Actinide speciation in glass leach-layers: An EXAFS study

Uranium L{sub 3} X-ray absorption data were obtained from two borosilicate glasses, which are considered as models for radioactive wasteforms, both before and after leaching. Surface sensitivity to uranium speciation was attained by a novel application of simultaneous fluorescence and electron-yield detection. Changes in speciation are clearly discernible, from U(VI) in the bulk to (UO{sub 2}){sup 2+}-uranyl in the leach layer. The leach-layer uranium concentration variations with leaching times are also determined from the data

DETERMINATION OF STRUCTURE AND VALENCE IN VANADIUM BRONZE BY X-RAY ABSORPTION SPECTROSCOPY

We used XANES to determine coordination geometry and charge state in a series of mixed valence vanadium bronzes, NaXV2O5 where x = 0.25, 0.40, and 0.75. Simple chemical arguments suggest that each additional positive charge added to the V205 lattice will switch one V5+ to V4+. Our results sugaest that this is generally true. The energy position and splitting of the V K-edge prepeak, 1s-to-3d, was a sensitive indicator of V valence(s). The intensity of the brepeak decreased as the first neighbor bonds increased in length

Investigation of annealed and metamict pyrochlore minerals by x-ray absorption spectroscopy. [Synthetic pyrochlores with general formula (RE)/sub 2/Ti/sub 2/O/sub 7/, RE = Er, Y/sub 2/, Gd/sub 2/, Dy, La]

Materials of the pyrochlore structure type exhibit a variety of interesting properties including phases capable of acting as hosts for actinides in radioactive wastes. Studies of curium doped gadolinium titanate phases (Gd/sub 2/Ti/sub 2/O/sub 7/) have been made which showed that the radiation damage ingrowth followed an exponential relationship. For the study reported here a series of synthetic pyrochlores were produced having the titanate phase with the general formula (RE)/sub 2/Ti/sub 2/O/sub 7/, RE = Er, Y/sub 2/, Gd/sub 2/, Dy, La. Additionally a set of metamict (radiation damaged) pyrochlores was examined in both a natural and post temperature annealed state. Experiments were conducted on these samples using the Extended X-ray Absorption Fine Structure (EXAFS) and X-ray Absorption Near Edge Structure (XANES) techniques. In summary, these studies show that in pyrochlore structure types the Ti-O cage undergoes changes due to radiation damage. The individual Ti-O bonds become more disordered which leads to a loss of short and long range order and, ultimately, to expansion of the bulk material. 2 refs., 2 figs