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Ion Adsorption at Clay-Mineral Surfaces: The Hofmeister Series for Hydrated Smectite Minerals

Published online by Cambridge University Press:  01 January 2024

Thomas Underwood ,
Valentina Erastova  and
H. Chris Greenwell
Thomas Underwood*
Affiliation:
Department of Earth Sciences, Durham University, Science Labs, Durham DH1 3LE, UK
Valentina Erastova
Affiliation:
Department of Earth Sciences, Durham University, Science Labs, Durham DH1 3LE, UK
H. Chris Greenwell*
Affiliation:
Department of Earth Sciences, Durham University, Science Labs, Durham DH1 3LE, UK
*
*E-mail address of corresponding author: thomas.underwood@durham.ac.uk
*E-mail address of corresponding author: chris.greenwell@durham.ac.uk
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Abstract

Many important properties of clay minerals are defined by the species of charge-balancing cation. Phenomena such as clay swelling and cation exchange depend on the cation species present, and understanding how the cations bind with the mineral surface at a fundamental level is important. In the present study the binding affinities of several different charge-balancing cations with the basal surface of the smectite mineral, montmorillonite, have been calculated using molecular dynamics in conjunction with the well-tempered metadynamics algorithm. The results follow a Hofmeister series of preferred ion adsorption to the smectite basal surfaces of the form:

K+ > Na+ > Ca2+ > Cs+ > Ba2+

The results also revealed the energetically favorable position of the ions above the clay basal surfaces. Key features of the free-energy profiles are illustrated by Boltzmann population inversions and analyses of the water structures surrounding the ion and clay surface. The results show that weakly hydrated cations (K+ and Cs+) preferentially form inner-sphere surface complexes (ISSC) above the ditrigonal siloxane cavities of the clay, while the more strongly hydrated cations (Na+) are able to form ISSCs above the basal O atoms of the clay surface. The strongly hydrated cations (Na+, Ca2+, and Ba2+), however, preferentially form outer-sphere surface complexes. The results provide insight into the adsorption mechanisms of several ionic species on montmorillonite and are relevant to many phenomena thought to be affected by cation exchange, such as nuclear waste disposal, herbicide/pesticide-soil interactions, and enhanced oil recovery.

Keywords

Binding AffinityCation ExchangeMolecular DynamicsMontmorilloniteWell-tempered Metadynamics
Type
Article
Information
Clays and Clay Minerals , Volume 64 , Issue 4 , August 2016 , pp. 472 - 487
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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