Direct Quantification of Chemical Warfare Agents and Related Compounds at Low ppt Levels: Comparing Active Capillary Dielectric Barrier Discharge Plasma Ionization and Secondary Electrospray Ionization Mass Spectrometry

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Author(s) Wolf, Jan-Christoph, Schaer, Martin, Siegenthaler, Peter, Zenobi, Renato
Publication Type Journal Items, Publication Status: Published
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Title Direct Quantification of Chemical Warfare Agents and Related Compounds at Low ppt Levels: Comparing Active Capillary Dielectric Barrier Discharge Plasma Ionization and Secondary Electrospray Ionization Mass Spectrometry
Author(s) Wolf, Jan-Christoph
Schaer, Martin
Siegenthaler, Peter
Zenobi, Renato
Journal or Series Title Analytical Chemistry
Volume Number 87
Issue Number 1
Start Page 723
End Page 729
ISSN 0003-2700
1520-6882
Publisher American Chemical Society
Publication Place Washington, DC
Publication Date 2015
Abstract A novel active capillary dielectric barrier discharge plasma ionization (DBDI) technique for mass spectrometry is applied to the direct detection of 13 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 agents (G-series, V-series, and "new" nerve agents), and 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 dependent 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 combination with hand-held instruments for CWAs on-site monitoring.
DOI 10.1021/ac5035874
Additional Notes Received 24 September 2014, Accepted 26 November 2014, Published online 26 November 2014
Document Type Article
Publication Status Published
Language English
Assigned Organisational Unit(s) 03430
Organisational Unit(s)
NEBIS System Number 000005465
Source Database ID WOS-000347590400077
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@article{Wlf2015,
  author = "Wolf, Jan-Christoph and Schaer, Martin and Siegenthaler, Peter and Zenobi, Renato",
  title = "{D}irect {Q}uantification of {C}hemical {W}arfare {A}gents and {R}elated {C}ompounds at {L}ow ppt {L}evels: {C}omparing {A}ctive {C}apillary {D}ielectric {B}arrier {D}ischarge {P}lasma {I}onization and {S}econdary {E}lectrospray {I}onization {M}ass {S}pectrometry",
  journal = "Analytical Chemistry",
  year = 2015,
  volume = "87",
  number = "1",
  pages = "723--729",
}


E-Citations record created: Tue, 03 Mar 2015, 10:26:25 CET