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Mechanism of the hydroxyl radical oxidation of methacryloyl peroxynitrate (MPAN) and its pathway toward secondary organic aerosol formation in the atmosphere

Nguyen, Tran B. and Bates, Kelvin H. and Crounse, John D. and Schwantes, Rebecca H. and Zhang, Xuan and Kjaergaard, Henrik G. and Surratt, Jason D. and Lin, Peng and Laskin, Alexander and Seinfeld, John H. and Wennberg, Paul O. (2015) Mechanism of the hydroxyl radical oxidation of methacryloyl peroxynitrate (MPAN) and its pathway toward secondary organic aerosol formation in the atmosphere. Physical Chemistry Chemical Physics, 17 (27). pp. 17914-17926. ISSN 1463-9076. https://resolver.caltech.edu/CaltechAUTHORS:20150701-104453949

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Abstract

Methacryloyl peroxynitrate (MPAN), the acyl peroxynitrate of methacrolein, has been suggested to be an important secondary organic aerosol (SOA) precursor from isoprene oxidation. Yet, the mechanism by which MPAN produces SOA through reaction with the hydroxyl radical (OH) is unclear. We systematically evaluate three proposed mechanisms in controlled chamber experiments and provide the first experimental support for the theoretically-predicted lactone formation pathway from the MPAN + OH reaction, producing hydroxymethyl-methyl-α-lactone (HMML). The decomposition of the MPAN–OH adduct yields HMML + NO_3 ( 75%) and hydroxyacetone + CO + NO_3 ( 25%), out-competing its reaction with atmospheric oxygen. The production of other proposed SOA precursors, e.g., methacrylic acid epoxide (MAE), from MPAN and methacrolein are negligible (<2%). Furthermore, we show that the beta-alkenyl moiety of MPAN is critical for lactone formation. Alkyl radicals formed cold via H-abstraction by OH do not decompose to HMML, even if they are structurally identical to the MPAN–OH adduct. The SOA formation from HMML, from polyaddition of the lactone to organic compounds at the particle interface or in the condensed phase, is close to unity under dry conditions. However, the SOA yield is sensitive to particle liquid water and solvated ions. In hydrated inorganic particles, HMML reacts primarily with H¬_2O to produce the monomeric 2-methylglyceric acid (2MGA) or with aqueous sulfate and nitrate to produce the associated organosulfate and organonitrate, respectively. 2MGA, a tracer for isoprene SOA, is semivolatile and its accommodation in aerosol water decreases with decreasing pH. Conditions that enhance the production of neutral 2MGA suppress SOA mass from the HMML channel. Considering the liquid water content and pH ranges of ambient particles, 2MGA will exist largely as a gaseous compound in some parts of the atmosphere.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1039/c5cp02001hDOIArticle
http://pubs.rsc.org/en/Content/ArticleLanding/2015/CP/C5CP02001HPublisherArticle
http://www.rsc.org/suppdata/c5/cp/c5cp02001h/c5cp02001h1.pdfPublisherSupporting Information
ORCID:
AuthorORCID
Bates, Kelvin H.0000-0001-7544-9580
Crounse, John D.0000-0001-5443-729X
Schwantes, Rebecca H.0000-0002-7095-3718
Kjaergaard, Henrik G.0000-0002-7275-8297
Surratt, Jason D.0000-0002-6833-1450
Laskin, Alexander0000-0002-7836-8417
Seinfeld, John H.0000-0003-1344-4068
Wennberg, Paul O.0000-0002-6126-3854
Additional Information:© 2015 the Owner Societies. Received 6th April 2015; Accepted 11th June 2015. First published online 12 Jun 2015. We acknowledge funding from the U.S. National Science Foundation (NSF) Division of Atmospheric and Geospace Sciences (AGS) grant AGS-1240604 and the U.S. Department of Energy (DOE) grant DE-SC0006626. TBN is supported by the NSF postdoctoral research fellowship (PRF) award AGS-1331360. We thank Dr. Dennis Fitz (UC Riverside) for assistance with the Fitz Aerometric NO2/APN instrument, Matthew Coggon (Caltech) for AMS data collection and processing, Dr. Nathan F. Dalleska (Caltech Global Environmental Center) for help with the HR-MS analysis software and for use of the pH probe, and Dr. Avram Gold and Dr. Zhenfa Zhang (University of North Carolina) for assistance in synthesizing MAE. The HPLC-UV/Vis-ESI/HRMS analysis was performed at the W. R. Wiley Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at PNNL. PNNL is operated for the DOE by Battelle Memorial Institute under contract #DE-AC06-76RL0 1830.
Funders:
Funding AgencyGrant Number
NSFAGS-1240604
Department of Energy (DOE)DE-SC0006626
NSF Postdoctoral Research FellowshipAGS-1331360
Department of Energy (DOE)DE-AC06-76RL0 1830
Issue or Number:27
Record Number:CaltechAUTHORS:20150701-104453949
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20150701-104453949
Official Citation:Nguyen, T. B., Bates, K. H., Crounse, J. D., Schwantes, R. H., Zhang, X., Kjaergaard, H. G., . . . Wennberg, P. O. (2015). Mechanism of the hydroxyl radical oxidation of methacryloyl peroxynitrate (MPAN) and its pathway toward secondary organic aerosol formation in the atmosphere. [10.1039/C5CP02001H]. Physical Chemistry Chemical Physics, 17(27), 17914-17926. doi: 10.1039/c5cp02001h
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:58734
Collection:CaltechAUTHORS
Deposited By: Joanne McCole
Deposited On:01 Jul 2015 19:45
Last Modified:03 Oct 2019 08:39

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