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Conversion of gaseous nitrogen dioxide to nitrate and nitrite on aqueous surfactants

Kinugawa, Takashi and Enami, Shinichi and Yabushita, Akihiro and Kawasaki, Masahiro and Hoffmann, Michael R. and Colussi, Agustin J. (2011) Conversion of gaseous nitrogen dioxide to nitrate and nitrite on aqueous surfactants. Physical Chemistry Chemical Physics, 13 (11). pp. 5144-5149. ISSN 1463-9076. https://resolver.caltech.edu/CaltechAUTHORS:20110323-104317166

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Abstract

The hydrolytic disproportionation of gaseous NO2 on water's surface (2 NO_2 + H_2O → HONO + NO_3- + H+) (R1) has long been deemed to play a key, albeit unquantifiable role in tropospheric chemistry. We recently found that (R1) is dramatically accelerated by anions in experiments performed on aqueous microjets monitored by online electrospray mass spectrometry. This finding let us rationalize unresolved discrepancies among previous laboratory results and suggested that under realistic environmental conditions (R1) should be affected by everpresent surfactants. Herein, we report that NO_2(g) uptake is significantly enhanced by cationic surfactants, weakly inhibited by fulvic acid (FA, a natural polycarboxylic acid) and anionic surfactants, and unaffected by 1-octanol. Surfactants appear to modulate interfacial anion coverage via electrostatic interactions with charged headgroups. We show that (R1) should be the dominant mechanism for the heterogeneous conversion of NO_2(g) to HONO under typical atmospheric conditions throughout the day. The photoinduced reduction of NO_2 into HONO on airborne soot might play a limited role during daytime.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1039/c0cp01497d DOIArticle
http://pubs.rsc.org/en/Content/ArticleLanding/2011/CP/c0cp01497dPublisherArticle
ORCID:
AuthorORCID
Enami, Shinichi0000-0002-2790-7361
Hoffmann, Michael R.0000-0002-0432-6564
Colussi, Agustin J.0000-0002-3400-4101
Additional Information:© 2011 the Owner Societies. Received 13th August 2010, Accepted 7th January 2011. S. E. appreciates the Japan Society for the Promotion of Sciences Postdoctoral Fellowships for Research Abroad. This work was supported by National Science Foundation Grant ATM-0714329.
Funders:
Funding AgencyGrant Number
Japan Society for the Promotion of Science (JSPS)UNSPECIFIED
NSFATM-0714329
Issue or Number:11
Record Number:CaltechAUTHORS:20110323-104317166
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20110323-104317166
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:23073
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:29 Mar 2011 17:58
Last Modified:03 Oct 2019 02:43

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