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

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

doi:10.1021/acs.jpclett.5b02121

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

Journal Article · 26 October 2015 · Journal of Physical Chemistry Letters

DOI: https://doi.org/10.1021/acs.jpclett.5b02121 · OSTI ID:1252724

Richards-Henderson, Nicole K. ^[1]; Goldstein, Allen H. ^[2]; Wilson, Kevin R. ^[1]

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Univ. of California, Berkeley, CA (United States)

In this paper 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. Lastly, 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.

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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

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 22 Vol. 6; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (25)

Atmospheric Aerosols: Composition, Transformation, Climate and Health Effects Pöschl, Ulrich Angewandte Chemie International Edition, Vol. 44, Issue 46 https://doi.org/10.1002/anie.200501122	journal	November 2005
The Reaction of Nitric Oxide with Organic Peroxyl Radicals Padmaja, S.; Huie, R. E. Biochemical and Biophysical Research Communications, Vol. 195, Issue 2 https://doi.org/10.1006/bbrc.1993.2079	journal	September 1993
Diurnal, seasonal and weekdays–weekends variations of ground level ozone concentrations in an urban area in greater Cairo Khoder, M. I. Environmental Monitoring and Assessment, Vol. 149, Issue 1-4 https://doi.org/10.1007/s10661-008-0208-7	journal	February 2008
Weekend/weekday differences of ozone, NOx, Co, VOCs, PM10 and the light scatter during ozone season in southern California Qin, Y. Atmospheric Environment, Vol. 38, Issue 19 https://doi.org/10.1016/j.atmosenv.2004.01.035	journal	June 2004
On the hydrophobicity of nitrogen dioxide: Could there be a “lens” effect for NO2 reaction kinetics? Squadrito, Giuseppe L.; Postlethwait, Edward M. Nitric Oxide, Vol. 21, Issue 2 https://doi.org/10.1016/j.niox.2009.05.008	journal	September 2009
Modeling the Multiday Evolution and Aging of Secondary Organic Aerosol During MILAGRO 2006 Dzepina, Katja; Cappa, Christopher D.; Volkamer, Rainer M. Environmental Science & Technology, Vol. 45, Issue 8 https://doi.org/10.1021/es103186f	journal	April 2011
Lubricating Oil Dominates Primary Organic Aerosol Emissions from Motor Vehicles Worton, David R.; Isaacman, Gabriel; Gentner, Drew R. Environmental Science & Technology, Vol. 48, Issue 7 https://doi.org/10.1021/es405375j	journal	March 2014
Reaction of Organic Peroxyl Radicals with ^• NO ₂ and ^• NO in Aqueous Solution: Intermediacy of Organic Peroxynitrate and Peroxynitrite Species Goldstein, Sara; Lind, Johan; Merenyi, Gabor The Journal of Physical Chemistry A, Vol. 108, Issue 10 https://doi.org/10.1021/jp037431z	journal	March 2004
The Influence of Molecular Structure and Aerosol Phase on the Heterogeneous Oxidation of Normal and Branched Alkanes by OH Ruehl, Christopher R.; Nah, Theodora; Isaacman, Gabriel The Journal of Physical Chemistry A, Vol. 117, Issue 19 https://doi.org/10.1021/jp401888q	journal	May 2013
Alkyl Nitrate Formation from the Reactions of C ₈ –C ₁₄ n -Alkanes with OH Radicals in the Presence of NO _x : Measured Yields with Essential Corrections for Gas–Wall Partitioning Yeh, Geoffrey K.; Ziemann, Paul J. The Journal of Physical Chemistry A, Vol. 118, Issue 37 https://doi.org/10.1021/jp500631v	journal	April 2014
Rate Coefficients for the Reactions of Some C ₃ to C ₅ Hydrocarbon Peroxy Radicals with NO Eberhard, Jürg; Howard, Carleton J. The Journal of Physical Chemistry A, Vol. 101, Issue 18 https://doi.org/10.1021/jp9640282	journal	May 1997
Mechanism and Thermochemistry of Peroxynitrite Decomposition in Water Merényi, Gábor; Lind, Johan; Goldstein, Sara The Journal of Physical Chemistry A, Vol. 103, Issue 29 https://doi.org/10.1021/jp984686h	journal	July 1999
Single-particle mass spectrometry of tropospheric aerosol particles: TROPOSPHERIC AEROSOL PARTICLES Murphy, D. M.; Cziczo, D. J.; Froyd, K. D. Journal of Geophysical Research: Atmospheres, Vol. 111, Issue D23 https://doi.org/10.1029/2006JD007340	journal	September 2006
Ubiquity and dominance of oxygenated species in organic aerosols in anthropogenically-influenced Northern Hemisphere midlatitudes: UBIQUITY AND DOMINANCE OF OXYGENATED OA Zhang, Q.; Jimenez, J. L.; Canagaratna, M. R. Geophysical Research Letters, Vol. 34, Issue 13 https://doi.org/10.1029/2007GL029979	journal	July 2007
Heterogeneous oxidation of atmospheric aerosol particles by gas-phase radicals George, I. J.; Abbatt, J. P. D. Nature Chemistry, Vol. 2, Issue 9 https://doi.org/10.1038/nchem.806	journal	August 2010
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. Physical Chemistry Chemical Physics, Vol. 17, Issue 6 https://doi.org/10.1039/C4CP04927F	journal	January 2015
Oxidation of a model alkane aerosol by OH radical: the emergent nature of reactive uptake Houle, F. A.; Hinsberg, W. D.; Wilson, K. R. Physical Chemistry Chemical Physics, Vol. 17, Issue 6 https://doi.org/10.1039/C4CP05093B	journal	January 2015
The importance of phase in the radical-initiated oxidation of model organic aerosols: reactions of solid and liquid brassidic acid particles Renbaum, Lindsay H.; Smith, Geoffrey D. Physical Chemistry Chemical Physics, Vol. 11, Issue 14 https://doi.org/10.1039/b816799k	journal	January 2009
Quantifying the reactive uptake of OH by organic aerosols in a continuous flow stirred tank reactor Che, Dung L.; Smith, Jared D.; Leone, Stephen R. Physical Chemistry Chemical Physics, Vol. 11, Issue 36 https://doi.org/10.1039/b904418c	journal	January 2009
Solubility of nitric oxide in aqueous and nonaqueous solvents Shaw, Anthony W.; Vosper, Alan J. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 73, Issue 0 https://doi.org/10.1039/f19777301239	journal	January 1977
Megacities and Atmospheric Pollution Molina, Mario J.; Molina, Luisa T. Journal of the Air & Waste Management Association, Vol. 54, Issue 6 https://doi.org/10.1080/10473289.2004.10470936	journal	June 2004
Evolution of Organic Aerosols in the Atmosphere Jimenez, J. L.; Canagaratna, M. R.; Donahue, N. M. Science, Vol. 326, Issue 5959 https://doi.org/10.1126/science.1180353	journal	December 2009
Modeling organic aerosols in a megacity: potential contribution of semi-volatile and intermediate volatility primary organic compounds to secondary organic aerosol formation Hodzic, A.; Jimenez, J. L.; Madronich, S. Atmospheric Chemistry and Physics, Vol. 10, Issue 12 https://doi.org/10.5194/acp-10-5491-2010	journal	January 2010
Weekly patterns of México City's surface concentrations of CO, NO_x, PM₁₀ and O₃ during 1986–2007 Stephens, S.; Madronich, S.; Wu, F. Atmospheric Chemistry and Physics, Vol. 8, Issue 17 https://doi.org/10.5194/acp-8-5313-2008	journal	January 2008
The heterogeneous reaction of hydroxyl radicals with sub-micron squalane particles: a model system for understanding the oxidative aging of ambient aerosols Smith, J. D.; Kroll, J. H.; Cappa, C. D. Atmospheric Chemistry and Physics, Vol. 9, Issue 9 https://doi.org/10.5194/acp-9-3209-2009	journal	January 2009

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Pulsed Corona Discharge Induced Hydroxyl Radical Transfer Through the Gas-Liquid Interface Ajo, Petri; Kornev, Iakov; Preis, Sergei Scientific Reports, Vol. 7, Issue 1 https://doi.org/10.1038/s41598-017-16333-1	journal	November 2017
Chemical evolution of atmospheric organic carbon over multiple generations of oxidation Isaacman-VanWertz, Gabriel; Massoli, Paola; O’Brien, Rachel Nature Chemistry, Vol. 10, Issue 4 https://doi.org/10.1038/s41557-018-0002-2	journal	February 2018
Heterogeneous OH oxidation of secondary brown carbon aerosol Schnitzler, Elijah G.; Abbatt, Jonathan P. D. Atmospheric Chemistry and Physics, Vol. 18, Issue 19 https://doi.org/10.5194/acp-18-14539-2018	journal	January 2018
Organic peroxy radical chemistry in oxidation flow reactors and environmental chambers and their atmospheric relevance Peng, Zhe; Lee-Taylor, Julia; Orlando, John J. Atmospheric Chemistry and Physics, Vol. 19, Issue 2 https://doi.org/10.5194/acp-19-813-2019	journal	January 2019
Effects of inorganic salts on the heterogeneous OH oxidation of organic compounds: insights from methylglutaric acid–ammonium sulfate Lam, Hoi Ki; Shum, Sze Man; Davies, James F. Atmospheric Chemistry and Physics, Vol. 19, Issue 14 https://doi.org/10.5194/acp-19-9581-2019	journal	January 2019
Heterogeneous OH oxidation of secondary brown carbon aerosol Schnitzler, Elijah G.; Abbatt, Jonathan P. D. Atmospheric Chemistry and Physics Discussions https://doi.org/10.5194/acp-2018-198	posted_content	March 2018

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