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The prediction of band edge potentials in photocatalytic materials is an important but challenging task. In contrast, bandgaps can be easily determined through absorption spectra. Here, we present two simple theoretical approaches for the determination of band edge potentials which are based on the electron negativity and work function of each constituent atom. We use these approaches to determine band edge potentials in semiconducting metallic oxides and sulfides, such as titanium dioxide (TiO 2 ), chalcopyrite (CuFeS 2 ), pyrite (FeS 2 ), covellite (CuS), and chalcocite (Cu 2 S) with respect to an absolute scale (eV) and an electrochemical scale (V). Until now, there is little information on iron and copper sulfides referring to these thermodynamic parameters. TiO 2 (Titania p25) was used as reference semiconductor to validate the calculation procedures using experimental values by X-ray diffraction analysis (XRD), diffuse reflectance spectrometry (DRS), and electron paramagnetic resonance spectroscopy (EPR). The production of key chemical species such as reactive oxygen species (ROS) and reactive sulfur species (RSS) has been theoretically and experimentally determined by EPR., (© 2023. The Author(s), under exclusive licence to European Photochemistry Association, European Society for Photobiology.)

The accessibility to clean water is essential for humans, yet nearly 250 million people die yearly due to contamination by cholera, dysentery, arsenicosis, hepatitis A, polio, typhoid fever, schistosomiasis, malaria, and lead poisoning, according to the World Health Organization. Therefore, advanced materials and techniques are needed to remove contaminants. Here, we review nanohybrids combining conducting polymers and zinc oxide for the photocatalytic purification of waters, with focus on in situ polymerization, template synthesis, sol-gel method, and mixing of semiconductors. Advantages include less corrosion of zinc oxide, less charge recombination and more visible light absorption, up to 53%., Competing Interests: Conflict of interestThe author declares no conflict of interest., (© The Author(s), under exclusive licence to Springer Nature Switzerland AG 2022.)

Amitriptyline (AMT) is the most widely used tricyclic antidepressant and is classified as a recalcitrant emergent contaminant because it has been detected in different sources of water. Its accumulation in water and soil represents a risk for different living creatures. To remove amitriptyline from wastewater, the Advanced Oxidation Processes (AOPs) stands up as an interesting option since generate highly oxidized species as hydroxyl radicals (OH) by environmentally friendly mechanism. In this work, the oxidation and mineralization of AMT solution have been comparatively studied by 3 Electrochemical AOPs (EAOPs) where the OH is produced by anodic oxidation of H 2 O (AO-H 2 O 2 ), or by electro-Fenton (EF) or photoelectro-Fenton (PEF). PEF process with a BDD anode showed the best performance for degradation and mineralization of this drug due to the synergistic action of highly reactive physiosorbed BDD (OH), homogeneous OH and UVA radiation. This process achieved total degradation of AMT at 50 min of electrolysis and 95% of mineralization after 360 min of treatment with 0.5 mmol L -1 Fe 2+ at 100 mA cm -2 . Six aromatic intermediates for the drug mineralization were identified in short time of electrolysis by GC-MS, including a chloroaromatic by-product formed from the attack of active chlorine. Short-chain carboxylic acids like succinic, malic, oxalic and formic acid were quantified by ion-exclusion HPLC. Furthermore, the formation of NO 3 - ions was monitored. Finally, the organic intermediates identified by chromatographic techniques were used to propose the reaction sequence for the total mineralization of AMT., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

The sustainable transformation of basic chemicals into organic compounds of industrial interest using mild oxidation processes has proved to be challenging. The production of cyclohexanol and cyclohexanone from cyclohexane is of interest to the nylon manufacturing industry. However, the industrial oxidation of cyclohexane is inefficient. Heterogeneous photocatalysis represents an alternative way to synthesize these products, but the optimization of this process is difficult. In this work, the yields of photocatalytic cyclohexane conversion using Degussa P-25 under visible light were optimized. To improve cyclohexanol production, acetonitrile was used as an inert photocatalytic solvent. Experiments showed that the use of the optimized conditions under solar light radiation did not affect the cyclohexanol/cyclohexanone ratio. In addition, the main radical intermediary produced in the reaction was detected by the electronic paramagnetic resonance technique.

The photocatalytic activity of hydrogenated TiO 2 was evaluated in the photooxidation of methyl orange (MO). The hydrogenation of TiO 2 was carried out by calcination of a mixture of TiO 2 P-25 and NaBH 4 , at 300 and 350°C for blue TiO 2 and black TiO 2 , respectively. An experimental design was made for the determination of the best reaction conditions for the oxidation of MO. The influence of catalyst dosage and pH on photocatalytic efficiency was optimized, and the degradation percentage of MO was the response factor. The photocatalytic reaction was performed using a Xenon lamp that simulates the solar light spectrum for the activation of the catalyst. It was determined that both blue and black TiO 2 show the greatest activity at pH = 2 and 0.8 g/L of catalyst. Additionally, the positive influence of hydrogen peroxide in the photocatalytic activity of both hydrogenated catalysts was determined. In parallel, COD and TOC were also studied. PRACTITIONER POINTS: The extent of titania reduction by hydrogenation is dependent on the reaction time with sodium borohydride. The extent of titania reduction affects the photocatalytic activity in the oxidation of methyl orange. An excess of catalyst reduction inhibits the oxidation of the dye because of the increase of recombination points. The best reaction conditions were determined by multivariate optimization as pH 2 and 0.8 g L -1 of hydrogenated catalyst. The addition of hydrogen peroxide into the reaction system improves the oxidation yield attributed to their electron accepting capacity., (© 2018 Water Environment Federation.)

Oxidation and removal of organic micropollutants (OMPs) on ultrapure (UPW) and natural water (NW) by ozone (O 3 ) and ozone/powdered activated carbon (O 3 /PAC) have been studied. The OMPs atrazine (ATZ, herbicide), carbamazepine (CBZ, anticonvulsant), diclofenac (DCL, anti-inflammatory) and triclosan (TCS, antimicrobial) are incorporated continuously and uncontrolled on water treatment systems (e.g., drinking water treatment plants, wastewater treatment plants). Batch experiments on ultrapure and natural water showed that ATZ treated with O 3 and O 3 /PAC has the slowest transformation rate (>90% at 30min reaction) while CBZ, DCL and TCS were oxidized very fast (>90% at ~5min). The radical scavenger tert-Butyl alcohol (TBA) was used to evaluate the contribution of HO on the OMPs oxidation. TBA, a hydrophilic compound with low adsorbability, was used as a strong HO scavenger to assess the role of the OH radical in the oxidation of the OMPs studied. ATZ oxidation was mainly driven by OH radicals. On the contrary, CBZ, DCL and TCS were removed by direct reaction with ozone. Infrared analysis (FTIR) showed changes in the PAC surface functional groups of the carbon exposed to ozone, decreasing its basic properties. The acute toxicity assays of the OMPs mixture dissolved in UPW performed with D. magna was significantly reduced by ozonation. The addition of PAC to the ozonation process, strongly improved the acute toxicity removal. Short chain mono- and di-carboxylic acids were identified as some of the oxidation intermediates formed during ozone treatment., (Copyright © 2016 Elsevier B.V. All rights reserved.)

In this work the electrochemical oxidation of losartan, an emerging pharmaceutical pollutant, was studied. Electrochemical oxidation was carried out in batch mode, in an open and undivided cell of 100cm(3) using a boron-doped diamond (BDD)/stainless steel system. With Cl(-) medium 56% of mineralization was registered, while with the trials containing SO4(2-) as supporting electrolyte a higher mineralization yield of 67% was reached, even obtaining a total removal of losartan potassium at 80mAcm(-2) and 180min of reaction time at pH 7.0. Higher losartan potassium concentrations enhanced the mineralization degree and the efficiency of the electrochemical oxidation process. During the mineralization up to 4 aromatic intermediates were identified by ultra high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS). Moreover, short-linear carboxylic acids, like oxalic, succinic and oxamic were detected and quantified by ion-exclusion HPLC. Finally, the ability of the electrochemical oxidation process to mineralize dissolved commercial tablets containing losartan was achieved, obtaining TOC removal up to 71% under optimized conditions (10mAcm(-2), 0.05M Na2SO4, pH 7.0 and 25°C and 360min of electrolysis)., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Organic micropollutants (OMPs) are ubiquitous in natural waters even in places where the human activity is limited. The presence of OMPs in natural water sources for human consumption encourages the evaluation of different water purification technologies to ensure water quality. In this study, the Biobío river (Chile) was selected since the watershed includes urban settlements and economic activities (i.e. agriculture, forestry) that incorporate a variety of OMPs into the aquatic environment, such as pesticides, pharmaceuticals and personal care products. Atrazine (herbicide), caffeine (psychotropic), diclofenac (anti-inflammatory) and triclosan (antimicrobial) in Biobío river water and in different stages of a drinking and two wastewater treatment plants downstream Biobío river were determined using solid phase extraction (SPE) and liquid chromatography/tandem mass spectrometry (LC-MS/MS) and electrospray ionization (ESI). Quantification of these four compounds showed concentrations in the range of 8 ± 2 to 55 ± 10 ng L(-1) in Biobío river water, 11 ± 2 to 74 ± 21 ng L(-1) in the drinking water treatment plant, and 60 ± 10 to 15,000 ± 1300 ng L(-1) in the wastewater treatment plants. Caffeine was used as an indicator of wastewater discharges. Because conventional water treatment technologies are not designed to eliminate some emerging organic pollutants, alternative treatment processes, UV and UV/H2O2, were employed. The transformation of atrazine, carbamazepine (antiepileptic), diclofenac and triclosan was investigated at laboratory scale. Both processes were tested at different UV doses and the Biobío river water matrix effects were evaluated. Initial H2O2 concentration used was 10 mg L(-1). Results showed that, the transformation profile obtained using UV/H2O2 at UV doses up to 900 mJ cm(-2), followed the trend of diclofenac > triclosan > atrazine > carbamazepine. Furthermore acute toxicity tests with Daphnia magna were carried out after UV/H2O2 treatments of the OMPs mixture studied. At the lower UV doses tested (300 mJ cm(-2)) a higher toxicity was observed, suggesting the formation of toxic intermediates in the course of the reaction. As expected, at higher UV doses the toxicity declined. Considering the treatment of the mixture of ATZ, CBZ, DCL and TCS with a UV dose of 1200 mJ cm(-2) and 10 mg L(-1) of H2O2 the acute toxicity results exhibits values for Daphnia magna immobilization equal to 20 and 42% evaluated after 24 and 48 h, respectively., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Norflurazon (4-chloro-5-(methylamino)-2-[3-(trifluoromethyl)phenyl]pyridazin-3(2H)-one; C12H9ClF3N3O) is an excellent weed controlling agent being practiced in the agricultural lands. The excessive addition or the undissolved Norflurazon (maximum solubility 28 mg/L at 25 °C) enters into the aquatic environment and causes the adverse effects associated with its high concentration. To avoid the perilous effects, visible light assisted photocatalysis set-up coupled with the 42 kHz ultrasound producing bath type sonicator is used to completely mineralize the Norflurazon. TiO2, ZnO and gold loaded zinc oxide nanocatalysts were utilized to study the mineralization of Norflurazon. Au-ZnO shows the greater efficiency for the sonophotocatalytic removal of Norflurazon among the various nanocatalysts employed to study the mineralization. The order of Norflurazon mineralization was sonophotocatalysis > sonocatalysis > photocatalysis. The additive effect was achieved for the sonophotocatalytic degradation. The high performance liquid chromatography (HPLC) and liquid chromatography-mass spectrometric (LCMS) analyses were employed to identify the various intermediates produced during the mineralization. The identification of four pseudo molecular ions and various intermediates using the LCMS analysis evidently suggests the sonophotocatalytic degradation was preceded in various decay pathways. A suitable mechanism has been proposed for the sonophotocatalytic mineralization of Norflurazon., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Waste water from the wine industry is characterized by a high concentration of dissolved organic matter and the presence of natural phenolic compounds with low biodegradability. High concentrations of phenolic compounds may cause environmental pollution and risks to human health. In this article caffeic acid (CA) was used as a model compound of wine effluent because it is refractory to the conventional wastewater treatments. The oxidation of caffeic acid in water solution (0.01 g L(-1)) by heterogeneous photocatalysis and photo-Fenton reaction was studied using UVA. The optimal conditions for each treatment were performed by multivariate experimental design. The optimal conditions for heterogeneous photocatalysis were pH 5.3 and 0.9 g L(-1) TiO2. In the case of photo-Fenton treatment, optimized variable were 82.4 μmol L(-1) of Fe(2+) and 558.6 μmol L(-1) of H2O2. The degradation profiles of CA were monitored by UV-Vis, HPLC, TOC and COD. To reach 90% of CA removal, 40 and 2 min of reaction, respectively, were required by heterogeneous and photo-Fenton processes, respectively. For comparison purposes, the reactions were also performed under solar light. The use of solar light does not change the efficiency of the photo-Fenton reaction, yet the performance of the heterogeneous process was significantly improved, reaching 90% of degradation in 15 min.

Biodegradation of tributyltin (TBT) by four tin resistant Gram negative bacteria isolated from extremely contaminated river sediments in the Atacama Desert in Chile was studied. Moraxella osloensis showed the greatest resistance and degradation capability of TBT, producing less toxic by-products, such as dibutyltin (DBT) and inorganic tin. In 7 days, approximately 80 % of TBT degradation was achieved, generating close to 20 % of DBT as degradation product. The degradation rate constant (k) was 0.022 [day(-1)] and TBT half-life (t1/2) in culture was 4.3 days. Debutylation is stated a probable mechanism of TBT degradation.

Ethnic groups from the Atacama Desert (known as Atacameños) have been exposed to natural arsenic pollution for over 5000 years. This work presents an integral study that characterizes arsenic species in water used for human consumption. It also describes the metabolism and arsenic elimination through urine in a chronically exposed population in northern Chile. In this region, water contained total arsenic concentrations up to 1250 μg L(-1), which was almost exclusively As(V). It is also important that this water was ingested directly from natural water sources without any treatment. The ingested arsenic was extensively methylated. In urine 93% of the arsenic was found as methylated arsenic species, such as monomethylarsonic acid [MMA(V)] and dimethylarsinic acid [DMA(V)]. The original ingested inorganic species [As(V)], represent less than 1% of the total urinary arsenic. Methylation activity among individuals can be assessed by measuring primary [inorganic As/methylated As] and secondary methylation [MMA/DMA] indexes. Both methylation indexes were 0.06, indicating a high biological converting capability of As(V) into MMA and then MMA into DMA, compared with the control population and other arsenic exposed populations previously reported.

TiO₂anatase powder was prepared by means of the sol-gel method with titanium(IV) butoxide as precursor. The formation of a tetragonal crystal structure of TiO₂anatase at 500 °C was confirmed by X-ray powder diffraction. The characterization of the samples synthesized was complemented by scanning electron microscopy, diffuse reflectance infrared Fourier transform spectroscopy, nitrogen adsorption-desorption isotherms (Brunauer-Emmett-Teller) and diffuse reflectance spectroscopy. The photocatalytic activity of the TiO₂anatase powder was evaluated in the degradation of caffeic acid in aqueous solution under ultraviolet radiation. A central composite circumscribed design was used to assess the weight of the experimental variables, pH and amount of catalyst in the percentage of caffeic acid degraded and the optimal conditions. The optimized conditions were found to be pH = 5.2 and a load of TiO₂of 1.1 g L⁻¹. Under these conditions more than 90% of caffeic acid degradation was achieved after 30 min of lamp irradiation. At this time the mineralization reached was almost 60%.

An experimental study of the homogeneous Fenton and photo-Fenton degradation of 4-amidophenol (paracetamol, PCT) is presented. For all the operation conditions evaluated, PCT degradation is efficiently attained by both Fenton and photo-Fenton processes. Also, photonic efficiencies of PCT degradation and mineralization are determined under different experimental conditions, characterizing the influence of hydrogen peroxide (H2O2) and Fe(II) on both contaminant degradation and sample mineralization. The maximum photonic degradation efficiencies for 5 and 10 mg L(-1) Fe(II) were 3.9 (H2O2 = 189 mg L(-1)) and 5 (H2O2 = 378 mg L(-1)), respectively. For higher concentrations of oxidant, H2O2 acts as a "scavenger" radical, competing in pollutant degradation and reducing the reaction rate. Moreover, in order to quantify the consumption of the oxidizing agent, the specific consumption of the hydrogen peroxide was also evaluated. For all operating conditions of both hydrogen peroxide and Fe(II) concentration, the consumption values obtained for Fenton process were always higher than the corresponding values observed for photo-Fenton. This implies a less efficient use of the oxidizing agent for dark conditions.

An attempt has been made to render the visible light driven photocatalytic activity to the TiO2 nanocatalysts by loading 1 wt% of rare earth (RE) nanoclusters (Gd(3+), Nd(3+) and Y(3+)) using a low frequency (42 kHz) producing commercial sonicator. The STEM-HAADF analysis confirms that the RE nanoclusters were residing at the surface of the TiO2. Transmission electron microscopic (TEM) and X-ray diffraction (XRD) analyses confirm that the loading of RE nanoclusters cannot make any significant changes in the crystal structure of TiO2. However, the optical properties of the resulted nanocatalysts were significantly modified and the nanocatalysts were employed to study the sonocatalytic, photocatalytic and sonophotocatalytic decolorization as well as mineralization of Acid Blue 113 (AB113). Among the experimented nanocatalysts maximum degradation of AB113 was achieved in the presence Y(3+)-TiO2 nanocatalysts. The decolorization of AB113 in the presence and absence of Y(3+) loaded TiO2 ensues the following order sonolysis

This article presents experimental results on 47 μmol L(-1) sulfathiazole (STZ) degradation by Fenton and photo-Fenton reactions using multivariate analysis. The optimal experimental conditions for reactions were obtained by Response Surface Methodology (RSM). In the case of the Fenton reactions there were 192 μmol L(-1) ferrous ions (Fe(II)) and 1856 μmol L(-1) hydrogen peroxide (H2O2), as compared with 157 μmol L(-1) (Fe(II)) and 1219 μmol L(-1) (H2O2) for photo-Fenton reactions. Under these conditions, around 90% of STZ degradation were achieved after 8 minutes treatment by Fenton and photo-Fenton reactions, respectively. Moreover, a marked difference was observed in the total organic carbon (TOC) removal after 60-min treatment, achieving 30% and 75% for the Fenton and photo-Fenton reactions, respectively. Acetic, maleic, succinic and oxamic acids could be identified as main Fenton oxidation intermediates. A similar pattern was found in the case of photo-Fenton reaction, including the presence of oxalic acid and ammonia at short periods of irradiation with UV-A. The calculated values of Average Oxidation State (AOS) corroborate the formation of oxidized products from the initial steps of the reaction.

Anomalously high levels of mercury in sediment in the Lenga estuary, Chile are comparable to the most contaminated sites previously reported elsewhere. Total mercury (Hgtotal) concentrations range from 0.5 to 129 mg kg(-1) and organic mercury (Hgorg) from 11 to 53 μg kg(-1). The highest levels are in areas near the previous wastewater outfall of a chlo-alkali plant. The results show that the proportion of Hgorg/Hgtotal in the sediment varies by more than two orders of magnitude (0.02-5.7%) according to the concentration of Hgtotal. No correlation between the concentration of Hgorg and Hgtotal was found. The lack of correlation does contrast with the findings of other authors in culture media. Our results indicate that even at very high concentrations of Hgtotal and organic matter do not influence organic mercury formation in estuary sediments. The disparity in Hgtotal and Hgorg concentrations also attests to environmental differences in the formation., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Photocatalytic degradation of phenylmercury was studied using TiO2 in aqueous suspension assisted by UV-A irradiation. Reaction conditions, such as pH and amount of TiO2 were set using a factorial design of experiments resulting in a greater influence of pH on phenylmercury degradation. Hg (II) reduction and simultaneous oxidation of aromatic group was observed. Optimum reaction conditions were obtained under nitrogen atmosphere at pH 10 and 0.35 g/L(-1) TiO2. Under these conditions almost 100% reduction of mercury was reached after 30 min UV irradiation. Total mercury reduction was achieved after 40 min reaction under saturated oxygen. Furthermore, phenol and diphenylmercury were identified as intermediate products of oxidation. It was observed that a major fraction of the reduced mercury was removed as metallic vapor by gas stripping, whereas a minor fraction was adsorbed on the catalyst surface, probably as Hg(OH)2. Under optimal conditions obtained by multivariable analysis, total mineralization of organic matter was achieved after about 60-min irradiation.

In the work presented here, a photocatalytic system using titanium Degussa P-25 in suspension was used to evaluate the degradation of 20mg 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 TiO(2) 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 TiO(2) 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., (Copyright © 2010 Elsevier Ltd. All rights reserved.)

This paper discusses the degradation of the antibiotic ampicillin (AMP) by Fenton and photo-Fenton reactions. The influence of the three main variables that govern the degradation kinetic (pH, H(2)O(2) and Fe(II) concentrations) was evaluated with a circumscribed central composite (CCC) model and a response surface methodology (RSM). The optimal conditions for Fenton and photo-Fenton reactions are very similar: pH 3.5, around 400 micromol L(-1) H(2)O(2) and 87 micromol L(-1) Fe(II). Under such optimized conditions, the complete AMP removal was reached after 10 min and 3 min for Fenton and photo-Fenton reactions, respectively. A very similar removal profile in the first 2 min of reaction was observed for both systems with a high degree of degradation (close to 90%). After a 2-min treatment, the Fenton reaction became slower, and the IR product analysis suggests the formation of different oxidation intermediates. This observation was confirmed by the COD and TOC evolution during the reactions. The oxidation degree, measured as Average Oxidation State (AOS), indicates that the photo-Fenton reaction produces faster most of the oxidation intermediates. The antibacterial activity (AA) of the oxidized samples was determined using the inhibition halo methodology on agar plates cultured with Staphylococcus aureus bacteria. The course of AA is concomitant with the AMP removal, which indicates that the long-term intermediates do not present antibiotic properties., (Copyright (c) 2010 Elsevier B.V. All rights reserved.)

The present study provides results describing the degradation performance of the Sulfamethazine (SMT) antibiotic via photo-Fenton treatment. Experiments were carried out using 1 L solution samples of SMT (50 mg L(-1)) under different conditions. HPLC results reveal that both Fenton and photo-Fenton reactions were able to completely remove SMT antibiotic from the studied samples in less than 2 min treatment. Half-life times and kinetic parameters (assuming a pseudo-first-order kinetics at reaction initial stage, far from the equilibrium) for SMT degradation were determined and discussed. Hence, appropriate Fenton reagent loads are given to attain different targets proposed. TOC and HPLC data also revealed the presence of reaction intermediates; thus toxicity assays were performed regarding bacterial growth rate. The toxicity of an SMT solution was shown to increase during its degradation by means of photo-Fenton reactions., (Copyright (c) 2010 Elsevier Ltd. All rights reserved.)

An in situ arsenic removal method applicable to highly contaminated water is presented. The method is based in the use of steel wool, lemon juice and solar radiation. The method was evaluated using water from the Camarones River, Atacama Desert in northern Chile, in which the arsenic concentration ranges between 1000 and 1300 microg L(-1). Response surface method analysis was used to optimize the amount of zero-valent iron (steel wool) and the citrate concentration (lemon juice) to be used. The optimal conditions when using solar radiation to remove arsenic from natural water from the Camarones river are: 1.3 g L(-1) of steel wool and one drop (ca. 0.04 mL) of lemon juice. Under these conditions, removal percentages are higher than 99.5% and the final arsenic concentration is below 10 microg L(-1). This highly effective arsenic removal method is easy to use and inexpensive to implement.

This work studied the photocatalysed oxidation of the antibiotic oxolinic acid (OA) in an annular reactor operated with immobilized TiO(2) on sintered glass cylinders (SGC). Experiments were carried out in 1l solution of OA (18 mg l(-1)) at pH 9 with oxygen bubbling. Irradiation was performed with black light (36 W). The reaction was monitored by COD, TOC and average oxidation state (AOS) calculations. The antibacterial activity of intermediates was followed using the inhibition halo technique on Escherichia coli cultures. The initial antibiotic concentration decreases in one order of magnitude after 60 min irradiation, and was completely eliminated at 100 min reaction. The TOC was reduced in 54% and the AOS reach values around +3 indicating the formation of low molecular weight carboxylic acids. The oxidation reaction fit well with the Langmuir-Hinshelwood kinetic model indicating the dependence of reaction rate with initial adsorption step. The antibacterial activity of the solution decreases with antibiotic removal, demonstrating that intermediates do not present antibiotic activity.

Titanium dioxide was obtained in its pure form (TiO2) and in the presence of urea (u-TiO2) and thiourea (t-TiO2) using the sol-gel technique. The obtained powders were characterized by BET surface area analysis, Infrared Spectroscopy, Diffuse Reflectance Spectroscopy and the Rietveld refinement of XRD measurements. All the prepared catalysts show high anatase content (>99%). The a and b-cell parameters of anatase increase in the order TiO2u-TiO2>TiO2. The photocatalytic activities of the samples were determined on flumequine under solar-simulated irradiation. The most active catalysts were u-TiO2 and t-TiO2, reaching values over 90% of flumequine degradation after 15 min irradiation, compared with values of 55% for the pure TiO2 catalyst. Changing simultaneously the catalyst amount (t-TiO2) and pH, multivariate analysis using the response surface methodology was used to determine the roughly optimal conditions for flumequine degradation. The optimized conditions found were pH below 7 and a catalyst amount of 1.6 g L(-1).

This paper presents experimental results on the imidacloprid removal from wastewater using homogeneous photo-Fenton reactions illuminated with black light lamps. Multivariate experimental design was used to identify the effect of initial Fe(II) and H(2)O(2) concentrations on process performance. The initial iron concentration played a key role in the process kinetics, whereas hydrogen peroxide concentration directly affected the extent of the oxidation process. Imidacloprid degradation proceeded via two distinctive kinetics regimes, an initial stage of rapid imidacloprid reduction, followed by a slower oxidation process until complete removal. Under optimal conditions, more than 50% imidacloprid degradation was observed after less than 1 min treatment, and TOC and COD removal up to 65% and 80%, respectively, were measured after all hydrogen peroxide was consumed. Raw imidacloprid samples presented significant acute toxicity to Daphnia magna and genotoxic effects on Bacillus subtilis sp. Such toxic effects remained detectable even after significant pesticide removal had been achieved, due to the presence of toxic by-products. Both acute toxicity and genotoxicity disappeared after considerable mineralization resulting in final low molecular weight by-products. Results obtained here confirm that design and operation of photo-Fenton processes should focus on toxicity removal rather than on specific target pollutants.

Degradation of 2.5 mM EDTA-Fe solution was performed in a coupled photocatalytic-biological reactor. The system consists of a photochemical annular reactor filled with TiO2 immobilized on glass Raschig rings coupled with an activated sludge continuous reactor. Around 50% of EDTA degradation was reached after 150 min irradiation. Simultaneously a four-fold increase in biodegradability, measured as BOD5/COD ratio, was observed. The activated sludge is not capable to degrade the complex EDTA-Fe but it removed partially the COD and efficiently the BOD5 of the photochemically treated solution.

The interactions of TiO2 with phospholipid bilayers found in cell membrane walls were observed to perturb the bilayer structure under UVA light irradiation. The structure changes in the phospholipid bilayers upon contact with TiO2 under light and in the dark were followed by X-ray diffraction. Hydration effects at the semiconductor-phospholipid interface played an important role in the degradation of dimyristoylphosphatidylcholine (DMPC) and dimyristoylphosphatidylethanolamine (DMPE) bilayers taken as cell wall lipid bilayer models. Evidence is provided that the fluidity of the phospholipid bilayers plays a significant role when interacting in the dark with the TiO2 or in processes mediated by TiO2 under light irradiation.

Leather tanning effluents are a source of severe environmental impacts. In particular, the unhairing stage, belonging to the beamhouse processes, generates an alkaline wastewater with high concentrations of organic matter, sulphides, suspended solids, and salts, which shows significant toxicity. The objective of this work was to evaluate the biodegradation of this industrial wastewater by combined oxidative and biological treatments. An advanced oxidation process (AOP) with Fenton's reagent was used as batch pretreatment. The relationships of H2O2/Fe2+ and H2O2/COD were 9 and 4, respectively, reaching an organic matter removal of about 90%. Subsequently, the oxidised beamhouse effluent was fed to an activated sludge system, at increasing organic load rates (OLR), in the range of 0.4 to 1.6 g COD/L x day. The biological organic matter removal of the pre-treated wastewater ranged between 35% and 60% for COD, and from 60% to 70% for BOD. Therefore, sequential AOP pretreatment and biological aerobic treatment increased the overall COD removal up to 96%, compared to 60% without pretreatment. Bioassays with D. magna and D. pulex showed that this kind of treatment achieves only a partial toxicity removal of the tannery effluent.

Multivariate experimental design was applied to the treatment of a cellulose conventional bleaching effluent in order to evaluate the use of the Fenton reagent under solar light irradiation. The effluent was characterised by the general parameters total organic carbon (TOC), chemical oxygen demand and color, and it was analysed for chlorinated low molecular weight compounds using GC-MS. The main parameters that govern the complex reactive system: Fe(II) and H(2)O(2) initial concentration, and temperature were simultaneously studied. Factorial experimental design allowed to assign the weight of each variable in the TOC removal after 15 min of reaction. Temperature had an important effect in the organic matter degradation, especially when the ratio of Fenton reagents was not properly chosen. Fenton reagent under solar irradiation proved to be highly effective for these types of wastewaters. A 90% TOC reduction was achieved in only 15 min of treatment. In addition, the GC-MS analysis showed the elimination of the chlorinated organic compounds initially detected in the studied bleaching effluents.

Mineralization of a 5 mM EDTA solution at pH 3 was evaluated via TOC removal under UV-C irradiation in the presence of H2O2 at various conditions. The highest TOC removal (78%) was obtained using a 40:1 H2O2/EDTA molar ratio, after 540 min irradiation. However, a 20:1 ratio gave slightly lower results, being economically more attractive. Best results of TOC removal were obtained under pH controlled conditions. Addition of TiO2 (1 g l(-1)) was detrimental, even in the presence of H2O2, indicating that at this concentration, TiO2 inhibits the mineralization, probably by scattering or by screening of the light.

Photocatalysis using ZnO-Fe2O3 coupled catalyst removed partially the organic matter dissolved in kraft black liquor obtained from pinus wood cooking. The photo-assisted oxidation using different ZnO/Fe2O3 ratios was studied following the CO, evolution during the course of the reaction. A synergy of the composite improves the mineralization observed. The optimal ZnO to Fe2O3 ratio varied from 0.5 to 0.7 which allowed the highest mineralization rates.

The photocatalytic degradation of three reactive azo dyes (yellow-2, orange-16 and red-2) and one anthraquinone reactive dye (blue-19) was studied. The reactions were carried out in a reactor with recirculation using TiO2 immobilised on glass Raschig rings (system A) and compared with a batch system using the catalyst in aqueous suspension (system B). Both reaction systems were irradiated with a 125 W, lambda > 254 nm lamp. The suspended TiO2 system was also studied using a 125 W 360 nm lamp (system C). Kinetic studies indicated a rapid colour removal, following the order B > A > C. The same trend was observed in COD and TOC removal profiles. The energy consumption per order of magnitude of catalytic degradation of the dyes was lower in the batch reactor (system B) than in the reactor with recirculation and immobilised TiO2 (system A).

The oxidation of a 186 ppm 6-chlorovanillin solution was performed using impregnated TiO2 glass rings in a 1 l photochemical reactor. Fifty per cent degradation was obtained after 60 min with recirculation of the solution. Then, oxidised samples were submitted under aerobic conditions to bacterial degradation in the Pseudomonas paucimobilis (S37) and Burkholderia cepacia (PZK). Both selected aerobic bacteria degrade more efficiently the photocatalysed samples, being PZK strain better than S37. A first-order kinetic was observed in both systems photocatalytic and bacterial degradation.

A cellulose bleaching effluent (E1) was degraded in batch conditions by photocatalysis using TiO2 and ZnO supported on glass Raschig rings. The effluent was completely decolourised and the total phenol content was reduced by 85% after 120 min treatment with both catalysts. Partial mineralization of the organic matter was confirmed by total organic carbon (TOC) reduction, approximately 50%. The residual organic matter shows a low acute toxicity as compared to the initial values and AOX values are strongly reduced after the photocatalytic oxidation. Molecular mass distribution showed that high molecular mass compounds were almost completely degraded.

The degradation, by several advanced oxidation reactions, of a pulp mill ECF bleaching effluent, was studied. The initial biodegradability of the organic matter present in the effluent, estimated as the BOD5/COD, was low (0.3). When the effluent was submitted to ozonation and to five different advanced oxidation systems (O3/UV, O3/UV/ZnO, O3/UV/TiO2, O2/UV/ZnO, O2/UV/TiO2), the biodegradability increase significantly. After five minutes of reaction, the O3/UV system appears as the most efficient in to transform the organic matter to more biodegradable forms. A similar effect was observed when the effluent was submitted to an activated sludge treatment. The COD, TOC and toxicity reduction correlated well with the biodegradability enhancement after AOPs treatments.