Heterotrophic anodic denitrification coupled with cathodic metals recovery from on-site smelting wastewater with a bioelectrochemical system inoculated with mixed Castellaniella species

Abstract

Although Castellaniella species are crucial for denitrification, there is no report on their capacity to carry out denitrification and anode respiration simultaneously in a bioelectrochemical system (BES). Herein, the ability of a mixed inoculum of electricigenic Castellaniella species to perform simultaneous denitrification and anode respiration coupled with cathodic metals recovery was investigated in a BES. Results showed that 500 mg/L NO₃^--N significantly decreased power generation, whereas 100 and 250 mg/L NO₃^--N had a lesser impact. The single-chamber MFCs (SCMFCs) fed with 100 and 250 mg/L NO₃^--N concentrations achieved a removal efficiency higher than 90% in all cycles. In contrast, the removal efficiency in the SCMFCs declined dramatically at 500 mg/L NO₃^--N, which might be attributable to decreased microbial viability as revealed by SEM and CLSM. EPS protein content and enzymatic activities of the biofilms decreased significantly at this concentration. Cyclic voltammetry results revealed that the 500 mg/L NO₃^--N concentration decreased the redox activities of anodic biofilms, while electrochemical impedance spectroscopy showed that the internal resistance of the SCMFCs at this concentration increased significantly. In addition, BES inoculated with the Castellaniella species was able to simultaneously perform heterotrophic anodic denitrification and cathodic metals recovery from real wastewater. The BES attained Cu²⁺, Hg²⁺, Pb²⁺, and Zn²⁺ removal efficiencies of 99.86 ± 0.10%, 99.98 ± 0.014%, 99.98 ± 0.01%, and 99.17 ± 0.30%, respectively, from the real wastewater. Cu²⁺ was bio-electrochemically reduced to Cu⁰ and Cu₂O, whereas Hg⁰ and HgO constituted the Hg species recovered via bioelectrochemical reduction and chemical deposition, respectively. Furthermore, Pb²⁺ and Zn²⁺ were bio-electrochemically reduced to Pb⁰ and Zn⁰, respectively. Over 89% of NO₃^--N was removed from the BES anolyte during the recovery of the metals. This research reveals promising denitrifying exoelectrogens for enhanced power generation, NO₃^--N removal, and heavy metals recovery in BES.

Keywords: Bioelectrochemical system; Castellaniella species; Denitrifying exoelectrogens; Metals recovery; Nitrate.