Degradation of Sulfur Mustard on Moist Sand as Determined by ¹³C Solid‐State Magic Angle Spinning Nuclear Magnetic Resonance

Abstract

The degradation of sulfur mustard, bis(2‐chloroethyl) sulfide, on three types of moist sand at 22°C and 35°C was followed using ¹³C solid state‐magic angle spinning nuclear magnetic resonance (SSMAS NMR). The sulfur mustard degraded completely on moist sand within 8 weeks at 22°C and 1 week at 35°C, whereas degradation on dry sand at 22°C required more than 6 weeks. The major product, the toxic sulfonium ion H‐2TG, and the minor product, nontoxic thiodiglycol, were detected on all sand samples. The intermediate chlorohydrin was detected on one sand at 22°C, and evidence for the intermediates CH‐TG and H‐TG was detected on this same sand at 35°C. The H‐2TG that was initially formed degraded to thiodiglycol; completion of this degradation would require months. The lack of reaction on the ambient substrates, plus the formation of sulfonium ions, similar to the products that were previously seen in water and on moist soil, suggested that the sand functioned as a support on which the reaction between sulfur mustard and water occurred.

Keywords:

• chlorohydrin
• CH‐TG
• H‐TG
• H‐2TG
• sulfonium ion
• sulfur mustard
• thiodiglycol

Acknowledgments

The authors thank Drs. James Savage, H. Dupont Durst, and Mark Brickhouse for programmatic support. The work described in this report was performed under SAIC Contract No. DAAD13‐03‐D‐0017. The authors acknowledge Mr. David Sorrick for the supply of ¹³C‐labeled sulfur mustard, Mr. Carroll Cook for assistance with the agent operations, Mr. Wendel Shuely for stimulating discussions about the kinetics, and Messrs. Michael Simini and Joseph Kiple for the samples of sand.