A three-dimensional bioelectrochemical system (3D-BES) with both electrocatalytic and biodegradation functions was designed and developed to enhance iodine-containing hormone removal from micro-polluted oligotrophic drinking water sources and to reduce energy consumption. Thyroxine (T4) removal efficiency was 99.0% in the 3D-BES amendment with TiO2@GAC as the particle electrodes, which was 20.5% higher than the total efficiency of single biodegradation (28.7%) plus electrochemical decomposition (49.8%). The high T4 removal efficiency was a result of biochemical synergistic degradation, enhancement of electron transfer and utilization, enrichment of functional microorganisms, and the expression of dehalogenation functional genes. The electron transfer was increased by 1.63 times in 3D-BES compared to the 2D-BES, which contributed to: (i) ∼17.8% enhancement of dehalogenation, (ii) 2.35 times enhancement of the attenuation rate, and (iii) 60% reduction in energy consumption. Moreover, the aggregation of microorganisms and the hydrophobic T4 onto TiO2@GAC shortened the transfer distance of matter and energy, which induced the degradation steps to be shortened and the toxic decay to be accelerated from T4 and its metabolites. These comprehensive functions also enhanced the 31.8% ATPase activity, 7.3% abundance of the functional reductive dehalogenation genera, and 52.3% dehalogenation genes expression for Pseudomonas, Ancylobacter, and Dehalogenimonas, which contributed to an increase in T4 removal. This work provides an environmental-friendly biochemical synergistic method for the detoxification of T4 polluted water.
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