Cadmium immobilization during nitrate-reducing Fe(II) oxidation by Acidovorax sp. BoFeN1: Contribution of bacterial cells and secondary minerals

Abstract

Microbially nitrate-reducing Fe(II) oxidation (NRFO) is widespread in anoxic environments at circumneutral pH, in which Fe(II) oxidation is considered to be mainly catalyzed by nitrite via chemodenitrification after microbial nitrate reduction. Cadmium (Cd) is toxic to organisms, and its availability is strongly affected by iron (oxyhydr)oxides and/or bacteria. However, it remains unclear how NRFO affects the fate of Cd with environmentally relevant concentrations, and the relative contributions of microbes and secondary minerals to Cd immobilization during NRFO. Here, Acidovorax sp. BoFeN1, a typical NRFO bacterium, was used to investigate the Cd immobilization during NRFO at pH 7.0 with 0.1, 0.5, and 1.0 mg/L Cd, respectively. Higher initial Cd concentration resulted in a higher amount of Cd immobilized in precipitates, but showed stronger inhibition on nitrate reduction, acetate metabolism, and cell growth. The presence of Cd barely influenced the Fe(II) oxidation during NRFO or chemodenitrification, but retarded the mineral transformation to secondary crystalline minerals, i.e., lepidocrocite and goethite. The extracellular polymeric substances deposited in the bacteria-mineral precipitates were rich in tyrosine-like and tryptophan-like proteins with negatively charged amino and carboxyl groups. The STEM-HAADF images with EDX mapping demonstrated that Cd was strongly co-localized with Fe on the cell surface and in the periplasm. Cadmium immobilization experiments with bacterial cells or during chemodenitrification indicated that the bacterial cells and secondary minerals formed during chemodenitrification are comparably important for Cd immobilization in the Cd0.1 treatment, while the secondary minerals played a predominant role in Cd immobilization in the Cd0.5 and Cd1.0 treatments. These results suggested that Cd was likely associated with the secondary iron minerals, which precipitated with the proteins on the cell surface and in the periplasm. Our findings provide a comprehensive understanding of the roles of Cd, bacterial cells, and secondary minerals formed via chemodenitrification, as well as their interactions during the complicated NRFO process at circumneutral pH.