[1] Breaking waves on the ocean surface produce bubbles that, upon bursting, inject seawater constituents into the atmosphere. Nascent aerosols were generated by bubbling zero-air through flowing seawater within an RH-controlled chamber deployed at Bermuda and analyzed for major chemical and physical characteristics. The composition of feed seawater was representative of the surrounding ocean. Relative size distributions of inorganic aerosol constituents were similar to those in ambient air. Ca 2+ was significantly enriched relative to seawater (median factor = 1.2). If in the form of CaCO 3 , these enrichments would have important implications for pH-dependent processes. Other inorganic constituents were present at ratios indistinguishable from those in seawater. Soluble organic carbon (OC) was highly enriched in all size fractions (median factor for all samples = 387). Number size distributions exhibited two lognormal modes. The number production flux of each mode was linearly correlated with bubble rate. At 80% RH, the larger mode exhibited a volume centroid of $5-mm diameter and included $95% of the inorganic sea-salt mass; water comprised 79% to 90% of volume. At 80% RH, the smaller mode exhibited a number centroid of 0.13-mm diameter; water comprised 87% to 90% of volume. The median mass ratio of organic matter to sea salt in the smallest size fraction (geometric mean diameter = 0.13 mm) was 4:1. These results support the hypothesis that bursting bubbles are an important global source of CN and CCN with climatic implications. Primary marine aerosols also influence radiative transfer via multiphase processing of sulfur and other climate-relevant species.Citation: Keene, W. C., et al. (2007), Chemical and physical characteristics of nascent aerosols produced by bursting bubbles at a model air-sea interface,
[1] Alkyl nitrates have been observed in remote oceanic regions of the troposphere and in the surface ocean. The mechanism for their production in the oceans is not known. A likely source is the reaction of ROO + NO (where R is an alkyl group). Steady-state laboratory experiments show that alkyl nitrates are produced in the aqueous phase via this reaction, with branching ratios of 0.23 ± 0.04, 0.67 ± 0.03, and 0.71 ± 0.04 for methyl, ethyl, and propyl nitrate respectively. The branching ratios in aqueous solution are significantly higher than in the gas phase. Irradiation of surface seawaters yield rates of alkyl nitrate production on the order of 10, suggesting that the reaction of ROO and NO is an important source of alkyl nitrates in seawater.
[1] Marine aerosols produced by bursting bubbles at the ocean surface are highly enriched in organic matter (OM) relative to seawater. The importance of this OM in the photochemical evolution of marine aerosols, particularly as a source of reactive oxidants, is unknown but likely significant. To investigate oxidant production, nascent aerosols were generated by bubbling zero air through flowing Sargasso seawater and photochemical production of OH radical and hydroperoxide were quantified in aqueous aerosol extracts exposed to solar radiation. Extrapolation to ambient conditions indicates that OM photolysis was the primary in situ source for both OH (1.1 Â 10 À8 M s À1 ) and hydroperoxides (1.7 Â 10 À8 M s À1 ) in nascent aerosols; NO 3 À photolysis was the primary source in aged, acidified aerosols (1.4 Â 10 À7 and 4.1 Â 10 À8 M s À1 , respectively). In situ OH photoproduction was comparable to gas-phase uptake whereas H 2 O 2 photoproduction was slower. Results provide important constraints for poorly quantified oxidant sources in marine aerosols. Citation:
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