Journal
ATMOSPHERIC ENVIRONMENT
Volume 95, Issue -, Pages 105-112Publisher
PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.atmosenv.2014.06.026
Keywords
Secondary organic aerosol; Biogenic volatile organic compounds; Chemical kinetics; Multiphase chemistry
Funding
- National Science Foundation [AGS-1106569]
- California Agricultural Experiment Station [CA-D*-LAW-6403-RR]
- Directorate For Geosciences [1105049] Funding Source: National Science Foundation
- Directorate For Geosciences
- Div Atmospheric & Geospace Sciences [1106569] Funding Source: National Science Foundation
- Div Atmospheric & Geospace Sciences [1105049] Funding Source: National Science Foundation
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Green leaf volatiles (GLVs) are a class of oxygenated hydrocarbons released from vegetation, especially during mechanical stress or damage. The potential for GLVs to form secondary organic aerosol (SOA) via aqueous-phase reactions is not known. Fog events over vegetation will lead to the uptake of GLVs into water droplets, followed by aqueous-phase reactions with photooxidants such as the hydroxyl radical (OH). In order to determine if the aqueous oxidation of GLVs by OH can be a significant source of secondary organic aerosol, we studied the partitioning and reaction of five GLVs: cis-3-hexen-1-ol, cis-3-hexenyl acetate, methyl salicylate, methyl jasmonate, and 2-methyl-3-butene-2-ol. For each GLV we measured the kinetics of aqueous oxidation by OH, and the corresponding SOA mass yield. The second-order rate constants for GLVs with OH were all near diffusion controlled, (5.4-8.6) x 10(9) M-1 s(-1) at 298 K, and showed a small temperature dependence, with an average activation energy of 9.3 kJ mol(-1) Aqueous-phase SOA mass yields ranged from 10 to 88%, although some of the smaller values were not statistically different from zero. Methyl jasmonate was the most effective aqueous-phase SOA precursor due to its larger Henry's law constant and high SOA mass yield (68 +/- 8%). While we calculate that the aqueous-phase SOA formation from the five GLVs is a minor source of aqueous-phase SOA, the availability of other GLVs, other oxidants, and interfacial reactions suggest that GLVs overall might be a significant source of SOA via aqueous reactions. (C) 2014 Elsevier Ltd. All rights reserved.
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