Abstract
AbstractSensitive and reliable analysis of alkylphosphonic acids (APAs) and 2-(N,N-dialkylamino)ethanesulfonic acids (SAs), the degradation products of chemical warfare agents (CWAs), is one of the most important tasks for verification of the Chemical Weapons Convention (CWC). Unambiguous identification of these chemicals is required in a variety of environmental matrices, including soil and water. These acids with low volatility are very polar, and efficient and reliable methylation methods for their derivatization are needed for analysis with gas chromatography–mass spectrometry (GC–MS). In this study, the derivatization conditions for trimethylsilyldiazomethane (TMSDAM) methylation were optimized for rapid GC–MS screening. Optimized methylation of APAs and SAs with TMSDAM was compared with methylation with diazomethane. The TMSDAM methylation of SAs and benzilic acid was further compared with silylation with N-methyl-N-(tert-butyldimethylsilyl)trifluoroacetamide. The significance and necessity of cation exchange prior to derivatization and analysis were tested on samples with a high inorganic background. A recommendation to use the method for methylation of water samples and aqueous extracts using TMSDAM is given. The robustness of the method was illustrated by the successful identification of APAs and SAs in aqueous samples from proficiency tests organized by the Organisation for the Prohibition of Chemical Weapons.
Publisher
Springer Science and Business Media LLC
Subject
General Physics and Astronomy,General Environmental Science,General Biochemistry, Genetics and Molecular Biology,General Materials Science,General Chemistry
Reference45 articles.
1. Amphaisri K, Palit M, Mallard G. Thermally assisted methylation and subsequent silylation of scheduled acids of chemical weapon convention for on-site analysis and its comparison with the other methods of methylation. J Chromatogr A. 2011;1218:972–80. https://doi.org/10.1016/j.chroma.2010.12.065.
2. Barr JR, Driskell WJ, Aston LS, Martinez RA. Quantitation of metabolites of the Nerve Agents Sarin, Soman, Cyclohexylsarin, VX, and Russian VX in human urine using isotope-dilution gas chromatography–tandem mass spectrometry. J Anal Toxicol. 2004;28:372–8. https://doi.org/10.1093/jat/28.5.372.
3. Black R, Read R, Riches J, Siegenthaler P, Kuitunen M-L. Derivatisation for gas chromatography. In: Vanninen P, editor. Recommended operating procedures for analysis in the verification of chemical disarmament, 2017 edition. Helsinki: University of Helsinki. 2017; p. 131–152. ISBN 978-951-51-3916-0.
4. Black RM, Muir B. Derivatisation reactions in the chromatographic analysis of chemical warfare agents and their degradation products. J Chromatogr A. 2003;1000:253–81. https://doi.org/10.1016/S0021-9673(03)00183-3.
5. Crenshaw MD, Cummings DB. Demonstration of (trimethylsilyl)diazomethane for the derivatization of acids containing amino and hydroxy groups. In: Proceedings of the ERDEC scientific conference on chemical and biological defense research, Aberdeen Proving Ground, MD, USA; 17–20 Nov 1998; p. 715–721.
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