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Volume 18, issue 5 | Copyright
Atmos. Chem. Phys., 18, 3299-3319, 2018
© Author(s) 2018. This work is distributed under
the Creative Commons Attribution 4.0 License.

Research article 07 Mar 2018

Research article | 07 Mar 2018

Non-methane organic gas emissions from biomass burning: identification, quantification, and emission factors from PTR-ToF during the FIREX 2016 laboratory experiment

Abigail R. Koss1,2,3,a, Kanako Sekimoto1,2,4, Jessica B. Gilman2, Vanessa Selimovic5, Matthew M. Coggon1,2, Kyle J. Zarzana1,2, Bin Yuan1,2,b, Brian M. Lerner1,2,c, Steven S. Brown2,3, Jose L. Jimenez1,3, Jordan Krechmer1,3,c, James M. Roberts2, Carsten Warneke1,2, Robert J. Yokelson5, and Joost de Gouw1,2,3 Abigail R. Koss et al.
  • 1Cooperative Institute for Research in Environmental Sciences, University of Colorado Boulder, Boulder, CO, USA
  • 2NOAA Earth System Research Laboratory, Chemical Sciences Division, Boulder, CO, USA
  • 3Department of Chemistry, University of Colorado Boulder, Boulder, CO, USA
  • 4Graduate School of Nanobioscience, Yokohama City University, Yokohama, Japan
  • 5Department of Chemistry and Biochemistry, University of Montana, Missoula, MT, USA
  • anow at: Department of Civil and Environmental Engineering, Massachusetts Institute of Technology, Cambridge, MA, USA
  • bnow at: Institute for Environmental and Climate Research, Jinan University, Guangzhou, China
  • cnow at: Aerodyne Research, Inc., Billerica, MA, USA

Abstract. Volatile and intermediate-volatility non-methane organic gases (NMOGs) released from biomass burning were measured during laboratory-simulated wildfires by proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF). We identified NMOG contributors to more than 150 PTR ion masses using gas chromatography (GC) pre-separation with electron ionization, H3O+ chemical ionization, and NO+ chemical ionization, an extensive literature review, and time series correlation, providing higher certainty for ion identifications than has been previously available. Our interpretation of the PTR-ToF mass spectrum accounts for nearly 90% of NMOG mass detected by PTR-ToF across all fuel types. The relative contributions of different NMOGs to individual exact ion masses are mostly similar across many fires and fuel types. The PTR-ToF measurements are compared to corresponding measurements from open-path Fourier transform infrared spectroscopy (OP-FTIR), broadband cavity-enhanced spectroscopy (ACES), and iodide ion chemical ionization mass spectrometry (I CIMS) where possible. The majority of comparisons have slopes near 1 and values of the linear correlation coefficient, R2, of > 0.8, including compounds that are not frequently reported by PTR-MS such as ammonia, hydrogen cyanide (HCN), nitrous acid (HONO), and propene. The exceptions include methylglyoxal and compounds that are known to be difficult to measure with one or more of the deployed instruments. The fire-integrated emission ratios to CO and emission factors of NMOGs from 18 fuel types are provided. Finally, we provide an overview of the chemical characteristics of detected species. Non-aromatic oxygenated compounds are the most abundant. Furans and aromatics, while less abundant, comprise a large portion of the OH reactivity. The OH reactivity, its major contributors, and the volatility distribution of emissions can change considerably over the course of a fire.

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Short summary
Non-methane organic gases (NMOGs) were detected by proton-transfer-reaction mass spectrometry (PTR-ToF) during an extensive laboratory characterization of wildfire emissions. Identifications for PTR-ToF ion masses are proposed and supported by a combination of techniques. Overall excellent agreement with other instrumentation is shown. Scalable emission factors and ratios are reported for many newly reported reactive species. An analysis of chemical characteristics is presented.
Non-methane organic gases (NMOGs) were detected by proton-transfer-reaction mass spectrometry...