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Atmosphere 2018, 9(12), 476;

The Impact of Divalent Cations on the Enrichment of Soluble Saccharides in Primary Sea Spray Aerosol

Department of Chemistry and Biochemistry, University of California San Diego, La Jolla, CA 92093, USA
Department of Chemistry, University of Wisconsin Madison, Madison, WI 53706, USA
Atmospheric Sciences & Global Change Division, Pacific Northwest National Laboratory, Richland, WA 99354, USA
Department of Chemistry, University of Iowa, Iowa City, IA 52242, USA
Author to whom correspondence should be addressed.
Received: 31 October 2018 / Revised: 26 November 2018 / Accepted: 1 December 2018 / Published: 4 December 2018
(This article belongs to the Special Issue Ocean Contributions to the Marine Boundary Layer Aerosol Budget)
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Field measurements have shown that sub-micrometer sea spray aerosol (SSA) is significantly enriched in organic material, of which a large fraction has been attributed to soluble saccharides. Existing mechanistic models of SSA production struggle to replicate the observed enhancement of soluble organic material. Here, we assess the role for divalent cation mediated co-adsorption of charged surfactants and saccharides in the enrichment of soluble organic material in SSA. Using measurements of particle supersaturated hygroscopicity, we calculate organic volume fractions for molecular mimics of SSA generated from a Marine Aerosol Reference Tank. Large enhancements in SSA organic volume fractions (Xorg > 0.2) were observed for 50 nm dry diameter (dp) particles in experiments where cooperative ionic interactions were favorable (e.g., palmitic acid, Mg2+, and glucuronic acid) at seawater total organic carbon concentrations (<1.15 mM C) and ocean pH. Significantly smaller SSA organic volume fractions (Xorg < 1.5 × 10−3) were derived from direct measurements of soluble saccharide concentrations in collected SSA with dry diameters <250 nm, suggesting that organic enrichment is strongly size dependent. The results presented here indicate that divalent cation mediated co-adsorption of soluble organics to insoluble surfactants at the ocean surface may contribute to the enrichment of soluble saccharides in SSA. The extent to which this mechanism explains the observed enhancement of saccharides in nascent SSA depends strongly on the concentration, speciation, and charge of surfactants and saccharides in the sea surface microlayer. View Full-Text
Keywords: aerosols; organic; enrichment; sea spray aerosols aerosols; organic; enrichment; sea spray aerosols

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Schill, S.R.; Burrows, S.M.; Hasenecz, E.S.; Stone, E.A.; Bertram, T.H. The Impact of Divalent Cations on the Enrichment of Soluble Saccharides in Primary Sea Spray Aerosol. Atmosphere 2018, 9, 476.

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