Speciation of neptunium during sorption and diffusion in natural clay

In argillaceous rocks, which are considered as a potential host rock for nuclear waste repositories, sorption and diffusion processes govern the migration behaviour of actinides like neptunium. For the safety analysis of such a repository, a molecular-level understanding of the transport and retardation phenomena of radioactive contaminants in the host rock is mandatory. The speciation of Np during sorption and diffusion in Opalinus Clay was studied at near neutral pH using a combination of spatially resolved synchrotron radiation techniques. During the sorption and diffusion experiments, the interaction of 8 mu M Np(V) solutions with the clay lead to the formation of spots at the clay-water interface with increased Np concentrations as determined by mu-XRF. Several of these spots are correlated with areas of increased Fe concentration. Np L-3-edge mu-XANES spectra revealed that up to 85% of the initial Np(V) was reduced to Np(IV). Pyrite could be identified by mu-XRD as a redox-active mineral phase responsible for the formation of Np(IV). The analysis of the diffusion profile within the clay matrix after an in-diffusion experiment for two months showed that Np(V) is progressively reduced with diffusion distance, i.e. Np(IV) amounted to approximate to 12% and approximate to 26% at 30 mu m and 525 mu m, respectively.