Complete Defluorination and Mineralization of Perfluorooctanoic Acid by a Mechanochemical Method Using Alumina and...

Perfluorooctanoic acid (PFOA) is a persistent organic pollutant that has received concerns worldwide due to its extreme resistance to conventional degradation. A mechanochemical (MC) method was developed for complete degradation of PFOA by using alumina (Al₂O₃) and potassium persulfate (PS) as comilling agents. After ball milling for 2 h, the MC treatment using Al₂O₃ or PS caused conversion of PFOA to either 1-H-1-perfluoroheptene or dimers with a defluorination efficiency lower than 20%, but that using both Al₂O₃ and PS caused degradation of PFOA with a defluorination of 100% and a mineralization of 98%. This method also caused complete defluorination of other C3∼C6 homologues of PFOA. The complete defluorination of PFOA attributes to Al₂O₃ and PS led to the weakening of the C-F bond in PFOA and the generation of hydroxyl radical (•OH), respectively. During the MC degradation, Al₂O₃ strongly anchors PFOA through COO^--Al coordination and in situ formed from Lewis-base interaction and PS through hydrogen bond. Meanwhile, mechanical effects induce the homolytic cleavage of PS to produce SO₄^•-, which reacts with OH group of Al₂O₃ to generate •OH. The degradation of PFOA is initiated by decarboxylation as a result of weakened C-COO^- due to Al³⁺ coordination. The subsequent addition of •OH, elimination of HF, and reaction with water induce the stepwise removal of all carboxyl groups and F atoms as CO₂ and F^-_, respectively. Thus, complete defluorination and mineralization are achieved.