Enrichment of saccharides at the air–water interface: a quantitative comparison of sea surface microlayer and foam
Thilina Jayarathne A D , Dilini Kirindigoda Gamage A , Kimberly A. Prather B C and Elizabeth A. Stone A *A Department of Chemistry, University of Iowa, Iowa City, IA 52242, USA.
B Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, CA 92093, USA.
C Scripps Institution of Oceanography, University of California, San Diego, La Jolla, CA 92093, USA.
D Present address: Bristol Myers Squibb, 1 Squibb Drive, New Brunswick, NJ 08901, USA.
Environmental Chemistry 19(8) 506-516 https://doi.org/10.1071/EN22094
Submitted: 12 August 2022 Accepted: 31 January 2023 Published: 3 March 2023
© 2022 The Author(s) (or their employer(s)). Published by CSIRO Publishing. This is an open access article distributed under the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License (CC BY-NC-ND)
Environmental context. Saccharides contribute substantially to dissolved organic carbon in the ocean and are enriched at the ocean surface. In this study, we demonstrate that saccharides are more enriched in persistent whitecap foam compared to the sea surface. The maturation of bubbles at the air–water interface is thus expected to enhance the enrichment of organic matter at the ocean surface and ultimately in the sea spray aerosol that forms when bubbles burst at the ocean surface.
Rationale. Organic matter accumulates at the ocean surface. Herein, we provide the first quantitative assessment of the enrichment of dissolved saccharides in persistent whitecap foam and compare this enrichment to the sea surface microlayer (SSML) during a 9 day mesocosm experiment involving a phytoplankton bloom generated in a Marine Aerosol Reference Tank (MART).
Methodology. Free monosaccharides were quantified directly, total saccharides were determined following mild acid hydrolysis and the oligo/polysaccharide component was determined as the difference between total and free monosaccharides.
Results. Total saccharides contributed a significant fraction of dissolved organic carbon (DOC), accounting for 13% of DOC in seawater, 27% in SSML and 31% in foam. Median enrichment factors (EFs), calculated as the ratio of the concentrations of saccharides relative to sodium in SSML or foam to that of seawater, ranged from 1.7 to 6.4 in SSML and 2.1–12.1 in foam. Based on median EFs, xylitol, mannitol, glucose, galactose, mannose, xylose, fucose, rhamnose and ribose were more enriched in foam than SSML.
Discussion. The greatest EFs for saccharides coincided with high chlorophyll levels, indicating increasing ocean surface enrichment of saccharides during phytoplankton blooms. Higher enrichments of organic matter in sea foam over the SSML indicate that surface active organic compounds become increasingly enriched on persistent bubble film surfaces. These findings help to explain how marine organic matter becomes highly enriched in sea spray aerosol that is generated by bursting bubbles at the ocean surface.
Keywords: carbohydrates, dissolved organic carbon, enrichment factor, phytoplankton bloom, sea surface microlayer, sugar alcohols, ultrafiltration, whitecap foam.
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