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Reductive defluorination of aqueous perfluorinated alkyl surfactants : effects of ionic headgroup and chain length

Park, Hyunwoong and Vecitis, Chad D. and Cheng, Jie and Choi, Wonyong and Mader, Brian T. and Hoffmann, Michael R. (2009) Reductive defluorination of aqueous perfluorinated alkyl surfactants : effects of ionic headgroup and chain length. Journal of Physical Chemistry A, 113 (4). pp. 690-696. ISSN 1089-5639. http://resolver.caltech.edu/CaltechAUTHORS:20090410-134802114

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Abstract

Perfluorinated chemicals (PFCs) are distributed throughout the environment. In the case of perfluorinated alkyl carboxylates and sulfonates, they can be classified as persistent organic pollutants since they are resistant to environmentally relevant reduction, oxidation, and hydrolytic processes. With this in mind, we report on the reductive defluorination of perfluorobutanoate, PFBA (C_3F_7CO_2−), perfluorohexanoate, PFHA (C_5F_(11)CO_2−), perfluorooctanoate, PFOA (C_7F_(15)CO_2−), perfluorobutane sulfonate, PFBS (C_4F_9SO_3−), perfluorohexane sulfonate, PFHS (C_6F_(13)SO_3−), and perfluorooctane sulfonate, PFOS (C_8F_(17)SO_3−) by aquated electrons, eaq−, that are generated from the UV photolysis (λ = 254 nm) of iodide. The ionic headgroup (-SO_3− vs -CO_2−) has a significant effect on the reduction kinetics and extent of defluorination (F index = −[F−]_(produced)/[PFC]_(degraded)). Perfluoroalkylsulfonate reduction kinetics and the F index increase linearly with increasing chain length. In contrast, perfluoroalkylcarboxylate chain length appears to have a negligible effect on the observed kinetics and the F index. H/F ratios in the gaseous fluoro-organic products are consistent with measured F indexes. Incomplete defluorination of the gaseous products suggests a reductive cleavage of the ionic headgroup occurs before complete defluorination. Detailed mechanisms involving initiation by aquated electrons are proposed.


Item Type:Article
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http://dx.doi.org/10.1021/jp807116qDOIArticle
http://pubs.acs.org/doi/abs/10.1021/jp807116qPublisherArticle
ORCID:
AuthorORCID
Hoffmann, Michael R.0000-0002-0432-6564
Additional Information:© 2009 American Chemical Society. Received: August 8, 2008; Revised Manuscript Received: October 20, 2008. This work was supported by the 3M Corporation (D. Bacon). The authors also thank Dr. N. Dalleska (Environmental Analytical Center) for comments and analytic support.
Funders:
Funding AgencyGrant Number
3M CorporationUNSPECIFIED
Issue or Number:4
Record Number:CaltechAUTHORS:20090410-134802114
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20090410-134802114
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:13932
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:03 Aug 2009 22:27
Last Modified:14 Dec 2015 20:27

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