Articles | Volume 17, issue 3
Atmos. Chem. Phys., 17, 2103–2162, 2017
Atmos. Chem. Phys., 17, 2103–2162, 2017

Review article 13 Feb 2017

Review article | 13 Feb 2017

Nitrate radicals and biogenic volatile organic compounds: oxidation, mechanisms, and organic aerosol

Nga Lee Ng1,2, Steven S. Brown3,4, Alexander T. Archibald5, Elliot Atlas6, Ronald C. Cohen7, John N. Crowley8, Douglas A. Day9,4, Neil M. Donahue10, Juliane L. Fry11, Hendrik Fuchs12, Robert J. Griffin13, Marcelo I. Guzman14, Hartmut Herrmann15, Alma Hodzic16, Yoshiteru Iinuma15, José L. Jimenez9,4, Astrid Kiendler-Scharr12, Ben H. Lee17, Deborah J. Luecken18, Jingqiu Mao19,20,a, Robert McLaren21, Anke Mutzel15, Hans D. Osthoff22, Bin Ouyang23, Benedicte Picquet-Varrault24, Ulrich Platt25, Havala O. T. Pye18, Yinon Rudich26, Rebecca H. Schwantes27, Manabu Shiraiwa28, Jochen Stutz29, Joel A. Thornton17, Andreas Tilgner15, Brent J. Williams30, and Rahul A. Zaveri31 Nga Lee Ng et al.
  • 1School of Chemical and Biomolecular Engineering, Georgia Institute of Technology, Atlanta, GA, USA
  • 2School of Earth and Atmospheric Sciences, Georgia Institute of Technology, Atlanta, GA, USA
  • 3NOAA Earth System Research Laboratory, Chemical Sciences Division, Boulder, CO, USA
  • 4Department of Chemistry and Biochemistry, University of Colorado, Boulder, CO, USA
  • 5National Centre for Atmospheric Science, University of Cambridge, Cambridge, UK
  • 6Department of Atmospheric Sciences, RSMAS, University of Miami, Miami, FL, USA
  • 7Department of Chemistry, University of California at Berkeley, Berkeley, CA, USA
  • 8Max-Planck-Institut für Chemie, Division of Atmospheric Chemistry, Mainz, Germany
  • 9Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO, USA
  • 10Center for Atmospheric Particle Studies, Carnegie Mellon University, Pittsburgh, PA, USA
  • 11Department of Chemistry, Reed College, Portland, OR, USA
  • 12Institut für Energie und Klimaforschung: Troposphäre (IEK-8), Forschungszentrum Jülich, Jülich, Germany
  • 13Department of Civil and Environmental Engineering, Rice University, Houston, TX, USA
  • 14Department of Chemistry, University of Kentucky, Lexington, KY, USA
  • 15Atmospheric Chemistry Department, Leibniz Institute for Tropospheric Research, Leipzig, Germany
  • 16Atmospheric Chemistry Observations and Modeling, National Center for Atmospheric Research, Boulder, CO, USA
  • 17Department of Atmospheric Sciences, University of Washington, Seattle, WA, USA
  • 18National Exposure Research Laboratory, US Environmental Protection Agency, Research Triangle Park, NC, USA
  • 19Program in Atmospheric and Oceanic Sciences, Princeton University, Princeton, NJ, USA
  • 20Geophysical Fluid Dynamics Laboratory/National Oceanic and Atmospheric Administration, Princeton, NJ, USA
  • 21Centre for Atmospheric Chemistry, York University, Toronto, Ontario, Canada
  • 22Department of Chemistry, University of Calgary, Calgary, Alberta, Canada
  • 23Department of Chemistry, University of Cambridge, Cambridge, UK
  • 24Laboratoire Interuniversitaire des Systemes Atmospheriques (LISA), CNRS, Universities of Paris-Est Créteil and ì Paris Diderot, Institut Pierre Simon Laplace (IPSL), Créteil, France
  • 25Institute of Environmental Physics, University of Heidelberg, Heidelberg, Germany
  • 26Department of Earth and Planetary Sciences, Weizmann Institute, Rehovot, Israel
  • 27Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA, USA
  • 28Department of Chemistry, University of California Irvine, Irvine, CA, USA
  • 29Department of Atmospheric and Oceanic Sciences, University of California, Los Angeles, CA, USA
  • 30Department of Energy, Environmental and Chemical Engineering, Washington University in St. Louis, St. Louis, MO, USA
  • 31Atmospheric Sciences and Global Change Division, Pacific Northwest National Laboratory, Richland, WA, USA
  • anow at: Geophysical Institute and Department of Chemistry and Biochemistry, University of Alaska Fairbanks, Fairbanks, AK, USA

Abstract. Oxidation of biogenic volatile organic compounds (BVOC) by the nitrate radical (NO3) represents one of the important interactions between anthropogenic emissions related to combustion and natural emissions from the biosphere. This interaction has been recognized for more than 3 decades, during which time a large body of research has emerged from laboratory, field, and modeling studies. NO3-BVOC reactions influence air quality, climate and visibility through regional and global budgets for reactive nitrogen (particularly organic nitrates), ozone, and organic aerosol. Despite its long history of research and the significance of this topic in atmospheric chemistry, a number of important uncertainties remain. These include an incomplete understanding of the rates, mechanisms, and organic aerosol yields for NO3-BVOC reactions, lack of constraints on the role of heterogeneous oxidative processes associated with the NO3 radical, the difficulty of characterizing the spatial distributions of BVOC and NO3 within the poorly mixed nocturnal atmosphere, and the challenge of constructing appropriate boundary layer schemes and non-photochemical mechanisms for use in state-of-the-art chemical transport and chemistry–climate models.

This review is the result of a workshop of the same title held at the Georgia Institute of Technology in June 2015. The first half of the review summarizes the current literature on NO3-BVOC chemistry, with a particular focus on recent advances in instrumentation and models, and in organic nitrate and secondary organic aerosol (SOA) formation chemistry. Building on this current understanding, the second half of the review outlines impacts of NO3-BVOC chemistry on air quality and climate, and suggests critical research needs to better constrain this interaction to improve the predictive capabilities of atmospheric models.

Short summary
Oxidation of biogenic volatile organic compounds by NO3 is an important interaction between anthropogenic and natural emissions. This review results from a June 2015 workshop and includes the recent literature on kinetics, mechanisms, organic aerosol yields, and heterogeneous chemistry; advances in analytical instrumentation; the current state NO3-BVOC chemistry in atmospheric models; and critical needs for future research in modeling, field observations, and laboratory studies.
Final-revised paper