Isoprene is the precursor for number of alcohol, organosulfate, and organonitrate species observed in ambient secondary organic aerosol (SOA). Recent laboratory and field work has suggested that isoprene-derived epoxides may be crucial intermediates that can explain the existence of these compounds in SOA. To confirm this hypothesis, the specific hydroxy epoxides observed in gas phase isoprene photooxidation experiments (as well as several other related species) were synthesized and the bulk phase aqueous reactions of these species in the presence of sulfate and nitrate were studied via nuclear magnetic resonance (NMR) techniques. The results indicate that both primary and tertiary organosulfates and organonitrates are efficiently formed from the potential SOA reactions of isoprene-derived epoxides. However, the tertiary organonitrates are shown to undergo rapid nucleophilic substitution reactions (in which nitrate is substituted for by water or sulfate) over the whole range of SOA pH, while the tertiary organosulfates are found to undergo a much slower acid-dependent hydrolysis reaction. The primary organonitrates and organosulfates under study were found to be stable against nucleophilic substitution reactions, even at low pH. This finding provides a potential explanation for the fact that organosulfates are more commonly detected in ambient SOA than are organonitrates.

Isoprene (the most abundant nonmethane hydrocarbon emitted into the atmosphere) is known to undergo oxidation to 2-methyl-1,2,3,4-butanetetraol, a hydrophilic compound present in secondary organic aerosol (SOA) in the atmosphere. Recent laboratory work has shown that gas phase hydroxy epoxides are produced in the low NOx photooxidation of isoprene and that these epoxides are likely to undergo efficient acid-catalyzed hydrolysis on SOA to 2-methyl-1,2,3,4-butanetetraol at typical SOA acidities. In order to confirm this hypothesis, the specific hydroxy epoxides observed in the isoprene photooxidation experiment (as well as several other related species) were synthesized, and the hydrolysis kinetics of all species were studied via nuclear magnetic resonance (NMR) techniques. It was determined that the isoprene-derived hydroxy epoxides should undergo efficient hydrolysis under atmospheric conditions, particular on lower pH SOA. An empirical structure-reactivity model was constructed that parametrized the hydrolysis rate constants according to the carbon substitution pattern on the epoxide ring and number of neighboring hydroxy functional groups. Compared to the previously studied similar nonfunctionalized epoxides, the presence of a hydroxy group at the alpha position to the epoxy group was found to reduce the hydrolysis rate constant by a factor of 20, and the presence of a hydroxy group at the beta position to the epoxy group was found to reduce the hydrolysis rate constant by a factor of 6.

[1] As part of the International Polar Year research program, we conducted a survey of surface marine sediments from box cores along a section extending from the Bering Sea to Davis Strait via the Canadian Archipelago. We used bulk elemental and isotopic compositions, together with biomarkers and principal components analysis, to elucidate the distribution of marine and terrestrial organic matter in different regions of the North American Arctic margin. Marked regional contrasts were observed in organic carbon loadings, with the highest values (!1 mg C m À2 sediment) found in sites along Barrow Canyon and the Chukchi and Bering shelves, all of which were characterized by sediments with low oxygen exposure, as inferred from thin layers (<2 cm) of Mn oxihydroxides. We found strong regional differences in inorganic carbon concentrations, with sites from the Canadian Archipelago and Lancaster Sound displaying elevated values (2-7 wt %) and highly depleted 14 C compositions consistent with inputs from bedrock carbonates. Organic carbon:nitrogen ratios, stable carbon isotopes, and terrigenous organic biomarkers (lignin phenols and cutin acids) all indicate marked regional differences in the proportions of marine and terrigenous organic matter present in surface sediments. Regions such as Barrow Canyon and the Mackenzie River shelf were characterized by the highest contributions of landderived organic matter, with compositional characteristics that suggested distinct sources and provenance. In contrast, sediments from the Canadian Archipelago and Davis Strait had the smallest contributions of terrigenous organic matter and the lowest organic carbon loadings indicative of a high degree of post-depositional oxidation.

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