How iron-bearing minerals affect the biological reduction of Sb(V): A newly discovered function of nitrate reductase

As a toxic element of global concern, the elevated concentration of antimony (Sb) in the environment has attracted increasing attention. Microorganisms have been reported as important driving forces for Sb transformation. Iron (Fe) is the most important metal associated element of Sb, however, how Fe-bearing minerals affect the biological transformation of Sb is still unclear. In this study, the effects of Fe-bearing minerals on biological Sb(V) reduction were investigated by employing a marine Shewanella sp. CNZ-1 (CNZ-1). Our results showed that the presence of hematite, magnetite and ferrihydrite (1 g/L) resulted in a decrease in Sb(III) concentration of ~19-31 % compared to the Fe(III)-minerals free system. The calculated Sb(V) reduction rates are 0.0256 (R² 0.71), 0.0389 (R² 0.87), 0.0299 (R² 0.96) and 0.0428 (R² 0.95) h^-1 in the hematite-, magnetite-, ferrihydrite-supplemented and Fe(III)-minerals free systems, respectively. The cube-shaped Sb₂O₃ was characterized as a reductive product by using XRD, XPS, FTIR, TG and SEM approaches. Differential proteomic analysis showed that flagellar protein, cytochrome c, electron transfer flavoprotein, nitrate reductase and polysulfide reductase (up-regulation >1.5-fold, p value <0.05) were supposed to be included in the electron transport pathway of Sb(V) reduction by strain CNZ-1, and the key role of nitrate reductases was further highlighted during this reaction process based on the RT-qPCR and confirmatory experiments. Overall, these findings are beneficial to understand the environmental fate of Sb in the presence of Fe-bearing minerals and provide guidance in developing the bacteria/enzyme-mediated control strategy for Sb pollution.