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Discussion papers
https://doi.org/10.5194/acp-2019-516
© Author(s) 2019. This work is distributed under
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/acp-2019-516
© Author(s) 2019. This work is distributed under
the Creative Commons Attribution 4.0 License.

Research article 14 Jun 2019

Research article | 14 Jun 2019

Review status
This discussion paper is a preprint. It is a manuscript under review for the journal Atmospheric Chemistry and Physics (ACP).

OH-chemistry of non-methane organic gases (NMOG) emitted from laboratory and ambient biomass burning smoke: evaluating the influence of furans and oxygenated aromatics on ozone and secondary NMOG formation

Matthew M. Coggon1,2, Christoper Y. Lim3, Abigail R. Koss1,2,a, Kanako Sekimoto1,2,4, Bin Yuan1,2,b, Jessica B. Gilman2, David H. Hagan3, Vanessa Selimovic5, Kyle Zarzana1,2, Steven S. Brown2, James M. Roberts2, Markus Müller6, Robert Yokelson5, Armin Wisthaler7,8, Jordan E. Krechmer9, Jose L. Jimenez1,10, Christopher Cappa11, Jesse Kroll3, Joost de Gouw1,10, and Carsten Warneke1,2 Matthew M. Coggon et al.
  • 1Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO, USA
  • 2NOAA Earth Systems Research Laboratory Chemical Sciences Division, Boulder, CO, USA
  • 3Department of Civil and Environmental Engineering, Massachusetts Institute of Technology, Cambridge, MA, USA
  • 4Graduate School of Nanobioscience, Yokohama City University, Yokohama, Kanagawa, Japan
  • 5Department of Chemistry and Biochemistry, University of Montana, Missoula, MT, USA
  • 6Ionicon Analytik, Innsbruck, Austria
  • 7Institute for Ion Physics and Applied Physics, University of Innsbruck, Innsbruck, Austria
  • 8Department of Chemistry, University of Oslo, Oslo, Norway
  • 9Aerodyne Research, Inc., Billerica, MA, USA
  • 10Department of Chemistry, University of Colorado, Boulder, CO, USA
  • 11Department of Civil and Environmental Engineering, University of California, Davis, CA, USA
  • anow at: Department of Civil and Environmental Engineering, Massachusetts Institute of Technology, Cambridge, MA, USA
  • bnow at: Institute for Environment and Climate Research, Jinan University, Guangzhou, China

Abstract. Chamber oxidation experiments conducted at the Fire Sciences Laboratory in 2016 are evaluated to identify important chemical processes contributing to the OH chemistry of biomass burning non-methane organic gases (NMOG). Based on the decay of primary carbon measured by proton transfer reaction time-of-flight mass spectrometry (PTR-ToF-MS), it is confirmed that furans and oxygenated aromatics are among the NMOG emitted from western United States fuel types with the highest reactivities towards OH. The oxidation processes and formation of secondary NMOG masses measured by PTR-ToF-MS and iodide clustering time-of-flight chemical ionization mass spectrometry (I-CIMS) is interpreted using a box model employing a modified version of the Master Chemical Mechanism (v. 3.3.1) that includes the OH oxidation of furan, 2-methylfuran, 2,5-dimethylfuran, furfural, 5-methylfurfural, and guaiacol. The model supports the assignment of major PTR-ToF-MS and I-CIMS signals to a series of anhydrides and hydroxy furanones formed primarily through furan chemistry. This mechanism is applied to a Lagrangian box model used previously to model a real biomass burning plume. The updated mechanism reproduces the decay of furans and oxygenated aromatics and the formation of secondary NMOG, such as maleic anhydride. Based on model simulations conducted with and without furans, it is estimated that furans contributed up to 10 % of ozone and over 90 % of maleic anhydride formed within the first 4 hours of oxidation. It is shown that maleic anhydride is present in a biomass burning plume transported over several days, which demonstrates the utility of anhydrides as tracers for aged biomass burning plumes.

Matthew M. Coggon et al.
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Short summary
Wildfire emissions significantly contribute to adverse air quality; however, the chemical processes that lead to hazardous pollutants, such as ozone, are not fully understood. In this study, we describe laboratory experiments where we simulate the atmospheric chemistry of smoke emitted from a range of biomass fuels. We show that certain understudied compounds, such as furans and phenolic compounds, are significant contributors to pollutants formed as a result of typical atmospheric oxidation.
Wildfire emissions significantly contribute to adverse air quality; however, the chemical...
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