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Volume 15, issue 23 | Copyright
Atmos. Chem. Phys., 15, 13377-13392, 2015
https://doi.org/10.5194/acp-15-13377-2015
© Author(s) 2015. This work is distributed under
the Creative Commons Attribution 3.0 License.

Research article 03 Dec 2015

Research article | 03 Dec 2015

Organic nitrate aerosol formation via NO3 + biogenic volatile organic compounds in the southeastern United States

B. R. Ayres1, H. M. Allen1,2, D. C. Draper1,3, S. S. Brown4, R. J. Wild4, J. L. Jimenez5,6, D. A. Day5,6, P. Campuzano-Jost5,6, W. Hu5,6, J. de Gouw5,6, A. Koss5,6, R. C. Cohen7, K. C. Duffey7, P. Romer7, K. Baumann8, E. Edgerton8, S. Takahama9, J. A. Thornton10, B. H. Lee10, F. D. Lopez-Hilfiker10, C. Mohr10,11, P. O. Wennberg12, T. B. Nguyen12, A. Teng12, A. H. Goldstein13, K. Olson13, and J. L. Fry1 B. R. Ayres et al.
  • 1Department of Chemistry, Reed College, Portland, OR, USA
  • 2Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA, USA
  • 3Department of Chemistry, University of California, Irvine, CA, USA
  • 4Earth System Research Laboratory, National Oceanic and Atmospheric Administration, Boulder, CO, USA
  • 5Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO, USA
  • 6Department of Chemistry and Biochemistry, University of Colorado, Boulder, CO, USA
  • 7Department of Chemistry, University of California at Berkeley, CA, USA
  • 8Applied Research Associates, Inc., Research Triangle Park, NC, USA
  • 9Department of Environmental Engineering, École polytechnique fédérale de Lausanne (EPFL), Switzerland
  • 10Department of Atmospheric Sciences, University of Washington, Seattle, WA, USA
  • 11Karlsruhe Institute of Technology, Karlsruhe, Germany
  • 12Division of Geological and Planetary Sciences and Division of Engineering and Applied Science, California Institute of Technology, Pasadena, CA, USA
  • 13Department of Environmental Science, Policy, and Management, University of California, Berkeley, CA, USA

Abstract. Gas- and aerosol-phase measurements of oxidants, biogenic volatile organic compounds (BVOCs) and organic nitrates made during the Southern Oxidant and Aerosol Study (SOAS campaign, Summer 2013) in central Alabama show that a nitrate radical (NO3) reaction with monoterpenes leads to significant secondary aerosol formation. Cumulative losses of NO3 to terpenes are correlated with increase in gas- and aerosol-organic nitrate concentrations made during the campaign. Correlation of NO3 radical consumption to organic nitrate aerosol formation as measured by aerosol mass spectrometry and thermal dissociation laser-induced fluorescence suggests a molar yield of aerosol-phase monoterpene nitrates of 23–44 %. Compounds observed via chemical ionization mass spectrometry (CIMS) are correlated to predicted nitrate loss to BVOCs and show C10H17NO5, likely a hydroperoxy nitrate, is a major nitrate-oxidized terpene product being incorporated into aerosols. The comparable isoprene product C5H9NO5 was observed to contribute less than 1 % of the total organic nitrate in the aerosol phase and correlations show that it is principally a gas-phase product from nitrate oxidation of isoprene. Organic nitrates comprise between 30 and 45 % of the NOy budget during SOAS. Inorganic nitrates were also monitored and showed that during incidents of increased coarse-mode mineral dust, HNO3 uptake produced nitrate aerosol mass loading at a rate comparable to that of organic nitrate produced via NO3 + BVOCs.

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This paper reports atmospheric gas- and aerosol-phase field measurements from the southeastern United States in summer 2013 to demonstrate that the oxidation of biogenic volatile organic compounds by nitrate radical produces a substantial amount of secondary organic aerosol in this region. This process, driven largely by monoterpenes, results in a comparable aerosol nitrate production rate to inorganic nitrate formation by heterogeneous uptake of HNO3 onto dust particles.
This paper reports atmospheric gas- and aerosol-phase field measurements from the southeastern...
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