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Molecular Dynamics Simulations of Anion Exclusion in Clay Interlayer Nanopores

Published online by Cambridge University Press:  01 January 2024

Christophe Tournassat ,
Ian C. Bourg ,
Michael Holmboe ,
Garrison Sposito  and
Carl I. Steefel
Christophe Tournassat*
Affiliation:
Université d’Orléans — CNRS/INSU — BRGM, UMR 7327 Institut des Sciences de la Terre d’Orléans, 45071, Orléans, France Earth and Environmental Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California, USA
Ian C. Bourg
Affiliation:
Earth and Environmental Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California, USA Department of Civil and Environmental Engineering and Princeton Environmental Institute, Princeton, New Jersey, USA
Michael Holmboe
Affiliation:
Department of Chemistry, Umeå University, Sweden
Garrison Sposito
Affiliation:
Earth and Environmental Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California, USA Department of Environmental Science, Policy and Management, University of California, Berkeley, California, USA
Carl I. Steefel
Affiliation:
Earth and Environmental Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California, USA
*
*E-mail address of corresponding author: c.tournassat@brgm.fr
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Abstract

The aqueous chemistry of water films confined between clay mineral surfaces remains an important unknown in predictions of radioelement migration from radioactive waste repositories. This issue is particularly important in the case of long-lived anionic radioisotopes (129I-, 99TcO4-, 36Cl-) which interact with clay minerals primarily by anion exclusion. For example, models of ion migration in clayey media do not agree as to whether anions are completely or partially excluded from clay interlayer nanopores. In the present study, this key issue was addressed for Cl- using MD simulations for a range of nanopore widths (6 to 15 Å) overlapping the range of average pore widths that exists in engineered clay barriers. The MD simulation results were compared with the predictions of a thermodynamic model (Donnan Equilibrium model) and two pore-scale models based on the Poisson-Boltzmann equation under the assumption that interlayer water behaves as bulk liquid water. The simulations confirmed that anion exclusion from clay interlayers is greater than predicted by the pore-scale models, particularly at the smallest pore size examined. This greater anion exclusion stems from Cl- being more weakly solvated in nano-confined water than it is in bulk liquid water. Anion exclusion predictions based on the Poisson-Boltzmann equation were consistent with the MD simulation results, however, if the predictions included an ion closest approach distance to the clay mineral surface on the order of 2.0 ± 0.8 Å. These findings suggest that clay interlayers approach a state of complete anion exclusion (hence, ideal semi-permeable membrane properties) at a pore width of 4.2 ± 1.5 Å.

Keywords

Anion ExclusionClayDonnan Equilibrium ModelInterlayerMolecular DynamicsNanoporesPoisson-BoltzmannSemi-Permeable Membrane
Type
Article
Information
Clays and Clay Minerals , Volume 64 , Issue 4 , August 2016 , pp. 374 - 388
Copyright
Copyright © The Clay Minerals Society 2016

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Footnotes

This paper is published as part of a special issue on the subject of ‘Computational Molecular Modeling’. Some of the papers were presented during the 2015 Clay Minerals Society-Euroclay Conference held in Edinburgh, UK.

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