ACP Atmospheric Chemistry and Physics ACP Atmos. Chem. Phys. 1680-7324 Copernicus Publications Göttingen, Germany 10.5194/acp-13-2893-2013 Comparison of different real time VOC measurement techniques in a ponderosa pine forest Kaser L. 1 Karl T. https://orcid.org/0000-0003-2869-9426 2 Schnitzhofer R. 1 Graus M. 3 4 Herdlinger-Blatt I. S. 1 DiGangi J. P. 5 8 Sive B. https://orcid.org/0000-0003-0352-8807 6 7 Turnipseed A. 2 Hornbrook R. S. https://orcid.org/0000-0002-6304-6554 2 Zheng W. 2 Flocke F. M. 2 Guenther A. https://orcid.org/0000-0001-6283-8288 2 Keutsch F. N. 5 Apel E. 2 Hansel A. https://orcid.org/0000-0002-1062-2394 1 Institute of Ion Physics and Applied Physics, University of Innsbruck, Innsbruck, Austria Atmospheric Chemistry Division, National Center for Atmospheric Research, Boulder, CO, USA Chemical Sciences Division, NOAA Earth System Research Laboratory, Boulder, CO, USA Cooperative Institute for Research in Environmental Sciences (CIRES), University of Colorado, Boulder, CO, USA Department of Chemistry, University of Wisconsin-Madison, Madison, WI, USA Department of Chemistry, Appalachian State University, Boone, NC, USA Environmental Science Program, Appalachian State University, Boone, NC, USA now at: Civil & Environmental Engineering, Princeton University, Princeton, NJ, USA 11 03 2013 13 5 2893 2906 Copyright: © 2013 L. Kaser et al. 2013 This work is licensed under the Creative Commons Attribution 3.0 Unported License. To view a copy of this licence, visit https://creativecommons.org/licenses/by/3.0/ This article is available from https://acp.copernicus.org/articles/13/2893/2013/acp-13-2893-2013.html The full text article is available as a PDF file from https://acp.copernicus.org/articles/13/2893/2013/acp-13-2893-2013.pdf

Volatile organic compound (VOC) mixing ratios measured by five independent instruments are compared at a forested site dominated by ponderosa pine (<i>Pinus Ponderosa</i>) during the BEACHON-ROCS field study in summer 2010. The instruments included a Proton Transfer Reaction Time of Flight Mass Spectrometer (PTR-TOF-MS), a Proton Transfer Reaction Quadrupole Mass Spectrometer (PTR-MS), a Fast Online Gas-Chromatograph coupled to a Mass Spectrometer (GC/MS; TOGA), a Thermal Dissociation Chemical Ionization Mass Spectrometer (PAN-CIMS) and a Fiber Laser-Induced Fluorescence Instrument (FILIF). The species discussed in this comparison include the most important biogenic VOCs and a selected suite of oxygenated VOCs that are thought to dominate the VOC reactivity at this particular site as well as typical anthropogenic VOCs that showed low mixing ratios at this site. Good agreement was observed for methanol, the sum of the oxygenated hemiterpene 2-methyl-3-buten-2-ol (MBO) and the hemiterpene isoprene, acetaldehyde, the sum of acetone and propanal, benzene and the sum of methyl ethyl ketone (MEK) and butanal. Measurements of the above VOCs conducted by different instruments agree within 20%. The ability to differentiate the presence of toluene and cymene by PTR-TOF-MS is tested based on a comparison with GC-MS measurements, suggesting a study-average relative contribution of 74% for toluene and 26% for cymene. Similarly, 2-hydroxy-2-methylpropanal (HMPR) is found to interfere with the sum of methyl vinyl ketone and methacrolein (MVK + MAC) using PTR-(TOF)-MS at this site. A study-average relative contribution of 85% for MVK + MAC and 15% for HMPR was determined. The sum of monoterpenes measured by PTR-MS and PTR-TOF-MS was generally 20–25% higher than the sum of speciated monoterpenes measured by TOGA, which included α-pinene, β-pinene, camphene, carene, myrcene, limonene, cineole as well as other terpenes. However, this difference is consistent throughout the study, and likely points to an offset in calibration, rather than a difference in the ability to measure the sum of terpenes. The contribution of isoprene relative to MBO inferred from PTR-MS and PTR-TOF-MS was smaller than 12% while GC-MS data suggested an average of 21% of isoprene relative to MBO. This comparison demonstrates that the current capability of VOC measurements to account for OH reactivity associated with the measured VOCs is within 20%.

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