Effect of the anode material, applied current and reactor configuration on the atenolol toxicity during an electrooxidation process.

Atenolol (ATL) is a beta-blocker pharmaceutical product which is excreted mainly unchanged and may represent a long-term risk for organisms present in the sea and in fresh water. Due to its low biodegradation rate, electrochemical advanced oxidation processes (EAOPs) can be used to remove this compound. In this work, ATL ecotoxicity was analyzed in the presence of sodium sulfate (Na2SO4), which is widely used as supporting electrolyte in EAOPs. Ecotoxicity values were expressed as the pollutant concentration that leads to a 50% inhibition of the root elongation of Lactuca sativa seeds in relation to the control (EC50(5 days)). The obtained values for ATL showed an EC50(5 days) of 1377 mg L-1 towards Lactuca sativa. When Na2SO4 was added, the toxicity of the sample increased but no synergy was detected between both compounds. With 2 g L-1 Na2SO4, ATL showed an EC50(5 days) of 972 mg L-1; and with 4 g L-1 Na2SO4 and higher concentrations, EC50 value for ATL was 0 mg L-1. Statistical tools were used to obtain the zones of the [ATL]-[Na2SO4] plane which are toxic towards Lactuca sativa. Solutions containing ATL and Na2SO4 were treated by electrooxidation. Two anode materials (a boron-doped diamond electrode and a microporous Sb-doped SnO2 ceramic one); three operation currents (0.4, 0.6 and 1 A); and two reactor configurations (one-compartment reactor and two-compartment reactor separated by a cation exchange membrane) were used. Lactuca sativa seeds and Vibrio fischeri bacterium tests were employed to evaluate the toxicity of the solutions before and after applying the electrooxidation process. In all the tests, the ecotoxicity of the treated sample increased. This fact is owing to the persulfate presence in the solution due to the sulfate electrochemical oxidation. Nevertheless, none of the final samples were toxic towards Vibrio fischeri because ecotoxicity values were lower than 10 TU; and, in the case of the one-compartment reactor, practically all of them were also non-toxic towards Lactuca sativa. The toxicity of the treated samples increased when using the two-compartment reactor in the presence of the BDD anode, and when the operation current was increased. This is attributed to the highest formation of persulfates. Amongst all the tests performed in this work, the lowest toxicity value (i.e., 3 TU) together with the complete mineralization and degradation degrees was achieved with the two-compartment reactor using the BDD anode and operating at 0.6 A.

Novel Sb-doped SnO2 ceramic anode coated with a photoactive BiPO4 layer for the photoelectrochemical degradation of an emerging pollutant.

In the present work, a study about the electrochemical and photoelectrochemical degradation of an emerging pollutant using an Sb-doped SnO2 anode coated with a photocatalytic layer of BiPO4 has been performed. The electrochemical characterization of the material was carried out by means of linear sweep voltammetry, light-pulsed chronoamperometry and electrochemical impedance spectroscopy. These studies confirmed that the material is photoactive at intermediate potential values (around 2.5 V), and that the charge transfer resistance decreases in the presence of light. A positive effect of the illuminated area on the degradation degree of norfloxacin was observed: at 15.50 mA cm-2, the degradation rate was 83.37% in the absence of light, 92.24% with an illuminated area of 5.7 cm2, and it increased up to 98.82% with an illuminated area of 11.4 cm2. The kinetics of the process were evaluated, and the by-products of the degradation were identified by ion chromatography and HPLC. In the case of the mineralization degree, the effect of light is less significant, especially at higher current densities. The specific energy consumption of the process was lower in the photoelectrochemical experiments as compared to the experiments in dark conditions. At intermediate current densities (15.50 mA cm-2) a decrease in energy consumption of 53% was achieved by illuminating the electrode.

Norfloxacin mineralization under light exposure using Sb-SnO2 ceramic anodes coated with BiFeO3 photocatalyst.

Advanced Oxidation Processes have been proven to be an efficient way to remove organic pollutants from wastewaters. In this work, a ceramic electrode of Sb-SnO2 (BCE) with a layer of the photocatalytic material BiFeO3 (BFO-BCE), has been characterized electrochemically and further tested for norfloxacin photo-electrooxidation in the presence and absence of light. The electrode photoactivity was highly enhanced thanks to the presence of BiFeO3, as confirmed by Linear Sweep Voltammetry, chronoamperometry and potentiometry, and Electrochemical Impedance Spectroscopy. Additionally, working in galvanostatic mode, a high mineralization of norfloxacin was achieved after 240 min, reaching 62% at 25 mA cm-2 under light conditions. This value is comparatively higher than the 40% achieved with the BCE. The oxidation byproducts were followed by ionic chromatography and HPLC analysis, which also allowed us to propose an oxidation pathway of the norfloxacin molecule. Finally, some indicators of the reactor performance such as the Mineralization Current Efficiency and the specific energy consumption were analyzed, revealing that lower current densities (8.3 mA cm-2) led to higher current efficiencies, and that light improved both the current efficiency and energy consumption.

Study of the chlorfenvinphos pesticide removal under different anodic materials and different reactor configuration.

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.

Comparison between an electrochemical reactor with and without membrane for the nor oxidation using novel ceramic electrodes.

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.

Effect of the CuO addition on a Sb-doped SnO2 ceramic electrode applied to the removal of Norfloxacin in chloride media by electro-oxidation.

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.

Analysis of norfloxacin ecotoxicity and the relation with its degradation by means of electrochemical oxidation using different anodes.

In this work, ecotoxicological bioassays based on Lactuca sativa seeds and bioluminescent bacterium (Vibrio fischeri) have been carried out in order to quantify the toxicity of Norfloxacin (NOR) and sodium sulfate solutions, before and after treating them using electrochemical advanced oxidation. The effect of some process variables (anode material, reactor configuration and applied current) on the toxicity evolution of the treated solution has been studied. A NOR solution shows an EC50(5 days) of 336 mg L-1towards Lactuca sativa. This threshold NOR concentration decreases with sodium sulfate concentration, in solutions that contain simultaneously Norfloxacin and sodium sulfate. In every case considered in this work, the electrochemical advanced oxidation process increased the toxicity (towards both Lactuca sativa and Vibrio fischeri) of the solution. This toxicity increase is mainly due to the persulfate formation during the electrochemical treatment. From a final solution toxicity point of view, the best results were obtained using a BDD anode in a divided reactor applying the lowest current intensity.

Evaluation of the Zn2+ transport properties through a cation-exchange membrane by chronopotentiometry.

In this work the effect of zinc concentration, pH, and boric acid concentration on the zinc transport properties through an IONICS 67-HMR-412 cation-exchange membrane was evaluated. The limiting current density and the transport numbers were determined by means of chronopotentiometry. A model between the limiting current density and the bulk zinc concentration was established, assuming a potential relationship between the zinc transport number through the membrane and the bulk zinc concentration together with the Levich equation for the DBL thickness. A decrease in the initial pH value of the solutions causes considerable modifications both in the plateau region and in the overlimiting current density region of the current-membrane potential curves. The results show that the presence of boric acid produces the precipitation of zinc metaborate on the anodic layer of the cation-exchange membrane.

Effect of pH and chloride concentration on the removal of hexavalent chromium in a batch electrocoagulation reactor.

In this work, the effect of pH and chloride ions concentration on the removal of Cr(VI) from wastewater by batch electrocoagulation using iron plate electrodes has been investigated. The initial solution pH was adjusted with different concentrations of H(2)SO(4). The presence of chloride ions enhances the anode dissolution due to pitting corrosion. Fe(2+) ions formed during the anode dissolution cause the reduction of Cr(VI) to form Cr(III), which are co-precipitated with Fe(3+) ions at relatively low pH. The reduction degree of Cr(VI) to Cr(III) and the solubility of metal hydroxide species (both chromic and iron hydroxides) depend on pH. At higher concentrations of H(2)SO(4), the reduction of Cr(VI) to Cr(III) by Fe(2+) ions is preferred, but the coagulation of Fe(3+) and Cr(III) is favoured at the lower H(2)SO(4) concentrations.