Effects of pH and coexisting chemicals on photolysis of perfluorooctane sulfonate using an excited xenon dimer lamp.

Vacuum ultraviolet (VUV) photolysis at the wavelength of 172 nm in a sulfate solution was introduced as a more efficient process for perfluorooctane sulfonate (PFOS) degradation than ultraviolet (UV) photolysis at 254 nm. The effects of pH and coexisting chemicals on VUV photolysis under the coexistence of 100 mM sulfate were investigated. VUV irradiation successfully degraded PFOS, and the degradation rate was 5.5 times higher than by UV photolysis. Direct VUV photolysis was inferred to mainly contribute to PFOS degradation. PFOS degradation by VUV irradiation was enhanced at pH less than 2 due to sulfate radicals generated via VUV photolysis of sulfate ions. Consequently, VUV photolysis was superior to UV photolysis for PFOS removal on both the removal rate and energy efficiency. However, the inorganic chemicals phosphoric acid and nitric acid strongly inhibited PFOS degradation, probably by masking PFOS from VUV rays by their VUV absorption. Accordingly, PFOS separation from inorganic materials such as phosphate and nitrate will be recommended for the application of VUV techniques for PFOS removal. In this research, organic solvent abstraction was inferred to be one of candidates for PFOS separation.

Impact of humic acid on the photoreductive degradation of perfluorooctane sulfonate (PFOS) by UV/Iodide process.

Iodide photolysis under UV illumination affords an effective method to produce hydrated electrons (eaq-) in aqueous solution. Therefore, UV/Iodide photolysis can be utilized for the reductive degradation of many recalcitrant pollutants. However, the effect of naturally occurring organic matter (NOM) such as humic and fulvic acids (HA/FA), which may impact the efficiency of UV/Iodide photoreduction, is poorly understood. In this study, the UV photoreductive degradation of perfluorooctane sulfonate (PFOS) in the presence of I- and HA is studied. PFOS undergoes a relatively slow direct photoreduction in pure water, a moderate level of degradation via UV/Iodide, but a rapid degradation via UV/Iodide/HA photolysis. After 1.5 h of photolysis, 86.0% of the initial [PFOS] was degraded in the presence of both I- and HA with a corresponding defluorination ratio of 55.6%, whereas only 51.7% of PFOS was degraded with a defluorination ratio of 4.4% via UV/Iodide illumination in the absence of HA. The relative enhancement in the presence of HA in the photodegradation of PFOS can be attributed to several factors: a) HA enhances the effective generation of eaq- due to the reduction of I2, HOI, IO3- and I3- back to I-; b) certain functional groups of HA (i.e., quinones) enhance the electron transfer efficiency as electron shuttles; c) a weakly-bonded association of I- and PFOS with HA increases the reaction probability; and d) absorption of UV photons by HA itself produces eaq-. The degradation and defluorination efficiency of PFOS by UV/Iodide/HA process is dependent on pH and HA concentration. As pH increases from 7.0 to 10.0, the enhancement effect of HA improves significantly. The optimal HA concentration for the degradation of 0.03 mM PFOS is 1.0 mg L-1.

Boiling significantly promotes photodegradation of perfluorooctane sulfonate.

The application of photochemical processes for perfluorooctane sulfonate (PFOS) degradation has been limited by a low treatment efficiency. This study reports a significant acceleration of PFOS photodegradation under boiling condition compared with the non-boiling control. The PFOS decomposition rate increased with the increasing boiling intensity, but declined at a higher hydronium level or under oxygenation. These results suggest that the boiling state of solution resulted in higher effective concentrations of reactants at the gas-liquid interface and enhanced the interfacial mass transfer, thereby accelerating the PFOS decomposition. This study broadens our knowledge of PFOS photodegradation process and may have implications for development of efficient photodegradation technologies.

Ferric ion mediated photodecomposition of aqueous perfluorooctane sulfonate (PFOS) under UV irradiation and its mechanism.

Perfluorooctane sulfonate (PFOS) recently has received much attention due to its global distribution, environmental persistence and bioaccumulation. The methods for PFOS decomposition are very limited due to its inertness. In this report we first found the photodecomposition of PFOS under UV was greatly accelerated by addition of ferric ions. In the presence of ferric ion (100 µM), PFOS (20 µM) decreased to below the detection limit within 48 h, with the rate constant of 1.67 d(-1), which was 50 times higher than that by direct photolysis (0.033 d(-1)). Besides fluoride and sulfate ions, C2-C8 perfluorocarboxylic acids (PFCAs) were identified as the main intermediates. It was found that addition of PFOS into the FeCl3 aqueous solution led to reduction of UV absorption, and the presence of ferric ion reduced the response of PFOS as analyzed by UPLC-MS/MS, which indicated that PFOS formed a complex with ferric ion. The ESR detection indicated that the electronic state of Fe(3+)-PFOS complex changed during reaction. And the role of oxygen and hydroxyl radical on the defluorination of PFOS was investigated. Accordingly the mechanism for PFOS photodecomposition in the presence of ferric ion was proposed.

Solvent-free sonochemical preparation of alpha-aminophosphonates catalyzed by 1-hexanesulphonic acid sodium salt.

1-Hexanesulphonic acid sodium salt was found to be an efficient catalyst for the green synthesis of alpha-aminophosphonates by the coupling of aldehydes/ketone, an amine and triethyl phosphite under ultrasound irradiation at ambient temperature for appropriate time to furnish the desired product in good to excellent yield under solvent-free condition. This catalyst provides clean conversion; greater selectivity and easy workup make this protocol practical and economically attractive.

Photodegradation of perfluorooctane sulfonate by UV irradiation in water and alkaline 2-propanol.

Perfluorooctane sulfonate (PFOS) is the environmentally concerned compound because of its persistence and bioaccumulative properties. Since photodegradation of PFOS is not yet experimentally confirmed, photodegradation study of PFOS in water and alkaline 2-propanol solution was conducted. Aqueous and alkaline 2-propanol solution of PFOS (40 microM) was irradiated with a low-pressure mercury lamp (254 nm, 32 W) by internal irradiation for 10 d, and then PFOS, fluoride and sulfate ions, and the other degradation products were analyzed. Photodegradation of PFOS was confirmed in both media. PFOS was degraded by 8% after 1 day and by 68% after 10 days irradiation compared to the initial concentration in water. In alkaline 2-propanol, 76 and 92% of PFOS was degraded after 1 and 10 days irradiation, respectively. Photodegradation of PFOS in alkaline 2-propanol was much faster and effective than in water, as the photodegradation rate constants were 0.93 days(-1) in alkaline 2-propanol and 0.13 days(-1) in water, respectively. Formation of fluoride and sulfate was also confirmed by ion chromatography and X-ray diffraction analysis. From observation of the degradation products, two major degradation pathways of PFOS were considered: via C8HF17 and C8F17OH, respectively, resulting in short-chain fluorinated compounds such as C7HF15 and C7F15OH by stepwise removal of CF2. Formation of short-chain fluorocarbons such as CF4, C2F6, and C3F8 were also confirmed. This is the first study to confirm photodegradation of PFOS in water and alkaline 2-propanol.

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.

Kinetics of degradation by immobilized cells with ultrasonic irradiation.

Linear alkylbenzene sulphonate (LAS) decompositions by immobilized cells with ultrasonic irradiation were investigated at the optimized condition in order to gain insight into the kinetics of the decomposition process. Firstly, by analyzing the decomposition process of LAS theoretically, showed the kinetic model of suspending cells and immobilized cells both followed the MONOD model (namely micro=micromaxs/(ks+s) during wastewater treatment, then discussed the kinetics model of LAS degradation by immobilized cells with ultrasonic irradiation at the presupposition conditions, and then the two unknown parameters ([See text]) in the gained model were researched at the condition of laboratory. Moreover, experiments have been done to validate the parameters ([See text]) in the kinetics equation, the result shows the valid kinetics equation of LAS degradation is at the LAS concentration of 30-80 mg/L:

Photolytic treatment of aqueous linear alkylbenzene sulfonate.

Treatment of a model detergent compound, linear alkylbenzene sulfonate (LAS), using photolytic processes was studied. In the photolytic degradation of LAS, both ultraviolet (UV) light at 254 nm wavelength and its combination with hydrogen peroxide (H2O2) were investigated. Based on first-order rate constants, it was shown that 5000 mg/L of H2O2 for degradation of a 100-mg/L solution of linear alkylbenzene sulfonate was optimum. Addition of H2O2 at different illumination times with UV light at 254 nm did not improve first-order rate constants compared with the addition of H2O2 at the start of illumination. Degradation rates of the model compound (LAS) with three detergents were compared.