Treatment of Organics in Wastewater Using Electrogenerated Gaseous Oxidants.

This work focuses on the comparison of the performance of direct electrochemical oxidation with indirect electrolysis mediated by gaseous oxidants in the treatment of diluted wastewater. To do this, energy consumptions of the electrolysis using mixed metal oxide (MMO) electrodes are compared with those required for the production and use of chlorine dioxide in the degradation of methomyl contained in aqueous solutions. Results demonstrate the feasibility of the mediated oxidation process and that this process is competitive with direct oxidation. The oxidants are produced under optimized conditions using the same anodic material applied for the direct degradation of organics, thus avoiding efficiency losses associated with mass transfer limitations in the degradation of dilute organic solutions. Thus, using the ClO2 gaseous oxidant, a concentration of 0.1 mM of methomyl from a solution containing 500 mL is completely removed with an energy consumption as low as 50 Wh. The application of the same energy to a direct electrolytic process for treating the same wastewater can only reach less than half of this removal. These findings may have a very important application in the use of electrochemical technology to achieve the remediation of persistent pollutants in wastewater, where their low concentrations typically make direct processes very inefficient.

Hydrogen peroxide electrogeneration from O2 electroreduction: A review focusing on carbon electrocatalysts and environmental applications.

Hydrogen peroxide (H2O2) stands as one of the foremost utilized oxidizing agents in modern times. The established method for its production involves the intricate and costly anthraquinone process. However, a promising alternative pathway is the electrochemical hydrogen peroxide production, accomplished through the oxygen reduction reaction via a 2-electron pathway. This method not only simplifies the production process but also upholds environmental sustainability, especially when compared to the conventional anthraquinone method. In this review paper, recent works from the literature focusing on the 2-electron oxygen reduction reaction promoted by carbon electrocatalysts are summarized. The practical applications of these materials in the treatment of effluents contaminated with different pollutants (drugs, dyes, pesticides, and herbicides) are presented. Water treatment aiming to address these issues can be achieved through advanced oxidation electrochemical processes such as electro-Fenton, solar-electro-Fenton, and photo-electro-Fenton. These processes are discussed in detail in this work and the possible radicals that degrade the pollutants in each case are highlighted. The review broadens its scope to encompass contemporary computational simulations focused on the 2-electron oxygen reduction reaction, employing different models to describe carbon-based electrocatalysts. Finally, perspectives and future challenges in the area of carbon-based electrocatalysts for H2O2 electrogeneration are discussed. This review paper presents a forward-oriented viewpoint of present innovations and pragmatic implementations, delineating forthcoming challenges and prospects of this ever-evolving field.

Electro-oxidation of tetracycline in ethanol-water mixture using DSA-Cl2 anode and stimulating/monitoring the formation of organic radicals.

Recent studies reported a new strategy of electro-oxidation of organic compounds using methanol as solvent. Considering its well-known toxicity, this work sought to evaluate the use of ethanol as an alternative solvent for pollutants degradation. Therefore, thorough analyses were performed in order to evaluate tetracycline (TC) electro-oxidation using DSA-Cl2 anode in ethanol-H2O solutions. The effects of solvent mixture, pH and current density on the degradation efficiency were evaluated. TC degradation in methanol-water and ethanol-water media resulted in very close removals of 95% and 90%, respectively, after 15 min of electrolysis at 10 mA cm-2. In ethanol medium, the increase in current densities from 10 to 25 mA cm-2 did not lead to significant changes in removal efficiency. The variation of the initial pH of the solution showed that the best removal efficiencies were obtained at neutral pH resulting in TC removals up to 90%, which is actually related to the molecular structure of TC. Through analysis using electron paramagnetic resonance (EPR), the formation of radicals such as hydroxyethyl (CH3●CHOH), hydroxyl (●OH) and ethoxy (CH3CH2O●) were detected, which effectively contributed toward the pollutant oxidation.

Detection of radicals produced during electro-oxidation of atrazine using commercial DSA®-Cl2 in methanol media: Keys to understand the process.

This work reports the radicals detected and identified during the degradation of atrazine in methanol medium in the presence and absence of different proportions of water (0%, 5%, and 10%). The determination of these radicals is an important step to understand the electrolysis processes in methanol medium and contribute to clarify the degradation mechanism. Furthermore, the parameters for the successful removal of the contaminant were optimized and the results showed that the application of the technique led to the removal of nearly 99.8% of atrazine after 1 h of electrolysis. The oxidation kinetics was found to be very fast and most of the atrazine molecule in the medium was degraded in the first hour of electrolysis. The results obtained from a thorough analysis conducted with a view to evaluating the effects of different current densities and initial pH values on atrazine degradation showed that the application of higher current densities resulted in lower energy consumption, as this led to faster removal of atrazine. Additionally, the initial pH of the solution was found to favor the formation of different species of active chlorine. The radicals formed during the electro-oxidation process were detected by electron paramagnetic resonance spectroscopy and include hydroxyl, methoxy and hydroxymethyl. The use of methanol for the degradation of pollutants is a highly promising technique and this work shows that the identification of the different radicals formed in the process can be the key to understanding the degradation mechanism.

Electrochemical degradation of a methyl paraben and propylene glycol mixture: Interference effect of competitive oxidation and pH stability.

Endocrine disrupting compounds (EDCs) are one of the many classes of harmful pollutants frequently found in water resources. Even at low concentrations, EDCs might accumulate in the organisms and interfere on numerous processes controlled by hormones. Parabens, for example, are preservatives widely used in pharmaceutical and cosmetic industries, but several studies related them to human breast cancer. It is well-known that electrochemical technologies are an efficient alternative for wastewater treatment, promoting the appropriate destruction of EDCs. However, most studies are applied to single target contaminant solutions, which may neglect the impact from co-exited inorganic/organic pollutants. Based on that, this study aimed to elucidate the interfering effects of two target organic contaminants of very different nature during electrochemical mediated process. For that, methyl paraben (MeP) and propylene glycol (PG) were selected as models of aromatic/phenolic and carboxylate compounds versus low-molecular aliphatic alcohols. These two compounds are often together used in preservative blends and cosmetic/pharmaceutical formulations. PG is not a harmful chemical, but it is present in several types of effluents in relatively high concentrations. Thus, it may interfere on the degradation of numerous pollutants of low concentrations. The electrochemical treatment of a mixture containing 100 mg L-1 MeP +1000 mg L-1 PG showed that both contaminants suffered interfering effects. The presence of MeP negatively interfered on PG degradation; the carboxylate compound is more easily oxidized even at lower molecular concentration. On the other hand, the presence of PG showed an unexpected positive effect on MeP degradation, that was not reflected on its mineralization. The results indicate that in addition to the expected effect of anodic competition, polymerization and copolymerization reactions may also occur in the studied system. The use of an acidic buffer medium increased the removal of both contaminants and favored the oxidation pathway over the polymerization. In this case, the increase in the removal was reflected in the mineralization process, which increased up to 6 times when the mixture was treated in the buffered medium.

Modeling of photolytic degradation of sulfamethoxazole using boosted regression tree (BRT), artificial neural network (ANN) and response surface methodology (RSM); energy consumption and intermediates study.

This study explores the boosted regression trees (BRT), artificial neural network (ANN) and response surface methodology (RSM) to model and optimize the operational variables for the simulation of the Photolytic degradation of Sulfamethoxazole (SMX) and concurrent total organic carbon (TOC) removal, based on the experimental data set. Four candidate variables involving initial pH (2-11), initial SMX concentration (50-200 mg L-1), temperature (15-45 °C) and time (6-120 min) were considered for simultaneous optimization of SMX and TOC degradation. The result revealed that all the three models are statistically considerable as the values of R, R2, adj-R2 are >0.85, thus be deemed to work well in data fitting, prediction, and optimization, nevertheless, the values of R, R2, adj-R2, RMSE, MAE and AAD are far better for ANN and BRT than RSM method. The ∼100% SMX degradation conditions were found to be as follows: treatment time: 25 min, pH: 2.0, temperature: 35 °C and SMX concentration: 50 mg L-1, while the maximum possible removal of TOC under the given conditions was ∼25%. The percentage contribution (PC) of each variable was deduced by ANOVA analysis of proposed quadratic models which indicated that time and pH are important factors than temperature and SMX concentration. The photolytic intermediates and inorganic ions of SMX, were identified and a potential route of transformation was also proposed.

Electro-oxidation of tetracycline in methanol media on DSA®-Cl2.

The electro-oxidation of tetracycline (TeC) in methanol medium containing chloride or sulfate ions was evaluated using a DSA®-Cl2 in a flow reactor and compared with BDD. The results show that after 30 min of electrolysis no TeC is detected by liquid chromatography when chloride is used as supporting electrolyte. On the other hand, after 90 min of electrolysis using a BDD anode only 61% of TeC was removed from solutions with chloride, but in the presence of sulfate the removal reaches 94%. This evidences that the oxidizing species generated during electrochemical oxidation control the process and the mechanism of degradation of the TeC. Besides that, it was possible to infer that only a small amount of methanol might convert to formaldehyde or formic acid, although they were not detected according to the nil changes in the FTIR spectra or in the HPLC chromatograms recorded.

Fatigue resistance, electrochemical corrosion and biological response of Ti-15Mo with surface modified by amorphous TiO2 nanotubes layer.

The objective of this work was a systemic evaluation of the anodizing treatment in a ß-type Ti-15Mo alloy to grow a TiO2 nanostructured layer for osseointegration improvement. The technical viability of the surface modification was assessed based on the resistance to mechanical fatigue, electrochemical corrosion, and biological response. By using an organic solution of NH4 F in ethylene glycol, a well-organized array of 90 nm diameter nanotubes was obtained with a potential of 40 V for 6 h, while undefined nanotubes of 25 nm diameter were formed with a potential of 20 V for 1 h. Nevertheless, the production of the 90 nm diameter nanotubes was followed by micrometer pits that significantly reduced the fatigue performance. The undefined nanotubes of 25 nm diameter, besides the greater cell viability and improved osteoblastic cell differentiation in comparison to the as-polished surface, were not deleterious to the fatigue and corrosion properties. This result strengthens the necessity of an overall evaluation of the anodizing treatment, particularly the fatigue resistance, before suggesting it for the design of implants. © 2018 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 107B: 86-96, 2019.

Performance of (in)active anodic materials for the electrooxidation of phenolic wastewaters from cashew-nut processing industry.

This study investigated the anodic oxidation of phenolic wastewater generated by cashew-nut processing industry (CNPI) using active (Ti/RuO2-TiO2) and inactive (boron doped diamond, BDD) anodes. During electrochemical treatment, various operating parameters were investigated, such as current density, chemical oxygen demand (COD), total phenols, O2 production, temperature, pH, as well as current efficiency and energy consumption. After electrolysis under optimized working conditions, samples were evaluated by chromatography and toxicological tests against L. sativa. When both electrode materials were compared under the same operating conditions, higher COD removal efficiency was achieved for BDD anode; achieving lower energy requirements when compared with the values estimated for Ti/RuO2-TiO2. The presence of Cl- in the wastewater promoted the electrogeneration of strong oxidant species as chlorine, hypochlorite and mainly hypochlorous acid, increasing the efficiency of degradation process. Regarding the temperature effect, BDD showed slower performances than those achieved for Ti/RuO2-TiO2. Chromatographic and phytotoxicity studies indicated formation of some by-products after electrolytic process, regardless of the anode evaluated, and phytotoxic action of the effluent. Results encourage the applicability of the electrochemical method as wastewater treatment process for the CNPI, reducing depuration time.

Photo-assisted electrochemical degradation of sulfamethoxazole using a Ti/Ru0.3Ti0.7O2 anode: Mechanistic and kinetic features of the process.

This study examined the photo-assisted electrochemical degradation and mineralization of the antibiotic contaminant sulfamethoxazole (SMX). All the experiments were perform using a flow electrolytic cell, in which the influence of the current density (10-60 mA cm-2) and sodium chloride (0.02-0.10 mol L-1) in the supporting electrolyte composition was analyzed. The results showed that the total SMX and 50% TOC removal was achieved in the current density range used. As expected, the degradation kinetics presented a pseudo first order behavior and the rate constant increased from 0.05 min-1 to 0.50 min-1 as the current density raised from 10 to 60 mA cm-1. In addition, the values of the electrical energy per order (EEO) increased from 0.67 to 1.06 kW/hm-3 order-1 as the current density increased from 10 to 60 mAcm-2 and drop from 8.82 to 0.57 kW/hm-3 order-1 at supporting electrolyte concentration of 0.02-0.1 mol L-1. The reaction intermediates identified by liquid chromatography-mass spectrometry allowed proposing a mechanism for the degradation. The use of photo assistance in the electrochemical process involved simultaneous reactions, for example, aromatic ring substitutions and hydroxylation. These reactions led to aromatic rings opening that generated simpler organic molecules, making possible the mineralization of the SMX molecule. Probable degradation pathways were proposed and discussed. Comparison of the efficiencies of the photocatalytic, electrochemical (EC) and photo-assisted electrochemical (PAEC) techniques revealed that the combined process showed a synergism for TOC removal.

Treatment of actual effluents produced in the manufacturing of atrazine by a photo-electrolytic process.

The photo-assisted electrochemical degradation of a real effluent of the atrazine manufacturing process containing atrazine, simazine, hydroxy-triazine and propazine was carried out galvanostatically using a pilot-scale tubular flow reactor prototype containing DSA® and Ti as cathode. The effluent was mainly characterized by a high amount of NaCl, required in the synthesis route used, and it was used as taken in the factory. The variables for process optimization were the current density (3.0, 6.0, and 9.0 mA cm-2) and flow rate (300 and 3,000 L h-1). These later values produces laminar and turbulent flow regimes, with Reynolds numbers of 1,100 and 11,000, respectively. None of the four organics contained in the waste is refractory to the photo-electrochemical treatment and they are depleted with the photo-electrolytic technology using large current densities and appropriate electric charge passed. Both direct electrochemical process and mediated anodic oxidation occur during the treatment. First process occurs at turbulent flow condition and low current densities, while the chemical oxidation process happens at laminar flow condition and high current densities. Atrazine and propazine are efficiently removed at laminar flow conditions, with an almost total depletion for the largest current densities. On the contrary, simazine is efficiently removed in turbulent flow conditions and intermediate current density, with removals higher than 90% for 20 kWh m-3. These results have great significance because they demonstrate the applicability of the electrochemical technology in the treatment of real industrial wastes with a cell specially designed to attain high efficiency in the removal of pollutants.

Inactivation, lysis and degradation by-products of Saccharomyces cerevisiae by electrooxidation using DSA.

The yeast Saccharomyces cerevisiae, a microorganism with cell walls resistant to many types of treatments, was chosen as a model to study electrochemical disinfection process using dimensionally stable anodes (DSA). DSA electrodes with nominal composition of Ti/RuO2TiO2 and Ti/RuO2TiO2IrO2 were evaluated in 0.05 mol L-1 Na2SO4 containing yeast. The results showed inactivation about of 100 % of the microorganisms at Ti/RuO2TiO2 by applying 20 and 60 mA cm-2 after 120 min of electrolysis, while a complete inactivation at Ti/RuO2IrO2TiO2 electrode was achieved after 180 min at 60 mA cm-2. When chloride ions were added in the electrolyte solution, 100 % of the yeast was inactivated at 20 mA cm-2 after 120 min of electrolysis, independent of the anode used. In the absence of chloride, the energy consumption (EC) was of 34.80 kWh m-3, at 20 mA cm-2 by using Ti/RuO2TiO2 anode. Meanwhile, in the presence of chloride, EC was reduced, requiring 30.24 and 30.99 kWh m-3 at 20 mA cm-2, for Ti/RuO2TiO2 and Ti/RuO2IrO2TiO2 electrodes, respectively, The best performance for cell lysis was obtained in the presence of chloride with EC of 88.80 kWh m-3 (Ti/RuO2TiO2) and 91.85 kWh m-3 (Ti/RuO2IrO2TiO2) to remove, respectively, 92 and 95 % of density yeast. The results clearly showed that yeast, as a model adopted, was efficiently inactivated and lysed by electrolysis disinfection using DSA-type electrodes.

Mechanistic proposal for the electrochemical and sonoelectrochemical oxidation of thiram on a boron-doped diamond anode.

A comparative study was carried out of sonochemical (SCh), electrochemical (ECh) and sonoelectrochemical (SECh) strategies for the degradation of the fungicide thiram in dilute aqueous solution. The SCh and SECh studies were performed using a sonicator equipped with an 11 mm titanium-alloy probe and operated at 20 kHz with a power intensity of 523 W cm(-2). In the ECh and SECh investigations, galvanostatic electrolyses were implemented using a single compartment electrochemical cell with a boron-doped diamond electrode as anode and applied current densities in the range 10-50 mA cm(-2). For these processes, the decrease in concentration of thiram was monitored by high performance liquid chromatographic (HPLC) analysis and values of current efficiency and energy consumption were determined. The results showed that the rate of degradation of thiram and the amount of energy consumed were directly proportional to the applied current density, while current efficiency was inversely related to current density. The kinetics of thiram degradation followed a pseudo first order model with apparent rate constants in the region of 10(-3)min(-1). Thiram in aqueous solution was subjected to "exhaustive" degradation by ECh and SECh processes for 5h at applied current densities of 35 mA cm(-2) and the intermediates/byproducts so-formed were identified by HPLC-mass spectrometry. Mechanisms of the degradation reactions have been proposed on the basis of the results obtained.

Route of electrochemical oxidation of the antibiotic sulfamethoxazole on a mixed oxide anode.

The appearance of pharmaceutical compounds and their bioactive transformation products in aquatic environments is becoming an issue of increasing concern. In this study, the electrochemical oxidation of the widely used antibiotic sulfamethoxazole (SMX) was investigated using a commercial mixed oxide anode (Ti/Ru0.3Ti0.7O2) and a single compartment filter press-type flow reactor. The kinetics of SMX degradation was determined as a function of electrolyte composition, applied current density, and initial pH. Almost complete (98 %) degradation of SMX could be achieved within 30 min of electrolysis in 0.1 mol L(-1) NaCl solution at pH 3 with applied current densities ≥20 mA cm(-2). Nine major intermediates of the reaction were identified by LC-ESI-Q-TOF-MS (e.g., C6H9NO2S (m/z = 179), C6H4NOCl (m/z = 141), and C6H6O2 (m/z = 110)). The degradation followed various routes involving cleavage of the oxazole and benzene rings by hydroxyl and/or chlorine radicals, processes that could occur before or after rupture of the N-S bond, followed by oxidation of the remaining moieties. Analysis of the total organic carbon content revealed that the antibiotic was partially mineralized under the conditions employed and some inorganic ions, including NO3 (-) and SO4 (2-), could be identified. The results presented herein demonstrate the efficacy of the electrochemical process using a Ti/Ru0.3Ti0.7O2 anode for the remediation of wastewater containing the antibiotic SMX.

Electrochemical and sonoelectrochemical processes applied to amaranth dye degradation.

Amaranth dye is an organic compound largely used in the food and beverage industries with potential toxicity effects on humans. It can be found as a pollutant species in aquatic environments and has been classified as an endocrine disruptor. This study describes amaranth degradation upon ultrasonication associated with an electrochemical system that uses a boron-doped diamond anode BDD, defined as a sonoelectrochemical process. Ninety-minute electrolyses were performed using current densities in the 10-50 mA cm(-2) range, and the concentration decay, pH, energy and current efficiencies, as well as the discoloration rate were evaluated. The amaranth concentration decayed as a function of electrolysis time and the reactions obeyed pseudo first-order kinetics, with an apparent constant rate between 10(-1) and 10(-3)min(-1). The electrochemical and sonoelectrochemical processes at 35 mA cm(-2) yielded TOC removal values between 92.1% and 95.1% respectively, after 90 min. Current efficiency values obtained for both processes were 18.2% and 23.6%. Exhaustive 5h electrolysis was performed and the degradation products were identified by HPLC-MS. A mechanism for the degradation of amaranth was proposed based on an analysis of the aromatic and aliphatic intermediates.

Electrochemical degradation of the dimethyl phthalate ester on a fluoride-doped Ti/ß-PbO2 anode.

The electrooxidation of the dimethyl phthalate (DMP) ester was galvanostatically carried out in a filter-press reactor using a fluoride-doped lead dioxide (ß-PbO2,F) film electrodeposited on a Ti substrate. The variables investigated were the nature of the supporting electrolyte (NaCl and Na2SO4), pH (3, 7, and 10), current density (10, 20, 40, 60, and 80mAcm(-2)), and temperature (10, 20, 30, 40, and 50°C). The removal of DMP was monitored through high performance liquid chromatography (HPLC) and total organic carbon (TOC) analysis. The best conditions were obtained using Na2SO4 and at low current densities, independent of the solution pH or temperature. These conditions led to the highest levels of current efficiencies and complete combustion. However, the TOC removal levels were low, due to the generation of highly oxidized intermediates, which was confirmed by the intermediates detected by HPLC.

Comparing atrazine and cyanuric acid electro-oxidation on mixed oxide and boron-doped diamond electrodes.

The breakdown of pesticides has been promoted by many methods for clean up of contaminated soil and wastewaters. The main goal is to decrease the toxicity of the parent compound to achieve non-toxic compounds or even, when complete mineralization occurs, carbon dioxide and water. Therefore, electrochemical degradation (potentiostatic and galvanostatic) of both the pesticide atrazine and cyanuric acid (CA) at boron-doped diamond (BDD) and Ti/Ru0.3Ti0.7O2 dimensionally stable anode (DSA) electrodes, in different supporting electrolytes (NaCl and Na2SO4), is presented with the aim of establishing the influence of the operational parameters on the process efficiency. The results demonstrate that both the electrode material and the supporting electrolyte have a strong influence on the rate of atrazine removal. In the chloride medium, the rate of atrazine removal is always greater than in sulfate under all conditions employed. Furthermore, in the sulfate medium, atrazine degradation was significant only at the BDD electrode. The total organic carbon (TOC) load decreased by 79% and 56% at the BDD and DSA electrodes, respectively, in the chloride medium. This trend was maintained in the sulfate medium but the TOC removal was lower (i.e. 33% and 13% at BDD and DSA electrodes, respectively). CA, a stable atrazine degradation intermediate, was also studied and it is efficiently removed using the BDD electrode in both media, mainly when high current densities are employed. The use of the BDD electrode in the chloride medium not only degrades atrazine but also mineralized cyanuric acid leading to the higher TOC removal.

SnO(2)-based materials for pesticide degradation.

This study presents the results of the degradation of the pesticide atrazine using electrochemical and photo-assisted electrochemical degradation techniques using SnO(2)-containing electrode of nominal composition electrodes of composition Ti/Ru(X)Sn(1-X)O(2) (where X=0.10, 0.15, 0.20, 0.25 and 0.30). The materials were characterized ex situ and in situ in order to correlate the observed atrazine removal rates with electrode morphology/composition. The results obtained demonstrate the effectiveness of the photo-assisted electrochemical degradation. Using purely electrochemical methods the rate of atrazine removal is almost zero at all the electrodes studied. However, the application of photo-assisted degradation results in almost complete atrazine removal in 1h of electrolysis. The efficiency of atrazine degradation does not seem to be greatly affected by the electrode material or by SnO(2) content, but the overall COD removal is dependent on the SnO(2) content. Overall, the SnO(2)-containing electrodes do not reach the level of COD removal (maximum approximately 21%) seen for the Ti/Ru(0.3)Ti(0.7)O(2) electrode. An interesting correlation between the morphology factor (phi) and chemical oxygen demand removal is observed.