New diamond coatings for a safer electrolytic disinfection.

In this work, a new coating of boron-doped diamond ultra-nanocrystalline (U-NBDD), tailored to prevent massive formation of perchlorates during disinfection, is evaluated as electrode for the reclaiming of treated secondary wastewater by the electrochemically assisted disinfection process. Results obtained are compared to those obtained by using a standard electrode (STD) that was evaluated as a standard in previous research showing outstanding performance for this application. First tests were carried out to evaluate the chlorine speciation obtained after the electrolysis of synthetic chloride solutions at two different ranges of current densities. Concentrations of hypochlorite obtained using the U-NBDD anode at 25 mA cm-2 were 1.5-fold higher, outperforming STD anode; however, at 300 mA cm-2, an overturn on the behavior of anodes occurs where the amount of hypochlorite produced on STD anode was 1.5-fold higher. Importantly, at low current density the formation of chlorates and perchlorates is null using U-NBDD. Then, the disinfection of the real effluent of the secondary clarifier of a municipal wastewater treatment facility is assessed, where inactivation of Escherichia coli is achieved at low charge applied per volume electrolyzed (0.08 A h L-1) at 25 mA cm-2 using the U-NBDD. These findings demonstrate the appropriateness of the strategy followed in this work to obtain safer electro-disinfection technologies for the reclaiming of treated wastewater.

Sustainable integrated process for cogeneration of oxidants for VOCs removal.

This study upgrades the sustainability of environmental electrochemical technologies with a novel approach consisting of the in-situ cogeneration and use of two important oxidants, hydrogen peroxide (H2O2) and Caro's acid (H2SO5), manufactured with the same innovative cell. This reactor was equipped with a gas diffusion electrode (GDE) to generate cathodically H2O2, from oxygen reduction reaction, a boron doped diamond (BDD) electrode to obtain H2SO5, via anodic oxidation of dilute sulfuric acid, and a proton exchange membrane to separate the anodic and the cathodic compartment, preventing the scavenging effect of the interaction of oxidants. A special design of the inlet helps this cell to reach simultaneous efficiencies as high as 99% for H2O2 formation and 19.7% for Caro's acid formation, which means that the cogeneration reaches efficiencies over 100% in the uses of electric current to produce oxidants. The two oxidants' streams produced were used with different configurations for the degradation of three volatile organic compounds (benzene, toluene, and xylene) in a batch reactor equipped with a UVC-lamp. Among different alternatives studied, the combination H2SO5/H2O2 under UVC irradiation showed the best results in terms of degradation efficiency, demonstrating important synergisms as compared to the bare technologies.

Advanced oxidation and a metrological strategy based on CLC-MS for the removal of pharmaceuticals from pore & surface water.

In this work, it is studied the photolysis, electrolysis, and photo-electrolysis of a mixture of pharmaceutics (sulfadiazine, naproxen, diclofenac, ketoprofen and ibuprofen) contained in two very different types of real water matrices (obtained from surface and porewater reservoirs), trying to clarify the role of the matrix on the degradation of the pollutants. To do this, a new metrological approach was also developed for screening of pharmaceuticals in waters by capillary liquid chromatography mass spectrometry (CLC-MS). This allows the detection at concentrations lower than 10 ng mL-1. Results obtained in the degradation tests demonstrate that inorganic composition of the water matrix directly influences on the efficiency of the drugs removal by the different EAOPs and better degradation results were obtained for experiments carried out with surface water. The most recalcitrant drug studied was ibuprofen for all processes evaluated, while diclofenac and ketoprofen were found to be the easiest drugs for being degraded. Photo-electrolysis was found to be more efficient than photolysis and electrolysis, and the increase in the current density was found to attain a slight improvement in the removal although with an associated huge increase in the energy consumption. The main reaction pathways for each drug and technology were also proposed.

Highly Efficient Electrochemical Production of Hydrogen Peroxide Using the GDE Technology.

This work examines the role of oxygen supply in the improvement of the hydrogen peroxide (H2O2) electrochemical production efficiency and the generation of high H2O2 concentrations in electrochemical processes operated in a discontinuous mode. To conduct this study, a highly efficient Printex L6 carbon-based gas diffusion electrode (GDE) as a cathode was employed for the electrogeneration of H2O2 in a flow-by reactor and evaluated the effects of lowering the operation temperature (to increase solubility) and increasing the air supply in the system on H2O2 electrogeneration. The results obtained in this study show that unlike what is expected in flow-through reactors, the efficiency in the H2O2 production is not affected by the solubility of oxygen when GDE is employed in the electrochemical process (using the flow-by reactor); i.e., the efficiency of H2O2 production is not significantly dependent on O2 solubility, temperature, and pressure. The application of the proposed PL6C-based GDE led to the generation of accumulated H2O2 of over 3 g L-1 at a high current density. It should be noted, however, that the application of the electrocatalyst at lower current densities resulted in higher energy efficiency in terms of H2O2 production. Precisely, a specific production of H2O2 as high as 131 g kWh-1 was obtained at 25 mA cm-2; the energy efficiency (in terms of H2O2 production) values obtained in this study based on the application of the proposed GDE in a flow-by reactor at low current densities were found to be within the range of values recorded for H2O2 production techniques that employ flow-through reactors.

Electrospray Deposition of Catalyst Layers with Ultralow Pt Loading for Cost-Effective H2 Production by SO2 Electrolysis.

The hybrid sulfur (HyS) thermochemical cycle has been considered as a promising approach for the massive production of clean hydrogen without CO2 emissions. The key to advance this technology and to enhance the cycle efficiency is to improve the electrocatalytic oxidation of SO2, which is the pivotal reaction within this process. Hence, this paper investigates, for the first time, the effect of electrospray and air gun deposition techniques and the influence of very low Pt loadings (<0.3 mg Pt/cm2) on catalyst durability and activity. The variation of electrochemical active surface area (ECSA) with the number of cycles demonstrates the significant impact of the electrode fabrication method and catalyst loading on the catalyst durability with considerable ECSA values for electrosprayed electrodes. Electrodes prepared with low platinum loadings (0.05 mg Pt/cm2) exhibit elevated catalyst activity and stability under sulfuric acid conditions and maintain a crucial current density after 5 h of electrolysis. This work extends the understanding of the SO2-depolarized electrolysis (SDE) process and gives suggestions for further improvements in the catalyst layer fabrication, which provides potential support for the large-scale research and application of the HyS cycle.

Electrochemical Production of Hydrogen Peroxide in Perchloric Acid Supporting Electrolytes for the Synthesis of Chlorine Dioxide.

This work focuses on the electrochemical production of hydrogen peroxide in supporting electrolytes containing perchlorate ions for being used as a reagent in the reduction of chlorates to produce chlorine dioxide, as a first step in the manufacture of portable ClO2 production devices. This study evaluates the effect of the current density, pressure, and temperature on the production of hydrogen peroxide, and concentrations over 400 mg L-1 are reached. The average rate for the formation of hydrogen peroxide is 9.85 mg h-1, and the effect of increasing electrolyte concentration (3.0 and 30.0 g L-1 perchloric acid), intensity, and pressure results in values of, respectively, -2.99, -4.49, and +7.73 mg h-1. During the manufacturing process, hydrogen peroxide is decomposed through two mechanisms. The average destruction rate is 1.93 mg h-1, and the effects of the three factors results in values of, respectively, +0.07, +0.11, and -0.12 mg h-1. Solutions of this hydrogen peroxide produced electrochemically in a perchloric acid aqueous electrolyte were used to reduce chlorates in strongly acidic media and produce chlorine dioxide. Conversions of around 100% were obtained, demonstrating that this electrochemical product can be used efficiently to reduce chlorates to chlorine dioxide.

Assessing the viability of electro-absorption and photoelectro-absorption for the treatment of gaseous perchloroethylene.

This work focuses on the development of electro-absorption and photoelectro-absorption technologies to treat gases produced by a synthetic waste containing the highly volatile perchloroethylene (PCE). To do this, a packed absorption column coupled with a UV lamp and an undivided electrooxidation cell was used. Firstly, it was confirmed that the absorption in a packed column is a viable method to achieve retention of PCE into an absorbent-electrolyte liquid. It was observed that PCE does not only absorb but it was also transformed into phosgene and other by-products. Later, it was confirmed that the electro-absorption process influenced the PCE degradation, favoring the transformation of phosgene into final products. Opposite to what is expected, carbon dioxide is not the main product obtained, but carbon tetrachloride and trichloroacetic acid. Both species are also hazardous but their higher solubility in water opens possibilities for a successful and more environmental-friendly removal. The coupling with UV-irradiation has a negative impact on the degradation of phosgene. Finally, a reaction mechanism was proposed for the degradation of PCE based on the experimental observations. Results were not as expected during the planning of the experimental work but it is important to take in mind that PCE decomposition occurs in wet conditions, regardless of the applied technology, and this work is a first approach to try to solve the treatment problems associated to PCE gaseous waste flows in a realistic way.

Electrochemically assisted dewatering for the removal of oxyfluorfen from a coagulation/flocculation sludge.

This work focuses on the evaluation of the electrochemical dewatering of sludge obtained in the coagulation of wastes polluted with oxyfluorfen. To do this, sludge samples were treated, aiming not only to reduce the sludge volume, but also to facilitate the degradation of oxyfluorfen contained in the cake via electrolysis with a boron-doped diamond anode. Results show that water can be effectively recovered through three sequential stages. First, a gravity-driven stage, that can recover around 60% of initial volume and where no oxyfluorfen is dragged. Then, a second stage that involves the application of pressure and which accounts for the recuperation of an additional 25% of the total volume of the water removed and in which oxyfluorfen also remained in the cake. Finally, an electrochemical stage, which involves the application of electricity with increasing electric fields (1.0, 2.0, 4.0, and 16.0 V cm-1), accounting for the recovery of the rest of water released and where an electrolytic degradation of oxyfluorfen is obtained, whose extension depends on the electrode configuration used in the electro-dewatering cell. This electrode configuration also influences the retention or loss of oxyfluorfen from the cake, being the optimum choice the placement of the cathode downstream, next to the outlet of the dewatering cell.

Selection of anodic material for the combined electrochemical-biological treatment of lindane polluted soil washing effluents.

This paper focuses on the removal of lindane from soil washing effluents (SWEs) using combined electrochemical -biological processes. In particular, it has been evaluated the influence of the anodic material used in the electrolysis of the SWE on the biodegradability and toxicity of the effluents. Four anode materials were tested: Boron Doped Diamond (BDD), Carbon Felt (CF), and Mixed Metal Oxides Anodes with iridium and ruthenium (MMO-Ir and MMO-Ru). These materials were tested at different current densities and electric current charges applied. Lindane, TOC, sulphate, and chlorine species concentrations were monitored during electrochemical experiments, showing important differences in their evolution during the treatment. In spite of reaching a good removal of lindane with all the materials tested, results showed that Boron Doped Diamond working at 15 mA cm-2 achieved the best biodegradability results in the electrolyzed effluents, because the ratio BOD5/COD increased from 0.2 to 0.5, followed by Carbon Felt anode. Regarding toxicity, Carbon Felt decreased toxicity by 80%. Opposite to what it was expected, MMO anodes did not achieve biodegradability improvement and they only showed reduction in toxicity at high electrical charges.

Biodegradability improvement and toxicity reduction of soil washing effluents polluted with atrazine by means of electrochemical pre-treatment: Influence of the anode material.

This work focuses on the partial anodic electro-oxidation of atrazine-polluted soil washing effluents (SWE) in order to reduce its toxicity and to improve its biodegradability. Concretely it has been evaluated the influence of the anodic material used. It is hypothesized that such partial oxidation step could be considered as a pre-treatment for a subsequent biological treatment. At first, atrazine was extracted from a polluted soil by means of a surfactant-aided soil-washing process. Then, four different anodic materials were studied in partial electro-oxidation pre-treatment batch experiments at different electric charges applied: Boron Doped Diamond (BDD), Carbon Felt (CF), and Mixed Metal Oxides Anodes with Iridium and Ruthenium. Atrazine, TOC, surfactant and sulphate species concentrations, as well as changes in toxicity and biodegradability, were monitored during electrochemical experiments, showing important differences in their evolution during the treatment. It was observed that BDD was the most powerful anodic material to completely degrade atrazine. The other materials achieve an atrazine degradation rate about 75%. Regarding mineralization of the organics in SWE, BDD overtakes clearly the rest of anodes tested. CF obtains good atrazine removal but low mineralization results. All the anodes tested slightly reduced the ecotoxicity of the water effluents. About the biodegradability, only the effluent obtained after the pre-treatment with BDD presented a high biodegradability. In this sense, it must be highlighted the mineralization obtained during the BDD pre-treatment was very strong. These results globally indicate that it is necessary to find a compromise between reaching efficient atrazine removal and biodegradability improvement, while also simultaneously avoiding strong mineralization. Additional efforts should be made to find the most adequate working conditions.

Biological treatment of wastewater polluted with an oxyfluorfen-based commercial herbicide.

Fluoxil-24 is a commercial herbicide based on oxyfluorfen (a hazardous non-soluble organochlorinated compound) and additional compounds used as solvents. The aim of this work is to study the biotreatability of this commercial herbicide in water through batch experiments performed at different temperatures (15, 20, 25 and 30 °C) and initial concentrations (85, 150, 300 and 500 mg L-1 of oxyfluorfen). Activated sludge from an oil refinery wastewater treatment plant was acclimated and used for biodegradation experiments. Two main mechanisms, volatilization and biodegradation, were observed to be responsible of the herbicide removal. Fluoxil-24 removal efficiencies between approximately 40% and 80% were reached after 70 h, depending on the conditions used, and oxyfluorfen was not completely removed. Regarding the influence of the temperature, thermal inhibition problems appeared at 30 °C, and the volatilization rate of solvents increased, causing oxyfluorfen to become unavailable for microorganisms. An increase of herbicide initial concentration did not clearly affect the herbicide removal efficiency, whereas it negatively affected the biological mechanism. The experimental results were fitted to a mathematical model that included both simultaneous mechanisms of volatilization and Monod biodegradation kinetics. The model was able to predict the experimental results, and the calculated model parameters confirmed the effect of the variables under study.

Improving the catalytic effect of peroxodisulfate and peroxodiphosphate electrochemically generated at diamond electrode by activation with light irradiation.

Boron doped diamond (BDD) anode has been used to oxidatively remove Rhodamine B (RhB), as persistent organic pollutant, from synthetic wastewater by electrolysis, photoelectrolysis and chemical oxidation containing sulfate and phosphate as supporting electrolytes. RhB is effectively oxidized by electrolysis and by chemical oxidation with the oxidants separately produced by electrolyzing sulfate or phosphate solutions (peroxodisulfate and peroxodiphosphate, respectively). The results showed that light irradiation improved the electrolysis of RhB due to the activation of oxidants under irradiation at high current densities. Meanwhile, the efficiency of the chemical oxidation approach by ex situ electrochemical production of oxidants was not efficient to degrade RhB.

Driving force behind electrochemical performance of microbial fuel cells fed with different substrates.

The performance of miniaturized microbial fuel cells operating with five different substrates (acetate, lactate, glucose and octanoate) were studied with the aim to identify the reason for its different performance. In all cases, the COD removal rate was about 650 mg COD L-1 d-1. However, the bio-electrochemical performance of the MFC was very different, showing the MFC fed with acetate the best performance: 20 A m-2 as maximum current density, 2 W m-2 of maximum power density, 0.376 V of OCV and 12.6% of CE. In addition, the acetate showed the best bio-electrochemical performance in the polarization curves and cyclic voltammetries. These polarization curves were modelled and the key to explain the better electrical performance of acetate was its lower ohmic losses. When working with acetate, its ohmic losses were one log-unit below those attained by the other substrates. These lower ohmic losses were not associated to the electrolyte conductivity of the fuel but to the lower ohmic loses of the biofilm generated.

Improving biodegradability of soil washing effluents using anodic oxidation.

In this work, a combination of electrochemical and biological technologies is proposed to remove clopyralid from Soil Washing Effluents (SWE). Firstly, soil washing was carried out to extract clopyralid from soil. After that, four different anodes-Ir-MMO, Ru-MMO, pSi-BDD and Carbon Felt (CF)-were evaluated in order to increase the biodegradability of the SWE. CF was selected because was the only one able to transform the pesticide to a more biodegradable compounds without completely mineralizing it. Finally, biological oxidation tests were performed to determine the aerobic biodegradability of the SWE generated. From the obtained results, it was observed that at the beginning of the electrolysis the toxicity slightly increased and the biodegradability decreases. However, for electric current charges over 2.5 A·h dm-3 the toxicity drastically decreased, showing an EC50 of 143 mg L-1, and the BOD5/COD ratio increased from 0.02 to 0.23.

Influence of sludge age on the performance of MFC treating winery wastewater.

The objective of this paper was to determine the influence of sludge age on microbial fuel cell (MFC) performance for generating electricity and removing organic matter from winery wastewater. Six Solid Retention Times (SRT) were used: 1.2, 1.4, 1.8, 2.3, 3.5 and 7.0 d. Results demonstrate that the electricity generation increases by decreasing the SRT, selecting electrogenic microorganisms, once the specific organic loading rate (SOLR) increased and the competition for substrate was reduced. Decreasing the SRT, coulombic efficiency can be increased from 3.4% to almost 42.2% and maximum power density from 58 to 890 mW m(-2). However the SRT did not influence on organic matter removal in biological treatment, because only a small part of COD was removed oscillating around 600 mg L(-1) d(-1)and it was very similar at all SRT studied.

Removal of oxyfluorfen from ex-situ soil washing fluids using electrolysis with diamond anodes.

In this research, firstly, the treatment of soil spiked with oxyfluorfen was studied using a surfactant-aided soil-washing (SASW) process. After that, the electrochemical treatment of the washing liquid using boron doped diamond (BDD) anodes was performed. Results clearly demonstrate that SASW is a very efficient approach in the treatment of soil, removing the pesticide completely by using dosages below 5 g of sodium dodecyl sulfate (SDS) per Kg of soil. After that, complete mineralization of organic matter (oxyflourfen, SDS and by-products) was attained (100% of total organic carbon and chemical oxygen demand removals) when the washing liquids were electrolyzed using BDD anodes, but the removal rate depends on the size of the particles in solution. Electrolysis of soil washing fluids occurs via the reduction in size of micelles until their complete depletion. Lower concentrations of intermediates are produced (sulfate, chlorine, 4-(trifluoromethyl)-phenol and ortho-nitrophenol) during BDD-electrolyzes. Finally, it is important to indicate that, sulfate (coming from SDS) and chlorine (coming from oxyfluorfen) ions play an important role during the electrochemical organic matter removal.

Combined soil washing and CDEO for the removal of atrazine from soils.

In this work, it is studied the removal of atrazine from spiked soils by soil washing using surfactant fluids, followed by the treatment of the resulting washing waste by electrolysis with boron doped diamond (BDD) anode. Results confirm that combination of both technologies is efficient for the removal and total mineralization of atrazine. Ratio surfactant/soil is a key parameter for the removal of atrazine from soil and influences significantly in the characteristic of the wastewater produced, affecting not only to the total organic load but also to the mean size of micelles. The higher the ratio surfactant soil, the lower is the size of the particles. Electrolyses of this type of waste attain the complete mineralization. TOC and COD are removed from the start of the treatment but the key of the treatment is the reduction in size of the micelles, which lead to a higher negative charge in the surface and to the faster depletion of the surfactant as compared with the pesticide.

Break-up of oil-in-water emulsions by electrochemical techniques.

Electrochemically-assisted technologies can be successfully applied to the treatment of oil-in-water (O/W) emulsions. In this work, it is studied the influence of the main parameters (electrical charge passed, pH, electrolyte, oil content and operation mode) in the efficiency of these processes, when aluminium electrodes are used. The pH was found to be the most significant parameter, and good removal efficiencies were only obtained for pHs in the range 5-9. The electrical charge passed was observed to be directly related to the aluminium supplied to the waste. For a given oil concentration it is required that a minimum electrical charge is passed to break-up the emulsion. Further increases in the electrical charge lead to increase in the COD removal. The influence of the oil concentration is related to that of the electrical charge passed: for a given dose of aluminium, the higher the oil content the lower the COD-removal efficiency. Likewise, to produce the break-up of the emulsion it is required a minimum dose of aluminium (electrical charge passed), lower doses do not attain the rupture of the emulsion. The type of electrolyte and its concentration were also found to influence the process efficiency. Better efficiencies were obtained in the treatment of chloride-containing wastes and for low concentration of electrolyte. The destabilization of the O/W emulsion was found to be favoured in the discontinuous operation mode. Bridging flocculation is a primary destabilization mechanism that can explain the experimental results obtained in this work.