Atomistic Computer Simulations of Uranyl Adsorption on Hydrated Illite and Smectite Surfaces
A quantitative understanding of the molecular-scale mechanisms of radionuclide sorption on different clay minerals is crucial for the development and safe implementation of geological nuclear waste disposal technologies. We apply classical molecular dynamics (MD) computer simulations to study the ad...
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MDPI AG
2024-01-01
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| Series: | Minerals |
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| Online Access: | https://www.mdpi.com/2075-163X/14/1/109 |
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| author | Anna D. Krot Irina E. Vlasova Evgeny V. Tararushkin Andrey G. Kalinichev |
| author_facet | Anna D. Krot Irina E. Vlasova Evgeny V. Tararushkin Andrey G. Kalinichev |
| author_sort | Anna D. Krot |
| collection | DOAJ |
| description | A quantitative understanding of the molecular-scale mechanisms of radionuclide sorption on different clay minerals is crucial for the development and safe implementation of geological nuclear waste disposal technologies. We apply classical molecular dynamics (MD) computer simulations to study the adsorption of uranyl on the external basal surfaces of two typical clay models. In the illite model, negative charge is primarily localized in the tetrahedral sheets, while in the lower-charge smectite model, the isomorphic substitutions are introduced in the octahedral sheet. The comparison of atomic density distributions at the clay surfaces and adsorption-free energies profiles as a function of distance from these surfaces demonstrates that overall U behavior at the basal clay surface is quite similar for illite and smectite. Uranyl is sorbed as a mixture of outer-sphere aqua complexes [UO<sub>2</sub>(H<sub>2</sub>O)<sub>5</sub>]<sup>2+</sup> and hydrolyzed aqua complexes [UO<sub>2</sub>(H<sub>2</sub>O)<sub>4–5</sub>OH]<sup>+</sup> on both surfaces. The structural and compositional differences between the models do not greatly affect the uranyl’s nearest coordination environment and are mainly reflected in the specific localization and orientation of the uranyl ions at both surfaces and in the magnitude of the adsorption-free energies. The observed quantitative characteristics of uranyl interactions with illite and smectite surfaces will help to better understand U behavior during the sorption process on clay minerals for the entire range of mixed-layer illite–smectite structures. A comparison of two versions of the ClayFF force field in the simulations made it possible to more accurately and quantitatively evaluate some subtle features of the uranyl–clay interactions and to obtain a more precise composition of uranyl complex with the modified ClayFF force field (ClayFF-MOH). |
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| language | English |
| last_indexed | 2024-03-08T10:39:44Z |
| publishDate | 2024-01-01 |
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| series | Minerals |
| spelling | doaj.art-c70854c722254f9993e914c79099790f2024-01-26T17:53:03ZengMDPI AGMinerals2075-163X2024-01-0114110910.3390/min14010109Atomistic Computer Simulations of Uranyl Adsorption on Hydrated Illite and Smectite SurfacesAnna D. Krot0Irina E. Vlasova1Evgeny V. Tararushkin2Andrey G. Kalinichev3Department of Chemistry, Lomonosov Moscow State University, 119991 Moscow, RussiaDepartment of Chemistry, Lomonosov Moscow State University, 119991 Moscow, RussiaDepartment of Chemistry, Lomonosov Moscow State University, 119991 Moscow, RussiaLaboratoire SUBATECH (UMR 6457—IMT Atlantique, Nantes Université, CNRS/IN2P3), 44300 Nantes, FranceA quantitative understanding of the molecular-scale mechanisms of radionuclide sorption on different clay minerals is crucial for the development and safe implementation of geological nuclear waste disposal technologies. We apply classical molecular dynamics (MD) computer simulations to study the adsorption of uranyl on the external basal surfaces of two typical clay models. In the illite model, negative charge is primarily localized in the tetrahedral sheets, while in the lower-charge smectite model, the isomorphic substitutions are introduced in the octahedral sheet. The comparison of atomic density distributions at the clay surfaces and adsorption-free energies profiles as a function of distance from these surfaces demonstrates that overall U behavior at the basal clay surface is quite similar for illite and smectite. Uranyl is sorbed as a mixture of outer-sphere aqua complexes [UO<sub>2</sub>(H<sub>2</sub>O)<sub>5</sub>]<sup>2+</sup> and hydrolyzed aqua complexes [UO<sub>2</sub>(H<sub>2</sub>O)<sub>4–5</sub>OH]<sup>+</sup> on both surfaces. The structural and compositional differences between the models do not greatly affect the uranyl’s nearest coordination environment and are mainly reflected in the specific localization and orientation of the uranyl ions at both surfaces and in the magnitude of the adsorption-free energies. The observed quantitative characteristics of uranyl interactions with illite and smectite surfaces will help to better understand U behavior during the sorption process on clay minerals for the entire range of mixed-layer illite–smectite structures. A comparison of two versions of the ClayFF force field in the simulations made it possible to more accurately and quantitatively evaluate some subtle features of the uranyl–clay interactions and to obtain a more precise composition of uranyl complex with the modified ClayFF force field (ClayFF-MOH).https://www.mdpi.com/2075-163X/14/1/109uranylclayillitesmectitebasal surfacestructural properties |
| spellingShingle | Anna D. Krot Irina E. Vlasova Evgeny V. Tararushkin Andrey G. Kalinichev Atomistic Computer Simulations of Uranyl Adsorption on Hydrated Illite and Smectite Surfaces Minerals uranyl clay illite smectite basal surface structural properties |
| title | Atomistic Computer Simulations of Uranyl Adsorption on Hydrated Illite and Smectite Surfaces |
| title_full | Atomistic Computer Simulations of Uranyl Adsorption on Hydrated Illite and Smectite Surfaces |
| title_fullStr | Atomistic Computer Simulations of Uranyl Adsorption on Hydrated Illite and Smectite Surfaces |
| title_full_unstemmed | Atomistic Computer Simulations of Uranyl Adsorption on Hydrated Illite and Smectite Surfaces |
| title_short | Atomistic Computer Simulations of Uranyl Adsorption on Hydrated Illite and Smectite Surfaces |
| title_sort | atomistic computer simulations of uranyl adsorption on hydrated illite and smectite surfaces |
| topic | uranyl clay illite smectite basal surface structural properties |
| url | https://www.mdpi.com/2075-163X/14/1/109 |
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