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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: [email protected]
*E-mail address of corresponding author: [email protected]
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Abstract

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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

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.

References

Aaqvist, J., 1990 Ion-water interaction potentials derived from free energy perturbation simulations The Journal of Phyical Chemistry 94 8021–8024.CrossRefGoogle Scholar
Barducci, A. Bussi, B. and Parrinello, M., 2008 Well-tempered metadynamics: A smoothly converging and tunable free energy method Physical Review Letters 100 020603.CrossRefGoogle ScholarPubMed
Benson, L.V., 1982 A tabulation and evaluation of ion exchange data on smectites Environmental Geology 4 23–29.CrossRefGoogle Scholar
Berendsen, H.J.C. Grigera, J.R. and Straatsma, T.P., 1987 The missing term in effective pair potentials The Journal of Physical Chemistry 91 6269–6271.CrossRefGoogle Scholar
Bergaya, F. Theng, B. and Lagaly, G. e., 2006 Handbook of Clay Science Amsterdam Elsevier Science.Google Scholar
Boek, E.S. and Sprik, M., 2003 Ab initio molecular dynamics study of the hydration of a sodium smectite clay The Journal of Physical Chemistry B 107 3251–3256.CrossRefGoogle Scholar
Boek, E.S. Coveney, P.V. and Skipper, N.T., 1995 Monte Carlo molecular modeling studies of hydrated Li-, Na-, and K-smectites: Understanding the role of potassium as a clay swelling inhibitor The Journal of the American Chemical Society 117 12608–12617.CrossRefGoogle Scholar
Bonomi, M. Branduardi, D. Bussi, G. Camilloni, C. Provasi, D. Raiteri, P. Donadio, D. Marinelli, F. Pietrucci, F. Broglia, R.A. and Parrinello, M., 2009 PLUMED: A portable plugin for free energy calculations with molecular dynamics Computer Physics Communications 180 1961–1972.CrossRefGoogle Scholar
Bourg, I.C. and Sposito, G., 2011 Ion Exchange Phenomena; Handbook of Soil Science, Properties and Processes 2nd edition Boca Raton, Florida, USA CRC Press.Google Scholar
Bowers, G.M. Bish, D.L. and Kirkpatrick, R.J., 2008 H2O and cation structure and dynamics in expandable clays: 2H and 39K NMR investigations of hectorite The Journal of Physical Chemistry C 112 6430–6438.CrossRefGoogle Scholar
Brown, D.R. and Kevan, L., 1988 Aqueous coordination and location of exchangeable copper (2+) cations in montmorillonite clay studied by electron spin resonance and electron spin echo modulation Journal of the American Chemical Society 110 2743–2748.CrossRefGoogle Scholar
Chang, F.R.C. Skipper, N.T. and Sposito, G., 1995 Computer simulation of interlayer molecular structure in sodium montmorillonite hydrates Langmuir 11 2734–2741.CrossRefGoogle Scholar
Chen, C.C. and Hayes, K.F., 1999 X-ray absorption spectroscopy investigation of aqueous Co(II) and Sr (II) sorption at clay-water interfaces Geochimica et Cosmochimica Acta 63 3205–3215.CrossRefGoogle Scholar
Coveney, P.V. and Wan, S., 2016.On the calculation of equilibrium thermodynamic properties from molecular dynamics Physical Chemistry Chemical PhysicsCrossRefGoogle Scholar
Cygan, R.T. Liang, J.J. and Kalinichev, A.G., 2004 Molecular models of hydroxide, oxyhydroxide, and clay phases and the development of a general force field The Journal of Phyical Chemistry B 108 1255–1266.CrossRefGoogle Scholar
Downs, R.T. and Hall-Wallace, M., 2003 The American Mineralogist crystal structure database American Mineralogist 88 247–250.Google Scholar
Eisenman, G., 1962 Cation selective glass electrodes and their mode of operation Biophysical Journal 2 259–323.CrossRefGoogle ScholarPubMed
Gast, R.G., 1969 Standard free energies of exchange for alkali metal cations on Wyoming bentonite Soil Science Society of America Journal 33 37–41.CrossRefGoogle Scholar
Gast, R.G., 1972 Alkali metal cation exchange on Chambers montmorillonite Soil Science Society of America Journal 36 14–19.CrossRefGoogle Scholar
Greathouse, J.A. Refson, K. and Sposito, G., 2000 Molecular dynamics simulation of water mobility in magnesium-smectite hydrates Journal of the American Chemical Society 122 11459–11464.CrossRefGoogle Scholar
Greathouse, J.A. Hart, D.B. Bowers, G.M. Kirkpatrick, R.J. and Cygan, R.T., 2015 Molecular simulation of structure and diffusion at smectite-water interfaces: Using expanded clay interlayers as model nanopores The Journal of Physical Chemistry C 119 17126–17136.CrossRefGoogle Scholar
Greenwell, H.C. Jones, W. Coveney, P.V. and Stackhouse, S., 2006 On the application of computer simulation techniques to anionic and cationic clays: A materials chemistry perspective Journal of Materials Chemistry 16 708–723.CrossRefGoogle Scholar
Hanshaw, B.B., 1964.Cation-exchange constants for clays from electrochemical measurements 12th Annual Meeting of the Clay Minerals Society, USACrossRefGoogle Scholar
Heinz, H. Lin, T.-J. Mishra, R.K. and Emami, F.S., 2013 Thermodynamically consistent force fields for the assembly of inorganic, organic, and biological nanostructures: The INTERFACE force field Langmuir 29 1754–1765.CrossRefGoogle ScholarPubMed
Hunter, J.D., 2007 Matplotlib: A 2D graphics environment Computing in Science and Engineering 9 90–95.CrossRefGoogle Scholar
Koneshan, S. Lynden-Bell, R.M. and Rasaiah, J.C., 1998 Friction coefficients of ions in aqueous solution at 25°C The Journal of the American Chemical Society 120 12041–12050.CrossRefGoogle Scholar
Marry, V. and Turq, P., 2003 Microscopic simulations of interlayer structure and dynamics in bihydrated heteroionic montmorillonites The Journal of Physical Chemistry B 107 1832–1839.CrossRefGoogle Scholar
Marry, V. Dubois, E. Malikova, N. Breu, J. and Haussler, W., 2013 Anisotropy of water dynamics in clays: insights from molecular simulations for experimental QENS analysis The Journal of Physical Chemistry C 117 15106–15115.CrossRefGoogle Scholar
Michaud-Agrawal, N. Denning, E.J. Woolf, T.B. and Beckstein, O., 2011 MDAnalysis: a toolkit for the analysis of molecular dynamics simulations Journal of Computational Chemistry 32 2319–2327.CrossRefGoogle ScholarPubMed
Nakano, M. Kawamura, K. and Ichikawa, Y., 2003 Local structural information of Cs in smectite hydrates by means of an EXAFS study and molecular dynamics simulations Applied Clay Science 23 15–23.CrossRefGoogle Scholar
Ngouana, W BF and Kalinichev, A.G., 2014 Structural arrangements of isomorphic substitutions in smectites: Molecular simulation of the swelling properties, interlayer structure, and dynamics of hydrated Cs-montmorillonite revisited with new clay models The Journal of Physical Chemistry C 118 12758–12773.CrossRefGoogle Scholar
Papelis, C. and Hayes, K.F., 1996 Distinguishing between interlayer and external sorption sites of clay minerals using X-ray absorption spectroscopy Colloids and Surfaces A: Physicochemical and Engineering Aspects 107 89–96.CrossRefGoogle Scholar
Park, S.H. and Sposito, G., 2002 Structure of water adsorbed on a mica surface Physical Review Letters 89 085501.CrossRefGoogle ScholarPubMed
Pronk, S. Páll, S. Schulz, R. Larsson, P. Bjelkmar, P. Apostolov, R. Shirts, M.R. Smith, J.C. Kasson, P.M. van der Spoel, D. and Hess, B., 2013 GROMACS 4.5: a high-throughput and highly parallel open source molecular simulation toolkit Bioinformatics 29 845–854.CrossRefGoogle ScholarPubMed
Rotenberg, B. Marry, V. Vuilleumier, R. Malikova, N. Simon, C. and Turq, P., 2007 Water and ions in clays: Unraveling the interlayer/micropore exchange using molecular dynamics Geochimica et Cosmochimica Acta 71 5089–5101.CrossRefGoogle Scholar
Rotenberg, B. Morel, J.-P. Marry, V. Turq, P. and Morel-Desrosiers, N., 2009 On the driving force of cation exchange in clays: Insights from combined microcalorimetry experiments and molecular simulation Geochimica et Cosmochimica Acta 73 4034–4044.CrossRefGoogle Scholar
Rotenberg, B. Marry, V. Malikova, N. and Turq, P., 2010 Molecular simulation of aqueous solutions at clay surfaces Journal of Physics: Condensed Matter 22 284114.Google ScholarPubMed
Shroll, R.M. and Smith, D.E., 1999 Molecular dynamics simulations in the grand canonical ensemble: Application to clay mineral swelling The Journal of Chemical Physics 111 9025–9033.CrossRefGoogle Scholar
Smith, D.E. and Dang, L.X., 1994 Computer simulations of cesium-water clusters: Do ion-water clusters form gas-phase clathrates? The Journal of Chemical Physics 101 7873.CrossRefGoogle Scholar
Smith, D.E. and Dang, L.X., 1994 Computer simulations of NaCl association in polarizable water The Journal of Chemical Physics 100 3757.CrossRefGoogle Scholar
Strawn, D.G. and Sparks, D.L., 1999 The use of XAFS to distinguish between inner-and outer-sphere lead adsorption complexes on montmorillonite Journal of Colloid and Interface Science 216 257–269.CrossRefGoogle ScholarPubMed
Suter, J.L. Anderson, R.L. Greenwell, H.C. and Coveney, P.V., 2009 Recent advances in large-scale atomistic and coarse-grained molecular dynamics simulation of clay minerals Journal of Materials Chemistry 19 2482–2493.CrossRefGoogle Scholar
Swenson, J. Bergman, R. and Howells, W.S., 2000 Quasielastic neutron scattering of two-dimensional water in a vermiculite clay The Journal of Chemical Physics 113 2873–2879.CrossRefGoogle Scholar
Teppen, B.J. and Miller, D.M., 2006 Hydration energy determines isovalent cation exchange selectivity by clay minerals Soil Science Society of America Journal 70 31–40.CrossRefGoogle Scholar
Tesson, S. Salanne, M. Rotenberg, B. Tazi, S. and Marry, V., 2016 Classical polarizable force field for clays: Pyrophyllite and talc The Journal of Physical Chemistry C 120 3749–3758.CrossRefGoogle Scholar
Tribello, G.A. Bonomi, M. Branduardi, D. Camilloni, C. and Bussi, G., 2014 PLUMED 2: New feathers for an old bird Computer Physics Communications 185 604–613.CrossRefGoogle Scholar
Underwood, T. Erastova, V. Cubillas, P. and Greenwell, H.C., 2015 Molecular dynamic simulations of montmorillonite—organic interactions under varying salinity: An insight into enhanced oil recovery The Journal of Physical Chemistry C 119 7282–7294.CrossRefGoogle Scholar
Viani, A. Gualtieri, A.F. and Artioli, G., 2002 The nature of disorder in montmorillonite by simulation of X-ray powder patterns American Mineralogist 87 966–975.CrossRefGoogle Scholar
William Humphrey, A.D., 1996 VMD: visual molecular dynamics Journal of Molecular Graphics 14 33–38.CrossRefGoogle Scholar
Zhang, P.C. Brady, P.V. Arthur, S.E. Zhou, W.Q. Sawyer, D. and Hesterberg, D.A., 2001 Adsorption of barium (II) on montmorillonite: an EXAFS study Colloids and Surfaces A: Physicochemical and Engineering Aspects 190 239–249.CrossRefGoogle Scholar
Zhang, Y. and Cremer, P.S., 2006 Interactions between macromolecules and ions: the Hofmeister series Current Opinion in Chemical Biology 10 658–663.CrossRefGoogle ScholarPubMed