Large enhancement in the heterogeneous oxidation rate of organic aerosols by hydroxyl radicals in the presence of nitric oxide
Abstract
The heterogeneous lifetime of an organic molecule in an aerosol exposed to hydroxyl radicals (OH) is thought to be weeks in the troposphere, which is orders of magnitude slower than the analogous gas phase reactions (hours). Here, we report an unexpectedly large acceleration in the effective heterogeneous OH reaction rate in the presence of NO. This 10-50 fold acceleration originates from free radical chain reactions, propagated by alkoxy radicals that form inside the aerosol by the reaction of NO with peroxy radicals, which do not appear to produce chain terminating products (e.g., alkyl nitrates), unlike gas phase mechanisms. A kinetic model, constrained by experiments, suggests that in polluted regions heterogeneous oxidation plays a much more prominent role in the daily chemical evolution of organic aerosol than previously believed.
- Authors:
-
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Univ. of California, Berkeley, CA (United States)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1252724
- Alternate Identifier(s):
- OSTI ID: 1378651
- Grant/Contract Number:
- AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry Letters
- Additional Journal Information:
- Journal Volume: 6; Journal Issue: 22; Journal ID: ISSN 1948-7185
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; organic aerosols; chain reaction; oxidation; stochastic
Citation Formats
Richards-Henderson, Nicole K., Goldstein, Allen H., and Wilson, Kevin R. Large enhancement in the heterogeneous oxidation rate of organic aerosols by hydroxyl radicals in the presence of nitric oxide. United States: N. p., 2015.
Web. doi:10.1021/acs.jpclett.5b02121.
Richards-Henderson, Nicole K., Goldstein, Allen H., & Wilson, Kevin R. Large enhancement in the heterogeneous oxidation rate of organic aerosols by hydroxyl radicals in the presence of nitric oxide. United States. https://doi.org/10.1021/acs.jpclett.5b02121
Richards-Henderson, Nicole K., Goldstein, Allen H., and Wilson, Kevin R. Tue .
"Large enhancement in the heterogeneous oxidation rate of organic aerosols by hydroxyl radicals in the presence of nitric oxide". United States. https://doi.org/10.1021/acs.jpclett.5b02121. https://www.osti.gov/servlets/purl/1252724.
@article{osti_1252724,
title = {Large enhancement in the heterogeneous oxidation rate of organic aerosols by hydroxyl radicals in the presence of nitric oxide},
author = {Richards-Henderson, Nicole K. and Goldstein, Allen H. and Wilson, Kevin R.},
abstractNote = {The heterogeneous lifetime of an organic molecule in an aerosol exposed to hydroxyl radicals (OH) is thought to be weeks in the troposphere, which is orders of magnitude slower than the analogous gas phase reactions (hours). Here, we report an unexpectedly large acceleration in the effective heterogeneous OH reaction rate in the presence of NO. This 10-50 fold acceleration originates from free radical chain reactions, propagated by alkoxy radicals that form inside the aerosol by the reaction of NO with peroxy radicals, which do not appear to produce chain terminating products (e.g., alkyl nitrates), unlike gas phase mechanisms. A kinetic model, constrained by experiments, suggests that in polluted regions heterogeneous oxidation plays a much more prominent role in the daily chemical evolution of organic aerosol than previously believed.},
doi = {10.1021/acs.jpclett.5b02121},
journal = {Journal of Physical Chemistry Letters},
number = 22,
volume = 6,
place = {United States},
year = {Tue Oct 27 00:00:00 EDT 2015},
month = {Tue Oct 27 00:00:00 EDT 2015}
}
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Works referencing / citing this record:
Organic peroxy radical chemistry in oxidation flow reactors and environmental chambers and their atmospheric relevance
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Heterogeneous OH oxidation of secondary brown carbon aerosol
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Effects of inorganic salts on the heterogeneous OH oxidation of organic compounds: insights from methylglutaric acid–ammonium sulfate
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Pulsed Corona Discharge Induced Hydroxyl Radical Transfer Through the Gas-Liquid Interface
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