Heterogeneous photocatalytic removal of the herbicide clopyralid and its comparison with UV/H2O2 and ozone oxidation techniques

Clopyralid is a herbicide that has recently been reported to occur in drinking water at concentrations above the Permitted Concentration Value (PCV) of 0.1 μg/L for an individual pesticide (EU directive 98/83/EC). An extensive laboratory study on clopyralid removal with UV/TiO₂, was carried out and was compared to UV/H₂O₂ and O₃ removal efficiencies. The effectiveness of three TiO₂ photocatalysts (Degussa P25, VP Aeroperl, Hombifine N) was studied and Degussa P25 was selected since it outperformed the other two. Complete removal of clopyralid was achieved with UV/TiO₂ in about 90 min at an optimum catalyst concentration of 1 g/L. Pseudo-zero-order kinetics were suitable to describe the first stage of the photocatalytic reaction in the concentration range 0.078–0.521 mM. pH was found to significantly affect the removal rates of clopyralid due to changes in TiO₂ surface charges and clopyralid ionisation degree. The rate constant was maximum at pH 5 and its value was 2.1 × 10⁻⁶ ± 4.3 × 10⁻⁷ M min⁻¹. Pure oxygen bubbled in solution was found to slightly affect unfavourably the photocatalytic removal of clopyralid as compared to air. With UV/H₂O₂ and O₃ systems, the initial removal rates were high but these systems were not effective in achieving high removal percentages overall.     

Kinetic study of the manganese‐based catalytic hydrogen peroxide oxidation of a persistent azo‐dye

BACKGROUND: The discharge of synthetic dyes by the textile industry into the environment poses concerns due to their persistence and toxicity. New efficient treatment processes are required to effectively degrade these dyes. The aim of this work was to study the degradation of a persistent dye (Drimarene Brilliant Reactive Red K‐4BL, C.I.147) using H₂O₂ oxidation catalysed by an Mn(III)‐saltren catalyst and to develop a kinetic model for this system. RESULTS: Dye oxidation with H₂O₂ was significantly improved by the addition of the catalyst. As the pH was increased from 3 to 10, the oxidation rates increased significantly. The kinetic model developed in this study was found to adequately explain the experimental results. In particular, dye oxidation can be described at high pH by pseudo‐first‐order kinetics. A Michaelis–Menton type equation was developed from the model and was found to adequately describe the effect of H₂O₂ and catalyst concentrations on the apparent pseudo‐first‐order rate constant. Optimum catalyst and H₂O₂ concentrations of 500 mg L^?1 and 6.3 g L^?1, respectively, were found to give maximum reaction rates. CONCLUSION: Catalytic H₂O₂ oxidation was found to be effective for the removal of persistent dye and the results obtained in this work are of significance for design and scale‐up of a treatment process. Copyright © 2009 Society of Chemical Industry     

Effect of electro discharge machining (EDM) on the AISI316L SS white layer microstructure and corrosion resistance

The localised corrosion resistance of austenitic stainless steels is strongly influenced by the quality of finished surface. EDM machining induces substantial changes by the high thermal gradients generated by electric sparks. Experimental techniques such as roughness measurement, scanning electron microscopy (SEM), energy dispersive microanalysis (EDX) and X-ray diffraction technique, reveal micro-geometrical, microstructural, chemical and mechanical changes. These changes lead to white and heat-affected layers with a depth less than 100 μm. The white layer is a melted material characterised by dendritic structure and constituted by austenite, chromium carbide and ε-carbide. The heat-affected layer is characterised by very large grain size comparatively to the bulk material. Electrochemical test coupled with metallographic examinations using SEM reveals a weakening of the resistance to pitting and intergranular corrosion comparatively to diamond polished surface. This weakening is correlated to differences in structure and chemical composition of white layer. Susceptibility to stress corrosion cracking has been attributed to the field of tensile residual stresses resulting from thermal effects. The removal of the white layer material by polishing or wire brushing restores the corrosion resistance of the AISI316L SS.     

Interfacial behaviour from pull-out tests of steel and aluminium fibres in unsaturated polyester matrix

This study aims at implementing an interfacial model to capture the role of interfaces in polyester-based composites reinforced by metallic fibres. A pull-out test of single aluminium and steel fibres embedded in unsaturated polyester matrix is performed. Finite element computation is performed to simulate the typical response of the pull-out test based on an interfacial model. The implemented model relies on a nonlinear relationship assumed between the interfacial shear and interfacial separation. A sensitivity analysis is conducted to reveal the effect of each parameter of the interfacial model. The identification of these parameters with respect to the experimental conditions is also attempted. The predictions show a perfect matching with the experimental trends if a two-term expression is accounted for as an interfacial response. The model outcome reveals superior interfacial performance of the aluminium/unsaturated polyester composite.     

Water repellent treatment for cotton fabrics with long-chain fluoropolymer and its short-chain eco-friendly alternative

Abstract

As the long-chain fluorochemical molecules used to obtain water and stain repellent textiles persist in the environment, chemical suppliers are trying to develop new products in order to find ecological alternatives. The current most developed substituents are based on molecules with shorter fluorine-carbon chains. In the current work, a long-chain fluoropolymer and its short-chain homologue were applied on cotton fabrics at different finishing conditions. Textile properties such as wettability, air permeability, mechanical properties and handle properties, for untreated and treated cotton samples were investigated. Laundering test was also performed to predict the durability of the finishing. The obtained results demonstrated that cotton samples treated with short-chain fluoropolymer show good water repellency and good washing durability. The use of short-chain fluoropolymers, as nontoxic and eco-friendly finishing chemicals, has allowed obtaining comparable performances to those produced with long chain fluoropolymer.     

Solvent effects on phenolic contents and biological activities of the halophyte Limoniastrum monopetalum leaves

Limoniastrum monopetalum is a traditional medicinal species which leaf infusion exhibits antidysenteric properties against infectious diseases. In this study, ten kinds of leaf extracts were used to examine the effect of extraction solvent system with varying polarities on polyphenol contents and DPPH scavenging activity. Then the superoxide scavenging activity and the reducing power of the most promising solvent extracts were evaluated too. Moreover, the efficiency of the best leaf extract has been investigated against pathogenic bacteria and yeast. Eventually leaf extract was hydrolyzed by acid and the phenolics identified by RP-HPLC. Results showed that phenolic contents and antioxidant activities varied considerably as function of solvent polarity. Leaf extract using pure methanol showed the highest polyphenol content (15.85 mg GAE/g DW). Moreover, antiradical capacities against DPPH and superoxide, and reducing power were maxima in acetone/water (8:2) of leaf extract. However, the latter showed a slight antimicrobial activity against human pathogen strains such as Staphylococcus aureus, Micrococcus luteus and Candida holmii. The HPLC analysis revealed several phenolic compounds in L. monopetalum leaf including vanillic and gallic acids as major phenolics. Our findings identified the appropriate solvent for extracting halophyte phenolics which might provide a rich and novel source of natural antioxidants as food additives replacing synthetic ones in food industry.     

Effect of municipal solid waste compost and sewage sludge use on wheat (Triticum durum): growth,heavy metal accumulation,and antioxidant activity

BACKGROUND: Inappropriate utilisation of biosolids may adversely impact agrosystem productivity. Here, we address the response of wheat (Triticum durum) to different doses (0, 40, 100, 200 and 300 t ha^?1) of either municipal solid waste (MSW) compost or sewage sludge in a greenhouse pot experiment. Plant growth, heavy metal uptake, and antioxidant activity were considered. RESULTS: Biomass production of treated plants was significantly enhanced at 40 t ha^?1 and 100 t ha^?1 of MSW compost (+48% and +78% relative to the control, respectively). At the same doses of sewage sludge, the increase was only 18%. Higher doses of both biosolids restricted significantly the plant growth, in concomitance with the significant accumulation of heavy metals (Ni²⁺, Pb²⁺, Cu²⁺ and Zn²⁺), especially in leaves. Leaf activities of antioxidant enzymes (ascorbate peroxidase, glutathione reductase, catalase and superoxide dismutase) were unchanged at 40 t ha^?1 MSW compost or sewage sludge, but were significantly stimulated at higher doses (200–300 t ha^?1), together with higher leaf concentration of reduced glutathione. CONCLUSION: This preliminary study suggests that a MSW supply at moderate doses (100 t ha^?1) could be highly beneficial for wheat productivity. Copyright © 2010 Society of Chemical Industry     

Effects of abrasive type cooling mode and peripheral grinding wheel speed on the AISI D2 steel ground surface integrity

In this work the AISI D2 steel ground surface integrity was evaluated at different grinding conditions. Two sets of experiments were conducted. The first and the second sets are referred to as conventional grinding tests (CGTs) and high-speed grinding tests (HSGTs), respectively. For the CGTs two different types of abrasives (aluminium oxide and sol–gel alumina) and two cooling modes (oil-based grinding fluid and cryogenic cooling) were tested at a peripheral wheel speed v_s=22 m/s. For the HSGTs, an electroplated cBN grinding wheel was used at a peripheral wheel speed ranging from 60 to 260 m/s. Experimental results show that the grindability and the surface integrity of the AISI D2 steel could be substantially improved by using the sol–gel grinding wheel and cooling by liquid nitrogen comparatively with conditions using aluminium oxide and cooling with oil-based grinding fluid. These conditions reduce the grinding force components, lower the level of tensile residual stresses and expand the range of stock removals rate for which compressive residual stresses can be obtained. In this case the stock removal rate could be increased 7 times and still having compressive residual stresses. These experimental results were further explored and it was possible to establish linear relationships between the specific energy and the amplitudes of the surface residual stresses when grinding under the CGTs conditions. This relationship is very useful for process control and optimization. Results of the HSGTs show that the highest levels of the compressive surface residual stresses were obtained at a peripheral wheel speed v_s=120 m/s (σ_∥=?520 MPa, σ_⊥=?770 MPa). These values are much higher than those measured at the ground surface generated using the sol–gel grinding wheel and cooling by liquid nitrogen (σ_∥=?295 MPa, σ_⊥=?250 MPa). Further, the CGTs and HSGTs results were used to establish the burn-free and burn conditions in relation with the specific grinding energy. It was shown that condition using the sol–gel grinding wheel and cooling with liquid nitrogen and condition using cBN grinding wheel at peripheral wheel speed up to 180 m/s generate specific grinding energy that are significantly lower than the burning threshold energy.