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Size distribution dynamics reveal particle-phase chemistry in organic aerosol formation

Shiraiwa, Manabu and Yee, Lindsay D. and Schilling, Katherine A. and Loza, Christine L. and Craven, Jill S. and Zuend, Andreas and Ziemann, Paul J. and Seinfeld, John H. (2013) Size distribution dynamics reveal particle-phase chemistry in organic aerosol formation. Proceedings of the National Academy of Sciences of the United States of America, 110 (29). pp. 11746-11750. ISSN 0027-8424. PMCID PMC3718153. http://resolver.caltech.edu/CaltechAUTHORS:20130903-105605191

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Abstract

Organic aerosols are ubiquitous in the atmosphere and play a central role in climate, air quality, and public health. The aerosol size distribution is key in determining its optical properties and cloud condensation nucleus activity. The dominant portion of organic aerosol is formed through gas-phase oxidation of volatile organic compounds, so-called secondary organic aerosols (SOAs). Typical experimental measurements of SOA formation include total SOA mass and atomic oxygen-to-carbon ratio. These measurements, alone, are generally insufficient to reveal the extent to which condensed-phase reactions occur in conjunction with the multigeneration gas-phase photooxidation. Combining laboratory chamber experiments and kinetic gas-particle modeling for the dodecane SOA system, here we show that the presence of particle-phase chemistry is reflected in the evolution of the SOA size distribution as well as its mass concentration. Particle-phase reactions are predicted to occur mainly at the particle surface, and the reaction products contribute more than half of the SOA mass. Chamber photooxidation with a midexperiment aldehyde injection confirms that heterogeneous reaction of aldehydes with organic hydroperoxides forming peroxyhemiacetals can lead to a large increase in SOA mass. Although experiments need to be conducted with other SOA precursor hydrocarbons, current results demonstrate coupling between particle-phase chemistry and size distribution dynamics in the formation of SOAs, thereby opening up an avenue for analysis of the SOA formation process.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1073/pnas.1307501110 DOIArticle
http://www.pnas.org/content/110/29/11746PublisherArticle
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3718153/PubMed CentralArticle
ORCID:
AuthorORCID
Shiraiwa, Manabu0000-0003-2532-5373
Zuend, Andreas0000-0003-3101-8521
Seinfeld, John H.0000-0003-1344-4068
Additional Information:© 2013 National Academy of Sciences. Edited by Mark H. Thiemens, University of California at San Diego, La Jolla, CA, and approved June 13, 2013 (received for review April 21, 2013). Published online before print July 1, 2013. We thank Xuan Zhang and Matt Coggon for assistance in the experiments. This work was supported by US Department of Energy Grant DE-SC0006626 and National Science Foundation Grant AGS-1057183. M.S. is supported by a Japan Society for the Promotion of Science Postdoctoral Fellowship for Research Abroad. Author contributions: M.S., L.D.Y., and J.H.S. designed research; M.S., L.D.Y., K.A.S., C.L.L., and J.S.C. performed research; M.S., L.D.Y., K.A.S., C.L.L., J.S.C., A.Z., and P.J.Z. analyzed data; M.S., L.D.Y., K.A.S., and C.L.L. wrote the supplement; and M.S., and J.H.S. wrote the paper.
Funders:
Funding AgencyGrant Number
Department of Energy (DOE)DE-SC0006626
NSFAGS-1057183
Japan Society for the Promotion of Science (JSPS)UNSPECIFIED
Subject Keywords:gas-particle interactions; heterogeneous chemistry; intermediate volatility organic compounds; alkane
PubMed Central ID:PMC3718153
Record Number:CaltechAUTHORS:20130903-105605191
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20130903-105605191
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:41053
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:17 Sep 2013 20:24
Last Modified:25 Jul 2017 20:33

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