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Molecular Simulation of Cesium Adsorption at the Basal Surface of Phyllosilicate Minerals

Published online by Cambridge University Press:  01 January 2024

Sebastien Kerisit ,
Masahiko Okumura ,
Kevin M. Rosso  and
Masahiko Machida
Sebastien Kerisit*
Affiliation:
Physical Sciences Division, Pacific Northwest National Laboratory, 99354, Richland, Washington, USA
Masahiko Okumura
Affiliation:
Center for Computational Science and e-Systems, Japan Atomic Energy Agency, 5-1-5 Kashiwanoha, Kashiwa, Chiba 277-8587, Japan
Kevin M. Rosso
Affiliation:
Physical Sciences Division, Pacific Northwest National Laboratory, 99354, Richland, Washington, USA
Masahiko Machida
Affiliation:
Center for Computational Science and e-Systems, Japan Atomic Energy Agency, 5-1-5 Kashiwanoha, Kashiwa, Chiba 277-8587, Japan
*
*E-mail address of corresponding author: sebastien.kerisit@pnnl.gov
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Abstract

A better understanding of the thermodynamics of radioactive cesium uptake at the surfaces of phyllosilicate minerals is needed to understand the mechanisms of selective adsorption and help guide the development of practical and inexpensive decontamination techniques. In this work, molecular dynamics simulations were carried out to determine the thermodynamics of Cs+ adsorption at the basal surface of six 2:1 phyllosilicate minerals, namely pyrophyllite, illite, muscovite, phlogopite, celadonite, and margarite. These minerals were selected to isolate the effects of the magnitude of the permanent layer charge (⩽2), its location (tetrahedral vs. octahedral sheet), and the octahedral sheet structure (dioctahedral vs. trioctahedral). Good agreement was obtained with the experiments in terms of the hydration free energy of Cs+ and the structure and thermodynamics of Cs+ adsorption at the muscovite basal surface, for which published data were available for comparison. With the exception of pyrophyllite, which did not exhibit an inner-sphere free energy minimum, all phyllosilicate minerals showed similar behavior with respect to Cs+ adsorption; notably, Cs+ adsorption was predominantly inner-sphere, whereas outer-sphere adsorption was very weak with the simulations predicting the formation of an extended outer-sphere complex. For a given location of the layer charge, the free energy of adsorption as an inner-sphere complex varied linearly with the magnitude of the layer charge. For a given layer charge location and magnitude, adsorption at phlogopite (trioctahedral sheet structure) was much less favorable than at muscovite (dioctahedral sheet structure) due to electrostatic repulsion between adsorbed Cs+ and the H atom of the OH- ion directly below the six-membered siloxane ring cavity. For a given layer charge magnitude and octahedral sheet structure, adsorption to celadonite (octahedral sheet layer charge) was favored over adsorption to muscovite (tetrahedral sheet layer charge) due to the increased distance to the surface K+ ions and the decreased distance to the O atom of the OH- ion directly below the surface cavity.

Keywords

Adsorption Free EnergyCesiumCLAYFFInner-SphereLayer ChargeMicaMolecular DynamicsOuter-SpherePotential of Mean Force(001) Surface
Type
Article
Information
Clays and Clay Minerals , Volume 64 , Issue 4 , August 2016 , pp. 389 - 400
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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