Thermal and hydrothermal degradations of adsorbed sulfur mustard (HD) on activated carbon particles from a chemical protective over-garment were studied. Carbon loaded with 5 wt. HD was heated in a closed reactor at temperatures up to 160 °C for 0.5-6 h and analyzed by solid-state ~(13)C MAS NMR. On dry carbon at room temperature, HD was stable for months. On a thoroughly pre-wetted carbon, adsorbed HD partially degraded to thiodigly-col (TDG) and TDG-sulfoxide (TDG-SO) within 2-3 months. Heating dry HD-loaded carbon to 160 °C caused partial degradation within 4 h to 1,4-thioxane, along with 1,4-dithiane and vinyl sulfides. Complete degradation within 2.5 h to the same products occurred upon hydrothermal treatment of the HD-loaded carbon, using a water/carbon ratio of 0.3:1. With higher water/carbon ratios of 0.6:1-5:1 at temperatures of 120 °C and above, adsorbed HD hydrolyzed rapidly within 0.5 h. The latter reaction led to the formation of TDG concurrent with either thioxane (at 160 °C) or TDG-SO and TDG-dimer (at 120 °C). The mechanisms of the observed degradation processes are discussed.
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