Organic nitrate chemistry and its implications for nitrogen budgets in an isoprene- and monoterpene-rich atmosphere: constraints from aircraft (SEAC(4)RS) and ground-based (SOAS) observations in the Southeast US

Details

• Journal Title:
  Atmospheric Chemistry and Physics
• Personal Author:
  Fisher, Jenny A. ; Jacob, Daniel J. ; Travis, Katherine R. ; Kim, Patrick S. ; Marais, Eloise A. ; Chan Miller, Christopher ; Yu, Karen ; Zhu, Lei ; Yantosca, Robert M. ; Sulprizio, Melissa P. ; Mao, Jingqiu ; Wennberg, Paul O. ; Crounse, John D. ; Teng, Alex P. ; Nguyen, Tran B. ; St. Clair, Jason M. ; Cohen, Ronald C. ; Romer, Paul ; Nault, Benjamin A. ; Wooldridge, Paul J. ; Jimenez, Jose L. ; Campuzano-Jost, Pedro ; Day, Douglas A. ; Hu, Weiwei ; Shepson, Paul B. ; Xiong, Fulizi ; Blake, Donald R. ; Goldstein, Allen H. ; Misztal, Pawel K. ; Hanisco, Thomas F. ; Wolfe, Glenn M. ; Ryerson, Thomas B. ; Wisthaler, Armin ; Mikoviny, Tomas
• NOAA Program & Office:
  OAR (Oceanic and Atmospheric Research) ; ESRL (Earth System Research Laboratory) ; CIRES (Cooperative Institute for Research in Environmental Sciences) ; CSL (Chemical Sciences Laboratory) ; GFDL (Geophysical Fluid Dynamics Laboratory)
• Description:
  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 similar to aEuro-25aEuro- x aEuro-25aEuro-km(2) resolution over North America. We evaluate the model using aircraft (SEAC(4)RS) 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 25-50aEuro-% of observed RONO2 in surface air, and we find that another 10aEuro-% 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 10aEuro-% of observed boundary layer RONO2 were in the particle phase. We find that aerosol uptake followed by hydrolysis to HNO3 accounts for 60aEuro-% of simulated gas-phase RONO2 loss in the boundary layer. Other losses are 20aEuro-% by photolysis to recycle NOx and 15aEuro-% by dry deposition. RONO2 production accounts for 20aEuro-% 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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• Source:
  Atmospheric Chemistry and Physics, 16(9), 5969-5991.
• DOI:
  https://doi.org/10.5194/acp-16-5969-2016
• Document Type:
  Journal Article
• Funding:
  Grant no. NA13OAR4310071
• Rights Information:
  CC BY
• Compliance:
  Submitted
• Main Document Checksum:
  urn:sha256:57e7eb04b291ad3702c2c0f12ec63bf1c3e1fe812f6642263bc13fce444d3866
• Download URL:
  https://repository.library.noaa.gov/view/noaa/21575/noaa_21575_DS1.pdf
• File Type:
  [PDF - 3.01 MB ]