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Volume 16, issue 9
Atmos. Chem. Phys., 16, 5969-5991, 2016
https://doi.org/10.5194/acp-16-5969-2016
© Author(s) 2016. This work is distributed under
the Creative Commons Attribution 3.0 License.
Atmos. Chem. Phys., 16, 5969-5991, 2016
https://doi.org/10.5194/acp-16-5969-2016
© Author(s) 2016. This work is distributed under
the Creative Commons Attribution 3.0 License.

Research article 17 May 2016

Research article | 17 May 2016

Organic nitrate chemistry and its implications for nitrogen budgets in an isoprene- and monoterpene-rich atmosphere: constraints from aircraft (SEAC4RS) and ground-based (SOAS) observations in the Southeast US

Jenny A. Fisher1,2, Daniel J. Jacob3,4, Katherine R. Travis3, Patrick S. Kim4, Eloise A. Marais3, Christopher Chan Miller4, Karen Yu3, Lei Zhu3, Robert M. Yantosca3, Melissa P. Sulprizio3, Jingqiu Mao5,6, Paul O. Wennberg7,8, John D. Crounse7, Alex P. Teng7, Tran B. Nguyen7,a, Jason M. St. Clair7,b, Ronald C. Cohen9,10, Paul Romer9, Benjamin A. Nault10,c, Paul J. Wooldridge9, Jose L. Jimenez11,12, Pedro Campuzano-Jost11,12, Douglas A. Day11,12, Weiwei Hu11,12, Paul B. Shepson13,14, Fulizi Xiong13, Donald R. Blake15, Allen H. Goldstein16,17, Pawel K. Misztal16, Thomas F. Hanisco18, Glenn M. Wolfe18,19, Thomas B. Ryerson20, Armin Wisthaler21,22, and Tomas Mikoviny21 Jenny A. Fisher et al.
  • 1Centre for Atmospheric Chemistry, School of Chemistry, University of Wollongong, Wollongong, NSW, Australia
  • 2School of Earth and Environmental Sciences, University of Wollongong, Wollongong, NSW, Australia
  • 3Harvard John A. Paulson School of Engineering and Applied Sciences, Harvard University, Cambridge, MA, USA
  • 4Department of Earth and Planetary Sciences, Harvard University, Cambridge, MA, USA
  • 5Program in Atmospheric and Oceanic Sciences, Princeton University, Princeton, NJ, USA
  • 6Geophysical Fluid Dynamics Laboratory/National Oceanic and Atmospheric Administration, Princeton, NJ, USA
  • 7Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA, USA
  • 8Division of Engineering and Applied Science, California Institute of Technology, Pasadena, CA, USA
  • 9Department of Chemistry, University of California at Berkeley, Berkeley, CA, USA
  • 10Department of Earth and Planetary Science, University of California at Berkeley, Berkeley, CA, USA
  • 11Department of Chemistry and Biochemistry, University of Colorado, Boulder, CO, USA
  • 12Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO, USA
  • 13Department of Chemistry, Purdue University, West Lafayette, IN, USA
  • 14Department of Earth, Atmospheric and Planetary Sciences, Purdue University, West Lafayette, IN, USA
  • 15Department of Chemistry, University of California Irvine, Irvine, CA, USA
  • 16Department of Environmental Science, Policy, and Management, University of California at Berkeley, Berkeley, CA, USA
  • 17Department of Civil and Environmental Engineering, University of California at Berkeley, Berkeley, CA, USA
  • 18Atmospheric Chemistry and Dynamics Laboratory, NASA Goddard Space Flight Center, Greenbelt, MD, USA
  • 19Joint Center for Earth Systems Technology, University of Maryland Baltimore County, Baltimore, MD, USA
  • 20Chemical Sciences Division, Earth System Research Lab, National Oceanic and Atmospheric Administration, Boulder, CO, USA
  • 21Department of Chemistry, University of Oslo, Oslo, Norway
  • 22Institute for Ion Physics and Applied Physics, University of Innsbruck, Innsbruck, Austria
  • anow at: Department of Environmental Toxicology, University of California at Davis, Davis, CA, USA
  • bnow at: Atmospheric Chemistry and Dynamics Laboratory, NASA Goddard Space Flight Center, Greenbelt, MD, USA and Joint Center for Earth Systems Technology, University of Maryland Baltimore County, Baltimore, MD, USA
  • cnow at: Department of Chemistry and Biochemistry and Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO, USA

Abstract. Formation of organic nitrates (RONO2) during oxidation of biogenic volatile organic compounds (BVOCs: isoprene, monoterpenes) is a significant loss pathway for atmospheric nitrogen oxide radicals (NOx), but the chemistry of RONO2 formation and degradation remains uncertain. Here we implement a new BVOC oxidation mechanism (including updated isoprene chemistry, new monoterpene chemistry, and particle uptake of RONO2) in the GEOS-Chem global chemical transport model with  ∼  25  ×  25 km2 resolution over North America. We evaluate the model using aircraft (SEAC4RS) and ground-based (SOAS) observations of NOx, BVOCs, and RONO2 from the Southeast US in summer 2013. The updated simulation successfully reproduces the concentrations of individual gas- and particle-phase RONO2 species measured during the campaigns. Gas-phase isoprene nitrates account for 25–50 % of observed RONO2 in surface air, and we find that another 10 % is contributed by gas-phase monoterpene nitrates. Observations in the free troposphere show an important contribution from long-lived nitrates derived from anthropogenic VOCs. During both campaigns, at least 10 % of observed boundary layer RONO2 were in the particle phase. We find that aerosol uptake followed by hydrolysis to HNO3 accounts for 60 % of simulated gas-phase RONO2 loss in the boundary layer. Other losses are 20 % by photolysis to recycle NOx and 15 % by dry deposition. RONO2 production accounts for 20 % of the net regional NOx sink in the Southeast US in summer, limited by the spatial segregation between BVOC and NOx emissions. This segregation implies that RONO2 production will remain a minor sink for NOx in the Southeast US in the future even as NOx emissions continue to decline.

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We use new airborne and ground-based observations from two summer 2013 campaigns in the southeastern US, interpreted with a chemical transport model, to understand the impact of isoprene and monoterpene chemistry on the atmospheric NOx budget via production of organic nitrates (RONO2). We find that a diversity of species contribute to observed RONO2. Our work implies that the NOx sink to RONO2 production is only sensitive to NOx emissions in regions where they are already low.
We use new airborne and ground-based observations from two summer 2013 campaigns in the...
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