Pu和Tc在北山新场花岗岩及其裂隙填充物中的扩散行为

    Diffusion Behavior of Pu and Tc in Beishan Xinchang Granite and Its Fissure Filling

    • 摘要: 为评估我国高放废物深地质处置库预选区场址的长期安全性,针对我国北山预选区新场花岗岩及其裂隙填充物,系统开展了关键放射性核素238Pu和99Tc的扩散行为实验。通过恒定源贯穿扩散法测定了低氧条件下核素在北山新场花岗岩完整样片及北山新场花岗岩裂隙填充物中的有效扩散系数(De),结果显示:对于北山新场花岗岩完整样片和北山新场花岗岩裂隙填充物,有效扩散系数的大小顺序均为:De(HTO)>De(Tc)>De(Pu);由于北山新场花岗岩完整样片的致密度远大于其裂隙填充物的致密度,导致HTO、238Pu和99Tc在北山新场花岗岩完整样片中的有效扩散系数远小于其在裂隙填充物中的有效扩散系数。本研究证实,相对HTO而言,北山新场花岗岩及其裂隙物均对238Pu和99Tc的迁移具有一定程度上的阻滞效果,但对Pu效果更显著,可能是Pu与这两种介质存在更复杂的吸附反应。值得注意的是,花岗岩完整岩片对某些核素可能不能简单当作均匀介质对待,其中可能存在优势通道,不利于核素的阻滞。

       

      Abstract: The present study aims to systematically evaluate the barrier performance of the Xinchang granite and its fracture system in Beishan candidate area of China’s high-level radioactive waste(HLRW) deep geological disposal repository against key radionuclides. By adopting the internationally recognized constant-source through-diffusion experimental method, migration parameters of HTO(as a reference tracer) and two key radionuclides, 238Pu and 99Tc, were determined in both media under strictly controlled low-oxygen experimental conditions(O2 concentration<1×10−6). The experimental results show that effective diffusion coefficients present obvious variability in the intact Xinchang granite samples: De(HTO)=(2.1±0.0)×10−13 m2/s>De(Tc)=(5.3±2.1)×10−14 m2/s>De(Pu)=(2.5±0.5)×10−14 m2/s. This suggests that, compared to HTO, a neutral molecule, \mathrmTcO_4^- anions and Pu(Ⅳ) colloids/ions are more strongly retarded. Notably, the diffusion coefficients increase significantly in the fracture infill, as demonstrated by: De(HTO)=(3.9±0.3)×10−10 m2/s>De(Tc)=(2.9±0.3)×10−10 m2/s>De(Pu)=(1.1±0.4)×10−12 m2/s. Comparative analysis reveals that the diffusion coefficients in granite are on average 2-3 orders of magnitude lower than those in fracture infill. This mainly results from the much higher porosity in fracture infill, as it is not compacted in the diffusion column. This, in turn, directly confirms the critical controlling role of rock mass integrity on nuclide migration. Compared with HTO, both intact granite and fracture filling materials show some retardation effect on Pu and Tc migration, especially Pu, which may indicate that more complex reaction exist to immobilize Pu. It is particularly worrying that under the low oxygen conditions, 238Pu mainly exists in the form of Pu(OH)4 colloids, and its effective diffusion coefficient decreases by about 2 orders magnitude compared to HTO, indicating its extremely strong retention in the granite system. Although 99Tc migrated as \mathrmTcO_4^- anions, part of 99Tc(Ⅶ) may be reduced to less soluble 99Tc(Ⅳ) by the reductive effect of iron minerals in Beishan granite. This study confirms through systematic diffusion experiments that the Xinchang New Field granite system has significant natural retardation for key radionuclides especially the intact granite section, which constitutes an effective barrier for nuclide migration. These experimental data provide important baseline parameters for the safety assessment of China’s HLRW disposal repository and also provide a scientific basis for the optimization of engineering barrier design for the repository. It is recommended that the migration behavior of radionuclides under the coupling action of temperature-stress-chemical field should be further considered in subsequent research to more comprehensively evaluate the long-term safety of the disposal system.

       

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