Second reporting of the scientific-technical outcome of WP 4.2: - chemical and redox behavior of the investigated radionuclides in the different systems through microbial mediated processes.

First studies have been carried out in stalactite-like biofilms from the uranium mine Königstein (Germany), where the mining activities had been stopped in 1990 and the uranium mine has been partially flooded for remediation. In the acidic, sulphate-rich waters with high concentration of heavy metals and radionuclides (uranium) as contaminants, biofilms are formed and occur as gelatinous filaments, and as stalactite-like snotites. The analyses of the bacterial diversity of these biofilms showed a dominance of Ferrovum myxofaciens, an acidophilic, autotrophic, iron oxidizing bacteria, which belongs to the Betaproteobacteria. Ferrous iron is oxidized strongly catalyzed by Fe(II)-oxidizing bacteria with the consequence of producing oxidizing conditions within the biofilm with high oxygen concentration. Fiber-optic oxgyen microprofiles, carried out in these snotites are in a good agreement with electro-chemical measurements. The oxygen concentration is decreasing slowly from the edge versus center of the snotite biofilm. Electrochemical redox potential micoprofilings were carried out in these snottite-biofilms by a miniaturized platinum redox electrode with a tip diameter of 10 µm, too. In the bulk solution a redox potential of 728 mV +- 9.5 mV was measured in comparison to an increased redox potential of 834.5 mV +- 10.21 mV within the snottite-biofilm. We guess that the different geochemical conditions are due to the oxidation of ferrous iron catalyzed by Fe(II) oxidizing bacteria and that they will have an influence on the uranium speciations. A pH-Eh diagram for the U-S-O-H-C system at 15 °C was constructed using the geochemical speciation code “Geochemist´s Workbench” Version 8.0.8 / ACT2 Version 8.0.8 and the most recent NEA database for Uranyl Silicates and solid Uranates (Guillaumont et al., 2003), supplemented with solubility data for Uranophane (Nguyen et al., 1992) and CaU2O7.3H2O(s) (Altmaier et al., 2006) and the analytical data of the bulk water for the calculation of the field stability boundaries of different uranium species. The plotting of the measured pH and Eh values into this diagram showed that the theoretical stability fields of U species are defined in areas characterized by higher pH or lower Eh. The measured values indicate that aqueous Uranium(VI) Sulfate Complexations were formed in the biofilm as well as in the bulk solution. Only the changing of the local conditions (e.g. closure of the underground galleries) will lead to substantial changes and the formation of solid uranium(IV) species.