物理化学学报

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Eu(III)在蒙脱石上的吸附及碳酸根和磷酸根对其吸附的影响

常明凯, 胡娜, 李遥, 鲜东帆, 周万强, 王静一, 时燕琳, 刘春立   

  1. 北京大学化学与分子工程学院, 放射化学与辐射化学重点学科实验室, 北京分子科学国家研究中心, 北京 100871
  • 收稿日期:2020-03-13 修回日期:2020-04-16 录用日期:2020-04-17 发布日期:2020-04-27
  • 通讯作者: 刘春立 E-mail:liucl@pku.edu.cn
  • 基金资助:
    国家自然科学基金(U1730245,U1530112,11475008)资助项目

Sorption of Eu(III) on Montmorillonite and Effects of Carbonate and Phosphate on Its Sorption

Mingkai Chang, Na Hu, Yao Li, Dongfan Xian, Wanqiang Zhou, Jingyi Wang, Yanlin Shi, Chunli Liu   

  1. Beijing National Laboratory for Molecular Sciences, Fundamental Science Laboratory on Radiochemistry & Radiation Chemistry, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. China
  • Received:2020-03-13 Revised:2020-04-16 Accepted:2020-04-17 Published:2020-04-27
  • Supported by:
    The project was supported by the National Natural Science Foundation of China (U1730245, U1530112, 11475008).

摘要: 锕系核素在处置库围岩和缓冲回填材料中的吸附和迁移参数是处置库安全评价的重要数据模块之一,而Eu(III)由于其与三价锕系元素An(III)相似的离子半径和化学性质常被用于模拟三价锕系元素的化学行为。本文通过批式吸附实验研究了固液比、接触时间、离子强度、pH、碳酸根及磷酸根等对Eu(III)在蒙脱石上吸附的影响,重点关注了吸附机理和表面种态。研究结果表明,低pH时Eu(III)在蒙脱石上的吸附方式为外层配位吸附,近中性时为内层配位吸附,高pH时则以表面沉淀的方式被吸附。离子强度的增大对Eu(III)在低pH时的吸附产生抑制作用。低pH时碳酸根对Eu(III)吸附的影响不明显,但在高pH时其会改变Eu(III)的表面吸附种态。尽管磷酸根本身的吸附非常弱,但磷酸根会显著增强Eu(III)的吸附。X射线光电子能谱结果和磷酸根吸附实验说明Eu(III)在蒙脱石表面上形成了EuPO4沉淀。本工作研究了蒙脱石/Eu(III)二元体系和蒙脱石/Eu(III)/阴离子三元体系的吸附行为,并用光谱技术探究了其吸附种态,为理解三价锕系核素在蒙脱石上的吸附行为提供了重要参考。

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

MSC2000: 

  • O647