Effect of copper ions on glucose fermentation pathways in bioelectrochemical system.

Toxic metal ions were previously found to be effective removed by anodic biofilms under the coexistence of organics in bioelectrochemical system (BES). However, the effect of toxic metal ions on the organics fermentation pathways remains unclear. To investigate the pathway systematically, the glucose fermentation pathways were discussed under different Cu2+ concentrations. After introducing Cu2+, more acetate and less propionate were observed, implying that the metabolic reaction of glucose fermentation altered from mixed acid type to acetogenesis type. This pattern produced more "food" (acetate or hydrogen) for methanogens, thus, the methane content increased by 19.67%, 39.51%, and 27.71% in the presence of 0.1, 1, and 7 mg L-1 Cu2+ compared to the blank, respectively. Increased Cu2+ concentrations resulted in the decrease of current production, which was associated with the decrease of electricigen (Geobacter). Consistent with the change of fermentation type, the fermenters (Klebsiella and norank_f__norank_o__Bacteroidales) that related to the production of acetate increased, while the dominant methanogens (Methaospirillum) didn't decrease until the Cu2+ concentration reached 7 mg L-1.

Inhibitory effect of cadmium(II) ion on anodic electrochemically active biofilms performance in bioelectrochemical systems.

Cadmium(II) ion can affect the anode performance of bioelectrochemical systems (BES); however, how the presence of Cd2+ affect the extracellular electron transfer of anodic electrochemically active biofilms (EABs), the microbial viability and species composition of microorganism on the anode remain poorly understood. Here, we investigated the inhibitory effect of Cd2+ at different concentrations on the electrochemical performance and the biofilm community in mixed-culture enriched BES. The electrochemical performance of the BES was not inhibited at 2 mg L-1 Cd2+, while higher concentrations of 5-20 mg L-1 resulted in the decrease in the maximum power density, with 0.34 ±â€¯0.01 W m-2 at 5 mg L-1, 0.28 ±â€¯0.01 W m-2 at 10 mg L-1, and 0.17 ±â€¯0 W m-2 at 20 mg L-1, respectively. When adding 30 mg/L Cd2+, there was almost no power output. The decline of the power output was possibly ascribed to the suppressed viability and the change of species richness as evident from confocal laser scanning microscopy and microbial community analysis. Cyclic voltammogram and electrochemical impedance spectroscopy revealed that high concentration of Cd2+ exceeding 5 mg L-1 can inhibit the secretion of outer membrane cytochromes, thus reducing the electron transfer between the EABs and the anode surface. Analysis of bacterial structures showed a decrease in Geobacter accompanied by an increase in Stenotrophomonas and Azospira in response to Cd2+ at 10 and 20 mg L-1. This study added to the in-depth analysis of the inhibition of Cd2+ on EABs, and provided new insights into the removing Cd2+ and organics simultaneously in BES.

Electrochemical and microbial community responses of electrochemically active biofilms to copper ions in bioelectrochemical systems.

Heavy metals play an important role in the conductivity of solution, power generation and activity of microorganisms in bioelectrochemical systems (BESs). However, effect of heavy metal on the process of exoelectrogenesis metabolism and extracellular electron transfer of electrochemically active biofilms (EABs) was poorly understood. Herein, we investigated the impact of Cu2+ at gradually increasing concentration on the morphological and electrochemical performance and bacterial communities of anodic biofilms in mixed-culture BESs. The voltage output decreased continuously and dropped to zero at 10 mg L-1, which was attributed to the toxic inhibition that cased anodic biofilm damage and decreased secretion of outer membrane cytochromes. When stopping the introduction of Cu2+ to anodic chamber, the maximum voltage production recovered 75.1% of the voltage produced from BES and coulombic efficiency was higher but acetate removal rate was lower than that before Cu2+ addition, demonstrating the recovery capability of EABs was higher compared to nonelectroactive bacteria. Moreover, SEM-EDS and XPS suggested that most of Cu2+ was adsorbed by the anode electrode and reduced by EABs on anode. Compared to the open-circuit BES, the flow of electrons through a circuit could improve the reduction of copper. Community analysis showed a decrease in Geobacter accompanied by an increase in Stenotrophomonas in response to Cu2+ shock in anodic chamber.