Direct Gas-Phase Detection of Nerve and Blister Warfare Agents Utilizing Active Capillary Plasma Ionization Mass Spectrometry

Abstract

Ultrasensitive direct gas-phase detection of chemical warfare agents (CWAs) is demonstrated utilizing active capillary plasma ionization and triple quadrupole mass spectrometry (MS) instrumentation. Four G- agents, two V-agents and various blistering agents [including sulfur mustard (HD)] were detected directly in the gas phase with limits of detection in the low parts per trillion (ng m(-3)) range. The direct detection of HD was shown for dry carrier gas conditions, but signals vanished when humidity was present, indicating a possible direct detection of HD after sufficient gas phase pretreatment. The method provided sufficient sensitivity to monitor directly the investigated volatile CWAs way below their corresponding minimal effect dose, and in most cases even below the eight hours worker exposure concentration. In general, the ionization is very soft, with little to no in-source fragmentation. Especially for the G-agents, some dimer formation occurred at higher concentrations. This adds complexity, but also further selectivity, to the corresponding mass spectra. Our results show that the active capillary plasma ionization is a robust, sensitive, "plug and play" ambient ionization source suited (but not exclusively) to the very sensitive detection of CWAs. It has the potential to be used with portable MS instrumentation.

Direct and Sensitive Detection of CWA Simulants by Active Capillary Plasma Ionization Coupled to a Handheld Ion Trap Mass Spectrometer

“…Due to reduced toxicity and legal restrictions, nerve agent simulants were used in this study instead of intact CWA. However as mentioned above, the capability of ACI to ionize intact warfare agents was already shown [13]. Here, we focus on the increase in sensitivity of portable MS instrumentation by application of the ACI.…”

A Radical-Mediated Pathway for the Formation of [M + H]+ in Dielectric Barrier Discharge Ionization

“…The gas-phase sample generation system was similar to the one used in previous studies [20]. Briefly, a pressurized sample reservoir was connected via a fused silica capillary (ID 40 μm) to a hollow heating cartridge held at 200°C.…”

High-throughput screening of PAHs and polar trace contaminants in water matrices by direct solid-phase microextraction coupled to a dielectric barrier discharge ionization source

“…Ambient mass spectrometry's noteworthy growth has led to the reporting of over 40 different techniques [2,[8][9][10], of which spray-based (e.g., desorption electrospray ionization, DESI) and plasma-based (e.g., direct analysis in real time, DART) techniques dominate the field. Among the plasma-based approaches, dielectric barrier discharge ionization (DBDI) has become increasingly widespread within recent years, and has been successfully coupled to both gas and liquid chromatography for highly sensitive analysis [11][12][13][14][15][16][17]. By further combining ambient mass spectrometry with solidphase microextraction (SPME), a high-throughput, simple, and environmentally friendly detection method can be achieved thanks to a simultaneous solvent-free enrichment and cleanup of the sample [18][19][20][21][22][23][24][25].…”