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Richards-Henderson NK, Goldstein AH, Wilson KR. Large enhancement in the heterogeneous oxidation rate of organic aerosols by hydroxyl radicals in the presence of nitric oxide. J Phys Chem Lett. 2015;6(22):4451-5doi: 10.1021/acs.jpclett.5b02121.
Richards-Henderson, N. K., Goldstein, A. H., & Wilson, K. R. (2015). Large enhancement in the heterogeneous oxidation rate of organic aerosols by hydroxyl radicals in the presence of nitric oxide. The journal of physical chemistry letters, 6(22), 4451-5. https://doi.org/10.1021/acs.jpclett.5b02121
Richards-Henderson, Nicole K, et al. "Large enhancement in the heterogeneous oxidation rate of organic aerosols by hydroxyl radicals in the presence of nitric oxide." The journal of physical chemistry letters vol. 6,22 (2015): 4451-5. doi: https://doi.org/10.1021/acs.jpclett.5b02121
Richards-Henderson NK, Goldstein AH, Wilson KR. Large enhancement in the heterogeneous oxidation rate of organic aerosols by hydroxyl radicals in the presence of nitric oxide. J Phys Chem Lett. 2015 Nov 19;6(22):4451-5. doi: 10.1021/acs.jpclett.5b02121. Epub 2015 Oct 29. PMID: 26505970.
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J Phys Chem Lett. 2015 Nov 19;6(22):4451-5. doi: 10.1021/acs.jpclett.5b02121. Epub 2015 Oct 29.

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

The journal of physical chemistry letters

Nicole K Richards-Henderson, Allen H Goldstein, Kevin R Wilson

Affiliations

  1. Chemical Sciences Division, Lawrence Berkeley National Laboratory , Berkeley, California 94720, United States.
  2. Department of Environmental Science, Policy and Management, University of California Berkeley , Berkeley, California 94720, United States.

PMID: 26505970 DOI: 10.1021/acs.jpclett.5b02121

Abstract

In the troposphere, the heterogeneous lifetime of an organic molecule in an aerosol exposed to hydroxyl radicals (OH) is thought to be weeks, 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.

Keywords: chain reaction; organic aerosols; oxidation; stochastic

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