Efficient cephalexin degradation using active chlorine produced on ruthenium and iridium oxide anodes: Role of bath composition, analysis of degradation pathways and degradation extent

The elimination of cephalexin (CPX) using electro-generated Cl₂-active on Ti/RuO₂-IrO₂ anode was assessed in different effluents: deionized water (DW), municipal wastewater (MWW) and urine. Single Ti/RuO₂ and Ti/IrO₂ catalysts were prepared to compare their morphologies and electrochemical behavior against the binary DSA. XRD and profile refinement suggest that Ti/RuO₂-IrO₂ forms a solid solution, where RuO₂ and IrO₂ growths are oriented by the TiO₂ substrate through substitution of Ir by Ru atoms within its rutile-type structure. SEM reveals mud-cracked structures with flat areas for all catalysts, while EDS analysis indicates atomic ratios in the range of the oxide stoichiometries in the nominal concentrations used during synthesis. A considerably higher CPX degradation is achieved in the presence of NaCl than in Na₂SO₄ or Na₃PO₄ media due to the active chlorine generation. A faster CPX degradation is reached when the current density is increased or the pH value is lowered. This last behavior may be ascribed to an acid-catalyzed reaction between HClO and CPX. Degradation rates of 22.5, 3.96, and 0.576 μmol L⁻¹ min⁻¹ were observed for DW, MWW and urine, respectively. The lower efficiency measured in these last two effluents was related to the presence of organic matter and urea in the matrix. A degradation pathway is proposed based on HPLC-DAD and HPLC-MS analysis, indicating the fast formation (5 min) of CPX-(S)-sulfoxide and CPX-(R)-sulfoxide, generated due the Cl₂-active attack at the CPX thioether. Furthermore, antimicrobial activity elimination of the treated solution is reached once CPX, and the initial by-products are considerably eliminated. Finally, even if only 16% of initial TOC is removed, BOD₅ tests prove the ability of electro-generated Cl₂-active to transform the antibiotic into biodegradable compounds. A similar strategy can be used for the abatement of other recalcitrant compounds contained in real water matrices such as urine and municipal wastewaters.