Np-237 sorption onto montmorillonite and corundum


Np-237 sorption onto montmorillonite and corundum

Elo, O.; Huittinen, N.; Müller, K.; Heim, K.; Hölttä, P.; Lehto, J.

The bentonite buffer in Engineered Barrier Systems (EBS), planned for spent nuclear fuel (SNF) repositories, consists mainly of the clay mineral montmorillonite. Montmorillonite and other aluminosilicates are known to retain radionuclides found in the SNF, thus, contributing to the retention or immobilization of these metal ions in the environment. The neptunyl cation, NpO2+, is rather soluble, poorly sorbed, and readily mobile under environmental conditions making it highly relevant for research concerning SNF repository safety. In the present study we have investigated the sorption of neptunium on the clay mineral montmorillonite under carbonate free, but environmentally relevant conditions. The interaction of neptunium with α-Al2O3 (corundum) has also been investigated in order to study the aluminol surface sites present on clay minerals, which are regarded as the main adsorption sites for radionuclide attachment. We have performed batch sorption studies both as a function of pH and as a function of neptunium concentration 5×10-10 M-5×10-6 M. The NpO2+ uptake on the two different minerals is rather weak. Sorption on the mineral surfaces begins at pH 7, and at pH 8 which is the pH-value expected to prevail in the deep underground in Olkiluoto, Finland, the final disposal site for the Finnish SNF, only ~ 10% of the actinyl ion is retained. To gain insight into the surface speciation of neptunium on the two minerals, we performed in situ ATR-FT-IR spectroscopic investigations at pH 9 and 10. Upon NpO2+ sorption onto corundum and montmorillonite we observe a shift of the antisymmetric stretch vibration of the neptunyl ion from 818 cm-1 obtained for the free aquo ion to 790 cm-1. The large shift of the asymmetric stretch vibration indicates the formation of an inner-sphere bound neptunium com-plex on the mineral surface. A similar shift has previously been observed by Gückel et al. (2013) for NpO2+ sorption onto gibbsite (α-Al(OH)3). In contrast to the results obtained in Gückel et al., where neptunium desorption could not be observed after flushing the mineral film on the ATR crystal, we see a high reversibility of the sorption on both corundum and montmorillonite. This high reversibility of the sorption process speaks for a weaker bonding to the surface. In upcoming EXAFS (Extended X-ray Absorption Fine Structure) measurements, we hope to be able to find an explanation for the deviating desporption behaviour of NpO2+ on montmorillonite and corundum in comparison to gibbsite. In addition, information on structural parameters and the complexation mechanism of neptunium sorption onto montmorillonite and corundum will be obtained.

Keywords: neptunium; sorption; in situ ATR-FT-IR; montmorillonite; corundum

  • Poster
    Advanced Techniques in Actinide Spectroscopy 2014 (ATAS 2014), 03.-07.11.2014, Dresden, Germany

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Publ.-Id: 21176