Uptake of Eu(III) by C-S-H phases in CaCl2 solution in presence of EDTA: A molecular dynamics study

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry Pub Date : 2025-04-29 DOI:10.1016/j.comptc.2025.115271

Iuliia Androniuk, Aline K. Thumm, Andrej Skerencak-Frech, Marcus Altmaier, Xavier Gaona

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Abstract

The presence of organic ligands in radioactive waste influences radionuclide mobility and sorption in cement. Although EDTA is often assumed to have minimal impact, recent experiments indicate reduced Eu(III)/Cm(III) uptake by calcium silicate hydrate (C-S-H) at high EDTA concentrations in CaCl₂ solutions. We used molecular dynamics (MD) simulations and potential of mean force calculations to investigate complexation and sorption mechanisms. Focusing on the (001) surface of C-S-H, we analyzed radionuclide behavior in the presence of organic ligands under repository-relevant conditions. Solution-phase simulations identified three probable Eu/EDTA/Ca complexes. Sorption at two common sites was examined. Site-specific analysis shows that Ca–Eu(III)–EDTA complexes remain stable in solution, significantly reducing Eu(III) uptake by C-S-H. These findings align with experiments and highlight the role of ternary complex formation in limiting radionuclide retention in cementitious environments.

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EDTA存在下CaCl2溶液中C-S-H相对Eu（III）的吸收：分子动力学研究

放射性废物中有机配体的存在影响放射性核素在水泥中的迁移和吸附。虽然EDTA通常被认为影响很小，但最近的实验表明，在高EDTA浓度的氯化钙溶液中，水合硅酸钙（C-S-H）对Eu(III)/Cm（III）的吸收减少。我们使用分子动力学（MD）模拟和平均力势能计算来研究络合和吸附机理。重点关注C-S-H的（001）表面，我们分析了有机配体存在下放射性核素在储存库相关条件下的行为。溶液相模拟确定了三种可能的Eu/EDTA/Ca配合物。研究了两个共同位置的吸附。位点特异性分析表明，Ca-Eu (III) -EDTA配合物在溶液中保持稳定，显著降低了C-S-H对Eu（III）的吸收。这些发现与实验一致，并突出了三元配合物形成在限制胶结环境中放射性核素保留中的作用。

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来源期刊

Computational and Theoretical Chemistry CHEMISTRY, PHYSICAL-

CiteScore

4.20

自引率

10.70%

发文量

331

审稿时长

31 days

期刊介绍： Computational and Theoretical Chemistry publishes high quality, original reports of significance in computational and theoretical chemistry including those that deal with problems of structure, properties, energetics, weak interactions, reaction mechanisms, catalysis, and reaction rates involving atoms, molecules, clusters, surfaces, and bulk matter.