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Tropospheric aerosol as a reactive intermediate

Colussi, Agustín J. and Enami, Shinichi and Yabushita, Akihiro and Hoffmann, Michael R. and Liu, Wei-Guang and Mishra, Himanshu and Goddard, William A., III (2013) Tropospheric aerosol as a reactive intermediate. Faraday Discussions, 165 . pp. 407-420. ISSN 1359-6640. https://resolver.caltech.edu/CaltechAUTHORS:20140203-095934074

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Abstract

In tropospheric chemistry, secondary organic aerosol (SOA) is deemed an end product. Here, on the basis of new evidence, we make the case that SOA is a key reactive intermediate. We present laboratory results on the catalysis by carboxylate anions of the disproportionation of NO_2 ‘on water’: 2NO_2 + H_2O = HONO + NO_3^− + H^+ (R1), and supporting quantum chemical calculations, which we apply to reinterpret recent reports on (i) HONO daytime source strengths vis-à-vis SOA anion loadings and (ii) the weak seasonal and latitudinal dependences of NO_x decay kinetics over several megacities. HONO daytime generation via R1 should track sunlight because it is generally catalyzed by the anions produced during the photochemical oxidation of pervasive gaseous pollutants. Furthermore, by proceeding on the everpresent substrate of aquated airborne particulates, R1 can eventually overtake the photolysis of NO_2: NO_2 + hν = NO + O(^3P) (R2), at large zenith angles. Thus, since R1 leads directly to ˙OH-radical generation via HONO photolysis: HONO + hν = NO + ˙OH, whereas the path initiated by R2 is more circuitous and actually controlled by the slower photolysis of O_3: O_3 + hν (+H_2O) = O_2 + 2˙OH, the competition between R1 and R2 provides a mechanistic switch that buffers ˙OH concentrations and NO_2 decay (via R1 and/or NO_2^+ ˙OH = HNO_3) from actinic flux variations.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://pubs.rsc.org/en/Content/ArticleLanding/2013/FD/c3fd00040kPublisherArticle
http://dx.doi.org/10.1039/C3FD00040KDOIArticle
ORCID:
AuthorORCID
Colussi, Agustín J.0000-0002-3400-4101
Enami, Shinichi0000-0002-2790-7361
Hoffmann, Michael R.0000-0001-6495-1946
Liu, Wei-Guang0000-0002-6633-7795
Goddard, William A., III0000-0003-0097-5716
Additional Information:© 2013 Royal Society of Chemistry. Received 14th March 2013, Accepted 3rd April 2013. First published online 08 Apr 2013. SE is grateful to the Japan Science and Technology Agency (JST) PRESTO program and Steel Foundation for Environmental Protection Technology. AY is grateful to grant-in-aid from JSPS (Grant 23651014). This work was supported, in part, by NSF Grant AC1238977.
Funders:
Funding AgencyGrant Number
Japan Science and Technology Agency (JST) PRESTO ProgramUNSPECIFIED
Steel Foundation for Environmental Protection TechnologyUNSPECIFIED
Japan Society for the Promotion of Science (JSPS)23651014
NSFAC1238977
Record Number:CaltechAUTHORS:20140203-095934074
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20140203-095934074
Official Citation:Tropospheric aerosol as a reactive intermediate Agustín J. Colussi, Shinichi Enami, Akihiro Yabushita, Michael R. Hoffmann, Wei-Guang Liu, Himanshu Mishra and William A. Goddard, III Faraday Discuss., 2013, 165, 407-420 DOI: 10.1039/C3FD00040K
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:43618
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:03 Feb 2014 18:37
Last Modified:03 Mar 2020 13:01

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