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

Journal Article · · Environmental Science and Technology
 [1];  [2];  [3];  [4];  [1];  [5];  [6]
  1. Sandia National Lab. (SNL-CA), Livermore, CA (United States)
  2. Univ. of Bristol. (United Kingdom)
  3. Sandia National Lab. (SNL-CA), Livermore, CA (United States); Univ. of Helsinki (Finland)
  4. Univ. of Manchester (United Kingdom); California Inst. of Technology (CalTech), La Canada Flintridge, CA (United States). Jet Propulsion Lab.
  5. Ford Motor Company, Dearborn, MI (United States)
  6. Univ. of Bristol. (United Kingdom); Univ. of the Western Cape, Bellville (South Africa)
+ Show Author Affiliations

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.

Research Organization:
Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC04-94AL85000
OSTI ID:
1492346
Report Number(s):
SAND--2019-0140J; 671357
Journal Information:
Environmental Science and Technology, Journal Name: Environmental Science and Technology Journal Issue: 3 Vol. 53; ISSN 0013-936X
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY