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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

Journal Article


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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.

UOW Authors


  •   Fisher, Jenny
  •   Jacob, Daniel J. (external author)
  •   Travis, Katherine R. (external author)
  •   Kim, Patrick S. (external author)
  •   Marais, Eloise A. (external author)
  •   Miller, Christopher C. (external author)
  •   Yu, Karen (external author)
  •   Zhu, Lei (external author)
  •   Yantosca, Robert M. (external author)
  •   Sulprizio, Melissa P. (external author)
  •   Mao, Jingqiu (external author)
  •   Wennberg, Paul O. (external author)
  •   Crounse, John D. (external author)
  •   Teng, Alex P. (external author)
  •   Nguyen, Tran B. (external author)
  •   St. Clair, Jason M. (external author)
  •   Cohen, Ronald C. (external author)
  •   Romer, Paul (external author)
  •   Nault, Benjamin A. (external author)
  •   Wooldridge, Paul J. (external author)
  •   Jimenez, Jose L. (external author)
  •   Campuzano-Jost, Pedro (external author)
  •   Day, Douglas A. (external author)
  •   Hu, Weiwei (external author)
  •   Shepson, Paul B. (external author)
  •   Xiong, Fulizi (external author)
  •   Blake, Donald R. (external author)
  •   Goldstein, Allen H. (external author)
  •   Misztal, Pawel K. (external author)
  •   Hanisco, Thomas (external author)
  •   Wolfe, Glenn M. (external author)
  •   Ryerson, Thomas B. (external author)
  •   Wisthaler, Armin (external author)
  •   Mikoviny, Tomas (external author)

Publication Date


  • 2016

Citation


  • Fisher, J. A., Jacob, D. J., Travis, K. R., Kim, P. S., Marais, E. A., Miller, C. Chan., 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. & Mikoviny, T. (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. Atmospheric Chemistry and Physics, 16 (9), 5969-5991.

Scopus Eid


  • 2-s2.0-84969781190

Ro Full-text Url


  • http://ro.uow.edu.au/cgi/viewcontent.cgi?article=4829&context=smhpapers

Ro Metadata Url


  • http://ro.uow.edu.au/smhpapers/3806

Number Of Pages


  • 22

Start Page


  • 5969

End Page


  • 5991

Volume


  • 16

Issue


  • 9

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.

UOW Authors


  •   Fisher, Jenny
  •   Jacob, Daniel J. (external author)
  •   Travis, Katherine R. (external author)
  •   Kim, Patrick S. (external author)
  •   Marais, Eloise A. (external author)
  •   Miller, Christopher C. (external author)
  •   Yu, Karen (external author)
  •   Zhu, Lei (external author)
  •   Yantosca, Robert M. (external author)
  •   Sulprizio, Melissa P. (external author)
  •   Mao, Jingqiu (external author)
  •   Wennberg, Paul O. (external author)
  •   Crounse, John D. (external author)
  •   Teng, Alex P. (external author)
  •   Nguyen, Tran B. (external author)
  •   St. Clair, Jason M. (external author)
  •   Cohen, Ronald C. (external author)
  •   Romer, Paul (external author)
  •   Nault, Benjamin A. (external author)
  •   Wooldridge, Paul J. (external author)
  •   Jimenez, Jose L. (external author)
  •   Campuzano-Jost, Pedro (external author)
  •   Day, Douglas A. (external author)
  •   Hu, Weiwei (external author)
  •   Shepson, Paul B. (external author)
  •   Xiong, Fulizi (external author)
  •   Blake, Donald R. (external author)
  •   Goldstein, Allen H. (external author)
  •   Misztal, Pawel K. (external author)
  •   Hanisco, Thomas (external author)
  •   Wolfe, Glenn M. (external author)
  •   Ryerson, Thomas B. (external author)
  •   Wisthaler, Armin (external author)
  •   Mikoviny, Tomas (external author)

Publication Date


  • 2016

Citation


  • Fisher, J. A., Jacob, D. J., Travis, K. R., Kim, P. S., Marais, E. A., Miller, C. Chan., 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. & Mikoviny, T. (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. Atmospheric Chemistry and Physics, 16 (9), 5969-5991.

Scopus Eid


  • 2-s2.0-84969781190

Ro Full-text Url


  • http://ro.uow.edu.au/cgi/viewcontent.cgi?article=4829&context=smhpapers

Ro Metadata Url


  • http://ro.uow.edu.au/smhpapers/3806

Number Of Pages


  • 22

Start Page


  • 5969

End Page


  • 5991

Volume


  • 16

Issue


  • 9