title: Peroxidase-mediated degradation of perfluorooctanoic acid.
abstract: Concentrations of aqueous-phase perfluorooctanoic acid (PFOA), a representative perfluorinated aliphatic (PFA) compound, are shown to be reduced effectively via reaction with horseradish peroxidase (HRP), hydrogen peroxide, and a phenolic cosubstrate (4-methoxyphenol). Reaction rate profiles are pseudo-first order, yielding an apparent best-fit removal rate constant of k1 = 0.003/min (r2 = 0.96, n = 14). Approximately 68% depletion of the parent compound and 98% depletion of its related acute aquatic toxicity are achieved in 6 h. Because no PFOA removal is observed in the absence of cosubstrate and/or following consumption thereof, we conclude that radical intermediate species generated during reaction between HRP and 4-methoxyphenol mediate nonspecific depletion of PFOA and that these intermediates may be sufficiently reactive to sever the extremely stable C-F bonds of PFOA. These results are consistent with measurements of reaction by-products, including fluoride ion and various aliphatic species of shortened chain length. Based on these findings, we conclude that PFA degradation may occur via one of two mechanisms: Kolbe decarboxylation followed by stepwise conversion of -CF2 units to CO2 and fluoride ion, or radical abstraction from a double bond with subsequent fragmentation. Our results indicate that under appropriate conditions, enzymatic degradation may comprise a natural transformation pathway for PFAs. Moreover, we anticipate that appropriately engineered enzymatic processes may hold promise for treatment of PFOA-contaminated waters. This, to the best of our knowledge, is the first report to substantiate the efficacy of HRP-catalyzed reactions for contaminant removal via degradative reactions versus polymerization reactions.
authors.affiliation: Department of Civil and Environmental Engineering, University of Virginia, Charlottesville, Virginia 22904, USA.
authors.forename: Lisa M
authors.initials: LM
authors.lastname: Colosi
authors.forename: Roger A
authors.initials: RA
authors.lastname: Pinto
authors.forename: Qingguo
authors.initials: Q
authors.lastname: Huang
authors.forename: Walter J
authors.initials: WJ
authors.lastname: Weber
mesh_terms: D002210:Caprylates / Q000378:metabolism* / Q000633:toxicity; D005466:Fluorocarbons / Q000378:metabolism* / Q000633:toxicity; D010544:Peroxidases / Q000378:metabolism*
chemical_list: D002210:Caprylates; D005466:Fluorocarbons; C023036:perfluorooctanoic acid; D010544:Peroxidases