Analysis of chemical warfare agents: I. Use of aliphatic thiols in the trace level determination of Lewisite compounds in complex matrices

A series of normal aliphatic thiols have been used to derivatise the chemical warfare agents Lewisites I and II (LI and LII) in hydrocarbon matrices. Varying the chain length of the thiol allowed adjustment of derivative tR by 5.9 min for Lewisite I and 5.3 min for Lewisite II. Linear regression analysis of the chain length of the thiol derivatives of the Lewisite species, and that of a series of normal alkanes against tR, allowed regression models to be developed for each set of compounds. Application of the models allowed thiol reagents to be chosen to give derivatives of Lewisites I and II that eluted before and after the major hydrocarbon contaminant. Limits of detection were comparable for all thiol derivatives analysed by GC–MS in the selection ion monitoring mode (all below 1 μg ml−1). The robustness of this approach was illustrated by successful identification of Lewisite I in samples from the Sixth Proficiency Test (organised by the Organisation for the Prohibition of Chemical Weapons, OPCW) in a matrix of 1 mg ml−1 diesel oil.