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

Kim, Michelle J. and Zoerb, Matthew C. and Campbell, Nicole R. and Zimmermann, Kathryn J. and Blomquist, Byron W. and Huebert, Barry J. and Bertram, Timothy H. (2016) Revisiting benzene cluster cations for the chemical ionization of dimethyl sulfide and select volatile organic compounds. Atmospheric Measurement Techniques, 9 (4). pp. 1473-1484. ISSN 1867-1381. http://resolver.caltech.edu/CaltechAUTHORS:20160601-142456597

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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 (> 1 ncps ppt^(−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 (R^2 > 0.95, 10 s averages) over a wide range of sampling conditions.


Item Type:Article
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URLURL TypeDescription
http://dx.doi.org/10.5194/amt-9-1473-2016DOIArticle
http://www.atmos-meas-tech.net/9/1473/2016/PublisherArticle
Additional Information:© Author(s) 2016. This work is distributed under the Creative Commons Attribution 3.0 License. Received: 20 Jul 2015 – Published in Atmos. Meas. Tech. Discuss.: 01 Oct 2015. Revised: 26 Feb 2016 – Accepted: 02 Mar 2016 – Published: 05 Apr 2016. This work was supported by a National Science Foundation (NSF) CAREER Award (grant no. AGS-1151430), the Office of Science (Office of Biological and Environmental Research), US Department of Energy (grant no. DE-SC0006431), and National Aeronautics and Space Administration (NNX12AL94G). The authors thank the entire High Wind Gas Exchange Study science team. A special thanks to the WHOI Marine Operations staff, Captain Kent Sheasley and the capable crew of the R/V Knorr. The authors also thank Emma Mungall and Jonathan Abbatt of the University of Toronto for helpful discussions. Edited by: J. Abbatt
Funders:
Funding AgencyGrant Number
NSFAGS-1151430
Department of Energy (DOE)DE-SC0006431
NASANNX12AL94G
Record Number:CaltechAUTHORS:20160601-142456597
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20160601-142456597
Official Citation:Kim, M. J., Zoerb, M. C., Campbell, N. R., Zimmermann, K. J., Blomquist, B. W., Huebert, B. J., and Bertram, T. H.: Revisiting benzene cluster cations for the chemical ionization of dimethyl sulfide and select volatile organic compounds, Atmos. Meas. Tech., 9, 1473-1484, doi:10.5194/amt-9-1473-2016, 2016.
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:67552
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:01 Jun 2016 21:49
Last Modified:01 Jun 2016 21:49

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