Quantitative analysis of radiocesium retention onto birnessite and todorokite

Although the Cs adsorption onto soil minerals has been widely studied, the structural factor of Mn oxides affecting the adsorption behavior of trace amounts of Cs is unclear. In order to elucidate the adsorption mechanisms of radioactive Cs at trace levels and the role of Mn oxides on Cs migration in the terrestrial environment, the Cs adsorption onto birnessite and todorokite was investigated for a wide range of concentrations (1 x 10(-10) mol/L to 0.1 mol/L) and an ion-exchange model was used to interpret the adsorption data. Although birnessite showed a higher Cs adsorption capacity than todorokite, most of the Cs adsorbed onto birnessite was desorbed by ion exchange. Two types of adsorption sites were observed for todorokite. Despite low density, the selectivity coefficient was much higher for the T-1 site (Log(Na) K-Cs(sel) = 4.2) than for the T-2 site (LogNa K-Cs(sel)=-0.6). Sequential extraction was carried out at Cs concentrations of 1 x 10(-9) mol/L and 1 x 10(-3) mol/L. At lower concentrations, approximately 34% of the adsorbed Cs was residual in the todorokite after the sequential extraction; this value was much higher than the results for the Cs-adsorbed birnessite as well as the Cs-adsorbed todorokite at higher concentrations. The present results indicate that the structural factors of Mn oxides significantly affect the retention capacity of radioactive Cs. Aside from phyllosilicate minerals, todorokite also contributes to the fixation of radioactive Cs in soils.