Role of Pyrogenic Carbon in Parallel Microbial Reduction of Nitrobenzene in the Liquid and Sorbed Phases

Surface functional groups and graphitic carbons make up the electroactive components of pyrogenic carbon. The role of pyrogenic carbon with different contents of electroactive components in mediating electron transfer in biochemical reactions has not been systematically studied. Here, we determined the electron exchange capacity (EEC) of pyrogenic carbon to be 0.067-0.120 mmol e-·(g of pyrogenic carbon)-1, and the maximum electrical conductivity (EC) was 4.85 S·cm-1. Nitrobenzene was simultaneously reduced in both the liquid and sorbed phases by Shewanella oneidensis MR-1 in the presence of pyrogenic carbon. Pyrogenic carbon did not affect the aqueous nitrobenzene reduction, and the reduction of sorbed nitrobenzene was much slower than that of the aqueous species. Enhancing contents of oxygenated functional moieties in pyrogenic carbon with HNO3 oxidation elevated bioreduction rates of the aqueous and sorbed species. Anthraquinone groups were deemed as the most likely oxygenated functional redox compounds on the basis of both voltammetric curve tests and spectroscopic analysis. The reactivity of pyrogenic carbon in mediating the reduction of sorbed nitrobenzene was positively correlated with its EC, which was demonstrated to be related to condensed aromatic structures. This work elucidates the mechanism for pyrogenic carbon-mediated biotransformation of nitrobenzene and helps properly evaluate the role of pyrogenic carbon in biogeochemical redox processes happening in nature.