氢铝土作为阴离子放射性核素吸附剂的分子动力学模拟

IF 3.1 3区 地球科学 Q1 GEOCHEMISTRY & GEOPHYSICS
Artem A. Glushak , Evgeny V. Tararushkin , Grigory S. Smirnov , Andrey G. Kalinichev
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引用次数: 0

摘要

水云母是富铝水泥的水化产物,在水泥化学中被称为 AFm 相。从结构上看,它属于层状双氢氧化物或 "阴离子粘土",带正电荷的晶体层需要在层间空间存在带负电荷的离子。因此,AFm 相可作为水溶液中阴离子放射性核素(如 35Cl-、125I-、129I-、131I-)的潜在吸附剂。在此,我们使用经典分子动力学模拟来分析含有 Cl- 和 I- 的 AFm 相的结构和性质。经典的 ClayFF 力场用于定量研究阴离子和 H2O 分子在这些相的夹层中及其与 CsCl 和 CsI 水溶液界面上的结构、能量和迁移率。在这项研究中,我们发现 AFm 相的基底 (001) 表面可以强烈吸附水合 Cl- 和 I- 阴离子,这是因为界面羟基提供了氢键,但主要是因为它们对暴露在表面的结构性 Ca 阳离子具有强大的吸引力。然而,我们的模拟结果表明,I- 的吸附力比 Cl- 弱,因此 I- 的混沌效应更强,导致其表面迁移率更高。我们还使用艾林-葡萄园方法研究了 AFm 相中 Cl- 和 I- 阴离子的层间扩散迁移率,结果表明它们明显低于较大纳米孔中的迁移率。因此,此类阴离子放射性核素最有可能通过硬化水泥的纳米孔和微孔进行迁移。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Molecular dynamics simulation of hydrocalumite as adsorbent for anionic radionuclides

Molecular dynamics simulation of hydrocalumite as adsorbent for anionic radionuclides

Hydrocalumite, is a hydration product of aluminum-rich cements, and is known in cement chemistry as an AFm phase. Structurally, it belongs to the family of layered double hydroxides, or “anionic clays”, where positively charged crystal layers require the presence of negatively charged ions in the interlayer space. Therefore, AFm phases can serve as potential adsorbents for anionic radionuclides (e.g., 35Cl, 125I, 129I, 131I) from aqueous solutions. Here we use classical molecular dynamic simulations to analyze the structure and properties of AFm phases containing Cl and I. The classical ClayFF force field is used to quantitatively study the structure, energetics and mobility of anions and H2O molecules in the interlayers of these phases and at their interfaces with CsCl and CsI aqueous solutions. In this study we report that the basal (001) surfaces of AFm phases can strongly adsorb hydrated Cl and I anions due to the donated hydrogen bonds from the interfacial hydroxyls, but primarily due to their strong attraction to the structural Ca cations exposed at the surface. However, our simulations show that the adsorption of I is weaker than that of Cl, leading to the higher surface mobility of I due to its stronger chaotropic effect. The interlayer diffusional mobility of the Cl and I anions in the AFm phases is also investigated by using the Eyring-Vineyard approach and is shown to be significantly lower than in larger nanopores. Hence, the most likely transport of such anionic radionuclides takes place through the nano- and micro-pores of hardened cement.

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来源期刊
Applied Geochemistry
Applied Geochemistry 地学-地球化学与地球物理
CiteScore
6.10
自引率
8.80%
发文量
272
审稿时长
65 days
期刊介绍: Applied Geochemistry is an international journal devoted to publication of original research papers, rapid research communications and selected review papers in geochemistry and urban geochemistry which have some practical application to an aspect of human endeavour, such as the preservation of the environment, health, waste disposal and the search for resources. Papers on applications of inorganic, organic and isotope geochemistry and geochemical processes are therefore welcome provided they meet the main criterion. Spatial and temporal monitoring case studies are only of interest to our international readership if they present new ideas of broad application. Topics covered include: (1) Environmental geochemistry (including natural and anthropogenic aspects, and protection and remediation strategies); (2) Hydrogeochemistry (surface and groundwater); (3) Medical (urban) geochemistry; (4) The search for energy resources (in particular unconventional oil and gas or emerging metal resources); (5) Energy exploitation (in particular geothermal energy and CCS); (6) Upgrading of energy and mineral resources where there is a direct geochemical application; and (7) Waste disposal, including nuclear waste disposal.
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