Use of a small overpotential approximation to analyze Geobacter sulfurreducens biofilm impedance

The electrochemical impedance of Geobacter sulfurreducens biofilms reflects the extracellular electron transfer mechanisms determining the rate of current output. Binned into two characteristic parameters, conductance and capacitance, biofilm impedance has received significant attention. The goal of this study was to evaluate a small overpotential approximation for extracellular electron transfer in G. sulfurreducens biofilms. Our motivation was to determine whether conductance over biofilm growth behaved linearly with respect to limiting current. Biofilm impedance was tracked during growth using electrochemical impedance spectroscopy (EIS) and electrochemical quartz crystal microbalance (eQCM). We showed that normalization of the biofilm impedance is useful for characterizing the changes during growth. When the conductance and capacitance were compared to the biofilm current, we found that: 1) conductance had a linear response and 2) constant phase elements (CPE) had a saturating response that coincided with the limiting current. We provided a framework using a simple iV relationship that predicted the conductance-current slope to be 9.57 V-1. CPEs showed more variability across biofilm replicates than conductance values. Although G. sulfurreducens biofilms were used here, other electrochemically active biofilms exhibiting catalytic waves could be studied using the same methods.