Tropospheric aerosol as a reactive intermediate

Agustín J. Colussi, Shinichi Enami, Akihiro Yabushita, Michael R. Hoffmann, Wei Guang Liu, Himanshu Mishra, William A. Goddard

Research output: Contribution to journalArticle

12 Citations (Scopus)

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 NO2 'on water': 2NO2 + H2O = HONO + NO3- + 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 NOx 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 NO2: NO2 + 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 O3: O3 + hν (+H2O) = O2 + 2OH, the competition between R1 and R2 provides a mechanistic switch that buffers OH concentrations and NO2 decay (via R1 and/or NO2 + OH = HNO3) from actinic flux variations.

Original languageEnglish
Pages (from-to)407-420
Number of pages14
JournalFaraday Discussions
Volume165
DOIs
Publication statusPublished - Oct 18 2013

Fingerprint

Photolysis
Aerosols
Anions
photolysis
aerosols
daytime
anions
zenith
decay
sunlight
carboxylates
particulates
Catalysis
catalysis
contaminants
Buffers
switches
buffers
Switches
chemistry

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

Cite this

Colussi, A. J., Enami, S., Yabushita, A., Hoffmann, M. R., Liu, W. G., Mishra, H., & Goddard, W. A. (2013). Tropospheric aerosol as a reactive intermediate. Faraday Discussions, 165, 407-420. https://doi.org/10.1039/c3fd00040k

Tropospheric aerosol as a reactive intermediate. / Colussi, Agustín J.; Enami, Shinichi; Yabushita, Akihiro; Hoffmann, Michael R.; Liu, Wei Guang; Mishra, Himanshu; Goddard, William A.

In: Faraday Discussions, Vol. 165, 18.10.2013, p. 407-420.

Research output: Contribution to journalArticle

Colussi, AJ, Enami, S, Yabushita, A, Hoffmann, MR, Liu, WG, Mishra, H & Goddard, WA 2013, 'Tropospheric aerosol as a reactive intermediate', Faraday Discussions, vol. 165, pp. 407-420. https://doi.org/10.1039/c3fd00040k
Colussi AJ, Enami S, Yabushita A, Hoffmann MR, Liu WG, Mishra H et al. Tropospheric aerosol as a reactive intermediate. Faraday Discussions. 2013 Oct 18;165:407-420. https://doi.org/10.1039/c3fd00040k
Colussi, Agustín J. ; Enami, Shinichi ; Yabushita, Akihiro ; Hoffmann, Michael R. ; Liu, Wei Guang ; Mishra, Himanshu ; Goddard, William A. / Tropospheric aerosol as a reactive intermediate. In: Faraday Discussions. 2013 ; Vol. 165. pp. 407-420.
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