AMERICIUM CO-PRECIPITATION WITH THE SMECTITE HECTORITE: POWDER AND POLARIZED EXAFS INSIGHTS

 

N. Finck1,2, K. Dardenne1

 

1 Institute for Nuclear Waste Disposal (INE), Karlsruhe Institute of Technology, Campus North, P.O. Box 3640, D-76021 Karlsruhe, Germany. (Correspondence: Nicolas.finck@kit.edu)

2 Helmholtz Virtual Institute “Advanced Solid-Aqueous RadioGeochemistry”, Germany.

 

KEYWORDS: Actinides, Smectite, EXAFS

 

Clay minerals are major sorbing solids in deep nuclear waste repositories. They may also form as secondary phase upon alteration of the waste matrix over geological time scale in the presence of ground water. The precipitation of such alteration phases, like hectorite for example [1], represents a significant retention potential for radionuclides, including actinides (An) [2]. The immobilization of An(III) may occur by surface adsorption and by incorporation in the bulk structure. Recent investigations [3] showed the possibility to incorporate Lu(III) in octahedral sites of hectorite by co-precipitation.

Hectorite was co-precipitated in presence of Am(III). After characterization of the bulk structure (XRD) of the Am(III)-containing samples associated with the synthesis protocol [3,4], the Am(III) local chemical environment was probed by X-ray absorption spectroscopy. In the precursor phase (brucite) prepared as oriented sample, powder EXAFS data point to Am(III) located in an octahedral environment and polarized EXAFS data suggest an anisotropic environment around Am and thus a structural association with the solid phase. Powder EXAFS data indicate that Am(III) is six-fold coordinated by oxygen in the doped hectorite and the detection of next nearest Mg/Si backscatterers strongly corroborate with a clay-related environment. In contrast, higher number of oxygen backscatterers were detected for surface adsorbed Am(III), as well as lower number of Mg/Si neighbors.

 

[1] H.U. Zwicky, et al., Mater. Res. Soc. Symp. Proc. 127, 129-136 (1989).

[2] J.I. Kim, et al., Engineer. Geol. 52, 221-230 (1999).

[3] N. Finck, et al., Environ. Sci. Technol. 43, 8807-8812 (2009).

[4] K.A. Carrado, et al., Clay. Miner. 32, 29-40 (1997).