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.

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.

Degradation of antibiotic ciprofloxacin by different AOP systems using electrochemically generated hydrogen peroxide.

The present work reports the degradation of the antibiotic ciprofloxacin (CIP) by different advanced oxidative process systems (UV; Anodic Oxidation; H2O2; H2O2/UV; H2O2/Fe2+ and H2O2/UV/Fe2+) in an electrochemical cell using gas diffusion electrode (GDE) for the synthesis of hydrogen peroxide. CIP degradation and mineralization were evaluated by high efficiency liquid chromatography (HPLC) and total organic carbon (TOC) techniques. Of all the systems investigated, the photoelectro-Fenton system presented the best degradation efficiency; this system promoted highly significant mineralization percentages of 54.8% and 84.6% in 90 and 360 min, and relatively lower energy consumption rates of 4110.0 and 9808.2 kWh kg-1 TOC, respectively. In 6 h period of experiment, the main degradation products of ciprofloxacin were identified, and the aliphatic acids obtained helped confirm the rupture of the aromatic ring. The application of the photoelectro-Fenton process with in situ eletroctrogeneration of H2O2 using GDE has proved to be suitably promising for the treatment of organic pollutants.

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.