Mid-chain ketocarboxylic acids in the remote marine atmosphere: Distribution patterns and possible formation mechanisms

In remote marine aerosol samples collected from the North Pacific ocean, Enewetak Atoll, American Samoa, and New Zealand, series of mid-chain ketocarboxylic acids in the range of C₆-C₁₈ were detected. All the positional isomers, except for the 2-oxo and 3-oxo species, were detected for major ketoacid families (e.g. C₉, C₁₁ and C₁₃). Higher ketoacid concentrations (up to 19 ng/m³) were obtained in the northern North Pacific aerosol samples, which generally showed an odd carbon-numbered predominance with 5-oxoundecanoic acid being the major species. By contrast, lower concentrations were obtained in the lower-latitude or subtropical aerosol samples, where even carbon-numbered ketoacids were relatively abundant.The distribution patterns of the odd carbon-numbered ketoacids could not be explained by the primary emissions from source materials including terrestrial higher plants, soil particles, and ocean surfaces. We consider that the isomeric ketocarboxylic acids are produced in the atmosphere by the photochemical oxidation of semi-volatile monocarboxylic acids, which are counterparts of the oxidative degradation of unsaturated fatty acids emitted from seawater surfaces. Atmospheric production of the ketoacids is seemingly enhanced in the northern North Pacific, probably due to an enhanced primary productivity.