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Atmospheric Measurement Techniques An interactive open-access journal of the European Geosciences Union
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Volume 2, issue 2
Atmos. Meas. Tech., 2, 703–712, 2009
https://doi.org/10.5194/amt-2-703-2009
© Author(s) 2009. This work is distributed under
the Creative Commons Attribution 3.0 License.
Atmos. Meas. Tech., 2, 703–712, 2009
https://doi.org/10.5194/amt-2-703-2009
© Author(s) 2009. This work is distributed under
the Creative Commons Attribution 3.0 License.

  12 Nov 2009

12 Nov 2009

MS/MS studies for the selective detection of isomeric biogenic VOCs using a Townsend Discharge Triple Quadrupole Tandem MS and a PTR-Linear Ion Trap MS

M. Müller1, L. H. Mielke2, M. Breitenlechner1, S. A. McLuckey2, P. B. Shepson2,3,4, A. Wisthaler1, and A. Hansel1 M. Müller et al.
  • 1Institut für Ionenphysik, University of Innsbruck, Innsbruck, Austria
  • 2Department of Chemistry, Purdue University, West Lafayette, 47907, USA
  • 3Department of Earth and Atmospheric Sciences, Purdue University, West Lafayette, 47907, USA
  • 4Purdue Climate Change Research Center, Purdue University, West Lafayette, 47907, USA

Abstract. We performed MS/MS investigations of biogenic volatile organic compounds (BVOC) using a triple quadrupole tandem mass spectrometer (QqQ-MS) equipped with a Townsend Discharge ion source and a Proton Transfer Reaction Linear Ion Trap (PTR-LIT) mass spectrometer. Both instruments use H2O chemical ionization to produce protonated molecules. Here we report a study of the application of these instruments to determine methyl vinyl ketone (MVK) and methacrolein (MACR) and a series of monoterpenes (α-pinene, β-pinene, 3-carene, limonene, myrcene, ocimene) and sesquiterpenes (humulene and farnesene). Both instruments achieved sub-ppb detection limits in the single MS mode and in the MS/MS mode for differentiating MVK and MACR. Collision induced dissociation (CID) of protonated monoterpenes and sesquiterpenes was studied under the relatively high-energy, single-to-few collision conditions of the QqQ-MS instrument and under the low-energy, multiple collision conditions of the PTR-LIT. Differences and similarities in the breakdown curves obtained are discussed. In addition, we performed MS4 of protonated limonene to illustrate the analytical power of the PTR-LIT. In spite of the progress we have made, the selective on-line mass-spectrometric detection of individual monoterpenes or sesquiterpenes in complex mixtures currently does not yet seem to be possible.

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