Identification of complexes formed between sulphur mustards and arsenic-containing chemical warfare agents

Large quantities of toxic chemical warfare material, such as mixtures of sulphur mustard (HD) and arsenic-containing chemical warfare agents (As-CWAs) have been submerged in the Baltic Sea region after World War II. Little is known about the possible reactivity between HD and As-CWAs. In this study, we used simple reaction mixtures and ultra-high performance liquid chromatography combined with mass spectrometric techniques to study the reactivity of HD and the half-mustard 2-chloroethyl ethyl sulphide (CEES) with As-CWAs. Altogether 22 novel As-CWA-HD- and As-CWA-CEES-complexes were identified. Eight of the As-CWA-HD-complexes were also detected in environmental samples collected from known CWA dumping sites in the Baltic Sea region. Because the As-CWA-HD- and As-CWA-CEES-complexes have structural moieties of both S-mustards and As-CWAs, they might have toxic properties of both CWA-types. Therefore, their occurrence in the environment is concerning and their potential negative effect on the wellbeing of marine biota and humans should be investigated in the future. This is the first time alkylation of As-CWAs is reported, providing new knowledge on the reactivity of S-mustards. The results increase the understanding of the environmental fate of HD and is valuable for the assessment of the environmental threat of sea-dumped CWAs.