Capillary column gas chromatography-ammonia and deuterated ammonia chemical ionization mass spectrometry of sulfur vesicants

Capillary column gas chromatography-ammonia and deuterated ammonia chemical ionization mass spectrometry was found to be a highly specific technique for the detection and identification of three long-chain sulfur vesicants, 2-chloroethyl (2-chloroethoxy)ethyl sulfide, sesquimustard and bis(2-chloroethylthio)ethyl]ether. All three vesicants exhibited significant (M + NX₄)⁺ (where X = H or ²H) pseudo-molecular ions and structurally significant chemical ionization fragmentation ions during capillary column gas chromatographic-ammonia chemical ionization mass spectrometric analysis. This method was utilized during analysis of contaminated painted panels circulated during the 3rd round robin verification exercise (1991). Chemical ionization data obtained during this exercise complemented the electron impact data obtained for sesquimustard and bis(2-chloroethylthio)ethyl]ether and the specificity of the technique enabled the confirmation of 2-chloroethyl (2-chloroethyoxy)ethyl sulfide, a compound masked by hydrocarbons in the painted panel extracts.