Supported TiO2 in Ceramic Materials for the Photocatalytic Degradation of Contaminants of Emerging Concern in Liquid Effluents: A Review.

The application of TiO2 as a slurry catalyst for the degradation of contaminants of emerging concern (CEC) in liquid effluents has some drawbacks due to the difficulties in the catalyst reutilization. Thus, sophisticated and expensive separation methods are required after the reaction step. Alternatively, several types of materials have been used to support powder catalysts, so that fixed or fluidized bed reactors may be used. In this context, the objective of this work is to systematize and analyze the results of research inherent to the application of ceramic materials as support of TiO2 in the photocatalytic CEC removal from liquid effluents. Firstly, an overview is given about the treatment processes able to degrade CEC. In particular, the photocatalysts supported in ceramic materials are analyzed, namely the immobilization techniques applied to support TiO2 in these materials. Finally, a critical review of the literature dedicated to photocatalysis with supported TiO2 is presented, where the performance of the catalyst is considered as well as the main drivers and barriers for implementing this process. A focal point in the future is to investigate the possibility of depurating effluents and promote water reuse in safe conditions, and the supported TiO2 in ceramic materials may play a role in this scope.

Synthesis of Catechol Derived Rosamine Dyes and Their Reactivity toward Biogenic Amines.

Functional organic dyes play a key role in many fields, namely in biotechnology and medical diagnosis. Herein, we report two novel 2,3- and 3,4-dihydroxyphenyl substituted rosamines (3 and 4, respectively) that were successfully synthesized through a microwave-assisted protocol. The best reaction yields were obtained for rosamine 4, which also showed the most interesting photophysical properties, specially toward biogenic amines (BAs). Several amines including n- and t-butylamine, cadaverine, and putrescine cause spectral changes of 4, in UV-Vis and fluorescence spectra, which are indicative of their potential application as an effective tool to detect amines in acetonitrile solutions. In the gas phase, the probe response is more expressive for spermine and putrescine. Additionally, we found that methanolic solutions of rosamine 4 and n-butylamine undergo a pink to yellow color change over time, which has been attributed to the formation of a new compound. The latter was isolated and identified as 5 (9-aminopyronin), whose solutions exhibit a remarkable increase in fluorescence intensity together with a shift toward more energetic wavelengths. Other 9-aminopyronins 6a, 6b, 7a, and 7b were obtained from methanolic solutions of 4 with putrescine and cadaverine, demonstrating the potential of this new xanthene entity to react with primary amines.

Removal of a mixture of pharmaceuticals sulfamethoxazole and diclofenac from water streams by a polyamide nanofiltration membrane.

Wastewater treatment plants are not specially designed to remove pharmaceutically active compounds (PhACs), since these substances are toxic and bio-refractory. This paper aims to investigate and optimize the performance of the Trisep TS80 nanofiltration (NF) membrane for the removal of a mixture of two of the most detected PhACs in municipal wastewaters worldwide, sulfamethoxazole and diclofenac. Several NF tests were carried out to study the rejections of these contaminants both spiked in demineralized water, filtrated water taken from Mondego River and secondary effluent coming from a municipal wastewater treatment plant. Among the several studied operating variables, pH was the one that most affected the contaminant rejection and membrane permeability. In the case of synthetic effluent, an applied pressure of 10 bar and pH 7 were determined as the best operating conditions, which allowed almost total chemical oxygen demand retention and a global contaminant rejection of 96.3% to be achieved. The application of different water matrices (river water and secondary municipal effluent) had no relevant impact on process efficiency. Vibrio fischeri luminescence inhibition tests revealed that treatment by nanofiltration reduced acute toxicity of all studied effluents.

Integrating the Fenton's Process with Biofiltration by to Reduce Chemical Oxygen Demand of Winery Effluents.

The discharge of poorly decontaminated winery wastewater remains a serious environmental problem in many regions, and the industry is welcoming improved treatment methods. Here, an innovative decontamination approach integrating Fenton's process with biofiltration by Asian clams is proposed. The potential of this approach was assessed at the pilot scale using real effluent and by taking an actual industrial treatment system as a benchmark. Fenton peroxidation was observed to remove 84% of the effluent's chemical oxygen demand (COD), reducing it to 205 mg L. Subsequent biofiltration decreased the effluent's COD to approximately zero, well below the legal discharge limit of 150 mg L, in just 3 d. The reduction of the effluent's organic load through Fenton's process did not decrease its toxicity toward , but the effluent was much less harmful after biofiltration. The performance of the treatment proposed exceeded that of the integrated Fenton's process-sequencing batch reactor design implemented in the winery practice, where a residence time of around 10 d in the biological step typically results in 80 to 90% of COD removal. The method proposed is effective and compatible with typical winery budgets and potentially contributes to the management of a nuisance species.

Olive mill effluent depuration by ozonation and Fenton processes enhanced by iron wastes.

The aim of the present work was to compare the potential of iron industry wastes to enhance ozone and hydrogen peroxide action on the degradation of olive mill wastewaters (OMWs). The results attained show a higher efficiency for ozonation using a lower catalyst load. Nevertheless, Fenton's process led to a larger amount of chemical oxidation demand (COD) removed per mole of oxidant applied. It was concluded that hydroxyl radicals are responsible for the pollutant abatement. High eco-toxicity decay was observed after the treatments. Furthermore, a preliminary analysis of the iron shavings' stability was made by reusing it in two feed-batch trials. It was concluded that while activity was maintained for Fenton's, a decrease of about 20% was verified for catalytic ozonation. Comparing these results with the ones obtained for the same processes applied to an actual OMW, a lower percentage of COD abatement was achieved. However, when reporting the amount of COD removed per mole of oxidant used, the difference between effluents are not so high. This should be taken into account when deciding which process should be implemented at an industrial scale. With the outcomes of this research it was possible to conclude that integrating waste management with wastewater treatment was feasible.

Application of Fenton oxidation to reduce the toxicity of mixed parabens.

The aims of the present work were to assess the application of a chemical process to degrade a mixture of parabens and determine the influence of a natural river water matrix on toxicity. Model effluents containing either a single compound, namely methylparaben, ethylparaben, propylparaben, butylparaben, benzylparaben or p-hydroxybenzoic acid, or to mimic realistic conditions a mixture of the six compounds was used. Fenton process was applied to reduce the organic charge and toxic properties of the model effluents. The efficiency of the decontamination has been investigated using a chemical as well as a toxicological approach. The potential reduction of the effluents' toxicity after Fenton treatment was evaluated by assessing (i) Vibrio fischeri luminescence inhibition, (ii) lethal effects amongst freshwater Asian clams (Corbicula fluminea), and (iii) the impact on mammalian neuronal activity using brain slices. From the environmental point of view such a broad toxicity analysis has been performed for the first time. The results indicate that Fenton reaction is an effective method for the reduction of chemical oxygen demand of a mixture of parabens and their toxicity to V. fischeri and C. fluminea. However, no important differences were found between raw and treated samples in regard to mammalian neuronal activity.

Nanofiltration and Fenton's process over iron shavings for surfactants removal.

The presence of surfactants in wastewater composition tends to jeopardize the efficiency of the traditional aerobic treatment processes. In this regard, the application of Fenton's reaction and nanofiltration as single processes and integrated (nanofiltration followed by Fenton's process) was investigated on the abatement of a solution containing two surfactants usually found in effluents coming from detergent industry (dodecylbenzene--DDB and sodium lauryl ether sulphate--SLES). The potential of a solid waste (iron shavings) as catalyst in the Fenton's process was evaluated and the reaction system was optimized regarding the key operating parameters (iron and hydrogen peroxide concentration and pH). The highest chemical oxygen demand (COD) degradation (66%) was attained for pH 3, [H2O2] = 32 mM and 50 g/L of iron shavings. Besides, it was concluded that oxidation was due to hydroxyl radicals adsorbed on the metal surface even if bulk interaction between hydrogen peroxide and dissolved iron cannot be neglected. The main variables ruling nanofiltration were evaluated (pH, temperature and cross-flow rate). Eighty-four percent of COD rejection was determined at pH 7.5, cross-flow 14.4 cm3 s(-1), 20 degrees C and 15 bar of pressure drop. Finally, nanofiltration followed by Fenton's process under the best conditions was integrated; however, no significant improvement was attained with 85% of COD being globally removed.

Olive mill wastewater treatment strategies to obtain quality water for irrigation: A review.

The olive mill industry is a relevant sector in the economy of Mediterranean countries, while it involves high consumption of water and the production of effluents with high environmental impact. The efficient treatment of olive mill wastewater (OMW) is of high relevance, particularly for these countries. Climate changes are leading to increasing periods of droughts, and water recovery from polluted streams is essential to ensure the sustainability of this scarce resource. A combination of various technologies involving physical, chemical, and biological processes has been developed for OMW treatment. However, the treatments studied have limitations such as the operation costs, difficulty of industrial scale-up, and the fact that the vast majority do not lead to suitable treated water for discharge/reuse. As such, it is urgent to develop a solution capable of efficiently treating this effluent, overcoming the disadvantages of existing processes to convert OMW from a serious environmental problem into a valuable source of water and nutrients. In this review, several studies based on the OMW treatment are critically discussed, from conventional approaches such as the physical (e.g. centrifugation, filtration, and adsorption) and biological (anaerobic digestion and anaerobic co-digestion) processes, to the most recent technologies such as advanced membrane filtration, advanced oxidation processes (AOPs) and sulfate radical based AOPs (SR-AOPs). Due to the complexity of the effluent, OMW cannot be efficiently treated by a single process, requiring a sequence of technologies before reaching the required characteristics for discharge into water courses or use in crop irrigation. Reviewing the published results in this matter, it seems that the sequence of processes encompassing ozonation, anaerobic digestion, and SR-AOPs could be the ideal combination for this purpose. However, membrane technologies may be necessary in the final stage of treatment so that the effluent meets legal discharge or irrigation limits.

Treatment of a simulated phenolic effluent by heterogeneous catalytic ozonation using Pt/Al2O3.

Non-catalytic and catalytic ozonation over Pt/Al2O3 were considered in the treatment of a synthetic effluent composed of six phenolic acids usually present in olive mill wastewaters. In both processes the medium pH affected the rate of ozone decomposition and the formation of hydroxyl radicals. The optimum values were achieved for the catalytic system under pH 7 with 93.0 and 47.7%, respectively, of total phenol content and chemical oxygen demand (COD) removal, after 120 minutes of reaction. For pH 3, the catalytic ozonation followed a free radical pathway perceived by the presence of radical scavengers. No significant structural differences were observed between the fresh and used solid catalyst in X-ray diffraction analysis. Aluminium leaching behaviour was also evaluated at the end of each experiment. Moreover, a sequence of feed-batch trials involving the catalyst reutilization exhibited almost constant activity during the operation time. Eco-toxicological tests were performed for both processes, revealing that the treated effluent still presents some ecological impact, although it is lower than that for the raw wastewater.

Low-cost materials for swine wastewater treatment using adsorption and Fenton's process.

Untreated swine wastewater (SW) discharge leads to serious consequences such as water quality decreasing related to eutrophication and proliferation of harmful algae containing cyanotoxins, which can cause acute intoxication in humans. The use of untreated pig farming effluent as fertilizer can lead to the accumulation of polluting compounds. Biological treatments can degrade organic matter but have the disadvantage of requiring large areas and high retention times and demonstrating low efficiencies in the degradation of refractory compounds such as pharmaceutical compounds. In this ambit, the performance of four low-cost materials was evaluated for treatment of a swine wastewater using physical-chemical processes such as adsorption and Fenton's process. The tested materials are two natural resources, red volcanic rock from Canary (RVR) Islands and black volcanic rock (BVR) from Azores, and two industry residues, red mud (RM) and iron filings (IF). Among the tested materials, only IFs are catalytically active for Fenton's peroxidation. Still, RVR, BVR, and RM were efficient adsorbents removing up to 67% of COD. The combination between adsorption followed by Fenton's process using IF as catalyst showed interesting results. When RM is applied as adsorbent in the diluted effluent, it was able to remove 67% and 90% of COD for adsorption and adsorption followed by IF Fenton, respectively. At those conditions, the resultant treated effluent accomplishes the requirements for direct discharge in the natural water courses as well as the parameters for water reusing.

Heterogeneous photosensitization for water reuse in cellars: evaluation of silica, spongin, and chitosan as carrier material.

Photosensitization, a powerful oxidation reaction, offers significant potential for wastewater treatment in the context of industrial process water reuse. This environmentally friendly process can be crucial in reducing water consumption and industrial pollution. The ultimate goal is to complete process water reuse, creating a closed-loop system that preserves the inherent value of water resources. The photosensitized oxidation reaction hinges on three essential components: the photosensitizer, visible light, and oxygen. In this study, we assess the performance of three distinct materials-silica, chitosan, and spongin-as carrier materials for incorporating the phthalocyanine photosensitizer (ZnPcS4) in the heterogenous photosensitization process. Among the three materials under study, chitosan emerged as the standout performer in reactor hydrodynamic performance. In the photooxidation process, the photosensitizer ZnPcS4 exhibited notable efficacy, resulting in a significant reduction of approximately 20 to 30% in the remaining COD concentration of the cellar wastewater. Chitosan demonstrated exceptional hydrodynamic characteristics and displayed a favorable response to pH adjustments within the range of 8 to 10, outperforming the other two carrier materials. To further enhance the efficiency of continuous operation, exploring methods for mitigating photosensitizer bleaching within the reaction medium and investigating the impact of different pH values on the process optimization would be prudent.

Organic biowastes blend selection for composting industrial eggshell by-product: experimental and statistical mixture design.

Composting is one of the technologies recommended for pre-treating industrial eggshells (ES) before its application in soils, for calcium recycling. However, due to the high inorganic content of ES, a mixture of biodegradable materials is required to assure a successful procedure. In this study, an adequate organic blend composition containing potato peel (PP), grass clippings (GC) and wheat straw (WS) was determined by applying the simplex-centroid mixture design method to achieve a desired moisture content, carbon: nitrogen ratio and free air space for effective composting of ES. A blend of 56% PP, 37% GC and 7% WS was selected and tested in a self heating reactor, where 10% (w/w) of ES was incorporated. After 29 days of reactor operation, a dry matter reduction of 46% was achieved and thermophilic temperatures were maintained during 15 days, indicating that the blend selected by statistical approach was adequate for composting of ES.

Nanostructured photocatalysts for the abatement of contaminants by photocatalysis and photocatalytic ozonation: An overview.

The water scarcity, the presence of different contaminants in the worldwide waters and wastewaters and their impacts should motivate their good elimination and water management. With this, photocatalysis and photocatalytic ozonation are strong solutions to obtain good quality reclaimed water, for different applications. Nanostructured supported photo-active catalysts, such as the TiO2, WO3 or ZnO can positively affect the performance of such technologies. Therefore, different semiconductors materials have been aroused the interest of the scientific community, mainly due to its functional properties as well as characteristics imposed by the different nanostructures. With this, this work overviews different works and perspective on the TiO2 nanotubes and other semiconductors nanostructures, with the analysis of different works from 2001 to 2022. Aspects as the substrate effect, electrolyte nature, aspect ratio, electrolyte aging, and annealing treatment but also the effect of morphology, anodization time, applied voltage, temperature and viscosity are discussed. Modification of TiO2 nanotubes is also presented in this paper. The main objective of this work is to present and discuss the key parameters and their effects on the anodization of different semiconductors, as well as the results obtained until today on the degradation of different contaminants by photocatalysis and photocatalytic ozonation, as well as their use on the treatment of real wastewater. TiO2 nanotubes present unique properties and highly ordered configuration, which motivate their use on photo-driven technologies for the pollutant's abatement, even when compared to other nanostructures. However, photocatalysts with activity on the visible range and solar radiation, such as the WO3, can present higher performance and can decrease operational costs, and must be an important source and a key to find efficient and cost-friendly solutions.

Ozonation of Selected Pharmaceutical and Personal Care Products in Secondary Effluent-Degradation Kinetics and Environmental Assessment.

The efficiency of ozonation depends on the water matrix and the reaction time. Herein, these factors were addressed by assessing the removal of five pharmaceutical and personal care products (PPCPs) by ozonation. The main aims were: (i) to assess the effects of the water matrix on the degradation kinetics of PPCPs, individually and in mixture, following ozonation; and (ii) to assess the ecotoxicological impact of the ozone reaction time on the treatment of a spiked municipal wastewater (MW) added the five PPCPs over several species. The degradation of the PPCPs was faster in ultrapure water, with all PPCPs being removed in 20 min, whereas in the MW, a 30 min ozonation period was required to achieve a removal close to 100%. Increasing the number of PPCPs in the water matrix did not affect the time required for their removal in the MW. Regarding the ecotoxicity assessment, Raphidocelis subcapitata and Daphnia magna were the least sensitive species, whereas Lemna minor was the most sensitive. The temporal variation of the observed effects corroborates the degradation of the added PPCPs and the formation of toxic degradation by-products. The removal of the parent compounds did not guarantee decreased hazardous potential to biological species.

Sulfate radical based advanced oxidation processes for agro-industrial effluents treatment: A comparative review with Fenton's peroxidation.

Agro-industrial wastewater management becomes a major task while environmental regulations are becoming stricter worldwide. Agro-industrial wastewaters are known by high content of organic pollutants that cause an adverse effect on the water bodies. Industries are looking for efficient, easy-to-use and affordable treatment processes. Sulfate radical based advanced oxidation processes (S-AOPs) are arising as suitable alternatives for agro-industrial effluents treatment. In this review, the major findings regarding the application of this technology for real agro-industrial wastewater depuration are discussed. Moreover, these technologies are compared as an alternative to Fenton's process, which is a widely studied advanced oxidation process and with high efficiency in the treatment of agro-industrial effluents. The studies already carried out are promising, but there is still a great lack of studies in this area and using this technique.

Advanced oxidation processes for treatment of effluents from a detergent industry.

Ozonation, catalytic ozonation, Fenton's and heterogeneous Fenton-like processes were investigated as possible pretreatments of a low biodegradable and highly toxic wastewater produced by a detergent industry. The presence of a Mn-Ce-O catalyst in ozonation enhances the biodegradability and improves the degradation at low pH values. However, a high content of carbonyl compounds adsorbed on the recovered solid indicates some limitations for real-scale application. A commercial Fe2O3-MnOx catalyst shows higher activity as well as higher stability concerning carbon adsorption, but the leaching of metals is larger than for Mn-Ce-O. Regarding the heterogeneous Fenton-like route with an Fe-Ce-O catalyst, even though a high activity and stability are attained, the intermediates are less biodegradable than the original compounds, indicating that the resulting effluent cannot be conducted to an activated sludge post-treatment. The highest enhancement of effluent biodegradability is obtained with the classic homogeneous Fenton's process, with the BOD5/COD ratio increasing from 0.32 to 0.80. This process was scaled up and the treated effluent is now safely directed to a municipal wastewater treatment plant.

Biocompounds recovery from olive mill wastewater by liquid-liquid extraction and integration with Fenton's process for water reuse.

The olive mill wastewaters obtained from two different processes, press extraction olive mill wastewater (POMW) from Portugal and two-phase system olive mill wastewater (2POMW) from Spain, were treated to recover phenolic compounds and water sequentially, by the integration of liquid-liquid extraction with Fenton's processes. From the recovered fractions, squalene, oleic acid, tyrosol, syringic acid, and p-coumaric acid were identified, and oleic acid appears in a higher concentration for 2POMW wastewater for all used solvents compared to POMW samples. Recovered fractions presented higher antioxidant activity, but remained antioxidants were found in the residual water. The wastewaters coming from a two-phase extraction method (2POMW) present higher phytotoxicity according to germination index, but the application of Fenton's process was able to improve the water quality to be re-used since an increase on the water biodegradability (BOD5/COD) and toxicity reduction were achieved.

Adopting strategies to improve the efficiency of ozonation in the real-scale treatment of olive oil mill wastewaters.

In this experimental work the ozone action on the depuration of olive oil mill wastewater is studied for different operational conditions based on an actual industrial treatment plant. It was verified that the application of a Mn-Ce-O catalyst prepared at the laboratory, with a Mn/Ce molar proportion of 70/30, enhances the depuration efficiency and the effluent biodegradability. Ozonation operation at the natural pH of the effluent is recommended. Moreover, the integration of the Fenton process as a pretreatment improves the final chemical oxygen demand removal and enables a totally biodegradable effluent to be obtained, as confirmed by respirometric techniques.

Photocatalytic ozonation of parabens mixture using 10% N-TiO2 and the effect of water matrix.

Nitrogen-doped TiO2 was applied in photocatalytic ozonation reactions for the degradation of a mixture of five parabens under UVA radiation, being evaluated the influence of the reaction medium. The initial mixture parabens concentration considered in these experiments was 50 mg L-1. The parabens degradation rate was considerably enhanced under neutral pH, specially using a buffered solution, leading to a complete removal under 60 min and with transferred ozone dose (TOD) 36% lower compared to reaction under natural conditions. Isopropanol, known radical scavenger, impeded the complete contaminants removal, affecting the reaction route and by-products formation, but when KI was jointly added, total removal was achieved under 30 min and with a TOD of 25.9 mg L-1. Parabens depletion was also improved in the presence of Cl-, SO42- and HCO3-, commonly present in wastewaters. The use of river water (RW) and a secondary wastewater (SWW) as water matrices maintained the process efficiency with lower TOD required, and treated solutions presented lower phytotoxicity towards Lepidium sativum.

Unexpected effect of ozone on the paraben's mixture degradation using TiO2 supported nanotubes.

Titanium dioxide can present advantages when coupled with ozonation. Moreover, the catalytic ozonation can be enhanced by radiation. The main disadvantage of this technology is the use of a suspended catalyst entailing a separation step. Thus, catalytic ozonation was analysed using supported TiO2 nanotubes prepared by anodization at different voltages. The effect of different radiation sources on the catalytic ozonation of parabens was tested. The increase on voltage preparation led to plates with higher surface areas from 60 to 280 cm2. However, this did not improve the parabens mixture degradation during UVA photocatalytic ozonation. The use of sunlight radiation allows a significant reduction in terms of time necessary for total parabens degradation from 15 to 10 min. However, the amount of ozone required doubles. Catalytic ozonation presents worst results than single ozonation. This means that molecular ozone is the main responsible for degradation. No dissolved ozone was detected at the experiments with supported nanotubes which could mean that it was adsorbed on the catalysts surface decreasing the degradation rates. The presence of municipal wastewaters as matrix inhibited parabens degradation for both single and catalytic ozonation, mainly due to the trapping ozone effect. In fact, for the TOD of 4.5 mg/L it was just possible to remove about 80% of parabens when MWW compared to 100% when UP was used. Even so, the presence of supported nanotubes during ozonation seems to be required to reduce the toxicity of the resultant treated effluent. In fact, the wastewater luminescence inhibition decreased (from 100 to 43%) and germination index increased (from 7 to 97%) with catalytic ozonation which may enable treated water reuse.