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Volume 15, issue 19
Atmos. Chem. Phys., 15, 11257-11272, 2015
https://doi.org/10.5194/acp-15-11257-2015
© Author(s) 2015. This work is distributed under
the Creative Commons Attribution 3.0 License.
Atmos. Chem. Phys., 15, 11257-11272, 2015
https://doi.org/10.5194/acp-15-11257-2015
© Author(s) 2015. This work is distributed under
the Creative Commons Attribution 3.0 License.

Research article 09 Oct 2015

Research article | 09 Oct 2015

Observation of isoprene hydroxynitrates in the southeastern United States and implications for the fate of NOx

F. Xiong1, K. M. McAvey1, K. A. Pratt1,3, C. J. Groff1, M. A. Hostetler1, M. A. Lipton1, T. K. Starn4, J. V. Seeley5, S. B. Bertman6, A. P. Teng7, J. D. Crounse8, T. B. Nguyen8, P. O. Wennberg7,8, P. K. Misztal9, A. H. Goldstein9,10, A. B. Guenther11, A. R. Koss12,13, K. F. Olson9, J. A. de Gouw12,13, K. Baumann14, E. S. Edgerton14, P. A. Feiner15, L. Zhang15, D. O. Miller15, W. H. Brune15, and P. B. Shepson1,2 F. Xiong et al.
  • 1Department of Chemistry, Purdue University, West Lafayette, IN, USA
  • 2Department of Earth, Atmospheric and Planetary Sciences, Purdue University, West Lafayette, IN, USA
  • 3Department of Chemistry, University of Michigan, Ann Arbor, MI, USA
  • 4Department of Chemistry, West Chester University of Pennsylvania, West Chester, PA, USA
  • 5Department of Chemistry, Oakland University, Rochester, MI, USA
  • 6Department of Chemistry, Western Michigan University, Kalamazoo, MI, USA
  • 7Division of Engineering and Applied Science, California Institute of Technology, Pasadena, CA, USA
  • 8Division of Geophysical and Planetary Sciences, California Institute of Technology, Pasadena, CA, USA
  • 9Department of Environmental Science, Policy, & Management, University of California at Berkeley, Berkeley, CA, USA
  • 10Department of Civil and Environmental Engineering, University of California at Berkeley, Berkeley, CA, USA
  • 11Atmospheric Sciences and Global Change Division, Pacific Northwest National Laboratory, Richland, WA, USA
  • 12Cooperative Institute for Research in Environmental Sciences, Boulder, CO, USA
  • 13NOAA Earth System Research Laboratory, Boulder, CO, USA
  • 14Atmospheric Research & Analysis, Inc., Cary, NC, USA
  • 15Department of Meteorology, Pennsylvania State University, University Park, PA, USA

Abstract. Isoprene hydroxynitrates (IN) are tracers of the photochemical oxidation of isoprene in high NOx environments. Production and loss of IN have a significant influence on the NOx cycle and tropospheric O3 chemistry. To better understand IN chemistry, a series of photochemical reaction chamber experiments was conducted to determine the IN yield from isoprene photooxidation at high NO concentrations (> 100 ppt). By combining experimental data and calculated isomer distributions, a total IN yield of 9(+4/−3) % was derived. The result was applied in a zero-dimensional model to simulate production and loss of ambient IN observed in a temperate forest atmosphere, during the Southern Oxidant and Aerosol Study (SOAS) field campaign, from 27 May to 11 July 2013. The 9 % yield was consistent with the observed IN/(MVK+MACR) ratios observed during SOAS. By comparing field observations with model simulations, we identified NO as the limiting factor for ambient IN production during SOAS, but vertical mixing at dawn might also contribute (~ 27 %) to IN dynamics. A close examination of isoprene's oxidation products indicates that its oxidation transitioned from a high-NO dominant chemical regime in the morning into a low-NO dominant regime in the afternoon. A significant amount of IN produced in the morning high NO regime could be oxidized in the low NO regime, and a possible reaction scheme was proposed.

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Hydroxynitrates from isoprene oxidation were quantified both in the laboratory and through field studies. The yield of hydroxynitrates 9(+4/-3)% derived from chamber experiments was applied in a zero-dimensional model to simulate the production and loss of isoprene hydroxynitrates in an ambient environment during the 2013 Southern Oxidant and Aerosol Study (SOAS). NOx was determined to be the limiting factor for the formation of isoprene hydroxynitrates during SOAS.
Hydroxynitrates from isoprene oxidation were quantified both in the laboratory and through field...
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