On-matrix derivatization extraction of chemical weapons convention relevant alcohols from soil

•Method for derivatization extraction of CWC related alcohols was developed.•Method involved hexamethyldisilazane mediated in situ silylation of analytes on soil.•Recoveries of nitrogenous analytes were better than OPCW recommended procedure. Present study deals with the on-matrix derivatization–extraction of aminoalcohols and thiodiglycols, which are important precursors and/or degradation products of VX analogues and vesicants class of chemical warfare agents (CWAs). The method involved hexamethyldisilazane (HMDS) mediated in situ silylation of analytes on the soil. Subsequent extraction and gas chromatography–mass spectrometry analysis of derivatized analytes offered better recoveries in comparison to the procedure recommended by the Organization for the Prohibition of Chemical Weapons (OPCW). Various experimental conditions such as extraction solvent, reagent and catalyst amount, reaction time and temperature were optimized. Best recoveries of analytes ranging from 45% to 103% were obtained with DCM solvent containing 5%, v/v HMDS and 0.01%, w/v iodine as catalyst. The limits of detection (LOD) and limit of quantification (LOQ) with selected analytes ranged from 8 to 277 and 21 to 665ngmL−1, respectively, in selected ion monitoring mode.