Interaction of muscovite (001) with Pu~(3+) bearing solutions at pH 3 through ex-situ observations

摘要

The interaction of Pu~(3+) bearing solutions with the muscovite (001) basal plane is explored using a combination of ex-situ approaches including alpha-counting, to determine the Pu~(3+) adsorption isotherm, and X-ray reflectivity (XR) and resonant anomalous X-ray reflectivity (RAXR), to probe the interfacial structure and Pu-specific distribution, respectively. Pu uptake to the muscovite (001) surface from Pu~(3+) solutions in a 0.1M NaClO_4 background electrolyte at pH 3 follows an approximate Langmuir isotherm with an apparent adsorption constant, K_(app)=5×10~4M~(-1), and with a maximum coverage that is consistent with the amount needed to fully compensate the surface charge by trivalent Pu. The XR results show that the muscovite surface reacted with a 10~(-3)M Pu~(3+) solution (at pH 3 with 0.1M NaClO_4) and dried in the ambient environment, maintains a 30-40? thick layer, indicating the presence of a residual hydration layer (possibly including adventitious carbon). The RAXR results indicate that Pu sorbs on the muscovite surface with an intrinsically broad distribution with an average height of 18?, substantially larger than heights expected for any specifically adsorbed inner- or outer-sphere complexes. These results are discussed in the context of recent studies of cation adsorption trends on muscovite and the possible roles of Pu hydrolysis species in controlling the Pu-muscovite interactions.