Impact of Fe(II) on 99Tc diffusion behavior in illite

Abstract

A comprehensive understanding of the geochemical behavior of 99Tc is of great importance for safe disposal of radioactive waste and remediation of contaminated environmental sites. Illite is one of the most common constituents of clay rocks, and thus used in this work as a model system for studying the retention and transport of 99Tc in clay-rich systems. In this study, a through-diffusion technique was applied to investigate the diffusion behavior of Tc in compacted illite clay under oxic and anoxic conditions. Particular focus of this investigation was on the role of Fe(II) on the redox state and mobility of Tc in clay. As the diffusion cells contained stainless steel filters for confining the clay plug, 99Tc-diffusion in the filters was assessed first, followed by 99Tc diffusion in the illite column with or without Fe-loading. Two types of Fe(II) loadings in illite were considered, surface complexed Fe(II) on illite edge sites and Fe(II) added as pyrite grains. COMSOL Multiphysics was used to analyze the diffusion data. The measured filter porosity was about 0.2 and the effective diffusion coefficient, De, for Tc (as TcO4−) in the filter was 0.59 × 10−10 m2/s. Tc diffusion in illite under ambient conditions showed a typical anion diffusion behavior with De in the range 0.38-0.44 × 10−10 m2/s and the anion accessible porosity ε of approximately 0.2. In the presence of Fe(II), De for Tc migration in illite was one order of magnitude lower, showing that Fe(II) has a significant effect on the migration of 99Tc. Analysis of the Tc distribution in the system suggests that most Tc was retarded at the filters, especially the ones connected to the high concentration reservoir. The remaining Tc quantities were immobilized at sample boundaries next to the filters with higher concentrations observed in the domains close to the reservoirs. Almost no Tc was immobilized in the middle part of the sample, where the Fe(II) was preloaded. This observation contradicts the anticipation, because Tc was expected to be immobilized in the middle of the sample preloaded with Fe(II). A possible explanation is that a delocalized redox reaction may occur, which means that electrons from the oxidation of the preloaded Fe(II) in the central part of the cell are transferred to the filter via the walls of the steel diffusion cell. Tc reacts with the electrons in the filter at a relative slow rate, which results in most of the Tc retarded in the filter, while some small amounts of it may diffuse through the clay.