Degradation of Contaminants of Emerging Concern by Electrochemical Oxidation: Coupling of Ultraviolet and Ultrasound Radiations.

In this work, we study the electrochemical oxidation of methyl red, a dye present in textile industrial effluents, which is selected as the model for the degradation of Contaminants of Emerging Concern. The influence of the initial pollutant concentration (1-5 mg dm-3), applied current density (2-15 mA cm-2), and the coupling of ultraviolet or ultrasound radiation have been studied using a titanium plate as anode. The results show that electrochemical oxidation is able to efficiently remove methyl red, and the process efficiency decreases with the initial pollutant concentration. At high applied current densities, efficiency drastically decreases due to a less effective mass transfer of the pollutant on the anodic surface. On one hand, the coupling of ultrasound entails an antagonistic effect on the process efficiency, which is probably due to a massive formation of oxidant radicals followed by a fast recombination process. On the other hand, the coupling of ultraviolet radiation increases the process efficiency. Concomitantly to the oxidation processes, titanium electrode produces rising TiO2-anatase nanoparticles, boosting the mineralization process. This new finding sets up a significant improvement over conventional photocatalysis treatments using TiO2-anatase as a catalyst due to synergistic effects coming from the coupling of the electrochemical oxidation and photocatalysis process with Ti anode.

Scale-up of electrolytic and photoelectrolytic processes for water reclaiming: a preliminary study.

This work focuses on the scale-up of electrochemical and photoelectrochemical oxidation processes with diamond anodes for the removal of organic pollutants and disinfection of treated urban wastewater, two of the most important parameters for the reclaiming of wastewater. The removal of organics was studied with actual biologically treated urban wastewater intensified with 100 mg dm(-3) of caffeine, added as a trace organic pollutant. The disinfection was also studied with biologically treated urban wastewater, and Escherichia coli was used to monitor the efficiency of the process. Results obtained with a single DiaCell® 101 were compared with those obtained with a single-stack DiaCell® 1001 and with a pilot plant made up of five of these stacks. Results obtained demonstrate that scale-up is not a simple but a very complex process, in which not only the electrode and the irradiation dose are important but also mass transfer conditions. Enhanced mass transport conditions have a determining and very positive effect on the removal of organics and a negative effect on the disinfection. Likewise, ultraviolet (UV) irradiation affects in a different way in the different setups used, having a great influence on the removal of complex organics and on the speciation of oxidants produced during disinfection. This works helps to understand the key differences observed in the scale-up, and it is a first approach for future works focused on the real application of conductive diamond electrochemical oxidation.

Conductive diamond electrochemical oxidation of caffeine-intensified biologically treated urban wastewater.

In this work, the usefulness of Conductive Diamond Electrochemical Oxidation (CDEO) to degrade caffeine in real urban wastewater matrixes was assessed. The oxidation of actual wastewater intensified with caffeine (from 1 to 100 mg L(-1)) was studied, paying particular attention to the influence of the initial load of caffeine and the differences observed during the treatment of caffeine in synthetic wastewater. The results showed that CDEO is a technology that is capable of efficiently degrading this compound even at very low concentrations and that it can even be completely depleted. Profiles of the ionic species of S (SO4(2-)), N (NH4(+), NO3(-)) and Cl (ClO(-), ClO3(-) and ClO4(-)) were monitored and explained for plausible oxidation mechanisms. It was observed that the efficiency achieved is higher in the treatment of real wastewater than in the oxidation of synthetic wastewater because of the contribution of electrogenerated oxidant species such as hypochlorite. The formation of chlorate and perchlorate during electrochemical processes was observed, and a combined strategy to prevent this important drawback was successfully tested based on the application of low current densities with the simultaneous dosing of hydrogen peroxide.

Degradation of caffeine by conductive diamond electrochemical oxidation.

The use of Conductive-Diamond Electrochemical Oxidation (CDEO) and Sonoelectrochemical Oxidation (CDSEO) has been evaluated for the removal of caffeine of wastewater. Effects of initial concentration, current density and supporting electrolyte on the process efficiency are assessed. Results show that caffeine is very efficiently removed with CDEO and that depletion of caffeine has two stages depending on its concentration. At low concentrations, opposite to what it is expected in a mass-transfer controlled process, the efficiency increases with current density very significantly, suggesting a very important role of mediated oxidation processes on the removal of caffeine. In addition, the removal of caffeine is faster than TOC, indicating the formation of reaction intermediates. The number and relative abundance of them depend on the operating conditions and supporting electrolyte used. In chloride media, removal of caffeine is faster and more efficiently, although the occurrence of more intermediates takes place. CDSEO does not increase the efficiency of caffeine removal, but it affects to the formation of intermediates. A detailed characterization of intermediates by liquid chromatography time-of-flight mass spectrometry seems to indicate that the degradation of caffeine by CDEO follows an oxidation pathway similar to mechanism proposed by other advanced oxidation processes.

Conductive-diamond electrochemical oxidation of chlorpyrifos in wastewater and identification of its main degradation products by LC-TOFMS.

The electrochemical transformation of the organophosphorous insecticide chlorpyrifos (CPF) was investigated in wastewater. The oxidation of CPF was carried out in a single-compartment electrochemical flow cell working under batch operation mode, using diamond-based material as anode and stainless steel as cathode. In order to evaluate its persistence and degradation pathway, two different concentration levels (1.0 mg L(-1) and 0.1 mg L(-1)) were studied. Liquid chromatography/mass spectrometry was used for evaluation of the initial and electrolyzed solutions. The identification of CPF transformation products was performed by liquid chromatography-time of flight-mass spectrometry (LC-TOFMS). Results showed that CPF is completely removed at the end of treatment time. Analysis by LC-TOFMS allowed the identification of six degradation products (with Mw 154, 170, 197, 305 321 and 333). Three of the identified intermediates (Mw 170, 305 and 321) were completely removed at the end of electrolysis time. Interestingly, the formation of diethyl 3,5,6-trichloropyridin-2yl phosphate (chlorpyrifos oxon) and 3,5,6-trichloropyridin-2-ol was also found in previous reported degradation pathways using different degradation technologies.