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•A bio-electrochemical reactor was used to reduce AOX in pharmaceutical wastewater.•Lower cathode potentials were beneficial to AOX reduction of microorganisms.•Addition of methyl viologen improved the AOX reduction.•Methanogens did not participate in the dehalogenation of AOX.•Proportion of electrons used for AOX reduction decreased with decreasing potential.
A bio-electrochemical reactor (BER) operating at different cathode potentials ranging from −300 to −1000 mV (vs standard hydrogen electrode, SHE) was used to reduce adsorbable organic halogens (AOX) in pharmaceutical wastewater. Cathode polarization enriched the electron donor of the biological system. Thus, the AOX removal efficiency in the BER improved from 59.9% to 70.2%, and the AOX removal rate increased from 0.87 to 1.17 mg AOX/h when the cathode potential was reduced from −300 to −1000 mV with the addition of methyl viologen, a known redox mediator. The decrease of the cathode potential was also beneficial for methane production, and the inhibition of the methanogenic process enhanced the AOX removal. Additionally, cathode coulombic efficiency analysis demonstrated that the proportion of electrons used for AOX reduction decreases with decreasing potential, from 37.6% at −300 mV to 17.3% at −1000 mV, although the AOX removal efficiency improves.