Extracellular polymeric substances from Shewanella oneidensis MR-1 biofilms mediate the transformation of Ferrihydrite

Extracellular polymeric substances (EPS) of dissimilatory iron-reducing bacteria (DIRB) such as Shewanella oneidensis MR-1 play a crucial role in the biotransformation of iron-containing minerals, but the mechanism has not been fully deciphered. Herein, abiotic and biotic transformation of ferrihydrite (Fh) were compared to clarify the contributions of MR-1, EPS-free MR-1 (MR-1-EPS), loosely bound EPS (LB-EPS), and tightly bound EPS (TB-EPS). The results of abiotic Fh transformation indicated that EPS did not block the Fh surfaces and thus has an insignificant effect on the adsorbed Fe(II)-Fh interaction. The complexation of the Fe(III) intermediate (Fe(III)_active) with EPS, especially LB-EPS, however, inhibited the nucleation of secondary Fe minerals and changed the crystallization pathway. For biotic Fh transformation, on the other hand, EPS had dual effects that accelerated Fh bioreduction due to the enhanced extracellular electron transfer (EET) and constrained the following Fh mineralization by cutting of the chain reactions leading to mineral crystallization. Our finding also suggested that the effects of EPS on Fh biotransformation largely depend on the chemical properties of EPS, especially the polar functional groups such as carboxyl and phosphate, because of their important abilities for the cell attachment and Fe(II)/Fe(III) binding.