Biogenic iron sulfide functioning as electron-mediating interface to accelerate dissimilatory ferrihydrite reduction...

Microbially driven iron and sulfur geochemical cycles co-exist ubiquitously in subsurface environments and are of environmental relevance. Shewanella species (dissimilatory metal-reducing bacteria) are capable of reducing Fe(III)-(oxyhydr)oxide minerals and diverse sulfur sources using corresponding metabolic pathways and producing FeS secondary minerals. In spite of the ability in promoting bacterial extracellular electron transfer (EET), the specific role of FeS in mediating EET between microbe/mineral interface is still unclear. In this work, the electron-mediating function of biogenic FeS on promoting the reduction of ferrihydrite by S. oneidensis MR-1 using thiosulfate as sulfur source was investigated in terms of Fe(III) reduction percentage, X-ray diffraction and scanning electron microscopy. The results showed that the microbial ferrihydrite reduction was pH-dependent and positively correlated with the addition of thiosulfate. In the presence of thiosulfate, biogenic FeS in nano-scale were formed and deposited on the surfaces of S. oneidensis MR-1 and ferrihydrite to build an interfacial electron transfer bridge between them. The addition of either thiosulfate and in-vitro FeS could rescue the entirely inactivated ability of the mutant (△omcA/mtrC) in ferrihydrite reduction to some extent, but which was obviously inferior to the wild-type strain. Meanwhile, the effect of the biogenic FeS in-situ coating on the surfaces of S. oneidensis MR-1 cells on promoting microbial ferrihydrite reduction was significantly superior to the in-vitro ones. Thus, the in-situ formed biogenic FeS secondary minerals were demonstrated to mediate and accelerate interfacial electron transfer from S. oneidensis MR-1 cells to ferrihydrite through interfacing with the bacterial EET routes, especially Mtr pathway. This work provides an insight into the secondary minerals-mediating interfacial electron transfer between microbes and minerals in the presence of biological S (-II), which has important biogeochemical and environmental implications.