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Publication - Professor Dudley Shallcross

    Reaction of Perfluorooctanoic Acid with Criegee Intermediates and Implications for the Atmospheric Fate of Perfluorocarboxylic Acids

    Citation

    Taatjes, CA, Khan, MAH, Eskola, AJ, Percival, CJ, Osborn, DL, Wallington, TJ & Shallcross, DE, 2019, ‘Reaction of Perfluorooctanoic Acid with Criegee Intermediates and Implications for the Atmospheric Fate of Perfluorocarboxylic Acids’. Environmental Science and Technology, vol 53., pp. 1245-1251

    Abstract

    The reaction of perfluorooctanoic acid with the smallest carbonyl oxide Criegee intermediate, CH2OO, has been measured and is very rapid, with a rate coefficient of (4.9 ± 0.8) × 10-10 cm3 s-1, similar to that for reactions of Criegee intermediates with other organic acids. Evidence is shown for the formation of hydroperoxymethyl perfluorooctanoate as a product. With such a large rate coefficient, reaction with Criegee intermediates can be a substantial contributor to atmospheric removal of perfluorocarboxylic acids. However, the atmospheric fates of the ester product largely regenerate the initial acid reactant. Wet deposition regenerates the perfluorocarboxylic acid via condensed-phase hydrolysis. Gas-phase reaction with OH is expected principally to result in formation of the acid anhydride, which also hydrolyzes to regenerate the acid, although a minor channel could lead to destruction of the perfluorinated backbone.

    Full details in the University publications repository