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A laccase from Oudemansiella canarii was immobilized using the crosslinked enzyme aggregate (CLEA) methodology and applied in the degradation of the anthraquinonic dye Remazol Brilliant Blue R (RBBR). The immobilized laccase was superior to the free laccase in both thermal and storage stabilities. Both immobilized and free laccase decolourized 100 mg/L RBBR within 24 h at 30 °C and pH 5.0, but the former was still efficient in degrading the dye after at least 6 cycles. The relationship between the decolorization rate and the RBBR concentration obeyed Michaelis–Menten kinetics, with KM of 0.126 ± 0.044 mmol/L and Vmax of 1.412 ± 0.295 µmol/min for free laccase and KM of 0.159 ± 0.050 mmol/L and Vmax of 1.214 ± 0.242 µmol/min for immobilized laccase. Fourier transform infra-red spectroscopy (FTIR) and mass spectrometry allowed to conclude that the O. canarii laccase acts not only on the chromophore group of the dye, but that it also cleaves other covalent bonds, causing an effective fragmentation of the molecule. The Microtox assay detected a significant diminution in toxicity, a finding corroborated by the phytotoxicity test performed with lettuce seeds. Our results indicate that the immobilized laccase from O. canarii could be useful in biological strategies aiming at degrading unwanted dyes in the environment. [ABSTRACT FROM AUTHOR]

The impact of cerium (Ce) and neodymium (Nd) rare-earth metal doping of TiO2 prepared by the hydrothermal method was investigated to tailor effective photocatalytic degradation of coloured wastewater under UV or visible illumination. The hydrothermal treatment of TiO2 decreased the pHpzc from 6.3 to 3.1–3.8 favouring the affinity for cationic water contaminants. Doping with Ce and Nd modified the crystallinity and the morphology of the photocatalysts and significantly increased the BET surface area and the adsorption capacity of cationic dyes. The photocatalytic activity under UV light irradiation decreased due to shielding of the catalyst active area by excessive amount of dye adsorbed. Conversely, the photocatalytic activity of the Ce and Nd doped TiO2 increased under visible light irradiation by 1.2 times as a result of the dye photosensitization effect. It was demonstrated that two-steps dark adsorption and photocatalytic reaction or one-step simultaneous adsorption and reaction can produce significantly different results for the photocatalytic degradation of dyes in coloured waters, the rate being controlled by the competitive adsorption of the reacting organics and the H2O/OH− species. The reaction is driven by the radical oxygen species (ROS) formed on the catalyst surface the nature of which, differs under UV or visible light irradiation. The Ce-doped TiO2 and Nd-doped TiO2 photocatalysts with 0.5% rare-earth content were found to be efficient in the degradation of MB in aqueous solution, removing the colour and reducing the toxicity of wastewaters. [ABSTRACT FROM AUTHOR]

In this study, treatment for the removal of 1,4-dioxane by ozone and by catalytic ozonation using CuO as the catalyst was investigated. While the removal of 1,4-dioxane was small (20%) and mineralization negligible after 6 h of ozonation treatment, the removals of 1,4-dioxane and total organic carbon increased by factors of 10.35 and 81.25, respectively, after catalytic ozonation in the presence of CuO. The mineralization during catalytic ozonation was favoured at pH 10 (94.91 min−1), although it proceeded even at pH 3 (54.41 min−1). The CuO catalyst decreased the equilibrium concentration of soluble ozone and favoured its decomposition to reactive oxidative species. Radical scavenging experiments demonstrated that superoxide radicals were the main species responsible for the degradation of 1,4-dioxane. Further scavenging experiments with phosphate confirmed the presence of Lewis active sites on the surface of CuO, which were responsible for the adsorption and decomposition of ozone. The reaction mechanism proceeded through the formation of ethylene glycol diformate, which quickly hydrolyzed to ethylene glycol and formic acid as intermediate products. The stability of CuO indicated weak copper leaching and high catalytic activity for five recycling cycles. The toxicity of the water, assessed by Vibrio fischeri bioluminescence assays, remained the same (low toxicity) after catalytic ozonation while it increased after treatment with ozonation alone. [ABSTRACT FROM AUTHOR]

Iron oxide with a high degree of purity was recovered from waste and used as an environmentally friendly, low-cost catalyst in the application of the photo-Fenton process to simulated petrochemical wastewater (SPW). Iron oxide nanoparticles were characterized by X-ray powder diffraction, transmission electron microscopy, N2 adsorption/desorption isotherms, zeta potential, toxicity and atomic absorption spectrometry. The experiments were performed in a batch photochemical reactor, at 20 ± 2.0°C and pH 3.0. The SPW was efficiently mineralized and oxidized using a low catalyst dosage. The results showed that the organic compounds present in the wastewater were not adsorbed onto the solid surface. The solid was found to be stable with negligible leaching and low toxicity. The kTOC/kCOD ratios were calculated and varied according to the process: for a homogeneous reaction, the ratio obtained was 0.31 and for the heterogenous photo-Fenton process, it was closer to 1. The chemical oxygen demand and total organic carbon removal values were very close, indicating that the SPW is immediately mineralized, without producing partially oxidized compounds. The residue-based goethite studied represents a good alternative to commercially available catalysts in terms of sources and availability. [ABSTRACT FROM AUTHOR]

The impact of cerium (Ce) and neodymium (Nd) rare-earth metal doping of TiO 2 prepared by the hydrothermal method was investigated to tailor effective photocatalytic degradation of coloured wastewater under UV or visible illumination. The hydrothermal treatment of TiO 2 decreased the pH pzc from 6.3 to 3.1-3.8 favouring the affinity for cationic water contaminants. Doping with Ce and Nd modified the crystallinity and the morphology of the photocatalysts and significantly increased the BET surface area and the adsorption capacity of cationic dyes. The photocatalytic activity under UV light irradiation decreased due to shielding of the catalyst active area by excessive amount of dye adsorbed. Conversely, the photocatalytic activity of the Ce and Nd doped TiO 2 increased under visible light irradiation by 1.2 times as a result of the dye photosensitization effect. It was demonstrated that two-steps dark adsorption and photocatalytic reaction or one-step simultaneous adsorption and reaction can produce significantly different results for the photocatalytic degradation of dyes in coloured waters, the rate being controlled by the competitive adsorption of the reacting organics and the H 2 O/OH - species. The reaction is driven by the radical oxygen species (ROS) formed on the catalyst surface the nature of which, differs under UV or visible light irradiation. The Ce-doped TiO 2 and Nd-doped TiO 2 photocatalysts with 0.5% rare-earth content were found to be efficient in the degradation of MB in aqueous solution, removing the colour and reducing the toxicity of wastewaters.

The self-cleaning and super hydrophilic properties of pristine TiO 2 and of TiO 2 doped with Er 3+ or Y 3+ transparent thin films deposited onto glass substrates were investigated. The thin films prepared by multiple dipping and drying cycles of the glass substrate into the pristine TiO 2 sol and Er 3+ or Y 3+ -doped TiO 2 sol were characterized by X-ray diffraction, UV-vis spectrophotometry, and atomic force microscopy (AFM). The self-cleaning photocatalytic activity of the thin films towards the removal of oleic acid deposited on the surface under UVA irradiation was evaluated. A remarkable enhancement was observed in the hydrophilic nature of the TiO 2 thin films under irradiation. The optical properties and wettability of TiO 2 were not affected by Er 3+ or Y 3+ doping. However, the photocatalytic degradation of oleic acid under UVA irradiation improved up to 1.83 or 1.95 fold as the Er 3+ or Y 3+ content increased, respectively, due to the enhanced separation of the photogenerated carriers and reduced crystallite size. AFM analysis showed that the surface roughness increased by increasing the Er 3+ or Y 3+ content due to the formation of large aggregates. This in turn contributes to the increase of the active surface area enhancing the photodegradation process. This study demonstrates that TiO 2 doped with low amounts of Er 3+ or Y 3+ down to 0.5 mol% can produce transparent, super-hydrophilic, thin film surfaces with remarkable self-cleaning properties., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)