Plutonium mobility and reactivity in a heterogeneous clay rock barrier accented by synchrotron-based microscopic chemical imaging.

The long-term safe disposal of radioactive waste corresponds to a challenging responsibility of present societies. Within deep geological waste disposal concepts, host rocks correspond to the ultimate safety barrier towards the environment. To assess the performance of such barriers over extended time scales, mechanistic information on the interaction between the radiotoxic, long-lived radionuclides like plutonium and the host rock is essential. Chemical imaging based on synchrotron microspectroscopic techniques was used to visualize undisturbed reactive transport patterns of Pu within pristine Opalinus Clay rock material. Pu+V is shown to be progressively reduced along its diffusion path to Pu+IV and Pu+III due to interaction with redox-active clay rock constituents. Experimental results and modeling emphasize the dominant role of electron-transfer reactions determining the mobility of Pu in reactive barrier systems. The effective migration velocity of Pu is controlled by the kinetic rates of the reduction to Pu+IV and Pu+III and the redox capacity of the involved electron donor pools. To advance our predictive capabilities further, an improved understanding of the nature and capacity of redox-active components of the reactive barrier material is fundamental. The findings represent an essential contribution to the evaluation of the long-term safety of potential nuclear waste repositories and have implications regarding the development of effective geological disposal strategies.

Mixed complexes of alkaline earth uranyl carbonates: a laser-induced time-resolved fluorescence spectroscopic study.

The interaction of the alkaline earth ions Mg(2+), Sr(2+) and Ba(2+) with the uranyl tricarbonato complex has been studied by time-resolved laser-induced fluorescence spectroscopy. In contrast to the non-luminescent uranyl tricarbonato complex at ambient temperature the formed products show luminescence properties. These have been used to determine the stoichiometry and complex stabilities of the formed compounds. As the alkaline earth elements are located in an outer shell of the complex the influence of the type of the alkaline earth element on the stability constant is not very drastic. The stability constants range from log beta113 degrees = 26.07+/-0.13 to log beta113 degrees = 26.93+/-0.25 for the first reaction step and from log beta213 degrees = 29.73+/-0.47 to log beta213 degrees = 30.79+/-0.29 for the overall complex formation with two alkaline earth ions.