Adsorption behavior of Se(IV) in calcium-based (natural) bentonite and sodium-based (engineered modified) bentonite

Cong Huang, Qiang Zhao, Wei Zhao, Xuebin Su, Rong Hua
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Abstract

Abstract Bentonite plays a significant role as a buffer backfill material in geological disposal due to its unique properties that are crucial for the safe containment of high-level radioactive waste. In this work, the impact of various factors on the adsorption of selenite (Se(IV)) by both calcium-based and sodium-based bentonite was examined using batch experiments. As a result, both types of bentonite achieve adsorption equilibrium with Se(IV) within approximately 120 h. The adsorption capacity decreases with increasing initial concentration of Se(IV), while it is positively influenced by longer contact times and higher temperatures. The partition coefficient ( K d ) exhibits a complex relationship with pH, initially decreasing, then increasing, and finally decreasing again. Additionally, ionic strength significantly affects the adsorption process. These observations suggest that Se(IV) adsorption on bentonite is pH-dependent and involves a non-spontaneous heat-absorbing process, likely a chemical reaction dominated by the ion-exchange form of chemisorption in a monomolecular layer. This process aligns well with the isothermal adsorption model and the simulated secondary kinetics of the Langmuir model. Furthermore, the adsorption of Se(IV) is notably hindered by the increased electrostatic repulsion between the negatively charged bentonite surface and the negatively charged species HSeO 3 2− and SeO 3 2− . The Fourier transform infrared spectra showed that the positions, intensities and shapes of the spectral characteristic peaks of the functional groups before and after adsorption did not change significantly.
钙基(天然)膨润土和钠基(工程改性)膨润土对硒(IV)的吸附行为
摘要膨润土作为缓冲回填材料在地质处置中发挥着重要作用,其独特的性能对高放射性废物的安全封存至关重要。通过批量实验考察了钙基膨润土和钠基膨润土对亚硒酸盐(Se(IV))吸附的影响因素。结果表明,两种膨润土均在约120 h内达到对Se(IV)的吸附平衡。随着Se(IV)初始浓度的增加,吸附量减小,而接触时间的延长和温度的升高对吸附量有正向影响。分配系数(kd)与pH呈先减小后增大,再减小的复杂关系。此外,离子强度显著影响吸附过程。这些观察结果表明,硒(IV)在膨润土上的吸附是ph依赖的,涉及一个非自发的吸热过程,可能是一个以单分子层中离子交换形式的化学吸附为主的化学反应。该过程符合等温吸附模型和Langmuir模型模拟的二次动力学。此外,带负电荷的膨润土表面与带负电荷的物质HSeO 32 -和SeO 32 -之间静电斥力的增加明显阻碍了Se(IV)的吸附。傅里叶变换红外光谱表明,吸附前后官能团光谱特征峰的位置、强度和形状没有明显变化。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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