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Size-resolved aerosol samples for subsequent quantitative determination ofpolymer sugars (polysaccharides) after hydrolysis to their subunit monomers(monosaccharides) were collected in surface air over the central Arctic Oceanduring the biologically most active summer period. The analysis was carriedout by novel use of liquid chromatography coupled with highly selective andsensitive tandem mass spectrometry. Polysaccharides were detected in particlesizes ranging from 0.035 to 10 μm in diameter with distinctfeatures of heteropolysaccharides, enriched in xylose, glucose + mannoseas well as a substantial fraction of deoxysugars. Polysaccharides, containingdeoxysugar monomers, showed a bimodal size structure with about 70% oftheir mass found in the Aitken mode over the pack ice area. Pentose (xylose)and hexose (glucose + mannose) had a weaker bimodal character and werelargely found with super-micrometer sizes and in addition with a minorsub-micrometer fraction. The concentration of total hydrolysable neutralsugars (THNS) in the samples collected varied over two orders of magnitude(1 to 160 pmol m<sup>−3</sup>) in the super-micrometer size fraction and to asomewhatlesser extent in sub-micrometer particles (4 to 140 pmol m<sup>−3</sup>). LowestTHNS concentrations were observed in air masses that had spent more than fivedays over the pack ice. Within the pack ice area, about 53% of the massof hydrolyzed polysaccharides was detected in sub-micrometer particles. Therelative abundance of sub-micrometer hydrolyzed polysaccharides could berelated to the length of time that the air mass spent over pack ice, with thehighest fraction (> 90%) observed for > 7 daysof advection. The aerosol samples collected onboard ship showed similarmonosaccharide composition, compared to particles generated experimentally insitu at the expedition's open lead site. This supports the existence of aprimary particle source of polysaccharide containing polymer gels from openleads by bubble bursting at the air–sea interface. We speculate that theoccurrence of atmospheric surface-active polymer gels with their hydrophilicand hydrophobic segments, promoting cloud droplet activation, could play apotential role as cloud condensation nuclei in the pristine high Arctic

Size-resolved atmospheric particulate polysaccharides in the high summer Arctic