title: Determination of Lewisites and their hydrolysis products in aqueous and multiphase samples by in-sorbent tube butyl thiolation followed by thermal desorption-gas chromatography-full scan mass spectrometry.
abstract: A rapid, sensitive and robust method for determining the chemical warfare agents Lewisites and their hydrolysis products in aqueous and multiphase sample matrices has been developed as an extension of the previous work (Terzic, 2010 [32]). In the new method, the acidification of the sample and use of 1-butanethiol derivatisation instead of trimethylsilylation significantly improved both, qualitative and quantitative aspects of targeted analysis of Lewisite species. The limit of detection was ≤100ng/ml in full scan MS, with sample volume of 10μl only. The whole sample preparation procedure took 9min, while the gas chromatography (GC)-mass spectrometry (MS) analysis cycle was under 22min. The method deals efficiently with the multiphase sample matrices offering a fast and simple alternative to the conventional approach of liquid-liquid extraction combined with derivatisation. Multiphase sample matrices can be encountered or formed when preparing environmental, industrial, waste or decontamination waste samples for a GC-MS analysis. The applicability and robustness of the method were demonstrated by the successful analysis of 11 years old OPCW Official Proficiency Test sample and a triphase liquid sample. The same equipment set-up, tubes and derivatising agent have been used for collection, preparation and analysis of Lewisites in air samples (Terzic et al., 2012 [35]). The minimal logistic requirements, ease of operation, versatility and other features aforementioned, make this method an excellent choice for an environmental or forensic field laboratory.
authors.affiliation: Organisation for the Prohibition of Chemical Weapons, Inspectorate Division, Johan de Wittlaan 32, 2517 JR, The Hague, The Netherlands. oliver.terzic@opcw.org
authors.forename: Oliver
authors.initials: O
authors.lastname: Terzic
authors.forename: Sandra
authors.initials: S
authors.lastname: Bartenbach
authors.forename: Pim
authors.initials: P
authors.lastname: de Voogt
mesh_terms: D001152:Arsenicals / Q000032:analysis*; D002619:Chemical Warfare Agents / Q000032:analysis*; D004867:Equipment Design; D008401:Gas Chromatography-Mass Spectrometry / Q000379:methods*; D006868:Hydrolysis; D057230:Limit of Detection; D052616:Solid Phase Extraction / Q000295:instrumentation / Q000379:methods*; D013438:Sulfhydryl Compounds / Q000737:chemistry
chemical_list: D001152:Arsenicals; D002619:Chemical Warfare Agents; D013438:Sulfhydryl Compounds; C035965:lewisite; C025540:n-butyl mercaptan
keywords: Aqueous samples; Chemical warfare agents; In-tube derivatisation; Lewisites; Multiphase samples; Thermal desorption–gas chromatography–mass spectrometry (TD–GC–MS)