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Title: The Reactive–Diffusive Length of OH and Ozone in Model Organic Aerosols

Abstract

We report that a key step in the heterogeneous oxidation of atmospheric aerosols is the reaction of ozone (O3) and hydroxyl radicals (OH) at the gas–particle interface. The formation of reaction products and free radical intermediates and their spatial distribution inside the particle is a sensitive function of the length over which these oxidants diffuse prior to reaction. The reactive–diffusive length of OH and ozone at organic aerosol interfaces is determined by observing the change in the effective uptake coefficient for size-selected model aerosols comprising a reactive core and a thin nanometer-sized (0–12 nm) organic shell. The core and shell materials are selected so that they are immiscible and adopt an assumed core–shell configuration. The results indicate a reactive–diffusive length of 1.4 nm for hydroxyl (OH) radicals in squalane and 1.0 nm for ozone in squalene. Measurements for a purely diffusive system allow for an estimate for diffusion constant (1.6 × 10-6 cm2/s) of ozone in squalane to be determined. In conclusion, the reactive–diffusive length offers a simple first order estimate of how shielding of aerosols by immiscible layers can alter estimates of oxidative lifetimes of aerosols in the atmosphere.

Authors:
 [1];  [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1456955
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 120; Journal Issue: 34; Related Information: © 2016 American Chemical Society.; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Lee, Lance, and Wilson, Kevin. The Reactive–Diffusive Length of OH and Ozone in Model Organic Aerosols. United States: N. p., 2016. Web. doi:10.1021/acs.jpca.6b05285.
Lee, Lance, & Wilson, Kevin. The Reactive–Diffusive Length of OH and Ozone in Model Organic Aerosols. United States. https://doi.org/10.1021/acs.jpca.6b05285
Lee, Lance, and Wilson, Kevin. 2016. "The Reactive–Diffusive Length of OH and Ozone in Model Organic Aerosols". United States. https://doi.org/10.1021/acs.jpca.6b05285. https://www.osti.gov/servlets/purl/1456955.
@article{osti_1456955,
title = {The Reactive–Diffusive Length of OH and Ozone in Model Organic Aerosols},
author = {Lee, Lance and Wilson, Kevin},
abstractNote = {We report that a key step in the heterogeneous oxidation of atmospheric aerosols is the reaction of ozone (O3) and hydroxyl radicals (OH) at the gas–particle interface. The formation of reaction products and free radical intermediates and their spatial distribution inside the particle is a sensitive function of the length over which these oxidants diffuse prior to reaction. The reactive–diffusive length of OH and ozone at organic aerosol interfaces is determined by observing the change in the effective uptake coefficient for size-selected model aerosols comprising a reactive core and a thin nanometer-sized (0–12 nm) organic shell. The core and shell materials are selected so that they are immiscible and adopt an assumed core–shell configuration. The results indicate a reactive–diffusive length of 1.4 nm for hydroxyl (OH) radicals in squalane and 1.0 nm for ozone in squalene. Measurements for a purely diffusive system allow for an estimate for diffusion constant (1.6 × 10-6 cm2/s) of ozone in squalane to be determined. In conclusion, the reactive–diffusive length offers a simple first order estimate of how shielding of aerosols by immiscible layers can alter estimates of oxidative lifetimes of aerosols in the atmosphere.},
doi = {10.1021/acs.jpca.6b05285},
url = {https://www.osti.gov/biblio/1456955}, journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
issn = {1089-5639},
number = 34,
volume = 120,
place = {United States},
year = {Wed Aug 10 00:00:00 EDT 2016},
month = {Wed Aug 10 00:00:00 EDT 2016}
}

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Cited by: 28 works
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Heterogeneous OH oxidation of secondary brown carbon aerosol
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