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Gas-Phase Reactions of Isoprene and Its Major Oxidation Products

Wennberg, Paul O. and Bates, Kelvin H. and Crounse, John D. and Dodson, Leah G. and McVay, Renee C. and Mertens, Laura A. and Nguyen, Tran B. and Praske, Eric and Schwantes, Rebecca H. and Smarte, Matthew D. and St Clair, Jason M. and Teng, Alexander P. and Zhang, Xuan and Seinfeld, John H. (2018) Gas-Phase Reactions of Isoprene and Its Major Oxidation Products. Chemical Reviews, 118 (7). pp. 3337-3390. ISSN 0009-2665. http://resolver.caltech.edu/CaltechAUTHORS:20180314-102355395

[img] PDF (Proposed mechanisms for oxidation of (1,4)-HC5 and (4,1)-HC5 by OH; mechanisms of reactions of OH with C5-β-hydroperoxyaldehydes formed following 1,6 H-shifts of Z-δ-(1,4)- and Z-δ-(4,1)-ISOPOO; photolysis mechanisms of C4 DHP carbonyl compounds formed...) - Supplemental Material
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Abstract

Isoprene carries approximately half of the flux of non-methane volatile organic carbon emitted to the atmosphere by the biosphere. Accurate representation of its oxidation rate and products is essential for quantifying its influence on the abundance of the hydroxyl radical (OH), nitrogen oxide free radicals (NO_x), ozone (O_3), and, via the formation of highly oxygenated compounds, aerosol. We present a review of recent laboratory and theoretical studies of the oxidation pathways of isoprene initiated by addition of OH, O_3, the nitrate radical (NO_3), and the chlorine atom. From this review, a recommendation for a nearly complete gas-phase oxidation mechanism of isoprene and its major products is developed. The mechanism is compiled with the aims of providing an accurate representation of the flow of carbon while allowing quantification of the impact of isoprene emissions on HO_x and NO_x free radical concentrations and of the yields of products known to be involved in condensed-phase processes. Finally, a simplified (reduced) mechanism is developed for use in chemical transport models that retains the essential chemistry required to accurately simulate isoprene oxidation under conditions where it occurs in the atmosphere—above forested regions remote from large NO_x emissions.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/acs.chemrev.7b00439DOIArticle
https://pubs.acs.org/doi/10.1021/acs.chemrev.7b00439PublisherArticle
https://pubs.acs.org/doi/suppl/10.1021/acs.chemrev.7b00439PublisherSupporting Information
ORCID:
AuthorORCID
Wennberg, Paul O.0000-0002-6126-3854
Bates, Kelvin H.0000-0001-7544-9580
Crounse, John D.0000-0001-5443-729X
McVay, Renee C.0000-0001-7766-5009
Schwantes, Rebecca H.0000-0002-7095-3718
Teng, Alexander P.0000-0002-6434-0501
Zhang, Xuan0000-0003-1548-8021
Seinfeld, John H.0000-0003-1344-4068
Additional Information:© 2018 American Chemical Society. Received: July 21, 2017; Publication Date (Web): March 9, 2018. Additional Data: Additional detailed treatments of the reactions can be found at http://dx.doi.org/10.22002/D1.247, where the full and reduced mechanisms are made available as computer-readable codes for communal use and development. We acknowledge support for this study by the Electric Power Research Institute, the National Science Foundation (AGS-1240604 and CHE-1508526), and the National Aeronautics and Space Administration (NNX14AP46G). P.O.W. thanks the University of Copenhagen and Henrik Kjaergaard for hosting his sabbatical during which much of this work was completed. He further thanks Henrik Kjaergaard, Kristian Møller, and Rasmus Otkjær for help with the H-shift chemistry. T.B.N. thanks the National Science Foundation AGS Postdoctoral Research Fellowship for support (AGS-1331360). L.G.D. was supported by an EPA STAR Fellowship and a Sandia Campus Executive Laboratory Directed Research and Development (LDRD) project. K.H.B. and M.D.S. acknowledge support from the National Science Foundation Graduate Research Fellowship program. The National Center for Atmospheric Research is sponsored by the National Science Foundation. Finally, we acknowledge the heroic effort of the anonymous reviewers; they provided excellent feedback that substantially improved our manuscript. The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
Electric Power Research Institute (EPRI)UNSPECIFIED
NSFAGS-1240604
NSFCHE-1508526
NASANNX14AP46G
NSF Graduate Research FellowshipAGS-1331360
Environmental Protection Agency (EPA)UNSPECIFIED
Sandia National LaboratoriesUNSPECIFIED
Record Number:CaltechAUTHORS:20180314-102355395
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20180314-102355395
Official Citation:Gas-Phase Reactions of Isoprene and Its Major Oxidation Products. Paul O. Wennberg, Kelvin H. Bates, John D. Crounse, Leah G. Dodson, Renee C. McVay, Laura A. Mertens, Tran B. Nguyen, Eric Praske, Rebecca H. Schwantes, Matthew D. Smarte, Jason M. St Clair, Alexander P. Teng, Xuan Zhang, and John H. Seinfeld. Chemical Reviews 2018 118 (7), 3337-3390. DOI: 10.1021/acs.chemrev.7b00439
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:85305
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:26 Mar 2018 21:44
Last Modified:25 Apr 2018 21:25

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