北山花岗岩断层充填物胶体的稳定性及其对Pu()的吸附

Stability of Beishan Granite Fault Gouge Material Colloids and Their Adsorption of Pu()

  • 摘要: 在地下水长期侵蚀作用下,花岗岩断层带裂隙中的充填物会发生溶解并形成胶体。该类胶体通常粒径小、表面带负电荷,易吸附阳离子型放射性核素,从而提高放射性核素在地下水环境中的迁移能力。本文分别采用胶体团聚动力学实验和批式吸附实验,探究了不同环境条件下,花岗岩断层充填物胶体的稳定性,以及Pu(Ⅴ)在该胶体表面的吸附动力学行为。团聚动力学实验结果表明,pH对胶体的稳定性影响较小,而阳离子种类和浓度对胶体的稳定性影响较大。在NaCl和CaCl2溶液体系中,胶体的临界团聚浓度分别为5.01×10−3、4.90×10−4 mol/L,说明Ca2+对胶体的团聚作用强于Na+。吸附动力学实验结果表明,胶体对Pu(Ⅴ)的吸附作用较强,40 h左右即可达到平衡。动力学模型拟合结果表明,Pu(Ⅴ)在胶体表面的吸附过程符合准二级动力学模型,属于化学吸附,其吸附效果与体系中Pu(Ⅴ)的赋存形态、浓度和体系的pH有关。

     

    Abstract: Colloids are heterogeneous systems consisting of finely dispersed phase suspended in a continuous phase, with particle sizes ranging from 1 nm to 1 000 nm. In the near-field environment of the deep geological disposal repository, colloid generation occurs through several pathways including hydrolysis of multivalent radionuclides in solidified waste forms, the dissolution of corrosion products in packaging containers, and the geochemical alteration at the interfaces of buffer/backfill materials. In the far-field environment, colloids are primarily formed through the dissolution of fracture-filling materials in the host rock, resulting in the generation of silicate and carbonate colloids. In China, granite is selected as the host rock type for the deep geological disposal repository. Due to tectonic activities, some granite regions develop extensive fracture networks and fragmentation zones, which are known as granite fault gouge. Under the long-term erosion of groundwater, the fault gouge material can dissolve and form fault gouge material colloids. The colloidal particle size of the fault gouge material colloids is small and the surface is negatively charged. Therefore, it easily adsorbs radionuclides and facilitates their migration. The stability of granite fault gouge material colloids under different environmental conditions and the adsorption kinetics of Pu(Ⅴ) on fault gouge material colloids were investigated in this paper by aggregation kinetics experiments and batch adsorption experiments, respectively. The mass concentration of granite fault gouge material colloids is 437 mg/L, which can be stable for 30 d in pure water system. The results of the aggregation kinetics experiments indicate that pH has a minor influence on the stability of the granite fault gouge material colloids, whereas the type and concentration of cations significantly affect colloidal stability. Two kinetics processes of aggregation of granite fault gouge material colloids are consistent with the DLVO (Derjaguin Landan Verwey Overbeek Theory) theory, including the reaction-limited aggregation stage and the diffusion-limited aggregation stage. The critical coagulation concentrations (CCC) of the colloids in NaCl and CaCl2 solution systems are determined to be 5.01×10−3 mol/L and 4.90×10−4 mol/L, respectively, demonstrating that Ca2+ induces markedly more pronounced aggregation of the fault gouge material colloids compared to Na+. The adsorption kinetics experiments reveal that the granite fault gouge material colloids exhibit strong adsorption affinity for Pu(Ⅴ), reaching adsorption equilibrium within approximately 40 h. The adsorption process of Pu(Ⅴ) on the granite fault gouge material colloids follows pseudo-second-order kinetics. This process is dependent on the concentrations of plutonium and colloids and may involve other interactions such as ion exchange and surface complexation.

     

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