Magnetite as a precursor for green rust through the hydrogenotrophic activity of the iron-reducing bacteria Shewanella putrefaciens.

Magnetite (Fe(II) Fe(III) 2 O4 ) is often considered as a stable end product of the bioreduction of Fe(III) minerals (e.g., ferrihydrite, lepidocrocite, hematite) or of the biological oxidation of Fe(II) compounds (e.g., siderite), with green rust (GR) as a mixed Fe(II) -Fe(III) hydroxide intermediate. Until now, the biotic transformation of magnetite to GR has not been evidenced. In this study, we investigated the capability of an iron-reducing bacterium, Shewanella putrefaciens, to reduce magnetite at circumneutral pH in the presence of dihydrogen as sole inorganic electron donor. During incubation, GR and/or siderite (Fe(II) CO3 ) formation occurred as secondary iron minerals, resulting from the precipitation of Fe(II) species produced via the bacterial reduction of Fe(III) species present in magnetite. Taking into account the exact nature of the secondary iron minerals and the electron donor source is necessary to understand the exergonic character of the biotic transformation of magnetite to GR, which had been considered to date as thermodynamically unfavorable at circumneutral pH. This finding reinforces the hypothesis that GR would be the cornerstone of the microbial transformations of iron-bearing minerals in the anoxic biogeochemical cycle of iron and opens up new possibilities for the interpretation of the evolution of Earth's history and for the understanding of biocorrosion processes in the field of applied science.

Pseudo-first-order reaction of chemically and biologically formed green rusts with HgII and C15H15N3O2: effects of pH and stabilizing agents (phosphate, silicate, polyacrylic acid, and bacterial cells).

The kinetics of Hg(II) and methyl red (MR) reduction by hydroxycarbonate green rust (GR1) and by hydroxysulfate green rust (GR2) were studied in the presence of naturally occurring organic and inorganic ligands (phosphate, polyacrylic acid, bacterial cells, silicate). The reducing ability of biogenic hydroxycarbonate green rust (GR1bio), obtained after microbial reduction of lepidocrocite by Shewanella putrefaciens, was also investigated and compared to those of chemically synthesized GR1 and GR2 (GR1ab and GR2ab). Pseudo first-order rate constants (kobs) of Hg(II) reduction (at pH 7.0, 8.2, and 9.5) and MR reduction (at pH 7.0) were determined and were normalized to the structural Fe(II) content of GRs (kFeII) and to the estimated concentration of surface Fe(II) sites (kS). The kS values ranged from 0.3 L mmol(-1) min(-1) to 43 L mmol(-1) min(-1) for the Hg reduction, and from 0.007 L mmol(-1) min(-1) to 3.4 L mmol(-1) min(-1) for the MR reduction. No significant discrepancy between GRab and GRbio was observed in term of reactivity. However, the reduction kinetics of MR was generally slower than the Hg(II) reduction kinetics for all tested GRs. While a slight difference in Hg(II) reduction rate was noted whatever the pH values (7.0, 8.2, or 9.5), the reduction of MR was significantly affected in the presence of ligands. A decrease by a factor of 2-200, depending on the type of ligand used, was observed. These data give new insights into the reactivity of GRs in the presence of co-occurring organic and inorganic ligands, and have major implications in the characterization of contaminated systems as well as water treatment processes.