关键词: 矿物-水界面, 吸附, 荧光, 表面配位, 沉淀

Abstract:

The environmental behaviours of actinides and fission products have been highly concerned due to their potential risks to human beings after entering the body through inhalation or food chains. The chemical reactions of actinides and fission products at mineral-water interface are the most important factors influencing the sorption, diffusion, migration and other processes of actinides and fission products in natural environments. Therefore, it is of great importance to investigate the chemical behaviours of these radioactive elements or nuclides in terms of environmental safety, especially in the area of safety assessment for geological disposal of high level radioactive wastes. However, the chemical behaviours of nuclides at mineral-water interface are complex and the investigations at a molecular level are challenging. To understand the chemical behaviours of trivalent actinides An(Ⅲ) in depth, non-radioactive Eu(Ⅲ) is used as an analogue of An(Ⅲ) due to their similar ionic sizes and chemical characteristics. In this study, batch sorption experiments and spectroscopic characterization methods were used to study the surface sorption species of Eu(Ⅲ) on montmorillonite and possible sorption mechanisms. We studied the effects of solid-liquid ratio, contacting time, ionic strength, pH, carbonate and phosphate on Eu(Ⅲ) sorption on montmorillonite. Our results indicated that the sorption percentage of Eu(Ⅲ) on montmorillonite was low in the range of pH 3.0 to 6.0, and much higher in the range of pH 7.0 to 10.0. The increase of ionic strength inhibited the sorption of Eu(Ⅲ) at low pH values, suggesting that the sorption of Eu(Ⅲ) on montmorillonite was mainly outer-sphere complexation in low pH conditions. Based on the results of fluorescence analysis, we can conclude that the sorption of Eu(Ⅲ) on montmorillonite is mainly outer-sphere complexation in low pH conditions, inner-sphere complexation in neutral pH conditions and surface induced precipitations in high pH conditions. Furthermore, we studied the sorption behaviours of Eu(Ⅲ) not only in montmorillonite/Eu(Ⅲ) binary system but also in montmorillonite/Eu(Ⅲ)/anion ternary system. Our results indicated that carbonate and phosphate could also influence the sorption of Eu(Ⅲ). Carbonate did not have an obvious influence on the sorption amount of Eu(Ⅲ), but it helped to change the surface sorption species of Eu(Ⅲ) on montmorillonite in high pH conditions. As for phosphate, although the sorption of phosphate onto montmorillonite was very weak, it could significantly enhance the sorption of Eu(Ⅲ) on montmorillonite. Because there were no reference data about fluorescence lifetime of Eu(Ⅲ)-phosphate species, we did XPS measurements and phosphate sorption experiments to find out the reason for phosphate enhancing effect. Our results proved that Eu(Ⅲ) precipitated as EuPO₄ on the surface of montmorillonite resulting in the enhancement of Eu(Ⅲ) sorption. This work is expected to provide a deeper understanding of the chemical behaviours of trivalent actinides An(Ⅲ) at mineral-water interface and predict the migration of An(Ⅲ) in the environment.

Key words: Mineral-water interface, Sorption, Fluorescence, Surface complexation, Precipitation