Adsorption of cesium and strontium on mesoporous silicas.

Studies are underway on the adsorption reactions of metal ions in confined spaces at the solid-water interface, but it is unclear how the effects of confinement differ for different types of ions. We investigated the effect of the pore size on the adsorption of two cations with different valence, Cs+ and Sr2+, on mesoporous silicas with different pore size distributions. The amount of Sr2+ adsorbed per unit surface area did not differ significantly among the silicas, whereas that of Cs+ was particularly high for silicas with a larger fraction of micropores. The results of X-ray absorption fine structure analysis showed that both ions form outer-sphere complexes with the mesoporous silicas. The results of adsorption experiments were analyzed by fitting using a surface complexation model with the cylindrical Poisson-Boltzmann equation and optimized capacitance of the Stern layer for different pore sizes, and we found that the intrinsic equilibrium constant for the adsorption of Sr2+ is constant regardless of the pore size, whereas that of Cs+ increases as the pore size decreases. The decrease in the relative permittivity of water inside pores with a decrease of the pore size can be interpreted to cause a change in the hydration energy of Cs+ in the second coordination sphere upon adsorption. The reasons for the different confinement effects on the adsorption reactions of Cs+ and Sr2+ were discussed based on the distance of the adsorbed ions from the surface and the chaotropic and kosmotropic nature of Cs+ and Sr2+, respectively.

Pore size effects on surface charges and interfacial electrostatics of mesoporous silicas.

Water in confinement becomes more structured than bulk water, and its properties, such as the dielectric constant, change. It remains unclear, however, how the interfacial reactions in confinement, such as the adsorption of ions on the surfaces of small pores, differ from those in larger spaces. We focused on the deprotonation reaction of hydroxyl groups, a fundamental surface reaction, and investigated the dependence of the surface charge density on pore size by determining the surface charge densities of six types of mesoporous silicas with micropores and mesopores at different ionic strengths and pH levels from batch titration tests. The surface complexation model assuming a potential distribution based on the Poisson-Boltzmann equation in cylindrical coordinates was fitted to the obtained surface charge densities to relate the electrostatics near the surface to the surface reaction. The results showed that the absolute values of the surface charge densities decreased with decreasing pore diameter due to the overlap of the electrical double layers. Furthermore, the capacitance of the Stern layer optimized by fitting decreased with decreasing pore diameter, especially in pores smaller than 4 nm in diameter, which suggested that the dielectric constants of water decreased near the surfaces of small pores.

Desorption kinetics of cesium from Fukushima soils.

Understanding the behaviors of Cs(+) in soils is crucial for evaluation of the impacts of disposal of soils contaminated by radiocesium, (137)Cs. The desorption rate of Cs(+) evaluated in relatively short periods of time may not be adequate for such a purpose. In this study, we investigated long-term desorption kinetics of (137)Cs and (133)Cs from soils collected in Fukushima Prefecture by batch desorption experiments in the presence of cation exchange resin as a sorbent. The sorbent can keep the concentration of Cs(+) in the aqueous phase low and prevent re-sorption of desorbed Cs(+). Up to 60% of (137)Cs was desorbed after 139 d in dilute KCl media, which was larger than the desorption by conventional short-term extraction with 1 M ammonium acetate. Desorption of (137)Cs continued even after this period. It was also found that high concentration of K(+) prevented desorption of Cs(+) in the initial stage of desorption, but the effect was alleviated with time. The desorbed fraction of stable Cs was smaller than that of (137)Cs. This indicated that (137)Cs may gradually move to more stable states in soils. The half-life of (137)Cs desorption from the slowest sorption site was estimated to be at least two years by a three-site desorption model.