Mineralization of bisphenol A by advanced oxidation processes

BACKGROUND: Endocrine disruptors, as in the case of bisphenol A (BPA), are increasingly found in aqueous effluents. The degree of mineralization of a bisphenol A (BPA) aqueous solution after applying several oxidation treatments has been investigated. RESULTS: UV‐C photolysis of BPA allowed calculation of the quantum yield, ϕ_λ=254 = 0.045 ± 0.005 mol Einstein⁻¹ but only 15% of the initial organic carbon content (TOC) was eliminated. Better results (80% conversion) were obtained after TiO₂ addition. Ozone inmediately reacts with BPA. Again, TiO₂ addition in the presence of O₃ was capable of increasing the mineralization level (60%). The photolytic ozonation of BPA was capable of completely eliminating TOC. The presence of activated carbon in the O₃/UV and O₃/UV/TiO₂ systems significantly enhanced the TOC removal reaction rate (100% conversion in 20 min). CONCLUSIONS: Processes such as ozonation or photolysis are capable of efficiently removing BPA from water however, mineralization levels are rather low. Addition of TiO₂ to O₃ or UV‐C significantly enhances TOC removal. The remaining organics still account for an average 20–40% of the initial organic carbon. The combination of O₃/UV‐C is capable of completely mineralizing BPA. Activated carbon and/or TiO₂ addition to the system O₃/UV‐C improves the TOC depletion rate. Copyright © 2008 Society of Chemical Industry     

Photocatalytic ozonation of gallic acid in water

Aqueous solutions of gallic acid have been treated with five different oxidation‐radiation processes: visible and ultraviolet A radiation (VUVA), TiO₂ adsorption, ozonation, VUVA/TiO₂ photocatalysis and VUVA/O₃/TiO₂ photocatalytic ozonation. With the exception of VUVA radiation and TiO₂ adsorption, ozone and photolytic processes allow for the total removal of gallic acid in a period between 50 and 90 min. The time taken to achieve 100% gallic acid conversion depends on the oxidation process applied, photocatalytic ozonation being the most effective technique. Throughout the process, oxalic and formic acids were identified as byproducts. Some other unidentified compounds probably related to pyruvic, malonic and maleic acids were also detected. The appearance of these compounds can be justified from direct reactions of both hydroxyl radical and ozone in water. Only photocatalytic ozonation leads to total mineralisation of the organic matter in less than 90 min. The photocatalyst used, TiO₂, showed good activity and stability (no leaching was observed) after five consecutive photocatalytic ozonation runs with the same semiconductor‐catalyst mass. Copyright © 2006 Society of Chemical Industry     

Advanced oxidation processes for the degradation of p‐hydroxybenzoic acid 1: Photo‐assisted ozonation

The oxidation of p‐hydroxybenzoic acid in aqueous solution by UV radiation and by photo‐assisted ozonation (UV+O₃) has been studied. The effects of temperature (10, 20, 30 and 40 °C), pH (2, 5, 7 and 9) and ozone partial pressure (0.10–0.38 kPa) on the conversion of p‐hydroxybenzoic acid were established. Experimental results indicated that the kinetics for both oxidation processes fit pseudo‐first‐order kinetics well. In the combined process, the overall kinetic rate constant was split into two components: direct oxidation by UV radiation (photolysis) and oxidation by free radicals (mainly OH·) generated in the system. The importance of these two reaction paths for each specific value of ozone partial pressure, temperature and pH was quantified. Lastly, a general expression is proposed for the reaction rate which takes into account the two reaction pathways and is a function of known operating variables. © 2001 Society of Chemical Industry     

Advanced oxidation processes for the degradation of p‐hydroxybenzoic acid 2: Photo‐assisted Fenton oxidation

Oxidation of p‐hydroxybenzoic acid in aqueous solution by the photo‐assisted Fenton reaction (Fe²⁺ + H₂O₂ + UV) has been studied. The effects of ferrous ion concentration (0.05, 0.14 and 0.29 mmol dm^?3), temperature (10, 20, 30 and 40 °C), and initial hydrogen peroxide concentration (0.7, 1.4, 2.2 and 2.9 mmol dm^?3) on the p‐hydroxybenzoic acid conversion were established. Experimental results indicate that the kinetics of this oxidation process fits pseudo‐first‐order kinetics well. The overall kinetic rate constant was split into two components: direct oxidation by UV radiation (photolysis) and oxidation by free radicals (mainly OH·) generated in the system. The importance of these two reaction paths for each specific value of ferrous ion concentration, temperature and initial hydrogen peroxide concentration was evaluated. A semi‐empirical expression is proposed for the overall reaction rate which takes into account both oxidation pathways and is a function of operating variables. © 2001 Society of Chemical Industry     

TiO2-Based Heterogeneous Photocatalytic Water Treatment Combined with Ozonation

The degradations of aliphatic carboxylic acids (formic acid, acetic acid, and propionic acid) were investigated by a combination of TiO₂-based photocatalysis and ozonation at pH = 2. The carboxylic acids were analyzed by high-performance liquid chromatography (HPLC), while the mineralization process was characterized by measuring the dissolved organic carbon (DOC) content. The efficiency of heterogeneous photocatalysis combined with ozonation was compared with that of ozonation and that of heterogeneous photocatalysis alone. In all cases, the combined system proved most effective in the oxidation of carboxylic acids. The degradation of carboxylic acids was accompanied by a continuous decrease in the DOC content, and aldehydes and carboxylic acids containing one carbon atom less than the starting material were formed as intermediates.     

Removal of organic contaminants in paper pulp effluents by AOPs: an economic study

The degradation of the organic content of a bleaching Kraft mill effluent was carried out using Advanced Oxidation Processes (AOPs). The study was focused on the identification of the AOP, or combination of AOPs, that showed the highest efficiency together with the lowest cost. Direct UV photolysis (UV), TiO₂ assisted‐photocatalysis (TiO₂/UV), Fenton, Fenton‐like, and photo‐Fenton reactions (Fe(II)/H₂O/UV), UV‐assisted ozonation (O₃/UV) and addition of Fe²⁺ and/or H₂O₂ to the TiO₂/UV and the O₃/UV systems, were used for the degradation of a conventional cellulose bleaching effluent. The effluent was characterized by the general parameters TOC, COD and color, and analyzed for chlorinated low molecular weight compounds using GC–MS. The costs of the systems per unit of TOC reduction were compared. Fenton, Fenton‐like and photo‐Fenton reactions achieved better levels of TOC degradation than photocatalysis and with lower cost's than photocatalytic treatments. Ozonation is an effective but rather expensive process. The use of UVA light, however, increased the effectiveness of ozonation with a significant decrease (>25%) in the operational cost. © 2002 Society of Chemical Industry     

Advanced oxidation of raw and biotreated textile industry wastewater with O3, H2O2 /UV‐C and their sequential application

The advanced chemical oxidation of raw and biologically pretreated textile wastewater by (1) ozonation, (2) H₂O₂ /UV − C oxidation and (3) sequential application of ozonation followed by H₂O₂ /UV − C oxidation was investigated at the natural pH values (8 and 11) of the textile effluents for 1 h. Analysis of the reduction in the pollution load was followed by total environmental parameters such as TOC, COD, UV–VIS absorption kinetics and the biodegradability factor, f_B. The successive treatment combination, where a preliminary ozonation step was carried out prior to H₂O₂ /UV − C oxidation without changing the total treatment time, enhanced the COD and TOC removal efficiency of the H₂O₂ /UV − C oxidation by a factor of 13 and 4, respectively, for the raw wastewater. In the case of biotreated textile effluent, a preliminary ozonation step increased COD removal of the H₂O₂ /UV − C treatment system from 15% to 62%, and TOC removal from 0% to 34%. However, the sequential process did not appear to be more effective than applying a single ozonation step in terms of TOC abatement rates. Enhancement of the biodegradability factor (f_B) was more pronounced for the biologically pretreated wastewater with an almost two‐fold increase for the optimized Advanced Oxidation Technologies (AOTs). For H₂O₂ /UV − C oxidation of raw textile wastewater, apparent zero order COD removal rate constants (k_app), and the second order OH· formation rates (r_i) have been calculated. © 2001 Society of Chemical Industry     

Photocatalytic degradation of organics in water in the presence of iron oxides: Influence of carboxylic acids

The effects of four carboxylic acids: malic, citric, tartaric and oxalic acids on the leaching of iron from two commercial iron oxides (hematite, α-Fe₂O₃, and magnetite, Fe₃O₄) have been investigated. The variables studied were the doses of iron oxides and carboxylic acids used as well as aqueous pH, temperature and the presence of hydrogen peroxide and/or UV-A radiation. On the whole, Fe₃O₄ led to higher amounts of leached iron than α-Fe₂O₃, and oxalic acid was the most effective carboxylic acid used. The importance of iron leaching has been considered to explain the photodegradation of bisphenol A (BPA) by UV-A/iron oxides systems. The influence of the presence of hydrogen peroxide and/or titania on the efficiency of these oxidation systems was also investigated. At the conditions tested, advanced oxidation with the UV-A/iron oxide/oxalic acid/H₂O₂/TiO₂ system led to the lowest BPA half life (<15 min) among those processes studied.     

Combination of Black‐Light Photo‐catalysis and Ozonation for Emerging Contaminants Degradation in Secondary Effluents

A water solution of emerging contaminants (ECs) was treated by advanced oxidation systems. Ozone‐based processes led to the highest ECs degradation rates. Regardless of the nature of the aqueous matrix, no differences in EC removal were obtained when O₃ was added. Mineralization occurred to some extent when activated carbon (AC) or O₃ were present. O₃, UVA/TiO₂/O₂, and UVA/TiO₂/O₃ processes were applied in runs carried out with low ECs concentration. Single ozonation and photocatalytic ozonation led to the complete ECs degradation in less than 5 min. When a secondary effluent was used, the efficiency of the technologies decreased. With the exception of caffeine, a detrimental effect of other organic/inorganic compounds present in secondary effluents was observed.     

Comparison of Ozone-based and other (VUV and TiO2/UV) Radical Generation Methods in Phenol Decomposition

The degradation reaction kinetics and chemical mechanism of phenol decomposition by ozonation, TiO₂-photocatalysis and vacuum ultraviolet (VUV) photolysis were investigated. The concentration dependences of the aromatic and aliphatic intermediates and the TOC content were compared as a function of the phenol conversion. The concentration profiles and the TOC curves obtained with each method were very similar. The results suggest a similar chemical mechanism for the transformation of phenol irrespective of the starting active component (a positive hole on the surface of the catalysts, a VUV photon, ozone or the hydroxyl radical).     

An investigation on the optimal location of ozonation within biological treatment for a tannery wastewater

The objective of this study was to evaluate the optimal location of ozonation within biological treatment for a typical tannery wastewater by giving special attention to biodegradability‐based chemical oxygen demand (COD) characterization. As treating the raw tannery effluent solely by biological treatment is not adequate to meet the discharge standards owing to the high level of biorecalcitrant COD at the outlet, the application of chemical oxidation, i.e. ozone together with biotreatment (pre‐ozonation or in mid‐ozonation or post‐ozonation) was investigated. The tannery effluent under investigation had initially inert soluble COD (S_I1) and particulate COD (X_I1) fractions corresponding to 9% and 13% of the total COD (C_T1), respectively, whereas each component of the biodegradable part—readily biodegradable COD (S_S1), rapidly hydrolysable COD (S_H1), and slowly hydrolysable COD (X_S1)—accounted for around 26% of the total COD (C_T1). Pre‐ozonation, undesirably competing with biotreatment for the removal of degradable organics, was shown to be insufficient both in terms of total COD (C_T1) and inert COD (C_I1) removal efficiencies. The scheme of biological treatment + ozonation + biological treatment could be applied successfully when 42.8 mg O₃ min^?1 was introduced for 5 min with a utilized ozone percentage of 76% at a point in biological treatment where the readily biodegradable COD (S_S1) was depleted through biochemical reactions. Such an alternative yielded satisfactory outcomes when both total COD (C_T) and inert COD (C_I) removal efficiencies per utilized ozone ratios were considered. With post‐ozonation, on the other hand, the highest inert COD (C_I) removal efficiencies together with an effluent quality meeting the discharge standards could be obtained. Copyright © 2006 Society of Chemical Industry     

Catalytic Ozonation of m-Dinitrobenzene

The efficiency of catalytic ozonation with homogeneous (containing dissolved ions of Fe²⁺, Mn²⁺, Cu²⁺, Ni²⁺, Co²⁺, V⁵⁺, Cr³⁺, Mo⁶⁺) and heterogeneous (MnO₂, Ni₂O_3, Fe₂O₃, CuO, Al₂O₃, CoO, V₂O₅, Cr₂O₃, MoO₃, TiO₂) catalysts and non-accompanied ozonation was compared for degradation of m-dinitrobenzene (m-DNB). Several transition metals in homogeneous and heterogeneous form improved significantly the ozone performance for degradation of m-DNB. This improvement was found to be due to supplementary formation of reactive species (hydroxyl radicals) and better ozone utilization. The effects observed were found to be strongly dependent on the treatment conditions.     

Bi2O3 nanoparticles incorporated porous TiO2 films as an effective p‐n junction with enhanced photocatalytic activity

Porous TiO₂ films decorated with Bi₂O₃ nanoparticles are fabricated via alkali‐hydrothermal of titanium (Ti) plate by varying the reaction time. The amorphous TiO₂ is transformed into anatase after annealing the films at 500°C in air. The p‐type Bi₂O₃ nanoparticles are successfully assembled on the surface of porous n‐type TiO₂ films through the ultrasonic‐assisted successive ionic layer adsorption and reaction (SILAR) technique to form Bi₂O₃/TiO₂ nanostructure by the two cycles. The obtained Bi₂O₃/TiO₂ films are consisted of a well‐ordered and uniform porous structure with an average pore diameter of about 100‐200 nm containing homogeneously dispersed Bi₂O₃ nanoparticles of ~5 nm diameter. Moreover, the resultant composites present excellent photocatalytic performance toward methyl blue (MB) degradation under UV and visible light irradiation, which could be mainly ascribed to the enhanced light adsorption capacity of unique composite structure and the formation of p‐n heterojunctions in the porous Bi₂O₃/TiO₂ films. This research is helpful to design and construct the highly efficient heterogeneous semiconductor photocatalysts.     

Photocatalytic oxidation of cyclohexane over TiO2 nanoparticles by molecular oxygen under mild conditions

The structure, physical characteristics and photocatalytic selective oxidation properties of nanometer‐size TiO₂ particles produced by a sol–gel method were studied by X‐ray diffraction (XRD), diffuse reflectance spectroscopy (DRS), X‐ray photoelectron spectroscopy (XPS), electron paramagnetic resonance (EPR) and photocatalytic selective oxidation measurements. Analysis of the XRD results shows that sol–gel‐produced TiO₂ nanoparticles have the anatase structure at annealing temperatures ≤973 K, that the rutile structure begins to emerge at annealing temperatures ≥973 K and the particles have the pure rutile structure at 1023 K. DRS indicates that the obtained TiO₂ nanoparticles exhibit a blue shift with decreasing crystallite size. Analysis of the XPS results shows that the TiO₂ nanoparticles have a lot of oxygen vacancies. The EPR spectrum of TiO₂ at 77 K is composed of a strong isotropic EPR Surface‐Ti³⁺ signal(I) at g = 1.926 and a weak broad Bulk‐Ti³⁺ signal (II) at g = 1.987. Quantitative EPR indicates that both signals show a size and temperature dependence. Photocatalytic oxidation of cyclohexane into cyclohexanol with high selectivity and activity has been obtained by activation of molecular oxygen over sol–gel‐produced TiO₂ nanoparticles under mild conditions in dry solvent, which reveals that the quantum size effect and surface state effect of nanoparticles are key points for governing the selective photocatalytic reaction. The photocatalytic oxidation mechanism under dry solvent is different from that in aqueous solutions. Copyright © 2003 Society of Chemical Industry     

Diclofenac removal from water by ozone and photolytic TiO2 catalysed processes

BACKGROUND: The aim of this work was to establish the efficiency of single ozonation at different pH levels (5, 7 and 9) and with different TiO₂ photolytic oxidizing systems (O₂/UV‐A/TiO₂, O₃/UV‐A/TiO₂ or UV‐A/TiO₂) for diclofenac removal from water, with especial emphasis on mineralization of the organic matter. RESULTS: In the case of single ozonation processes, results show fast and practically complete elimination of diclofenac, with little differences in removal rates that depend on pH and buffering conditions. In contrast, total organic carbon (TOC) removal rates are slow and mineralization degree reaches 50% at best. As far as photocatalytic processes are concerned, diclofenac is completely removed from the aqueous solutions at high rates. However, unlike single ozonation processes, TOC removal can reach 80%. CONCLUSION: In single ozonation processes, direct ozone reaction is mainly responsible for diclofenac elimination. Once diclofenac has disappeared, its by‐products are removed by reaction with hydroxyl radicals formed in the ozone decomposition and also from the reaction of diclofenac with ozone. In the photocatalytic processes hydroxyl radicals are responsible oxidant species of diclofenac removal as well as by‐products. Copyright © 2010 Society of Chemical Industry     

Enterococcus sp. Inactivation by Ozonation in Natural Water: Influence of H2O2 and TiO2 and Inactivation Kinetics Modeling

This article presents the results about the disinfectant power of treatments based on the application of ozone (578 mg O₃ h^?1) and ozone combined with TiO₂ (1 g L^?1) and H₂O₂ (0.04 mM) on Enterococcus sp., a bacteria indicator used in the control of water quality. The results show that all the ozone-based treatments under study achieve the inactivation of Enterococcus sp. solution in natural water. Moreover, the combination of ozone with H₂O₂ or TiO₂ lightly improves the inactivation of Enterococcus sp. compared to the ozonation. However, the treatment with O₃, H₂O₂ and TiO₂ is less effective than the use of O₃, O₃/H₂O₂ or O₃/TiO₂. Finally, the primary mathematical models are applied (Hom, biphasic and Mafart) and they adequately describe the disinfection kinetics of the ozonation treatments studied for Enterococcus sp.     

Solar photoassisted anodic oxidation of carboxylic acids in presence of Fe using a boron-doped diamond electrode

This paper reports a comparative study on the anodic oxidation of 2.5 l of 50 mg l⁻¹ TOC of formic, oxalic, acetic, pyruvic or maleic acid in 0.1 M Na₂SO₄ solutions of pH 3.0 with and without 1.0 mM Fe³⁺ as catalyst in the dark or under solar irradiation. Experiments have been performed with a batch recirculation flow plant containing a one-compartment filter-press electrolytic reactor equipped with a 20 cm² boron-doped diamond (BDD) anode and a 20 cm² stainless steel cathode, and coupled to a solar photoreactor. This system gradually accumulates H₂O₂ from dimerization of hydroxyl radical (OH) formed at the anode surface from water oxidation. Carboxylic acids in direct anodic oxidation are mainly oxidized by direct charge transfer and/or OH produced on BDD, while their Fe(III) complexes formed in presence of Fe³⁺ can also react with OH produced from Fenton reaction between regenerated Fe²⁺ with electrosynthesized H₂O₂ and/or photo-Fenton reaction. Fast photolysis of Fe(III)-oxalate and Fe(III)-pyruvate complexes under the action of sunlight also takes place. Chemical and photochemical trials of the same solutions have been made to better clarify the role of the different catalysts. Solar photoassisted anodic oxidation in presence of Fe³⁺ strongly accelerates the removal of all carboxylic acids in comparison with direct anodic oxidation, except for acetic acid that is removed at similar rate in both cases. This novel electrochemical advanced oxidation process allows more rapid mineralization of formic, oxalic and maleic acids, without any significant effect on the conversion of acetic acid into CO₂. The synergistic action of Fe³⁺ and sunlight in anodic oxidation can then be useful for wastewater remediation when oxalic and formic acids are formed as ultimate carboxylic acids of organic pollutants, but its performance is expected to strongly decay in the case of generation of persistent acetic acid during the degradation process.     

Ozone-Based Advanced Oxidation Processes for the Decomposition of N-Methyl-2-Pyrolidone in Aqueous Medium

The present study investigates the decomposition of N-Methyl-2-Pyrolidone (NMP) using conventional ozonation (O₃), ozonation in the presence of UV light (UV/O₃), hydrogen peroxide (O₃/H₂O₂), and UV/H₂O₂ processes under various experimental conditions. The influence of solution pH, ozone gas flow dosage, and H₂O₂ dosage on the degradation of NMP was studied. All ozone-based advanced oxidation processes (AOPs) were efficient in alkaline medium, whereas the UV/H₂O₂ process was efficient in acidic medium. Increasing ozone gas flow dosage would accelerate the degradation of NMP up to certain level beyond which no positive effect was observed in ozonation as well as UV light enhanced ozonation processes. Hydrogen peroxide dosage strongly influenced the degradation of NMP and a hydrogen peroxide dosage of 0.75 g/L and 0.5 g/L was found to be the optimum dosage in UV/H₂O₂ and O₃/H₂O₂ processes, respectively. The UV/O₃ process was most efficient in TOC removal. Overall it can be concluded that ozonation and ozone-based AOPs are promising processes for an efficient removal of NMP in wastewater.     

Catalytic Ozonation of Gasoline Compounds in Model and Natural Water in the Presence of Perfluorinated Alumina Bonded Phases

Gasoline compounds are one of the most widespread causes of soil and groundwater contamination. Their degradation in model and natural waters due to catalytic ozonation in the presence of perfluorooctylalumina (PFOA) is presented and discussed in this paper. The results obtained clearly indicate that the PFOA/O₃ system is effective mainly for ether (MTBE and ETBE) removal from both model and natural water. The catalytic activity of PFOA is not so significant in the case of BTEX ozonation. An investigation into by-product formation has shown that the concentration of both carboxylic acids (mainly oxalic acid) and carbonyl compounds (mainly acetone) increases after catalytic ozonation when compared with ozonation alone. A decrease of formic acid and formaldehyde takes place after the PFOA/O₃ system as opposed to the usage of ozonation alone.     

Degradation of 1‐amino‐4‐bromoanthraquinone‐2‐sulfonic acid using combined airlift bioreactor and TiO2‐photocatalytic ozonation

BACKGROUND: Traditional treatment systems failed to achieve efficient degradation of anthraquinone dye intermediates at high loading. Thus, an airlift internal loop reactor (AILR) in combination with the TiO₂‐photocatalytic ozonation (TiO₂/UV/O₃) process was investigated for the degradaton of 1‐amino‐ 4‐bromoanthraquinone‐2‐ sulfonic acid (ABAS). RESULTS: The AILR using Sphingomonas xenophaga as inoculum and granular activated carbon (GAC) as biocarrier, could run steadily for 4 months at 1000 mg L^?1 of the influent ABAS. The efficiencies of ABAS decolorization and chemical oxygen demand (COD) removal in AILR reached about 90% and 50% in 12 h, respectively. However, when the influent ABAS concentration was further increased, a yellow intermediate with maximum absorbance at 447 nm appeared in AILR, resulting in the decrease of the decolorization and COD removal efficiencies. Advanced treatment of AILR effluent indicated that TiO₂/UV/O₃ process more significantly improved the mineralization rate of ABAS bio‐decolorization products with over 90% TOC removal efficiency, compared with O₃, TiO₂/UV and UV/O₃ processes. Furthermore, the release efficiencies of Br^? and SO₄^2? could reach 84.5% and 80.2% during TiO₂/UV/O₃ treatment, respectively, when 91.5% TOC removal was achieved in 2 h. CONCLUSION: The combination of AILR and TiO₂/UV/O₃ was an economic and efficient system for the treatment of ABAS wastewater. © 2012 Society of Chemical Industry