A spectroscopic study of the stability of uranyl-carbonate complexes at 25–150 °C and re-visiting the data available for uranyl-chloride, uranyl-sulfate, and uranyl-hydroxide species

IF 5 1区地球科学 Q1 GEOCHEMISTRY & GEOPHYSICS

Geochimica et Cosmochimica Acta Pub Date : 2025-10-01 DOI:10.1016/j.gca.2024.04.023

A. Migdisov , E. Bastrakov , C. Alcorn , M. Reece , H. Boukhalfa , F.A. Capporuscio , C. Jove-Colon

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Abstract

The stabilities of uranyl-carbonate and uranyl-hydroxide aqueous complexes were experimentally determined at temperatures ranging from 25 to 125 °C using in situ UV–vis and Raman spectroscopic techniques. Combined with earlier determinations of the stability of chloride, sulfate, and hydroxide complexes at temperatures up to 250 °C, these data permit to create a consolidated dataset suitable for modeling of U(VI) mobilization in natural systems. The parameters of the Modified Ryzhenko-Bryzgalin and the Helgeson-Kirkham-Flowers (HKF) Equations of State (EoS) were derived based on this dataset and used for thermodynamic modeling different scenarios of U(VI) mobilization. These models suggest that at conditions relevant to natural systems, carbonate-mediated transport of U(VI) is likely suppressed by the high stability of solid UO₂(OH)₂ and Na₂U₂O₇. In contrast, sulfate-mediated mobilization mechanisms are highly efficient at acidic and near-neutral pH conditions and can lead to effective hydrothermal mobilization of U(VI).

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关于铀酰-碳酸盐络合物在 25-150 °C 温度下稳定性的光谱学研究，以及对铀酰-氯化物、铀酰-硫酸盐和铀酰-氢氧化物的现有数据的再研究

采用原位紫外-可见和拉曼光谱技术，在25 ~ 125℃的温度范围内测定了碳酸铀酰和氢氧化铀酰水溶液配合物的稳定性。结合氯、硫酸盐和氢氧化物配合物在高达250°C温度下的稳定性的早期测定，这些数据允许创建一个适用于自然系统中U（VI）动员建模的统一数据集。在此基础上推导了改进的Ryzhenko-Bryzgalin和Helgeson-Kirkham-Flowers （HKF）状态方程（EoS）的参数，并将其用于不同情景下U（VI）动员的热力学建模。这些模型表明，在与自然系统相关的条件下，固体UO2(OH)2和Na2U2O7的高稳定性可能抑制了碳酸盐介导的U（VI）转运。相比之下，硫酸盐介导的动员机制在酸性和接近中性的pH条件下是高效的，并且可以导致U（VI）的有效水热动员。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Geochimica et Cosmochimica Acta 地学-地球化学与地球物理

CiteScore

9.60

自引率

14.00%

发文量

437

审稿时长

6 months

期刊介绍： Geochimica et Cosmochimica Acta publishes research papers in a wide range of subjects in terrestrial geochemistry, meteoritics, and planetary geochemistry. The scope of the journal includes: 1). Physical chemistry of gases, aqueous solutions, glasses, and crystalline solids 2). Igneous and metamorphic petrology 3). Chemical processes in the atmosphere, hydrosphere, biosphere, and lithosphere of the Earth 4). Organic geochemistry 5). Isotope geochemistry 6). Meteoritics and meteorite impacts 7). Lunar science; and 8). Planetary geochemistry.