Headspace analysis of potassium chlorate using on-fiber SPME derivatization coupled with GC/MS

Potassium chlorate is a powerful oxidizer salt that, when mixed with a fuel source, has been used as a homemade explosive (HME). As an inorganic salt, potassium chlorate has no appreciable vapor pressure under ambient conditions and requires temperatures exceeding 300 °C for decomposition. However, detection of potassium chlorate by trained canines has been demonstrated, implying that it exudes a vapor signature with one or more volatile compounds, although no such species have been confirmed to date. In this work, solid-phase microextraction with a novel on-fiber derivatization reaction was used to interrogate the headspace of several potassium chlorate samples of varying purity, as well as that of related chlorinated salts and explosive mixtures. This analysis showed the presence of few volatile species in the headspace of potassium chlorate other than vaporous chlorine, detected as the derivatized product, chloro-2-propanol. Relative amounts of chloro-2-propanol could be compared between potassium chlorate variants, and could be detected in the presence of other volatile species associated with the fuels. [Display omitted] •Headspace analysis of the non-volatile salt, potassium chlorate, was completed.•A novel derivatization reaction was used to detect chlorine vapor by SPME-GC/MS.•The relative quantity of chlorine between potassium chlorate variants was compared.•Chlorine could be detected from potassium chlorate-based explosives.