ferrihydrite and ferrous-oxide

To understand trace radionuclide (uranium) migration occurring in rocks, a granitic batholith located at the Korea Atomic Energy Research Institute (KAERI) site was selected and investigated. The rock samples obtained from this site were examined using mineralogical methods, including scanning electron microscopy (SEM) and electron probe microanalysis (EPMA). The changes in the distribution pattern of uranium (U) and small amounts of trace elements, and the mineralogical textures affected by weathering, were examined. Based on the element distribution analyses, it was found that Fe2+ released from fresh biotite is oxidized in short geological time, forming amorphous iron oxides, such as ferrihydrite, around silicate minerals. In that case, the amorphous ferrihydrite does not show distinct adsorption for U. However, as it gradually crystallizes to goethite or hematite, the most U-rich phases were found to be associated with the secondary iron oxides having granular forms. This evidence suggests that the geological subsurface environment is favorable for the crystallized iron oxides to keep their structures more stable for a long time as compared with the amorphous phases. There is a possibility that the long residence of U which is in contact with the stable crystalline phases of iron may finally lead to the partial sequestration of U in their structure. Consequently, it seems that Fe-oxide crystallization can be a dominating mechanism for U uptake and controls long-term U transport in granites with low U contents.

Topics: Aluminum Silicates; Crystallization; Diffusion; Ferric Compounds; Ferrous Compounds; Korea; Silicon Dioxide; Trace Elements; Uranium

Using the isotope specificity of 57Fe Mössbauer spectroscopy, we report spectroscopic observations of Fe(II) reacted with oxide surfaces under conditions typical of natural environments (i.e., wet, anoxic, circumneutral pH, and about 1% Fe(II)). Mössbauer spectra of Fe(II) adsorbed to rutile (TiO2) and aluminum oxide (Al2O3) show only Fe(II) species, whereas spectra of Fe(II) reacted with goethite (alpha-FeOOH), hematite (alpha-Fe2O3), and ferrihydrite (Fe5HO8) demonstrate electron transfer between the adsorbed Fe(II) and the underlying iron(III) oxide. Electron-transfer induces growth of an Fe(III) layer on the oxide surface that is similar to the bulk oxide. The resulting oxide is capable of reducing nitrobenzene (as expected based on previous studies), but interestingly, the oxide is only reactive when aqueous Fe(II) is present. This finding suggests a novel pathway for the biogeochemical cycling of Fe and also raises important questions regarding the mechanism of contaminant reduction by Fe(II) in the presence of oxide surfaces.

Topics: Adsorption; Aluminum Oxide; Ferric Compounds; Ferritins; Ferrous Compounds; Iron Compounds; Iron Isotopes; Minerals; Oxidation-Reduction; Oxides; Spectroscopy, Mossbauer; Surface Properties; Titanium; Water