Electrochemical oxidation of 1H,1H,2H,2H-perfluorooctane sulfonic acid (6：2 FTS) on DSA electrode：Operating parameters and mechanism

The 6:2 FTS was the substitute for perfluorooctane sulfonate(PFOS) in the chrome plating industry in Japan. Electrochemical oxidation of 6:2 FTS was investigated in this study. The degradabilities of PFOS and 6:2 FTS were tested on the Ti/SnO2–Sb2O5–Bi2O3anode. The effects of current density,potential,and supporting electrolyte on the degradation of 6:2 FTS were evaluated. Experimental results showed that 6:2 FTS was more easily degraded than PFOS on the Ti/SnO2–Sb2O5–Bi2O3anode. At a low current density of 1.42 mA/cm2,6:2 FTS was not degraded on Ti/SnO2–Sb2O5–Bi2O3,while the degradation ratio increased when the current density ranged from 4.25 to 6.80 mA/cm2. The degradation of 6:2 FTS at current density of 6.80 mA/cm2 followed pseudo first-order kinetics with the rate constant of 0.074 hr-1. The anodic potential played an important role in the degradation of 6:2 FTS,and the pseudo first-order rate constants increased with the potential. The surface of Ti/SnO2–Sb2O5–Bi2O3was contaminated after electrolysis at constant potential of 3 V,while the fouling phenomenon was not observed at 5 V. The fouled anode could be regenerated by incinerating at 600°C. The intermediates detected by ultra-performance liquid chromatography coupled with a triple-stage quadrupole mass spectrometer(UPLC–MS/MS) were shorter chain perfluorocarboxylic acids. The 6:2 FTS was first attacked by hydroxyl radical,and then formed perfluorinated carboxylates,which decarboxylated and removed CF2 units to yield shorter-chain perfluorocarboxylic acids.     

An assessment of the toxicity of pyridinium chlorides and their biodegradation intermediates

Toxicity investigations were conducted for four pyridinium chlorides belonging to cationic surface-active substances (CSAS), which differed from each other in the numbers of methyl groups (CH(3)) in pyridinium ring.The crustacean Daphnia magna, the fish Lebistes reticulatus and the alga Scenedesmus quadricauda were chosen as biotests. Toxicity of examined preparations appeared to be very high but did not depend on their chemical structure. S. quadricauda was the most sensitive organism. Toxicity of intermediate products obtained in biological oxidation process was also examined. Biodegradation was conducted according to the "river water test". It was found that only partial degradation took place while pyridinium chlorides constituted main energy and carbon source. Presence of biodegradation intermediate products was shown on the basis of 1H NMR analysis. Intermediates were not toxic to any biotests.     

Evaluation of the efficiency of monopolar and bipolar BDD electrodes for electrochemical oxidation of anthraquinone textile synthetic effluent for reuse

The efficiency of the electrochemical degradation of synthetic wastewater containing an anthraquinone dye has been comparatively studied in two electrolytic cells with a synthetic boron-doped diamond (Si/BDD) as an anode. The first is an individual cell (Cell 1) with monopolar electrode BDD and the second (Cell 2) has two bipolar electrodes BDD self-polarized. The bulk electrolysis was performed at the same initial operating conditions in order to quantify the influence of the initial pH and current density on dye discoloration and global mineralization removal. The current efficiency and the consumption energy were also evaluated. When the same solutions have been comparatively treated with the two cells, a quite good mineralization is found in Cell 2. This result supposed more fraction of the applied current is used for the electrocombustion reaction on Cell 2 if compared to Cell 1 and small amount rest for the side reaction of oxygen evolution. The HPLC analyses confirmed this hypothesis and showed that the concentration trend of intermediates (sulfanilic acid, phthalate acid and salicylic acid) with electrolysis time was different on two cells. Phototoxicity tests show that the electrochemical oxidation with BDD electrodes could be useful as a pretreatment technique for reducing hazardous wastewater toxicity.     

Capability of novel ZnFe₂O₄ nanotube arrays for visible-light induced degradation of 4-chlorophenol

Highly ordered ZnFe₂O₄ nanotube arrays were successfully prepared by anodic aluminum oxide templates from sol-gel solution. The results from environmental scanning electron microscopy and X-ray photoemission spectroscopy indicated that the as-prepared samples were vertically aligned spinel ZnFe₂O₄ nanotube arrays, and the nanotubes were uniform along the axial direction with an average diameter of approximately 200 nm. The absorption edge of ZnFe₂O₄ nanotube arrays shifted to a higher energy in the UV-Vis absorption spectrum compared with that of ZnFe₂O₄ nanoparticles film. The synthesized ZnFe₂O₄ nanotube arrays exhibited excellent photocatalytic capability for degradation of 4-chlorophenol under visible-light irradiation. The main intermediate degradation species of 4-chlorophenol identified by liquid chromatography-mass technique were benzoquinone, hydroquinone, hydroxybenzoquinone and 2-peroxy-o-dihydroxybenzene. The degradation pathways of 4-chlorophenol under visible-light irradiation was derived and discussed by interpreting the observations of the intermediate species in the photocatalytic reactions.     

Heterogeneous photocatalytic decomposition of benzene on lanthanum-doped TiO2 film at ambient temperature

Lanthanum-doped anatase TiO₂ thin films on glass prepared via a sol–gel process have been shown to have much higher photocatalytic activity for the degradation of gaseous benzene than pure anatase TiO₂ thin film. The photodecomposition of benzene on both types of TiO₂ films follows the first-order kinetics while the CO₂ and CO formation followed the zero-order kinetics. GC/MS identification of the intermediates produced during the photodegradation of benzene revealed that doping lanthanum into TiO₂ thin film favors a cleavage of benzene ring. An optimal lanthanum amount with respect to photocatalytic activity was about 2.5 wt% (La₂O₃/TiO₂).     

氯苯及其电催化降解中间产物的高效液相色谱测定

建立了高效液相色谱测定氯苯及其电催化降解中间产物对氯苯酚、对苯二酚、邻苯二酚、苯酚、反丁烯二酸的方法,优化了色谱条件.采用外标法定量,方法线性关系良好,RSD在0.3%～1.7%之间,加标回收率在90.5%～104%之间,适用于氯苯电催化降解过程的追踪测定.     

Photodegradation of hydroxyfluorenes in ice and water: A comparison of kinetics,effects of water constituents,and phototransformation by-products

The photochemical behavior of organic pollutants in ice is poorly studied in comparison to aqueous photochemistry.Here we report a detailed comparison of ice and aqueous photodegradation of two representative OH-PAHs,2-hydroxyfluorene (2-OHFL) and 9-hydroxyfluorene (9-OHFL),which are newly recognized contaminants in the wider environment including colder regions.Interestingly,their photodegradation kinetics were clearly influenced by whether they reside in ice or water.Under the same simulated s...