Journal
ENVIRONMENTAL SCIENCE & TECHNOLOGY
Volume 43, Issue 5, Pages 1386-1392Publisher
AMER CHEMICAL SOC
DOI: 10.1021/es8029076
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Funding
- National Science Foundation [0753103]
- Henry Dreyfus Teacher-Scholar
- Directorate For Geosciences
- Div Atmospheric & Geospace Sciences [0753103] Funding Source: National Science Foundation
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Polyols and sulfate esters have recently been identified in the secondary organic aerosol (SOA) formed in the photooxidation of biogenic hydrocarbons both in the laboratory and under ambient atmospheric conditions. In the present study, the potential role of the reactions of epoxides in SOA to form diols and hydroxy sulfate esters is explored. Nuclear magnetic resonance methods were used to monitor the bulk reaction kinetics of the epoxide hydrolysis reactions for a number of simple epoxides. The experiments were carried out at various acid concentrations in order to confirm the acid-catalysis rate order and to determine the second-order rate constants for such reactions in aerosols under the previously studied laboratory conditions The measured rate and under ambient atmospheric conditions. constants depended systematically on the carbon substitution nature of the epoxide ring, with the tertiary epoxides characterized by the largest rate constants. The hydroxy sulfate yield was observed to depend linearly on the total sulfate concentration, with yields as high as 30% observed at high sulfate concentrations. Due to the large values of the observed rate constants, these reactions are expected to be efficient even for mostly neutralized tropospheric SOA, let alone the much more acidic SOA particles previously studied in laboratory the epoxide hydrolysis mechanism experiments. Therefore, appears to be a kinetically feasible route to the formation of the diols and hydroxy sulfate esters observed in the SOA resulting from the photooxidation of biogenic hydrocarbons.
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