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Atmospheric Measurement Techniques An interactive open-access journal of the European Geosciences Union
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Volume 9, issue 4 | Copyright
Atmos. Meas. Tech., 9, 1473-1484, 2016
https://doi.org/10.5194/amt-9-1473-2016
© Author(s) 2016. This work is distributed under
the Creative Commons Attribution 3.0 License.

Research article 05 Apr 2016

Research article | 05 Apr 2016

Revisiting benzene cluster cations for the chemical ionization of dimethyl sulfide and select volatile organic compounds

Michelle J. Kim1,a, Matthew C. Zoerb2,b, Nicole R. Campbell2, Kathryn J. Zimmermann2,c, Byron W. Blomquist3, Barry J. Huebert4, and Timothy H. Bertram2,d Michelle J. Kim et al.
  • 1Scripps Institution of Oceanography, University of California San Diego, La Jolla, CA, USA
  • 2Department of Chemistry and Biochemistry, University of California San Diego, La Jolla, CA, USA
  • 3University of Colorado, Cooperative Institute for Research in Environmental Sciences, Boulder, CO, USA
  • 4School of Oceanography and Earth Sciences and Technology, University of Hawaii, Manoa, Honolulu, HI, USA
  • anow at: Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA, USA
  • bnow at: Department of Chemistry and Biochemistry, California Polytechnic State University, San Luis Obispo, CA, USA
  • cnow at: School of Science and Technology, Georgia Gwinnett College, Lawrenceville, GA, USA
  • dnow at: Department of Chemistry, University of Wisconsin-Madison, Madison, WI, USA

Abstract. Benzene cluster cations were revisited as a sensitive and selective reagent ion for the chemical ionization of dimethyl sulfide (DMS) and a select group of volatile organic compounds (VOCs). Laboratory characterization was performed using both a new set of compounds (i.e., DMS, β-caryophyllene) as well as previously studied VOCs (i.e., isoprene, α-pinene). Using a field deployable chemical-ionization time-of-flight mass spectrometer (CI-ToFMS), benzene cluster cations demonstrated high sensitivity (>1ncpsppt−1) to DMS, isoprene, and α-pinene standards. Parallel measurements conducted using a chemical-ionization quadrupole mass spectrometer, with a much weaker electric field, demonstrated that ion–molecule reactions likely proceed through a combination of ligand-switching and direct charge transfer mechanisms. Laboratory tests suggest that benzene cluster cations may be suitable for the selective ionization of sesquiterpenes, where minimal fragmentation (<25%) was observed for the detection of β-caryophyllene, a bicyclic sesquiterpene. The in-field stability of benzene cluster cations using CI-ToFMS was examined in the marine boundary layer during the High Wind Gas Exchange Study (HiWinGS). The use of benzene cluster cation chemistry for the selective detection of DMS was validated against an atmospheric pressure ionization mass spectrometer, where measurements from the two instruments were highly correlated (R2>0.95, 10s averages) over a wide range of sampling conditions.

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Benzene cluster cations were revisited as a sensitive and selective reagent ion for the chemical ionization of dimethyl sulfide (DMS) and a select group of volatile organic compounds (VOCs). Laboratory and field measurements were used to assess the sensitivity of the ionization scheme under a wide array of operating condition. Underway measurements of DMS in the North Atlantic were validated against an atmospheric pressure ionization mass spectrometer.
Benzene cluster cations were revisited as a sensitive and selective reagent ion for the chemical...
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