Direct quantification of chemical warfare agents and related compounds at low ppt levels: comparing active capillary DBDI and SESI mass spectrometry
J-C Wolf, M. Schaer, P. Siegenthaler, R. Zenobi
A novel active capillary dielectric barrier discharge plasma ionization (DBDI) technique for mass spectrometry is applied to the direct detection of thirteen chemical warfare related compounds, including sarin, and compared to secondary electrospray ionization (SESI) in terms of selectivity and sensitivity.
The investigated compounds include an intact chemical warfare agent and structurally related molecules, hydrolysis products and/or precursors of highly toxic nerve (G-series, V-series and "new" nerve agents), blistering and incapacitating warfare agents. Well-defined analyte gas phase concentrations were generated by a pressure-assisted nanospray with consecutive thermal evaporation and dilution. Identification was achieved by selected reaction monitoring (SRM). The most abundant fragment ion intensity of each compound was used for quantification. For DBDI and SESI absolute gas phase detection limits in the low ppt range (in MS/MS mode) were achieved for all compounds investigated.
Although the sensitivity of both methods was comparable, the active capillary DBDI sensitivity was found to be dependant on the applied AC voltage, thus enabling direct tuning of the sensitivity and the in-source fragmentation, which may become a key feature in terms of field applicability. Our findings underline the applicability of DBDI and SESI for the direct, sensitive detection and quantification of several CWA types and their degradation products. Furthermore, they suggest the use of DBDI in combina-tion with handheld instruments for CWAs on-site monitoring.