Geochemistry of chemical weapon breakdown products on the seafloor: 1,4-thioxane in seawater.

The long-term fate of chemical weapon debris disposed of in the ocean some 50 years ago, now sinking into marine sediments and leaking into the ocean environment, is poorly known. Direct evidence exists showing chemical weapon agents actively being released on the sea floor with detrimental effects including harm to marine life. Thus there is strong interest in determining the fate and lifetime of these materials, their decomposition products, and the affected zones around these sites. Here we study the geochemical properties of a mustard gas breakdown product, 1,4-thioxane (TO), using Raman spectroscopy. We show that TO forms a hydrate with a help-gas (a second guest added to stabilize the hydrate), such as methane or hydrogen sulfide, with the hydrate stability regime some 10 degrees C above pure methane hydrate. The temperature, pressure, and reducing conditions required for hydrate formation commonly occur at known disposal sites. The TO solubility was measured in seawater and found to vary from 0.65 to 0.63 mol/kg water between 4.5 and 25.0 degrees C. Similar to other hydrate systems, the TO solubility decreased in the presence of hydrate. A low solubility in water coupled with its ability to form a hydrate within marine sediments can greatly decrease molecular mobility and increase its lifetime. These results demonstrate how unanticipated reactions with marine sediments can occur, and how little is known of the processes controlling the environmental science of these materials.