Mohamed Ksibi

Discoloration and detoxicification of a Congo red dye solution by means of ozone treatment for a possible water reuse

The objective of this study was to investigate the degradation and mineralization of an azo-dye, the Congo red, in aqueous solutions using ozone. Phytotoxicity and the inhibitory effects on the microbial activity of the raw and the ozonated solutions were also carried out with the aim of water reuse and environment protection. Decolorization of the aqueous solutions, disappearance of the parent compound, chemical oxygen demand (COD) and total organic carbon (TOC) removal were the main parameters monitored in this study. To control the mineralization of the Congo red, pH of the ozonated solution and heteroatoms released from the mother molecule such NH(4)(+), NO(3)(-) and SO(4)(2-) were determined. It was concluded that ozone by itself is strong enough to decolorize these aqueous solutions in the early stage of the oxidation process. Nonetheless, efficient mineralization had not been achieved. Significant drops in COD (54%) were registered. The extent of TOC removal was about 32%. Sulfur heteroatom was totally oxidized to SO(4)(2-) ions while the central -NN- azo ring was partially converted to NH(4)(+) and NO(3)(-). Results of the kinetic studies showed that ozonation of the selected molecule was a pseudo-first-order reaction with respect to dye concentration. The obtained results also demonstrate that ozone process reduced the phytotoxicity of the raw solution and enhanced the biodegradability of the treated azo-dyes-wastewater. Hence, this show that ozone remains one of the effective technologies for the discoloration and the detoxification of organic dyes in wastewater.

Olive mill wastewater degradation by Fenton oxidation with zero-valent iron and hydrogen peroxide.

The degradation of olive mill wastewater (OMW) with hydroxyl radicals generated from zero-valent iron and hydrogen peroxide has been investigated by means of chemical oxygen demand (COD) and phenolic compounds analyses. The effects of the H2O2 dose, the pH and the organic matter concentration have been studied. The optimal experimental conditions were found to have continuous presence of iron metal, acid pH (2.0-4.0), and relatively concentrated hydrogen peroxide (9.5M). Coloration of OMW disappeared and phenolic compound decreased to 50% of initial concentration after 3h reaction time. The application of zero-valent Fe/H2O2 procedure permitted high removal efficiencies of pollutants from olive mill wastewater. The results show that zero-valent Fe/H2O2 could be considered as an effective alternative solution for the treatment of OMW or may be combined with a classical biological process to achieve high quality of effluent water.

Photocatalytic degradation of 4-chlorophenol under P-modified TiO2/UV system: kinetics, intermediates, phytotoxicity and acute toxicity.

A series of phosphorus-modified titanium dioxide samples with varying P/Ti atomic ratio were conveniently prepared via a conventional solgel route. The effects of phosphorus content and calcination temperature on the crystalline structure, grain growth, surface area, and the photocatalytic activity of P-modified TiO2 were investigated. The XRD results showed that P species slow down the particle growth of anatase and increase the anatase-to-rutile phase transformation temperature to more than 900 degrees C. Kinetic studies on the P-modified TiO2 to degraded 4-chlorophenol had found that the TP5(500) prepared by adopting a P/Ti atomic ratio equal to 0.05 and calcined at 500 degrees C had an apparent rate constant equal to 0.0075 min(-1), which is superior to the performance of a commercial photocatalyst Degussa P25 K(app) = 0.0045 min(-1) and of unmodified TiO2 (TP0(500)) K(app) = 0.0022 min(-1). From HPLC analyses, various hydroxylated intermediates formed during oxidation had been identified, including hydroquinone (HQ), benzoquinone (BQ) and (4CC) 4-chlorocatechol as main products. Phytotoxicity was assessed before and after irradiation against seed germination of tomato (Lycopersicon esculentum) whereas acute toxicity was assessed by using Folsomia candida as the test organism. Intermediates products were all less toxic than 4-chlorophenol and a significant removal of the overall toxicity was accomplished.

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.

Label-free disposable immunosensor for detection of atrazine

This work reports the construction of a fast, disposable, and label-free immunosensor for the determination of atrazine. The immunosensor is based on a field effect transistor (FET) where a network of single-walled carbon nanotubes (SWCNTs) acts as the conductor channel, constituting carbon nanotubes field effect transistors (CNTFETs). Anti-atrazine antibodies were adsorbed onto the SWCNTs and subsequently the SWCNTs were protected with Tween 20 to prevent the non-specific binding of bacteria or proteins. The principle of the immunoreaction consists in the direct adsorption of atrazine specific antibodies (anti-atrazine) to SWCNTs networks. After exposed to increasing concentrations of atrazine, the CNTFETs could be used as useful label-free platforms to detect atrazine. Under the optimal conditions, a limit of detection as low as 0.001 ng mL(-1) was obtained, which is lower than that of other methods for the atrazine detection, and in a working range between 0.001 and 10 ng mL(-1). The average recoveries obtained for real water samples spiked with atrazine varied from 87.3% to 108.0%. The results show that the constructed sensors display a high sensitivity and could be useful tools for detecting pesticides like atrazine at low concentrations. They could be also applied to the determination of atrazine in environmental aqueous samples, such as seawater and riverine water.

UV and solar photo-degradation of naproxen: TiO2 catalyst effect, reaction kinetics, products identification and toxicity assessment

Direct photolysis and TiO2-photocatalytic degradation of naproxen (NPX) in aqueous solution were studied using a UV lamp and solar irradiation. The degradation of NPX was found to be in accordance with pseudo-first order kinetics, the photocatalytic process being more efficient than photolysis. The NPX removal by photolysis (pHinitial 6.5) was 83% after 3h, with 11% of chemical oxygen demand (COD) reduction, whereas the TiO2-UV process led to higher removals of both NPX (98%) and COD (25%). The apparent pseudo-first-order rate constant (kapp) for NPX degradation by photolysis ranged from 0.0050 min(-1) at pH 3.5 to 0.0095 min(-1) at pH 6.5, while it was estimated to be 0.0063 min(-1) under acidic conditions in photocatalysis, increasing by 4-fold at pH 6.5. Ultra High Performance Liquid chromatography (UHPLC) coupled with a triple quadrupole detector and also a hybrid mass spectrometer which combines the linear ion trap triple quadrupole (LTQ) and OrbiTrap mass analyser, were used to identify NPX degradation products. The main intermediates detected were 1-(6-methoxynaphtalene-2-yl) ethylhydroperoxide, 2-ethyl-6-methoxynaphthalene, 1-(6-methoxynaphtalen-2-yl) ethanol, 1-(6-methoxynaphtalen-2-yl) ethanone and malic acid. Solar photocatalysis of NPX showed COD removals of 33% and 65% after 3 and 4h of treatment, respectively, and some reduction of acute toxicity, evaluated by the exposure of Eisenia andrei to OECD soils spiked with NPX-treated solutions.

Titanium dioxide mediated photo-degradation of methyl orange by ultraviolet light

The photo-degradation of an aqueous solution containing the azo dye methyl orange (MO) is reported. Disappearance of color and substrate together with decreases in chemical oxygen demand (COD) and total organic carbon (TOC) content were observed. The effects of some auxiliary dyeing additives were also evaluated. The photo-decomposition followed pseudo-first-order kinetics. Some by-products and their photo-degradation pathways were identified. In addition, the toxicity and phytotoxicity of some by-products were tested using the earthworm (Eisenia andrei) avoidance test and the Bromus ramosus seed germination test. High sensitivity of E. andrei towards soil wetted with MO solution was observed, and germination of B. ramosus seeds was inhibited by MO solution, while no effects were seen for the same solution after photocatalytic oxidation.

Ecotoxicity of titanium silicon oxide (TiSiO4) nanomaterial for terrestrial plants and soil invertebrate species.

The huge evolution of nanotechnology and the commercialization of nanomaterials (NMs) positively contributed for innovation in several industrial sectors. Facing this rapid development and the emergence of NMs in the market, the release of this nanometric sized materials in the environment and the possible impact on different ecosystem components attracted the attention of researchers in the last few years. In our study we aimed to assess the impact of titanium silicon oxide nanomaterial (nano-TiSiO4) on soil biota to estimate a risk limit for this material. In the present research a battery of standardized ecotoxicological assays aimed at evaluating a wide range of endpoints (avoidance and reproduction of earthworms and collembolans, emergence/growth of four selected terrestrial plants) were carried out, using OECD artificial soil as test substrate spiked with aqueous suspension of different concentrations of nano-TiSiO4. The results showed a maximum avoidance percentage of 40% for earthworms (Esenia andrei) at the highest concentration tested (1000mgkg(-1) soildw of nano-TiSiO4). No significant effect on the reproductive function of both invertebrate species was recorded. Nevertheless, significant phytotoxic data was registered at least for the growth of dicotyledonous plant species (Lactuca sativa and Lycopersicon lycopersicum) with EC20 values ranging between 236 and 414 mg kg(-1) soildw of nano-TiSiO4 for L. sativa dry mass and fresh mass, respectively. Further, the characterization of nano-TiSiO4 in suspensions used to spike the soil, performed by Dynamic Light Scattering, showed the formation of aggregates with important average size diameter, thus demonstrating that the toxic effects observed were likely not size dependent. A deterministic PNEC (predicted no effect concentration) for this NM of 10.02mg kg(-1) soildw of nano-TiSiO4, is suggested, while no more ecotoxicological information exists.

Development of an electrochemical biosensor for alkylphenol detection.

In this work, electrochemical biosensors based on field effect transistors (FET) with single-walled carbon nanotubes (SWCNT) were constructed as disposable analytical devices to detect alkylphenols through immunoreaction using 4-nonylphenol (NP) as model analyte, and validated by comparison with enzyme-linked immunosorbent assay (ELISA). The calibration curve displays a working range with five concentrations between 5 and 500µgL(-1), and for each concentration, five biosensors were analysed for reproducibility estimation and two analytical measurements were performed for each biosensor for repeatability estimation. The accuracy of the biosensors was validated by analyzing NP contents in ten spiked artificial seawater samples and comparing these results to those obtained with the traditional ELISA methodology. Excellent analytical performance was obtained with reproducibility of 0.56±0.08%, repeatability of 0.5±0.2%, limit of detection for NP as low as 5µgL(-1), and average recovery between 97.8% and 104.6%. This work demonstrates that simple biosensors can be used to detect hazardous priority substances in seawater samples, even at low concentrations.

Solar Photocatalytic Decolorization and Degradation of Methyl Orange Using Supported TiO2

Abstract The photocatalytic degradation of Methyl orange has been investigated on dynamic solar pilot plant using nonwoven fibers coated with TiO2 as photocatalyst. The operational parameters, such as initial dye concentration and pH, were studied. Disappearance of color and substrate together with decreases in chemical oxygen demand (COD) and total organic carbon (TOC) content were observed. The photo-decomposition followed pseudo-firstorder kinetics. In addition, the toxicity of some by-products was tested using the earthworm (Eisenia andrei) avoidance test. High sensitivity of E. andrei towards soil wetted with MO solution was observed, while no effects were seen for the same solution after photocatalytic oxidation.