Mineralization Of Perfluorooctanoic Acid Research Articles

Can perfluorooctanoic acid be effectively degraded using β-PbO2 reactive electrochemical membrane?

Aqueous perfluorooctanoic acid (PFOA) elimination has raised significant concerns due to its persistence and bioaccumulation. Although β-PbO2 plate anodes have shown efficient mineralization of PFOA, it remains unclear whether PFOA can be effectively degraded using β-PbO2 reactive electrochemical membrane (REM). Herein, we assessed the performance of Ti/SnO2-Sb/La-PbO2 REM for PFOA removal and proposed a possible degradation mechanism. At a current density of 10 mA/cm2 and a membrane flux of 8500 (liters per square meter per hour, LMH), the degradation efficiency of 10 mg/L PFOA was merely 8.8%, whereas the degradation efficiency of 0.1 mg/L PFOA increased to 96.6%. Although the porous structure of the β-PbO2 REM provided numerous electroactive sites for PFOA, the generated oxygen bubbles in the pores could block the pore channels and adsorb PFOA molecules. These hindered the protonation process and significantly impeded the degradation of high-concentration PFOA. Quenching experiments indicated that •OH played dominant role in PFOA degradation. The electrical energy per order to remove 0.1 mg/L PFOA was merely 0.74 Wh/L, which was almost an order of magnitude lower than that of other anode materials. This study presents fresh opportunities for the electrochemical degradation of low-concentration PFOA using β-PbO2 REM.

Efficient defluorination of perfluorooctanoic acid enabled by single-atom Cu/reduced graphene oxide electrocatalytic anode and peroxymonosulfate activation

In this study, an electrocatalytic system using reduced graphene oxide supported single-atom copper (SA-Cu/rGO) anode was constructed for perfluorooctanoic acid (PFOA) defluorination. The successful doping of SA-Cu elevated the oxygen evolution potential and electrochemical active surface area of the anode and provided high electrocatalytic properties. Under optimum initial conditions with a peroxymonosulfate (PMS) concentration of 10 mM, a current density of 15 mA·cm−2, and an unadjusted pH of 7.75, the SA-Cu/rGO system achieved 98.8% removal ratio, 92.5% defluorination, and 94.4% mineralization of 20 mg·L-1 PFOA in 120 min. Kinetic studies indicate PFOA degradation following a pseudo-first-order model, with a rate constant of 4.7 × 10−2 min−1. The presence of PMS in the electrocatalytic system significantly improved the degradation rate and defluorination ratio. Radical trapping and quenching experiments confirmed that both ·OH and ·SO4- radicals contributed to PFOA degradation, with ·SO4- playing a more important role in defluorination. The system show high flexibility in initial PFOA concentrations (0.2–20 mg·L−1) and environmental pH values (3.0–10.0), as well as good durability. The electrocatalytic degradation mechanism of PFOA was proposed through determination of intermediates and density functional theory (DFT) calculation. The total short-chain perfluorocarboxylic acids (PFCAs) intermediates generated throughout the degradation were far from sufficient recovery of the PFOA loss, indicating that apart from the ·OH mediated decarboxylation-hydroxylation-elimination-hydrolysis (DHEH) pathway, the ·SO4- mediated decarboxylation-hydroxylation-oxidation-decarbonyl fluoride (DHOD) pathway may play a significant role in the near-complete defluorination and mineralization of PFOA. Moreover, DFT calculations suggest that the DHOD pathway is energetically favorable over DHEH. This study provides a further understanding of the defluorination mechanism of PFOA in electrocatalytic systems and demonstrates that electrochemical degradation with single-atom copper catalyst is an promising method for PFOA remediation in aqueous environment.

Electrochemical oxidation coupled with hydrated electron reduction in ultraviolet (UV)-sulfite system for complete defluorination and mineralization of Perfluorooctanoic Acid (PFOA)

Hydrated electron reduction in an ultraviolet (UV)-sulfite system and electrochemical oxidation on a boron doped diamond (BDD) anode both are efficient processes for the degradation of perfluorooctanoic acid (PFOA). However, hydrated electron reduction has inherent deficiency in the mineralization (i.e., converting organic carbon into CO2) of PFOA. Furthermore, toxic byproducts such as partially hydrodefluorinated carboxylic acids (HDCAs) and perfluorosulfonic acids (PFSAs) might give secondary pollution if the wholly hydrodefluorination of PFOA is not achieved. BDD electrochemical oxidation can obtain a high mineralization efficiency, but it leads to a low defluorination (i.e., transforming C−F bonds into F− ions) efficiency due to the generation of toxic volatile fluorinated alkanes. Herein, we report a coupled process that is hydrated electron reduction as pre-treatment and BDD electrochemical oxidation as post-treatment to achieve a complete defluorination and mineralization of PFOA, the results demonstrate that 50 mg/L PFOA can be 100 % deluorinated and mineralized under 5 h UV-sulfite reduction followed by 10 h electrochemical oxidation. This coupled process strongly inhibits the production of the toxic volatile fluorinated pollutants and quickly converts the residual toxic sulfite in UV-sulfite system to the sulfate. Mechanism investigation demonstrates that BDD oxidation is able to transform HDCAs and PFSAs formed by hydrated electron reduction to the perfluorocarboxylic acids (PFCAs) with shorter carbon chain than PFOA, which can be further defluorinated and mineralized.

Enhancing Interface Reactions by Introducing Microbubbles into a Plasma Treatment Process for Efficient Decomposition of PFOA.

Efficient destruction of perfluoroalkyl compounds in contaminated waters remains a challenge because of highly stable C-F bonds. In this study, mineralization of perfluorooctanoic acid (PFOA) with high concentration (∼30 mg/L) was realized in a needle-plate pulsed discharge reactor integrated with a water jet (NPDW) to which microbubbles (MBs) with different carrier gases (air, N2, and Ar) were introduced to enhance interfacial reactions. MBs effectively enrich dispersed PFOA from a bulk solution to a liquid surface to allow enhancing contact with reactive species and also expanding the plasma discharge area and channels. The PFOA removal efficiency in air and Ar discharge reached 81.5 and 95.3% in 2 h, respectively, with a defluorination ratio of no less than 50%. Energy requirements (EE/O) ranged from 216.49 to 331.95 kWh/m3. Aside from fluoride, PFOA was degraded to a range of short-chain perfluoroalkyl acids and, to a minor extent, at least 20 other fluorinated transformation products. PFOA degradation mechanisms were proposed, including decarboxylation, hydroxylation, hydrogenation reduction, and defluorination reactions. Real water matrices (groundwater, tap water, wastewater effluent, and surface water) showed moderate impact on treatment outcomes, demonstrating the robustness of the treatment process. The study demonstrated an environmentally friendly nonthermal plasma technology for effective PFOA degradation.

Efficient removal of PFOA with an In2O3/persulfate system under solar light via the combined process of surface radicals and photogenerated holes

The environmental persistence, high toxicity and wide spread presence of perfluorooctanoic acid (PFOA) in aquatic environment urgently necessitate the development of advanced technologies to eliminate PFOA. Here, the simultaneous application of a heterogeneous In2O3 photocatalyst and homogeneous persulfate oxidation (In2O3/PS) was demonstrated for PFOA degradation under solar light irradiation. The synergistic effect of direct hole oxidation and in-situ generated radicals, especially surface radicals, was found to contribute significantly to PFOA defluorination. Fourier infrared transform (FTIR) spectroscopy, Raman, electrochemical scanning microscope (SECM) tests and density functional theory (DFT) calculation showed that the pre-adsorption of PFOA and PS onto In2O3 surface were dramatically critical steps, which could efficiently facilitate the direct hole oxidation of PFOA, and boost PS activation to yield high surface−confined radicals, thus prompting PFOA degradation. Response surface methodology (RSM) was applied to regulate the operation parameters for PFOA defluorination. Outstanding PFOA decomposition (98.6%) and near-stoichiometric equivalents of fluorides release were achieved within illumination 10 h. An underlying mechanism for PFOA destruction was proposed via a stepwise losing CF2 unit. The In2O3/PS remediation system under solar light provides an economical, sustainable and environmentally friendly approach for complete mineralization of PFOA, displaying a promising potential for treatment of PFOA-containing water.

Electrochemical degradation of per- and poly-fluoroalkyl substances using boron-doped diamond electrodes

Electrochemical degradation using boron-doped diamond (BDD) electrodes has been proven to be a promising technique for the treatment of water contaminated with per- and poly-fluoroalkyl substances (PFAS). Various studies have demonstrated that the extent of PFAS degradation is influenced by the composition of samples and electrochemical conditions. This study evaluated the significance of several factors, such as the current density, initial concentration of PFAS, concentration of electrolyte, treatment time, and their interactions on the degradation of PFAS. A 24 factorial design was applied to determine the effects of the investigated factors on the degradation of perfluorooctanoic acid (PFOA) and generation of fluoride in spiked water. The best-performing conditions were then applied to the degradation of PFAS in wastewater samples. The results revealed that current density and time were the most important factors for PFOA degradation. In contrast, a high initial concentration of electrolyte had no significant impact on the degradation of PFOA, whereas it decreased the generation of F−. The experimental design model indicated that the treatment of spiked water under a current density higher than 14 mA cm−2 for 3–4 h could degrade PFOA with an efficiency of up to 100% and generate an F− fraction of approximately 40–50%. The observed high PFOA degradation and a low concentration of PFAS degradation products indicated that the mineralization of PFOA was effective. Under the obtained best conditions, the degradation of PFOA in wastewater samples was 44–70%. The degradation efficiency for other PFAS in these samples was 65–80% for perfluorooctane sulfonic acid (PFOS) and 42–52% for 6–2 fluorotelomer sulfonate (6-2 FTSA). The presence of high total organic carbon (TOC) and chloride contents was found to be an important factor affecting the efficiency of PFAS electrochemical degradation in wastewater samples. The current study indicates that the tested method can effectively degrade PFAS in both water and wastewater and suggests that increasing the treatment time is needed to account for the presence of other oxidizable matrices.

Mineralization of perfluorooctanoic acid by combined aerated electrocoagulation and Modified peroxi-coagulation methods

Perfluorooctanoic acid (PFOA) is a chemical used for both commercial and industrial applications. It has turned out to be worldwide anxiety owing to its extensive existence in the water bodies and subsequent harmful ecological effects. This study illustrates the significance of hybrid aerated electrocoagulation (EC) and modified peroxi-coagulation (PC) for the PFOA degradation in an aqueous solution. Consumable iron plate electrodes were employed as an electrode pair in both EC and modified PC processes. The laboratory tests were conducted in a batch reactor with a functioning capacity of 1 L. Aeration improved the EC process performance considerably. Higher than 56% PFOA and 38% defluorination occurred after 60 min of electrolysis with EC being operated at a pH of 3.6 and applied a current density of 78.34 Am−2. The performance of the modified PC process was considerably higher than that of the aerated EC process. More than 90% PFOA, 87%total organic carbon (TOC), and 71% deflorination were attained with modified PC process after 60 min of electrolysis operated at 78.34 Am−2 and initial pH of 3.6 when 50 mM hydrogen peroxide (H2O2) was added. The superior performance of the modified PC than aerated EC is mostly owing to the attack of in-site produced OH• radicals. PFOA decayed stepwise into small‒chain perfluoro carboxylic acids (PFCAs) and fluoride ions during modified PC oxidation.

Enhanced thermal activation of peroxymonosulfate by activated carbon for efficient removal of perfluorooctanoic acid

The chemical degradation performance of perfluorooctanoic acid (PFOA), one of the environmentally persistent contaminants, by fresh activated carbon (FAC) and nitrogen-doped activated carbon (NAC) which were used as heterogeneous catalysts in the presence of thermal activating peroxymonosulfate (PMS) were investigated and compared. In this study, the physicochemical properties of FAC and NAC are characterized by scanning electron microscope, Raman spectra, Fourier transform infrared spectra, X-ray photoelectron spectroscopy, and Brunauer Emmett Teller. Furthermore, the dosing amount of catalyst, the concentration of oxidant and the effect of catalytic oxidation are investigated. During the catalytic oxidation process, the concentrations of PFOA and its degradation products are determined by high-performance liquid chromatography combined with tandem mass spectrometry (HPLC-MS/MS). The mineralization efficiency of PFOA employing FAC and NAC coupled with thermal activation of PMS are evaluated via a combination approach of total organic carbon (TOC) and ion chromatography (IC). The results indicate that PFOA can be readily degraded at 60 °C with an optimum concentration of PMS and an appropriate dosage of FAC/NAC. During the degradation process FAC and NAC exhibit superior adsorption and catalytic performance as more acidic oxygen functional groups are obtained from surface modification, which can facilitate the decomposition of PMS and the mineralization of PFOA. Electron paramagnetic resonance detection confirms that both OH and SO4− exist during oxidation. Based on the identified products, a reaction pathway including adsorption, hydroxylation, and catalytic oxidation is proposed. The methods could not only be applied in a wide pH range to effectively remove PFOA, FAC/PMS and NAC/PMS could also be reused, which provide a feasible and cost-effective method for the degradation of PFOA in situ actual ground water remediation.

Electrochemical mineralization mechanisms of perfluorooctanoic acid in water assisted by low frequency ultrasound

The mineralization of perfluorooctanoic acid (PFOA) was investigated in electrochemical oxidation process (EC) with the assistance of low frequency ultrasound (US). The electrochemical degradation of PFOA was enhanced under the synergic effects of Ti/SnO2–Sb/Ce–PbO2 anode and US (20 kHz and 52 W). The influences of PFOA initial concentrations on its degradation were studied in EC and US-EC systems, while the effects of applied current densities were investigated in US-EC system. With the assistance of US, the increases of pseudo-first-order kinetic rate constant from 0.017 to 0.031 min−1, defluorination efficiency from 75.9% to 87.9%, mineralization efficiency from 71.9% to 86.1% and mineralization current efficiency from 0.66% to 0.77% were obtained at current density of 15 mA cm−2 and PFOA initial concentration of 60 mg L−1 during the reaction time of 180 min. The production and quenching of •OH were tested to emphasize the function of US in electrochemical mineralization of PFOA. In US-EC system, the electrochemical degradation performance of PFOA was enhanced not because of cavitation under US, but possibly because of the collapse of bubbles, anode surface cleaning, fast electron transfer on anode and higher •OH production under the assistance of US.

Rapid photochemical decomposition of perfluorooctanoic acid mediated by a comprehensive effect of nitrogen dioxide radicals and Fe3+/Fe2+ redox cycle

Developing efficient methods to degrade perfluorochemicals (PFCs), an emerging class of highly recalcitrant contaminants, are urgently needed in recent years, due to their persistence, high toxicity, and resistance to most regular treatment procedures. Here, a UV-photolysis system is reported for efficient mineralization of perfluorooctanoic acid (PFOA) via irradiation of ferric nitrate aqueous solution, where in-situ generating •NO2 and the effective Fe3+/Fe2+ redox cycle synergistically play great roles on rapidly mediating the mineralization of PFOA. A fast PFOA removal kinetics with first-order kinetic constants of 2.262 h−1 is observed at initial PFOA concentration of 5 ppm (50 mL volume), reaching ∼ 92 % removal efficiency within only 0.5-h irradiation. Near-stoichiometric fluoride ions liberation and high total organic carbon (TOC) removal efficiency (∼100 %) further validated the capability for completely destructive removal of PFOA. A tentative pathway for PFOA destruction is proposed. This work, by UV photolysis of abundant existing iron/nitrate-based systems in natural environment, provides an economical, sustainable and highly efficient approach for complete mineralization of perfluorinated chemicals.

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

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.

Photocatalytic degradation and mineralization of perfluorooctanoic acid (PFOA) using a composite TiO2 −rGO catalyst

The inherent resistance of perfluoroalkyl substances (PFASs) to biological degradation makes necessary to develop advanced technologies for the abatement of this group of hazardous substances. The present work investigated the photocatalytic decomposition of perfluorooctanoic acid (PFOA) using a composite catalyst based on TiO2 and reduced graphene oxide (95% TiO2/5% rGO) that was synthesized using a facile hydrothermal method. The efficient photoactivity of the TiO2-rGO (0.1gL−1) composite was confirmed for PFOA (0.24mmolL−1) degradation that reached 93±7% after 12h of UV–vis irradiation using a medium pressure mercury lamp, a great improvement compared to the TiO2 photocatalysis (24±11% PFOA removal) and direct photolysis (58±9%). These findings indicate that rGO provided the suited properties of TiO2-rGO, possibly as a result of acting as electron acceptor and avoiding the high recombination electron/hole pairs. The release of fluoride and the formation of shorter-chain perfluorocarboxilyc acids, that were progressively eliminated in a good match with the analysed reduction of total organic carbon, is consistent with a step-by-step PFOA decomposition via photogenerated hydroxyl radicals. Finally, the apparent first order rate constants of the TiO2-rGO UV–vis PFOA decompositions, and the intermediate perfluorcarboxylic acids were found to increase as the length of the carbon chain was shorter.

Nitrogen dioxide radicals mediated mineralization of perfluorooctanoic acid in aqueous nitrate solution with UV irradiation

Effective decomposition of perfluorooctanoic acid (PFOA) has received increasing attention in recent years because of its global occurrence and resistance to most conventional treatment processes. In this study, the complete mineralization of PFOA was achieved by the UV-photolysis of nitrate aqueous solution (UV/Nitrate), where the in-situ generated nitrogen dioxide radicals (NO2) efficiently mediated the degradation of PFOA. In particular, when the twinborn hydroxyl radicals were scavenged, the production of more NO2 radicals realized the complete mineralization of PFOA. DFT calculations further confirm the feasibility of PFOA removal with NO2. Near-stoichiometric equivalents of fluoride released rather than the related intermediates were detected in solution after decomposition of PEOA, further demonstrating the complete degradation of PFOA. Possible PFOA degradation pathways were proposed on the basis of experimental results. This work offers an efficient strategy for the complete mineralization of perfluorinated chemicals, and also sheds light on the indispensable roles of nitrogen dioxide radicals for environmental pollutants removal.

Factors influencing aqueous perfluorooctanoic acid (PFOA) photodecomposition by VUV irradiation in the presence of ferric ions

In this study, four photochemical reaction parameters, including the reaction atmosphere, extra inorganic oxidant, inorganic anion and organic matter, were investigated in an aqueous environment to determine their effects on perfluorooctanoic acid (PFOA) photodecomposition. The photochemical defluorination of PFOA was conducted by vacuum ultraviolet light (VUV) using ferric ions as the catalyst. Both direct photolysis and photocatalysis were involved in the reaction. PFOA was completely decomposed by VUV irradiation with and without ferric ions within 72 or 144h, respectively. There was no significant evidence indicating that the type of atmosphere (oxygen, nitrogen, or air) had any effect on the decomposition results. However, OH radicals generated during the photolysis process profoundly affected the decomposition of PFOA. The introduction of persulfate inhibited the mineralization of PFOA in the VUV/Fe3+ system. Inorganic anions hindered the defluorination of PFOA in the following order: HCO3−>SO42−>NO3−∼Cl−>ClO4−. The adverse effects of organic matter, including volatile organic compounds and dissolved natural organic compounds, were also examined. This study is beneficial to the understanding of the photodecomposition of other similar perfluorinated compounds (PFCs).

Ultrasound-enhanced electrochemical mineralization of perfluorooctanoic acid in aqueous solutions: Assessed by response surface methodology

Aims: The sonoelectrochemical mineralization of the synthetic aqueous solution of the perfluorooctanoic acid (PFOA) on Ti/PbO 2 anode was investigated using the response surface methodology based on a central composite design (CCD). Materials and Methods: The CCD was performed using three different variables such as current density (CD) (mA/cm 2 ), pH, and supporting electrolyte (EL) concentration (mM). The total organic carbon (TOC) removal was determined as an indicator of PFOA mineralization. A Shimadzu TOC analyzer was used to measure the TOC of the samples. The Ti/PbO 2 electrode was prepared using the electrochemical deposition method. In order to enhance the electrochemical mineralization, ultrasonic (US) radiation was used. The US frequency was 20 kHz. Results: The optimum conditions for PFOA mineralization in synthetic solution were EL concentration of 94 mM, pH of 2, and CD of 83.64 mA/cm 2 , which resulted in complete TOC removal. The results indicated that the most effective factor for PFOA mineralization was CD. Besides, the TOC removal efficiency significantly increased with increasing CD. Conclusions: Under optimum conditions, the mineralization of PFOA was almost completed after 90 min of sonoelectrolysis. Therefore, sonoelectrolysis was found to be a more effective technique for mineralization of an environmentally persistent compound.

Sonoelectrochemical mineralization of perfluorooctanoic acid using Ti/PbO 2 anode assessed by response surface methodology.

BackgroundPerfluorocarboxylic acids (PFCAs) are emerging pollutant and classified as fully fluorinated hydrocarbons containing a carboxylic group. PFCAs show intensively resistance against chemical and biological degradation due to their strong C–F bond. The Sonoelectrochemical mineralization of the synthetic aqueous solution of the perfluorooctanoic acid (PFOA) on Ti/PbO2 anode was investigated using the response surface methodology based on a central composite design with three variables: current density, pH, and supporting electrolyte concentration.MethodsThe defluorination ratio of PFOA was determined as an indicator of PFOA mineralization. Fluoride ion concentration was measured with an ion chromatograph unit. The Ti/PbO2 electrode was prepared using the electrochemical deposition method. The ultrasonic frequency was 20 kHz.ResultsThe optimum conditions for PFOA mineralization in synthetic solution were electrolyte concentration, pH, and current density of 94 mM, 2, and 83.64 mA/cm2, respectively. The results indicated that the most effective factor for PFOA mineralization was current density. Furthermore, the PFOA defluorination efficiency significantly enhanced with increasing current density. Under optimum conditions, the maximum mineralization of PFOA was 95.48 % after 90 min of sonoelectrolysis.ConclusionsSonoelectrolysis was found to be a more effective technique for mineralization of an environmentally persistent compound.

Complete mineralization of perfluorooctanoic acid (PFOA) by γ-irradiation in aqueous solution.

Decomposition of perfluorooctanoic acid (C7F15COOH, PFOA) has been gaining increasing interests because it is a ubiquitous environmental contaminant and resistant to the most conventional treatment processes. In this work, the rapid and complete mineralization of PFOA and simultaneous defluorination were achieved by γ-ray irradiation with a 60Co source. The degradation rate of PFOA by γ-ray irradiation would be high, and a pseudo-first-order kinetic rate constant of 0.67 h−1 could be achieved in the N2 satured condition at pH 13.0. The experimental results and quantum chemical calculation confirmed that two radicals, i.e., hydroxyl radical (·OH) and aqueous electrons (eaq−), were responsible for the degradation of PFOA, while only either eaq− or ·OH might not be able to accomplish complete mineralization of PFOA. The synergistic effects of ·OH and eaq− involved in the cleavage of C-C and C-F bonds, and therefore complete mineralization of PFOA were achieved. The intermediate products were identified and the degradation pathway was also proposed. The results of this study may offer a useful, high-efficient approach for complete mineralizing fluorochemicals and other persistent pollutants.

Oxidative–reductive photodecomposition of perfluorooctanoic acid in water

This article aims to elucidate on usefulness of vacuum ultraviolet (VUV) for photoreductive degradation of perfluorooctanoic acid (PFOA), a representative perfluorinated compound (PFC), in water for the first time. Bench-scale tests were conducted on oxidative and reductive (with aquated electron: e aq − ) mineralization of PFOA using low-pressure UV (LPUV) lamps and potassium iodide. Unlike with 254 nm wavelength (UVC), the reductive mineralization with VUV was very inefficient compared to the corresponding oxidative mineralization. The inefficiency is attributed to low reactivity of e aq − with PFOA and its fluorinated products than that of 185 nm photons. Direct VUV photolysis of PFOA and its products in reductive reaction conditions was not apparent due to a very big difference in reactivity of 185 and 254 nm photons with iodide. The results demonstrated that highly energetic VUV photons are not suitable for photoreductive degradations of PFCs involving e aq − , but they can be best used for oxidative degradations. These findings should serve as an important reference on VUV usage to decompose refractory micropollutants.

Decomposition of perfluorocarboxylic acids (PFCAs) by heterogeneous photocatalysis in acidic aqueous medium

Decomposition of perfluorocarboxylic acids (PFCAs) is of prime importance since they are recognized as persistent organic pollutants and are widespread in the environment. PFCAs with longer carbon chain length are particularly of interest because of their noted recalcitrance, toxicity, and bioaccumulation. Here in this study, we demonstrate efficient decomposition of three important PFCAs such as perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA) and perfluorodecanoic acid (PFDA) by heterogeneous photocatalysis with TiO 2 as a photocatalyst in acidic aqueous solutions. The PFCAs were decomposed into shorter carbon chain length PFCAs and fluoride ions. Photoholes of excited TiO 2 generated upon UV-irradiation are found to be the oxidation sites for PFCAs. Therefore, creation and sustenance of these photoholes in the acidic aqueous medium has enhanced the decomposition of PFCAs. Heterogeneous photocatalytic treatment achieved more than 99% decomposition and 38% complete mineralization of PFOA in 7 h. The decomposition of other PFCAs was as high as 99% with a defluorination efficiency of 38% for PFDA and 54% for PFNA. The presence of perchloric acid was found to enhance the decomposition by facilitating the ionization of PFCAs. The oxygen present in the medium served both as an oxidant and an electron acceptor. The mechanistic details of PFCA decomposition and their corresponding mineralization are elaborated.