Ultrasound-enhanced Magnéli phase Ti₄O₇ anodic oxidation of per- and polyfluoroalkyl substances (PFAS) towards remediation of aqueous film forming foams (AFFF)

Per-and polyfluoroalkyl substances (PFAS) remediation is still a challenge. In this study, we propose a hybrid system that combines electrochemical treatment with ultrasound irradiation, aiming for an enhanced degradation of PFAS. Equipped with a titanium suboxide (Ti₄O₇) anode, the electrochemical cell is able to remove perfluorooctanoic acid (PFOA) effectively. Under the optimal conditions (50 mA/cm² current density, 0.15 M Na₂SO₄ supporting electrolyte, and stainless steel/Ti₄O₇/stainless steel electrode configuration with a gap of ∼10 mm), the electrochemical process achieves ∼100 % PFOA removal and 43 % defluorination after 6 h. Applying ultrasound irradiation (130 kHz) alone offers a limited PFOA removal, with 33 % PFOA removal and 5.5 % defluorination. When the electrochemical process is combined with ultrasound irradiation, we observe a significant improvement in the remediation performance, with ∼100 % PFOA removal and 63.5 % defluorination, higher than the sum of 48.5 % (43 % achieved by the electrochemical process, plus 5.5 % by the ultrasound irradiation), implying synergistic removal/oxidation effects. The hybrid system also consistently shows the synergistic defluorination during degradation of other PFAS and the PFAS constituents in aqueous film forming foam (AFFF). We attribute the synergistic effect to an activated/cleaned electrode surface, improved mass transfer, and enhanced production of radicals.