Semiconducting hematite facilitates microbial and abiotic reduction of chromium

Semi-conducting Fe oxide minerals, such as hematite, are well known to influence the fate of contaminants and nutrients in many environmental settings through sorption and release of Fe(II) resulting from microbial or abiotic reduction. Studies of Fe oxide reduction by adsorbed Fe(II) have demonstrated that reduction of Fe(III) at one mineral surface can result in the release of Fe(II) on a different one. This process is termed "Fe(II) catalyzed recrystallization" and is believed to be the result of electron transfer through semi-conducting Fe (hydr)oxides. While it is well understood that Fe(II) plays a central role in redox cycling of elements, the environmental implications of Fe(II) catalyzed recrystallization require further exploration. Here, we demonstrate that hematite links physically separated redox reactions by conducting the electrons involved in those reactions. This is shown using an electrochemical setup where Cr reduction is coupled with a potentiostat or Shewanella putrefaciens, a metal reducing microbe, where electrons donated to hematite produce Fe(II) that ultimately reduces Cr. This work demonstrates that mineral semi-conductivity may provide an additional avenue for redox chemistry to occur in natural soils and sediments, because these minerals can link redox active reactants that could not otherwise react due to physical separation.