Study of the performance of a cylindrical flow-through electro-Fenton reactor using different arrangements of carbon felt electrodes: effect of key operating parameters.

In this work, a cylindrical flow-through electro-Fenton reactor containing graphite felt electrodes and an Fe(II) loaded resin was evaluated for the production of the Fenton reaction mixture and for the degradation of amoxicillin (AMX) and fecal coliforms containing aqueous solutions. First, the influence of several factors such as treatment time, current intensity, flow rate, and electrode position was investigated for the electrogeneration of H2O2 and the energetic consumption by means of a factorial design methodology using a 24 factorial matrix. Electric current and treatment time were found to be the pivotal parameters influencing the H2O2 production with contributions of 40.2 and 26.9%, respectively. The flow rate had low influence on the responses; however, 500 mL min-1 (with an average residence time of 1.09 min obtained in the residence time distribution analysis) allowed to obtain a better performance due to the high mass transport to and from the electrodes. As expected, polarization was also found to play an important role, since for the cathode-to-anode flow direction, lower H2O2 concentrations were observed when compared with the anode-to-cathode flow arrangement, indicating that part of the H2O2 produced in the cathode was destroyed at the anode. A fluorescence study of hydroxyl radical production, on the other hand, showed that higher yields were obtained using an anode-to-cathode flow direction (up to 3.88 µM), when compared with experiments carried out using a cathode-to-anode flow path (3.11 µM). The removal of a commercial formulation of the antibiotic AMX was evaluated in terms of total organic carbon, achieving up to 57.9% and 38.63% of pollutant mineralization using synthetic and real sanitary wastewater spiked, respectively. Finally, the efficiency of the process on the inactivation of fecal coliforms in sanitary wastewater samples was assessed, reducing 90% of the bacteria after 5 min of electrolysis.

Photo-assisted electrochemical advanced oxidation processes for the disinfection of aqueous solutions: A review.

Disinfection is usually the final step in water treatment and its effectiveness is of paramount importance in ensuring public health. Chlorination, ultraviolet (UV) irradiation and ozone (O3) are currently the most common methods for water disinfection; however, the generation of toxic by-products and the non-remnant effect of UV and O3 still constitute major drawbacks. Photo-assisted electrochemical advanced oxidation processes (EAOPs) on the other hand, appear as a potentially effective option for water disinfection. In these processes, the synergism between electrochemically produced active species and photo-generated radicals, improve their performance when compared with the corresponding separate processes and with other physical or chemical approaches. In photo-assisted EAOPs the inactivation of pathogens takes place by means of mechanisms that occur at different distances from the anode, that is: (i) directly at the electrode's surface (direct oxidation), (ii) at the anode's vicinity by means of electrochemically generated hydroxyl radical species (quasi-direct), (iii) or at the bulk solution (away from the electrode surface) by photo-electrogenerated active species (indirect oxidation). This review addresses state of the art reports concerning the inactivation of pathogens in water by means of photo-assisted EAOPs such as photo-electrocatalytic process, photo-assisted electrochemical oxidation, photo-electrocoagulation and cathodic processes. By focusing on the oxidation mechanism, it was found that while quasi-direct oxidation is the preponderant inactivation mechanism, the photo-electrocatalytic process using semiconductor materials is the most studied method as revealed by numerous reports in the literature. Advantages, disadvantages, trends and perspectives for water disinfection in photo-assisted EAOPs are also analyzed in this work.

Degradation of pharmaceutical compounds in water by oxygenated electrochemical oxidation: Parametric optimization, kinetic studies and toxicity assessment.

The pharmaceutical compounds sulfamethoxazole (SMX), propranolol (PRO) and carbamazepine (CBZ) are biorecalcitrant and frequently detected in waters causing negative impacts on human health and aquatic organisms. Electrochemical oxidation appears as an effective option for the removal of recalcitrant compounds and its enhancement is an important issue for the removal of emerging compounds in water. The contribution of this research lies in the comprehensive analysis of the oxygenated electro chemical oxidation of CBZ, SMX and PRO using Nb/BDD mesh anode. The effect of treatment time, current, pH and oxygen injection on the SMX, PRO and CBZ degradation was assessed using Na2SO4 as electrolyte, process optimization was performed, by-products were identified, kinetic and toxicity tests were carried out using different electrolytes. Finally, the process effectiveness was tested using real secondary effluent spiked with the mixture of the pharmaceutical compounds and the acute toxicity was determined. The obtained results indicated that the oxygenated electrochemical oxidation allows effective simultaneous SMX, PRO and CBZ degradation, which showed a significant dependence of treatment time, current and oxygen injection in Na2SO4 electrolyte. At 90 min of electrolysis the parent compounds were detected as well as eight by-products. At 150 min of treatment, further to the already determined by-products and the parent compounds, appeared phenol and p-benzoquinone. Based on the identified compounds, degradation pathways were explained as a result of two main mechanisms: transformation (hydroxylation, deamination, desulfunation) and bond rupture. The kinetic study indicated an increase of the first-order kinetic constant in the oxygenated electrochemical oxidation process using Na2SO4 and NaBr as electrolyte, nevertheless the constant decreased in the presence of NaCl. In the assays with secondary effluent spiked with SMX, PRO and CBZ, the oxygenation did not enhance the performance of the process, however; pharmaceuticals were degraded with a higher removal rates compared with the ones determined in the Na2SO4 synthetic solutions assays; the oxygenation enhanced the TOC and COD removal. The acute toxicity of spiked secondary effluent was reduced from the first few minutes of the electrochemical oxidation process.

Effect of electrolytes on the simultaneous electrochemical oxidation of sulfamethoxazole, propranolol and carbamazepine: behaviors, by-products and acute toxicity.

In this work, the effect of supporting electrolytes on the simultaneous electrochemical oxidation of the pharmaceuticals sulfamethoxazole (SMX), propranolol (PRO), and carbamazepine (CBZ) in aqueous solutions has been studied. Based on the identified by-products, the degradation mechanisms were proposed and the acute toxicity was evaluated for each electrolyte. Assays were carried out in batch mode in a 2 L undivided reactor using a niobium coated with boron-doped diamond (Nb/BDD) mesh anode and Ti cathode at 2.5 A in presence of different supporting electrolytes (Na2SO4, NaCl, or NaBr) at the same concentration of 7 mM. The degradation rates were higher in the assays with NaCl and NaBr. Reaction by-products were identified by gas chromatography-mass spectrometry. Indirect oxidation by electrogenerated reactive halogen species (RHS) was the main mechanism when halide ions were used as electrolytes. Ten by-products were detected using Na2SO4 as electrolyte, while 19 (12 non-halogenated and 7 halogenated) and 20 (10 non-halogenated and 10 halogenated) using NaCl and NaBr respectively. The proposed degradation pathways involve transformation (hydroxylation, deamination, desulfonation, and halogenation) and bond rupture to produce less molecular weight compounds and their further transformation until total degradation. Chlorinated and brominated by-products confirm halogenation reactions. The electrogenerated RHS presented a significant inhibition effect on Vibrio fischeri; nevertheless, acute toxicity was not presented using Na2SO4 as electrolyte and a pharmaceutical concentration of 5 µg/L. In this view, the role of the supporting electrolyte in electrochemical oxidation process is crucial since it strongly influence degradation rate, by-products, and acute toxicity.

Electrochemical carbamazepine degradation: Effect of the generated active chlorine, transformation pathways and toxicity.

Carbamazepine (CBZ) is a biorecalcitrant pharmaceutical compound frequently detected in wastewater and water bodies which has numerous negative effects on living organisms. In this investigation the effect of electrocatalytically generated active chlorine on CBZ degradation was studied using Nb/BDD or Ti/IrO2 anodes. Subsequently, a response surface methodology based on a factorial plan and central composite design was carried out to determine the contribution of individual factors and to obtain the optimal experimental parameters for CBZ abatement. Electric current and treatment time were found to be the pivotal parameters influencing the degradation efficiency with respective contributions of 45.19% and 35.44%. The anode material had lower influence on the response, however, using an Nb/BDD anode, the oxidation was more effective due to the increased production of OH radicals as well as HClO, Cl and ClO- species. Considering CBZ degradation and energetic consumption, the percentage of degraded CBZ was 88.70 ± 0.35% consuming 1.07 kWh m-3 (at 1.0 A, NaCl concentration of 14 mM after 12.45 min, using Nb/BDD anode). First order kinetic constant (k) value of 0.189 min-1 was obtained at optimal conditions when demineralized water was used for the NaCl supporting electrolyte, while k was lower when tap water or treated wastewaters were used for this purpose. Oxidation of CBZ yielded six aromatic intermediates, identified by gas chromatography - mass spectrometry technique and degradation pathways were proposed. The performed acute toxicity tests indicated an increase during the treatment, which was demonstrated to be mainly attributed to the remnant active chlorine.