Degradation of diclofenac via sequential reduction-oxidation by Ru/Fe modified biocathode dual-chamber bioelectrochemical system: Performance, pathways and degradation mechanisms

A sequential reduction-oxidation for DCF degradation was proposed by alternating anaerobic/aerobic conditions at Ru/Fe-biocathode in a dual-chamber bioelectrochemical system (BES). Results showed that Ru/Fe-electrode was successfully fabricated by in-situ electro-deposition, which was rough and uniformly distributed with Ru0 and Fe0 particles. The morphologic changing and biocompatibility were favorable to increase the surface area and enhance microbial adhesion on Ru/Fe-electrode. At an applied voltage of 0.6 V, the potential and impedance of Ru/Fe-biocathode were -0.80 V and 26 Ω, respectively, lower than that of carbon-felt-biocathode. It led to a higher DCF degradation efficiency of 93.2% under anaerobic conditions, which was superior to that of 88.0% under aerobic conditions. Using NaHCO3 as carbon source, DCF removal efficiency increased with increasing applied voltage, but decreased with increasing initial DCF concentration. Thirteen intermediates were measured, and two degradation pathways were proposed, among which sequential reduction-oxidation of DCF was the main pathway, dechlorination intermediates were first generated by [H] attacked under anaerobic conditions, further oxidized by microbes and OH attacked under aerobic conditions, achieving 69.6% of mineralization. After 4 d of reaction, microcystis aeruginosa growth inhibition rate decreased from 22.9 to 8.0%, signifying a significant reduction in biotoxicity. Bacteria (e.g. Nitrobacter, Nitrosomonas, Pseudofulvimonas, Aquamicrobium, Sulfurvermis, Lentimicrobiaceae, Anaerobineaceae, Bacteroidales, Hydrogenedensaceae, Dethiosulfatibacter and Azoarcus) for DCF degradation were enriched in Ru/Fe-biocathode. Microbes in Ru/Fe-biocathode had established defense mechanisms to acclimate to the unfriendly environment, while Ru/Fe-biocathode possessed higher nitrification and denitrification activities than carbon-felt-biocathode, and Ru/Fe-biocathode might be of aerobic and anaerobic biodegradation activities. DCF could be mineralized by the synergistic reaction between Ru/Fe and bacteria under sequential anaerobic/aerobic conditions.