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Chemical Composition of Secondary Organic Aerosol Formed from the Photooxidation of Isoprene

Surratt, Jason D. and Murphy, Shane M. and Kroll, Jesse H. and Ng, Nga L. and Hildebrandt, Lea and Sorooshian, Armin and Szmigielski, Rafal and Vermeylen, Reinhilde and Maenhaut, Willy and Claeys, Magda and Flagan, Richard C. and Seinfeld, John H. (2006) Chemical Composition of Secondary Organic Aerosol Formed from the Photooxidation of Isoprene. Journal of Physical Chemistry A, 110 (31). pp. 9665-9690. ISSN 1089-5639. https://resolver.caltech.edu/CaltechAUTHORS:20150818-105639496

[img] PDF (Electron impact (EI) mass spectra for 2-methyltetrols, C5 alkene triols, and 2-methyltetrol performate derivatives for their respective chromatographic peaks found in Figure 10) - Supplemental Material
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Abstract

Recent work in our laboratory has shown that the photooxidation of isoprene (2-methyl-1,3-butadiene, C5H8) leads to the formation of secondary organic aerosol (SOA). In the current study, the chemical composition of SOA from the photooxidation of isoprene over the full range of NO_x conditions is investigated through a series of controlled laboratory chamber experiments. SOA composition is studied using a wide range of experimental techniques:  electrospray ionization−mass spectrometry, matrix-assisted laser desorption ionization−mass spectrometry, high-resolution mass spectrometry, online aerosol mass spectrometry, gas chromatography/mass spectrometry, and an iodometric-spectroscopic method. Oligomerization was observed to be an important SOA formation pathway in all cases; however, the nature of the oligomers depends strongly on the NO_x level, with acidic products formed under high-NO_x conditions only. We present, to our knowledge, the first evidence of particle-phase esterification reactions in SOA, where the further oxidation of the isoprene oxidation product methacrolein under high-NO_x conditions produces polyesters involving 2-methylglyceric acid as a key monomeric unit. These oligomers comprise ∼22−34% of the high-NO_x SOA mass. Under low-NO_x conditions, organic peroxides contribute significantly to the low-NO_x SOA mass (∼61% when SOA forms by nucleation and ∼25−30% in the presence of seed particles). The contribution of organic peroxides in the SOA decreases with time, indicating photochemical aging. Hemiacetal dimers are found to form from C_5 alkene triols and 2-methyltetrols under low-NO_x conditions; these compounds are also found in aerosol collected from the Amazonian rainforest, demonstrating the atmospheric relevance of these low-NO_x chamber experiments.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/jp061734mDOIArticle
http://pubs.acs.org/doi/abs/10.1021/jp061734mPublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/jp061734mPublisherSupporting Information
ORCID:
AuthorORCID
Surratt, Jason D.0000-0002-6833-1450
Murphy, Shane M.0000-0002-6415-2607
Ng, Nga L.0000-0001-8460-4765
Sorooshian, Armin0000-0002-2243-2264
Maenhaut, Willy0000-0002-4715-4627
Claeys, Magda0000-0003-2278-8014
Flagan, Richard C.0000-0001-5690-770X
Seinfeld, John H.0000-0003-1344-4068
Additional Information:© 2006 American Chemical Society. Received: March 20, 2006; In Final Form: June 15, 2006. Research at Caltech was funded by the U.S. Environmental Protection Agency to Achieve Results (STAR) Program grant no. RD-83107501-0, managed by EPA's Office of Research and Development (ORD), National Center for Environmental Research (NCER), and by the U.S. Department of Energy, Biological, and Environmental Research Program DE-FG02-05ER63983; this work has not been subjected to the EPA's required peer and policy review and therefore does not necessarily reflect the views of the Agency and no official endorsement should be inferred. Jason Surratt was supported in part by the United States Environmental Protection Agency (EPA) under the Science to Achieve Results (STAR) Graduate Fellowship Program. Research at the Universities of Antwerp and Ghent was supported by the Belgian Federal Science Policy Office through the BIOSOL project (contract SD/AT/02A) and a visiting postdoctoral fellowship to Rafal Szmigielski, and by the Research Foundation − Flanders (FWO). We would like to thank John Greaves at the University of California, Irvine for the accurate mass measurements on the ESI-TOF instrument. We would like to also thank Paul Ziemann at the University of California, Riverside for his useful communications regarding peroxide measurements in SOA.
Funders:
Funding AgencyGrant Number
Environmental Protection Agency (EPA)RD-83107501-0
Department of Energy (DOE)DE-FG02-05ER63983
Belgian Federal Science Policy Office (BELSPO)SD/AT/02A
Fonds Wetenschappelijk Onderzoek - Vlaanderen (FWO)UNSPECIFIED
Issue or Number:31
Record Number:CaltechAUTHORS:20150818-105639496
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20150818-105639496
Official Citation:Chemical Composition of Secondary Organic Aerosol Formed from the Photooxidation of Isoprene Jason D. Surratt, Shane M. Murphy, Jesse H. Kroll, Nga L. Ng, Lea Hildebrandt, Armin Sorooshian, Rafal Szmigielski, Reinhilde Vermeylen, Willy Maenhaut, Magda Claeys, Richard C. Flagan, and John H. Seinfeld The Journal of Physical Chemistry A 2006 110 (31), 9665-9690 DOI: 10.1021/jp061734m
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:59721
Collection:CaltechAUTHORS
Deposited By: Irina Meininger
Deposited On:19 Aug 2015 21:57
Last Modified:03 Oct 2019 08:49

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