Kinetics of oxidative degradation/mineralization pathways of the antibiotic tetracycline by the novel heterogeneous electro-Fenton process with solid catalyst chalcopyrite

•A new electro-Fenton (EF) process using chalcopyrite as heterogeneous catalyst at neutral pH.•Synergistic effect of Fe2+ and Cu2+ ions released by chalcopyrite.•BDD anode is more efficient than Pt anode for tetracycline mineralization.•EF/Chalcopyrite is more efficient than conventional EF process.•Proposed oxidation pathway based on the identification of 19 intermediates.

The degradation of solutions of the antibiotic tetracycline (TC) has been studied by a novel electrochemical advanced oxidation process, consisting in electro-Fenton (EF) process using chalcopyrite as heterogeneous catalyst. In fact, chalcopyrite powder was the source of Fe2+ and Cu2+ ions instead of a soluble catalyst salt used in conventional EF. Experiments were performed in an undivided cell equipped with a Pt or boron-doped diamond (BDD) anode and a carbon felt cathode, where TC and its oxidation intermediate products were destroyed by hydroxyl radicals (OH) formed both, in the bulk solution from electrochemically induced Fenton's reaction (Fe2+ and H2O2) and Fenton's-like reaction (Cu+ and H2O2), and at the anode surface from water oxidation. The effects of operating parameters such as applied current, chalcopyrite concentration and anode material were investigated. TC decay followed pseudo-first-order reaction kinetics. The absolute rate constant for TC oxidation by OH was found to be 3.2 × 109 M−1 s−1, as determined by the competition kinetic method. EF process using chalcopyrite as heterogeneous catalyst showed to be more efficient than conventional EF, achieving almost total mineralization of the TC solution (98% of total organic carbon removal) after 360 min under optimum operating conditions. A plausible mineralization pathway for mineralization of TC aqueous solution by OH was proposed based on the identification of different oxidation by-products. Moreover, toxicity tests pointed out that this heterogeneous EF process was able to detoxify the TC solutions.

Graphical abstractDownload high-res image (86KB)Download full-size image