmental samples.

Solid-Phase Synthesis of Some Alkyl Hydrogen Methylphosphonates

Eleven alkyl hydrogen methylphosphonates of structure RO(HO) P(O)Me were made by phosphoramidite chemistry on hydroxymethyl polystyrene resin; R = Me, Et, n -Pr, i -Pr, n -Bu, n -hexyl, n -octyl, cyclohexyl, cycloheptyl, cyclooctyl, and 3,3-dimethylbutan-2-yl ie. pinacolyl or Me 3 C--CH(Me)--.

The development of an analytical method for urinary metabolites of the riot control agent 2-chlorobenzylidene malononitrile (CS)

The analysis of biomedical samples such as urine and blood can provide evidence of exposure to chemicals for a range of applications including occupational exposure monitoring, detection of drugs of abuse, performance enhancement in sport and investigations of poisoning and incapacitation. This paper reports the development of an analytical method for two suspected urinary metabolites of the riot control agent 2-chlorobenzylidene malononitrile (CS): 2-chlorohippuric acid and 2-chlorobenzyl-N-acetylcysteine. 2-Chlorohippuric acid was identified in all 2h post-exposure samples from a set of urine samples taken from army recruits exposed to low levels of thermally dispersed CS during training. 2-Chlorobenzyl-N-acetylcysteine, a metabolite known to be formed in the rat, was not identified in any of the samples. The lower limit of detection (LLOD) for 2-chlorohippuric acid and 2-chlorobenzyl-N-acetylcysteine was 1ng/ml and 0.5ng/ml in pooled urine from the pre-exposed subjects. 2-Chlorohippuric acid was rapidly excreted but was detectable in the urine of 17 of the 19 subjects tested 20h after exposure.

Applications of Mass Spectrometry in Investigations of Alleged Use of Chemical Warfare Agents

Chemical warfare agents were used extensively throughout the twentieth century. Many such uses are well documented; however some allegations of use of chemical warfare agents were not easily confirmed. During the early 1980s interest developed into investigation of alleged use by analytical techniques, particularly mass spectrometry. Since that time, many combined chromatographic – mass spectrometric methods have been developed, both for application to the analysis of environmental and biomedical samples and for investigation of physiological interactions of chemical warfare agents. Examples are given of some of the investigations in which the author has been involved, including those into Yellow Rain and uses of chemical warfare agents in Iraq and Iran. These examples illustrate the use of combined chromatographic-mass spectrometric methods and emphasise the importance of controls in analytical investigations.