Search

Highlights: [•] Fe0/additive mixtures are currently tested for environmental remediation. [•] Tools for reliable design of Fe0 walls are urgently needed. [•] A volumetric Fe0/sand ratio of 25% has been proven to be the most sustainable. [•] Improving Fe0/sand systems by admixing granular MnO2 minerals is tested herein. [•] Results clearly demonstrated the suitability of MnO2 addition for better Fe0 filters. [Copyright &y& Elsevier]

Highlights: [•] Fe0/additives mixtures are widely used for aqueous contaminant removal. [•] Reliable methods for designing Fe0 filtration systems are still lacking. [•] Additives have been mostly used to account for construction width requirements. [•] Various Fe0/sand ratios were tested for dye discoloration in dynamic systems. [•] Results revealed the 25% Fe0 system as the most efficient and sustainable. [Copyright &y& Elsevier]

As an electrochemical advanced oxidation process, the electro-Fenton (EF) process has gained significant importance in the treatment of wastewater and persistent organic pollutants in recent years. As recently reported in a bibliometric analysis, the number of scientific publications on EF have increased exponentially since 2002, reaching nearly 500 articles published in 2022 (Deng et al., 2022). The influence of the main operating parameters has been thoroughly investigated for optimization purposes, such as type of electrode materials, reactor design, current density, and type and concentration of catalyst. Even though most of the studies have been conducted at a laboratory scale, focusing on fundamental aspects and their applications to degrade specific pollutants and treat real wastewater, important large-scale attempts have also been made. This review presents and discusses the most recent advances of the EF process with special emphasis on the aspects more closely related to future implementations at the large scale, such as applications to treat real effluents (industrial and municipal wastewaters) and soil remediation, development of large-scale reactors, costs and effectiveness evaluation, and life cycle assessment. Opportunities and perspectives related to the heterogeneous EF process for real applications are also discussed. This review article aims to be a critical and exhaustive overview of the most recent developments for large-scale applications, which seeks to arouse the interest of a large scientific community and boost the development of EF systems in real environments., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The present study demonstrates, for the first time, the feasibility of a two-step process consisting of Electro-Fenton (EF) followed by microalgae to treat highly loaded real food processing wastewater along with resource recovery. In the first step, EF with a carbon felt cathode and Ti/RuO 2 -IrO 2 anode was applied at different current densities (3.16 mA cm -2 , 4.74 mA cm -2 and 6.32 mA cm -2 ) to decrease the amount of organic matter and turbidity and enhance biodegradability. In the second step, the EF effluents were submitted to microalgal treatment for 15 days using a mixed culture dominated by Scenedesmus sp., Chlorosarcinopsis sp., and Coelastrum sp. Results showed that current density impacted the amount of COD removed by EF, achieving the highest COD removal of 77.5% at 6.32 mA cm -2 with >95% and 74.3% of TSS and PO 4 3- removal, respectively. With respect to microalgae, the highest COD removal of 85% was obtained by the culture in the EF effluent treated at 6.32 mA cm -2 . Remarkably, not only 85% of the remaining organic matter was removed by microalgae, but also the totality of inorganic N and P compounds, as well as 65% of the Fe catalyst that was left after EF. The removal of inorganic species also demonstrates the high complementarity of both processes, since EF does not have the capacity to remove such compounds, while microalgae do not grow in the raw wastewater. Furthermore, a maximum of 0.8 g L -1 of biomass was produced after cultivation, with an accumulation of 32.2% of carbohydrates and 25.9% of lipids. The implementation of the two processes represents a promising sustainable approach for the management of industrial effluents, incorporating EF in a water and nutrient recycling system to produce biomass that could be valorized into clean fuels., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:, (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Wastewater treatment and simultaneous production of value-added products with microalgae represent a sustainable alternative. Industrial wastewater, characterized by high C/N molar ratios, can naturally improve the carbohydrate content in microalgae without the need for any external source of carbon while degrading the organic matter, macro-nutrients, and micro-nutrients. This study aimed to understand the treatment, reuse, and valorization mechanisms of real cooling tower wastewater (CWW) from a cement-processing industry mixed with domestic wastewater (DW) to produce microalgal biomass with potential for synthesis of biofuels or other value-added products. For this purpose, three photobioreactors with different hydraulic retention times (HRT) were inoculated simultaneously using the CWW-DW mixture. Macro- and micro-nutrient consumption and accumulation, organic matter removal, algae growth, and carbohydrate content were monitored for 55 days. High COD (> 80%) and macronutrient removals (> 80% of N and P) were achieved in all the photoreactors, with heavy metals below the limits established by local standards. The best results showed maximum algal growth of 1.02 g SSV L -1 and 54% carbohydrate accumulation with a C/N ratio of 31.24 mol mol -1 . Additionally, the harvested biomass presented a high Ca and Si content, ranging from 11 to 26% and 2 to 4%, respectively. Remarkably, big flocs were produced during microalgae growth, which enhanced natural settling for easy biomass harvesting. Overall, this process represents a sustainable alternative for CWW treatment and valorization, as well as a green tool for generating carbohydrate-rich biomass with the potential to produce biofuels and fertilizers., (© 2023. The Author(s).)

In this work, a TiO 2 -decorated electrode was fabricated by dip coating activated carbon fibers (ACF) with TiO 2 , which were then used as a cathode for the photoelectro-Fenton (PEF) treatment of the pharmaceutical enalapril, an angiotensin-converting enzyme inhibitor that has been detected in several waterways. The TiO 2 coating was found to principally improve the electrocatalytic properties of ACF for H 2 O 2 production via the 2-e - O 2 reduction, in turn increasing enalapril degradation by PEF. The effect of the current density on the mineralization of enalapril was evaluated and the highest TOC removal yield (80.5% in 3 h) was obtained at 8.33 mA cm -2 , in the presence of 0.5 mmol L -1 of Fe 2+ catalyst. Under those conditions, enalapril was totally removed within the first 10 min of treatment with a rate constant k = 0.472 min -1 . In contrast, uncoated ACF only achieved 60% of TOC removal in 3 h at 8.33 mA cm -2 . A degradation pathway for enalapril mineralization is proposed, based on the degradation by-products identified during treatment. Overall, the results demonstrate the promises of TiO 2 cathodes for PEF, a strategy that has often been overlooked in favor of photoelectrocatalysis (PEC) based on TiO 2 -modified photoanodes., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The modification of titanium dioxide (TiO 2 ) is a strategy to maximize the utilization of sunlight. Carbon quantum dots (CQDs) are carbon nanomaterials with outstanding optical and electronic properties that are suitable for that purpose. In this work, three types of hybrid TiO 2 /CQD photoelectrodes were synthesized following different methods: 1) deposition of a CQD layer on top of TiO 2 (labelled as TiO 2 -CQD); 2) deposition of a TiO 2 layer on top of CQDs (labelled as CQD-TiO 2 ) and; 3) deposition of a mixed CQD + TiO 2 layer (labelled as CQD + TiO 2 ). The photoelectrodes were investigated for the photoelectrocatalytic degradation of phenol as model pollutant under simulated solar light and TiO 2 -CQD showed the highest apparent reaction rate constant of k app  = 0.0117 min -1 with 40% of TOC removal in 6 h of treatment. CQDs were found to enhance photon absorption in the visible region of the electromagnetic spectrum and in turn phenol degradation by promoting the separation of photogenerated charge carriers through electron transfer via the Ti-O-C bonds formed at the TiO 2 -CQD interface. Finally, the performance of the TiO 2 -CQD photoanode was evaluated for the treatment of real wastewater from the membrane fabrication sector, confirming its photoelectrocatalytic efficiency under solar radiation with 93% of TOC removal in 8 h of treatment and k app  = 0.0058 min -1 ., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

This review presents an exhaustive overview on the mechanisms of Fe 3+ cathodic reduction within the context of the electro-Fenton (EF) process. Different strategies developed to improve the reduction rate are discussed, dividing them into two categories that regard the mechanistic feature that is promoted: electron transfer control and mass transport control. Boosting the Fe 3+ conversion to Fe 2+ via electron transfer control includes: (i) the formation of a series of active sites in both carbon- and metal-based materials and (ii) the use of other emerging strategies such as single-atom catalysis or confinement effects. Concerning the enhancement of Fe 2+ regeneration by mass transport control, the main routes involve the application of magnetic fields, pulse electrolysis, interfacial Joule heating effects, and photoirradiation. Finally, challenges are singled out, and future prospects are described. This review aims to clarify the Fe 3+ /Fe 2+ cycling process in the EF process, eventually providing essential ideas for smart design of highly effective systems for wastewater treatment and valorization at an industrial scale.

Bioelectrochemical systems (BES), mainly microbial fuel cells (MEC) and microbial electrolysis cells (MFC), are unique biosystems that use electroactive bacteria (EAB) to produce electrons in the form of electric energy for different applications. BES have attracted increasing attention as a sustainable, low-cost, and neutral-carbon option for energy production, wastewater treatment, and biosynthesis. Complex interactions between EAB and the electrode materials play a crucial role in system performance and scalability. The electron transfer processes from the EAB to the anode surface or from the cathode surface to the EAB have been the object of numerous investigations in BES, and the development of new materials to maximize energy production and overall performance has been a hot topic in the last years. The present review paper discusses the advances on innovative electrode materials for emerging BES, which include MEC coupled to anaerobic digestion (MEC-AD), Microbial Desalination Cells (MDC), plant-MFC (P-MFC), constructed wetlands-MFC (CW-MFC), and microbial electro-Fenton (BEF). Detailed insights on innovative electrode modification strategies to improve the electrode transfer kinetics on each emerging BES are provided. The effect of materials on microbial population is also discussed in this review. Furthermore, the challenges and opportunities for materials scientists and engineers working in BES are presented at the end of this work aiming at scaling up and industrialization of such versatile systems., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Three different visible-light photocatalysts (hematite (α-Fe 2 O 3 ), bismuth vanadate (BiVO 4 ) and Mo-doped bismuth vanadate (BiMoVO 4 )) deposited on transparent fluorine-doped SnO 2 (FTO) were evaluated for the solar-driven photoelectrocatalytic treatment of emerging pollutants. BiMoVO 4 was found to be the most effective photoanode, yielding the fastest degradation rate constant and highest mineralization efficiency using phenol as the oxidation probe. The BiMoVO 4 photoanode was then used to degrade the herbicide simazine in a photoelectrolytic cell combining photoelectrocatalysis (PEC) with photoelectron-Fenton (PEF) under solar light (SPEC-SPEC). Total simazine removal was achieved within 1 min of treatment (k app  = 4.21 min -1 ) at the optimum electrode potential of 2.5 V vs Ag/AgCl, with complete TOC removal in 2 h. The analysis of anionic species in solution during treatment showed that most of the nitrogen heteroatoms in the simazine structure were converted into NO 3 - following • OH addition to organic N. This innovative process combining BiMoVO 4 -PEC with PEF using solar light as a sustainable source of energy (SPEC-SPEF) achieved the highest degradation/mineralization efficiency ever reported for simazine treatment. Besides, this is the first work reporting the photo(electrochemical) degradation of this toxic herbicide., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Electro-Fenton (EF) is an emerging technology with well-known outstanding oxidation power; yet, its application to the treatment of inorganic contaminants has been largely disregarded. Thiosalts are contaminants of emerging concern in mine water, responsible for delayed acidity in natural waterways. In this study, EF was used to treat thiosalts in synthetic and real mine water. Thiosulfate (S 2 O 3 2- ) solutions were first used to optimize the main parameters affecting the process, namely, the current density (2.08-6.25 mA cm -2 ), temperature (4 vs 20 °C), and S 2 O 3 2- concentration (0.25-2 g L -1 was almost completely removed in 2 h of treatment at 6.25 mA cm 2 O 3 2- was almost completely removed in 2 h of treatment at 6.25 mA cm -2 , while temperature played no important role in the process efficiency. The optimal conditions were then applied to treat a real sample of contaminated mine water, resulting in complete S 2 O 3 2- and S 4 O 6 2- oxidation to SO 4 2- in 90 min at 6.25 mA cm -2 (95% removal in only 60 min). The reaction mechanisms were investigated in detail based on the quantification of the main degradation byproducts. This study opens new possibilities for EF application to the treatment of thiosalt-contaminated mine water and other oxidizable inorganic-impacted wastewaters.

We propose an unconventional electro-Fenton (EF) system with a nickel-foam (Ni-F) cathode and tripolyphosphate (3-PP) electrolyte at near-neutral pH (EF/Ni-F-3-PP) to overcome pH restrictions in EF while preventing Ni-F corrosion. Response surface modelling was used to optimize the main operating parameters with a model prediction analysis (R 2  = 0.99): pH = 5.8, Fe 2+  = 3.0 mM and applied current = 349.6 mA. Among the three variables, the pH exerted the highest influence on the process. Under optimal conditions, 100 % of phenol removal was achieved in 25 min with a pseudo-first-order apparent rate constant (k app ) of 0.2 min -1 , 3.2-fold higher than the k app of EF/Ni-F with SO 4 electrolyte at pH 3. A mineralization yield of 81.5 % was attained after 2 h; furthermore, it was found that 3-PP enhanced H 2- electrolyte at pH 3. A mineralization yield of 81.5 % was attained after 2 h; furthermore, it was found that 3-PP enhanced H 2 accumulation by preventing bulk H 2 accumulation by preventing bulk H 2 decomposition. Finally, toxicity evaluation revealed the formation of toxic by-products at the early stages of treatment, which were totally depleted after 2 h, demonstrating the detoxifying capacity of the system. In conclusion, this study shows for the first time the potential of Ni-F as a cathode for EF under near-neutral conditions, rendered possible by the 3PP electrolyte. Under these conditions, the Ni-F corrosion issue could be alleviated.2 decomposition. Finally, toxicity evaluation revealed the formation of toxic by-products at the early stages of treatment, which were totally depleted after 2 h, demonstrating the detoxifying capacity of the system. In conclusion, this study shows for the first time the potential of Ni-F as a cathode for EF under near-neutral conditions, rendered possible by the 3PP electrolyte. Under these conditions, the Ni-F corrosion issue could be alleviated., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

For the first time, a biomass-derived porous carbon cathode (WDC) was fabricated via a facile one-step pyrolysis of recovered wood-waste without any post-treatment. The WDC along with pyrophosphate (PP) as electrolyte were used in electro-Fenton (EF) at pH 8 for sulfathiazole (STZ) treatment. The H 2 O 2 accumulation capacity of WDC was optimized via the following parameters: pyrolysis temperature, applied current and electrolyte. Results showed that the WDC cathode prepared at 900 °C achieved the highest H 2 O 2 accumulation (13.80 mg L -1 in 3 h) due to its larger electroactive surface area (28.81 cm 2 ). Interestingly, it was found that PP decreased the decomposition rate of H 2 O 2 in solution as compared to conventional electrolyte, which resulted in higher H 2 O 2 accumulation. PP allowed operating EF at pH of 8 due to the formation of Fe 2+ -PP complexes in solution. Moreover, Fe 2+ -PP was able to activate oxygen to produce OH. In this way, the degradation of STZ took place through four main pathways: 1) via OH from the Fe 2+ -PP complex, 2) via OH from EF reactions, 3) via surface OH at the boron doped diamond electrode (BDD) and 4) via SO 4 - from BDD activation. Finally, microtox tests revealed that some toxic intermediates were generated during WDC/BDD/PP EF treatment, but they were removed at the end of the process., (Copyright © 2019 Elsevier B.V. All rights reserved.)

For the first time, real effluents from the micro-electronics industry were treated by paired advanced electrocatalysis, combining electro-Fenton (EF) with anodic oxidation (AO). A detailed characterization of the effluents was performed, showing that isopropanol (IPA) and acetone were the main constituents of the wastewater. Both compounds were completely degraded during the first 120 min of treatment. By monitoring the degradation intermediates, an oxidation pathway was proposed, which includes short-chain carboxylic acids as the main end-organic compounds. While carbon brush served as the cathode, two anode materials were utilized: boron-doped diamond (BDD) and carbon-PTFE cloth (CC). Despite the lower mineralization efficiency showed by CC as compared to BDD (76.5% of TOC removal with CC vs 94.0% of TOC removal with BDD after 4 h), CC showed potential to increase the BOD 5 /COD ratio of the effluent that reached 0.7 after only 45 min (0.6 in 30 min with BDD). These results suggest that the electrolysis time could be kept short, improving the cost-effectiveness of the process, especially if CC is used. Overall, the results point out the suitability of advanced electrocatalysis to treat real electronics wastewater with low energy requirements, short treatment times and cost-effective electrode materials., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Degradation of a widely used antibiotic, the para-aminosalicylic acid (PAS), and mineralization of its aqueous solution was investigated by electro-Fenton process using Pt/carbon-felt and boron-doped diamond (BDD)/carbon-felt cells with applied currents in the range of 50-1000 mA. This process produces the highly oxidizing species, the hydroxyl radical ( • OH), which is mainly responsible for the oxidative degradation of PAS. An absolute rate constant of 4.17 × 10 9  M -1  s -1 for the oxidation of PAS by ● OH was determined from the competition kinetics method. Degradation rate of PAS increased with current reaching an optimal value of 500 mA with complete disappearance of 0.1 mM PAS at 7 min using Pt/carbon-felt cell. The optimum degradation rate was reached at 300 mA for BDD/carbon-felt. The latter cell was found more efficient in total organic carbon (TOC) removal where a complete mineralization was achieved within 240 min. A multi-step mineralization process was observed with the formation of a number of aromatic intermediates, short-chain carboxylic acids, and inorganic ions. Eight aromatic intermediate products were identified using both LC-Q-ToF-MS and GC-MS techniques. These products were the result of hydroxylation of PAS followed by multiple additions of hydroxyl radicals to form polyhydroxylated derivatives. HPLC and GC/MS analyses demonstrated that extended oxidation of these intermediate products conducted to the formation of various short-chain carboxylic acids. Prolonged electrolysis resulted in a complete mineralization of PAS with the evolution of inorganic ions such as NO 3 - and NH 4 + . Based on the identified intermediates, carboxylic acids and inorganic ions, a plausible mineralization pathway is also deduced. The remarkably high degree of mineralization (100%) achieved by the present EF process highlights the potential application of this technique to the complete removal of salicylic acid-based pharmaceuticals from contaminated water.

A composite nickel-iron-foam (Ni-Fe-F) electrode was used as a cathode in the electro-Fenton (EF) process at circum-neutral pH in the presence of sodium tripolyphosphate (TPP) as supporting electrolyte. It was found that phenol degradation was dramatically improved by the synergistic effect of Ni-Fe-F and TPP, reaching 100% removal in 40 min, with k app  = (8.90 ± 0.12) × 10 -2 min -1 , which was about 18 times higher than that of Ni-Fe-F with sulfate as conventional electrolyte at pH 3.00 (k app  = (5.00 ± 0.14) × 10 -3 min -1 ). A (75.00 ± 1.67)% mineralization yield was attained after 4-h treatment time. Ni-Fe-F proved capable of providing the Fe 2+ ions necessary to catalyze the Fenton's reaction via a controlled chemical/electrochemical redox process. In addition, Ni-Fe-F promoted the chemical and electrochemical generation of H 2 O 2 . With respect to TPP, its chelation with Fe ions prevented iron precipitation at neutral and higher pH values, extending the pH range of the Fenton's reaction. Furthermore, the TPP ligand promoted the activation of molecular O 2 for the chemical production of OH, enhancing the process efficiency. By overcoming these common limitations of conventional EF in K 2 SO 4 electrolyte, the Ni-Fe-F/TPP system represents a more sustainable alternative for practical application of EF. A degradation pathway for phenol mineralization with homogeneous and heterogeneous OH produced by the EF Ni-Fe-F/TPP system is proposed based on the identification of the oxidation by-products., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

The relevant environmental hazard related to the presence of pharmaceuticals in water sources requires the development of high effective and suitable wastewater treatment technologies. In the present work, a hybrid process coupling electro-Fenton (EF) process and aerobic biological treatment (Bio-EF process) was implemented for the efficient and cost-effective mineralization of beta-blocker metoprolol (MPTL) aqueous solutions. Firstly, operating factors influencing EF process were assessed. MTPL solutions were completely mineralized after 4h-electrolysis under optimal operating conditions and BDD anode demonstrated its oxidation superiority. The absolute rate constant of MTPL oxidation byOH (kMTPL) was determined by the competition kinetics method and found to be (1.72±0.04)×10(9)M(-1)s(-1). A reaction pathway for the mineralization of the drug was proposed based on the identification of oxidation by-products. Secondly, EF process was used as pre-treatment. An increase of BOD5/COD ratio from 0.012 to 0.44 was obtained after 1h EF treatment, along with 47% TOC removal and a significant decrease of toxicity, demonstrating the feasibility of a post-biological treatment. Finally, biological treatment successfully oxidized 43% of the total TOC content. An overall 90% mineralization of MPTL solutions was achieved by the Bio-EF process, demonstrating its potentiality for treating wastewater containing pharmaceutical residues., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Some widely prescribed drugs are sparsely metabolized and end up in the environment. They can thus be a focal point of ecotoxicity, either themselves or their environmental transformation products. In this context, we present a study concerning furosemide, a diuretic, which is mainly excreted unchanged. We investigated its biotransformation by two environmental fungi, Aspergillus candidus and Cunninghamella echinulata. The assessment of its ecotoxicity and that of its metabolites was performed using the Microtox test (ISO 11348-3) with Vibrio fischeri marine bacteria. Three metabolites were identified by means of HPLC-MS and 1 H/ 13 C NMR analysis: saluamine, a known pyridinium derivative and a hydroxy-ketone product, the latter having not been previously described. This hydroxy-ketone metabolite was obtained with C. echinulata and was further slowly transformed into saluamine. The pyridinium derivative was obtained in low amount with both strains. Metabolites, excepting saluamine, exhibited higher toxicity than furosemide, being the pyridinium structure the one with the most elevated toxic levels (EC 50  = 34.40 ± 6.84 mg L -1 ). These results demonstrate that biotic environmental transformation products may present a higher environmental risk than the starting drug, hence highlighting the importance of boosting toxicological risk assessment related to the impact of pharmaceutical waste.

A coupled Bio-EF treatment has been applied as a reliable process for the degradation of the pharmaceuticals furosemide (FRSM) and ranitidine (RNTD) in aqueous medium, in order to reduce the high energy consumption related to electrochemical technology. In the first stage of this study, electrochemical degradation of the drugs was assessed by the electro-Fenton process (EF) using a BDD/carbon-felt cell. Biodegradability of the drugs solutions was enhanced reaching BOD5/COD ratios close to the biodegradability threshold of 0.4, evidencing the formation of bio-compatible by-products (mainly short-chain carboxylic acids) which are suitable for biological post-treatment. Moreover, toxicity evaluation by the Microtox(®) method revealed that EF pre-treatment was able of detoxifying both, FRSM and RNTD solutions, constituting another indicator of biodegradability of EF treated solutions. In the second stage, electrolyzed solutions were treated by means of an aerobic biological process. A significant part of the short-chain carboxylic acids formed during the electrochemical phase was satisfactorily removed by the used selected microorganisms. The results obtained demonstrate the efficiency and feasibility of the integrated Bio-EF process., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

The degradation of 0.20 mM sulfamethazine (SMT) solutions was investigated by heterogeneous electro-Fenton (EF) process using pyrite as source of Fe(2+) (catalyst) and pH regulator in an undivided electrochemical cell equipped either with a Pt or a BDD anode and carbon-felt as cathode. Effect of pyrite concentration and applied current on the oxidative degradation kinetics and mineralization efficiency has been studied. The higher oxidation power of the process, named "Pyrite-EF″ using BDD anode was demonstrated. Pyrite-EF showed a better performance for the oxidation/mineralization of the drug SMT in comparison to the classic EF process: 95% and 87% TOC removal by Pyrite-EF with BDD and Pt anodes, respectively, versus 90% and 83% by classical EF with BDD and Pt anodes, respectively. The rate constant of the oxidation of SMT by OH was determined by the competition kinetics method and found to be 1.87 × 10(9) mol(-1) L s(-1). Based on the identified reaction intermediates by HPLC and GS-MS, as well as released SO4(2-), NH4(+) and NO3(-) ions, a plausible reaction pathway was proposed for the mineralization of SMT during Pyrite-EF process. Toxicity assessment by means of Microtox method revealed the formation of some toxic intermediates during the treatment. However, toxicity of the solution was removed at the end of treatment., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Ranitidine (RNTD) is a widely prescribed histamine H2-receptor antagonist whose unambiguous presence in water sources appointed it as an emerging pollutant. Here, the degradation of 0.1 mM of this drug in aqueous medium was studied by electrochemical advanced oxidation processes (EAOPs) like anodic oxidation with electrogenerated H2O2 and electro-Fenton using Pt/carbon-felt, BDD/carbon-felt and DSA-Ti/RuO2–IrO2/carbon-felt cells. The higher oxidation power of the electro-Fenton process using a BDD anode was demonstrated. The oxidative degradation of RNTD by the electrochemically generated OH radicals obeyed a pseudo-first order kinetics. The absolute rate constant for its hydroxylation reaction was 3.39 × 109 M−1 s−1 as determined by the competition kinetics method. Almost complete mineralization of the RNTN solution was reached by using a BDD anode in both anodic oxidation with electrogenerated H2O2 and electro-Fenton processes. Up to 11 cyclic intermediates with furan moiety were detected from the degradation of RNTD, which were afterwards oxidized to short-chain carboxylic acids before their mineralization to CO2 and inorganic ions such as NH4+, NO3− and SO42−. Based on identified products, a plausible reaction pathway was proposed for RNTD mineralization. Toxicity assessment by the Microtox® method revealed that some cyclic intermediates are more toxic than the parent molecule. Toxicity was quickly removed following the almost total mineralization of the treated solution. Overall results confirm the effectiveness of EAOPs for the efficient removal of RNTD and its oxidation by-products from water.

In this work, the electrochemical degradation of the dye azure B in aqueous solutions was studied by electrochemical advanced oxidation processes (EAOPs), electro-Fenton, and anodic oxidation processes, using Pt/carbon-felt and boron-doped diamond (BDD)/carbon-felt cells with H₂O₂ electrogeneration. The higher oxidation power of the electro-Fenton (EF) process using BDD anode was demonstrated. The oxidative degradation of azure B by the electrochemically generated hydroxyl radicals ((•)OH) follows a pseudo-first-order kinetics. The apparent rate constants of the oxidation of azure B by (•)OH were measured according to pseudo-first-order kinetic model. The absolute rate constant of azure B hydroxylation reaction was determined by competition kinetics method and found to be 1.19 × 10(9) M(-1) s(-1). It was found that the electrochemical degradation of the dye leads to the formation of aromatic by-products which are then oxidized to aliphatic carboxylic acids before their almost mineralization to CO₂ and inorganic ions (sulfate, nitrate, and ammonium). The evolution of the TOC removal and time course of short-chain carboxylic acids during treatment were also investigated.