Co2+和Zn2+在致密同位态伊利石中的扩散和保留:双电层的作用

IF 3.1 3区 地球科学 Q1 GEOCHEMISTRY & GEOPHYSICS
Dimitra Zerva , Martin A. Glaus , John L. Provis , Sergey V. Churakov
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引用次数: 0

摘要

阳离子物质的表面扩散经常被用来解释在压实的粘土矿物和粘土岩中的扩散研究结果。然而,这一过程的潜在机制尚不清楚,控制扩散通量的因素尚未得到满意的量化。在本研究中,研究了离子特异性分子相互作用在粘土矿物-流体界面形成的双电层中的作用,特别是它们对57Co2+和65Zn2+示踪剂扩散输运的影响。为此,在压实伊利石中以Li+, Na+, K+和Cs+形式进行了不同背景电解质浓度的扩散实验。该系列碱阳离子水化焓降低(ΔHhyd),有效水化离子半径增大。扩散数据采用“两个位点的非静电表面络合/电双层”(2SPNE SC/EDL)模型进行解释。用有效扩散系数De和吸附分布系数Rd比较了57Co2+和65Zn2+在不同背景电解质浓度和同离子型伊利石中的扩散和吸附行为,用表面扩散比(φ)评价了表面扩散的程度。结果表明,ΔHhyd离子是控制表面电荷中和的关键因素,从而控制矿物表面扩散层和宏观孔隙中块状水之间的流动物质分布。虽然65Zn2+的Rd值高于57Co2+,但表面扩散现象与本研究的两种示踪剂同样相关。对于0.03 M和0.1 M背景电解质,φ服从Li≈Na>;K>;Cs的顺序,而在0.5 M电解质溶液中,大多数同位形式的表面扩散的贡献可以忽略不计。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Diffusion and retention of Co2+ and Zn2+ in compacted homocationic forms of illite: Role of the electrical double layer

Diffusion and retention of Co2+ and Zn2+ in compacted homocationic forms of illite: Role of the electrical double layer
Surface diffusion of cationic species has frequently been postulated to explain the results of diffusion studies in compacted clay minerals and clay rocks. However, the underlying mechanism of this process is not well understood, and the factors controlling the diffusive flux are not yet satisfactorily quantified. In this study, the role of ion-specific molecular interactions in the electric double layer formed at the clay mineral-fluid interface is investigated, particularly their effect on the diffusive transport of 57Co2+ and 65Zn2+ tracers. To this end, in-diffusion experiments were conducted at different background electrolyte concentrations in compacted illite with Li+, Na+, K+ and Cs+ forms. The alkali cations in this series have decreasing hydration enthalpy (ΔHhyd) and an increasing effective hydrated ion radius. The diffusion data were interpreted using the “two site protolysis non electrostatic surface complexation/electrical double layer” (2SPNE SC/EDL) model. The diffusion and sorption behaviour of 57Co2+ and 65Zn2+ in various background electrolyte concentrations and homoionic forms of illite was compared in terms of the effective diffusion coefficient De and the sorption distribution coefficient Rd. The extent of surface diffusion was assessed via surface diffusion ratio (φ). The results suggest that ΔHhyd of ions is a critical factor controlling surface charge neutralisation, and consequently the distribution of the mobile species between the diffuse layer near the mineral surface and the bulk-like water in macroscopic pores. Although 65Zn2+ has higher Rd values compared to 57Co2+, the surface diffusion phenomenon is equally relevant for both tracers studied in this work. For the 0.03 M and 0.1 M background electrolytes, φ follows the order LiNa>K>Cs, while in 0.5 M electrolyte solution the contribution of surface diffusion is negligible in most of the homocationic forms.
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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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