Chemical speciation of heterogeneously reduced Pu in synthetic brines

Summary X-ray absorption fine structure (XAFS) spectroscopy has been used to determine the speciation of Pu precipitates prepared by the heterogeneous reduction of Pu(VI) with Al and Fe in 5 M NaCl and an ERDA-6 brine, a simulant from the Waste Isolation Pilot Plant in Carlsbad, New Mexico. NaOCl was added to some of these solutions to determine its effect on Pu speciation. Analysis of the PuLIIIspectra showed that all solids consisted of PuO2+x-y(OH)2y·zH2O, compounds with characteristics identical to those prepared by hydrolysis and with Pu-O and Pu-Pu distances identical to those treated at elevated temperature. Additionally, reduction with Al gave compounds with different site distributions than reduction with Fe, and reduction with Al or the addition of NaOCl appeared to suppress the formation of oxo groups and their associated Pu(V) sites.