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This work studies the remediation of groundwater saturated with dense non-aqueous phase liquid (DNAPL) from lindane production wastes by electrochemical oxidation. DNAPL-saturated groundwater contains up to 26 chlorinated organic compounds (COCs), including different isomers of hexachlorocyclohexane (HCH). To do this, polluted groundwater was electrolysed using boron-doped diamond (BDD) and stainless steel (SS) as anode and cathode, respectively, and the influence of the current density on COCs removal was evaluated in the range from 5 to 50 mA cm-2. Results show that current densities higher than 25 mA cm-2 lead to the complete removal and mineralisation of all COCs identified in groundwater. The higher the current density, the higher the COCs removal rate. At lower current densities (5 mA cm-2), chlorobenzenes were completely removed, and degradations above 90 % were reached for COCs with more than five chlorine atoms in their molecules. The use of BDD anodes promotes the electrochemical generation of powerful reactive species, such as persulfate, hypochlorite or hydroxyl radicals, that contribute to the degradation and mineralisation of COCs. The applied current density also influences the generation of these species. Finally, no acute toxicity towards Vibrio fischeri was observed for the treated groundwater after the electrochemical oxidation performed at 5 and 10 mA cm-2. These findings demonstrate that electrochemical oxidation with BDD anodes at moderate current densities is a promising alternative for the remediation of actual groundwater contaminated with DNAPLs.

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This study presents an electrolysis system utilizing a novel self-circulation process of sulfate (SO42-) and persulfate (S2O82-) ions based on a boron-doped diamond (BDD) anode and an activated carbon fiber (ACF) cathode, which is designed to enable electrochemical remediation of environmental contaminants with reduced use of chemical reagents and minimized residues. The production of S2O82- and hydrogen peroxide (H2O2) on the BDD anode and ACF cathode, respectively, is identified as the source of active radicals for the contaminant degradation. The initiator, sulfate, is identified by comparing the degradation efficiency in NaSO4 and NaNO3 electrolytes. Quenching experiments and electron paramagnetic resonance (EPR) spectroscopy confirmed that the SO4-· and ·OH generated on the ACF cathode are the main reactive radicals. A comparison of the degradation efficiency and the generated S2O82-/H2O2 of the divided/undivided electrolysis system is used to demonstrate the superiority of the synergistic effect between the BDD anode and ACF cathode. This work provides evidence of the effectiveness of the philosophy of "catalysis in lieu of supplementary chemical agents" and sheds light on the mechanism of the generation and transmission of reactive species in the BDD and ACF electrolysis system, thereby offering new perspectives for the design and optimization of electrolysis systems.

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In this paper, the synthetic methyl orange (MO) dyeing wastewater treated by a reverse electrodialysis reactor (REDR) with 40 member pairs was investigated first. The boron-doped diamond (BDD) and carbon felt were adopted as an anode and a cathode in the REDR. The influences of operation parameters on the chemical oxygen demand (COD) removal efficiency were detected and explored. Then, a mathematical model of organic mineralizing was developed for the REDR to predict the variation of COD removal efficiency with treating time under the different operation conditions. Finally, the energy consumption of the wastewater treated by the REDR was analyzed. The results showed that raising the working fluid flowing velocity and electrode rinse solution flowrate improved the COD removal efficiency and instantaneous current efficiency (ICE), and reduced the total energy consumption (TEC) of the REDR. Raising the initial MO concentration could significantly reduce the TEC despite the COD removal efficiency being near. Since the main energy consumed by the REDR was salinity gradient energy (SGE) from waste heat conversion or the natural environment, the energy cost of REDR treating wastewater has been reduced significantly.

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The simultaneous electro-oxidation of Ni (II)-citrate and electrodeposition recovery of nickel metal were attempted in a combined electro-oxidation-electrodeposition reactor with a boron-doped diamond (BDD) anode and a polished titanium cathode. Effects of initial nickel citrate concentration, current density, initial pH, electrode spacing, electrolyte type, and initial electrolyte dosage on electrochemical performance were examined. The efficiencies of Ni (II)-citrate removal and nickel metal recovery were determined to be 100% and over 72%, respectively, under the optimized conditions (10 mA/cm2, pH 4.09, 80 mmol/L Na2SO4, initial Ni (II)-citrate concentration of 75 mg/L, electrode spacing of 1 cm, and 180 min of electrolysis). Energy consumption increased with increased current density, and the energy consumption was 0.032 kWh/L at a current density of 10 mA/cm2 (pH 6.58). The deposits at the cathode were characterized by scanning electron microscopy (SEM), energy-dispersive spectrometry (EDS), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). These characterization results indicated that the purity of metallic nickel in cathodic deposition was over 95%. The electrochemical system exhibited a prospective approach to oxidize metal complexes and recover metallic nickel.

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Antibiotics in the environment provoke serious consequences on living beings and can be effectively remediated by prominent advanced oxidation process. In this study, electrochemical advanced oxidation treatment in a lab-scale reactor for the degradation of florfenicol (FLO) was studied with the aid of boron-doped diamond anode (BDD). The results exhibited that the FLO degradation follows pseudo-first-order kinetics. As the current intensity rose from 60 mA to 250 mA, the FLO removal efficiency increased and the corresponding reaction rate constant increased from 0.0213 to 0.0343 min-1, which was likely due to the more efficient participation of free hydroxyl radical (•OH) generated at the BDD anode. Faster degradation and higher mineralization of electrolyzed FLO solution were achieved at higher current intensity as well as in higher SO42- concentration medium, as a consequence of catalytic participation of oxidants (free •OH as well as sulfate radical (SO4•-) and persulfate (S2O82-)). The increase in FLO concentration from 30 to 50 mg L-1 resulted in a reaction rate constant decrease (from 0.0235 to 0.0178 min-1). Eight transformation by-products (m/z = 372.99, 359.8, 338.0, 324.04, 199.00, 185.02, 168.99 and 78.989) and three inorganic ions (NO3-, Cl- and F-) were analyzed by UPLC‒Q‒TOF‒MS/MS and Ion‒chromatography, respectively. The Vibrio fischeri bioluminescence inhibition revealed an increase of toxicity during the electrochemical oxidation that could be attributed mostly to the generated organic chlorinated by-products (m/z = 372.99, 359.8) and inorganic species (ClO2- and ClO3-).

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The present manuscript focuses on the study of the electrochemical oxidation of the insecticide Chlorfenvinphos (CVP). The assays were carried out under galvanostatic conditions using boron-doped diamond (BDD) and low-cost tin dioxide doped with antimony (Sb-doped SnO2) as anodes. The influence of the operating variables, such as applied current density, presence or absence of a cation-exchange membrane and concentration of supporting electrolyte, was discussed. The results revealed that the higher applied current density the higher degradation and mineralization of the insecticide for both anodes. The presence of the membrane and the highest concentration of Na2SO4 studied (0.1 M) as a supporting electrolyte benefited the oxidation process of CVP using the BDD electrode, while with the ceramic anode the elimination of CVP was lower under these experimental conditions. Although the BDD electrode showed the best performance, ceramic anodes appear as an interesting alternative as they were able to degrade CVP completely for the highest applied current density values. Toxicity tests revealed that the initial solution of CVP was more toxic than the samples treated with the ceramic electrode, while using the BDD electrode the toxicity of the sample increased.

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Degradation of the Acid Black 210 dye (AB210) in synthetic and industrial effluent samples was performed, for the first time, using a heterogeneous electro-Fenton (EF) process with a CoFe2O4/NOM magnetic hybrid catalyst (Hb200). The technique was compared with electrochemical oxidation using electrogenerated hydrogen peroxide (AO-H2O2). The catalyst was synthesized by the sol-gel technique, using water with a high content of natural organic matter (NOM) as an eco-friendly solvent. Analyses using XRD, FTIR, and TEM showed the formation of hybrid nanostructures with average size of 4.85 nm. Electrochemical assays were performed with a GDE/BDD electrode pair, electrogenerated H2O2, and current density of 45.4 mA cm-2. For the synthetic solution of AB210 at pH 3, the EF process presented higher efficiency, compared to AO-H2O2, with the optimum condition achieved using a lower mass of the catalyst (30 mg) and a higher concentration of the dye (55 mg L-1). The EF method also showed superior performance in the treatment of an industrial effluent with high organic load, at pH 6, with almost complete mineralization of AB210 (95%) in 7 h, while the AO-H2O2 process achieved 82% mineralization. The Hb200 hybrid maintained excellent catalytic activity during reuse in 3 cycles, with only 10% lower mineralization efficiency in the last cycle. GC-MS analysis showed that most of the contaminants in the effluent, including bis(2-ethylhexyl) phthalate, one of the most toxic, were eliminated or transformed after the EF treatment with Hb200.

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This work propose the fabrication and characterization of a Pt microelectrode integrated with a silver quasi-reference counter electrode (Pt/AgQRCE) for real time amperometric measurements of hydrogen peroxide electrochemically generated by water oxidation on Nb-supported boron doped diamond (Ni/BDD) anode. The developed electroanalytical method requires a very small sample volume and has higher sensitivity when compared to the conventional spectrophotometric analysis using ammonium metavanadate. The experiments were performed with Nb/BDD anode applying current densities of 30, 60, 90 and 120 mA cm-2 in 0.10 mol L-1 HClO4 supporting electrolyte showed that H2O2 production increase in the first 90 min of electrolysis and then reaches a plateau in both off-line and real time measurements. For the first 90 min, the electrogeneration of H2O2 exhibited a pseudo zero-order kinetics. The results obtained by the electrochemical amperometric analysis were compared to a spectrophotometric methodology reported on the literature and, at 95% confidence level the two methods do not demonstrated significant difference.

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The electrochemical oxidation of the antibiotic Norfloxacin (NOR) in chloride media on different anodic materials was studied at two different electrochemical reactors. The results were compared with those obtained in sulphate media. The anodes under study were a commercial boron-doped diamond (BBD) and two different ceramic electrodes based on tin oxide doped with antimony oxide in the presence (CuO) and absence (BCE) of copper oxide as sintering aid. The reactors employed were a one-compartment reactor (OCR) and a two-compartment one with a membrane separating both electrodes (EMR). The use of the membrane clearly enhanced both NOR degradation and TOC mineralization for all the anodic materials studied since some parallel reactions were avoided. Additionally, two different pathways for NOR oxidation were observed as a function of the reactor employed. The EMR also favoured the ionic by-products generation and the electrolyte dechlorination. NO3- increased with the oxidation power of the anode employed and it was also enhanced by the EMR use. Chloride media favours ceramic electrodes performance independently of the reactor employed as they did not generate an excess of oxidants as BDD did. The BCE electrode is an interesting alternative to BDD since although its oxidative power was lower, it presented similar current efficiency with lower energy consumption.

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Glucocorticoids are widely used to treat a variety of diseases. Consequently, these compounds have been found in water and wastewater matrix. Despite studies have proven its toxicity, just a few works investigate techniques to degrade and mineralize them. To solve this issue, this work presents the degradation and mineralization of prednisone (PRED) by electrochemical advanced oxidation (EAO) using a boron-doped diamond supported on niobium (Nb/BDD) anode in synthetic and real wastewater. Cyclic voltammetry (CV) was performed to investigate the PRED oxidation mechanisms. CV suggest that PRED will be oxidized via HO• and other oxidants generated from the ions present in the liquid matrix (S2O82-, SO4•-, HClO, ClO- etc.). Different EAO conditions as initial pH (3, 7 and 11) and applied current densities (5, 10 and 20 mA cm-2) were evaluated. The best result was obtained at alkaline pH (11) and a current density of 20 mA cm-2, achieving 78% of degradation and 42% of mineralization. Using the best conditions, the EAO was applied as a polishing treatment stage to remove PRED from a biological pre-treated municipal wastewater spiked with PRED. The results indicate that EAO applied in the real matrix provides better results than the synthetic solution, probably associated with the presence of ions that can be electrochemically converted into oxidant species, resulting in higher kinetic constant, mineralization current efficiency and lower energetic consumption. Therefore, the EAO process without the addition of chemicals has proven to be an effective alternative as a tertiary treatment of municipal wastewater contaminated with PRED.

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Norfloxacin is employed as in veterinary and human medicine against gram-positive and gram-negative bacteria. Due to the ineffective treatment at the wastewater treatment plants it becomes an emergent pollutant. Electro-oxidation appears as an alternative to its effective mineralization. This work compares Norfloxacin electro-oxidation on different anodic materials: two ceramic electrodes (both based on SnO2 + Sb2O3 with and without CuO, named as CuO and BCE, respectively) and a boron doped diamond (BDD). First, the anodes were characterized by cyclic voltammetry, revealing that NOR direct oxidation occurred at 1.30 V vs. Ag/AgCl. The higher the scan rate the higher both the current density and the anodic potential of the peak. This behavior was analyzed using the Randles-Sevcik equation to calculate the Norfloxacin diffusion coefficient in aqueous media, giving a value of D = 7.80 × 10-6 cm2 s-1 at 25 °C), which is close to the predicted value obtained using the Wilke-Chang correlation. The electrolysis experiments showed that both NOR and TOC decay increased with the applied current density, presenting a pseudo-first order kinetic. All the anodes tested achieved more than 90% NOR degradation at each current density. The CuO is not a good alternative to BCE because although it acts as a catalyst during the first use, it is lost from the anode surface in the subsequent uses. According to their oxidizing power, the anodes employed are ordered as follows: BDD > BCE > CuO.

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The recirculating split-flow batch reactor with a cell divided into anolyte and catholyte compartments for oxidation mixture of cytostatic drugs (CD) was tested. In this study, kinetics and mechanisms of electrochemical oxidization of two mixtures: 5-FU/CP and IF/CP were investigated. The order of the CD degradation rate in single drug solutions and in mixtures was found to be 5-FU < CP < IF. In the 5-FU/CP mixture, kapp of 5-FU increased, while kapp of CP decreased comparing to the single drug solutions. No effect on the degradation rate was found in the CP/IF mixture. The presence of a second drug in the 5-FU/CP mixture significantly altered mineralization and nitrogen removal efficiency, while these processes were inhibited in IF/CP. The experiments in the different electrolytes showed that •OH and sulphate active species can participate in the drug's degradation. The kapp of the drugs was accelerated by the presence of Cl- ions in the solution. Chlorine active species played the main role in the production of gaseous nitrogen products and increased the mineralisation. Good results were obtained for the degradation and mineralisation processes in mixtures of drugs in municipal wastewater-treated effluent, which is beneficial from the technological and practical point of view.

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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 H2O2 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 H2O2 accumulation (13.80 mg L-1 in 3 h) due to its larger electroactive surface area (28.81 cm2). Interestingly, it was found that PP decreased the decomposition rate of H2O2 in solution as compared to conventional electrolyte, which resulted in higher H2O2 accumulation. PP allowed operating EF at pH of 8 due to the formation of Fe2+-PP complexes in solution. Moreover, Fe2+-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 Fe2+-PP complex, 2) via OH from EF reactions, 3) via surface OH at the boron doped diamond electrode (BDD) and 4) via SO4- 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.

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A growing number of electrochemical oxidation system was employed for the degradation of refractory contaminants. In this study, a boron-doped diamond (BDD) anode/Ti cathode equipped in the differential column batch reactor (DCBR) was utilized for electrochemical oxidation of ciprofloxacin (CIP). The feed solution within the DCBR system was confirmed as a uniform flow state through a computational fluid dynamics (CFD) simulation analysis. The results showed that the BDD anode/Ti cathode electrochemical system was with a high efficiency oxidation performance when treating the CIP contaminant. The CIP was completely degraded within 20 min, and over 50% DOC removed after 120 min. Therefore, two-stage electrochemical oxidation mechanism was proposed. Four major factors, the initial concentration, current density, pH, and electrolyte concentration, on the CIP degradation efficiency were systematically investigated. The CIP degradation curve followed pseudo first-order degradation kinetics. The electric efficiency per order (EE/O) of the electrochemical oxidation system was calculated to determine an optimal operation condition. Moreover, the oxidation intermediates were identified with a mass spectrometry (LC/MS/MS) and the degradation pathways were proposed in this study. The destruction of quinolone moiety and piperazine ring and fluorine substitution were the three possible degradation pathways during BDD anode oxidation process.

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The electrochemical degradation of ciprofloxacin-CIP (50 mg L-1 in 0.10 mol L-1 Na2SO4) was investigated using a double-sided Ti-Pt/ß-PbO2 anode in a filter-press flow reactor, with identification of oxidation intermediates and follow-up of antimicrobial activity against Escherichia coli. The effect of solution pH, flow rate, current density, and temperature on the CIP removal rate was evaluated. All of these parameters did affect the CIP removal performance; thus, optimized electrolysis conditions were further explored: pH = 10, qV = 6.5 L min-1, j = 30 mA cm-2, and θ = 25 °C. Therefore, CIP was removed within 2 h, whereas ~75% of the total organic carbon concentration (TOC) was removed after 5 h and then, the solution no longer presented antimicrobial activity. When the electrochemical degradation of CIP was investigated using a single-sided boron-doped diamond (BDD) anode, its performance in TOC removal was similar to that of the Ti-Pt/ß-PbO2 anode; considering the higher oxidation power of BDD, the surprisingly good comparative performance of the Ti-Pt/ß-PbO2 anode was ascribed to significantly better hydrodynamic conditions attained in the filter-press reactor used with this electrode. Five initial oxidation intermediates were identified by LC-MS/MS and completely removed after 4 h of electrolysis; since they have also been determined in other degradation processes, there must be similarities in the involved oxidation mechanisms. Five terminal oxidation intermediates (acetic, formic, oxamic, propionic, and succinic acids) were identified by LC-UV and all of them (except acetic acid) were removed after 10 h of electrolysis.

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Preliminary laboratory work has shown that electrochemical oxidation (ECO) is a promising technology for disinfection of harvested stormwater. This paper focuses on understanding how stormwater chemistry (e.g. pH, chloride, bicarbonate, ammonia and total organic carbon - that can vary substantially between sites) impacts the disinfection performance of ECO. Real stormwater samples from four different urban catchments were collected and tested for ECO performance in disinfecting stormwater pathogens using a boron doped diamond anode under the current density of 4.2 mA/cm2. Results showed that total disinfection of indigenous Escherichia coli (E. coli), as well as three different stormwater pathogens (Enterococci, Campylobacter and C. perfringens) was achievable for all four tested stormwater within 30 min. Compared to the synthetic stormwater, lower disinfection rates were observed in real stormwater which has more complex chemistry. Stormwater chloride concentration was the only tested parameter that had significant impact on the treatment performance, with higher initial stormwater chloride concentration leading to an increased disinfection rate. Disinfection by-products in the treated stormwater were well below the Australian Drinking Water Guideline value for health, with its production level positively correlated to the pH values of stormwater.

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In this study, the electrochemical degradation process of 5-fluorouracil (5-FU) in aqueous media was performed using a continuous flow reactor in an undivided cell (system I), and in a divided cell with a cationic membrane (Nafion® 424) (system II). In system I, 75% of 5-FU degradation was achieved (50 mg L-1) with a applied current density japp = 150 A m-2, volumetric flow rate qv = 13 L h-1, after 6 h of electrolysis (kapp = 0.004 min-1). The removal efficiency of 5-FU was higher (95%) when the concentration was 5 mg L-1 under the same conditions. Nitrates (22% of initial amount of N), fluorides (27%) and ammonium (10%) were quantified after 6 h of electrolysis. System II, 77% of 5-FU degradation was achieved (50 mg L-1) after 6 h of electrolysis (kapp = 0.004 min-1). The degradation rate of 5-FU was complete when the concentration was 5 mg L-1 under the same conditions. Nitrates (29% of initial amount of N), fluorides (25%) and ammonium (5%) were quantified after 6 h of electrolysis. In addition, the main organic byproducts identified by mass spectroscopy were aliphatic compound with carbonyl and carboxyl functionalities. Due to, the mineralization of 5-FU with acceptable efficiency of 88% found in system II (japp of 200 A m-2), this system seems to be more promising in the cytostatic drug removal. Moreover the efficiency of 5-FU removal in diluted solutions is better in system II than in system I.

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The combination of persulfates (peroxydisulfate (PDS) and peroxymonosulfate (PMS)) and electrolysis using boron-doped diamond (BDD) anode is a promising green advanced oxidation process. In comparison with electrolysis alone, electrochemical activation of persulfates at BDD anode considerably enhanced the degradation of carbamazepine (CBZ). The experimental results indicate that the surface-adsorbed hydroxyl radical (HO) played the dominant role. The generally proposed nonradical oxidation mechanism ignored hydroxyl radical (HO) oxidation because low concentration of radical scavenger (<10 M methanol or 5 M tertbutanol) could not effectively scavenge the surface-adsorbed HO. The quasi steady-state concentration of HO was estimated to be about 5.0-9.1 × 10-12 M for electrolysis with BDD anode, and it was increased to 1.1-1.6 × 10-11 M and 3.2-5.0 × 10-11 M for addition of 5 mM PDS and PMS, respectively. The results of cyclic voltammetry (CV) and chronoamperometry as well as evolution of dissolved oxygen (DO) reveal that the electrochemically activated persulfates molecule (PDS∗/PMS∗) promoted the production of HO via water dissociation at BDD anode and enhanced the direct electron transfer (DET) reaction, which otherwise inhibited the oxygen evolution side reaction. Therefore, higher current efficiency was achieved in electrochemical activation of persulfates process compared with electrolysis process. Additionally, the transformation products of CBZ were also investigated and their formation pathways were proposed.

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The degradation of 4-hydroxyphenylacetic acid, a ubiquitous component of olive oil mill wastewater (OOMW), has been studied by anodic oxidation with electrogenerated H2O2 (AO-H2O2), electro-Fenton (EF) and photoelectro-Fenton (PEF). Experiments were performed in either a 0.050M Na2SO4 solution or a real OOMW at pH 3.0, using a cell with a boron-doped diamond (BDD) anode and an air-diffusion cathode for H2O2 generation. Hydroxyl radicals formed at the BDD surface from water oxidation in all processes and/or in the bulk from Fenton's reaction between added Fe2+ and generated H2O2 in EF and PEF were the main oxidants. In both matrices, the oxidation ability of the processes increased in the order AO-H2O2

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In the present study, the electrochemical oxidation of real wastewaters discharged by textile industry was carried out using a boron-doped diamond (BDD) anode. The effect of operational variables, such as applied current density (20-100 mA·cm-2), NaCl concentration added to the real wastewaters (0-3 g·L-1), and pH value (2.0-10.0), on the kinetics of COD oxidation and on the energy consumption was carefully investigated. The obtained experimental results could be well matched with a proposed kinetic model, in which the indirect oxidation mediated by electrogenerated strong oxidants would be described through a pseudo-first-order kinetic constant k. Values of k exhibited a linear increase with increasing applied current density and decreasing pH value, and an exponential increase with NaCl concentration. Furthermore, high oxidation kinetics resulted in low specific energy consumption, but this conclusion was not suitable to the results obtained under different applied current density. Under the optimum operational conditions, it only took 3 h to complete remove the COD in the real textile wastewaters and the specific energy consumption could be as low as 11.12 kWh·kg-1 COD. The obtained results, low energy consumption and short electrolysis time, allowed to conclude that the electrochemical oxidation based on BDD anodes would have practical industrial application for the treatment of real textile wastewater.

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