Add time:08/13/2019 Source:sciencedirect.com
The chemical warfare agent O-ethyl S-(2-diisopropylaminoethyl) methyl phosphonothiolate (VX) and many related degradation products produce poorly diagnostic electron ionization (EI) mass spectra by transmission quadrupole mass spectrometry. Thus, chemical ionization (CI) is often used for these analytes. In this work, pseudomolecular ([M+H]+) ion formation from self-chemical ionization (self-CI) was examined for four VX degradation products containing the diisopropylamine functional group. A person-portable toroidal ion trap mass spectrometer with a gas chromatographic inlet was used with EI, and both fixed-duration and feedback-controlled ionization time. With feedback-controlled ionization, ion cooling (reaction) times and ion formation target values were varied. Evidence for protonation of analytes was observed under all conditions, except for the largest analyte, bis(diisopropylaminoethyl)disulfide which yielded [M+H]+ ions only with increased fixed ionization or ion cooling times. Analysis of triethylamine-d15 provided evidence that [M+H]+ production was likely due to self-CI. Analysis of a degraded VX sample where lengthened ion storage and feedback-controlled ionization time were used resulted in detection of [M+H]+ ions for VX and several relevant degradation products. Dimer ions were also observed for two phosphonate compounds detected in this sample.
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