Spectroscopic Studies on Colloid-borne Uranium(VI)

Information on molecular speciation provides a basis for the reliable assessment of actinide migration in the environment. We use several methods for the separation of colloids from liquids (e.g. ultracentrifugation, ultrafiltration) in combination with spectroscopic techniques (EXAFS, ATR-FTIR, Mössbauer) and modeling of surface complexation reactions. This enables us to investigate the speciation of colloid-borne uranium in waters occurring in or escaping from abandoned uranium mines during the remediation process. Mine flooding was simulated on a 100 L scale by mixing acid mine water of elevated U concentration with oxic, near-neutral groundwater until pH~5.5 was reached. The freshly formed colloids adsorbed 95% of the total uranium and consisted mainly of 2-line ferrihydrite (Fh) besides traces of aluminum, sulfur, silica, and carbon compounds. EXAFS analysis at the U-LIII absorption edge suggested a bidentate surface complex of UO22+ on FeO6 octahedra, but two minor backscattering contributions in close vicinity to the absorber remained unexplained. Since only Al could be excluded as backscattering atom, we studied U sorption on Fh at pH 5.5 in presence and in absence of sulfate, silicate, and atmospheric CO2 to clarify the bond structure.

EXAFS showed the unknown backscattering contributions in all the sorption samples regardless of the presence or absence of the tested components. Contrary to structural models proposed in the literature, bidentately complexed carbonate ligands do not explain our experimental EXAFS data. But ATR-IR spectra showed that U-carbonato complexes must be involved in the sorption of uranyl on Fh. These results are not contradictory if the carbonate ligands were bound monodentately. Nevertheless, carbon cannot act as backscattering atom in carbonate-free samples prepared in N2 atmosphere. We propose a new structural model including exclusively Fe, H, and O atoms in which the bidentately bound UO22+ is oriented in a way that yields a distance of ~2.9 Å to the O atom of an adjacent, edge-shared FeO6 octahedron. This model predicts a second Fe shell at ~4.35 Å which tightly fits the experimental data.

In summary, uranium may form different sorption complexes with colloidal ferric hydroxides: a binary bidentate uranyl complex with modified orientation, and ternary U-carbonato complexes with monodentate linkage of the carbonate ligand. The affinity of carbonate and uranyl to form such complexed surface species will increase when sorption sites with high affinity, as provided by colloidal Fh, are present.