Articles | Volume 16, issue 9
https://doi.org/10.5194/acp-16-5969-2016
© Author(s) 2016. This work is distributed under
the Creative Commons Attribution 3.0 License.
the Creative Commons Attribution 3.0 License.
https://doi.org/10.5194/acp-16-5969-2016
© Author(s) 2016. This work is distributed under
the Creative Commons Attribution 3.0 License.
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
Centre for Atmospheric Chemistry, School of Chemistry, University of Wollongong, Wollongong, NSW, Australia
School of Earth and Environmental Sciences, University of Wollongong, Wollongong, NSW, Australia
Daniel J. Jacob
Harvard John A. Paulson School of Engineering and Applied Sciences, Harvard University, Cambridge, MA, USA
Department of Earth and Planetary Sciences, Harvard University, Cambridge, MA, USA
Katherine R. Travis
Harvard John A. Paulson School of Engineering and Applied Sciences, Harvard University, Cambridge, MA, USA
Patrick S. Kim
Department of Earth and Planetary Sciences, Harvard University, Cambridge, MA, USA
Eloise A. Marais
Harvard John A. Paulson School of Engineering and Applied Sciences, Harvard University, Cambridge, MA, USA
Christopher Chan Miller
Department of Earth and Planetary Sciences, Harvard University, Cambridge, MA, USA
Karen Yu
Harvard John A. Paulson School of Engineering and Applied Sciences, Harvard University, Cambridge, MA, USA
Harvard John A. Paulson School of Engineering and Applied Sciences, Harvard University, Cambridge, MA, USA
Robert M. Yantosca
Harvard John A. Paulson School of Engineering and Applied Sciences, Harvard University, Cambridge, MA, USA
Melissa P. Sulprizio
Harvard John A. Paulson School of Engineering and Applied Sciences, Harvard University, Cambridge, MA, USA
Jingqiu Mao
Program in Atmospheric and Oceanic Sciences, Princeton University, Princeton, NJ, USA
Geophysical Fluid Dynamics Laboratory/National Oceanic and Atmospheric Administration, Princeton, NJ, USA
Paul O. Wennberg
Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA, USA
Division of Engineering and Applied Science, California Institute of Technology, Pasadena, CA, USA
John D. Crounse
Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA, USA
Alex P. Teng
Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA, USA
Tran B. Nguyen
Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA, USA
now at: Department of Environmental Toxicology, University of California at Davis, Davis, CA, USA
Jason M. St. Clair
Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA, USA
now 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
Ronald C. Cohen
Department of Chemistry, University of California at Berkeley, Berkeley, CA, USA
Department of Earth and Planetary Science, University of California at Berkeley, Berkeley, CA, USA
Paul Romer
Department of Chemistry, University of California at Berkeley, Berkeley, CA, USA
Benjamin A. Nault
Department of Earth and Planetary Science, University of California at Berkeley, Berkeley, CA, USA
now at: Department of Chemistry and Biochemistry and Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO, USA
Paul J. Wooldridge
Department of Chemistry, University of California at Berkeley, Berkeley, CA, USA
Jose L. Jimenez
Department of Chemistry and Biochemistry, University of Colorado, Boulder, CO, USA
Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO, USA
Pedro Campuzano-Jost
Department of Chemistry and Biochemistry, University of Colorado, Boulder, CO, USA
Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO, USA
Douglas A. Day
Department of Chemistry and Biochemistry, University of Colorado, Boulder, CO, USA
Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO, USA
Weiwei Hu
Department of Chemistry and Biochemistry, University of Colorado, Boulder, CO, USA
Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO, USA
Paul B. Shepson
Department of Chemistry, Purdue University, West Lafayette, IN, USA
Department of Earth, Atmospheric and Planetary Sciences, Purdue University, West Lafayette, IN, USA
Fulizi Xiong
Department of Chemistry, Purdue University, West Lafayette, IN, USA
Donald R. Blake
Department of Chemistry, University of California Irvine, Irvine, CA, USA
Allen H. Goldstein
Department of Environmental Science, Policy, and Management, University of California at Berkeley, Berkeley, CA, USA
Department of Civil and Environmental Engineering, University of California at Berkeley, Berkeley, CA, USA
Pawel K. Misztal
Department of Environmental Science, Policy, and Management, University of California at Berkeley, Berkeley, CA, USA
Thomas F. Hanisco
Atmospheric Chemistry and Dynamics Laboratory, NASA Goddard Space Flight Center, Greenbelt, MD, USA
Glenn M. Wolfe
Atmospheric Chemistry and Dynamics Laboratory, NASA Goddard Space Flight Center, Greenbelt, MD, USA
Joint Center for Earth Systems Technology, University of Maryland Baltimore County, Baltimore, MD, USA
Thomas B. Ryerson
Chemical Sciences Division, Earth System Research Lab, National Oceanic and Atmospheric Administration, Boulder, CO, USA
Armin Wisthaler
Department of Chemistry, University of Oslo, Oslo, Norway
Institute for Ion Physics and Applied Physics, University of Innsbruck, Innsbruck, Austria
Tomas Mikoviny
Department of Chemistry, University of Oslo, Oslo, Norway
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.
Download & links
- Article
(3086 KB) - Full-text XML
-
Supplement
(304 KB) - BibTeX
- EndNote
How to cite. Fisher, J. A., Jacob, D. J., Travis, K. R., Kim, P. S., Marais, E. A., Chan Miller, C., Yu, K., Zhu, L., Yantosca, R. M., Sulprizio, M. P., Mao, J., Wennberg, P. O., Crounse, J. D., Teng, A. P., Nguyen, T. B., St. Clair, J. M., Cohen, R. C., Romer, P., Nault, B. A., Wooldridge, P. J., Jimenez, J. L., Campuzano-Jost, P., Day, D. A., Hu, W., Shepson, P. B., Xiong, F., Blake, D. R., Goldstein, A. H., Misztal, P. K., Hanisco, T. F., Wolfe, G. M., Ryerson, T. B., Wisthaler, A., and Mikoviny, T.: 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, Atmos. Chem. Phys., 16, 5969–5991, https://doi.org/10.5194/acp-16-5969-2016, 2016.
Short summary
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...
Altmetrics
Final-revised paper
Preprint