Stochastic methods for aerosol chemistry: a compact molecular description of functionalization and fragmentation in the heterogeneous oxidation of squalane aerosol by OH radicals

Wiegel, A. A.; Wilson, K. R.; Hinsberg, W. D.; Houle, F. A.

doi:10.1039/c4cp04927f

Title: Stochastic methods for aerosol chemistry: a compact molecular description of functionalization and fragmentation in the heterogeneous oxidation of squalane aerosol by OH radicals

Journal Article · Tue Jan 06 00:00:00 EST 2015 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/c4cp04927f· OSTI ID:1616964

Wiegel, A. A. ^[1]; Wilson, K. R. ^[1]; Hinsberg, W. D. ^[2]; Houle, F. A. ^[1]

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
Columbia Hill Technical Consulting, Fremont, CA (United States)

The heterogeneous oxidation of organic aerosol by hydroxyl radicals (OH) can proceed through two general pathways: functionalization, in which oxygen functional groups are added to the carbon skeleton, and fragmentation, in which carbon–carbon bonds are broken, producing higher volatility, lower molecular weight products. An ongoing challenge is to develop a quantitative molecular description of these pathways that connects the oxidative evolution of the average aerosol properties (e.g. size and hygroscopicity) to the transformation of free radical intermediates. In order to investigate the underlying molecular mechanism of aerosol oxidation, a relatively compact kinetics model is developed for the heterogeneous oxidation of squalane particles by OH using free radical intermediates that convert reactive hydrogen sites into oxygen functional groups. Stochastic simulation techniques are used to compare calculated system properties over ten oxidation lifetimes with the same properties measured in experiment. The time-dependent average squalane aerosol mass, volume, density, carbon number distribution of scission products, and the average elemental composition are predicted using known rate coefficients. For functionalization, the calculations reveal that the distribution of alcohol and carbonyl groups is controlled primarily by the initial OH abstraction rate and to lesser extent by the branching ratio between secondary peroxy radical product channels. For fragmentation, the calculations reveal that the formation of activated alkoxy radicals with neighboring functional groups controls the molecular decomposition, particularly at high O/C ratios. Finally, this kinetic scheme provides a framework for understanding the oxidation chemistry of a model organic aerosol and informs parameterizations of more complex systems.

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Research Organization:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1616964

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Vol. 17, Issue 6; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 34 works

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