Autocatalytic degradation of perfluorooctanoic acid in a permanganate-ultrasonic system.

An autocatalytic system, permanganate-ultrasonic (PM-US) system, was applied to degrade perfluorooctanoic acid (PFOA) in aqueous solutions. After a 120-min ultrasonication, a PM dosage of 6 mM increased the pseudo first-order rate constant (k1) for PFOA decomposition from 3.5 × 10-3 to 13.0 × 10-3 min-1 and increased the pseudo zeroth-order rate constant (k2) for PFOA defluorination from 1.5 × 10-3 to 7.9 × 10-3 mM·min-1, respectively. The PFOA degradation rates increased proportionally with the enhanced production rates of MnO2 particles. An initial pH 4 condition was optimal for the PFOA degradation compared to highly acidic and neutral conditions. PFOA degradation could be significantly facilitated by increasing power density of ultrasonication from 60 to 180 W·L-1. While increasing solution temperature to 50 °C only slightly promoted the PFOA decomposition and defluorination to 1.15 and 1.07 times of that at 30 °C, respectively. The solution saturated with argon was more favorable for the PFOA degradation in the PM-US system than that saturated with air and oxygen. Co-dissolved Cu(II), Fe(II) and Fe(III) ions inhibited the PFOA degradation by forming metal-PFOA complexes. Based on the experimental results and intermediates analysis, mechanisms and pathways of PFOA decomposition and defluorination in the PM-US system were proposed.

Effect of surfactants on the degradation of perfluorooctanoic acid (PFOA) by ultrasonic (US) treatment.

Perfluorooctanoic acid (C7F15COOH, PFOA) is an aqueous anionic surfactant and a persistent organic pollutant. It can be easily adsorbed onto the bubble-water interface and both mineralized and degraded by ultrasonic (US) cavitation at room temperature. The aim of this study is to investigate whether the effect of US on the degradation of PFOA in solution can be enhanced by the addition of surfactant. To achieve this aim, we first investigated the addition of a cationic (hexadecyl trimethyl ammonium bromide, CTAB), a nonionic (octyl phenol ethoxylate, TritonX-100), and an anionic (sodium dodecyl sulfate, SDS) surfactant. We found the addition of CTAB to have increased the degradation rate the most, followed by TritonX-100. SDS inhibited the degradation rate. We then conducted further experiments characterizing the removal efficiency of CTAB at varying surfactant concentrations and solution pHs. The removal efficiency of PFOA increased with CTAB concentration, with the efficiency reaching 79% after 120 min at 25°C with a 0.12 mM CTAB dose.

Enhanced sonochemical degradation of perfluorooctanoic acid by sulfate ions.

This study investigated the effects of sulfate ions on the decomposition of perfluorooctanoic acid (PFOA) by ultrasonic (US) irradiation at various pHs, sulfate doses, powers and temperatures. The removal of PFOA was augmented with an increased sulfate ion concentration, with PFOA being almost completely decomposed in 90min at 25°C with a sulfate dose of 117mM. The two major mechanisms in the sulfate-assisted sonochemical system are the direct destruction of PFOA by cavitation and the indirect destruction of PFOA by sulfate free radicals. The decomposition of PFOA followed pseudo-first-order kinetics and was not influenced by pH. The reaction rate constants decreased with increases in temperature due to decreases in the surface tension of the solution.