Mineralization of the recalcitrant oxalic and oxamic acids by electrochemical advanced oxidation processes using a boron-doped diamond anode

Oxalic and oxamic acids are the ultimate and more persistent by-products of the degradation of N-aromatics by electrochemical advanced oxidation processes (EAOPs). In this paper, the kinetics and oxidative paths of these acids have been studied for several EAOPs using a boron-doped diamond (BDD) anode and a stainless steel or an air-diffusion cathode. Anodic oxidation (AO-BDD) in the presence of Fe²⁺ (AO-BDD-Fe²⁺) and under UVA irradiation (AO-BDD-Fe²⁺-UVA), along with electro-Fenton (EF-BDD), was tested. The oxidation of both acids and their iron complexes on BDD was clarified by cyclic voltammetry. AO-BDD allowed the overall mineralization of oxalic acid, but oxamic acid was removed much more slowly. Each acid underwent a similar decay in AO-BDD-Fe²⁺ and EF-BDD, as expected if its iron complexes were not attacked by hydroxyl radicals in the bulk. The faster and total mineralization of both acids was achieved in AO-BDD-Fe²⁺-UVA due to the high photoactivity of their Fe(III) complexes that were continuously regenerated by oxidation of their Fe(II) complexes. Oxamic acid always released a larger proportion of NH₄⁺ than NO₃⁻ ion, as well as volatile NO_x species. Both acids were independently oxidized at the anode in AO-BDD, but in AO-BDD-Fe²⁺-UVA oxamic acid was more slowly degraded as its content decreased, without significant effect on oxalic acid decay. The increase in current density enhanced the oxidation power of the latter method, with loss of efficiency. High Fe²⁺ contents inhibited the oxidation of Fe(II) complexes by the competitive oxidation of Fe²⁺ to Fe³⁺. Low current densities and Fe²⁺ contents are preferable to remove more efficiently these acids by the most potent AO-BDD-Fe²⁺-UVA method.     

Degradation of pharmaceutical beta-blockers by electrochemical advanced oxidation processes using a flow plant with a solar compound parabolic collector

The degradation of the beta-blockers atenolol, metoprolol tartrate and propranolol hydrochloride was studied by electro-Fenton (EF) and solar photoelectro-Fenton (SPEF). Solutions of 10 L of 100 mg L⁻¹ of total organic carbon of each drug in 0.1 M Na₂SO₄ with 0.5 mM Fe²⁺ of pH 3.0 were treated in a recirculation flow plant with an electrochemical reactor coupled with a solar compound parabolic collector. Single Pt/carbon felt (CF) and boron-doped diamond (BDD)/air-diffusion electrode (ADE) cells and combined Pt/ADE-Pt/CF and BDD/ADE-Pt/CF cells were used. SPEF treatments were more potent with the latter cell, yielding 95-97% mineralization with 100% of maximum current efficiency and energy consumptions of about 0.250 kWh g TOC⁻¹. However, the Pt/ADE-Pt/CF cell gave much lower energy consumptions of about 0.080 kWh g TOC⁻¹ with slightly lower mineralization of 88-93%, then being more useful for its possible application at industrial level. The EF method led to a poorer mineralization and was more potent using the combined cells by the additional production of hydroxyl radicals (^•OH) from Fenton’s reaction from the fast Fe²⁺ regeneration at the CF cathode. Organics were also more rapidly destroyed at BDD than at Pt anode. The decay kinetics of beta-blockers always followed a pseudo first-order reaction, although in SPEF, it was accelerated by the additional production of ^•OH from the action of UV light of solar irradiation. Aromatic intermediates were also destroyed by hydroxyl radicals. Ultimate carboxylic acids like oxalic and oxamic remained in the treated solutions by EF, but their Fe(III) complexes were photolyzed by solar irradiation in SPEF, thus explaining its higher oxidation power. NO₃⁻ was the predominant inorganic ion lost in EF, whereas the SPEF process favored the production of NH₄⁺ ion and volatile N-derivatives.     

Electrochemical degradation of β-blockers. Studies on single and multicomponent synthetic aqueous solutions

As far as we know, this is the first study reporting the electrochemical decontamination of solutions containing β-blockers, which are pharmaceutical pollutants with a high occurrence in natural waters. The oxidation ability of two pre-eminent, eco-friendly electrochemical advanced oxidation processes (EAOPs), namely anodic oxidation (AO) and electro-Fenton (EF), has been compared at lab-scale by carrying out bulk electrolyses at pH 3.0 at constant current using a carbon-felt cathode able to electrogenerate H₂O₂ in situ. The studies of single component aqueous solutions were focused on atenolol as a model β-blocker. The AO process was proven much more effective using a large surface area boron-doped diamond (BDD) anode than a Pt one, which was explained by the great amount of active hydroxyl radicals (BDD(OH)) and the minimization of their parasitic reactions. The EF process with a Pt anode and 0.2 mmol l⁻¹ Fe²⁺ showed even higher performance, with fast destruction of atenolol following pseudo-first order kinetics and fast mineralization because the oxidation process in the bulk allows overcoming the mass transport limitations. The time course of the concentration of the aromatic and short-chain carboxylic acid intermediates demonstrated the progressive detoxification of the solutions. Almost 100% of the initial N content was accumulated as NH₄⁺. Multicomponent solutions containing atenolol, metoprolol, and propranolol, which usually occur together in the aquatic environment, were treated by EF using the Pt/carbon felt cell. A high mineralization rate was observed up to the overall total organic carbon (TOC) removal, which allowed reducing the energy consumption. The absolute rate constant for the reaction of each β-blocker with OH was determined and the reactivity was found to increase in the order: atenolol (1.42 × 10⁹ l mol⁻¹ s⁻¹) < metoprolol (2.07 × 10⁹ l mol⁻¹ s⁻¹) < propranolol (3.36 × 10⁹ l mol⁻¹ s⁻¹).     

Advanced treatment of biologically pretreated coking wastewater by electrochemical oxidation using boron-doped diamond electrodes

Electrochemical oxidation is a promising technology to treatment of bio-refractory wastewater. Coking wastewater contains high concentration of refractory and toxic compounds and the water quality usually cannot meet the discharge standards after conventional biological treatment processes. This paper initially investigated the electrochemical oxidation using boron-doped diamond (BDD) anode for advanced treatment of coking wastewater. Under the experimental conditions (current density 20-60 mA cm⁻², pH 3-11, and temperature 20-60 °C) using BDD anode, complete mineralization of organic pollutants was almost achieved, and surplus ammonia-nitrogen (NH₃-N) was further removed thoroughly when pH was not adjusted or at alkaline value. Moreover, the TOC and NH₃-N removal rates in BDD anode cell were much greater than those in other common anode systems such as SnO₂ and PbO₂ anodes cells. Given the same target to meet the National Discharge Standard of China, the energy consumption of 64 kWh kgCOD⁻¹ observed in BDD anode system was only about 60% as much as those observed in SnO₂ and PbO₂ anode systems. Further investigation revealed that, in BDD anode cell, organic pollutants were mainly degraded by reaction with free hydroxyl radicals and electrogenerated oxidants (S₂O₈²⁻, H₂O₂, and other oxidants) played a less important role, while direct electrochemical oxidation and indirect electrochemical oxidation mediated by active chlorine can be negligible. These results showed great potential of BDD anode system in engineering application as a final treatment of coking wastewater.     

Propham mineralization in aqueous medium by anodic oxidation using boron-doped diamond anode: influence of experimental parameters on degradation kinetics and mineralization efficiency

This study aims the removal of a carbamate herbicide, propham, from aqueous solution by direct electrochemical advanced oxidation process using a boron-doped diamond (BDD) anode. This electrode produces large quantities of hydroxyl radicals from oxidation of water, which leads to the oxidative degradation of propham up to its total mineralization. Effect of operational parameters such as current, temperature, pH and supporting electrolyte on the degradation and mineralization rate was studied. The applied current and temperature exert a prominent effect on the total organic carbon (TOC) removal rate of the solutions. The mineralization of propham can be performed at any pH value between 3 and 11 without any loss in oxidation efficiency. The propham decay and its overall mineralization reaction follows a pseudo-first-order kinetics. The apparent rate constant value of propham oxidation was determined as 4.8×10⁻⁴ s⁻¹ at 100 mA and 35 °C in the presence of 50 mM Na₂SO₄ in acidic media (pH: 3). A general mineralization sequence was proposed considering the identified oxidation intermediates.     

Treatment of high strength hexamine-containing wastewater by electro-Fenton method

A novel Electro-Fenton (EF–Fere) method, applied H₂O₂ and electrogenerated ferrous ion, was investigated for treating the hexamine-containing wastewater. The performance of Fe²⁺ generation in the electrolytic system was first evaluated, including the factors of the cathode material, initial pH, initial ferric concentration (Fe_i), and current density. When initial pH exceeded 2.5, the current efficiency dramatically decreased, which was due to the formation of Fe(OH)₃. Between 3000 and 10,000 mg/l of Fe_i, the initial current efficiency of Fe²⁺ generation was almost constant (85–87%), which dropped sharply to 39% at 1000 mg/l. In EF–Fere experiments, the COD removal efficiency attained above 94% after 5 h of reaction. The relationship between the temperature, dissolved oxygen, and COD was discussed. The changes in hexamine and its oxidation intermediates (methanol, formaldahyde, formate, ammonium and nitrate) during the reaction were also investigated. Three additional experiments using H₂O₂/Fe²⁺, H₂O₂/Fe³⁺, and direct electrolysis were also conducted to treat the hexamine-containing wastewater for comparison. The results showed that the EF–Fere method was the most efficient.     

Mineralization of salicylic acid in acidic aqueous medium by electrochemical advanced oxidation processes using platinum and boron-doped diamond as anode and cathodically generated hydrogen peroxide

Solutions containing 164 mg L(-1) salicylic acid of pH 3.0 have been degraded by electrochemical advanced oxidation processes such as anodic oxidation, anodic oxidation with electrogenerated H(2)O(2), electro-Fenton, photoelectro-Fenton and solar photoelectro-Fenton at constant current density. Their oxidation power has been comparatively studied in a one-compartment cell with a Pt or boron-doped diamond (BDD) anode and a graphite or O(2)-diffusion cathode. In the three latter procedures, 0.5mM Fe(2+) is added to the solution to form hydroxyl radical (()OH) from Fenton's reaction between Fe(2+) and H(2)O(2) generated at the O(2)-diffusion cathode. Total mineralization is attained for all methods with BDD and for photoelectro-Fenton and solar photoelectro-Fenton with Pt. The poor decontamination achieved in anodic oxidation and electro-Fenton with Pt is explained by the slow removal of most pollutants by ()OH formed from water oxidation at the Pt anode in comparison to their quick destruction with ()OH produced at BDD. ()OH generated from Fenton's reaction oxidizes rapidly all aromatic pollutants, but it cannot destroy final Fe(III)-oxalate complexes. Solar photoelectro-Fenton treatments always yield quicker degradation rate due to the very fast photodecarboxylation of these complexes by UVA irradiation supplied by solar light. The effect of current density on the degradation rate, efficiency and energy cost of all methods is examined. The salicylic acid decay always follows a pseudo-first-order kinetics. 2,3-Dihydroxybenzoic, 2,5-dihydroxybenzoic, 2,6-dihydroxybenzoic, alpha-ketoglutaric, glycolic, glyoxylic, maleic, fumaric, malic, tartronic and oxalic acids are detected as oxidation products. A general reaction sequence for salicylic acid mineralization considering all these intermediates is proposed.     

Synergistic effect between ultraviolet irradiation and electrochemical oxidation for removal of humic acids and pharmaceuticals

The fate of pharmaceuticals in the aquatic environment is significantly affected by the presence of humic acids (HA). In this work, the synergistic effect of electrochemical oxidation (EO) and ultraviolet irradiation (UVI) was evaluated for HA removal and for the simultaneous degradation of three pharmaceuticals (carbamazepine, propranolol and sulfamethoxazole) in presence of HA. The effectiveness of EO, UVI and their combination for HA removal was assessed using different operating parameters, such as type of anode (Nb/BDD and Ti/IrO₂), supporting electrolyte (NaCl, NaBr and Na₂SO₄), current density (8.1, 16.1, 28.2, 40.3, and 48.4 mA/cm²), pH (3, 7 and 9) and NaCl electrolyte concentration (7, 14 and 21 mM). The use of non‐active anode Nb/BDD, NaCl electrolyte and combination EO‐UVI was the most efficacious option for HA removal, due to the production of hydroxyl radicals as well as active chlorine species (HClO, Cl^● and ClO^?) generated by anodic oxidation and by UVI. The effectiveness of the EO process was enhanced coupling EO with UVI, however the energetic consumption increased. The composition of the electrolyte was the pivotal parameter since a complete degradation of the pharmaceuticals was achieved by both processes EO and EO‐UVI using NaCl as electrolyte; this is attributed to the indirect oxidation by electrogenerated active chlorine which dominates the pharmaceuticals degradation.     

Hydroxyl radical involvement in the decomposition of hydrogen peroxide by ferrous and ferric-nitrilotriacetate complexes at neutral pH

The relative rates of degradation of three hydroxyl radical probe compounds (atrazine, fenuron and parachlorobenzoic acid (pCBA)) by Fe^III/H₂O₂ (pH = 2.85), Fe^IIINTA/H₂O₂ (neutral pH), Fe^II/O₂, Fe^IINTA/O₂, Fe^II/H₂O₂ and Fe^IINTA/H₂O₂ (neutral pH) have been investigated using the competitive kinetic method. Experiments were carried out in batch and in semi-batch reactors, in the dark, at 25 °C. The data showed that the three probe compounds could be degraded by all the systems studied, and in particular by Fe^IINTA/H₂O₂ and Fe^IIINTA/H₂O₂ at neutral pH. The relative rate constants of degradation of the three probe compounds obtained for all the systems tested were identical and equal to 1.45 ± 0.03 and 0.47 ± 0.02 for k_Atrazine/k_pCBA and k_Fenuron/k_pCBA, respectively. These values as well as the decrease of the rates of degradation of the probe compounds upon the addition of hydroxyl radical scavengers (tert-butanol, bicarbonate ions) suggest that the degradation of atrazine, fenuron and pCBA by Fe^IINTA/O₂, Fe^IINTA/H₂O₂ and Fe^IIINTA/H₂O₂ is initiated by hydroxyl radicals.     

Degradation of 2,4-dinitrotoluene by persulfate activated with zero-valent iron

The oxidation of 2,4-dinitrotoluene (DNT) by persulfate (S₂O₈²⁻) activated with zero-valent iron (Fe^o) was studied through a series of batch experiments. The mechanism for Fe^o activation was investigated by comparing with Fe²⁺, and the effects of persulfate-to-iron ratio and pre-reduction on DNT oxidation were examined. DNT was stable in the presence of persulfate and transformed only when Fe^o was added. Most DNT was degraded oxidatively by Fe^o-activated persulfate, whereas direct reduction of DNT by Fe^o was unimportant. The rate of DNT degradation increased with higher Fe^o dose, presumably due to increasing activation of persulfate by Fe^o and Fe²⁺. In contrast to the Fe^o-persulfate system, where complete oxidation DNT was achieved, only ≤ 20% of DNT was degraded and the reaction was terminated rapidly when Fe^o was replaced with equimolar Fe²⁺. This indicates that Fe^o is more effective than Fe²⁺ as activating agent and potentially more suitable for environmental applications. The reduction products of DNT were more rapidly oxidized by persulfate than DNT, suggesting that converting the nitro groups of NACs to amino groups prior to oxidation can greatly enhance their oxidation. This suggests that a sequential Fe^o reduction-persulfate oxidation process may be an effective strategy to promote NAC degradation.     

Mineralization enhancement of a recalcitrant pharmaceutical pollutant in water by advanced oxidation hybrid processes

Degradation of the biorecalcitrant pharmaceutical micropollutant ibuprofen (IBP) was carried out by means of several advanced oxidation hybrid configurations. TiO₂ photocatalysis, photo-Fenton and sonolysis - all of them under solar simulated illumination - were tested in the hybrid systems: sonophoto-Fenton (FS), sonophotocatalysis (TS) and TiO₂/Fe²⁺/sonolysis (TFS). In the case of the sonophoto-Fenton process, the IBP degradation (95%) and mineralization (60%) were attained with photo-Fenton (FH). The presence of ultrasonic irradiation slightly improves the iron catalytic activity. On the other hand, total removal of IBP and elimination of more than 50% of dissolved organic carbon (DOC) were observed by photocatalysis with TiO₂ in the presence of ultrasound irradiation (TS). In contrast only 26% of mineralization was observed by photocatalysis with H₂O₂ (TH) in the absence of ultrasound irradiation. Additional results showed that, in the TFS system, 92% of DOC removal and complete degradation of IBP were obtained within 240 min of treatment. The advanced oxidation hybrid systems seems to be a promising alternative for full elimination/mineralization for the recalcitrant micro-contaminant IBP.     

An innovative ultrasound, Fe and TiO2 photoassisted process for bisphenol a mineralization

This paper explores the degradation of a model pollutant, bisphenol A, by an advanced oxidation process that combines sonolysis, Fe²⁺, and TiO₂ in a photoassisted process. Experiments were done under saturated oxygen conditions. The effect of different Fe²⁺ (0.56 and 5.6 mg/L) and TiO₂ (10 and 50 mg/L) concentrations was investigated on both the elimination and mineralization of the pollutant. A pronounced synergistic effect that led to the complete and rapid elimination of dissolved organic carbon (DOC) was observed even at low catalyst loadings. In this system, almost a complete removal of DOC (93%) was observed after 4 h using 10 and 5.6 mg/L of TiO₂ and Fe²⁺, respectively, whereas at the same time, only 5, 6, and 22% of DOC was removed by an individual process alone (TiO₂ photocatalysis, ultrasound, and photo-Fenton, respectively). In this system, ultrasound has the principal role of eliminating the initial substrate and providing hydrogen peroxide for the photocatalytic systems, while photo-Fenton and TiO₂ photocatalysis are mainly responsible for the transformation of the intermediates in CO₂ and H₂O. The role of H₂O₂ generated from the sonochemical process is also discussed.     

Sonophotolytic degradation of azo dye reactive black 5 in an ultrasound/UV/ferric system and the roles of different organic ligands

The sonophotolytic advance oxidation system (US/UV/Fe³⁺) could achieve synergistic degradation of reactive black 5 (RB5), as compared to UV/Fe³⁺ and US/Fe³⁺ systems. A synergy factor of 2.5 based on the pseudo-first-order degradation rate constant (k_obs) was found, along with enhancements in organic detoxification and mineralization. The presence of organic ligands could affect the US/UV/Fe³⁺ system differently. Oxalate, citrate, tartrate and succinate could enhance the RB5 degradation, while NTA and EDTA exhibited strong inhibitions. The influence of these ligands on k_obs(RB5) in the US/UV/Fe(III)-ligand systems followed the sequence of oxalate > tartrate > succinate > citrate > without ligand > NTA > EDTA, while they could be degraded simultaneously with the k_obs(ligand) order of oxalate > citrate > tartrate > succinate > NTA > EDTA. Monitoring of iron species and the generated H₂O₂ and •OH revealed that the ligands in the US/UV/Fe(III)-ligand system could play different mechanistic roles: (1) promoting H₂O₂ production, (2) accelerating Fenton reaction, and (3) competing with RB5 for reacting with •OH. Among the ligands, oxalate exhibited the most significant enhancement of RB5 oxidation in the sonophotolytic system, and the process was pH-dependent. An initial reaction lag in RB5 degradation was observed when Fe²⁺ was used in lieu of Fe³⁺ as the catalyst in the sonophotolytic system.     

Electrochemical oxidation of organics in water: Role of operative parameters in the absence and in the presence of NaCl

The electrochemical oxidation of organics in water was investigated theoretically and experimentally to determine the role of several operative parameters on the performances of the process in the presence and in the absence of sodium chloride. Theoretical considerations were used to design the experimental investigation and were confirmed by the results of the electrochemical oxidation of oxalic acid (OA) at boron doped diamond (BDD) or IrO₂-Ta₂O₅ (DSA-O₂) anodes in a continuous batch recirculation reaction system equipped with a parallel plate undivided electrochemical cell. Polarization curves and chronoamperometric measurements indicated that, in the presence of chlorides, the anodic oxidation of OA is partially replaced by an indirect oxidation process. This result was confirmed by electrolyses experiments that show that, in the presence of suitable amount of chlorides, oxidation of OA takes place mainly by a homogeneous process. Interestingly, a very different influence of the nature of the anodic material, the flow rate and the current density on the performances of the process arises in the absence and in the presence of chlorides so that optimization of the two processes requires very different operative conditions. In the absence of chlorides, high current efficiency (CE) is obtained at BDD when most part of the process is under charge transfer controlled kinetics, i.e. when low current densities and high flow rates are imposed. On the other hand, in the presence of NaCl, higher CE are generally obtained at DSA anode when high current densities and low flow rates are imposed, i.e. when a high concentration of chemical oxidants is obtained as a result of the chloride oxidation. The effect of other operative parameters such as the OA concentration and the pH were further investigated.     

Comparison of the ozonation and Fenton process performances for the treatment of antibiotic containing manure

An integrated treatment method based on magnesium salt extraction followed by chemical oxidation was used for the treatment of a veterinary antibiotic, oxytetracycline (OTC) contaminated cow manure since animal manure can be an important source for antibiotic pollution in the environment. Pretreatment with magnesium salt enhanced the efficiencies of subsequent oxidation processes by extracting 63.9% of OTC from the manure thereby making it more favorable for oxidation with the hydroxyl radicals produced by the Fenton and ozone oxidation processes. Both the 24 h Fenton oxidation process with 434 mM H₂O₂ and 43.4 mM Fe²⁺ doses and the 1-h ozonation process with an applied ozone dose of 2.5 mg min^− 1 provided more than 90% OTC removal from the manure slurry. However, the second-order OTC removal rate constant of Fenton process (119 M^− 1s^− 1) was remarkably lower than that obtained with the ozonation process (548 M^− 1s^− 1). The oxidant dose was a significant factor for the efficiency of the Fenton treatment but not for the ozone treatment. The efficiencies of both the Fenton and ozone oxidation processes were not affected by the pH adjustment of the manure slurry.     

Development of a TiO2 modified optical fiber electrode and its incorporation into a photoelectrochemical reactor for wastewater treatment

Electrochemical advanced oxidation processes (EAOPs) are used to chemically burn non biodegradable complex organic compounds that are present in polluted effluents. A common approach involves the use of TiO₂ semiconductor substrates as either photocatalytic or photoelectrocatalytic materials in reactors that produce a powerful oxidant (hydroxyl radical) that reacts with pollutant species. In this context, the purpose of this work is to develop a new TiO₂ based photoanode using an optic fiber support. The novel arrangement of a TiO₂ layer positioned on top of a surface modified optical fiber substrate, allowed the construction of a photoelectrochemical reactor that works on the basis of an internally illuminated approach. In this way, a semi-conductive optical fiber modified surface was prepared using 30 μm thickness SnO₂:Sb films on which the photoactive TiO₂ layer was electrophoretically deposited. UV light transmission experiments were conducted to evaluate the transmittance along the optical fiber covered with SnO₂:Sb and TiO₂ showing that 43% of UV light reached the optical fiber tip. With different illumination configurations (external or internal), it was possible to get an increase in the amount of photo-generated H₂O₂ close to 50% as compared to different types of TiO₂ films. Finally, the electro-Fenton photoelectrocatalytic Oxidation process studied in this work was able to achieve total color removal of Azo orange II dye (15 mg L⁻¹) and a 57% removal of total organic carbon (TOC) within 60 min of degradation time.     

Solar Fenton and solar TiO2 catalytic treatment of ofloxacin in secondary treated effluents: Evaluation of operational and kinetic parameters

Two different technical approaches based on advanced oxidation processes (AOPs), solar Fenton homogeneous photocatalysis (hv/Fe²⁺/H₂O₂) and heterogeneous photocatalysis with titanium dioxide (TiO₂) suspensions were studied for the chemical degradation of the fluoroquinolone ofloxacin in secondary treated effluents. A bench-scale solar simulator in combination with an appropriate photochemical batch reactor was used to evaluate and select the optimal oxidation conditions of ofloxacin spiked in secondary treated domestic effluents. The concentration profile of the examined substrate during degradation was determined by UV/Vis spectrophotometry. Mineralization was monitored by measuring the dissolved organic carbon (DOC). The concentrations of Fe²⁺ and H₂O₂ were the key factors for the solar Fenton process, while the most important parameter of the heterogeneous photocatalysis was proved to be the catalyst loading. Kinetic analyses indicated that the photodegradation of ofloxacin can be described by a pseudo-first-order reaction. The rate constant (k) for the solar Fenton process was determined at different Fe²⁺ and H₂O₂ concentrations whereas the Langmuir-Hinshelwood (LH) kinetic expression was used to assess the kinetics of the heterogeneous photocatalytic process. The conversion of ofloxacin depends on several parameters based on the various experimental conditions, which were investigated. A Daphnia magna bioassay was used to evaluate the potential toxicity of the parent compound and its photo-oxidation by-products in different stages of oxidation. In the present study solar Fenton has been demonstrated to be more effective than the solar TiO₂ process, yielding complete degradation of the examined substrate and DOC reduction of about 50% in 30 min of the photocatalytic treatment.     

Electrochemical degradation of bisphenol A on different anodes

Laboratory experiments were carried out on the kinetics, pathways and mechanisms of electrochemical (EC) degradation of bisphenol A (BPA) on four types of anodes, Ti/boron-doped diamond (BDD), Ti/Sb-SnO₂, Ti/RuO₂ and Pt. There were considerable differences among the anodes in their effectiveness and performance of BPA electrolysis. BPA was readily destructed at the Ti/Sb-SnO₂ and Ti/BDD anodes, the Pt anode had a moderate ability to remove BPA, and the Ti/RuO₂ anode was incapable of effectively oxidising BPA. The intermediate products of EC degradation of BPA were detected and quantified by high-performance liquid chromatography (HPLC), and a general BPA degradation pathway was proposed based on the analytical results. It was suggested that OH radicals produced by water electrolysis attacked BPA to form hydroxylated BPA derivatives that were then transformed into one-ring aromatic compounds. These compounds underwent ring breakage, which led to the formation of aliphatic acids that were eventually mineralised by electrolysis to CO₂. Compared to the Pt and Ti/RuO₂ anodes, the Ti/Sb-SnO₂ and Ti/BDD anodes were found to have higher oxygen evolution potentials and higher anodic potentials for BPA electrolysis under the same current condition. However, the stability and durability of the Ti/Sb-SnO₂ anode still needs to be greatly improved for actual application. In comparison, with its high durability and good reactivity for organic oxidation, the Ti/BDD anode appears to be the more promising one for the effective EC treatment of BPA and similar endocrine disrupting chemical (EDC) pollutants.     

Cation exchange during subsurface iron removal

Subsurface iron removal (SIR), or in-situ iron removal, is an established treatment technology to remove soluble iron (Fe²⁺) from groundwater. Besides the adsorptive-catalytic oxidation theory, it has also been proposed that the injection of O₂-rich water onsets the exchange of adsorbed Fe²⁺ with other cations, such as Ca²⁺ and Na⁺. In sand column experiments with synthetic and natural groundwater it was found that cation exchange (Na⁺-Fe²⁺) occurs during the injection-abstraction cycles of subsurface iron removal. The Fe²⁺ exchange increased at higher Na⁺ concentration in the injection water, but decreased in the presence of other cations in the groundwater. Field results with injection of elevated O₂ concentrations (0.55 mM) showed increased Fe removal efficacy; the operational parameter V/Vi (abstraction volume with [Fe]<2 μM divided by the injection volume) increased from an average 7 to 16, indicating that not the exchangeable Fe²⁺ on the soil material is the limiting factor during injection, but it is the supply of O₂ to the available Fe²⁺.     

Kinetics of electro-oxidation of ammonia-N, nitrites and COD from a recirculating aquaculture saline water system using BDD anodes

The viability of the electro-oxidation technology provided with boron doped diamond (BDD) electrodes for the treatment and reuse of the seawater used in a Recirculating Aquaculture System (RAS) was evaluated in this work.The influence of the applied current density (5-50 A m⁻²) in the removal of Total Ammonia Nitrogen (TAN), nitrite and chemical oxygen demand (COD) was analyzed observing that complete TAN removal together with important reductions of the other considered contaminants could be achieved, thus meeting the requirements for reuse of seawater in RAS systems.TAN removal, mainly due to an indirect oxidation mechanism was described by a second order kinetics while COD and nitrite removal followed zero-th order kinetics. The values of the kinetic constants for the anodic oxidation of each compound were obtained as a function of the applied current density (k_TAN = 7.86 × 10⁻⁵·exp(6.30 × 10⁻² J); k₂NO = 3.43 × 10⁻² J; k_COD = 1.35 × 10⁻² J). The formation of free chlorine and oxidation by-products, i.e., trihalomethanes (THMs) was followed along the electro-oxidation process. Although a maximum concentration of 1.7 mg l⁻¹ of total trihalomethanes was detected an integrated process combining electrochemical oxidation in order to eliminate TAN, nitrite and COD and adsorption onto activated carbon to remove the residual chlorine and THMs is proposed, as an efficient alternative to treat and reuse the seawater in fish culture systems. Finally, the energy consumption of the treatment has been evaluated.