Assessment of new hydrogen peroxide activators in water and comparison of their active species toward contaminants of emerging concern.

Advanced oxidation processes are the most efficient tool to thwart the overaccumulation of harmful organic compounds in the environment. In this direction bioinspired metal complexes may be a viable solution for oxidative degradations in water. However, their synthesis is often elaborated and their scalability consequently low. This study presents alternative easy-to-synthesize bioinspired metal complexes to promote degradations in water. The metals employed were iron and manganese ions, hence cheap and highly accessible ions. The complexes were tested toward Phenol, Estrone, Triclosan, Oxybenzone, Diclofenac, Carbamazepine, Erythromycin, Aspartame, Acesulfame K, Anisole and 2,4-Dinitrotoluene. The reaction favoured electron-rich compounds reaching a removal efficiency of over 90%. The central ion plays a crucial role. Specifically, Mn(II) induces a non-radical pathway while iron ions a predominant radical one (⋅OH is predominant). The iron systems resulted more versatile toward contaminants, while the manganese ones showed a higher turn-over number, hence higher catalytic behaviour.

A Comprehensive Review on Modification of Titanium Dioxide-Based Catalysts in Advanced Oxidation Processes for Water Treatment.

It has become necessary to develop effective strategies to prevent and reduce water pollution as a result of the increase in dangerous pollutants in water reservoirs. Consequently, there is a need to design new catalyst materials to promote the efficiency of advanced oxidation processes (AOPs) in the field of wastewater treatment plant to ensure the mineralization of trace organic contaminants. A notable approach gaining attention involves the coupling of sulfate radicals-based AOPs to photocatalysis or electrocatalysis processes, aiming to achieve the complete removal of refractory contaminants into water and carbon dioxide. Titanium dioxide as metal oxide has received great attention for its catalytic application in water purification. TiO2 catalysts offer a multitude of advantages in AOPs. They are characterized by their high photocatalytic activity under both ultraviolet and visible light, making them environmentally friendly due to the absence of toxic byproducts during oxidation. Their versatility is remarkable, finding utility in various AOPs, from photocatalysis to photo-Fenton processes. TiO2's durability ensures long-lasting catalytic activity, which is crucial for continuous treatment processes, and their cost-effectiveness is particularly advantageous. Furthermore, their chemical stability allows it to withstand varying pH conditions. However, the large band gap energy and low electrical conductivity hinder the catalytic reaction effectiveness. This review aims to examine various approaches to enhance the catalytic performance of titanium dioxide, with the objective of enabling more efficient water purification methods.

A facile approach to modify cellulose nanocrystal for the adsorption of perfluorooctanoic acid.

Cellulose-based materials are a sustainable alternative to polymers derived from petroleum. Cellulose nanocrystal (CNC) is a biopolymer belonging to this family; it is commonly known for its important physical and chemical properties and ability to form a film. Modifying CNC via electrostatic interaction provided by cationic polymers is a facile and promising technique to enlarge the application of CNC. Herein, we report the preparation of films, from blends of negatively charged CNC and positively charged poly (trimethyl aminoethyl methacrylate) (PTMAEMA). The interaction between CNC and PTMAEMA was verified by using a quartz crystal microbalance with dissipation monitoring (QCM-D), as well as by measuring the particle size and ζ-potential of the casting mixture. To favor the application of the nanocomposite film in water treatment, the film was supported on Whatman™ paper, and adsorption tests were conducted using perfluorooctanoic acid (PFOA) as a model compound for the family of persistent fluorinated pollutants known as PFAS (per- and polyfluoroalkyl substances).

CaCu3Ti4O12 Perovskite Materials for Advanced Oxidation Processes for Water Treatment.

The many pollutants detected in water represent a global environmental issue. Emerging and persistent organic pollutants are particularly difficult to remove using traditional treatment methods. Electro-oxidation and sulfate-radical-based advanced oxidation processes are innovative removal methods for these contaminants. These approaches rely on the generation of hydroxyl and sulfate radicals during electro-oxidation and sulfate activation, respectively. In addition, hybrid activation, in which these methods are combined, is interesting because of the synergistic effect of hydroxyl and sulfate radicals. Hybrid activation effectiveness in pollutant removal can be influenced by various factors, particularly the materials used for the anode. This review focuses on various organic pollutants. However, it focuses more on pharmaceutical pollutants, particularly paracetamol, as this is the most frequently detected emerging pollutant. It then discusses electro-oxidation, photocatalysis and sulfate radicals, highlighting their unique advantages and their performance for water treatment. It focuses on perovskite oxides as an anode material, with a particular interest in calcium copper titanate (CCTO), due to its unique properties. The review describes different CCTO synthesis techniques, modifications, and applications for water remediation.

Photoelectrocatalytic Degradation of Methylene Blue on Electrodeposited Bismuth Ferrite Perovskite Films.

Electrodeposited bismuth ferrite (BiFeO3) thin films on fluorine-doped tin oxide (FTO) substrate were employed as photoanodes in the photoelectrocatalytic degradation of methylene blue. The BiFeO3 thin films electrodeposited for 300 s, 600 s, 1200 s, 1800 s and 3600 s were characterised with XRD, field emission scanning electron microscopy (FESEM) and UV-vis diffuse reflectance spectroscopy. SEM images displayed different morphology at different electrodeposition times which affects the photoelectrocatalytic (PEC) performances. The FESEM cross-sectional area was used to measure the thickness of the film. The optical properties showed that the band gaps of the photoanodes were increasing as the electrodeposition time increased. The photocurrent response obtained showed that all thin film photoanodes responded to visible light and lower charge transfer resistance (from electrochemical impedance spectroscopy studies) was observed with photoanodes electrodeposited at a shorter time compared to those at a longer time. The PEC application of the photoanode for the removal of methylene blue (MB) dye in water showed that the percentage degradation decreased with an increase in electrodeposition time with removal rates of 97.6% and 70% observed in 300 s and 3600 s electrodeposition time, respectively. The extent of mineralisation was measured by total organic carbon and reusability studies were carried out. Control experiments such as adsorption, photolysis, photocatalysis and electrocatalysis processes were also investigated in comparison with PEC. The electrodeposition approach with citric acid exhibited improved electrode stability while mitigating the problem of catalyst leaching or peeling off during the PEC process.

N-Doped HNT/TiO2 Nanocomposite by Electrospinning for Acetaminophen Degradation.

In this study, we combined electrospinning of a large amount of halloysite (HNT, 95%) with nitriding to produce N-HNT-TiO2 composite nanofibers (N-H95T5 hereafter) to be used for acetaminophen (ACT) photodegradation. Investigation of the morphological and structural properties of the obtained materials did not highlight any significant difference in their morphological features and confirmed that nitrogen was evenly distributed in the samples. Photocatalytic tests under visible light showed that acetaminophen photodegraded faster in the presence of samples with nitrogen (N-H95T5) than without (H95T5 nanofibers). Moreover, the N-H95T5 nanocomposite photocatalytic activity did not change after repeated utilization (five cycles). The addition of scavengers during photocatalytic tests showed the key implication of OH•-, O2•- and h+ radicals in acetaminophen degradation. These results indicated that N-H95T5 composite nanofibers could be considered a cheap multifunctional material for photodegradation and could open new prospects for preparing tunable photocatalysts.

Adsorptive Removal of Rhodamine B Dye Using Carbon Graphite/CNT Composites as Adsorbents: Kinetics, Isotherms and Thermodynamic Study.

The study of the adsorption efficiency of new carbon/CNT composites was undertaken to remove a cationic dye, Rhodamine B (RhB), from dye-contaminated wastewater. Indeed, we investigated the effect of different experimental parameters such as time, initial concentration of dye and temperature on the adsorption of RhB by the carbon composites (KS44-0 and KS44-20). The results showed that the adsorption uptake increased with the initial concentration and solution temperature while maintaining a relatively constant pH. The presence of the carbon nanotubes provided more active sites for dye removal and improved the adsorption behavior of Rhodamine B dye. The analysis of the experimental data was conducted using model equations, such as Langmuir, Freundlich and Temkin isotherms. As regards the Freundlich isotherm model, it was the best fit for the equilibrium data obtained from the experiments. The applicability of the pseudo-second-order equation could be explained assuming that the overall adsorption rate is limited by the rate of adsorbate transport that occurs on the pore surfaces of adsorbents. Furthermore, the intraparticle diffusion and Bangham models were used to investigate the diffusion mechanism of RhB absorption onto carbon composites. They showed that multiple adsorption stages occurred simultaneously via pore surface diffusion. Concerning the thermodynamic parameters (∆G°, ∆H°, and ∆S°), they were calculated and explained in the mean of the chemical structure of the adsorbate. Negative standard Gibbs free energy change values (ΔG°ads) at all temperatures suggested that the adsorption process was spontaneous, and the positive values of the standard enthalpy change of adsorption (∆H°ads) revealed the reaction to be endothermic. The values of standard enthalpy (ΔH°ads) and activation energy (Ea) indicated that the adsorption process corresponds to physical sorption. The mechanisms for the removal of Rhodamine B dye from wastewater using carbon composite were predicted. RhB is a planar molecule that is readily adsorbed, in which adsorbed molecules are bound by hydrophobic or other weak interactions due to the π-π interactions between the dyes' aromatic backbones and the hexagonal skeleton of graphite and carbon nanotubes. Thus, the graphite carbon/carbon nanotube composite is believed to play a major role in organic pollutant reduction.

Recent progress on chemical modification of cellulose nanocrystal (CNC) and its application in nanocomposite films and membranes-A comprehensive review.

Cellulose nanocrystal (CNC) has recently gained much attention due to its unique properties such as abundancy, biodegradability, high strength, large surface area, functional ability, template structure, and sustainability. To broaden its application and enhance its compatibility with other materials, CNC can be modified via different methods. The modification is based on introducing new functions, including esterification, silylation, carbamation, polymerization, and so on. The application can concern many fields, such as polymer reinforcement, packaging, water treatment, textiles, biosensors, etc. Herein, we summarize the main approaches employed for the chemical modification and the use of the modified CNC material in the preparation of nanocomposite films and membranes, along with some emerging applications.

Synthesis and Characterization of Activated Carbon Co-Mixed Electrospun Titanium Oxide Nanofibers as Flow Electrode in Capacitive Deionization.

Flow capacitive deionization is a water desalination technique that uses liquid carbon-based electrodes to recover fresh water from brackish or seawater. This is a potential second-generation water desalination process, however it is limited by parameters such as feed electrode conductivity, interfacial resistance, viscosity, and so on. In this study, titanium oxide nanofibers (TiO2NF) were manufactured using an electrospinning process and then blended with commercial activated carbon (AC) to create a well distributed flow electrode in this study. Field emission scanning electron microscope (FESEM), X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and energy dispersive X-ray (EDX) were used to characterize the morphology, crystal structure, and chemical moieties of the as-synthesized composites. Notably, the flow electrode containing 1 wt.% TiO2NF (ACTiO2NF 1 wt.%) had the highest capacitance and the best salt removal rate (0.033 mg/min·cm2) of all the composites. The improvement in cell performance at this ratio indicates that the nanofibers are uniformly distributed over the electrode's surface, preventing electrode passivation, and nanofiber agglomeration, which could impede ion flow to the electrode's pores. This research suggests that the physical mixture could be used as a flow electrode in capacitive deionization.

3D Self-Supported Nitrogen-Doped Carbon Nanofiber Electrodes Incorporated Co/CoOx Nanoparticles: Application to Dyes Degradation by Electro-Fenton-Based Process.

We developed free-standing nitrogen-doped carbon nanofiber (CNF) electrodes incorporating Co/CoOx nanoparticles (NPs) as a new cathode material for removing Acid Orange 7 (AO7; a dye for wool) from wastewater by the heterogeneous electro-Fenton reaction. We produced the free-standing N-doped CNF electrodes by electrospinning a polyacrylonitrile (PAN) and cobalt acetate solution followed by thermal carbonation of the cobalt acetate/PAN nanofibers under a nitrogen atmosphere. We then investigated electro-Fenton-based removal of AO7 from wastewater with the free-standing N-doped-CNFs-Co/CoOx electrodes, in the presence or not of Fe2+ ions as a co-catalyst. The electrochemical analysis showed the high stability of the prepared N-doped-CNF-Co/CoOx electrodes in electrochemical oxidation experiments with excellent degradation of AO7 (20 mM) at acidic to near neutral pH values (3 and 6). Electro-Fenton oxidation at 10 mA/cm2 direct current for 40 min using the N-doped-CNF-Co/CoOx electrodes loaded with 25 wt% of Co/CoOx NPs led to complete AO7 solution decolorization with total organic carbon (TOC) removal values of 92.4% at pH 3 and 93.3% at pH 6. The newly developed N-doped-CNF-Co/CoOx electrodes are an effective alternative technique for wastewater pre-treatment before the biological treatment.

Application and Analysis of Bipolar Membrane Electrodialysis for LiOH Production at High Electrolyte Concentrations: Current Scope and Challenges.

The objective of this work was to evaluate obtaining LiOH directly from brines with high LiCl concentrations using bipolar membrane electrodialysis by the analysis of Li+ ion transport phenomena. For this purpose, Neosepta BP and Fumasep FBM bipolar membranes were characterized by linear sweep voltammetry, and the Li+ transport number in cation-exchange membranes was determined. In addition, a laboratory-scale reactor was designed, constructed, and tested to develop experimental LiOH production tests. The selected LiCl concentration range, based on productive process concentrations for Salar de Atacama (Chile), was between 14 and 34 wt%. Concentration and current density effects on LiOH production, current efficiency, and specific electricity consumption were evaluated. The highest current efficiency obtained was 0.77 at initial concentrations of LiOH 0.5 wt% and LiCl 14 wt%. On the other hand, a concentrated LiOH solution (between 3.34 wt% and 4.35 wt%, with a solution purity between 96.0% and 95.4%, respectively) was obtained. The results of this work show the feasibility of LiOH production from concentrated brines by means of bipolar membrane electrodialysis, bringing the implementation of this technology closer to LiOH production on a larger scale. Moreover, being an electrochemical process, this could be driven by Solar PV, taking advantage of the high solar radiation conditions in the Atacama Desert in Chile.

A Simple 1D Convection-Diffusion Model of Oxalic Acid Oxidation Using Reactive Electrochemical Membrane.

In recent years, electrochemical methods utilizing reactive electrochemical membranes (REM) have been recognized as the most promising technologies for the removal of organic pollutants from water. In this paper, we propose a 1D convection-diffusion-reaction model concerning the transport and oxidation of oxalic acid (OA) and oxygen evolution in the flow-through electrochemical oxidation system with REM. It allows the determination of unknown parameters of the system by treatment of experimental data and predicts the behavior of the electrolysis setup. There is a good agreement in calculated and experimental data at different transmembrane pressures and initial concentrations of OA. The model provides an understanding of the processes occurring in the system and gives the concentration, current density, potential, and overpotential distributions in REM. The dispersion coefficient was determined as a fitting parameter and it is in good agreement with literary data for similar REMs. It is shown that the oxygen evolution reaction plays an important role in the process even under the kinetic limit, and its contribution decreases with increasing total organic carbon flux through the REM.

Modeling the Formation of Gas Bubbles inside the Pores of Reactive Electrochemical Membranes in the Process of the Anodic Oxidation of Organic Compounds.

The use of reactive electrochemical membranes (REM) in flow-through mode during the anodic oxidation of organic compounds makes it possible to overcome the limitations of plate anodes: in the case of REM, the area of the electrochemically active surface is several orders of magnitude larger, and the delivery of organic compounds to the reaction zone is controlled by convective flow rather than diffusion. The main problem with REM is the formation of fouling and gas bubbles in the pores, which leads to a decrease in the efficiency of the process because the hydraulic resistance increases and the electrochemically active surface is shielded. This work aims to study the processes underlying the reduction in the efficiency of anodic oxidation, and in particular the formation of gas bubbles and the recharge of the REM pore surface at a current density exceeding the limiting kinetic value. We propose a simple one-dimensional non-stationary model of the transport of diluted species during the anodic oxidation of paracetamol using REM to describe the above effects. The processing of the experimental data was carried out. It was found that the absolute value of the zeta potential of the pore surface decreases with time, which leads to a decrease in the permeate flux due to a reduction in the electroosmotic flow. It was shown that in the solution that does not contain organic components, gas bubbles form faster and occupy a larger pore fraction than in the case of the presence of paracetamol; with an increase in the paracetamol concentration, the gas fraction decreases. This behavior is due to a decrease in the generation of oxygen during the recombination reaction of the hydroxyl radicals, which are consumed in the oxidation reaction of the organic compounds. Because the presence of bubbles increases the hydraulic resistance, the residence time of paracetamol-and consequently its degradation degree-increases, but the productivity goes down. The model has predictive power and, after simple calibration, can be used to predict the performance of REM anodic oxidation systems.

Activated Carbon Blended with Reduced Graphene Oxide Nanoflakes for Capacitive Deionization.

Capacitive deionization is a second-generation water desalination technology in which porous electrodes (activated carbon materials) are used to temporarily store ions. In this technology, porous carbon used as electrodes have inherent limitations, such as low electrical conductivity, low capacitance, etc., and, as such, optimization of electrode materials by rational design to obtain hybrid electrodes is key towards improvement in desalination performance. In this work, different compositions of mixture of reduced graphene oxide (RGO) and activated carbon (from 5 to 20 wt% RGO) have been prepared and tested as electrodes for brackish water desalination. The physico-chemical and electrochemical properties of the activated carbon (AC), reduced graphene oxide (RGO), and as-prepared electrodes (AC/RGO-x) were characterized by low-temperature nitrogen adsorption measurement, scanning electron microscope (SEM), X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), Fourier transform infra-red (FT-IR), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). Among all the composite electrodes, AC/RGO-5 (RGO at 5 wt%) possessed the highest specific capacitance (74 F g-1) and the highest maximum salt adsorption capacity (mSAC) of 8.10 mg g-1 at an operating voltage ∆E = 1.4 V. This shows that this simple approach could offer a potential way of fabricating electrodes of accentuated carbon network of an improved electronic conductivity that's much coveted in CDI technology.

Comparative Investigation of Activated Carbon Electrode and a Novel Activated Carbon/Graphene Oxide Composite Electrode for an Enhanced Capacitive Deionization.

Capacitive deionization is an emerging brackish water desalination technology whose principle lies in the utilization of porous electrodes (activated carbon materials) to temporarily store ions. Improving the properties of carbon material used as electrodes have been the focus of recent research, as this is beneficial for overall efficiency of this technology. Herein, we have synthesized a composite of activated carbon/graphene oxide electrodes by using a simple blending process in order to improve the hydrophilic property of activated carbon. Graphene oxide (GO) of different weight ratios was blended with commercial Activated carbon (AC) and out of all the composites, AC/GO-15 (15 wt.% of GO) exhibited the best electrochemical and salt adsorption performance in all operating conditions. The as prepared AC and AC/GO-x (x = 5, 10, 15 and 20 wt.% of GO) were characterized by cyclic voltammetry and their physical properties were also studied. The salt adsorption capacity (SAC) of AC/GO-15 at an operating window of 1.0 V is 5.70 mg/g with an average salt adsorption rate (ASAR) of 0.34 mg/g/min at a 400 mg/L salt initial concentration and has a capacitance of 75 F/g in comparison to AC with 3.74 mg/g of SAC, ASAR of 0.23 mg/g/min and a capacitance of 56 F/g at the same condition. This approach could pave a new way to produce a highly hydrophilic carbon based electrode material in CDI.

Electro-oxidation of secondary effluents from various wastewater plants for the removal of acetaminophen and dissolved organic matter.

Electro-oxidation of acetaminophen (ACT) in three different doped secondary effluents collected from a conventional Municipal Waste Water Treatment Plant (MWWTP), a MWWTP using a membrane bioreactor (WWTP MBR) and a lab-scale MBR treating source-separated urine (Urine MBR) was investigated by electro-Fenton (EF) coupled with anodic oxidation (AO) using sub-stoichiometric titanium oxide anode (Ti4O7). After 8 h of treatment, 90 ± 15%, 76 ± 3.8% and 46 ± 1.3% of total organic carbon removal was obtained for MWWTP, MWWTP-MBR and Urine-MBR respectively, at a current intensity of 250 mA, pH of 3 and [Fe2+] = 0.2 mM. Faster degradation of ACT was observed in the WWTP MBR because of the lower amount of competitive organic matter, however, >99% degradation of ACT was obtained after 20 min for all effluents. The acute toxicity of the treated effluent was measured using Microtox® tests. Results showed an initial increase in toxicity, which could be assigned to formation of more toxic by-products than parent compounds. From 3D excitation and emission matrix fluorescence (3DEEM), different reactivity was observed according to the nature of the organic matter. Particularly, an increase of low molecular weight organic compounds fluorescence was observed during Urine MBR treatment. This could be linked to the slow decrease of the acute toxicity during Urine MBR treatment and ascribed to the formation and recalcitrance of toxic organic nitrogen and chlorinated organic by-products. By comparison, the acute toxicity of other effluents decreased much more rapidly. Finally, energy consumption was calculated according to the objective to achieve (degradation, absence of toxicity, mineralization).

A 2D Convection-Diffusion Model of Anodic Oxidation of Organic Compounds Mediated by Hydroxyl Radicals Using Porous Reactive Electrochemical Membrane.

In recent years, electrochemical methods utilizing reactive electrochemical membranes (REM) have been considered as a promising technology for efficient degradation and mineralization of organic compounds in natural, industrial and municipal wastewaters. In this paper, we propose a two-dimensional (2D) convection-diffusion-reaction model concerning the transport and reaction of organic species with hydroxyl radicals generated at a TiOx REM operated in flow-through mode. It allows the determination of unknown parameters of the system by treatment of experimental data and predicts the behavior of the electrolysis setup. There is a good agreement in the calculated and experimental degradation rate of a model pollutant at different permeate fluxes and current densities. The model also provides an understanding of the current density distribution over an electrically heterogeneous surface and its effect on the distribution profile of hydroxyl radicals and diluted species. It was shown that the percentage of the removal of paracetamol increases with decreasing the pore radius and/or increasing the porosity. The effect becomes more pronounced as the current density increases. The model highlights how convection, diffusion and reaction limitations have to be taken into consideration for understanding the effectiveness of the process.

Towards Electrochemical Water Desalination Techniques: A Review on Capacitive Deionization, Membrane Capacitive Deionization and Flow Capacitive Deionization.

Electrochemical water desalination has been a major research area since the 1960s with the development of capacitive deionization technique. For the latter, its modus operandi lies in temporary salt ion adsorption when a simple potential difference (1.0-1.4 V) of about 1.2 V is supplied to the system to temporarily create an electric field that drives the ions to their different polarized poles and subsequently desorb these solvated ions when potential is switched off. Capacitive deionization targets/extracts the solutes instead of the solvent and thus consumes less energy and is highly effective for brackish water. This paper reviews Capacitive Deionization (mechanism of operation, sustainability, optimization processes, and shortcomings) with extension to its counterparts (Membrane Capacitive Deionization and Flow Capacitive Deionization).

Highly efficient and stable FeIIFeIII LDH carbon felt cathode for removal of pharmaceutical ofloxacin at neutral pH.

The traditional electro-Fenton (EF) has been facing major challenges including narrow suitable range of pH and non-reusability of catalyst. To overcome these drawbacks we synthesized FeIIFeIII-layered double hydroxide modified carbon felt (FeIIFeIII LDH-CF) cathode via in situ solvo-thermal process. Chemical composition and electrochemical characterization of FeIIFeIII LDH-CF were tested and analyzed. The apparent rate constant of decay kinetics of ofloxacin (OFC) with FeIIFeIII LDH-CF (0.18 min-1) at pH 7 was more than 3 times higher than that of homogeneous EF (0.05 min-1) at pH 3 with 0.1 mM Fe2+ under same current density (9.37 mA cm-2). Also, a series of experiments including evolution of solution pH, iron leaching, OFC removal with trapping agent and quantitative detection of hydroxyl radicals (OH) were conducted, demonstrating the dominant role of OH generated by surface catalyst via ≡ FeII/FeIII on LDH cathode for degradation of organics as well contributing to high efficiency and good stability at neutral pH. Besides, formation and evolution of aromatic intermediates, carboxylic acids and inorganic ions (F-, NH4+ and NO3-) were identified by High-Performance Liquid chromatography, Gas Chromatography-Mass Spectrometry and ionic chromatography analyses. These findings allowed proposing a plausible degradation pathway of OFC by OH generated in the heterogeneous EF process.

Electrochemical advanced oxidation processes using novel electrode materials for mineralization and biodegradability enhancement of nanofiltration concentrate of landfill leachates.

The objective of this study was to implement electrochemical advanced oxidation processes (EAOPs) for mineralization and biodegradability enhancement of nanofiltration (NF) concentrate from landfill leachate initially pre-treated in a membrane bioreactor (MBR). Raw carbon felt (CF) or FeIIFeIII layered double hydroxides-modified CF were used for comparing the efficiency of homogeneous and heterogeneous electro-Fenton (EF), respectively. The highest mineralization rate was obtained by heterogeneous EF: 96% removal of dissolved organic carbon (DOC) was achieved after 8 h of electrolysis at circumneutral initial pH (pH0 = 7.9) and at 8.3 mA cm-2. However, the most efficient treatment strategy appeared to be heterogeneous EF at 4.2 mA cm-2 combined with anodic oxidation using Ti4O7 anode (energy consumption = 0.11 kWh g-1 of DOC removed). Respirometric analyses under similar conditions than in the real MBR emphasized the possibility to recirculate the NF retentate towards the MBR after partial mineralization by EAOPs in order to remove the residual biodegradable by-products and improve the global cost effectiveness of the process. Further analyses were also performed in order to better understand the fate of organic and inorganic species during the treatment, including acute toxicity tests (Microtox®), characterization of dissolved organic matter by three-dimensional fluorescence spectroscopy, evolution of inorganic ions (ClO3-, NH4+ and NO3-) and identification/quantification of degradation by-products such as carboxylic acids. The obtained results emphasized the interdependence between the MBR process and EAOPs in a combined treatment strategy. Improving the retention in the MBR of colloidal proteins would improve the effectiveness of EAOPs because such compounds were identified as the most refractory. Enhanced nitrification would be also required in the MBR because of the release of NH4+ from mineralization of refractory organic nitrogen during EAOPs.