Mechanism of carboxylic acid photooxidation in atmospheric aqueous phase: Formation, fate and reactivity

In the first part of the work, we investigated the reactivity toward photogenerated hydroxyl radicals (OH) of seven monocarboxylic acids and six dicarboxylic acids found in natural cloud water. This leads to the proposition of a schematic degradation pathway linking glutaric acid (C5) to complete mineralization into CO2. We report a detailed mechanism on the succinic acid reactivity toward OH leading to the formation of malonic, glyoxylic and consequently oxalic acids and a comparison with reported pathways proposed by the CAPRAM (Chemical Aqueous Phase RAdical Mechanism) is discussed. We also investigated the photooxidation of formic acid under atmospherically relevant conditions leading to the possible formation of oxalic acid via radical mediated recombination.The second part focuses on the polychromatic irradiation (closed to solar irradiation) of a collected cloud aqueous phase showing that irradiation of cloud water leads to the formation of both formic and acetic acids. Carboxylic acid formation increases in the presence of photogenerated hydroxyl radicals from hydrogen peroxide, showing that photooxidation could play a key role in the formation of carboxylic acids under atmospherically relevant conditions.

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► We investigated the chemical photooxidantion of carboxylic acids under atmospherically relevant aqueous media.
► Hydroxyl radical reactivity with formic acid leads to the formation in small amounts of oxalic acid.
► Photochemistry of cloud water is responsible for the increase of carboxylic acids concentration in such medium.