99Tc is an important radionuclides related to repository safety assessment. The mobility pertechnetate (TcO4−) can be reduced to immobility technetium(IV) hydrous oxides (TcO2·nH2O) by Fe(II)-bearing minerals. In China, Gaomiaozi (GMZ) bentonite is regarded as the favorable candidate backfilling material
for the HLW repository, which is contained some FeO. The diffusion behavior of 99Tc was investigated in GMZ bentonite by through- and out-diffusion methods. The effective diffusion coefficient (De), the accessible porosity (εacc), apparent diffusion coefficient (Da) and distribution coefficient (Kd) were decreased with the increasing of dry density. The De values were (2.8 ± 0.2) × 10−11 m2/s and (3.5 ± 0.2) × 10−12 m2/s at dry density of 1,600 and 1,800 kg/m3, respectively. It was indicated that the dominating species was TcO4− during the diffusion processing. While, out-diffusion results showed that part of TcO4− may be reduced by Fe(II). The relationship of De and εacc could be described by Archie’s law with exponent n = 2.4 for 99Tc diffusion in GMZ bentonite. Furthermore, the relationship between Da and dry density (ρ) was exponential.