Removal of carbamazepine from urban wastewater by sulfate radical oxidation

The occurrence of bioactive trace pollutants such as pharmaceuticals in natural waters is an emerging issue. Numerous pharmaceuticals are not completely removed in conventional wastewater treatment plants. Advanced oxidation processes may represent an interesting alternative to completely mineralize organic trace pollutants. In this article, we show that sulfate radicals generated from peroxymonosulfate/Co^II are more efficient than hydroxyl radicals generated from the Fenton’s reagent (H₂O₂/Fe^II) for the degradation of the pharmaceutical compound, carbamazepine. The second-order rate constant for the reaction of SO₄ ^·− with carbamazepine is 1.92·10⁹ M⁻¹ s⁻¹. In laboratory grade water and in real urban wastewater, SO₄ ^·− yielded a faster degradation of carbamazepine compared to HO^· . Under strongly oxidizing conditions, a nearly complete mineralization of carbamazepine was achieved, while under mildly oxidizing conditions, several intermediates were identified by LC–MS. These results show for the first time in real urban wastewater that sulfate radicals are more selective than hydroxyl radicals for the oxidation of an organic pollutant and may represent an interesting alternative in advanced oxidation processes.     

Structural effect on photocatalytic degradation of metallised azo dyes in aqueous TiO2 suspension

Three metallised azo dyes were investigated under TiO₂‐photocatalytic and photosensitised conditions in aqueous buffering solutions. The degradation follows apparent first‐order kinetics. The size and strength of intramolecular conjugation determine the light‐fastness of the investigated dyes. Compared with ¹O₂ produced in photosensitised process, the more powerful *OH radicals in TiCO₂ photocatalytic process are highly reactive towards the investigated azo dyes. And as a result, the TiO₂‐photocatalysis makes little less distinction in the degradation kinetic data of the azo dyes compared with the photosensitised degradation of them.     

Biopolymer-supported TiO2 as a sustainable photocatalyst for wastewater treatment: a review

The rising water pollution by pesticides, pharmaceuticals and dyes is a major health issue calling for advanced remediation methods such as photocatalysis with titanium dioxide (TiO₂), yet the use of TiO₂ displays issues of aggregation, mass loss, recovery, and reusability. These issues have been recently solved by synthesizing biopolymer-supported photocatalysts using cheap, biodegradable and safe biopolymers such as chitosan, alginate, cellulose, cyclodextrin, guar gum and starch. Here we review biopolymer-supported TiO₂ photocatalysts for the removal of organic compounds, with focus on preparation methods, photo and chemical stability, reusability, and adsorptive capacity. We discuss applications of immobilized photocatalysts at the industrial scale.

     

Removal of methylene blue by coupling black carbon adsorption with TiO2 photodegradation

In this study, the removal of methylene blue (MB) by the coupling of black carbon (BC) and TiO₂ was investigated. The effects of different parameters such as catalyst dose, sorbent, initial concentrations of dye, pH of the solutions, recycles on discoloration, and chemical oxidation demand (COD) reduction of MB were monitored to optimize the reaction conditions. The discoloration and COD conversation rate of MB obtained by the coupling process were 100% after 90?min irradiation. The synergistic effect of MB-adsorption on BC followed by degradation through TiO₂ photocatalysis was proved by FT–IR spectrophotometer. The BC as by-product of natural materials is a promising adsorbent for waste water treatment.     

Degradation and reduction of acute toxicity of environmentally persistent perfluorooctanoic acid (PFOA) using VUV photolysis and TiO2 photocatalysis in acidic and basic aqueous solutions

Degradation and toxicity reduction of perfluorooctanoic acid (PFOA) were investigated using TiO₂ adsorption, vacuum ultraviolet (VUV) photolysis, and VUV/TiO₂ photocatalysis in acidic and basic aqueous solutions. Chemical analyses of PFOA and its selected by-products and an acute toxicity assessment using the luminescent bacteria Vibrio fischeri (Microtox®) were conducted during and after the various treatment methods. PFOA was found to be best treated by VUV/TiO₂ at pH 4 with HClO₄, as illustrated by the almost complete degradation of PFOA within 360?min and rapid removal of acute microbial toxicity within 60?min. This difference in the efficiency may be attributed to the strong oxidation effectiveness of the radical species generated in acidic media and the electron scavenger effect of the addition of HClO₄ in VUV/TiO₂ photocatalysis. In addition, the proposed method could effectively decompose other perfluorocarboxylic acid (PFCA) species (C₃–C₇ perfluoroalkyl groups) if the initial intermediates formed were longer-chain species that degraded stepwise into shorter-chain compounds by VUV photolysis and VUV/TiO₂ photocatalysis in acidic and basic aqueous solutions.     

Photocatalytic removal of nitrogen oxides via titanium dioxide

We studied the removal of nitrogen oxides pollutants via TiO₂ Degussa P25 powder by photocatalysis. Parameters such as mass of catalyst, geometric irradiated surface, catalyst morphology, and thermal treatment were tested to explain the photocatalytic concentration decrease of nitrogen oxides. According to our working conditions, the conversion rates increased until an optimal value of the TiO₂ weight, 35% of NO concentration and around 20% of NOx, was decomposed by the photocatalysis. The NOx removal increased proportionally with the irradiated geometric surface. The structural transformation of anatase to rutile performed by thermal treatment involved the decrease of the photocatalytic activity.     

Photodegradation of Ibuprofen,Cetirizine, and Naproxen by PAN-MWCNT/TiO<Subscript>2</Subscript>–NH<Subscript>2</Subscript> nanofiber membrane under UV light irradiation

Background

In this study, the photodegradation of three pharmaceuticals, namely Ibuprofen (IBP), Naproxen (NPX), and Cetirizine (CIZ) in aqueous media was investigated under UV irradiation. The photocatalyst used in this work consists of surface functionalized titanium dioxide (TiO₂–NH₂) nanoparticles grafted into Polyacrylonitrile (PAN)/multi-walled carbon nanotube composite nanofibers. Surface modification of the fabricated composite nanofibers was illustrated using XRD, FTIR, and SEM analyses.

Results

Sets of experiments were performed to study the effect of pharmaceuticals initial concentration (5–50 mg/L), solution pH (2–9), and irradiation time on the degradation efficiency. The results demonstrated that more than 99% degradation efficiency was obtained for IBP, CIZ, and NPX within 120, 40, and 25 min, respectively.

Conclusions

Comparatively, the photocatalytic degradation of pharmaceuticals using PAN-CNT/TiO₂–NH₂ composite nanofibers was much more efficient than with PAN/TiO₂–NH₂ composite nanofibers.

     

Dichlorvos degradation studied by 31P-NMR

We studied the hydrolysis and TiO₂ photocatalysis of the pesticide dichlorvos at pH 2.6–9 using phosphorus-31 nuclear magnetic resonance (³¹P NMR). We found that the hydrolysis of dichlorvos led to the formation of dimethyl phosphate at pH 5.6–9. On the other hand, TiO₂ photocatalysis decomposed dichlorvos into dimethyl phosphate, which further reacted to form monomethyl phosphate at pH 2.6 and 9. Monomethylphosphate was hydrolysed into phosphate at pH 2.6. ³¹P NMR is therefore a promising tool to study the degradation of organophosphorus pesticides.     

Bisphenol A endocrine disruptor complete degradation using TiO2 photocatalysis with ozone

Bisphenol A is an endocrine disruptor. Complete mineralization of bisphenol A is therefore a primary environmental issue. Here, the combination of ozonation and photocatalysis by TiO₂ is proposed for the degradation and final mineralization of bisphenol A. TiO₂ films deposited onto two sides of an Al lamina show good stability and high surface roughness. We used a specific experimental setup employing two facing ultraviolet lamps and TiO₂ layers, together with an ozone flux. High-performance liquid chromatography–mass spectrometry determinations on bisphenol A solutions sampled at different reaction times and Fourier Transform Infrared analyses of the oxide at the end of the reaction were performed to study the reaction intermediates and the overall degradation mechanism. Our results show that pollutant mineralization achieved with the combined method is far higher, of 55% in the case of 0.3 mM bisphenol A, than those obtained by individual treatments such as photolysis (<3%), ozonation (6%), photocatalysis (6%), and by other combined processes: photolytic ozonation (13%) and catalytic ozonation (15%). This finding is explained by the occurrence of highly synergistic effects.     

The effects of different methods of catalyst preparation on the hydro-electric plasma TiO2-catalyzed degradation of 2,4-dinitrophenol

Hydro-electric plasma technology in the presence of TiO₂ catalyst used to treat 2,4-dinitrophenol (2,4-DNP) simulated wastewater is reported. The catalytic activity of TiO₂ prepared by ammonia precipitation was greater than the activity of the TiO₂ prepared by NaOH precipitation. The presence of chloride ions during the preparation process of TiO₂ had a large negative effect on the catalytic activity. The catalytic activity of TiO₂ calcined at 673 K was significantly higher than the activity of the TiO₂ that was calcined at higher and lower temperatures. After being calcined at 673 K, TiO₂ was mainly in the anatase phase and degraded 81% of the 2,4-DNP after 10 min of treatment.     

Sonocatalytic degradation of tetracycline antibiotic in aqueous solution by sonocatalysis

Tetracycline (TC), one of the most common antibiotics, is often poorly bio-degraded in conventional wastewater treatment plants. In this study, the sonocatalytic degradation of TC was investigated using TiO₂ nano-particles as catalyst. The effect of pH, initial TC concentrations, reaction times, and H₂O₂ concentrations were evaluated. The efficacy of ultrasonic irradiation alone in the removal of this pollutant was negligible but removal efficiency increased upon addition of TiO₂ up to 250 mg L^?1; increase of pH and initial TC concentration attenuated TC degradation. Addition of H₂O₂ raised the removal efficiency so that complete removal of TC was achieved within 75 min.     

First approach of the selective treatment of water by heterogeneous photocatalysis

Photocatalytic reactions using titanium dioxide are of great interest due to their possible applications to solar energy storage and detoxification of wastewater. However, TiO₂ has usually given a very poor selectivity. Here we show that, using binary mixtures, it is possible to selectively degrade one molecular substance without any concentration change of another substance. We have studied the influence of the pH and TiO₂ concentration on the selectivity of the degradation of benzamide and 4-hydroxybenzoic acid. With appropriate modifications of both parameters, the selectivity can be improved.     

Rapid photocatalytic degradation of the recalcitrant dye amaranth by highly active N-WO<Subscript>3</Subscript>

Dye wastewater is a major source of toxic aromatic amines released into the environment. Semiconductor photocatalysis is a clean, solar-driven process for the treatment of dye wastewater. To enhance applicability of semiconductor photocatalysis, the catalyst used should be visible light active. Here we report a facile synthesis of a highly visible-light-active nitrogen-doped tungsten oxide, N-WO₃, by thermal decomposition of peroxotungstic acid–urea complex. The structure and properties of N-WO₃ are characterized by X-ray photoelectron spectroscopy and X-ray absorption near-edge spectroscopy. The photodegradation of amaranth catalyzed by N-WO₃ is evaluated in a batch system under visible and ultraviolet A (UVA) light. Our results show successful doping of N in both interstitial and substitutional sites and the presence of N₂-like species. The N doping surprisingly expands the usable portion of the solar spectrum up to the near-infrared region and enhances the photocatalytic activity. At typical experimental conditions such as 25 mg/L of amaranth, 1 g/L of N-WO₃, and pH 7, 100 % degradation of amaranth is achieved within 2 h under both visible and UVA light. The photocatalytic activity of N-WO₃ is maintained in repeated cycles, indicating its exceptional photostability. To the best of our knowledge, this is the first time that a reusable, highly visible-light-active N-WO₃ can be obtained through thermal decomposition of peroxotungstic acid–urea complex.     

Investigation of the effects of humic acid and H<Subscript>2</Subscript>O<Subscript>2</Subscript> on the photocatalytic degradation of atrazine assisted by microwave

A solution of atrazine in a TiO₂ suspension, an endocrine disruptor in natural water, was tentatively treated by microwave-assisted photocatalytic technique. The effects of mannitol, oxygen, humic acid, and hydrogen dioxide on the photodegradation rate were explored. The results could be deduced as follows: the photocatalytic degradation of atrazine fits the pseudo-first-order kinetic well with k = 0.0328 s^?1, and ·OH was identified as the dominant reactant. Photodegradation of atrazine was hindered in the presence of humic acid, and the retardation effect increased as the concentration of humic acid increased. H₂O₂ displayed a significant negative influence on atrazine photocatalysis efficiency. Based on intermediates identified with gas chromatography-mass spectrometry (GC-MS) and Liquid chromatography-mass spectrometry (LC-MS/MS) techniques, the main degradation routes of atrazine are proposed.     

Wassertechnische Strategien zur Reduzierung der Trinkwasserbelastung durch Arzneimittelwirkstoffe

Results The available research results concerning the application of innovative methods of wastewater and drinking water purification to eliminate pharmaceuticals are summarized in the present paper. An increase of the activated sludge (aerobic sludge) age to 8–10 days in treatment plants can improve the metabolization of less persistent pharmaceutical agents whereas expansion of the sojourn time beyond 10 days will not result in a remarked increase of degradation for most pharmaceutical substances. First results have shown that wastewater treatment plants with integrated membrane bioreactors (MBR) using micro- and ultrafiltration membranes do not provide significantly better results compared to the conventional wastewater treatment plants with respect to the removal of organic micropollutants (including pharmaceutical residues). The use of powdered carbon in biologically treated wastewater is able to reduce pharmaceutical residues up to 80?% in the run-off water. Pilot studies scrutinize the treatment of highly contaminated effluents via catalytic photooxidation. Regarding the suitability of the method to reduce the contamination of drinking and wastewater with pharmaceuticals yet only few data from laboratory scale testing are available. Activated carbon filtration is preferably used for drinking water treatment. Primarily against the background of disinfection, ozonation is widely used for drinking water treatment, but for wastewater treatment the method is still at the experimental stage and will hardly become of practical importance because of high costs. Sustainable wastewater separation is grounded on decentralized concepts by considering material cycles (recycling) at the place of origin. In the long term, separation measures can significantly contribute to declining drug concentrations in drinking water. Regarding the quarrying of drinking water by bank filtration water, river water or artificially enriched ground water, end-of-pipe techniques are vital. Most commonly, activated carbon or activated carbon combined with ozonization is applied and assures a high drinking water quality. Discussion The advantages and disadvantages of the different water treatment methods mainly concern the varying degrees of effectiveness with respect to the elimination of very persistent pharmaceutical agents, the generation of problematical metabolites and additional waste materials, hygienic problems, energy needs and the necessity to employ appropriate technical staff for operation. Although the biodegradation of very persistent drugs cannot be enhanced by an extension of the activated sludge age, this modification should be considered in sewage plants to reduce the contamination with less persistent medical agents. Compared with conventional wastewater treatment, membrane bioreactors provide the advantage of a better control of biological activities on the plant and a comparably small plant size but high investment and operation costs. Additionally, pharmaceuticals such as carbamazepin are only insufficiently removed from wastewater by membrane bioreactors. The regular use of powdered activated carbon in sewage treatment plants would also increase the costs of wastewater treatment and would additionally exclude the further use of sewage sludge in agriculture. Currently, in Germany the further use of sewage sludge is handled differently by the Federal States and discussed controversially. The implementation of ozonation as an additional treatment method in wastewater treatment plants is not realistic because of cost concerns. Additionally, the method produces analytically as yet not assessed metabolites with unknown (eco-)toxicological impacts. For this reason ozonation should currently not be applied unless the reaction products are removed subsequently by filtration through activated carbon. For industrial sewage photooxidation is in a state of testing but an application for municipal wastewater is, up to now, out of question. When river bank filtration is used for the supply of drinking water the use of activated carbon for purification should be essential. The lifetime of the filters is often defined by the filter capacities to eliminate radiocontrast media (e.?g., iopamidole, amidotrizoic acid). Many water supply companies already apply the ozonization prior to activated carbon filtration which supports the elimination of pharmaceuticals from the sewage. The unique developmental potential of the wastewater separation can be seen in the possibility to link up these methods with sustainable exploitation techniques and concepts (re-use of sanitized water, production of fertilizer, compost and biogas). Wastewater separation will not make ‘middle/end-of-pipe’ techniques dispensable but will make their handling more effective because concentrations of pharmaceutical agents are higher in separated effluents compared to those usually found in municipal wastewater, which in mixing sewage systems is even diluted by surface runoff. Conclusions Following today’s state of knowledge activated carbon filtration (eventually coupled with ozonization) is best suited to remove drug residues and other xenobiotics from raw water. Water works that do not apply the activated carbon filtration technique for cleanup of bank filtration water should consider an upgrade. The ozonization is primarily required for disinfection of the water. As no acute health hazard proceeds from drinking water contamination by pharmaceuticals at the present time, the upgrade of wastewater treatment plants by one of the aforementioned innovative methods is currently not required in view of drinking water quality. This offers the opportunity to develop sustainable approaches that already aim to reduce drug contaminations of wastewater and hence of ground-, surface- and drinking water. Recommendations and perspectives On a short- to mid-term perspective enriched sewage of hospitals, nursing homes and other medical facilities should be collected and treated separately. From a technical point of view the conditioning of separated hospital effluents (yellow- and greywater) via activated carbon or membrane filtration is possible but should be combined with disinfection. On a mid- and long-term scale sustainable sanitary concepts based on wastewater separation (black-, grey- and/or rainwater) associated with the recycling of mineral nutrients (nitrogen, phosphorous and potassium) should be realized for development, industry and trade areas, buildings with public lavatories, airports, motorway service areas, and large office and hotel buildings. Strategies focusing primarily on up-grading of municipal wastewater treatment plants are currently existing but the related technologies are largely in a test phase. This is why a particular technique should not be favored at the moment. The combination of various techniques (i.?e., ozonization combined with activated carbon filtration) is known to be very efficient for the removal of pharmaceutical residues from water, but the combination cannot be expected to become of importance in treatment of domestic wastewater because of high costs. Moreover, improvement of wastewater treatment technologies to remove pharmaceutical residues will not make the employment of end-of-pipe techniques in water works redundant and therefore will not lead to saving of expenses.     

Photodegradation of an azo dye by silver-doped nano-particulate titanium dioxide

The synthesis of silver doped nano-particulate titanium dioxide (Ag/TiO₂) using a microemulsion method and an investigation of its photocatalytic activity for the degradation of Acid Red 27 in distilled water under UV-irradiation is reported. The prepared Ag/TiO₂ is characterized using transmission electron microscopy, X-ray diffraction, and energy-dispersive X-ray spectroscopy. The size of the Ag nanoparticles is around 5–15?nm, with almost uniform distribution on the TiO₂ particles. The efficiency of the photocatalytic process is evaluated to establish the optimum conditions, found to be at 2?wt% of Ag loading on TiO₂, catalyst dosage of 400?mg?L^?1, and calcination temperature of 300°C. Complete decolorization of the dye solution on Ag/TiO₂ was observed in 20?min of UV irradiation in the optimum conditions.     

Photocatalytic oxidation of the textile dye basic red 18 with irradiated titanium dioxide

One of the major problems of textile wastewater is the presence of dye materials, because colour is visible to the public even if the dye concentration is lower than other pollutants, and needs therefore to be removed from the wastewater before it is discharged. Techniques based on “advanced oxidative processes” such as photocatalysed oxidation seem to be very promising for industrial wastewater treatment, especially for decolourization of textile effluents. In this work, we describe the photocatalytic degradation of the textile dye Basic Red 18 (BR 18) in aqueous solution using two different types of TiO₂ as photocatalyst: Degussa P25 (80% anatase) and Framitalia (100% anatase). Photooxidation of BR 18 was followed by HPLC analysis, and kinetic parameters were evaluated in order to optimise the treatment procedure. The results obtained in this work showed that the colour became virtually zero and the chemical oxygen demand (COD) is strongly reduced at the end of the treatment. The obtained results are compared with the efficiency of decolourization using the H₂O₂/UV System. Finally, marine mussel test was used to evaluate the efficiency of photocatalytic oxidation with TiO₂ in terms of ecotoxicity. A significant reduction of cumulative mortality was observed for the treated effluent.     

Quantification of TiO2 and ZnO nanoparticles in wastewater using inductively coupled plasma optical emission spectrometry

Abstract

The applicability of inductively coupled plasma optical emission spectrometry has been examined for determination titanium dioxide and zinc oxide nanoparticles in industrial wastewater samples. The extraction and preconcentration of the nanoparticles were achieved using ligandless ultrasound-assisted surfactant-based dispersive liquid–liquid microextraction. Under optimized conditions, the developed method had limits of detection (LOD) of 2.7?ng L^?1 for Ti and 3.6?ng L^?1 for Zn resulting from dissolved TiO₂ and ZnO nanoparticles. The relative standard deviation values for intraday precision were 2.5% and 3.1% for TiO₂ and ZnO, while the interday precision was 4.5% and 5.0%. Percentage recoveries ranging from 98% to 100% were obtained. Finally, the applicability of the method was examined by analyzing spiked samples and wastewater samples collected from textile, cosmetic and paint industries.     

Ag–TiO2 doped photo catalytic degradation of Procion blue H-B dye in textile washwater

The photocatalytic degradation of Procion blue H-B dye in biodegraded textile washwater has been investigated for the complete removal of color and maximum reduction of chemical oxygen demand (COD). Pseudomonas putida was utilized for obtaining biodegraded textile washwater. In this process, silver-doped TiO₂ photocatalyst was prepared and experiments were carried out to study the effects of UV and mercury lamp irradiations on COD reduction and removal of color. The thus prepared silver-doped TiO₂ catalyst was characterized by thermogravimetric and differential thermal analysis, UV-visible spectrometer, X-ray diffraction, scanning electron microscope, energy dispersive X-ray microanalysis, and BET surface area techniques. Adsorption studies were also carried out to evaluate the fitness of isotherm models. The results show that the silver-doped TiO₂ has enhanced the photodegradation of Procion blue H-B dye under UV and mercury lamp irradiations. The enhanced activity of silver-doped TiO₂ is due to the enrichment of electron–hole separation by electron trapping of silver particles.