Advances in Photocatalytic Membrane Reactor.

Photocatalytic membrane reactors (PMRs) are a promising technology that combines the benefits of photocatalysis and membrane separation [...].

Hybrid system coupling ozonation and nanofiltration with functionalized catalytic ceramic membrane for ibuprofen removal.

The investigations on the removal of ibuprofen (IBU) in a hybrid system coupling ozonation and nanofiltration with functionalized catalytic ceramic membrane are presented. The gaseous ozone into feed water in concentration of 11 g Nm-3 was supplied. Positive influence of catalytic ozonation on ibuprofen decomposition was observed. The application of catalytic nanofiltration membrane led to the ibuprofen removal of 91% after the first 15 min from the beginning of the O3/NF process, while at the same time, for the pristine membrane, it was equal to 76%. The investigations revealed incomplete degradation of drug under pH 3 after 2 h, i.e., 89%. On the other hand, the addition of inorganic salts did not affect the catalytic ibuprofen removal efficiency. Under acidic pH, the highest permeate flux decline (26%) was noted, whereas no differences between permeate flux measured under natural and alkaline conditions were observed. During the treatment process, three IBU by-products were detected, which significantly affected the permeate toxicity; however, after 2 h of catalytic nanofiltration, the product of treatment process was found as non-toxic.

Ozone Diffusion through a Hollow Fiber Membrane Contactor for Pharmaceuticals Removal and Bromate Minimization.

Recently, ozonation has been advocated as a solution to tackle emerging contaminants. Hollow fiber membrane contactors (HFMC) have a lower residual ozone concentration than bubble reactors that could limit the formation of potential ozonation by-products, especially bromates that are regulated in drinking water. The aim of this study was to evaluate ozonation with HFMC for pharmaceutical abatement and bromate minimization compared to bubble columns in wastewater. A HFMC, composed of 65 polytetrafluoroethylene hollow fibers with a 0.45 mm/0.87 mm inner/external diameter and a 0.107 m² exchange surface, was used for the ozonation of real-treated wastewater spiked with 2 µM of p-chlorobenzoic acid (p-CBA) and 3 mg.L-1 of bromide. p-CBA was tracked to monitor the production of strongly-oxidant hydroxyl radicals from the decomposition of the molecular ozone. At 100% p-CBA abatement, 1600 µg.L-1 of bromate was formed with the HFMC, whereas 3486 µg.L-1 was formed with the bubble column. These results demonstrate that HFMC can produce a significant amount of hydroxyl radicals while limiting bromate formation in real-treated wastewater. The test water was also spiked with carbamazepine and sulfamethoxazole to evaluate the abatement efficiency of the process. Short contact times (approximately 2s) achieved high rates of pharmaceuticals removal without bromate formation.

Understanding Aging Mechanisms in the Context of UV Irradiation of a Low Fouling and Self-Cleaning PVDF-PVP-TiO2 Hollow-Fiber Membrane.

In the context of designing a photocatalytic self-cleaning/low-fouling membrane, the stability of PVDF-PVP-TiO2 hollow-fiber membranes under UV irradiation has been studied. The effect of irradiation power, aqueous environment composition and fouling state on the properties of the membranes has been investigated. With this aim, SEM observations, chemical analysis and tensile strength measurements have been conducted. The results indicate that pristine membranes that undergo UV irradiation in ultra-pure water are significantly degraded due to attacks of OH° radicals. However, when methylene blue, used as a model pollutant, is introduced in the aqueous environment, OH° radicals preferentially react with this molecule rather than the membranes, successfully preserving the original properties of the latter. The presence of an adsorbed BSA layer (pre-fouling by immersion) on the surface of the membrane delays membrane aging, as the BSA layer is degraded by radicals instead of the membrane material. The degradation of the BSA layer also validates the self-cleaning properties of the membrane. However, when membranes are pre-fouled by filtration of a 2 g/L BSA solution, delay to aging is less. This is because OH° radicals do not reach BSA molecules that are trapped inside the membrane pores, and therefore react with the membrane material.

Impact of Pre-Ozonation during Nanofiltration of MBR Effluent.

This study aimed to investigate the impact of real MBR effluent pre-ozonation on nanofiltration performances. Nanofiltration experiments were separately run with non-ozonated real MBR effluent, ozonated real MBR effluent and synthetic ionic solution mimicking the ionic composition of the real MBR effluent. The specific UV absorbance and the chemical oxygen demand were monitored during ozonation of real effluent, and the mineralization rate was calculated through the quantitative analysis of dissolved organic carbon. The membrane structure was characterized using SEM on virgin and fouled membrane surfaces and after different cleaning steps. The results confirm the low effect of the ozonation process in terms of organic carbon mineralization. However, the chemical oxygen demand and the specific UV absorbance were decreased by 50% after ozonation, demonstrating the efficiency of ozonation in degrading a specific part of the organic matter fraction. A benefic effect of pre-ozonation was observed, as it limits both fouling and flux decrease. This study shows that the partial mineralization of dissolved and colloidal organic matter by ozonation could have a positive effect on inorganic scaling and decrease severe NF membrane fouling.

Performance of PVDF-TiO2 Membranes during Photo-Filtration in the Presence of Inorganic and Organic Components.

In this study, the anti-fouling performance of PVDF-TiO2 composite membranes, indicated by their permeate flux, was studied with different types of synthetic feed solutions. Photo-filtration (filtration under continuous UV irradiation) of solutions containing inorganic and organic components, which are ubiquitous in drinking/natural water, was performed to evaluate their influence on the photo-induced properties and performance of the membranes. The results indicated that inorganic fouling was unlikely to occur on PVDF-TiO2 membranes, and the presence of common inorganic ions in drinking water did not hinder their performance. However, in the particular case where a small amount of Cu2+ coexisted alongside HCO3- in the feed solution, inorganic fouling occurred, causing severe flux decline and prohibiting the photo-induced properties of the membranes. On the other hand, when used to filter organic fouling solutions, the membranes showed strong resistance to sodium alginate fouling, and less so for humic acids. In terms of separation efficiency, the membranes showed no advantages when operated in photo-filtration mode, as the rejection rate of both foulants under photo-filtration was not higher than that under normal filtration. In the case of humic acids, the photodegradation of humic substances into smaller compounds that were able to enter the permeate stream led to a lower rejection rate. Nevertheless, photo-filtration of these organic foulants still offered a higher permeate flux than normal filtration, up to a certain concentration level (5 mg/L for humic acids and 50 mg/L for sodium alginate).

Influence of Preparation Temperature on the Properties and Performance of Composite PVDF-TiO2 Membranes.

Composite PVDF-TiO2 membranes are studied extensively in literature as effective anti-fouling membranes with photocatalytic properties. Yet, a full understanding of how preparation parameters affect the final membrane structure, properties and performance has not been realized. In this study, PVDF-TiO2 membranes (20 wt% TiO2/PVDF) were fabricated via the non-solvent-induced phase separation (NIPS) method with an emphasis on the preparation temperature. Then, a systematic approach was employed to study the evolution of the membrane formation process and membrane properties when the preparation temperature changed, as well as to establish a link between them. Typical asymmetric membranes with a high porosity were obtained, along with a vast improvement in the permeate flux compared to the neat PVDF membranes, but a reduction in mechanical strength was also observed. Interestingly, upon the increase in preparation temperature, a significant transition in membrane morphology was observed, notably the gradual diminution of the finger-like macrovoids. Other membrane properties such as permeability, porosity, thermal and mechanical properties, and compression behavior were also influenced accordingly. Together, the establishment of the ternary phase diagrams, the study of solvent-nonsolvent exchange rate, and the direct microscopic observation of membrane formation during phase separation, helped explain such evolution in membrane properties.

Ozonation using hollow fiber contactor technology and its perspectives for micropollutants removal in water: A review.

Membrane contactor is a device generally used for the removal or the absorption of a gas into another fluid. The membrane acts as a barrier between the two phases and mass transfer occurs by diffusion and not by dispersion. This article is a review of the application of membrane contactor technology for ozonation applied to water treatment. The challenge of removing micropollutants is also discussed. In the first part, the ozonation process is mentioned, in particular chemical reactions induced by ozone and its advantages and disadvantages. In the second part, generalities on membrane contactor technology using hollow fibers are presented. Then, the benefit of using a membrane contactor for the elimination of micropollutants is shown through a critical analysis of the influence of several parameters on the ozonation efficiency. The impact of the membrane material is also highlighted. Finally, several modeling approaches are presented as a tool for a better understanding of the phenomena occurring in the contactor and a possible optimization of this process.

Ozonation as a pretreatment process for nanofiltration brines: Monitoring of transformation products and toxicity evaluation.

Considerable interest has been given to using nanofiltration (NF) in lieu of reverse osmosis for water reclamation schemes due to lower energy consumption, higher flux rates while ensuring good micropollutants rejection. The application NF results in the generation of a large concentrated waste stream. Treatment of the concentrate is a major hurdle for the implementation of membrane technologies since the concentrate is usually unusable due to a large pollutants content. This work focuses on the application of ozonation as pretreatment of urban NF concentrates, the generation of transformation products and their relative toxicity. Three pharmaceutical micropollutants largely encountered in water cycle were selected as target molecules: acetaminophen, carbamazepine and atenolol. Through accurate-mass Q-TOF LC-MS/MS analyses, more than twenty ozonation products were detected, structure proposals and formation pathways were elaborated. Attempts were made to understand the correlation between the transformation products and acute toxicity on Vibrio fischeri strain. It is the first time that an integrated study reported on the ozonation of pharmaceuticals in urban membrane concentrates, in terms of transformation products, kinetics, degradation mechanisms, as well as toxicity assessment.

Correlation between degradation pathway and toxicity of acetaminophen and its by-products by using the electro-Fenton process in aqueous media.

The evolution of the degradation by-products of an acetaminophen (ACE) solution was monitored by HPLC-UV/MS and IC in parallel with its ecotoxicity (Vibrio fischeri 81.9%, Microtox® screening tests) during electro-Fenton (EF) oxidation performed on carbon felt. The aromatic compounds 2-hydroxy-4-(N-acetyl) aminophenol, 1,4-benzoquinone, benzaldehyde and benzoic acid were identified as toxic sub-products during the first stage of the electrochemical treatment, whereas aliphatic short-chain carboxylic acids (oxalic, maleic, oxamic, formic, acetic and fumaric acids) and inorganic ions (ammonium and nitrate) were well identified as non-toxic terminal sub-products. Electrogenerated hydroxyl radicals then converted the eco-toxic and bio-refractory property of initial ACE molecule (500 mL, 1 mM) and subsequent aromatic sub-products into non-toxic compounds after 2 h of EF treatment. The toxicity of every intermediate produced during the mineralization of ACE was quantified, and a relationship was established between the degradation pathway of ACE and the global toxicity evolution of the solution. After 8 h of treatment, a total organic carbon removal of 86.9% could be reached for 0.1 mM ACE at applied current of 500 mA with 0.2 mM of Fe2+ used as catalyst.

Influence of volumetric reduction factor during ozonation of nanofiltration concentrates for wastewater reuse.

Global population growth induces increased threat on drinking water resources. One way to address this environmental issue is to reuse water from wastewater treatment plant. The presence of pathogenic microorganisms and potentially toxic organic micropollutants does not allow a direct reuse of urban effluents. Membrane processes such reverse osmosis (RO) or nanofiltration (NF) can be considered to effectively eliminate these pollutants. The integration of membrane processes involves the production of concentrated retentates which require being disposed. To date, no treatment is set up to manage safely this pollution. This work focuses on the application of ozonation for the treatment of NF retentates in the framework of the wastewater reuse. Ozonation is a powerful oxidation process able to react and degrade a wide range of organic pollutants. Four pharmaceutical micropollutants were selected as target molecules: acetaminophen, carbamazepine, atenolol and diatrozic acid. This study highlighted that NF represents a viable alternative to the commonly used RO process ensuring high retention at much lower operating costs. Ozonation appears to be effective to degrade the most reactive pollutants toward molecular ozone but is limited for the reduction of refractory ozone pollutants due to the inhibition of the radical chain by the high content of organic matter in the retentates. The ozonation process appears to be a promising NF retentate treatment, but additional treatments after ozonation are required to lead to a zero liquid discharge treatment scheme.

Evidence of solute-solute interactions and cake enhanced concentration polarization during removal of pharmaceuticals from urban wastewater by nanofiltration.

The objective of this paper is to help understanding the distinctive influence of the matrix and of the flux decline (e.g. through the cake enhanced concentration polarization (CECP) phenomenon) on the removal mechanisms of four pharmaceutically active compounds (PhACs) from wastewater treatment plant (WWTP) effluent by nanofiltration (NF). PhACs which are commonly encountered in secondary treated effluent were spiked in various matrix (real and synthetic) to investigate the separate and synergetic effects of the organic and ionic environment on PhACs rejection by two commercial membranes (NF-90 and NF-270). With pure water, rejection of NF membranes is dependent on the type of PhACs and of the permeate flux variations. Then, it appeared that the rejection of PhACs by NF-90 was poorly influenced by the type of compounds, because of the prevalence of steric mechanisms, but rather influenced by permeate flux variations and thus to fouling. For this tight NF membrane, CECP impacts PhACs rejection at the start of filtration while after a dense cake is formed, it became enhanced. On the contrary, rejections of PhACs by the NF-270 were enhanced during the filtration of the real wastewater in comparison with spiked pure water. It appeared that for loose-NF membranes, PhACs rejection is mainly governed by solute-solute interactions (EfOM-compound association) or electrostatic membrane-solute interactions. Finally, it seems that calcium concentration of the effluent is a critical parameter for the rejection of PhACs as it alters both the availability of sites for PhACs association and the fouling layer density. Rejections of the NF-270 were negatively impacted in the presence of Ca2+. Such a study has practical implications for further understanding of the fate of trace organic compounds during nanofiltration of wastewater for reuse applications.

Toxicity removal assessments related to degradation pathways of azo dyes: Toward an optimization of Electro-Fenton treatment.

The degradation pathway of Acid Orange 7 (AO7) by Electro-Fenton process using carbon felt cathode was investigated via HPLC-UV and LC-MS, IC, TOC analysis and bioassays (Vibrio Fischeri 81.9% Microtox(®) screening tests). The TOC removal of AO7 reached 96.2% after 8 h treatment with the optimal applied current density at -8.3 mA cm(-2) and 0.2 mM catalyst concentration. The toxicity of treated solution increased rapidly to its highest value at the early stage of electrolysis (several minutes), corresponding to the formation of intermediate poisonous aromatic compounds such as 1,2-naphthaquinone (NAPQ) and 1,4-benzoquinone (BZQ). Then, the subsequent formation of aliphatic short-chain carboxylic acids like acetic acid, formic acid, before the complete mineralization, leaded to a non-toxic solution after 270 min for 500 mL of AO7 (1 mM). Moreover, a quantitative analysis of inorganic ions (i.e. ammonium, nitrate, sulfate) produced during the course of degradation could help to verify molar balance with regard to original nitrogen and sulfur elements. To conclude, a clear degradation pathway of AO7 was proposed, and could further be applied to other persistent pharmaceuticals in aquatic environment.

Study of photocatalytic degradation of tributyltin, dibutylin and monobutyltin in water and marine sediments.

This study reports on the first assessment of the treatment of sediments contaminated by organotin compounds using heterogeneous photocatalysis. Photocatalysis of organotins in water was carried out under realistic concentration conditions (µgL(-1)). Degradation compounds were analyzed by GC-ICP-MS; a quasi-complete degradation of tributyltin (TBT) in water (99.8%) was achieved after 30min of photocatalytic treatment. The degradation by photolysis was about (10%) in the same conditions. For the first time decontamination of highly polluted marine sediments (certified reference material and harbor sediments) by photocatalysis proves that the use of UV and the production of hydroxyl radicals are an efficient way to treat organotins adsorbed onto marine sediment despite the complexity of the matrix. In sediment, TBT degradation yield ranged from 32% to 37% after only 2h of irradiation (TiO2-UV) and the by-products: dibutyltin (DBT) and monobutyltin (MBT) were degraded very rapidly in comparison with TBT. It was shown that during photocatalysis of organotins in sediments, the hydroxyl radical attack and photolysis are the two ways for the degradation of adsorbed TBT.