Study of hybrid membrane filtration and photocatalysis for removal of perfluorooctanoic acid (PFOA) in groundwater.

Groundwater contamination in Thailand from leaking of leachate due to improper solid waste disposal can cause contamination by PFOA (one of the perfluorinated compounds). This study proposed a new idea for the removal of PFOA from groundwater using a combination of membrane filtration and photocatalysis. Spiked groundwater samples were treated by nanofiltration and the rejected part was sent to a UV contact tank for photocatalysis. All samples were analyzed by high-performance liquid chromatography-tandem mass spectrometer (HPLC-MS/MS). The results showed that the removal efficiency of nanofiltration was 99.62%, and the rejected part was degraded by photocatalysis at an efficiency of 59.64%. Thus, the contaminants released to the environment were only 34.23%, which is around three times lower than nanofiltration alone. The results of this technical feasibility study proved that hybrid membrane filtration and photocatalysis are able to remove and degrade the contaminants in the rejected part significantly before being released to the environment, which has been the biggest gap in the processing of membrane filtration, and should be studied further in other aspects, such as fouling effects, energy consumption, and operating costs in a long-term pilot run.

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.

Removal of PFOA in groundwater by Fe0 and MnO2 nanoparticles under visible light.

The main objective of this study was to find a cost-effective, efficient and environmentally-friendly solution to remove perfluorooctanic acid (PFOA) from groundwater by using Fe0 and MnO2 nanoparticles. The selected method was expected to be applicable to the remediation of PFOA-contaminated groundwater. Phytotoxicity of the nanoparticle treatment was studied to demonstrate the safe application of the nanomaterials. Zero-valent Fe (100 mg L-1) and MnO2 (100 mg L-1) nanoparticles, produced in our lab, were used to remove PFOA up to 10 mg L-1. The test was conducted under visible light with or without addition of 0.88 mol L-1 H2O2 in a pH range of 0.5-11.0 for a duration of 18 h. Using Fe nanoparticles, a higher percentage of PFOA was removed under extreme acidic environment of pH 0.5 than under the basic environment of pH 11.0, and a minimum removal rate was reached under the neutral environment. The Fe nanoparticles were more efficient than the MnO2 nanoparticles at pH 0.5 with a removal rate of 69.7% and 89.7% without and with H2O2 addition, respectively. Phytotoxicity study showed that the treatment by Fe nanoparticles under mild pH reduced the phytotoxicity of groundwater-associated PFOA to Arabidopsis thaliana. The Fe nanoparticles did not show negative effect to A. thaliana under the experimental conditions used in this study.

Photochemical defluorination of aqueous perfluorooctanoic acid (PFOA) by Fe(0)/GAC micro-electrolysis and VUV-Fenton photolysis.

Perfluorooctanoic acid (PFOA) is extremely persistent and bioaccumulative in the environment; thus, it is very urgent to investigate an effective and moderate technology to treat the pollution of PFOA. In this study, a process combined iron and granular activated carbon (Fe(0)/GAC) micro-electrolysis with VUV-Fenton system is employed for the remediation of PFOA. Approximately 50 % PFOA (10 mg L(-1)) could be efficiently defluorinated under the following conditions: pH 3.0, dosage of Fe 7.5 g L(-1), dosage of GAC 12.5 g L(-1), and concentration of H2O2 22.8 mmol L(-1). Meanwhile, during the process, evident defluorination was observed and the concentration of fluoride ion was eventually 3.23 mg L(-1). The intermediates including five shorter-chain perfluorinated carboxylic acids (PFCAs), i.e., C7, C6, C5, C4, and C3, were also analyzed by high-performance liquid chromatography tandem mass spectrometry (HPLC/MS/MS) and defluorination mechanisms of PFOA was proposed, which involved photochemical of OH·, direct photolysis (185-nm VUV), and photocatalytic degradation of PFOA in the presence of Fe(3+) (254-nm UV).

Perfluorooctanoic Acid Degradation Using UV-Persulfate Process: Modeling of the Degradation and Chlorate Formation.

In this study, we investigated the destruction and by-product formation of perfluorooctanoic acid (PFOA) using ultraviolet light and persulfate (UV-PS). Additionally, we developed a first-principles kinetic model to simulate both PFOA destruction and by-product and chlorate (ClO3(-)) formation in ultrapure water (UW), surface water (SW), and wastewater (WW). PFOA degradation was significantly suppressed in the presence of chloride and carbonate species and did not occur until all the chloride was converted to ClO3(-) in UW and for low DOC concentrations in SW. The model was able to simulate the PS decay, pH changes, radical concentrations, and ClO3(-) formation for UW and SW. However, our model was unable to simulate PFOA degradation well in WW, possibly from PS activation by NOM, which in turn produced sulfate radicals.

[Photocatalytic degradation kinetics of perfluorooctanoic acid (PFOA) in TiO2 dispersion and its mechanism].

Decomposition of perfluorooctanoic acid (PFOA) is of prime importance since it is recognized as a persistent organic pollutant and is widespread in the environment. Heterogeneous photocatalytic decomposition of PFOA by TiO2 (P25) was investigated under 254 nm UV light. Experimental conditions including initial pH, TiO2 content and PFOA concentration, were varied to demonstrate their effects on the decomposition of PFOA. It was observed that the photocatalytic degradation kinetics of PFOA could be fitted to the quasi-first-order equation. The pH played a determinant role in the decomposition of PFOA and the presence of O2 increased the degradation rate. Optimal conditions for a complete removal were obtained using 1.5 g x L(-1) TiO2 at pH 3 in air atmosphere, with a rate constant of 0.420 6 h(-1). The contribution experiments of various reactive species produced during the photocatalysis were also investigated with the addition of different scavengers and it was found that photogenerated holes (h+) was the major reactive species which was responsible for 66.1% of the degradation rate, and the *OH was involved in PFOA degradation as well. In addition, the photocatalytic experiment with the addition of NaF indicated that the adsorption of PFOA was of primary importance for the photocatalytic decomposition. Perfluorocarboxylic acids (PFCAs) with shorter carbon chain length as intermediates and products were identified with UPLC-QTOF/MS, and a possible mechanism for PFOA decomposition was proposed.

Photochemical decomposition of perfluorooctanoic acid mediated by iron in strongly acidic conditions.

The performance of a ferric ion mediated photochemical process for perfluorooctanoic acid (PFOA) decomposition in strongly acidic conditions of pH 2.0 was evaluated in comparison with those in weakly acidic conditions, pH 3.7 or pH 5.0, based on iron species composition and ferric ion regeneration. Complete decomposition of PFOA under UV irradiation was confirmed at pH 2.0, whereas perfluoroheptanoic acid (PFHpA) and other intermediates were accumulated in weakly acidic conditions. Iron states at each pH were evaluated using a chemical equilibrium model, Visual MINTEQ. The main iron species at pH 2.0 is Fe(3+) ion. Although Fe(3+) ion is consumed and is transformed to Fe(2+) ion by photochemical decomposition of PFOA and its intermediates, the produced Fe(2+) ion will change to Fe(3+) ion to restore chemical equilibrium. Continuous decomposition will occur at pH 2.0. However, half of the iron cannot be dissolved at pH 3.7. The main species of dissolved iron is Fe(OH)(2+). At pH 3.7 or higher pH, Fe(3+) ion will only be produced from the oxidation of Fe(2+) ion by hydroxyl radical produced by Fe(OH)(2+) under UV irradiation. These different mechanisms of Fe(3+) regeneration that prevail in strongly and weakly acidic conditions will engender different performances of the ferric ion.

Perfluorooctanoic acid degradation in the presence of Fe(III) under natural sunlight.

Due to the high bond dissociation energy (BDE) of CF bonds (116 kcal/mol), perfluorooctanoic acid (PFOA) is a highly recalcitrant pollutant. Herein, we demonstrate a novel method to decompose PFOA in the presence of sunlight and ferric iron (Fe(III)). Under such conditions, 97.8 ± 1.7% of 50 µM PFOA decomposed within 28 days into shorter-chain intermediates and fluoride (F(-)), with an overall defluorination extent of 12.7 ± 0.5%. No PFOA was removed under visible light, indicating that UV radiation is required for PFOA decomposition. Spectroscopic analysis indicates that the decomposition reaction is likely initiated by electron-transfer from PFOA to Fe(III), forming Fe(II) and an unstable organic carboxyl radical. An alternative mechanism for the formation of this organic radical involves hydroxyl radicals, detected by electron paramagnetic resonance (EPR). The observation that PFOA can be degraded by Fe(III) under solar irradiation provides mechanistic insight into a possibly overlooked natural attenuation process. Because Fe(III) is abundant in natural waters and sunlight is essentially free, this work represents a potentially important step toward the development of simple and inexpensive remediation strategies for PFOA-contaminated water.

Photocatalytic degradation of perfluorooctanoic acid with beta-Ga2O3 in anoxic aqueous solution.

Perfluorooctanoic acid (PFOA) is a new-found hazardous persistent organic pollutant, and it is resistant to decomposition by hydroxyl radical (HO*) due to its stable chemical structure and the high electronegativity of fluorine. Photocatalytic reduction of PFOA with beta-Ga2O3 in anoxic aqueous solution was investigated for the first time, and the results showed that the photoinduced electron (e(cb-)) coming from the beta-Ga2O3 conduction band was the major degradation substance for PFOA, and shorter-chain perfluorinated carboxylic acids (PFCAs, CnF2n+i1COOH, 1 < or = n < or = 6) were the dominant products. Furthermore, the concentration of F- was measured by the IC technique and defluorination efficiency was calculated. After 3 hr, the photocatalytic degradation efficiency was 98.8% and defluorination efficiency was 31.6% in the presence of thiosulfate and bubbling N2. The degradation reaction followed first-order kinetics (k = 0.0239 min(-1), t1/2 = 0.48 hr). PFCAs (CnF2n+1COOH, 1 < or = n < or = 7) were detected and measured by LC-MS and LC-MS/MS methods. It was deduced that the probable photocatalytic degradation mechanism involves e(cb-) attacking the carboxyl of CnF2n+1COOH, resulting in decarboxylation and the generation of CnF2n+1*. The produced CnF2n+1* reacted with H2O, forming CnF2n+1OH, then CnF2n+1OH underwent HF loss and hydrolysis to form CnF2n+1COOH.

Efficient photocatalytic decomposition of perfluorooctanoic acid by indium oxide and its mechanism.

Perfluorooctanoic acid (C(7)F(15)COOH, PFOA) has increasingly attracted worldwide concerns due to its global occurrence and resistance to most conventional treatment processes. Though TiO(2)-based photocatalysis is strong enough to decompose most organics, it is not effective for PFOA decomposition. We first find that indium oxide (In(2)O(3)) possesses significant activity for PFOA decomposition under UV irradiation, with the rate constant about 8.4 times higher than that by TiO(2). The major intermediates of PFOA were C(2)-C(7) shorter-chain perfluorocarboxylic acids, implying that the reaction proceeded in a stepwise manner. By using diffuse reflectance infrared Fourier transform spectroscopy, (19)F magic angle spinning nuclear magnetic resonance, and electron spin resonance, we demonstrate that the terminal carboxylate group of PFOA molecule tightly coordinates to the In(2)O(3) surface in a bidentate or bridging configuration, which is beneficial for PFOA to be directly decomposed by photogenerated holes of In(2)O(3) under UV irradiation, while PFOA coordinates to TiO(2) in a monodentate mode, and photogenerated holes of TiO(2) preferentially transform to hydroxyl radicals, which are inert to react with PFOA. PFOA decomposition in wastewater was inhibited by bicarbonate and other organic matters; however, their adverse impacts can be mostly avoided via pH adjustment and ozone addition.

A novel liquid plasma AOP device integrating microwaves and ultrasounds and its evaluation in defluorinating perfluorooctanoic acid in aqueous media.

A simplified and energy-saving integrated device consisting of a microwave applicator and an ultrasonic homogenizer has been fabricated to generate liquid plasma in a medium possessing high dielectric factors, for example water. The microwave waveguide and the ultrasonic transducer were interconnected through a tungsten/titanium alloy stick acting both as the microwave antenna and as the horn of the ultrasonic homogenizer. Both microwaves and ultrasonic waves are simultaneously transmitted to the aqueous media through the tungsten tip of the antenna. The microwave discharge liquid plasma was easily generated in solution during ultrasonic cavitation. The simple device was evaluated by carrying out the degradation of the perfluorooctanoic acid (PFOA), a system highly recalcitrant to degradation by conventional advanced oxidation processes (AOPs). PFOA is 59% degraded in an aqueous medium after only 90 s of irradiation by the plasma. Intermediates were identified by electrospray mass spectral techniques in the negative ion mode.

UV photolysis of perfluorooctanoic acid (PFOA) in dilute aqueous solution.

Perfluorooctanoic acid (PFOA) is very persistent in the environment and widely detected in the water environment. Only some advanced methods with extreme reaction conditions are shown to be capable of degrading the compound efficiently, and almost all the earlier investigations used very high PFOA concentrations. The compound is detected normally at very low concentrations in the water environment, while mild reaction conditions for its degradation are preferable. This article aimed to elucidate photodegradation of PFOA in dilute aqueous solutions by combined UV wavelengths (185 nm+254 nm) and 254 nm using a newly designed UV jacket. PFOA degradation was greatly enhanced with the combined wavelengths with almost one hundred percent PFOA removals in four-hour reaction. The removals were well described by the first-order reaction kinetic. The removal efficiencies and rate values significantly decreased with smaller initial PFOA concentrations. But defluorination was greatly enhanced with smaller PFOA concentrations possibly due to accelerated decomposition of fluorinated intermediates of PFOA. Formic acid and acetic acid were two tentatively identified intermediates of PFOA photolysis while the former was a major intermediate predominantly controlling solution pH during the oxidation. The results demonstrated that PFOA photolysis by the combined wavelengths with mild reaction conditions can be greatly enhanced by proper design of UV jacket and reactor system.

Photochemical decomposition of perfluorooctanoic acid in aqueous periodate with VUV and UV light irradiation.

The photochemical decomposition of perfluorooctanoic acid (PFOA) in aqueous periodate (IO(4)(-)) was investigated under two types of low-pressure mercury lamps: one emits at 254nm light (UV light) and the other emits both 254 nm and 185 nm light (VUV light). PFOA decomposed efficiently under VUV light irradiation while it decomposed poorly under UV light irradiation. The addition of IO(4)(-) significantly increased the rate of decomposition and defluorination of PFOA irradiated with UV light whereas it decreased both processes under VUV irradiation. Reactive radical (IO(3)) generated by photolysis of IO(4)(-) initiated the oxidation of PFOA in UV process. Aquated electrons (e(aq)(-)), generated from water homolysis, scavenged IO(4)(-) resulting in decrease of reactive radical species production and PFOA decomposition. The shorter-chain perfluorocarboxylic acids (PFCAs) formed in a stepwise manner from long-chain PFCAs.

Photo-reductive defluorination of perfluorooctanoic acid in water.

Globally distributed and highly stable, perfluorooctanoic acid (PFOA) has prompted much concern regarding its accumulation in the natural environment and its threats to ecosystems. Therefore, it is desirable to develop an effective treatment against PFOA pollution. In this study, a photo-reduction method is developed and evaluated for the decomposition of perfluorooctanoic acid (PFOA) in aqueous phase with potassium iodide (KI) as a mediator. The experiment was conducted under 254 nm irradiation at room temperature and pH 9 under anaerobic conditions. Ultraviolet photolysis of iodide solutions led to the generation of hydrated electrons (e(aq)(-), E(aq/e) degrees = -2.9 V), which contributed to the defluorination of PFOA. Defluorination was confirmed by fluoride release of 98%, indicating almost complete defluorination of PFOA. Kinetic analysis indicated that the PFOA decomposition fit the first-order model with a rate constant of 7.3 x 10(-3) min(-1). Besides fluoride ions, additional intermediates identified and quantified include formic acid, acetic acid, and six short-chain perfluorocarboxylic acids (C1-C6). Furthermore, small amounts of CF(3)H and C(2)F(6) were also detected as reaction products by using GC/MS. With observation of the degradation products and verification via an isotopic labeling method, two major defluorination pathways of PFOA are proposed: direct cleavage of C-F bonds attacked by hydrated electrons as the nucleophile; and stepwise removal of CF(2) by UV irradiation and hydrolysis. This method was applied to the decomposition of PFOA in wastewater issued from a fluorochemical plant and proved to be effective.

Ferric ion mediated photochemical decomposition of perfluorooctanoic acid (PFOA) by 254nm UV light.

The great enhancement of ferric ion on the photochemical decomposition of environmentally persistent perfluorooctanoic acid (PFOA) under 254nm UV light was reported. In the presence of 10microM ferric ion, 47.3% of initial PFOA (48microM) was decomposed and the defluorination ratio reached 15.4% within 4h reaction time. While the degradation and defluorination ratio greatly increased to 80.2% and 47.8%, respectively, when ferric ion concentration increased to 80microM, and the corresponding half-life was shortened to 103min. Though the decomposition rate was significantly lowered under nitrogen atmosphere, PFOA was efficiently decomposed too. Other metal ions like Cu(2+) and Zn(2+) also slightly improved the photochemical decomposition of PFOA under irradiation of 254nm UV light. Besides fluoride ion, other intermediates during PFOA decomposition including formic acid and five shorter-chain perfluorinated carboxylic acids (PFCAs) with C7, C6, C5, C4 and C3, respectively, were identified and quantified by IC or LC/MS. The mixture of PFOA and ferric ion had strong absorption around 280nm. It is proposed that PFOA coordinates with ferric ion to form a complex, and its excitation by 254nm UV light leads to the decomposition of PFOA in a stepwise way.

Photodegradation of perfluorooctanoic acid by 185 nm vacuum ultraviolet light.

The photodegradation of persistent and bioaccumulative perfluorooctanoic acid (PFOA) in water by 185 nm vacuum ultraviolet (VUV) light was examined to develop an effective technology to deal with PFOA pollution. PFOA degraded very slowly under irradiation of 254 nm UV light. However, 61.7% of initial PFOA was degraded by 185 nm VUV light within 2 h, and defluorination ratio reached 17.1%. Pseudo first-order-kinetics well simulated its degradation and defluorination. Besides, fluoride ion formed in water, 4 shorter-chain perfluorinated carboxylic acids (PFCAs), that is, perfluoroheptanoic acid, perfluorohexanoic acid, perfluoropentanoic acid, and perfluorobutanoic acid. These were identified as intermediates by LC-MS measurement. These PFCAs consecutively formed and further degraded with irradiation time. According to the mass balance calculation, no other byproducts were formed. It was proposed that PFCAs initially are decarboxylated by 185 nm light, and the radical thus formed reacts with water to form shorter-chain PFCA with one less CF2 unit.

Light-induced degradation of perfluorocarboxylic acids in the presence of titanium dioxide.

The UV-photon-induced degradation of heptafluorobutanoic acid was investigated in acidic aqueous solutions in the presence of titanium dioxide. Heptafluorobutanoic acid could be degraded with this photocatalyst in a light-induced reaction generating carbon dioxide and fluoride anions. Carbon dioxide evolution in a significant amount occurred only in the presence of molecular oxygen and the photocatalyst. The light-induced degradation of trifluoroacetic acid, pentafluoropropanoic acid, nonafluorobutanoic acid, pentadecafluorooctanoic acid, nonafluorobutanesulfonic acid, and heptadecafluorooctanesulfonic acid in the presence of titanium dioxide was also studied. The perfluorocarboxylic acids under investigation are degraded to generate CO(2) and fluoride anions while both perfluorinated sulfonic acids are persistent under the experimental conditions employed in this study. For all compounds photonic efficiencies of the mineralization reaction were estimated to be smaller than 1x10(-5). To increase the photocatalytic activity mixed systems containing homogeneous phosphotungstic acid and heterogeneous titanium dioxide catalysts were also investigated. In the mixtures of these two photocatalysts, the formation rate of CO(2) increased with illumination time.

Photodegradation of perfluorooctanoic acid in water under irradiation of 254 nm and 185 nm light by use of persulfate.

The photodegradation of perfluorooctanoic acid (PFOA) in water using two types of low-pressure mercury lamps, one emitting 254 nm and the other emitting 254 nm and 185 nm, by use of persulfate (K2S2O8) as an oxidant was investigated. PFOA was significantly decomposed under irradiation of 185 nm light, while it was very slow and negligible under 254 nm light irradiation. This was due to its strong absorption of PFOA from deep UV-region to 220 nm and a weak absorption from 220-460 nm. The addition of K2S2O8 led to efficient PFOA decomposition and defluorination no matter what light irradiation. Sulfate radical anion (SO4-), generated by photolysis of K2S2O8, initiated the oxidation of PFOA. Under irradiation of 185 nm light, PFOA was jointly decomposed through 185 nm light photolysis and initiation of sulfate radical. However, under irradiation of 254 nm light, PFOA decomposition was only initiated by sulfate radical. PFOA decomposed and defluorinated much faster under oxygen atmosphere than under nitrogen atmosphere, which suggested that oxygen molecules played an important role in PFOA decomposition.