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

Abstract

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 (X org > 0.2) were observed for 50 nm dry diameter (d p) particles in experiments where cooperative ionic interactions were favorable (e.g., palmitic acid, Mg 2+, and glucuronic acid) at seawater total organic carbon concentrations (<1.15 mM C) and ocean pH. Significantly smaller SSA organic volume fractions (X org < 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 tomore » 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.« less

Authors:
 [1];  [2];  [3];  [3]; ORCiD logo [4]
  1. University of California San Diego, La Jolla, CA (United States); Univ. of Wisconsin, Madison, WI (United States)
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  3. University of Iowa, Iowa City, IA (United States)
  4. Univ. of Wisconsin, Madison, WI (United States)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)
OSTI Identifier:
1494918
Report Number(s):
PNNL-SA-140085
Journal ID: ISSN 2073-4433; ATMOCZ
Grant/Contract Number:  
AC05-76RL01830
Resource Type:
Accepted Manuscript
Journal Name:
Atmosphere (Basel)
Additional Journal Information:
Journal Name: Atmosphere (Basel); Journal Volume: 9; Journal Issue: 12; Journal ID: ISSN 2073-4433
Publisher:
MDPI
Country of Publication:
United States
Language:
English
Subject:
54 ENVIRONMENTAL SCIENCES; 59 BASIC BIOLOGICAL SCIENCES; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; aerosol chemistry; sea spray; sea spray aerosol; sea spray chemistry; submicron sea spray aerosol; surfactant layers; organic surfactants; Biogeochemical cycles

Citation Formats

Schill, Steven R., Burrows, Susannah M., Hasenecz, Elias A., Stone, Elizabeth A., and Bertram, Timothy H. The Impact of Divalent Cations on the Enrichment of Soluble Saccharides in Primary Sea Spray Aerosol. United States: N. p., 2018. Web. doi:10.3390/atmos9120476.
Schill, Steven R., Burrows, Susannah M., Hasenecz, Elias A., Stone, Elizabeth A., & Bertram, Timothy H. The Impact of Divalent Cations on the Enrichment of Soluble Saccharides in Primary Sea Spray Aerosol. United States. doi:10.3390/atmos9120476.
Schill, Steven R., Burrows, Susannah M., Hasenecz, Elias A., Stone, Elizabeth A., and Bertram, Timothy H. Tue . "The Impact of Divalent Cations on the Enrichment of Soluble Saccharides in Primary Sea Spray Aerosol". United States. doi:10.3390/atmos9120476. https://www.osti.gov/servlets/purl/1494918.
@article{osti_1494918,
title = {The Impact of Divalent Cations on the Enrichment of Soluble Saccharides in Primary Sea Spray Aerosol},
author = {Schill, Steven R. and Burrows, Susannah M. and Hasenecz, Elias A. and Stone, Elizabeth A. and Bertram, Timothy H.},
abstractNote = {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.},
doi = {10.3390/atmos9120476},
journal = {Atmosphere (Basel)},
number = 12,
volume = 9,
place = {United States},
year = {2018},
month = {12}
}

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Figures / Tables:

Figure 1 Figure 1: Conceptual overview of soluble organic distribution in the sea surface microlayer (SSML) for the (A) macromolecule-derived mechanism, shown here as the lipid A head group of lipopolysaccharides (LPS), (B) ion-mediated co-adsorption mechanism put forth by Burrows et al. [57] and (C) divalent cation mediated co-adsorption (this paper).

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