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Organic nitrate aerosol formation via NO_3 + biogenic volatile organic compounds in the southeastern United States

Ayres, B. R. and Allen, H. M. and Draper, D. C. and Brown, S. S. and Wild, R. J. and Jimenez, J. L. and Day, D. A. and Campuzano-Jost, P. and Hu, W. and de Gouw, J. and Koss, A. and Cohen, R. C. and Duffey, K. C. and Romer, P. and Baumann, K. and Edgerton, E. and Takahama, S. and Thornton, J. A. and Lee, B. H. and Lopez-Hilfiker, F. D. and Mohr, C. and Wennberg, P. O. and Nguyen, T. B. and Teng, A. and Goldstein, A. H. and Olson, K. and Fry, J. L. (2015) Organic nitrate aerosol formation via NO_3 + biogenic volatile organic compounds in the southeastern United States. Atmospheric Chemistry and Physics, 15 (23). pp. 13377-13392. ISSN 1680-7324. https://resolver.caltech.edu/CaltechAUTHORS:20160115-095029693

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Abstract

Gas- and aerosol-phase measurements of oxidants, biogenic volatile organic compounds (BVOCs) and organic nitrates made during the Southern Oxidant and Aerosol Study (SOAS campaign, Summer 2013) in central Alabama show that a nitrate radical (NO_3) reaction with monoterpenes leads to significant secondary aerosol formation. Cumulative losses of NO_3 to terpenes are correlated with increase in gas- and aerosol-organic nitrate concentrations made during the campaign. Correlation of NO_3 radical consumption to organic nitrate aerosol formation as measured by aerosol mass spectrometry and thermal dissociation laser-induced fluorescence suggests a molar yield of aerosol-phase monoterpene nitrates of 23–44 %. Compounds observed via chemical ionization mass spectrometry (CIMS) are correlated to predicted nitrate loss to BVOCs and show C_(10)H_(17)NO_5, likely a hydroperoxy nitrate, is a major nitrate-oxidized terpene product being incorporated into aerosols. The comparable isoprene product C_5H_9NO_5 was observed to contribute less than 1 % of the total organic nitrate in the aerosol phase and correlations show that it is principally a gas-phase product from nitrate oxidation of isoprene. Organic nitrates comprise between 30 and 45 % of the NOy budget during SOAS. Inorganic nitrates were also monitored and showed that during incidents of increased coarse-mode mineral dust, HNO_3 uptake produced nitrate aerosol mass loading at a rate comparable to that of organic nitrate produced via NO_3 + BVOCs.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.5194/acp-15-13377-2015DOIArticle
http://www.atmos-chem-phys.net/15/13377/2015/PublisherArticle
http://dx.doi.org/10.5194/acp-15-13377-2015-supplementDOISupplemental Material
ORCID:
AuthorORCID
Jimenez, J. L.0000-0001-6203-1847
Wennberg, P. O.0000-0002-6126-3854
Additional Information:© Author(s) 2015. This work is distributed under the Creative Commons Attribution 3.0 License. Received: 12 May 2015 – Published in Atmos. Chem. Phys. Discuss.: 16 Jun 2015. Revised: 26 Oct 2015 – Accepted: 14 Nov 2015 – Published: 03 Dec 2015. We would like to acknowledge Anne Marie Carlton, Jim Moore and all of the colleagues that helped to set up this study. B. R. Ayres, H. M. Allen, D. C. Draper, and J. L. Fry gratefully acknowledge funding from the National Center for Environmental Research (NCER) STAR Program, EPA no. RD-83539901 and NOAA NA13OAR4310063. D. A. Day, P. Campuzano-Jost, and J. L. Jimenez thank NSF AGS-1243354 and NOAA NA13OAR4310063; R. C. Cohen thanks NSF AGS-1120076 and AGS-1352972.
Funders:
Funding AgencyGrant Number
Environmental Protection Agency (EPA)RD-83539901
National Oceanic and Atmospheric Administration (NOAA)NA13OAR4310063
NSFAGS-1243354
NSFAGS-1120076
NSFAGS-1352972
Issue or Number:23
Record Number:CaltechAUTHORS:20160115-095029693
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20160115-095029693
Official Citation:Ayres, B. R., Allen, H. M., Draper, D. C., Brown, S. S., Wild, R. J., Jimenez, J. L., Day, D. A., Campuzano-Jost, P., Hu, W., de Gouw, J., Koss, A., Cohen, R. C., Duffey, K. C., Romer, P., Baumann, K., Edgerton, E., Takahama, S., Thornton, J. A., Lee, B. H., Lopez-Hilfiker, F. D., Mohr, C., Wennberg, P. O., Nguyen, T. B., Teng, A., Goldstein, A. H., Olson, K., and Fry, J. L.: Organic nitrate aerosol formation via NO3 + biogenic volatile organic compounds in the southeastern United States, Atmos. Chem. Phys., 15, 13377-13392, doi:10.5194/acp-15-13377-2015, 2015.
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:63701
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:19 Jan 2016 21:02
Last Modified:03 Oct 2019 09:30

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