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Title: Large enhancement in the heterogeneous oxidation rate of organic aerosols by hydroxyl radicals in the presence of nitric oxide

Journal Article · · Journal of Physical Chemistry Letters
 [1];  [2];  [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Univ. of California, Berkeley, CA (United States)

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.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1252724
Alternate ID(s):
OSTI ID: 1378651
Journal Information:
Journal of Physical Chemistry Letters, Vol. 6, Issue 22; ISSN 1948-7185
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 27 works
Citation information provided by
Web of Science

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Cited By (5)

Organic peroxy radical chemistry in oxidation flow reactors and environmental chambers and their atmospheric relevance journal January 2019
Heterogeneous OH oxidation of secondary brown carbon aerosol journal January 2018
Effects of inorganic salts on the heterogeneous OH oxidation of organic compounds: insights from methylglutaric acid–ammonium sulfate journal January 2019
Pulsed Corona Discharge Induced Hydroxyl Radical Transfer Through the Gas-Liquid Interface journal November 2017
Chemical evolution of atmospheric organic carbon over multiple generations of oxidation journal February 2018