Atmospheric Measurement Techniques Discussions www.atmos-meas-tech-discuss.net 1867-8610 1 1 2008 10.5194/amtd-1-401-2008 http://www.atmos-meas-tech-discuss.net/1/401/2008/ http://www.atmos-meas-tech-discuss.net/1/401/2008/amtd-1-401-2008.html http://www.atmos-meas-tech-discuss.net/1/401/2008/amtd-1-401-2008.pdf 401 433 2008-12-04 Measurement of atmospheric sesquiterpenes by proton transfer reaction-mass spectrometry (PTR-MS) S. Kim saewung@ucar.edu T. Karl D. Helmig R. Daly R. Rasmussen A. Guenther Advanced Study Program, National Center for Atmospheric Research, Boulder, CO, USA Atmospheric Chemistry Division, National Center for Atmospheric Res., Boulder, CO, USA Institute of Arctic and Alpine Research, University of Colorado, Boulder CO, USA Oregon Graduate Institute, Beaverton, OR, USA The ability to measure sesquiterpenes (SQT; C15H24) by a Proton-Transfer-Reaction Mass Spectrometer (PTR-MS) was investigated with SQT standards, prepared by a capillary diffusion method, and the estimated mixing ratios, derived from the counts of product ions and proton transfer reaction constants were intercompared with measured mixing ratios, measured by a complementary Gas Chromatograph (GC) coupled to a Flame Ionization Detector (GC-FID). Product ion distributions due to soft-ionization occurring in a selected ion drift tube via proton transfer were measured as a function of collision energies. Results after the consideration of the mass discrimination of the PTR-MS system suggest that quantitative SQT measurements within 20% accuracy can be achieved with PTR-MS if two major product ions (m/z 149+ and 205+) out of seven major product ions (m/z 81+, 95+, 109+, 123+, 135+, 149+ and 205+) are accounted for. Bicyclic sesquiterpenes, i.e. β-caryophyllene and α-humulene, showed considerable fragmentation causing the accuracy of their analysis to be reduced to 50% if only the parent ion (m/z 205) is considered. These findings were applied to a field dataset collected above a deciduous forest at the PROPHET (Program for Research on Oxidants: Photochemistry, Emissions, and Transport) research station in 2005. Inferred Average daytime ecosystem scale mixing ratios (fluxes) of isoprene, sum of monoterpenes (MT), and sum of SQT exhibited values of 15 μg m−3 (4.5 mg m−2 h−1), 1.2 μg m−3 (0.21 mg m−2 h−1) and 0.0016 μg m−3 (0.10 mgm−2 h−1) respectively. 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