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TiO2 Photocatalysts for Degradation of Micropollutants in Water
... Nowadays, water pollution is a worldwide problem, according to UNESCO between two, and three billion people lack access to water [1]. Nevertheless, human activities, industrial development, and the emerging contaminants such as textile dyes, active pharmaceutical ingredients, and personal care products pollute water bodies. ...
Pd/ZnO nanocomposites were successfully synthesized by means of one and two pot synthesis and applied in the photodegradation of Rh6G. The nanocomposites were characterized by XRD, SEM, TEM, FTIR and micro-Raman spectroscopies. It was found the presence of PdZn2, PdO and agglomerated particles in the support surface for the Palladium-based nanocomposites fabricated by one-pot route; the two-step method allowed the formation of spherical Pd nanoparticles, with homogeneous distribution in the nanocomposite matrix, with an average size of 2.16 nm. The results show higher photocatalytic efficiency for the samples fabricated under the two-step approach compared to the one-pot synthesis. Based on experimental results, density functional theory (DFT) calculations were carried out to understand the enhancement photocatalytic of Pd/ZnO nanocomposites. To achieve it, the ZnO (001) and (101) surfaces were built and decorated by different Pd coverages. The theoretical results indicated two different photocatalytic mechanisms. In ZnO (001) case, the electrons flowed from surface to Pd, generating the superoxide radical anion (⋅O2−). Furthermore, the density of states of the ZnO (001) surface was modified by impurity Pd–d states at proximity to the conduction states, which may work as electron acceptors states. On the other hand, we found that the electrons flow from Pd to ZnO (101) surface, inducing the formation of ⋅OH and ⋅O2− for the degradation of Rh6G. The density of states of the ZnO (101) revealed a reduction in its bandgap, due to Pd–d states localized above valence states. Hence, our theoretical results suggest that the Pd–d states may facilitate the mobility of electrons and holes in (001) and (101) surfaces, respectively, reducing the rate of charge recombination.
The European Water Framework Directive (WFD) (2000/60/EC) is the most visionary piece of European environmental legislation that aims to achieve good water status of both surface water and groundwater bodies. The Directive provides a fundamental basis for surface water monitoring activities in the European Member States. The objective of this study is to investigate the occurrence of micropollutants in the Yesilirmak River and to develop a cost-effective monitoring strategy based on spatiotemporal data. A 2-year seasonal monitoring program was conducted between 2016 and 2018, and the water samples were analyzed for 45 priority substances as defined by the WFD and 250 national river basin–specific pollutants. In the basin, 166 pollutants were quantified in at least one of the samples with individual concentrations ranging from 6 × 10⁻⁶μg/L to 100 mg/L. Fifty-four pollutants with a frequency of occurrence greater than 5% were selected for further evaluation. Based on statistical evaluation of the data, 20 pollutants were identified as the pollutants of primary concern. These 20 pollutants were grouped under three categories (metals, biocides, and industrial organic compounds) and their spatiotemporal distributions in the basin were assessed to establish a monitoring strategy specific to each pollutant category. The results of the study revealed that the common season for the monitoring of all pollutant categories was the spring. This study provides a generic methodology for the development of a cost-effective water quality monitoring strategy, which can be applicable for use in different basins and pollutant datasets.
The persistence of many micropollutants in water and wastewater is of great concern to the contemporary scientific community. Several types of advanced techniques such as heterogeneous photocatalysis are being used for the degradation of micropollutants in waters from domestic, industrial, and agricultural activities. Thus, structured photocatalytic systems are a great alternative in the development of photocatalytic reactors and continuous water treatment systems, as they present good autonomy during the treatment process. Many aspects such as type and geometry of the catalytic structure to be developed must be carefully chosen for the proper functioning of the system, as well as the best routes by which the photocatalysts will be immobilized. In this sense, this work brings the main photocatalytic coating techniques in low-cost structures for the treatment of water and wastewater contaminated with micropollutants. The methodologies and synthesis parameters that can influence the final result of the coating were highlighted, as well as the ability to reuse photocatalysts and methods for pretreating the structural surface. The dip-coating technique was the most reported among the current works due to its simplicity and, predominantly, the pretreatment techniques of the structure are still cleaning the surface with water, soap, and also some alcohols.
Despite a large number of publications in the field, photocatalytic water treatment is still somewhat disconnected from real world application, where there is a clear potential for use. Publications which focus upon overcoming implementation hurdles are often overlooked, but are key in making photocatalytic water purification a reality. This perspective aims to address this, drawing attention to recent developments in materials design, reactor setup and testing methods which take steps towards application beyond the laboratory.
This paper compares the removal degrees of selected contaminants of emerging concern in water solutions during advanced oxidation processes (AOPs), such as H2O2, O3, UV, UV/TiO2, UV/H2O2, and UV/O3. The tested micropollutants belong to the following groups: pharmaceuticals, dyes, UV filters, hormones, pesticides, and food additives. The highest removal rate of pharmaceutical compounds was observed during the UV/TiO2 process. The decomposition of hormones in this process exceeded 96% and the concentration of the UV filter dioxybenzone was reduced by 75%. The pesticide triallat and the food additive butylated hydroxytoluene were most effectively oxidized by the UV process and their removal degrees exceeded 90%. The lowest removal degree in all examined processes was observed in the case of caffeine. Toxicological analysis conducted in post-processed water samples indicated the generation of several oxidation by-products with a high toxic potential. The presence of those compounds was confirmed by the GC-MS analysis. The performance of the UV/O3 process leads to the increase of the toxicity of post-processed water solutions, especially solutions containing degradation by-products of carbamazepine, diclofenac sodium salt, acridine, trialatte, triclosan, and β-estradiol were characterized by high toxicity.
Little is known about the mechanisms influencing the differences in attenuation of antibiotics between rivers. In this study, the natural attenuation of four antibiotics (azithromycin, clarithromycin, sulfapyridine, and sulfamethoxazole) during transport along the Thames River, UK, over a distance of 8.3 km, and the Katsura River, Japan, over a distance of 7.6 km was compared. To assist interpretation of the field data, the individual degradation and sorption characteristics of the antibiotics were estimated by laboratory experiments using surface water or sediment taken from the same rivers. Azithromycin, clarithromycin, and sulfapyridine were attenuated by 92, 48, and 11% in the Thames River stretch. The first-order decay constants of azithromycin and sulfapyridine were similar to those in the Katsura River, while that of clarithromycin was 4.4 times higher. For sulfamethoxazole, the attenuation was limited in both rivers. Loss of sulfapyridine was attributed to both direct and indirect photolysis in the Thames River, but to only direct photolysis in the Katsura River. Loss of azithromycin and clarithromycin was attributed to sorption to sediment in both rivers. The probable explanation behind the difference in loss rates of clarithromycin between the two rivers was considered to be sediment sorption capacity.
The photocatalytic degradation of the model pollutant carbamazepine (CBZ) was investigated under simulated solar irradiation with an N-doped TiO₂-coated Al₂O₃ photocatalytic membrane, using different water types. The photocatalytic membrane combines photocatalysis and membrane filtration in a single step. The impact of each individual constituent such as acidity, alkalinity, dissolved organic matter (DOM), divalent cations (Mg(2+) and Ca(2+)), and Cl(-) on the degradation of CBZ was examined. CBZ in water was efficiently degraded by an N-doped TiO₂-coated Al₂O₃ membrane. However, elements added to the water, which simulate the constituents of natural water, had an impact on the CBZ degradation. Water alkalinity inhibited CBZ degradation mostly due to increase in pH while radical scavenging by carbonate was more dominant at higher values (>200 mg/L as CaCO₃). A negative effect of Ca(2+) addition on photocatalytic degradation was found only in combination with phosphate buffer, probably caused by deposition of CaHPO₄ or CaHPO₄·2H₂O on the catalyst surface. The presence of Cl(-) and Mg(2+) ions had no effect on CBZ degradation. DOM significantly inhibited CBZ degradation for all tested background organic compounds. The photocatalytic activity of N-doped TiO₂-coated Al₂O₃ membranes gradually decreased after continuous use; however, it was successfully regenerated by 0.1% HCl chemical cleaning. Nevertheless, dissolution of metals like Al and Ti should be monitored following acid cleaning.
Water quality is currently a subject of increasing concern, especially because of the emerging pollutants contaminating aquatic environment. The aim of this study was to verify the presence of emerging pollutants in the Iguaçu River, from source to mouth, such as: pharmaceuticals, including acetylsalicylic acid (ASA), salicylic acid, ketoprofen (KET), naproxen (NAP), gemfibrozil and fenofibrate; female sex hormones, including estradiol (E1), ethinylestradiol (EET) and estrone (E2); UV filters, including 4-methylbenzylidene camphor and octylmethoxycinnamate; and caffeine (CAF). The extracted pollutants were purified using solid phase extraction and then analysed by liquid chromatography with diode array detection and gas chromatography-tandem mass spectrometry. All analysed compounds were detected in at least one site in one sample. The analysis revealed maximum concentrations of 27.0 μg L–1 CAF, 5.17 μg L–1 ASA, 0.34 μg L–1 of NAP, 0.62 μg L–1 KET, 1.42 μg L–1 E1, 1.48 μg L–1 EET, and 0.94 μg L–1 E2. The results indicated that Iguaçu river water is contaminated with emerging pollutants and nutrients and that this may be due to domestic sewage and water from tributary rivers mixing with Iguaçu river water. Statistical analysis demonstrated that the study of emerging environmental contaminants is a useful tool to determine if contamination is due to domestic sewage input once traditional physical, chemical and spectroscopic analyses have been insufficient to prove an anthropogenic influence.
Pharmaceutics and personal care products (PPCPs) are raising growing concern due to their widespread usage and resistance to conventional remediation techniques. Several of them raise significant health and environmental concerns, especially when present in complex mixtures. Due to their chemical resistance, Advanced Oxidation Processes (AOPs) are needed for their complete removal from surface and wastewaters. In the present work, photocatalysis by titanium dioxide (TiO2) under UV and simulated solar irradiation was adopted to degrade tetracycline hydrochloride, paracetamol, caffeine and atenolol, both as single pollutants and in mixtures. All molecules showed high removal and mineralization degrees. Moreover, no interference effects decreased the efficiency of the processes in the case of pollutant mixtures, achieving 60% of mineralization after 6 h. An immobilized TiO2 system was also developed by depositing titania on titanium meshes. A 50% mineralization degree of the pollutant mixture was obtained after 6 h, revealing a suitable efficiency for field applications. Eventually, the impact of the matrix composition on the photocatalytic efficiency was investigated by studying the reaction both in simulated drinking water and in commercial bottled mineral water. The scavenger role played by HCO3(-) species appears to be dominant in inhibiting the mineralization.
In the present scenario, environmental laws have become stringent towards health, economy and reduction of pollution. The pollution is a result of discharge of various organic and inorganic substances into the environment. The sources of pollution include domestic agricultural and industrial water. Conventional techniques such as chemical precipitation, carbon adsorption, ion exchange, evaporations and membrane processes are found to be effective in treatment of waste and sewage water. Recently, biological treatments have gained popularity to remove toxic and other harmful substances. The objective of the paper is to make comprehensive review including the performance of each technique in treatment of waste and sewage water. The research directions are also suggested based on the review.
Carbamazepine is one of the pharmaceutical compounds frequently detected in the receiving waters and water bodies. The main objective of this study was to develop a quadratic model to predict carbamazepine (CBZ) photocatalytic removal through a response surface methodology. A factorial plan (linear model; 24 experiments) was used to determine the contribution of individual factors (pH, CBZ concentration, photocatalyst concentration, and treatment time) and interactions among the factors. Pollutant concentration and treatment time were found to be the most important parameters influencing the oxidation rate, with respective contributions of 19.22 and 71.55 %. Central composite methodology was then applied to determine the optimal experimental parameters for CBZ oxidation. The highest percentage of CBZ removed was 94.67 ± 0.51 %, recorded using a pH of 5, a minimal CBZ concentration of 10 mg/L, a photocatalyst concentration of 1.14 g/L, and a treatment time of 90 min. The effects of different anions (NO3− and SO42−) and cations (Cu2+, Cr3+, Zn2+) were also studied. Copper was found to have both catalytic and inhibitory effects on CBZ removal rate.
Heterotrophic system for carbon sequestration is gaining importance in the recent decades. Carbonic anhydrase (CA) is a major enzyme involved in carbon sequestration and biomineralization process. In this paper, we evaluate the effect of pesticide on CA activity using inhibitory assay. 2,4-D, being one of the most extensively used pesticide, being deleterious to soil health, its usage should be minimized to regain the soil health. Maximum inhibitory constant (Ki) was observed for 5% 2,4-D (49.53 mM) followed by 5% glyphosate (43.92 mM). The maximum Km increase with increase in pesticide concentration by 3.05-fold was in case of glyphosate which was higher than that of 2,4-D (2.08-fold) and dichlorvos (2.38-fold). Moreover, we evaluated the carbon sequestration using CA enzyme in the soil microcosm. In the present study, we identified the negative impact of 2,4-D on carbonic anhydrase produced by Bacillus halodurans PO15. The inhibition was a mixed type and had significantly lowered the carbon reduction to about 2.38 ± 0.17% in a soil microcosm study. Based on the molecular docking, the inhibition was contributed due to weak H-bonding interaction with amino acid residues (Gly65, Gly95, Val147, Ser150 and Gly65, Ser146, and Ser150).
Titanium dioxide (TiO2) is well-known as an active photocatalyst for degradation of various organic pollutants. Over the years, a wide range of TiO2 nanoparticles with different phase compositions, crystallinities, and surface areas have been developed. Due to the different methods and conditions used to synthesize these commercial TiO2 nanoparticles, the properties and photocatalytic performance would also be different from each other. In this study, the photocatalytic removal of 2,4-dichlorophenoxyacetic acid (2,4-D) and 2,4,5- trichlorophenoxyacetic acid (2,4,5-T) was investigated on commercial Evonik P25, Evonik P90, Hombikat UV100 and Hombikat N100 TiO2 nanoparticles. Upon photocatalytic tests, it was found that overall, the photocatalytic activities of the P25 and the P90 were higher than the N100 and the UV100 for the removal of both 2,4-D and 2,4,5-T. The high activities of the P25 and the P90 could be attributed to their phase compositions, which are made up of a mixture of anatase and rutile phases of TiO2. Whereas, the UV100 and the N100 are made up of 100% anatase phase of TiO2. The synergistic effect of the anatase/rutile mixture was reported to slow down the recombination rate of photogenerated electron-hole pairs. Consequently, the photocatalytic activity was increased on these TiO2 nanoparticles.
Trace organic contaminant (TrOC) studies in Australia have, to date, focused on wastewater effluents, leaving a knowledge gap of their occurrence and risk in freshwater environments. This study measured 42 TrOCs including industrial compounds, pesticides, and pharmaceuticals and personal care products by liquid chromatography tandem mass spectrometry at 73 river sites across Australia quarterly for 1 yr. Trace organic contaminants were found in 92% of samples, with a median of three compounds detected per sample (maximum 18). The five most commonly detected TrOCs were the pharmaceuticals salicylic acid (82%, maximum = 1530 ng/L), paracetamol (also known as acetaminophen; 45%, maximum = 7150 ng/L), and carbamazepine (27%, maximum = 682 ng/L), caffeine (65%, maximum = 3770 ng/L), and the flame retardant (2-chloroethyl) phosphate (44%, maximum = 184 ng/L). Pesticides were detected in 28% of the samples. To determine the risk posed by the detected TrOCs to the aquatic environment, hazard quotients were calculated by dividing the maximum concentration detected for each compound by the predicted no-effect concentrations. Three of the 42 compounds monitored (the pharmaceuticals carbamazepine and sulfamethoxazole and the herbicide simazine) had a hazard quotient >1, suggesting that they may be causing adverse effects at the most polluted sites. A further 10 compounds had hazard quotients >0.1, indicating a potential risk; these included four pharmaceuticals, three personal care products, and three pesticides. Most compounds had hazard quotients significantly <0.1. The number of TrOCs measured in this study was limited and further investigations are required to fully assess the risk posed by complex mixtures of TrOCs on exposed biota.
Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.
Brookite is the least studied TiO2 photocatalyst due to the difficulties usually encountered in order to obtain it as a pure phase. In this review, a comprehensive survey of the different methods available for preparing brookite powders and films is reported. Attention has been paid both to the most traditional methods, such as hydrothermal processes at high temperatures and pressures, and to environmentally benign syntheses using water soluble compounds and water as the solvent. Papers reporting the photocatalytic activity of pure and brookite-based samples have been reviewed.
The prototypical photocatalyst TiO2 exists in different polymorphs, the most common forms are the anatase- and rutile-crystal structures. Generally, anatase is more active than rutile, but no consensus exists to explain this difference. Here we demonstrate that it is the bulk transport of excitons to the surface that contributes to the difference. Utilizing high -quality epitaxial TiO2 films of the two polymorphs we evaluate the photocatalytic activity as a function of TiO2-film thickness. For anatase the activity increases for films up to ~5 nm thick, while rutile films reach their maximum activity for ~2.5 nm films already. This shows that charge carriers excited deeper in the bulk contribute to surface reactions in anatase than in rutile. Furthermore, we measure surface orientation dependent activity on rutile single crystals. The pronounced orientation-dependent activity can also be correlated to anisotropic bulk charge carrier mobility, suggesting general importance of bulk charge diffusion for explaining photocatalytic anisotropies.
The global population is increasing and because of this, the world may experience great fresh water scarcity. Our water resources are limited and, hence, water treatment and recycling methods are the only alternatives for getting fresh water in the coming decades. Therefore, there is a great need for the development of a suitable, inexpensive and rapid wastewater treatment techniques and reuse or conservation methods in the present century. The different types of water treatment and recycling techniques have been discussed in terms of their basic principles, applications, costs, maintenance and suitability. Additionally, a systematic approach to water treatment and recycling involving their understanding, evaluation and selection parameters has been presented. A brief guideline for the selection of the appropriate technologies for specific applications has been evaluated. This review adds to the global discussions on water scarcity solutions.
This study provides the first investigation on the occurrence of human pharmaceuticals in the tropical aquatic environment of Malaysia. Water samples were collected at seven different sites along the Langat River and effluents from five sewage treatment plants (STPs) in Langat River Basin. Samples were extracted by solid phase extraction (SPE) and analyzed using liquid chromatography coupled with a tandem mass spectrometry (LC-MS/MS) for 18 pharmaceuticals from six therapeutic classes and one metabolite. Fifteen out of these 19 pharmaceuticals were detected in the river water samples. Mefenamic acid, salicylic acid and glibenclamide were detected in all river water samples indicating their ubiquitous nature and resistance to degradation under the warm and humid tropical conditions. The median concentrations of detected pharmaceuticals ranged from less than the method detection limit (<MDL) for furosemide, loratadine, salbutamol, perindopril, metoprolol and nifedipine to 112.7?ng?L-1 for diclofenac. A similar number of pharmaceuticals were detected in the STPs effluents samples. Several of these pharmaceuticals, namely salbutamol, atenolol, metoprolol, mefenamic acid, salicylic acid and furosemide were detected in all the STPs effluents samples. The median concentrations for the detected pollutants ranged between <MDL for lovastatin and amlodipine to 1994?ng?L-1 for metformin. The highest concentration detected in the river water samples was for acetaminophen (346.3?ng?L-1) and in STPs effluents was for metformin (34228?ng?L-1). The concentrations of most analytes found in this study were comparable to those reported in the other parts of the world. However, this is the first time amlodipine is detected in the environmental samples.
Titanium dioxide nanoparticles consisting of pure anatase, anatase-rich, brookite-rich, and pure brookite modifications were synthesized and characterized by X-ray diffraction, field emission-scanning electron microscopy and nitrogen adsorption. The phase transformations among the three modifications of TiO(2) (anatase, brookite, and rutile) and the photocatalytic activities of these nanoparticles were investigated by heat treatment over the temperature range from 400 to 800 °C and by the photooxidation of methanol, respectively. Direct transformation of anatase and brookite to rutile was observed, while in the case of the anatase-brookite mixture, anatase transforms firstly to brookite and then to rutile. The photocatalytic activity measurements indicate that brookite nanoparticles exhibit higher photocatalytic activities than anatase, and a comparable activity to that of the anatase-rich nanoparticles. The phase transformations and photocatalytic results are discussed regarding their dependence on crystallite size, surface area, and phase composition.
The civilian, commercial, and defense sectors of most advanced industrialized nations are faced with a tremendous set of environmental problems related to the remediation of hazardous wastes, contaminated groundwaters, and the control of toxic air contaminants. Problems with hazardous wastes at military installations are related in part to the disposal of chemical wastes in lagoons, underground storage tanks, and dump sites. Typical wastes of concern include heavy metals, aviation fuel, military-vehicle fuel, solvents and degreasing agents, and chemical byproducts from weapons manufacturing. In the civilian sector, the elimination of toxic and hazardous chemical substances such as the halogenated hydrocarbons from waste effluents and previously contaminated sites has become a major concern. General classes of compounds of concern include: solvents, volatile organics, chlorinated volatile organics, dioxins, dibenzofurans, pesticides, PCB's, chlorophenols, asbestos, heavy metals, and arsenic compounds. Advanced physicochemical processes such as semiconductor photocatalysis are intended to be both supplementary and complementary to some of the more conventional approaches to the destruction or transformation of hazardous chemical wastes such as high-temperature incineration, amended activated sludge digestion, anaerobic digestion, and conventional physicochemical treatment. 441 refs.
We investigated the degradation of carbamazepine by photolysis/ultraviolet (UV)-C only and titanium dioxide photocatalysis. The degradation of carbamazepine by UV-only and titanium-dioxide-only (adsorption) reactions were inefficient, however, complete degradation of carbamazepine was
observed by titanium dioxide photocatalysis within 30 min. The rate of degradation increased as initial carbamazepine concentration decreased, and the removal kinetics fit well with the Langmuir‐Hinshelwood model. The addition of methanol, a radical scavenger, decreased carbamazepine
removal, suggesting that the hydroxide radical played an important role during carbamazepine degradation. The addition of oxygen during titanium dioxide photocatalysis accelerated hydroxide radical production, thus improving mineralization activity. The photocatalytic degradation was more
efficient at a higher pH, whereas the removal of carbamazepine and acridine (a major intermediate) were more efficient under aerobic conditions. The mineralization of carbamazepine during photocatalysis produced various ionic by-products such as ammonium and nitrate by way of nitrogen dioxide.
Water quality issues are a major challenge that humanity is facing in the twenty-first century. Here, we review the main groups of aquatic contaminants, their effects on human health, and approaches to mitigate pollution of freshwater resources. Emphasis is placed on chemical pollution, particularly on inorganic and organic micropollutants including toxic metals and metalloids as well as a large variety of synthetic organic chemicals. Some aspects of waterborne diseases and the urgent need for improved sanitation in developing countries are also discussed. The review addresses current scientific advances to cope with the great diversity of pollutants. It is organized along the different temporal and spatial scales of global water pollution. Persistent organic pollutants (POPs) have affected water systems on a global scale for more than five decades; during that time geogenic pollutants, mining operations, and hazardous waste sites have been the most relevant sources of long-term regional and local water pollution. Agricultural chemicals and waste-water sources exert shorter-term effects on regional to local scales.
Even though heterogeneous photocatalysis appeared in many forms, photodegradation of organic pollutants has recently been the most widely investigated. By far, titania has played a much larger role in this scenario compared to other semiconductor photocatalysts due to its cost effectiveness, inert nature and photostability. Extensive literature analysis has shown many possibilities of improving the efficiency of photodecomposition over titania by combining the photoprocess with either physical or chemical operations. The resulting combined processes revealed a flexible line of action for wastewater treatment technologies. The choice of treatment method usually depends upon the composition of the wastewater. However, a lot more is needed from engineering design and modelling for successful application of the laboratory scale techniques to large-scale operation. The present review paper seeks to offer an overview of the dramatic trend in the use of the TiO2 photocatalyst for remediation and decontamination of wastewater, report the recent work done, important achievements and problems.
Micropollutants have been linked to freshwater and human toxicity. Their occurrence in water bodies arises from different causes, including the discharge of effluents from conventional urban wastewater treatment plants, which are not designed for their removal. The addition of an advanced treatment process for this purpose will allow a toxicity reduction; however, such will also imply further resources and energy use resulting in other environmental impacts. Energy use is a particularly relevant hotspot of the environmental impacts associated with advanced treatments; therefore, solar-based treatments have great potential in this field. The present study assessed the environmental impacts via life cycle assessment (LCA) of five solar-based treatments – solar photolysis (with and without H2O2), photocatalysis using TiO2 (with and without H2O2) and circumneutral photo-Fenton – using a pilot-scale compound parabolic collector photoreactor to select the most suitable option for the removal of micropollutants (carbamazepine, diclofenac and sulfamethoxazole; 5 μg/L) from a secondary-treated wastewater. The ranking of solar treatments per highest generated impacts is, overall, as follows: circumneutral photo-Fenton > TiO2-P25/H2O2 > TiO2-P25 > solar/H2O2 > solar. While solar photolysis uses fewer resources and energy, thus generating lower environmental impacts, the common incomplete mineralization of the parent micropollutants implies that toxicity reduction cannot be guaranteed in this case. Aiming for a balance between ecotoxicity reduction and the impacts caused by the application of each technology, the solar TiO2-P25 treatment, which was here investigated by LCA for the first time to remove organic micropollutants from secondary-treated urban wastewater, appears to be the most suitable option at the studied conditions (and when TiO2 is reused at least 5 times). One of the environmental downfalls of the assessed treatments is the energy required to produce the chemicals, and so the importance of minimizing external energy use during the application of advanced treatment processes is reinforced.
A process combining three steps has been developed as tertiary treatment for waste water in order to remove micropollutants not eliminated by a conventional waste water treatment plant (WWTP). These three processes are ozonation, photocatalysis and granulated activated carbon adsorption. This process has been developed through three scales: laboratory, pilot and pre-industrial scale. At each scale, its efficiency has been assessed on different waste waters: laboratory-made water, industrial waste water (one from a company cleaning textiles and another from a company preparing culture media, both being in continuous production mode) and municipal waste water. At laboratory scale, a TiO2-based photocatalytic coating has been produced and the combination of ozonation-UVC photocatalytic treatment has been evaluated on a laboratory-made water containing 22 micropollutants. The results showed an efficient activity leading to complete or partial degradation of all compounds and an effective carbon for residual micropollutants adsorption was highlighted. Experiments at pilot scale (100 L of water treated at 500 L/h from a tank of 200 L) corroborated the results obtained at lab-scale. Moreover, tests on municipal waste water showed a decrease in toxicity, measured on Daphnia Magma, and a decrease in micropollutant concentration after treatment. Finally, a pre-industrial container was built and evaluated as tertiary treatment at the WWTP Duisburg-Vierlinden. It is shown that the main parameters for the efficiency of the process are the flow rate and the light intensity. The photocatalyst plays a role by degrading the more resistant micropollutants. Adsorption permits an overall elimination >95% of all molecules detected.
Titanium dioxide (TiO2) is widely used in a variety of products including cosmetics. TiO2 in its nanoparticle form (nano‐TiO2) is now the only form used as an ultraviolet (UV) filter in sunscreens, but also in some day creams, foundations and lip balms. While its efficacy as a UV filter is proven in the prevention of skin cancers and sunburns, some concerns have been raised about its safety. Indeed, considering its small size, nano‐TiO2 is suspected to penetrate dermal, respiratory or gastrointestinal barriers, disseminate in the body and therefore constitute a potential risk to the consumer. At the skin level, most studies performed in humans or animals showed that nano‐TiO2 did not penetrate beyond the outer layers of stratum corneum to viable cells and did not reach the general circulation, either in healthy or in compromised skin. The Scientific Committee on Consumer Safety (SCCS) considers nano‐TiO2 as a non‐sensitizer and as mild‐ or non‐irritant to skin and concludes in no evidence of carcinogenicity (supported by the European Chemicals Agency), mutagenicity or reproductive toxicity after dermal exposure to nano‐TiO2. According to the SCCS, nano‐TiO2 from sunscreens does not present any health risk when applied on the skin at a concentration up to 25%. However, the SCCS does not recommend the use of nano‐TiO2 in formulations that may lead to exposure of the consumer's lungs by inhalation (sprayable products and powders). Indeed, even if human data are sparse and inconsistent, lung inflammation was reported in animals. In 2016, the EU Cosmetic Regulation made nano‐TiO2 as an authorized UV filter, except in products that could lead to exposure of the lungs. After oral exposure, nano‐TiO2 absorption and toxicity are limited. The incidental oral exposure to nano‐TiO2 contained in lip balms is thus not expected to induce adverse health effects.
The paper proposes discussions of some concrete datasets resulted for three solutions of wastewaters management systems applied in case of a Romanian petroleum chemical company. These management options, differing especially in type (centralized or decentralized system) and wastewaters treatment system, were emphasized, mainly by real datasets on treatment performance, polluting species removals, risk of some residuals in treated effluents and natural watercourse nearby, but also environmental impact assessment, using the alternative methodology of global pollution index (I*GP). Interpreting datasets based on in-time analyzed physical-chemical quality indicators and river characteristics, it was estimated the standard quality classification of receiving watercourse as ‘medium’ (water quality indice, WQI = 55.58 − 67.47), affected more or less by treated effluents discharged in it. The environmental risks of some selected residuals in treated effluents and natural aquatic receptor were assessed by the risk quotient (RQ) which appreciated the risk of residuals towards aquatic life as no to low-medium level, with few exceptions. The impact assessment results conclude an admissible pollution status of natural water receptor due to company wastewaters mechanical-chemical-biological treatment plant activities, in decentralized (I*GP = 1.73) and centralized (I*GP = 1.83) system, but generating discomfort effects to aquatic life due to only mechanical-chemical treatment plant operating in decentralized system (I*GP = 2.205). Direct discharge of un-treated industrial wastewaters had been interdicted. These real results underline that decentralized systems are reliable, qualitatively efficient and costly effective, offering long-term solution, and that all wastewaters management strategies of petroleum chemical company had been adapted to specific on-site functioning situations.
With the rising of the aquaculture since the 1980s, China has become the only country that the output of aquaculture production exceeded the catches since 1997. However, the environmental contamination problems caused by application of pharmaceuticals in the aquaculture industry have been increasingly serious in recent years. This review summarized and discussed the studies on the pharmaceutical pollution in the aquaculture of China, and the research topics included distribution of sulfonamides in the coastal zone, characterization of residual antibiotics in aquaculture water in southeastern coast, pollution characterization of antibiotics in the Pearl River Delta, and antibiotic resistance genes (ARGs) existed in the Beijiang River. Countermeasures against pharmaceuticals pollution in aquaculture were addressed including rules released by the Chinese government (e.g., the Ministry of Agriculture). Issues on ecological prevention, vaccination prevention, drug prevention in aquaculture were further discussed. Some methods for remediation of polluted surface water in aquaculture, e.g., chemical oxidation, biological remediation, and photocatalytic degradation, were also introduced.
In this study, the concentrations of 15 pharmaceuticals were monitored during four seasons (February, May, July, and November 2010) along a 32 km stretch of a highly wastewater polluted watercourse (River Rakkolanjoki, Lake Haapajärvi) in eastern Finland. The aim was to study the seasonal variation in the elimination of the pharmaceuticals and the stability of the compounds along the watercourse. The analysis was carried out using a liquid chromatography tandem mass spectrometry (LC-MS/MS) method combined with extraction and preconcentration on HLB solid phase extraction (SPE) cartridges. Pharmaceutical concentrations were determined at 9 points along the watercourse, and loads and removal of parent compounds were calculated using flow data from the discharge point and the last sampling point. The pharmaceuticals were found in concentrations ranging from low ng l-1 to low µg l-1 values at the discharge point and at concentrations of 0 – 556 ng l-1 at the last sampling point. The rate of elimination of the pharmaceutical load was significantly higher in May and July than in February and November. There were clear differences in the stability of the individual compounds along the watercourse. Carbamazepine was not eliminated during any season, while ibuprofen, ketoprofen and sertraline were fully eliminated over the studied stretch of river during the summer months. Other compounds showed continuous elimination independent of the season, indicating different elimination paths, such as sorption, biodegradation and phototransformation, for the studied compounds.
Environmentally sustainable solutions for wastewater management including the improvement of water quality and water recycling are considered key priority areas globally. The challenges facing our water resources are unprecedented due to the presence of organic and inorganic pollutants derived from numerous anthropogenic activities. This situation has been further complicated by emerging persistent contaminants such as pharmaceuticals which possess low biodegradability and resistance to chemical and biological treatments. Excretion of pharmaceuticals and their metabolites via human waste, improper disposal and veterinary applications is recognized as the principal sources of pharmaceuticals ending up in various compartments of the environment. Heterogeneous photocatalysis using semiconductor titanium dioxide (TiO2) has proven to be a promising treatment method for the degradation of pharmaceuticals.
Considerable amounts of pharmaceuticals are used in human and veterinary medicine, which are not efficiently removed during wastewater and slurries treatment and subsequently entering continuously into freshwater systems. The intrinsic biological activity of these non-regulated pollutants turns their presence in the aquatic environment into an ecological matter of concern. We present the first quantitative study relating the presence of pharmaceuticals and their predicted ecotoxicological effects with human population and livestock units. Four representative Iberian River basins (Spain) were studied: Llobregat, Ebro, Júcar and Guadalquivir. The levels of pharmaceuticals were determined in surface water and sediment samples collected from 77 locations along their stream networks. Predicted total toxic units to algae, Daphnia and fish were estimated for pharmaceuticals detected in surface waters. The use of chemometrics enabled the study of pharmaceuticals for: their spatial distribution along the rivers in two consecutive years; their potential ecotoxicological risk to aquatic organisms; and the relationships among their occurrence and predicted ecotoxicity with human population and animal farming pressure. The Llobregat and the Ebro River basins were characterized as the most polluted and at highest ecotoxicological risk, followed by Júcar and Guadalquivir. No significant acute risks of pharmaceuticals to aquatic organisms were observed. However potential chronic ecotoxicological effects on algae could be expected at two hot spots of pharmaceuticals pollution identified in the Llobregat and Ebro basins. Analgesics/antiinflammatories, antibiotics and diuretics were the most relevant therapeutic groups across the four river basins. Among them, hydrochlorothiazide and gemfibrozil, as well as azithromycin and ibuprofen were widely spread and concentrated pharmaceuticals in surface waters and sediments, respectively. Regarding their predicted ecotoxicity, sertraline, gemfibrozil and loratidine were identified as the more concerning compounds. Significantly positive relationships were found among levels of pharmaceuticals and toxic units and population density and livestock units in both surface water and sediment matrices.
Copyright © 2015. Published by Elsevier B.V.
The pollutants classified as "persistent organic pollutants (POPs)", are being subject to high concern among the scientific community due to their persistence in the environment. TiO2-based photocatalytic process has shown a great potential as a low-cost, environmentally friendly and sustainable treatment technology to remove POPs in sewage to overcome the shortcomings of the conventional technologies. However, this technology suffers from some main technical barriers that impede its commercialization, i.e., the inefficient exploitation of visible light, low adsorption capacity for hydrophobic contaminants, uniform distribution in aqueous suspension and post-recovery of the TiO2 particles after water treatment. To improve the photocatalytic efficiency of TiO2, many studies have been carried out with the aim of eliminating the limitations mentioned above. This review summarizes the recently developed countermeasures for improving the performance of TiO2-based photocatalytic degradation of organic pollutants with respect to the visible-light photocatalytic activity, adsorption capacity, stability and separability. The performance of various TiO2-based photocatalytic processes for POPs degradation and the underlying mechanisms were summarized and discussed. The future research needs for TiO2-based technology are suggested accordingly. This review will significantly improve our understanding of the process of photocatalytic degradation of POPs by TiO2-based particles and provide useful information to scientists and engineers who work in this field.
Copyright © 2015 Elsevier Ltd. All rights reserved.
Titanium dioxide (TiO 2) is a promising material for many emerging applications. Even more promising are the benefits offered by the material when its length scale is reduced to the nanometer range. Nanomaterials usually exhibit unique properties resulting from either the extremely large surface area-to-volume ratio or the quantum confinement effect of energy carriers. In this article we present an overview of recent progress in the synthesis of TiO 2 nanomaterials. The topics include synthesis of TiO 2 nanoparticles, nanorods, nanowires, nanotubes, and mesoporous/nanoporous materials using different preparation approaches such as sol–gel, sol, hydrothermal, solvothermal, and vapor deposition. The applications of TiO 2 nanomaterials are also briefly summarized.
Recently, many water treatment technologies, such as biological treatment, coagulation/precipitation techniques, Fenton oxidation treatments, and advanced oxidation techniques, have been assessed to address the worsening clean water shortage. This review summarizes these technologies and provides the background and principle of photocatalysis for advanced oxidation technology. In particular, this paper focuses on semiconductor TiO2 photocatalysts as well as the latest modifications of TiO2 photocatalyst, such as the introduction of metals or heteroatoms onto TiO2, physical modification of TiO2 for a variety of morphologies, and hybrid TiO2/nanocarbon composites, to improve the photocataytic activities for an advanced oxidation process. This review provides useful information to scientists and engineers in this field.
This paper summarizes recent research dealing with development of titanium dioxide (TiO2) used for environmental applications. TiO2 plays the most important role owing to its excellent chemical and physical properties. However, the TiO2 band edge lies in the UV region that makes them inactive under visible irradiation. In this regard, considerable efforts have been made to increase the visible light activity of TiO2 via the modification of its electronic and optical properties. Doping TiO2 using either anions or cations is one of the typical approaches that has been largely applied. Coupling TiO2 with a narrow bad gap semiconductor (MxOy/TiO2 or MxSy/TiO2) represents another approach. This work aims to encompass the new progress of TiO2 for an efficient application in water and wastewater treatment under visible light, emphasizes the future trends of TiO2 in the environment, and suggests new research directions, including preparation aspects for the development of this promising material.
There is a recent increase in the interest of designing high-performance photocatalysts using graphene-based materials. This review gathers some important aspects of graphene–TiO2, graphene oxide–TiO2, and reduced graphene oxide–TiO2 composites, which are of especial relevance as next generation photocatalysts. The methods used for the preparation of these materials, the associated mechanistic fundamentals, and the application of graphene-based composites on the photocatalytic degradation of pollutants are reviewed. Some structural, textural, and chemical properties of these materials and other photo-assisted applications, such as hydrogen production from water splitting and dye-sensitized solar cells, are also briefly included.
TiO2 photocatalysis is widely used in a variety of applications and products in the environmental and energy fields, including self-cleaning surfaces, air and water purification systems, sterilization, hydrogen evolution, and photoelectrochemical conversion. The development of new materials, however, is strongly required to provide enhanced performances with respect to the photocatalytic properties and to find new uses for TiO2 photocatalysis. In this review, recent developments in the area of TiO2 photocatalysis research, in terms of new materials from a structural design perspective, have been summarized. The dimensionality associated with the structure of a TiO2 material can affect its properties and functions, including its photocatalytic performance, and also more specifically its surface area, adsorption, reflectance, adhesion, and carrier transportation properties. We provide a brief introduction to the current situation in TiO2 photocatalysis, and describe structurally controlled TiO2 photocatalysts which can be classified into zero-, one-, two-, and three-dimensional structures. Furthermore, novel applications of TiO2 surfaces for the fabrication of wettability patterns and for printing are discussed.
Synthetic dyes are a major part of our life as they are found in the various products ranging from clothes to leather accessories to furniture. These carcinogenic compounds are the major constituents of the industrial effluents. Various approaches have been developed to remove organic dyes from the natural environment. Over the past few years, there has been an enormous amount of research with advanced oxidation processes (AOPs) as an effective method of wastewater treatment. Among AOPs, heterogeneous photocatalytic process using TiO2 nanomaterials appears as the most emerging destructive technology due to its cost effectiveness and the catalyst inert nature and photostability. This review deals with the photocatalytic degradation of organic dyes containing different functionalities using TiO2 nanomaterials in aqueous solution. It first discusses the photocatalytic properties of nanostructured TiO2. The photocatalytic degradation rate strongly depends on the basic structure of the molecule and the nature of auxiliary groups attached to the aromatic nuclei of the dyes. So, this review then explains the influence of structure of dyes on their photocatalytic degradation rates. The influences of different substitutes such as alkyl side chains, methyl, nitrate, hydroxyl and carboxylic groups as well as the presence of chloro atom have been discussed in detail.
Titanium dioxide (TiO2) photocatalysts have been shown to be effective at degrading a wide range of organic micropollutants during short-term batch experiments conducted under ideal laboratory solution conditions (e.g., deionized water). However, little research has been performed regarding longer-term photocatalyst performance in more complex matrices representative of contaminated water sources (e.g., wastewater effluent, groundwater). Here, a benchtop continuous-flow reactor was developed for the purpose of studying the activity, inhibition, and deactivation of immobilized TiO2 photocatalysts during water treatment applications. As a demonstration, degradation of four pharmaceutical micropollutants (iopromide, acetaminophen, sulfamethoxazole, and carbamazepine) was monitored in both a pH-buffered electrolyte solution and a biologically treated wastewater effluent (WWE) to study the effects of non-target constituents enriched in the latter matrix. Reactor performance was shown to be stable over 7 d when treating micropollutants in buffered electrolyte, with 7-d averaged kobs values (acetaminophen = 0.97 ± 0.10 h−1; carbamazepine = 0.50 ± 0.04 h−1; iopromide = 0.49 ± 0.03 h−1; sulfamethoxazole = 0.79 ± 0.06 h−1) agreeing closely with measurements from short-term circulating batch reactions. When reactor influent was switched to WWE, treatment efficiencies decreased to varying degrees (acetaminophen = 40% decrease; carbamazepine = 60%; iopromide = 78%; sulfamethoxazole = 54%). A large fraction of the catalyst activity was recovered upon switching back to the buffered electrolyte influent after 4 d, suggesting that much of the observed decrease resulted from reversible inhibition by non-target constituents (e.g., scavenging of photocatalyst-generated OH). However, there was also a portion of the decrease in activity that was not recovered, indicating WWE constituents also contributed to photocatalyst deactivation (acetaminophen = 6% deactivation; carbamazepine = 24%; iopromide = 16%; sulfamethoxazole = 25%). Experiments conducted using pretreated WWE and synthetic WWE mimic solutions indicated that both effluent organic matter and inorganic constituents in WWE contributed to the observed photocatalyst inhibition/deactivation. Analysis of immobilized TiO2 thin films after 4 d of continuous treatment of the WWE matrix indicated minor deterioration of the porous film and formation of surface precipitates enriched in Al and Ca. Results demonstrated the marked influence of non-target constituents present in complex matrices on long-term photocatalyst activity and highlighted the need for further study of this important issue to advance the development of practical photocatalytic water treatment technologies.
A novel TiO2-coconut shell powder (TCNSP) composite, prepared by the controlled sol-gel method with a subsequent heat treatment, was investigated as an innovative photocatalytic absorbent for the removal of carbamazepine (CBZ). CBZ is used worldwide as an antiepileptic drug, which has recently been recognized as an important organic pollutant increasingly found in wastewaters from urban areas and other aquatic environments. The granulation process was performed by using a semiautomated mass production line to produce sufficient quantities of TCNSP composites, possessing sufficient crush strength for commercialization. Physical properties of the TCNSP composite such as crystallinity, morphology, crush strength, and the Brunauer-Emmett-Teller (BET)-specific surface area were controlled by the mass ratio of titanium dioxide sol and coconut shell powder (CNSP). Calcination at 700°C produced anatase phase TiO2 in the TCNSP composites with a BET high surface area of 454 m(2)/g. Anatase crystallite size of the TCNSP composite increased from 2.37 to 15.11 nm with increasing calcination temperature from 500°C to 800°C. Calcinated TCNSP composites had higher CBZ removal efficiency (98%) than pure TiO2 (23%) and CNSP (34%) within a 40-min reaction time. Optimization of this innovative adsorption/photocatalytic process was obtained by a response surface methodology and a central composite design model, which indicated that this novel and sustainable technology was successful in removing CBZ from a solution.
The occurrence and distribution of a group of 17 organic micropollutants in surface and groundwater sources from Mexico City was determined. Water samples were taken from 7 wells, 4 dams and 15 tanks where surface and groundwater are mixed and stored before distribution. Results evidenced the occurrence of seven of the target compounds in groundwater: salicylic acid, diclofenac, di-2-ethylhexylphthalate (DEHP), butylbenzylphthalate (BBP), triclosan, bisphenol A (BPA) and 4-nonylphenol (4-NP). In surface water, 11 target pollutants were detected: same found in groundwater as well as naproxen, ibuprofen, ketoprofen and gemfibrozil. In groundwater, concentration ranges of salicylic acid, 4-NP and DEHP, the most frequently found compounds, were 1-464, 1-47 and 19-232ng/L, respectively; while in surface water, these ranges were 29-309, 89-655 and 75-2282ng/L, respectively. Eleven target compounds were detected in mixed water. Concentrations in mixed water were higher than those determined in groundwater but lower than the detected in surface water. Different to that found in ground and surface water, the pesticide 2,4-D was found in mixed water, indicating that some pollutants can reach areas where they are not originally present in the local water sources. Concentration of the organic micropollutants found in this study showed similar to lower to those reported in water sources from developed countries. This study provides information that enriches the state of the art on the occurrence of organic micropollutants in water sources worldwide, notably in megacities of developing countries.
Applied Catalysis B: Environmental j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / a p c a t b a b s t r a c t Fujishima and Honda (1972) demonstrated the potential of titanium dioxide (TiO 2) semiconductor mate-rials to split water into hydrogen and oxygen in a photo-electrochemical cell. Their work triggered the development of semiconductor photocatalysis for a wide range of environmental and energy applica-tions. One of the most significant scientific and commercial advances to date has been the development of visible light active (VLA) TiO 2 photocatalytic materials. In this review, a background on TiO 2 struc-ture, properties and electronic properties in photocatalysis is presented. The development of different strategies to modify TiO 2 for the utilization of visible light, including non metal and/or metal doping, dye sensitization and coupling semiconductors are discussed. Emphasis is given to the origin of visible light absorption and the reactive oxygen species generated, deduced by physicochemical and photo-electrochemical methods. Various applications of VLA TiO 2 , in terms of environmental remediation and in particular water treatment, disinfection and air purification, are illustrated. Comprehensive studies on the photocatalytic degradation of contaminants of emerging concern, including endocrine disrupting compounds, pharmaceuticals, pesticides, cyanotoxins and volatile organic compounds, with VLA TiO 2 are discussed and compared to conventional UV-activated TiO 2 nanomaterials. Recent advances in bac-terial disinfection using VLA TiO 2 are also reviewed. Issues concerning test protocols for real visible light activity and photocatalytic efficiencies with different light sources have been highlighted.
Clofibric acid (CA) and the herbicide mecoprop (MCPP) were detected in Swiss lakes from populated areas and in the North Sea in the low nanograms per liter range. Gas chromatography/mass spectrometry (GC/MS) and MS/MS were used to distinguish the two isomeric compounds (analyzed as the methyl esters). The concentrations of CA in the North Sea (1−2 ng/L) reach levels of those of “classical” environmental pollutants such as α- and γ-hexachlorocyclohexane. The data suggest a high mobility of CA in the aquatic environment. The changed relative concentrations of CA and MCPP in the North Sea as compared to those in the lakes and in comparison to produc tion figures indicate a much more persistent behavior for CA than for MCPP. The data also indicate that some pharmaceutical compounds need evaluation on ecotoxicological grounds in very much the same way as do agricultural chemicals.
Crystalline titanium dioxide particles were obtained through the thermohydrolysis at 60 °C of an aqueous TiCl4 precursor in the presence of various amino acids. These protein building blocks were employed to modify the phase distribution, size, and shape of the formed nanoparticles. The consequences of the presence of biological species during the different steps of the inorganic condensation were characterized by a variety of techniques, including X-ray diffraction, transmission electron microscopy, and thermogravimetric analysis coupled with differential scanning calorimetry. The amino acid side chain functions were shown to be of particular importance in regard to the modification of the TiO2 structure and morphology. More specifically, aspartic acid, glutamic acid, and serine allowed the formation of pure anatase nanoparticles. The pH of the reacting solution also proved to be a relevant parameter to control the particle size and shape. Explanations based on the actual knowledge on the titania/amino acids interface were proposed for every observed modification.
Charge separation characteristics of a high-activity, mixed-phase titania photocatalyst (Degussa P25) are probed by EPR spectroscopy. While previous proposals consider rutile as a passive electron sink hindering recombination in anatase, this research details the critical and active role of rutile in TiO2 formulations. The inactivity of pure-phase rutile is due in part to rapid rates of recombination. Yet, in mixed-phase TiO2, charges produced on rutile by visible light are stabilized through electron transfer to lower energy anatase lattice trapping sites. These results suggest that within mixed-phase titania (P25) there is a morphology of nanoclusters containing atypically small rutile crystallites interwoven with anatase crystallites. The transition points between these two phases allow for rapid electron transfer from rutile to anatase. Thus, rutile acts as an antenna to extend the photoactivity into visible wavelengths and the structural arrangement of the similarly sized TiO2 crystallites creates catalytic "hot spots" at the rutile-anatase interface.
The field of photocatalysis can be traced back more than 80 years to early observations of the chalking of titania-based paints and to studies of the darkening of metal oxides in contact with organic compounds in sunlight. During the past 20 years, it has become an extremely well researched field due to practical interest in air and water remediation, self-cleaning surfaces, and self-sterilizing surfaces. During the same period, there has also been a strong effort to use photocatalysis for light-assisted production of hydrogen. The fundamental aspects of photocatalysis on the most studied photocatalyst, titania, are still being actively researched and have recently become quite well understood. The mechanisms by which certain types of organic compounds are decomposed completely to carbon dioxide and water, for example, have been delineated. However, certain aspects, such as the photo-induced wetting phenomenon, remain controversial, with some groups maintaining that the effect is a simple one in which organic contaminants are decomposed, while other groups maintain that there are additional effects in which the intrinsic surface properties are modified by light. During the past several years, powerful tools such as surface spectroscopic techniques and scanning probe techniques performed on single crystals in ultra-high vacuum, and ultrafast pulsed laser spectroscopic techniques have been brought to bear on these problems, and new insights have become possible. Quantum chemical calculations have also provided new insights. New materials have recently been developed based on titania, and the sensitivity to visible light has improved. The new information available is staggering, but we hope to Offer an overview of some of the recent highlights, as well as to review some of the origins and indicate some possible new directions. (C) 2008 Elsevier B.V. All rights reserved
In recent years, there has been a tremendous amount of research and development in the area of photocatalysis (heterogeneous and homogeneous), a process included in a special class of oxidation techniques defined as Advanced Oxidation Processes (AOPs), all characterized by the same chemical feature, production of OH radicals. This paper reviews the use of sunlight to produce the OH radicals by TiO2 photocatalysis and photo-Fenton process. The reacting systems necessary for performing solar photocatalysis are described. The paper also summarizes most of the research carried out related to solar photocatalytic degradation of water contaminants, and how it could significantly contribute to the treatment of persistent toxic compounds. It outlines how to enhance the process efficiency by integration with biotreatment. Various solar reactors for photocatalytic water treatment mainly based on non-concentrating collectors built during the last few years are also described in detail in this review, as well as the use of the solar photocatalytic processes to inactivate microorganisms present in water, placing special emphasis on experimental systems made to optimize this disinfection technique.
A monitoring programme was carried out on wastewater, surface and drinking water on the NW area of Spain during the four seasons of a year period (November 2007-September 2008). This study covered a series of emerging pollutants of different classes, including pharmaceuticals, neutral and acidic organophosphorus flame retardant/plasticizers (OPs), triclosan, phenoxy-herbicides, insect repellents and UV filters. From the total set of 53 compounds, 19 were found in raw wastewater with median concentrations higher than 0.1 μg L(-1). Among them, salicylic acid, ibuprofen and the UV filter benzophenone-4 (BP-4) were the most concentrated, exceeding the 1 μg L(-1) median value. Subsequently, 11 of these contaminants are not efficiently enough removed in the small WWTPs tested and their median concentrations in effluents still surpassed the 0.1 μg L(-1), so that they can spread through surface water. These chemicals are the pharmaceuticals naproxen, diclofenac and atenolol; the OPs tri(2-chloroethyl) phosphate (TCEP), tri(chloropropyl) phosphate (TCPP), tri-n-butyl phosphate (TnBP), diphenyl phosphate (DPhP) and diethylhexyl phosphate (DEHP); and the sulphonate UV filters BP-4 and 2-phenylbenzimidazole-5-sulphonic acid (PBSA). These OPs were then the dominant emerging pollutants occurring in surface and drinking water, where they are detected in the 20-200 ng L(-1) range. Pharmaceuticals and UV filters are typically below the 10 ng L(-1) level. Finally, herbicides were only detected in the last sampling campaign under the 100 ng L(-1) drinking water European Union limit.