Microbially-mediated reductive dissolution of Fe-bearing minerals during freeze-thaw cycles

Abstract

Constraining the role of microbes in the structural iron (Fe) reduction of iron-bearing minerals improves our understanding of sediments and ice sheets as a source of dissolved Fe (dFe) to the oceans. However, bio-mediated structural Fe-reduction has yet to be studied in cryospheric environments. Here, we show that the Fe reducing psychrophile bacterium Shewanella vesiculosa, isolated from sea ice in Antarctica, reduced structural Fe in nontronite (NAu-2) and maghemite (γ-Fe2O3), common mineral phases in glacial ice, and marine sediments in Antarctica, during two freeze–thaw cycles (−10 °C to +15 °C), resulting in the release of dFe. The modification of turbostratically disordered nontronite (ferric iron dominant phase) to discrete ordered illite-like structure (ferrous iron dominant phase), and the aggregation of altered small maghemite particles with neoformation of vivianite (Fe3(PO4)2·nH2O) indicated the microbially induced reductive dissolution of nontronite and maghemite, respectively. The biotic Fe-reduction gradually decreased and ceased as the temperature approached freezing (−8 °C), however the rection reactivated in the thawing cycle (−7 to +15 °C). No discernable biotic Fe-reduction was measured for either mineral under freezing conditions, suggesting that temperature limits the activity of the microbes. Further, and regardless of temperatures during two freeze–thaw cycles, Fe-reduction was not observed in abiotic control. Overall, these results highlight the importance of microbially induced Fe reduction during seasonal freeze–thaw cycles of ice and sediments in continuous supplying bioavailable dFe to cryospheric environments and the often Fe-limited polar oceans.