4.8 Article

Unexpected Epoxide Formation in the Gas-Phase Photooxidation of Isoprene

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SCIENCE
卷 325, 期 5941, 页码 730-733

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AMER ASSOC ADVANCEMENT SCIENCE
DOI: 10.1126/science.1172910

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  1. Office of Science, U.S. Department of Energy
  2. U.S. Environmental Protection Agency [RD-833749]
  3. Royal Society of New Zealand
  4. NASA [NNX07AL33G, NNX08AD29G]
  5. [DE-FG02-05ER63983]
  6. NASA [NNX08AD29G, 103033] Funding Source: Federal RePORTER

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Emissions of nonmethane hydrocarbon compounds to the atmosphere from the biosphere exceed those from anthropogenic activity. Isoprene, a five-carbon diene, contributes more than 40% of these emissions. Once emitted to the atmosphere, isoprene is rapidly oxidized by the hydroxyl radical OH. We report here that under pristine conditions isoprene is oxidized primarily to hydroxyhydroperoxides. Further oxidation of these hydroxyhydroperoxides by OH leads efficiently to the formation of dihydroxyepoxides and OH reformation. Global simulations show an enormous flux-nearly 100 teragrams of carbon per year-of these epoxides to the atmosphere. The discovery of these highly soluble epoxides provides a missing link tying the gas-phase degradation of isoprene to the observed formation of organic aerosols.

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