北山花岗岩断层泥对Re()和Se()的吸附行为

    Adsorption of Re() and Se() on Fault Gouge of Beishan Granite

    • 摘要: 花岗岩是我国高放废物深地质处置库的重要候选围岩之一。然而,花岗岩体存在的裂隙和断层可能成为核素随地下水迁移的优势通道,对核素的阻滞产生不利影响。本研究以我国北山地区花岗岩断层填充物(断层泥)为研究对象,采用批式实验方法,探究了Re(Ⅶ)(作为Tc(Ⅶ)的化学类比物)和Se(Ⅳ)的吸附行为,结果表明:断层泥对Re(Ⅶ)和Se(Ⅳ)的吸附受溶液pH影响显著,在溶液pH=7.5时,其对Re(Ⅶ)和Se(Ⅳ)的平衡吸附容量分别为0.320 mg/g和1.07 mg/g;平衡吸附容量随着固液比增大而降低,随着初始浓度升高亦呈现减小趋势;吸附等温线符合Freundlich模型;升温有利于吸附,在本研究实验条件下,吸附过程为自发吸热过程。此外,有机酸(甲酸、草酸、柠檬酸和腐殖酸)的存在可增强Re(Ⅶ)和Se(Ⅳ)的吸附,对Se(Ⅳ)吸附的增强尤为明显;零价铁粉的添加显著提升了Se(Ⅳ)的平衡吸附容量,可能是由于还原固定所致。

       

      Abstract: In the research on geological disposal of high-level radioactive waste, granite is one of the candidate host rocks for deep geological repositories in China. However, the fractures and faults existing in granite bodies may become favorable channels for the migration of nuclides with groundwater, which adversely affects the retention performance of nuclides. To evaluate the retention performance of natural barriers, this study took the fault fillings(fault gouge) in the Beishan area of Gansu Province, China, as the research object and used batch experiments to investigate the adsorption behavior of Re(Ⅶ)(as a chemical analog of Tc(Ⅶ)) and Se(Ⅳ). The results show that the adsorption behavior of Re(Ⅶ) and Se(Ⅳ) by fault gouge is significantly affected by solution pH. At a solution pH of 7.5, the equilibrium adsorption capacity of Re(Ⅶ) and Se(Ⅳ) are 0.320 mg/g and 1.07 mg/g, respectively. The equilibrium adsorption capacity decreases with the increase of solid-liquid ratio and initial concentration. The adsorption process conforms to the Freundlich isothermal adsorption model, indicating that it allows multilayer adsorption. Thermodynamic studies show that increasing temperature favors the adsorption process, which is a spontaneous endothermic process. In addition, the presence of organic acids(formic acid, oxalic acid, citric acid, and humic acid) enhances the adsorption of Re(Ⅶ) and Se(Ⅳ) by fault gouge, with a more significant enhancement effect on Se(Ⅳ). The addition of zero-valent iron powder significantly enhances the equilibrium adsorption capacity of Se(Ⅳ), likely attributable to reductive immobilization.

       

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