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5079978 
Journal Article 
Reaction of Perfluorooctanoic Acid with Criegee Intermediates and Implications for the Atmospheric Fate of Perfluorocarboxylic Acids 
Taatjes, CA; Khan, MAH; Eskola, AJ; Percival, CJ; Osborn, DL; Wallington, TJ; Shallcross, DE 
2019 
1 
Environmental Science & Technology
ISSN: 0013-936X
EISSN: 1520-5851 
53 
3 
1245-1251 
English 
30589541 
WOS:000458220600021 
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.