Seasonal and longitudinal distributions of atmospheric water‐soluble dicarboxylic acids, oxocarboxylic acids, and α ‐dicarbonyls over the North Pacific

In order to assess the seasonal variability of atmospheric abundances of dicarboxylic acids, oxocarboxylic acids, and α ‐dicarbonyls over the North Pacific and Sea of Japan, aerosol samples were collected along the longitudinal transacts during six cruises between Canada and Japan. The back trajectory analyses indicate that aerosol samples collected in winter and spring are influenced by the East Asian outflow, whereas summer and fall samples are associated with the pristine maritime air masses. Molecular distributions of water‐soluble organics in winter and spring samples show the predominance of oxalic acid (C 2 ) followed by succinic (C 4 ) and malonic acids (C 3 ). In contrast, summer and fall marine aerosols are characterized by the predominance of C 3 over C 4 . Concentrations of dicarboxylic acids were higher over the Sea of Japan than the North Pacific. With a lack of continental outflow, higher concentrations during early summer are ascribed to atmospheric oxidation of organic precursors associated with high biological activity in the North Pacific. This interpretation is further supported by the high abundances of azelaic acid, which is a photochemical oxidation product of biogenic unsaturated fatty acids, over the Bering Sea in early summer when surface waters are characterized by high biological productivity. We found higher ratios of oxalic acid to pyruvic and glyoxylic acids (C 2 /Pyr and C 2 / ω C 2 ) and glyoxal and methylglyoxal (C 2 /Gly and C 2 /MeGly) in summer and fall than in winter and spring, suggesting a production of C 2 from the aqueous‐phase oxidation of oceanic isoprene. In this study, dicarboxylic acids account for 0.7–38% of water‐soluble organic carbon.