Degradation of the fluoroquinolone enrofloxacin by electrochemical advanced oxidation processes based on hydrogen peroxide electrogeneration

摘要

Solutions of the veterinary fluoroquinolone antibiotic enrofloxacin in 0.05M Na_2SO_4 of pH 3.0 have been comparatively degraded by electrochemical advanced oxidation processes such as anodic oxidation with electrogenerated H_2O_2 (AO-H_2O_2), electro-Fenton (EF), photoelectro-Fenton (PEF) and solar photoelectro-Fenton (SPEF) at constant current density. The study has been performed using an undivided stirred tank reactor of 100 ml and a batch recirculation flow plant of 2.51 with an undivided filter-press cell coupled to a solar photoreactor, both equipped with a Pt or boron-doped diamond (BDD) anode and a carbon-polytetrafluoromethylene gas diffusion cathode to generate H_2O_2 from O_2 reduction. In EF, PEF and SPEF, hydroxyl radical (~*OH) is formed from Fenton's reaction between added catalytic Fe~(2+) and generated H_2O_2. Almost total decontamination of enrofloxacin solutions is achieved in the stirred tank reactor by SPEF with BDD. The use of the batch recirculation flow plant showed that this process is the most efficient and can be viable for industrial application, becoming more economic and yielding higher mineralization degree with raising antibiotic content. This is feasible because organics are quickly oxidized with ~*OH formed from Fenton's reaction and at BDD from water: oxidation, combined with the fast photolysis of complexes of Fe(III) with generated carboxylic acids under solar irradiation. The lower intensity of UVA irradiation used in PEF with BDD causes a slower degradation. EF with BDD is less efficient since ~*OH cannot destroy the most persistent Fe(III)-oxalate and Fe(III)-oxamate complexes. AO-H_2O_2 with BDD yields the poorest mineralization because pollutants are only removed with ~·OH generated at BDD. All procedures are less potent using Pt as anode due to the lower production of ~·OH at its surface. Enrofloxacin decay always follows a pseudo first-order reaction. Its primary aromatic by-products and short intermediates including polyols, ketones, carboxylic acids and N-derivatives are detected by GC-MS and chromatographic techniques. The evolution of F~-, (NO_3)~- and (NH_4)~+ ions released to the medium during each process is also determined.