RESUMO

A commercial sulfamethoxazole + trimethoprim formulation has been degraded in 0.050 M Na2SO4 at pH 3.0 by electrochemical oxidation with electrogenerated H2O2 (EO-H2O2), electro-Fenton (EF), photoelectro-Fenton with a 6-W UVA lamp (PEF) and solar photoelectro-Fenton (SPEF). The tests were performed in an undivided cell with an IrO2-based, Pt or boron-doped diamond (BDD) anode and an air-diffusion cathode for H2O2 electrogeneration. The anode material had little effect on the accumulated H2O2 concentration. Both drugs always obeyed a pseudo-first-order decay with low apparent rate constant in EO-H2O2. Much higher values were found in EF, PEF and SPEF, showing no difference because the main oxidant was always OH formed from Fenton's reaction between H2O2 and added Fe2+. The solution mineralization increased in the sequence EO-H2O2 < EF < PEF < SPEF regardless of the anode. The IrO2-based and Pt anodes behaved similarly but BDD was always more powerful. In SPEF, similar mineralization profiles were found for all anodes because of the rapid removal of photoactive intermediates by sunlight. About 87% mineralization was obtained as maximum for the powerful SPEF with BDD anode. Addition of Cl- enhanced the decay of both drugs due to their quicker reaction with generated active chlorine, but the formation of persistent chloroderivatives decelerated the mineralization process. Final carboxylic acids like oxalic and oxamic were detected, yielding Fe(III) complexes that remained stable in EF with BDD but were rapidly photolyzed in SPEF with BDD, explaining its superior mineralization ability.

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RESUMO

A 3.0 L solar flow plant with a Pt/air-diffusion (anode/cathode) cell, a solar photoreactor and a photocatalytic photoreactor filled with TiO2-coated glass spheres has been utilized to couple solar photoelectro-Fenton (SPEF) and solar heterogeneous photocatalysis (SPC) for treating a 165mgL(-1) salicylic acid solution of pH 3.0. Organics were destroyed by OH radicals formed on the TiO2 photocatalyst and at the Pt anode during water oxidation and in the bulk from Fenton's reaction between added Fe(2+) and cathodically generated H2O2, along with the photolytic action of sunlight. Poor salicylic acid removal and mineralization were attained using SPC, anodic oxidation with electrogenerated H2O2 (AO-H2O2) and coupled AO-H2O2-SPC. The electro-Fenton process accelerated the substrate decay, but with low mineralization by the formation of byproducts that are hardly destroyed by OH. The mineralization was strongly increased by SPEF due to the photolysis of products by sunlight, being enhanced by coupled SPEF-SPC due to the additional oxidation by OH at the TiO2 surface. The effect of current density on the performance of both processes was examined. The most potent SPEF-SPC process at 150mAcm(-2) yielded 87% mineralization and 13% current efficiency after consuming 6.0AhL(-1). Maleic, fumaric and oxalic acids detected as final carboxylic acids were completely removed by SPEF and SPEF-SPC.

RESUMO

Here, the synergetic effect of coupling solar photoelectro-Fenton (SPEF) and solar heterogeneous photocatalysis (SPC) on the mineralization of 200mL of a 20mg L(-1) atrazine solution, prepared from the commercial herbicide Gesaprim, at pH 3.0 was studied. Uniform, homogeneous and adherent anatase-TiO2 films onto glass spheres of 5mm diameter were prepared by the sol-gel dip-coating method and used as catalyst for SPC. However, this procedure yielded a poor removal of the substrate because of the low oxidation ability of positive holes and OH formed at the catalyst surface to destroy it. Atrazine decay was improved using anodic oxidation (AO), electro-Fenton (EF), SPEF and coupled SPEF-SPC at 100mA. The electrolytic cell contained a boron-doped diamond (BDD) anode and H2O2 was generated at a BDD cathode fed with an air flow. The removal and mineralization of atrazine increased when more oxidizing agents were generated in the sequence AO

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RESUMO

The degradation of the Acid Yellow 36 (AY36) azo dye is studied by electro-Fenton (EF) and solar photoelectro-Fenton (SPEF) using a recirculation flow plant with an undivided cell containing a boron-doped diamond anode and an air-diffusion cathode for H2O2 electrogeneration, coupled with a solar photoreactor. A solution of 2.5L with 108 mg L⁻¹ of the dye and 0.5 mM Fe²(+) at pH 3.0 was comparatively treated at constant current. Hydroxyl radicals formed from Fenton's reaction and at the anode surface are the main oxidants. Total mineralization is almost achieved in SPEF, while EF yields poor TOC removal. Both processes are accelerated with increasing current. AY36 decays with similar rate in EF and SPEF following a pseudo first-order reaction, but the solution is more slowly decolorized because of the formation of conjugated byproducts. NH4(+) ion is released in SPEF, while NO3⁻ ion is mainly lost in EF. Tartronic, maleic, fumaric, oxalic, formic and oxamic acids are detected as generated carboxylic acids. Fe(III)-oxalate complexes are largely accumulated in EF and their quick photodecomposition in SPEF explains its higher oxidation power. The SPEF method yields greater current efficiency and lower energy cost as current decreases, and then it is more viable at low currents.

Assuntos