Atmos. Chem. Phys. Discuss., 12, 19349-19370, 2012
© Author(s) 2012. This work is distributed
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This discussion paper has been under review for the journal Atmospheric Chemistry and Physics (ACP). Please refer to the corresponding final paper in ACP.
Selective measurements of isoprene and 2-methyl-3-buten-2-ol based on NO+ ionization mass spectrometry
T. Karl1, A. Hansel2, L. Cappellin2,3, L. Kaser2, I. Herdlinger2, and W. Jud2
1NCAR Earth System Laboratory, National Center for Atmospheric Research, P.O. Box 3000, Boulder, Colorado 80307, USA
2Institut für Ionenphysik und Angewandte Physik, Leopold Franzens Universität Innsbruck, Technikerstrasse 25, 6020, Innsbruck, Austria
3IASMA Research and Innovation Centre, Fondazione Edmund Mach, Food Quality and Nutrition Area, Via E. Mach, 1, 38010, S. Michele a/A, Italy

Abstract. Biogenic VOC emissions are often dominated by 2-methyl-1,3-butadiene (isoprene) and 2-methyl-3-buten-2-ol (232 MBO). Here we explore the possibility for selectively distinguishing these species using NO+ as primary ion based on PTR-MS technology. High purity of NO+ (>90%) as a primary ion was achieved in laboratory and field experiments using a PTR-TOF-MS. Isoprene is ionized via charge transfer leading to the major product ion C5H8+ (>99%) (e.g. Spanel and Smith, 1998). 232 MBO undergoes a hydroxide ion transfer reaction resulting in the major product ion channel C5H9+ (>95%) (e.g. Amelynck et al., 2005). We show that both compounds are ionized with little fragmentation (<5%) under standard PTR-MS operating conditions. Typical sensitivities of 11.1±0.1 (isoprene) and 12.9±0.1 (232 MBO) ncps ppbv−1 were achieved, which correspond to limit of detections of 18 and 15 pptv, respectively for a 10 s integration time. Sensitivities decreased at higher collisional energies. Calibration experiments showed little humidity dependence. We tested the setup at a field site in Colorado dominated by ponderosa pine, a 232 MBO emitting plant species. Our measurements confirm 232 MBO as the dominant biogenic VOC at this site, exhibiting typical average daytime concentrations between 0.2–1.4 ppbv. The method is able to detect the presence of trace levels of isoprene (90–250 ppt) without any interference from 232 MBO, which would not be feasible using H3O+ ionization chemistry, and which currently also remains achallenge for other analytical techniques (e.g. gas chromatographic methods).

Citation: Karl, T., Hansel, A., Cappellin, L., Kaser, L., Herdlinger, I., and Jud, W.: Selective measurements of isoprene and 2-methyl-3-buten-2-ol based on NO+ ionization mass spectrometry, Atmos. Chem. Phys. Discuss., 12, 19349-19370, doi:10.5194/acpd-12-19349-2012, 2012.
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