Effect of humic acid on bioreduction of facet-dependent hematite by Shewanella putrefaciens CN-32

Interfacial reactions between iron (Fe) (hydr)oxide surfaces and the activity of bacteria during dissimilatory Fe reduction affect extracellular electron transfer. The presence of organic matter (OM) and exposed facets of Fe (hydr)oxides influence this process. However, the underlying interfacial mechanism of facet-dependent hematite and its toxicity toward microbes during bioreduction in the presence of OM remains unknown. Herein, humic acid (HA), as typical OM, was selected to investigate its effect on the bioreduction of hematite {100} and {001}. When HA concentration was increased from 0 to 500 mg L^-1, the bioreduction rates increased from 0.02 h^-1 to 0.04 h^-1 for hematite {100} and from 0.026 h^-1 to 0.05 h^-1 for hematite {001}. Since hematite {001} owned lower resistance than hematite {100} irrespective of the HA concentration, and hematite {100} was less favorable for reduction. Microscopy-based analysis showed that more hematite {001} nanoparticles adhered to the cell surface and were bound more closely to the bacteria. Moreover, less cell damage was observed in the HA-hematite {001} treatments. As the reaction progressed, some bacterial cells died or were inactivated; confocal laser scanning microscopy showed that bacterial survival was higher in the HA-hematite {001} treatments than in the HA-hematite {100} treatments after bioreduction. Spectroscopic analysis revealed that facet-dependent binding was primarily realized by surface complexation of carboxyl functional groups with structural Fe atoms, and that the binding order of HA functional groups and hematite was affected by the exposed facets. The exposed facets of hematite could influence the electrochemical properties and activity of bacteria, as well as the binding of bacteria and Fe oxides in the presence of OM, thereby governing the extracellular electron transfer and concomitant bioreduction of Fe (hydr)oxides. These results provide new insights into the interfacial reactions between OM and facet-dependent Fe oxides in anoxic, OM-rich soil and sediment environments.