title: Analysis of the sulphur mustard metabolites thiodiglycol and thiodiglycol sulphoxide in urine using isotope-dilution gas chromatography-ion trap tandem mass spectrometry.
abstract: A sensitive method has been developed for the trace analysis of the sulphur mustard metabolite thiodiglycol (TDG) in urine, and its oxidation product thiodiglycol sulphoxide (TDGO) after reduction to thiodiglycol. Thiodiglycol was extracted from urine by solid phase extraction onto a polymeric cartridge and, after isolation, converted to its bis-heptafluorobutyryl derivative with heptafluorobutyryl imidazole. An ion trap mass spectrometer in selected reaction monitoring mode detected spiked concentrations down to 0.2 ng/ml with a signal to noise ratio>3:1. Urine, from human volunteers with no known exposure to sulphur mustard, contained detectable but very low concentrations (<0.2 ng/ml) of thiodiglycol, consistent with previous observations using different methodologies. Combined concentrations of thiodiglycol and thiodiglycol sulphoxide were determined after reduction of the latter with titanium trichloride. In this case higher background levels (up to 3 ng/ml) were observed, consistent with the sulphoxide being the major excretion product of the two metabolites. The method was applied to urine samples, stored frozen for 13 years, from two casualties of accidental mustard poisoning. Levels of thiodiglycol were 1 and 3 ng/ml, which increased to 78 and 104 ng/ml after treatment of the urine with titanium trichloride.
authors.affiliation: Defence Science and Technology Laboratory, Porton Down, Salisbury, Wiltshire SP4 0JQ, UK. jriches@dstl.gov.uk
authors.forename: James
authors.initials: J
authors.lastname: Riches
authors.forename: Robert W
authors.initials: RW
authors.lastname: Read
authors.forename: Robin M
authors.initials: RM
authors.lastname: Black
mesh_terms: D005466:Fluorocarbons / Q000737:chemistry; D008401:Gas Chromatography-Mass Spectrometry / Q000379:methods*; D006801:Humans; D007553:Isotope Labeling; D008297:Male; D009151:Mustard Gas / Q000506:poisoning; D052616:Solid Phase Extraction; D013438:Sulfhydryl Compounds / Q000652:urine*; D013454:Sulfoxides / Q000652:urine*; D053719:Tandem Mass Spectrometry / Q000379:methods*
chemical_list: D005466:Fluorocarbons; D013438:Sulfhydryl Compounds; D013454:Sulfoxides; C073450:2,2'-sulfinylbisethanol; C007924:heptafluorobutyric anhydride; C047519:2,2'-thiodiethanol; D009151:Mustard Gas