Apparent diffusion coefficients and chemical species of neptunium (V) in compacted Na-montmorillonite

Abstract

Diffusion of neptunium (V) in compacted Na-montmorillonite was studied through the non-steady state diffusion method. In this study, two experimental attempts were carried out to understand the diffusion mechanism of neptunium. One was to establish the diffusion activation energy, which was then used to determine the diffusion process in the montmorillonite. The other was the measurement of the distribution of neptunium in the montmorillonite by a sequential batch extraction. The apparent diffusion coefficients of neptunium in the montmorillonite at a dry density of 1.0 Mg m −3 were from 3.7×10 −12 m 2 s −1 at 288 K to 9.2×10 −12 m 2 s −1 at 323 K. At a dry density of 1.6 Mg m −3, the apparent diffusion coefficients ranged between 1.5×10 −13 m 2 s −1 at 288 K and 8.7×10 −13 m 2 s −1 at 323 K. The activation energy for the diffusion of neptunium at a dry density of 1.0 Mg m −3 was 17.5±1.9 kJ mol −1. This value is similar to those reported for diffusion of other ions in free water, e.g., 18.4 and 17.4 kJ mol −1 for Na + and Cl −, respectively. At a dry density of 1.6 Mg·m −3, the activation energy was 39.8±1.9 kJ mol −1. The change in the activation energy suggests that the diffusion process changes depending on the dry density of the compacted montmorillonite. A characteristic distribution profile was obtained by the sequential extraction procedure for neptunium diffused in compacted montmorillonite. The estimated fraction of neptunium in the pore water was between 3% and 11% at a dry density of 1.6 Mg m −3 and at a temperature of 313 K. The major fraction of the neptunium in the montmorillonite was identified as neptunyl ions sorbed on the outer surface of the montmorillonite. These findings suggested that the activation energy for diffusion and the distribution profile of the involved nuclides could become powerful parameters in understanding the diffusion mechanism.