Rapid cycling of reactive nitrogen in the marine boundary layer. Ye, C., Zhou, X., Pu, D., Stutz, J., Festa, J., Spolaor, M., Tsai, C., Cantrell, C., Mauldin, R., L., Campos, T., Weinheimer, A., Hornbrook, R., S., Apel, E., C., Guenther, A., Kaser, L., Yuan, B., Karl, T., Haggerty, J., Hall, S., Ullmann, K., Smith, J., N., Ortega, J., & Knote, C. Nature, 532(7600):489-491, 2016.
Rapid cycling of reactive nitrogen in the marine boundary layer [link]Website  doi  abstract   bibtex   1 download  
Nitrogen oxides are essential for the formation of secondary atmospheric aerosols and of atmospheric oxidants such as ozone and the hydroxyl radical, which controls the self-cleansing capacity of the atmosphere. Nitric acid, a major oxidation product of nitrogen oxides, has traditionally been considered to be a permanent sink of nitrogen oxides. However, model studies predict higher ratios of nitric acid to nitrogen oxides in the troposphere than are observed. A "renoxification" process that recycles nitric acid into nitrogen oxides has been proposed to reconcile observations with model studies, but the mechanisms responsible for this process remain uncertain. Here we present data from an aircraft measurement campaign over the North Atlantic Ocean and find evidence for rapid recycling of nitric acid to nitrous acid and nitrogen oxides in the clean marine boundary layer via particulate nitrate photolysis. Laboratory experiments further demonstrate the photolysis of particulate nitrate collected on filters at a rate more than two orders of magnitude greater than that of gaseous nitric acid, with nitrous acid as the main product. Box model calculations based on the Master Chemical Mechanism suggest that particulate nitrate photolysis mainly sustains the observed levels of nitrous acid and nitrogen oxides at midday under typical marine boundary layer conditions. Given that oceans account for more than 70 per cent of Earth's surface, we propose that particulate nitrate photolysis could be a substantial tropospheric nitrogen oxide source. Recycling of nitrogen oxides in remote oceanic regions with minimal direct nitrogen oxide emissions could increase the formation of tropospheric oxidants and secondary atmospheric aerosols on a global scale.
@article{
 title = {Rapid cycling of reactive nitrogen in the marine boundary layer},
 type = {article},
 year = {2016},
 pages = {489-491},
 volume = {532},
 websites = {http://www.nature.com/doifinder/10.1038/nature17195},
 id = {c42868b5-f19c-3d2d-b4da-bb3838979255},
 created = {2017-04-12T23:44:41.539Z},
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 last_modified = {2020-08-21T23:00:49.215Z},
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 citation_key = {Ye2016},
 source_type = {article},
 notes = {Times Cited: 0 0 1476-4687},
 private_publication = {false},
 abstract = {Nitrogen oxides are essential for the formation of secondary atmospheric aerosols and of atmospheric oxidants such as ozone and the hydroxyl radical, which controls the self-cleansing capacity of the atmosphere. Nitric acid, a major oxidation product of nitrogen oxides, has traditionally been considered to be a permanent sink of nitrogen oxides. However, model studies predict higher ratios of nitric acid to nitrogen oxides in the troposphere than are observed. A "renoxification" process that recycles nitric acid into nitrogen oxides has been proposed to reconcile observations with model studies, but the mechanisms responsible for this process remain uncertain. Here we present data from an aircraft measurement campaign over the North Atlantic Ocean and find evidence for rapid recycling of nitric acid to nitrous acid and nitrogen oxides in the clean marine boundary layer via particulate nitrate photolysis. Laboratory experiments further demonstrate the photolysis of particulate nitrate collected on filters at a rate more than two orders of magnitude greater than that of gaseous nitric acid, with nitrous acid as the main product. Box model calculations based on the Master Chemical Mechanism suggest that particulate nitrate photolysis mainly sustains the observed levels of nitrous acid and nitrogen oxides at midday under typical marine boundary layer conditions. Given that oceans account for more than 70 per cent of Earth's surface, we propose that particulate nitrate photolysis could be a substantial tropospheric nitrogen oxide source. Recycling of nitrogen oxides in remote oceanic regions with minimal direct nitrogen oxide emissions could increase the formation of tropospheric oxidants and secondary atmospheric aerosols on a global scale.},
 bibtype = {article},
 author = {Ye, Chunxiang and Zhou, Xianliang and Pu, Dennis and Stutz, Jochen and Festa, James and Spolaor, Max and Tsai, Catalina and Cantrell, Christopher and Mauldin, Roy L. and Campos, Teresa and Weinheimer, Andrew and Hornbrook, Rebecca S. and Apel, Eric C. and Guenther, Alex and Kaser, Lisa and Yuan, Bin and Karl, Thomas and Haggerty, Julie and Hall, Samuel and Ullmann, Kirk and Smith, James N. and Ortega, John and Knote, Christoph},
 doi = {10.1038/nature17195},
 journal = {Nature},
 number = {7600}
}
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