Electro-Persulfate Processes for the Treatment of Complex Wastewater Matrices: Present and Future.

Complex wastewater matrices present a major environmental concern. Besides the biodegradable organics, they may contain a great variety of toxic chemicals, heavy metals, and other xenobiotics. The electrochemically activated persulfate process, an efficient way to generate sulfate radicals, has been widely applied to the degradation of such complex effluents with very good results. This review presents the fundamentals of the electro-persulfate processes, highlighting the advantages and limitations, followed by an exhaustive evaluation on the application of this process for the treatment of complex industrial effluents. An overview of the main relevant experimental parameters/details and their influence on the organic load removal is presented and discussed, having in mind the application of these technologies at an industrial scale. Finally, the future perspectives for the application of the electro-persulfate processes in the treatment of complex wastewater matrices is outlined.

Methiocarb Degradation by Electro-Fenton: Ecotoxicological Evaluation.

This paper studies the degradation of methiocarb, a highly hazardous pesticide found in waters and wastewaters, through an electro-Fenton process, using a boron-doped diamond anode and a carbon felt cathode; and evaluates its potential to reduce toxicity towards the model organism Daphnia magna. The influence of applied current density and type and concentration of added iron source, Fe2(SO4)3·5H2O or FeCl3·6H2O, is assessed in the degradation experiments of methiocarb aqueous solutions. The experimental results show that electro-Fenton can be successfully used to degrade methiocarb and to reduce its high toxicity towards D. magna. Total methiocarb removal is achieved at the applied electric charge of 90 C, and a 450× reduction in the acute toxicity towards D. magna, on average, from approximately 900 toxic units to 2 toxic units, is observed at the end of the experiments. No significant differences are found between the two iron sources studied. At the lowest applied anodic current density, 12.5 A m-2, an increase in iron concentration led to lower methiocarb removal rates, but the opposite is found at the highest applied current densities. The highest organic carbon removal is obtained at the lowest applied current density and added iron concentration.

Performance of Electrochemical Processes in the Treatment of Reverse Osmosis Concentrates of Sanitary Landfill Leachate.

Electrochemical technologies have been broadly applied in wastewaters treatment, but few studies have focused on comparing the performance of the different electrochemical processes, especially when used to treat highly-polluted streams. The electrochemical treatment of a reverse osmosis concentrate of sanitary landfill leachate was performed by means of electrocoagulation (EC), anodic oxidation (AO) and electro-Fenton (EF) processes, and the use of different electrode materials and experimental conditions was assessed. All the studied processes and experimental conditions were effective in organic load removal. The results obtained showed that EC, with stainless steel electrodes, is the cheapest process, although it presents the disadvantage of sludge formation with high iron content. At high applied current intensity, AO presents the best treatment time/energy consumption ratio, especially if the samples' initial pH is corrected to 3. However, pH correction from natural to 3 deeply decreases nitrogen-containing compounds' removal. For longer treatment time, the EF process with a carbon-felt cathode and a BDD anode, performed at natural iron content and low applied current intensity, is the most favorable solution.

Electrochemical treatment of concentrate from reverse osmosis of sanitary landfill leachate.

Conventional sanitary landfill leachate treatment has recently been complemented and, in some cases, completely replaced by reverse osmosis technology. Despite the good quality of treated water, the efficiency of the process is low and a large volume of reverse osmosis concentrate has to be either discharged or further treated. In this study, the use of anodic oxidation combined with electro-Fenton processes to treat the concentrate obtained in the reverse osmosis of sanitary landfill leachate was evaluated. The anodic oxidation pretreatment was performed in a pilot plant using an electrochemical cell with boron-doped diamond electrodes. In the electro-Fenton experiments, a boron-doped diamond anode and carbon-felt cathode were used, and the influence of the initial pH and iron concentration were studied. For the experimental conditions, the electro-Fenton assays performed at an initial pH of 3 had higher organic load removal levels, whereas the best nitrogen removal was attained when the electrochemical process was performed at the natural pH of 8.8. The increase in the iron concentration had an adverse impact on treatment under natural pH conditions, but it enhanced the nitrogen removal in the electro-Fenton assays performed at an initial pH of 3. The combined anodic oxidation and electro-Fenton process is useful for treating the reverse osmosis concentrate because it is effective at removing the organic load and nitrogen-containing species. Additionally, this process potentiates the increase in the biodegradability index of the treated effluent.

Electrochemical treatment of cork boiling wastewater with a boron-doped diamond anode.

Anodic oxidation at a boron-doped diamond anode of cork boiling wastewater was successfully used for mineralization and biodegradability enhancement required for effluent discharge or subsequent biological treatment, respectively. The influence of the applied current density (30-70 mA/cm2) and the background electrolyte concentration (0-1.5 g/L Na2SO4) on the performance of the electrochemical oxidation was investigated. The supporting electrolyte was required to achieve conductivities that enabled anodic oxidation at the highest current intensities applied. The results indicated that pollutant removal increased with the applied current density, and after 8 h, reductions greater than 90% were achieved for COD, dissolved organic carbon, total phenols and colour. The biodegradability enhancement was from 0.13 to 0.59 and from 0.23 to 0.72 for the BOD/COD ratios with BOD of 5 and 20 days' incubation period, respectively. The tests without added electrolyte were performed at lower applied electrical charges (15 mA/cm2 or 30 V) with good organic load removal (up to 80%). For an applied current density of 30 mA/cm2, there was a minimum of electric conductivity of 1.9 mS/cm (corresponding to 0.75 g/L of Na2SO4), which minimized the specific energy consumption.

Landfill leachate treatment by immediate one-step lime precipitation, carbonation, and phytoremediation fine-tuning.

The high pollutant load of sanitary landfill leachates poses a huge challenge in the search for efficient and environment friendly solutions for their treatment. The objective of this work was to study an integrated solution of environmentally friendly technologies - immediate one-step lime precipitation (IOSLP), carbonation (CB), and phytoremediation (Phyt) - to treat a sanitary landfill leachate. In the leachate sample treatment by IOSLP, the influence of CaO concentration (18.2-33.3 gCaO L-1) and stirring time (2-60 min) on the sludge sedimentability and pollutant removal was studied. Organic load and ammonia nitrogen (AN) removal increases with CaO added, as well as sludge volume. Stirring time has a small influence on organic load and AN removal, presenting a minimum for sludge volume. Thus, the best operational conditions were chosen as 27.6 gCaO L-1, and 40-min stirring time, with 64% chemical oxygen demand (COD) removal. Sludge humidity was 2.1%, making dewatering needless. IOSLP supernatant was submitted to CB by atmospheric CO2, and 100% removals in AN and hardness were attained. Effluents from IOSLP and IOSLP + CB were utilized in Phyt tests, with Vetiver (Chrysopogon zizanioides (L.) Roberty). The best COD removal (37%) during Phyt was attained for the samples treated by IOSLP + CB.

Sunlight-Driven AO7 Degradation with Perovskites (La,Ba)(Fe,Ti)O3 as Heterogeneous Photocatalysts.

Perovskites of the (La,Ba)(Fe,Ti)O3 family were prepared, characterized, and utilized as heterogeneous photocatalysts, activated by natural sunlight, for environmental remediation of Acid Orange 7 (AO7) aqueous solutions. Catalysts were prepared by the ceramic (CM) and the complex polymerization (CP) methods and characterized by XRD, SEM, EDS, and band gap energy. It was found that catalytic properties depend on the synthesis method and annealing conditions. In the photocatalytic assays with sunlight, different AO7 initial concentrations and perovskite amounts were tested. During photocatalytic assays, AO7 and degradation products concentrations were followed by HPLC. Only photocatalysis with BaFeO3-CM and BaTiO3-CP presented AO7 removals higher than that observed for photolysis. However, photolysis leads to the formation of almost exclusively amino-naphthol and sulfanilic acid, whereas some of the perovskites utilized form less-toxic compounds as degradation products, such as carboxylic acids (CA). Partial substitution of Ba by La in BaTiO3-CM does not produce any change in the photocatalytic properties, but the replacement of Ti by Fe in the La0.1Ba0.9TiO3 leads to reduced AO7 removal rate, but with the formation of CAs. The best AO7 removal (92%) was obtained with BaFeO3-CM (750 mg L-1), after 4 h of photocatalytic degradation with solar radiation.

Diclofenac photodegradation with the Perovskites BaFeyTi1-yO3 as catalysts.

Perovskite oxides BaFeyTi1-yO3, with y = 0, 0.6, 0.8 and 1, were prepared by ceramic (CM) and complex polymerization methods (CPM) and utilized in UV-LED (365 nm) photocatalytic degradation assays of 25 mg L-1 diclofenac (DIC) model solutions. BaTiO3-CM was also used in the photocatalytic degradation test of a real mineral water for human consumption spiked with 2 mg L-1 DIC. The XRD patterns of the synthesized perovskites showed cubic structure for those prepared by CPM, with distortions of the cubic lattice to hexagonal or tetragonal when prepared by CM, except for BaTiO3. All the perovskites showed good catalytic activity, higher than photolysis, except BaFeO3-CM that presented similar results. BaTiO3-CM and CPM and BaFeO3-CPM were also utilized in UV-LED photocatalytic DIC degradation assays with peroxydisulfate addition. BaFeO3-CPM and BaTiO3-CPM showed better ability to persulfate activation, but the highest mineralization degree was obtained with BaTiO3-CM. This last perovskite was also able to perform DIC degradation in a real matrix. The studied oxides show potentiality for photocatalytic degradation of organic compounds, with or without persulfate addition. A degradation mechanism is proposed.

Emerging contaminants removal from effluents with complex matrices by electrooxidation.

The electrooxidation of methiocarb and bisphenol A was studied in complex matrices, namely, simulated and real sanitary landfill leachate samples, using a boron-doped diamond anode. With simulated sanitary landfill leachate samples, the influence of the type and ratio of carbon source (glucose/humic acid) and electrolyte (NaCl or Na2SO4) on the emerging contaminants removal was assessed. Using real sanitary landfill leachate, the influence of current density was evaluated. The experimental results showed that electrooxidation, using a boron-doped diamond anode, can be successfully utilized to degrade methiocarb and bisphenol A when present in complex matrices, such as sanitary landfill leachate, and that methiocarb is more easily oxidized than bisphenol A. Furthermore, it was found that the presence of chloride and high humic acid content increases emerging contaminants removal rate, showing that electrooxidation at boron-doped diamond is particularly adequate to solve the problems raised by sanitary landfill leachate, even when contaminated with emerging contaminants.

Ecotoxicological evaluation of electrochemical oxidation for the treatment of sanitary landfill leachates.

In this study, the efficiency of electrochemical oxidation to treat a sanitary landfill leachate was evaluated by the reduction in physico-chemical parameters and in ecotoxicity. The acute toxicity of the sanitary landfill leachates, before and after treatment, was assessed with the model organism Daphnia magna. Electrochemical oxidation treatment was effective in the removal of organic load and ammonium nitrogen and in the reduction of metal ions concentrations. Furthermore, a reduction of 2.5-fold in the acute toxicity towards D. magna after 36 h of treatment was noticed. Nevertheless, the toxicity of the treated leachate is still very high, and further treatments are necessary in order to obtain a non-toxic effluent to this aquatic organism. Toxicity results were also compared with others described in the literature for different leachate treatments and test organisms.

Electro-Fenton oxidation of reverse osmosis concentrate from sanitary landfill leachate: Evaluation of operational parameters.

The electro-Fenton oxidation of a concentrate from reverse osmosis of a sanitary landfill leachate, with an initial chemical oxygen demand (COD) of 42 g L-1, was carried out using a carbon-felt cathode and a boron doped diamond anode. The influence of the applied current intensity, initial pH and dissolved iron initial concentration on the electro-Fenton process was assessed. For the experimental conditions used, results showed that the initial pH is the parameter that more strongly influences the current efficiency of the electro-Fenton process, being this influence more pronounced on the oxidation rate than on the mineralization rate of the organic matter. The increase in iron initial concentration was found to be detrimental, since the natural amount of iron present in the effluent, 73 mg L-1 of total iron and 61 mg L-1 of dissolved iron, was sufficient to ensure the electro-Fenton process at the applied intensities - 0.2-1.4 A. For the more favourable conditions studied, initial pH of 3 and natural iron concentration, it was found an increase in the organic load and nitrogen removals with the applied current intensity. For the highest current intensity applied, a COD removal of 16.7 g L-1 was achieved after 8-h experiments.

Electrochemical wastewater treatment: influence of the type of carbon and of nitrogen on the organic load removal.

Boron-doped diamond (BDD) and Ti/Pt/PbO2 anodes were utilized to perform the electrodegradation of synthetic samples containing humic acid in the presence of different organic and inorganic carbon-containing and nitrogen-containing compounds. The influence of the chloride ion in the degradation process of the different synthetic samples was also assessed. The results showed that the anodic oxidation process can efficiently degrade recalcitrant compounds such as humic acid. The presence of carbonate in solution enhances the nitrogen removal, whereas it hinders the oxidation of the organic compounds. When organic nitrogen is present, it is converted to NH4+, which in turn is oxidized to nitrate and to volatile nitrogen compounds. Hydroxyl radicals are more prone to oxidize the organic nitrogen than the ammonium nitrogen. The presence of chloride enhances the organic matter and nitrogen removal rates, BDD being the anode material that yields the highest removals.