We report a new method for the determination of the methyl, ethyl and isopropyl esters of methanesulfonic acid, and of dimethyl sulfate. Derivatisation with aqueous sodium thiocyanate gives a mixture of the corresponding alkylthiocyanates and alkylisothiocyanates which, unlike the underivatised analytes, are readily analysed by GC. On-column isomerisation is negligible. These lower alkyl derivatives are sufficiently volatile for static reaction headspace analysis, and detection limits obtained by electron impact MS are below 0.05 µg ml 21 with respect to the injection solution. The method was used to demonstrate that levels of methanesulfonic acid esters in a drug substance (a mesylate salt that had been processed using methanol and ethanol) are below 1 µg g 21 .