Glycosylated flavonoid kaempferitrin: Electroanalytical detection and the proposal of an oxidation mechanism supported by quantum chemical calculations.

In this work, the electrochemical behavior of the glycosylated flavonoid kaempferitrin was studied, and an electroanalytical methodology was developed for its determination in infusions of Bauhinia forficata using a boron-doped diamond electrode (BDD). The electrochemical behavior of the flavonoid was studied by cyclic voltammetry, and two irreversible oxidation peaks at 0.80 and 1.0 V vs Ag/AgCl were observed. The influence of the pH on the voltammograms was examined, and higher sensitivity was found at pH 7.0. The electrochemical process corresponding to peak 1 at 0.80 V is predominantly diffusion-controlled, as the study shows at varying scan rates. An analytical plot was obtained by square wave voltammetry at optimized experimental conditions (frequency = 100 s-1, amplitude = 90 mV, and step potential = 8 mV) in the concentration range from 3.4 µmol L-1 to 58 µmol L-1, with a linearity of 0.99. The limit of detection and limit of quantification values were 1.0 µmol L-1 and 3.4 µmol L-1, respectively. Three samples of Bauhinia forficata infusions (2 g of sample in 100 mL of water) were analyzed, and the KF values found were 5.0 × 10-4 mol L-1, 3.0 × 10-4 mol L-1, and 7.0 × 10-4 mol L-1, with recovery percentages of 98 %, 106 % and 94 %, respectively. Finally, experiments were performed with two other flavonoids (chrysin and apeginin) to compare and propose an electrochemical oxidation mechanism for kaempferitrin, which was supported by quantum chemical calculations.

Simultaneous voltammetric determination of 7-methyl-guanine and 5-methyl-cytosine using a cathodically pre-treated boron-doped diamond electrode.

Given the importance of identifying the presence of biomarkers of human diseases in DNA samples, the main objective of this work was to investigate, for the first time, the electro-catalytic oxidation of 7-methyl-guanine (7-mGua) and 5-methyl-cytosine (5-mCyt) on a boron doped diamond electrode pre-treated cathodically (red-BDDE), using differential pulse voltammetry (DPV) and cyclic voltammetry (CV). The anodic peak potentials of 7-mGua and 5-mCyt by DPV were at E = 1.04 V and E = 1.37 V at pH = 4.5, indicating excellent peak separation of approximately 330 mV between species. Using DPV, experimental conditions such as supporting electrolyte, pH and influence of interferents were also investigated to develop a sensitive and selective method for individual and simultaneous quantification of these biomarkers. The analytical curves for the simultaneous quantification of 7-mGua and 5-mCyt in the acid medium (pH = 4.5) were: concentration range of 0.50-5.00 µmol L-1 (r = 0.999), detection limit of 0.27 µmol L-1 for 7-mGua; from 3.00 to 25.00 µmol L-1 (r = 0.998), with a detection limit of 1.69 µmol L-1 for 5-mCyt. A new DP voltammetric method for the simultaneous detection and quantification of biomarkers 7-mGua and 5-mCyt using a red-BDDE is proposed.

Simultaneous degradation of 30 pharmaceuticals by anodic oxidation: Main intermediaries and by-products.

The anodic oxidation (AO) of 30 pharmaceuticals including antibiotics, hormones, antihistaminics, anti-inflammatories, antidepressants, antihypertensives, and antiulcer agents, in solutions containing different supporting electrolytes media (0.05 M Na2SO4, 0.05 M NaCl, and 0.05 M Na2SO4 + 0.05 M NaCl) at natural pH was studied. A boron-doped diamond (BDD) electrode and a stainless-steel electrode were used as anode and cathode, respectively, and three current densities of 6, 20, and 40 mA cm-2 were applied. The results showed high mineralization rates, above 85%, in all the tested electrolytic media. 25 intermediaries produced during the electrooxidation were identified, depending on the supporting electrolyte together with the formation of carboxylic acids, NO3-, SO42- and NH4+ ions. The formation of intermediates in chloride medium produced an increase in absorbance. Finally, a real secondary effluent spiked with the 30 pharmaceuticals was treated by AO applying 6 mA cm-2 at natural pH and without addition of supporting electrolyte, reaching c.a. 90% mineralization after 300 min, with an energy consumption of 18.95 kW h m-3 equivalent to 2.90 USD m-3. A degradation scheme for the mixture of emerging contaminants in both electrolytic media is proposed. Thus, the application of anodic oxidation generates a high concentration of hydroxyl radicals that favors the mineralization of the pharmaceuticals present in the spiked secondary effluent sample.

Solubilization of organic matter by electrochemical treatment of sludge: Influence of operating conditions.

Sludge generated after wastewater treatment represents an important challenge due to the large amounts produced and the need to adequately treat it. Anaerobic digestion is the preferred treatment process to obtain renewable energy as well as a biosolid with the potential to be reused in land application. This process generates biogas (methane and carbon dioxide) that may be used for energy co-generation. However, anaerobic digestion is limited by the hydrolysis step since bacteria need to break down organic matter and large molecules to allow conversion into biogas. In this study, electrochemical treatment of sludge is proposed to solubilize organic matter. Boron-doped diamond electrodes were used to treat waste activated sludge under different experimental conditions (current density, flow rate, time) to evaluate their influence on the solubilization of organic matter (in terms of chemical oxygen demand). The degree of solubilization ranged between 0.31 and 1.78%. Based on the results, optimal operating conditions were current density of 19.3 mA cm-2, flow rate of 4 L min-1, and treatment time of 30 min. Furthermore, treatment flow rate was found to play a key role in solubilization, as the process is controlled by mass transfer.

Understanding the dipyrone oxidation allying electrochemical and computational approaches.

Electroanalytical methodology by boron-doped diamond electrode (BDDE) associated to the square-wave voltammetry (SWV) for the determination of hydrolyzed dipyrone (DIP) in commercial formulations, raw natural waters and in human urine was developed. Through cyclic voltammetry (CV), it was shown that the oxidation of the DIP on the BDDE was irreversible with diffusional control. Computational studies suggested that the oxidation mechanism of DIP occurred with participation of two electrons and one proton. The analytical curves were obtained for concentrations of DIP ranging from 1.0 × 10-6 to 6.5 × 10-5 mol L-1 (r = 0.9994). The values of detection limit (LOD) and quantification limit (LOQ) of DIP were calculated from SWV and found to be 2.6 × 10-7 mol L-1 and 8.8 × 10-7 mol L-1. The methodology was effectively applied to real samples with the values of calculated recoveries varying between 91.0% and 117.3% and validated by iodometric titration experiments whose values were between 93.3% and 106.9%. The proposed methodology with BDDE represents an alternative tool and it has advantageous, such as very easy handling, low cost, no need for modification, low detection limit. Furthermore, it can be used for the routine analysis of DIP in different real samples.

Combined use of coagulation (M. oleifera) and electrochemical techniques in the treatment of industrial paint wastewater for reuse and/or disposal.

In this work, water-based paint (WBP) wastewater was treated using a natural coagulant, Moringa oleifera aqueous extract (MOAE), fortified with Ca2+ (from nitrate and chloride salts). In order to improve the quality of the treated wastewater and render it suitable for disposal, an electrolytic flow process was associated with the wastewater treatment using a filter-press reactor with a boron doped diamond (BDD) electrode. The feasibility of the treatment was evidenced by the reuse of the treated wastewater in the production of a new paint (manufactured by the company supplying the raw wastewater), whose quality was compatible with the water used by the manufacturer. The best conditions for the coagulation-flocculation process involved the use of 80 mL of MOAE (50 g/L of MO and 0.125 mol/L of Ca2+) for every 1.0 L of wastewater at pH 6.5. The limiting current density (35 mA/cm2) and an electrolysis time of 90 min (charge passed of 3.68 A h/L) were used in the electrochemical treatment. Biotoxicity assays using the brine shrimp Artemia salina revealed that the mortality (in %) of microcrustaceans was reduced from 100% (raw wastewater) to only 11% at the end of the electrolysis process, in addition to eliminating the strong odor and 85% of the organic load. Moreover, microbiological tests showed that the number of mesophiles decreased by more than six orders of magnitude and there was no growth of thermotolerant coliforms (TC).

Treatment of winery wastewater by anodic oxidation using BDD electrode.

The effective removal of organics from winery wastewater was obtained in real residual effluents from the wine industry using anodic oxidation (AO). The effluent had an initial organic load of [COD]0 of 3490 mg L-1 equal to [TOC]0 of 1320 mg L-1. In addition, more than 40 organic compounds were identified by means of GC-MS. Different density currents as well as the addition of electrolytes were tested during electrolysis. The results show the decay of [COD]t by 63.6% when no support electrolyte was added, whereas almost total mineralization and disinfection was reached after adding of 50 mM of sodium sulfate and sodium chloride and applying higher density currents. The presence of sulfate and chloride in large concentration favors the production of oxidants such as hydroxyl radicals and active chlorine species that react with organics in solution. Moreover, the addition of a supporting electrolyte to industrial wastewater increases conductivity, reduces cell potential and therefore, decreases the energy consumption of the AO process.

Treatment of paint manufacturing wastewater by coagulation/electrochemical methods: Proposals for disposal and/or reuse of treated water.

This paper describes and discusses an investigation into the treatment of paint manufacturing wastewater (water-based acrylic texture) by coagulation (aluminum sulfate) coupled to electrochemical methods (BDD electrode). Two proposals are put forward, based on the results. The first proposal considers the feasibility of reusing wastewater treated by the methods separately and in combination, while the second examines the possibility of its disposal into water bodies. To this end, parameters such as toxicity, turbidity, color, organic load, dissolved aluminum, alkalinity, hardness and odor are evaluated. In addition, the proposal for water reuse is strengthened by the quality of the water-based paints produced using the wastewater treated by the two methods (combined and separate), which was evaluated based on the typical parameters for the quality control of these products. Under optimized conditions, the use of the chemical coagulation (12 mL/L of Al2(SO4)3 dosage) treatment, alone, proved the feasibility of reusing the treated wastewater in the paint manufacturing process. However, the use of the electrochemical method (i = 10 mA/cm(2) and t = 90 min) was required to render the treated wastewater suitable for discharge into water bodies.

Mineralization of the textile dye acid yellow 42 by solar photoelectro-Fenton in a lab-pilot plant.

A complete mineralization of a textile dye widely used in the Chilean textile industry, acid yellow 42 (AY42), was studied. Degradation was carried out in an aqueous solution containing 100mgL(-1) of total organic carbon (TOC) of dye using the advanced solar photoelectro-Fenton (SPEF) process in a lab-scale pilot plant consisting of a filter press cell, which contains a boron doped diamond electrode and an air diffusion cathode (BDD/air-diffusion cell), coupled with a solar photoreactor for treat 8L of wastewater during 270min of electrolysis. The main results obtained during the degradation of the textile dye were that a complete transformation to CO2 depends directly on the applied current density, the concentration of Fe(2+) used as catalyst, and the solar radiation intensity. The elimination of AY42 and its organic intermediates was due to hydroxyl radicals formed at the anode surface from water oxidation and in the bulk from Fenton's reaction between electrogenerated H2O2 and added Fe(2+). The application of solar radiation in the process (SPEF) yield higher current efficiencies and lower energy consumptions than electro-Fenton (EF) and electro-oxidation with electrogenerated H2O2 (E OH2O2) by the additional production of hydroxyl radicals from the photolysis of Fe(III) hydrated species and the photodecomposition of Fe(III) complexes with organic intermediates. Moreover, some products and intermediates formed during mineralization of dye, such as inorganic ions, carboxylic acids and aromatic compounds were determined by photometric and chromatographic methods. An oxidation pathway is proposed for the complete conversion to CO2.

Degradation of conazole fungicides in water by electrochemical oxidation.

The electrochemical oxidation (EO) treatment in water of three conazole fungicides, myclobutanil, triadimefon and propiconazole, has been carried out at constant current using a BDD/SS system. First, solutions of each fungicide were electrolyzed to assess the effect of the experimental parameters such as current, pH and fungicide concentration on the decay of each compound and total organic carbon abatement. Then a careful analysis of the degradation by-products was made by high performance liquid chromatography, ion chromatography and gas chromatography coupled with mass spectrometry in order to provide a detailed discussion on the original reaction pathways. Thus, during the degradation of conazole fungicides by the electrochemical oxidation process, aromatic intermediates, aliphatic carboxylic acids and Cl(-) were detected prior to their complete mineralization to CO2 while NO3(-) anions remained in the treated solution. This is an essential preliminary step towards the applicability of the EO processes for the treatment of wastewater containing conazole fungicides.