Biostimulation of iron reduction and subsequent oxidation of sediment containing Fe-silicates and Fe-oxides: Effect of redox cycling on Fe(III) bioreduction

Sediment containing a mixture of iron (Fe)-phases, including Fe-oxides (mostly Al-goethite) and Fe-silicates (illites and vermiculite) was bioreduced in a long-term flow through column experiment followed by re-oxidation with dissolved oxygen. The objective of this study was (a) to determine the nature of the re-oxidized Fe(III), and (b) to determine how redox cycling of Fe would affect subsequent Fe(III)-bioavailability. In addition, the effect of Mn on Fe(III) reduction was explored. 57Fe-Mössbauer spectroscopy measurements showed that biostimulation resulted in partial reduction (20%) of silicate Fe(III) to silicate Fe(II) while the reduction of goethite was negligible. Furthermore, the reduction of Fe in the sediment was uniform throughout the column. When, after biostimulation, 3900 pore volumes of a solution containing dissolved oxygen was pumped through the column over a period of 81 days, approximately 46% of the reduced silicate Fe(II) was re-oxidized to silicate Fe(III). The Mössbauer spectra of the re-oxidized sample were similar to that of pristine sediment implying that Fe-mineralogy of the re-oxidized sediment was mineralogically similar to that of the pristine sediment. In accordance to this, batch experiments showed that Fe(III) reduction occurred at a similar rate although time until Fe(II) buildup started was longer in the pristine sediment than re-oxidized sediment under identical seeding conditions. This was attributed to oxidized Mn that acted as a temporary redox buffer in the pristine sediment. The oxidized Mn was transformed to Mn(II) during bioreduction but, unlike silicate Fe(II), was not re-oxidized when exposed to oxygen.