Atmospheric Chemistry and Physics (May 2016)
Organic nitrate chemistry and its implications for nitrogen budgets in an isoprene- and monoterpene-rich atmosphere: constraints from aircraft (SEAC<sup>4</sup>RS) and ground-based (SOAS) observations in the Southeast US
- J. A. Fisher,
- J. A. Fisher,
- D. J. Jacob,
- D. J. Jacob,
- K. R. Travis,
- P. S. Kim,
- E. A. Marais,
- C. Chan Miller,
- K. Yu,
- L. Zhu,
- R. M. Yantosca,
- M. P. Sulprizio,
- J. Mao,
- J. Mao,
- P. O. Wennberg,
- P. O. Wennberg,
- J. D. Crounse,
- A. P. Teng,
- T. B. Nguyen,
- T. B. Nguyen,
- J. M. St. Clair,
- J. M. St. Clair,
- R. C. Cohen,
- R. C. Cohen,
- P. Romer,
- B. A. Nault,
- B. A. Nault,
- P. J. Wooldridge,
- J. L. Jimenez,
- J. L. Jimenez,
- P. Campuzano-Jost,
- P. Campuzano-Jost,
- D. A. Day,
- D. A. Day,
- W. Hu,
- W. Hu,
- P. B. Shepson,
- P. B. Shepson,
- F. Xiong,
- D. R. Blake,
- A. H. Goldstein,
- A. H. Goldstein,
- P. K. Misztal,
- T. F. Hanisco,
- G. M. Wolfe,
- G. M. Wolfe,
- T. B. Ryerson,
- A. Wisthaler,
- A. Wisthaler,
- T. Mikoviny
Affiliations
- J. A. Fisher
- Centre for Atmospheric Chemistry, School of Chemistry, University of Wollongong, Wollongong, NSW, Australia
- J. A. Fisher
- School of Earth and Environmental Sciences, University of Wollongong, Wollongong, NSW, Australia
- D. J. Jacob
- Harvard John A. Paulson School of Engineering and Applied Sciences, Harvard University, Cambridge, MA, USA
- D. J. Jacob
- Department of Earth and Planetary Sciences, Harvard University, Cambridge, MA, USA
- K. R. Travis
- Harvard John A. Paulson School of Engineering and Applied Sciences, Harvard University, Cambridge, MA, USA
- P. S. Kim
- Department of Earth and Planetary Sciences, Harvard University, Cambridge, MA, USA
- E. A. Marais
- Harvard John A. Paulson School of Engineering and Applied Sciences, Harvard University, Cambridge, MA, USA
- C. Chan Miller
- Department of Earth and Planetary Sciences, Harvard University, Cambridge, MA, USA
- K. Yu
- Harvard John A. Paulson School of Engineering and Applied Sciences, Harvard University, Cambridge, MA, USA
- L. Zhu
- Harvard John A. Paulson School of Engineering and Applied Sciences, Harvard University, Cambridge, MA, USA
- R. M. Yantosca
- Harvard John A. Paulson School of Engineering and Applied Sciences, Harvard University, Cambridge, MA, USA
- M. P. Sulprizio
- Harvard John A. Paulson School of Engineering and Applied Sciences, Harvard University, Cambridge, MA, USA
- J. Mao
- Program in Atmospheric and Oceanic Sciences, Princeton University, Princeton, NJ, USA
- J. Mao
- Geophysical Fluid Dynamics Laboratory/National Oceanic and Atmospheric Administration, Princeton, NJ, USA
- P. O. Wennberg
- Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA, USA
- P. O. Wennberg
- Division of Engineering and Applied Science, California Institute of Technology, Pasadena, CA, USA
- J. D. Crounse
- Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA, USA
- A. P. Teng
- Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA, USA
- T. B. Nguyen
- Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA, USA
- T. B. Nguyen
- now at: Department of Environmental Toxicology, University of California at Davis, Davis, CA, USA
- J. M. St. Clair
- Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA, USA
- J. M. St. Clair
- 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
- R. C. Cohen
- Department of Chemistry, University of California at Berkeley, Berkeley, CA, USA
- R. C. Cohen
- Department of Earth and Planetary Science, University of California at Berkeley, Berkeley, CA, USA
- P. Romer
- Department of Chemistry, University of California at Berkeley, Berkeley, CA, USA
- B. A. Nault
- Department of Earth and Planetary Science, University of California at Berkeley, Berkeley, CA, USA
- B. A. Nault
- now at: Department of Chemistry and Biochemistry and Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO, USA
- P. J. Wooldridge
- Department of Chemistry, University of California at Berkeley, Berkeley, CA, USA
- J. L. Jimenez
- Department of Chemistry and Biochemistry, University of Colorado, Boulder, CO, USA
- J. L. Jimenez
- Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO, USA
- P. Campuzano-Jost
- Department of Chemistry and Biochemistry, University of Colorado, Boulder, CO, USA
- P. Campuzano-Jost
- Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO, USA
- D. A. Day
- Department of Chemistry and Biochemistry, University of Colorado, Boulder, CO, USA
- D. A. Day
- Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO, USA
- W. Hu
- Department of Chemistry and Biochemistry, University of Colorado, Boulder, CO, USA
- W. Hu
- Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO, USA
- P. B. Shepson
- Department of Chemistry, Purdue University, West Lafayette, IN, USA
- P. B. Shepson
- Department of Earth, Atmospheric and Planetary Sciences, Purdue University, West Lafayette, IN, USA
- F. Xiong
- Department of Chemistry, Purdue University, West Lafayette, IN, USA
- D. R. Blake
- Department of Chemistry, University of California Irvine, Irvine, CA, USA
- A. H. Goldstein
- Department of Environmental Science, Policy, and Management, University of California at Berkeley, Berkeley, CA, USA
- A. H. Goldstein
- Department of Civil and Environmental Engineering, University of California at Berkeley, Berkeley, CA, USA
- P. K. Misztal
- Department of Environmental Science, Policy, and Management, University of California at Berkeley, Berkeley, CA, USA
- T. F. Hanisco
- Atmospheric Chemistry and Dynamics Laboratory, NASA Goddard Space Flight Center, Greenbelt, MD, USA
- G. M. Wolfe
- Atmospheric Chemistry and Dynamics Laboratory, NASA Goddard Space Flight Center, Greenbelt, MD, USA
- G. M. Wolfe
- Joint Center for Earth Systems Technology, University of Maryland Baltimore County, Baltimore, MD, USA
- T. B. Ryerson
- Chemical Sciences Division, Earth System Research Lab, National Oceanic and Atmospheric Administration, Boulder, CO, USA
- A. Wisthaler
- Department of Chemistry, University of Oslo, Oslo, Norway
- A. Wisthaler
- Institute for Ion Physics and Applied Physics, University of Innsbruck, Innsbruck, Austria
- T. Mikoviny
- Department of Chemistry, University of Oslo, Oslo, Norway
- DOI
- https://doi.org/10.5194/acp-16-5969-2016
- Journal volume & issue
-
Vol. 16
pp. 5969 – 5991
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.
