The oxygen concentration and inherent Fe in bentonite have a significant influence on the Se(IV) sorption process.In this study,the sorption of selenite on natural bentonite was investigated using a batch experiment method,and the distribution coefficient(K_d)values were obtained in the pH range from 2.0 to 10.0 under oxic/anoxic conditions.The K_d values always reached a maximum value at a pH of 4 under oxic conditions and at a pH of 8 under anoxic conditions;meanwhile,the K_d value under anoxic conditions was larger than the value under oxic conditions,especially in regard to the maximum K_d values.The oxygen conditions have a significant influence on the ratio of redox-sensitive Fe^(2+)/Fe^(3+),which was closely related to the difference in the K_d values under both oxic/anoxic conditions.Ferric selenite and green rust could be responsible for the maximum K_d values under oxic/anoxic conditions.In the leaching experiments,we found that the Fe^(2+) in bentonite could replace Mg^(2+) and Al^(3+) in the octahedral sheet.Spectroscopy methods,such as Fourier transform infrared spectroscopy(FTIR),X-ray diffraction(XRD) and X-ray absorption spectroscopy(XAS) were used to characterize the surface properties of the samples after reaction.Overall,this study shows that the addition of Fe^(2+)-containing materials into backfill/buffer materials under anoxic condition could enhance the sorption of ^(79)Se(IV).
Jiangang HeXueling QiaoYanlin ShiYao LiXiaoyu YangWanqiang ZhouChunli Liu
The mobility and bioavailability of selenium is a major health and environmental issue and a main concern for geological disposal of high-level radioactive waste. Chemically and/or microbially mediated oxidation of insoluble Se-bearing particulate, such as iron selenides, to dissolved and mobile phases controls the transport and distribution of Se in the environment. The oxidation of ferroselite(FeSe2) by ferric iron was investigated in anoxic conditions. The redox reaction can be represented by: FeSe2 + 2Fe3+ = 2Se0 + 3Fe2+. Kinetic studies indicated that the reaction can be described by second-order rate law, with rate constants of 0.49±0.01, 0.85±0.02, 1.84±0.04, and 3.29±0.13 L mol-1 s-1 at pH 1.62, 1.87, 2.23, and 2.49, respectively. The positive correlation between reaction rate and pH implies that diffusion of Fe3+ oxidant to the mineral surface is the rate-determining step. The strong reactivity of FeSe2 towards Fe3+ suggests that ferric iron may play a significant role in FeSe2 oxidation process(e.g., by Se4+, O2, etc.) and Se0 should be the first reaction product. Also, it was shown that the reduction rate of Fe3+ or Se4+ by pyrite(FeS2) can be significantly increased in the presence of FeSe2, suggesting a stronger reactivity of FeSe2 compared with pyrite. The results obtained extend our knowledge about the subtle interaction between Se, pyrite and iron selenides in the environment, and give insight into the transfer of selenium from iron selenides to bio-available selenium(i.e., selenite and selenate) in the Se-rich environment.
MA BinNIE ZheLIU ChunLiKANG MingLiangBARDELLI FabrizioCHEN FanRongCHARLET Laurent
