Determination of lewisite constituents in aqueous samples using hollow-fibre liquid-phase microextraction followed by gas chromatography-mass spectrometry

• Published in: Analytical and bioanalytical chemistry 2014-08, Vol.406 (21), p.5103-5110
• Main Authors: Cheh, M. Y., Chua, H. C., Hopkins, F. B., Riches, J. R., Timperley, C. M., Lee, H. S. Nancy
• Format: Article
• Language: English
• Subjects: Analysis; Analysis of Chemicals Relevant to the Chemical Weapons Convention; Analytical Chemistry; Arsenic; Arsenicals - isolation & purification; Biochemistry; Biological & chemical weapons; Characterization and Evaluation of Materials; Chemical properties; Chemical warfare; Chemical Warfare Agents - isolation & purification; Chemical weapons; Chemistry; Chemistry and Materials Science; Chlorides - isolation & purification; Chromatography; Constituents; Extraction; Extraction (Chemistry); Food Science; Gas chromatography; Gas Chromatography-Mass Spectrometry; Humans; Hydrogen-Ion Concentration; Laboratories; Laboratory Medicine; Laboratory Proficiency Testing; Lewisite (Poison gas); Limit of Detection; Liquid Phase Microextraction - methods; Mass spectrometry; Mathematical analysis; Monitoring/Environmental Analysis; Osmolar Concentration; Prohibition; Reproducibility of Results; Research Paper; Scientific imaging; Signal-To-Noise Ratio; Solvents; Standard deviation; Sulfhydryl Compounds - chemistry; Water - chemistry; Water Pollutants, Chemical - isolation & purification; Weapons
• ISSN: 1618-2642; 1618-2650
• DOI: 10.1007/s00216-014-7751-6

The applicability of hollow-fibre liquid-phase microextraction for extracting 2-chlorovinyldichloroarsine (lewisite 1), bis(2-chlorovinyl)chloroarsine (lewisite 2), tris(2-chlorovinyl)arsine (lewisite 3) and arsenic trichloride from aqueous samples is reported. Parameters affecting the extraction efficiency of these chemicals were optimised. These parameters included the type of derivatising agent, extraction solvent, derivatisation method, pH, ionic strength, stirring speed and extraction time. A linear range between 0.002 and 0.2 μg/mL was established for the lewisites with good square regression coefficients (0.9955–0.9992). Good reproducibility with relative standard deviations (RSDs) from 8 to 10 % was achieved. The limit of detection was 0.002 μg/mL for the lewisites and 0.005 μg/mL for arsenic trichloride (3:1 signal-to-noise ratio). The extraction method was validated with a proficiency test sample issued by the Organisation for the Prohibition of Chemical Weapons (OPCW). The rapidity and precision of the new method should help deter against the employment of lewisite as a chemical warfare agent: its use could be confirmed easily from analysis of aqueous samples.