Tropospheric aerosol as a reactive intermediate

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

研究成果: Contribution to journalArticle査読

18 被引用数 (Scopus)

抄録

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.

本文言語英語
ページ(範囲)407-420
ページ数14
ジャーナルFaraday Discussions
165
DOI
出版ステータス出版済み - 10 18 2013
外部発表はい

All Science Journal Classification (ASJC) codes

  • 物理化学および理論化学

フィンガープリント

「Tropospheric aerosol as a reactive intermediate」の研究トピックを掘り下げます。これらがまとまってユニークなフィンガープリントを構成します。

引用スタイル