Solar Fenton and solar TiO2 catalytic treatment of ofloxacin in secondary treated effluents: Evaluation of operational and kinetic parameters

Two different technical approaches based on advanced oxidation processes (AOPs), solar Fenton homogeneous photocatalysis (hv/Fe²⁺/H₂O₂) and heterogeneous photocatalysis with titanium dioxide (TiO₂) suspensions were studied for the chemical degradation of the fluoroquinolone ofloxacin in secondary treated effluents. A bench-scale solar simulator in combination with an appropriate photochemical batch reactor was used to evaluate and select the optimal oxidation conditions of ofloxacin spiked in secondary treated domestic effluents. The concentration profile of the examined substrate during degradation was determined by UV/Vis spectrophotometry. Mineralization was monitored by measuring the dissolved organic carbon (DOC). The concentrations of Fe²⁺ and H₂O₂ were the key factors for the solar Fenton process, while the most important parameter of the heterogeneous photocatalysis was proved to be the catalyst loading. Kinetic analyses indicated that the photodegradation of ofloxacin can be described by a pseudo-first-order reaction. The rate constant (k) for the solar Fenton process was determined at different Fe²⁺ and H₂O₂ concentrations whereas the Langmuir-Hinshelwood (LH) kinetic expression was used to assess the kinetics of the heterogeneous photocatalytic process. The conversion of ofloxacin depends on several parameters based on the various experimental conditions, which were investigated. A Daphnia magna bioassay was used to evaluate the potential toxicity of the parent compound and its photo-oxidation by-products in different stages of oxidation. In the present study solar Fenton has been demonstrated to be more effective than the solar TiO₂ process, yielding complete degradation of the examined substrate and DOC reduction of about 50% in 30 min of the photocatalytic treatment.     

Photocatalytic degradation of reactive black 5 in aqueous solutions: Effect of operating conditions and coupling with ultrasound irradiation

The degradation of reactive black 5 (RB 5), a representative diazo dye found in textile effluents, by means of ultraviolet irradiation (9W UVA) over TiO(2) suspensions, ultrasound irradiation (80kHz, 135W) and their combined application was investigated. Several commercial TiO(2) catalysts were screened and an anatase Hombicat UV 100 sample exhibited considerable activity in terms of solution decoloration, COD and ecotoxicity reduction. Photocatalytic degradation increased with increasing TiO(2) loading (in the range 0.05-1g/L) and decreasing dye concentration (in the range 120-20mg/L) and solution pH (in the range 9-2.6). At the typical conditions employed in this study (60mg/L dye, 0.25mg/L catalyst, ambient pH=5.8, oxygen sparging), complete decoloration was achieved after 60min of reaction. Addition of H(2)O(2) up to 0.01M hindered degradation, scavenging the photogenerated holes and hydroxyl radicals. Ultrasound irradiation resulted in low decoloration, e.g. less than 10% after 60min at 60mg/L dye and oxygen sparging and slightly improved under an argon atmosphere. The simultaneous application of ultraviolet and ultrasound irradiation resulted in increased decoloration compared to that achieved by photocatalysis and sonolysis operating separately; moreover, the overall sonophotocatalytic effect was greater than the additive effect of the two processes, implying possible synergy.     

Synergetic effect between photocatalytic degradation and adsorption processes on the removal of phenolic compounds from olive mill wastewater

The photocatalytic degradation of two phenolic compounds, p-coumaric acid and caffeic acid, was performed with a suspended mixture of TiO₂ and powdered activated carbon (PAC) (at pH = 3.4 and 8). Adsorption, direct photolysis and photocatalytic degradation were studied under different pH and UV light sources (sunlight vs. 365 nm UV lamps). The potential for reusing this catalyst mixture in sequential photocatalytic runs was examined as well. Quantum yields for the direct photolysis of caffeic acid under solar and artificial 365 nm light were calculated (for the first time) as 0.005 and 0.011, respectively.A higher removal rate of contaminants by either adsorption or photocatalysis was obtained at a low pH (pH 4). Furthermore, the addition of PAC increased the removal efficiency of the phenolic compounds. Fast removal of the pollutants from the solution over three sequential runs was achieved only when both TiO₂ and PAC were present. This suggests that at medium phenolic concentrations, the presence of PAC as a co-sorbent reduces surface poisoning of the TiO₂ catalyst and hence improves photocatalysis degradation of phenolic pollutants.The adsorption equilibrium of caffeic acid or p-coumaric acid on TiO₂, PAC and the combined mixture of TiO₂ and PAC follows the Langmuir isotherm model. Experiments with PAC TiO₂ mixture and olive mill wastewater (anaerobically treated and diluted by a factor of 10) showed higher removal of polyphenols than of chemical oxygen demand (COD). 87% removal of total polyphenols, compared to 58% of COD, was achieved after 24 h of exposure to 365 nm irradiation (7.6 W/m²) in the presence of a suspended mixture of TiO₂ and PAC, indicating “self-selectivity” of polyphenols.     

Enhanced arsenic removal using mixed metal oxide impregnated chitosan beads

Mixed metal oxide impregnated chitosan beads (MICB) containing nanocrystalline Al₂O₃ and nanocrystalline TiO₂ were successfully developed. This adsorbent exploits the high capacity of Al₂O₃ for arsenate and the photocatalytic activity of TiO₂ to oxidize arsenite to arsenate, resulting in a removal capacity higher than that of either metal oxide alone. The composition of the beads was optimized for maximum arsenite removal in the presence of UV light. The mechanism of removal was investigated and a mode of action was proposed wherein TiO₂ oxidizes arsenite to arsenate which is then removed from solution by Al₂O₃. Pseudo-second order kinetics were used to validate the proposed mechanism. MICB is a more efficient and effective adsorbent for arsenic than TiO₂-impregnated chitosan beads (TICB), previously reported on, yet maintains a desirable life cycle, free of complex synthesis processes, toxic materials, and energy inputs.     

Enhancement of photocatalytic activity by metal deposition: characterisation and photonic efficiency of Pt, Au and Pd deposited on TiO2 catalyst

Pt, Au and Pd deposited TiO2 have been prepared and characterised by surface analytical methods such as surface area, XRD, and scanning electron micrograph and photophysical characterisation by diffuse reflectance spectroscopy. The photocatalytic activity of the doped catalysts was ascertained by the photo-oxidation of leather dye, acid green 16 in aqueous solution illuminated with low-pressure mercury lamp ( approximately 254 nm). The effect of metal contents on the photocatalytic activity was investigated. The highest photonic efficiency was observed with metal deposition level of less than 1 wt%.     

Photocatalytic degradation of nitrobenzene using titanium dioxide and concentrated solar radiation: chemical effects and scaleup

Photocatalytic degradation of nitrobenzene (NB) using titanium dioxide (Degussa P-25) as photocatalyst and concentrated solar radiation has been studied. The effects of various factors, such as the presence of anions common in the industrial wastewater, the initial pH and the addition of FeSO(4), were investigated. The intermediates detected were o, p,m-nitrophenols and dihhydroxy derivatives indicating that degradation proceeds via z.rad;OH radicals. Degradation of NB was studied in three reactors of different diameters to ascertain the effect of photon penetration depth on the degradation.     

Arsenic sorption on TiO2 nanoparticles: Size and crystallinity effects

Single solute As (III) and As (V) sorption on nano-sized amorphous and crystalline TiO₂ was investigated to determine: size and crystallinity effects on arsenic sorption capacities, possible As (III) oxidation, and the nature of surface complexes. Amorphous and crystalline nanoparticles were prepared using sol-gel synthesis techniques. For amorphous TiO₂, solute pH in the range of 4-9 had a profound impact on only As (V) sorption. As (III) and As (V) sorption isotherms indicated that sorption capacities of the different TiO₂ polymorphs were dependent on the sorption site density, surface area (particle size) and crystalline structure. When normalized to surface area, As (III) surface coverage on the TiO₂ surface remained almost constant for particles between 5 and 20 nm. However, As (V) surface coverage increased with the degree of crystallinity. X-ray absorption spectroscopic analysis provided evidence of partial As (III) oxidation on amorphous TiO₂ rather than crystalline TiO₂. The data also indicated that As (III) and As (V) form binuclear bidentate inner-sphere complexes with amorphous TiO₂ at neutral pH.     

Inactivation and surface interactions of MS-2 bacteriophage in a TiO2 photoelectrocatalytic reactor

Inactivation of MS-2 bacteriophage in a TiO₂ photoelectrocatalytic system was evaluated, wherein TiO₂ particles were coated onto an indium tin oxide (ITO) electrode and an electrical potential was applied under black light blue (BLB) irradiation. MS-2 phage inactivation was greatly enhanced by anodic potential, whereas cathodic potential completely inhibited inactivation. Experiments performed with radical scavengers showed that inactivation was primarily caused by hydroxyl radicals, both in the bulk phase and on the TiO₂ surface. Application of positive potential to the electrode was found to result in two distinct beneficial effects: (i) electrostatic attraction between the negatively charged viral capsid and catalyst surface, causing improved usage of surface-bound hydroxyl radical, in comparison to conventional TiO₂ photocatalytic disinfection; and (ii) higher reactive oxygen species production. Results also suggest that inactivation of various microorganisms including Escherichia coli, Staphylococcus aureus, Klebsiella pneumoniae, Bacillus subtilis spores and Cryptosporidium parvum oocyst was enhanced via positive potential induction to TiO₂.     

Analogies and differences between photocatalytic oxidation of chemicals and photocatalytic inactivation of microorganisms

This study reports the analogies and differences found when comparing TiO₂ photocatalytic treatment for chemical oxidation and microorganisms inactivation, using methylene blue and Escherichia coli as references, respectively. In both processes the activation is based on the same physicochemical phenomena and consequently a good correlation between them is observed when analyzing the effect of operational variables such as catalyst concentration or incident radiation flux, both factors influencing common stages such radiation absorption and generation of reactive oxygen species. However, different microbiological aspects (osmotic stress, repairing mechanism, regrowth, bacterial adhesion to the titania surface, etc) makes disinfection kinetics significantly more complex than the first-order profiles usually observed for the oxidation of chemical pollutants. Moreover, bacterial inactivation reactions are found to be extremely sensitive to the composition of water and modifications of the catalysts in comparison with the decolorization of the dye solutions, showing opposite behaviors to the presence of chlorides, incorporation of silver to the catalysts or the use of different types of immobilized TiO₂ systems. Therefore, the activity observed for the photocatalytic oxidation of organics can not be always extrapolated to photocatalytic disinfection processes.     

Photocatalytic degradation of aqueous pollutants using silica-modified TiO(2)

Photocatalytic degradation (PCD) of several aqueous pollutants was investigated using a porous silica-coated titanium dioxide (SiO(2)-TiO(2)) photocatalyst. Several cationic, neutral and anionic pollutants were tested. The results indicate that modifying the surface properties of TiO(2) using silica significantly enhances the PCD rate of the cationic pollutants. The rate enhancement decreased with an increase in substrate concentration, especially for the quaternary amines, and was attributed to the decrease in initial adsorption. However, no significant rate-increase resulted for acetate and phenol. Results suggest that the increased presence of cationic pollutants at the catalyst surface caused the rate enhancement.     

Treatment of textile dyehouse wastewater by TiO2 photocatalysis

The oxidative degradation of an actual textile dyehouse wastewater was investigated by means of photocatalysis in the presence of TiO2. The UV-A-induced photocatalytic oxidation over TiO2 suspensions was capable of decolorizing the effluent completely, as well as reducing chemical oxygen demand (COD) sufficiently (COD reduction generally varied between about 40% and 90% depending on the operating conditions) after 4 h of treatment. Two crystalline forms of TiO2, viz. anatase and rutile, were tested for their photocatalytic activity and anatase was found to be more active than rutile. The extent of photocatalytic degradation was found to increase with increasing TiO2 concentration up to 0.5 g/L TiO2, above which degradation remained practically constant, reaching a plateau. Furthermore, textile effluent degradation was enhanced at acidic conditions (i.e. pH = 3) and in the presence of hydrogen peroxide. To assess catalyst activity on repeated use, experiments were performed where the catalyst was recovered and reused; after three successive uses, TiO2 had sufficiently retained its photocatalytic activity. Finally, the luminescent marine bacteria Vibrio fischeri was used to assess the acute ecotoxicity of samples prior to and after the photocatalytic treatment and it was found that ecotoxicity was fully eliminated following photocatalytic oxidation.     

Recent developments in photocatalytic water treatment technology: A review

In recent years, semiconductor photocatalytic process has shown a great potential as a low-cost, environmental friendly and sustainable treatment technology to align with the “zero” waste scheme in the water/wastewater industry. The ability of this advanced oxidation technology has been widely demonstrated to remove persistent organic compounds and microorganisms in water. At present, the main technical barriers that impede its commercialisation remained on the post-recovery of the catalyst particles after water treatment.This paper reviews the recent R&D progresses of engineered-photocatalysts, photoreactor systems, and the process optimizations and modellings of the photooxidation processes for water treatment. A number of potential and commercial photocatalytic reactor configurations are discussed, in particular the photocatalytic membrane reactors. The effects of key photoreactor operation parameters and water quality on the photo-process performances in terms of the mineralization and disinfection are assessed. For the first time, we describe how to utilize a multi-variables optimization approach to determine the optimum operation parameters so as to enhance process performance and photooxidation efficiency. Both photomineralization and photo-disinfection kinetics and their modellings associated with the photocatalytic water treatment process are detailed. A brief discussion on the life cycle assessment for retrofitting the photocatalytic technology as an alternative waste treatment process is presented. This paper will deliver a scientific and technical overview and useful information to scientists and engineers who work in this field.     

Optical density and photonic efficiency of silica-supported TiO2 photocatalysts

Over the last years, many research groups have developed supported TiO2-based materials in order to improve the engineering applications of photocatalytic technologies. However, not many attempts have been made to evaluate the optical behavior of these materials. This work focuses on the study of the photonic efficiencies of silica-supported TiO2 photocatalysts following the photodegradation of dichloroacetic acid (DCA) as model compound. Catalysts with different types of silica support and titania loadings were tested and their activity was found to be in correlation with the results of the clusters size distribution of the TiO2 nanocrystals. The photonic efficiency of the supported photocatalysts depends extremely on the optical density of the solid suspensions. Influence of the textural properties of the support and the titania loading on the optical density as well as on the photonic efficiency of the materials are discussed. The dependence of the absorption of radiation by the suspension on the catalyst concentration is also analyzed.     

Evaluation of a photocatalytic reactor membrane pilot system for the removal of pharmaceuticals and endocrine disrupting compounds from water

A photocatalytic reactor membrane pilot system, employing UV/TiO₂ photocatalysis, was evaluated for its ability to remove thirty-two pharmaceuticals, endocrine disrupting compounds, and estrogenic activity from water. Concentrations of all compounds decreased following treatment, and removal followed pseudo-first-order kinetics as a function of the amount of treatment. Twenty-nine of the targeted compounds in addition to total estrogenic activity were greater than 70% removed while only three compounds were less than 50% removed following the highest level of treatment (4.24 kW h/m³). No estrogenically active transformation products were formed during treatment. Additionally, the unit was operated in photolytic mode (UV only) and photolytic plus H₂O₂ mode (UV/H₂O₂) to determine the relative amount of energy required. Based on the electrical energy per order (EEO), the unit achieved the greatest efficiency when operated in photolytic plus H₂O₂ mode for the conditions tested.     

Novel, bio-based, photoactive arsenic sorbent: TiO2-impregnated chitosan bead

A novel sorbent for arsenic, TiO₂-impregnated chitosan bead (TICB), has been synthesized and successfully tested. Kinetic plots, pH dependence, isotherm data, and bead morphology are reported. Equilibrium is achieved after 185 h in batch experiments with exposure to UV light. The TICB system performs similarly to the mass equivalent of neat TiO₂ nanopowder. The point of zero charge (pzc) for TICB was determined to be 7.25, and as with other TiO₂-based arsenic removal technologies, the optimal pH range for sorption is below this pH_pzc. Without exposure to UV light, TICB removes 2198 μg As(III)/g TICB and 2050 μg As(V)/g TICB. With exposure to UV light, TICB achieves photo-oxidation of As(III) to As(V), the less toxic and more easily sequestered arsenic form. UV irradiation also results in enhanced arsenic removal, reaching sorption capacities of 6400 μg As/g TICB and 4925 μg As/g TICB, where arsenic is initially added as As(III) and As(V), respectively. Because the TICB system obviates filtration post-treatment, TICB is superior to TiO₂ nanopowder from the perspective of implementation for decentralized water treatment.     

A practical demonstration of water disinfection using TiO2 films and sunlight

The scope of this study is the assessment of the efficiency of solar disinfection by heterogeneous photocatalysis with sol-gel immobilized (titanium dioxide) TiO2 films over glass cylinders. The solar disinfection process known as SODIS was considered as a reference. Spring water naturally polluted with coliform bacteria was exposed to sunlight in plastic bottles with and without TiO2 over simple solar collectors and the disinfection effectiveness was measured. Total and fecal coliforms quantification was performed by means of the chromogenic substrate method in order to obtain the efficiency of each disinfection treatment. The disinfection with TiO2 was more efficient than the SODIS process, inactivating total coliforms as well as fecal coliforms. On a sunny day (more than 1000 W m(-2) irradiance), it took the disinfection with immobilized TiO2 15 min of irradiation to inactivate the fecal coliforms to make them undetectable. For inactivation of total coliforms, 30 min was required, so that in less than half the time it takes SODIS, the treated water complies with the microbial standards for drinking water in Mexico. Another important part of this study has been to determine the bacterial regrowth in water after the disinfection processes were tested. After SODIS, bacterial regrowth of coliforms was observed. In contrast, when using the TiO2 catalyst, coliforms regrowth was not detected, neither for total nor for fecal coliforms. The disinfection process using TiO2 kept treated water free of coliforms at least for seven days after sun irradiation. This demonstration opens the possibility of application of this simple method in rural areas of developing countries.     

Optimization of capacity and kinetics for a novel bio-based arsenic sorbent, TiO2-impregnated chitosan bead

The optimization of TiO₂-impregnated chitosan beads (TICB) as an arsenic adsorbent is investigated to maximize the capacity and kinetics of arsenic removal. It has been previously reported that TICB can 1) remove arsenite, 2) remove arsenate, and 3) oxidize arsenite to arsenate in the presence of UV light and oxygen. Herein, it is reported that adsorption capacity for TICB is controlled by solution pH and TiO₂ loading within the bead and enhanced with exposure to UV light. Solution pH is found to be a critical parameter, whereby arsenate is effectively removed below pH 7.25 and arsenite is effectively removed below pH 9.2. A model to predict TICB capacity, based on TiO₂ loading and solution pH, is presented for arsenite, arsenate, and total arsenic in the presence of UV light. The rate of removal is increased with reductions in bead size and with exposure to UV light. Phosphate is found to be a direct competitor with arsenate for adsorption sites on TICB, but other relevant common background groundwater ions do not compete with arsenate for adsorption sites. TICB can be regenerated with weak NaOH and maintain full adsorption capacity for at least three adsorption/desorption cycles.     

Application of nano TiO(2) towards polluted water treatment combined with electro-photochemical method

A novel composite reactor was prepared and studied towards the degradation of organic pollutants in this work. In the reactor, a UV lamp was installed to provide energy to excite nano TiO(2), which served as photocatalyst, leading to the production of hole-electron pairs, and a three-electrode electrolysis system was used to accumulate H(2)O(2) which played an important role in the degradation process. The reactor was evaluated by the degradation process of rhodamine 6G (R-6G), and the data obtained in the experiments showed that the combination of the photochemical and electrochemical system raised the degradation rate of R-6G greatly; the working mechanism of the reactor was also discussed in the article. The prepared reactor was also utilized to treat polluted water from dyeing and printing process. After continuous treatment for 0.5h, chemical oxygen demand biochemical oxygen demand, quantity of bacteria and ammonia nitrogen of the polluted water were reduced by 93.9%, 87.6%, 99.9% and 67.5%, respectively, which indicated that the method used here could be used for effective organic dyes degradation.     

Degradation of the antibiotic oxolinic acid by photocatalysis with TiO2 in suspension

In the work presented here, a photocatalytic system using titanium Degussa P-25 in suspension was used to evaluate the degradation of 20 mg L⁻¹ of antibiotic oxolinic acid (OA). The effects of catalyst load (0.2-1.5 g L⁻¹) and pH (7.5-11) were evaluated and optimized using the surface response methodology and the Pareto diagram. In the range of variables studied, low pH values and 1.0 g L⁻¹ of TiO₂ favoured the efficiency of the process. Under optimal conditions the evolution of the substrate, chemical oxygen demand, dissolved organic carbon, toxicity and antimicrobial activity on Escherichia coli cultures were evaluated. The results indicate that, under optimal conditions, after 30 min, the TiO₂ photocatalytic system is able to eliminate both the substrate and the antimicrobial activity, and to reduce the toxicity of the solution by 60%. However, at the same time, ∼53% of both initial DOC and COD remain in solution. Thus, the photocatalytical system is able to transform the target compound into more oxidized by-products without antimicrobial activity and with a low toxicity. The study of OA by-products using liquid chromatography coupled with mass spectrometry, as well as the evaluation of OA degradation in acetonitrile media as solvent or in the presence of isopropanol and iodide suggest that the reaction is initiated by the photo-Kolbe reaction. Adsorption isotherm experiments in the dark indicated that under pH 7.5, adsorption corresponded to the Langmuir adsorption model, indicating the dependence of the reaction on an initial adsorption step.     

Mechanism of phenol photodegradation in the presence of pure and modified-TiO(2): A review

In recent years, the application of heterogeneous photocatalytic water purification processes has gained wide attention due to its effectiveness in degrading and mineralizing the recalcitrant organic compounds as well as the possibility of utilizing the solar UV and visible-light spectrum. By far, titania has played a much larger role in this scenario compared to other semiconductor photocatalysts due to its costly effectiveness, inert nature and photostability. A substantial amount of research has focused on the enhancement of TiO₂ photocatalysis by modification with metal, non-metal and ion doping.This paper aims to review and summarize the recent works on the titanium dioxide (TiO₂) photocatalytic oxidation of phenol and discusses various mechanisms of phenol photodegradation (indicating the intermediates products) and formation of OH radicals. Phenol degradation pathway in both systems, TiO₂/UV and doped-TiO₂/Vis, are described.