Abstract. The aqueous phase reaction of volatile organic compounds (VOCs) has not been considered in most analyses of atmospheric chemical processes. However, some experimental evidence has shown that, compared to the corresponding gas phase reaction, the aqueous chemical processes of VOCs in the bulk solutions and surfaces of ambient wet particles (cloud, fog, and wet aerosols) may potentially contribute to the products and formation of secondary organic aerosol (SOA). In the present study, we performed a laboratory experiment of the aqueous ozonolysis of isoprene at different pHs (3–7) and temperatures (4–25 °C). We detected three important kinds of products, including carbonyl compounds, peroxide compounds, and organic acids. Our results showed that the molar yields of these products were nearly independent of the investigated pHs and temperatures, those were (1) carbonyls: 56.7 ± 3.7 % formaldehyde, 42.8 ± 2.5 % methacrolein (MAC), and 57.7 ± 3.4 % methyl vinyl ketone (MVK); (2) peroxides: 53.4 ± 4.1 % hydrogen peroxide (H 2 O 2 ) and 15.1 ± 3.1 % hydroxylmethyl hydroperoxide (HMHP); and (3) organic acids: undetectable ( 2 O 2 + HMHP in the aqueous isoprene ozonolysis were much higher than those observed in the corresponding gas phase reaction. We suggest that these unexpected high yields of carbonyls and peroxides are related to the greater capability of condensed water, compared to water vapor, to stabilize energy-rich Criegee radicals. This aqueous ozonolysis of isoprene (and possibly other biogenic VOCs) could potentially occur on the surfaces of ambient wet particles and plants. Moreover, the high-yield carbonyl and peroxide products might provide a considerable source of aqueous phase oxidants and SOA precursors.
Understanding the aqueous phase ozonolysis of isoprene: distinct product distribution and mechanism from the gas phase reaction
Huichao Wang,D. Huang,Xuan Zhang,Yue-tao Zhao,Zhongming Chen
Published 2012 in Atmospheric Chemistry and Physics
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2012
- Venue
Atmospheric Chemistry and Physics
- Publication date
2012-08-07
- Fields of study
Chemistry, Environmental Science
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