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Importance of biogenic precursors to the budget of organic nitrates: observations of multifunctional organic nitrates by CIMS and TD-LIF during BEARPEX 2009

Beaver, M. R. and St. Clair, J. M. and Paulot, F. and Spencer, K. M. and Crounse, J. D. and LaFranchi, B. W. and Min, K. E. and Pusede, S. E. and Wooldridge, P. J. and Schade, G. W. and Park, C. and Cohen, R. C. and Wennberg, P. O. (2012) Importance of biogenic precursors to the budget of organic nitrates: observations of multifunctional organic nitrates by CIMS and TD-LIF during BEARPEX 2009. Atmospheric Chemistry and Physics, 12 (13). pp. 5773-5785. ISSN 1680-7316. https://resolver.caltech.edu/CaltechAUTHORS:20120813-101910446

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Abstract

Alkyl and multifunctional organic nitrates, molecules of the chemical form RONO_2, are products of chain terminating reactions in the tropospheric HO_x and NO_x catalytic cycles and thereby impact ozone formation locally. Many of the molecules in the class have lifetimes that are long enough that they can be transported over large distances. If the RONO_2 then decompose to deliver NO_x to remote regions they affect ozone production rates in locations distant from the original NO_x source. While measurements of total RONO_2 (ΣANs) and small straight chain alkyl nitrates are routine, measurements of the specific multifunctional RONO_2 molecules that are believed to dominate the total have rarely been reported and never reported in coincidence with ambient ΣANs measurements. Here we describe observations obtained during the BEARPEX 2009 experiment including ΣANs and a suite of multifunctional nitrates including isoprene derived hydroxynitrates, oxidation products of those nitrates, 2-methyl-3-buten-2-ol (MBO) derived hydroxynitrates, and monoterpene nitrates. At the BEARPEX field site, the sum of the individual biogenically derived nitrates account for two-thirds of the ΣANs, confirming predictions of the importance of biogenic nitrates to the NO_y budget. Isoprene derived nitrates, transported to the site, are a much larger fraction of the ΣANs at the site than the nitrates derived from the locally emitted MBO. Evidence for additional nitrates, possibly from nocturnal chemistry of isoprene and α-pinene, is presented.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.5194/acp-12-5773-2012DOIArticle
http://www.atmos-chem-phys.net/12/5773/2012/PublisherArticle
ORCID:
AuthorORCID
St. Clair, J. M.0000-0002-9367-5749
Paulot, F.0000-0001-7534-4922
Crounse, J. D.0000-0001-5443-729X
Cohen, R. C.0000-0001-6617-7691
Wennberg, P. O.0000-0002-6126-3854
Additional Information:© 2012 Author(s). This work is distributed under the Creative Commons Attribution 3.0 License. Published by Copernicus Publications on behalf of the European Geosciences Union. Received: 11 November 2011; Published in Atmos. Chem. Phys. Discuss.: 4 January 2012; Revised: 23 May 2012; Accepted: 6 June 2012; Published: 3 July 2012. This research was supported by the National Science Foundation (grants ATM-0934408 and ATM-0934345). We thank Sierra Pacific Industries for the use of their land, and the University of California, Berkeley, Center for Forestry, Blodgett Forest Research Station for cooperation in facilitating this research. MRB also thanks Ying Xie (US EPA) and Ellie Browne (UCB) for helpful comments on the manuscript. Edited by: J. Williams
Funders:
Funding AgencyGrant Number
NSFATM-0934408
NSFATM-0934345
Issue or Number:13
Record Number:CaltechAUTHORS:20120813-101910446
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20120813-101910446
Official Citation:Beaver, M. R., Clair, J. M. St., Paulot, F., Spencer, K. M., Crounse, J. D., LaFranchi, B. W., Min, K. E., Pusede, S. E., Wooldridge, P. J., Schade, G. W., Park, C., Cohen, R. C., and Wennberg, P. O.: Importance of biogenic precursors to the budget of organic nitrates: observations of multifunctional organic nitrates by CIMS and TD-LIF during BEARPEX 2009, Atmos. Chem. Phys., 12, 5773-5785, doi:10.5194/acp-12-5773-2012, 2012.
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:33119
Collection:CaltechAUTHORS
Deposited By: Aucoeur Ngo
Deposited On:13 Aug 2012 17:52
Last Modified:09 Mar 2020 13:19

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