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Ion-Exchange Modeling of Monovalent Alkali Cation Adsorption on Montmorillonite

Published online by Cambridge University Press:  01 January 2024

Yayu W. Li*
Department of Plant Science and Landscape Architecture, University of Connecticut, Storrs, CT 06269-4067, USA
Cristian P. Schulthess
Department of Plant Science and Landscape Architecture, University of Connecticut, Storrs, CT 06269-4067, USA
*E-mail address of corresponding author:


Ion-exchange modeling is one of the most widely used methods to predict ion adsorption data on clay minerals. The model parameters (e.g. number of adsorption sites and the cation adsorption capacity of each site) are optimized normally by curve fitting experimental data, which does not definitively identify the local environment of the adsorption sites. A new approach for constructing an ion-exchange model was pursued, whereby some of the parameters needed were obtained independently, resulting in fewer parameters being based on data-curve fitting. Specifically, a reversed modeling approach was taken in which the number of types of sites used by the model was based on a previous first-principles Density Functional Theory study, and the relative distribution of these sites was based on the clay’s chemical composition. To simplify the ion-exchange reactions involved, montmorillonite was Na-saturated to produce a well-controlled Na-montmorillonite (NaMnt) adsorbent. Ion adsorption data on NaMnt were collected from batch experiments over a wide range of pH, Cs+ concentrations, and in the presence of coexisting cations. Ion-exchange models were developed and optimized to predict these cation adsorption data on NaMnt. The maximum amount of adsorption of monovalent cations on NaMnt was obtained from the plateau of the adsorption envelope data at high pH. The remaining equilibrium constants (pK) were optimized by curve fitting the edges of the adsorption envelope data. The resultant three-site ion-exchange model was able to predict the retention of Li+, Na+, K+, and Cs+ very well as a function of pH. The model was then tested on adsorption envelopes of various combinations of these cations, and on Cs+ adsorption isotherms at three different pH values. The pK values were constant for all assays. The interlayer spacing of NaMnt was also analyzed to investigate its relation with cation adsorption strength. An X-ray diffraction study of the samples showed that the measured d001 values for these cations were consistent with their adsorption pK values. The Cs+ cation showed a strong ability to collapse the interlayer region of montmorillonite. In the presence of multiple competing cations, the broadening and presence of multiple d001 XRD peaks suggested that the cations in the interlayers may be segregated.

Original Paper
Copyright © Clay Minerals Society 2020

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Addiscott, T., Smith, J., & Bradbury, N. (1995). Critical evaluation of models and their parameters. Journal of Environmental Quality, 24, 803807.CrossRefGoogle Scholar
Amram, K., & Ganor, J. (2005). The combined effect of pH and temperature on smectite dissolution rate under acidic conditions. Geochimica et Cosmochimica Acta, 69, 25352546.CrossRefGoogle Scholar
Baeyens, B., & Bradbury, M. H. (1997). A mechanistic description of Ni and Zn sorption on Na-montmorillonite Part I: Titration and sorption measurements. Journal of Contaminant Hydrology, 27, 199222.CrossRefGoogle Scholar
Baeyens, B., & Bradbury, M. H. (2004). Cation exchange capacity measurements on illite using the sodium and cesium isotope dilution technique: Effects of the index cation, electrolyte concentration and competition: Modeling. Clays and Clay Minerals, 52, 421431.CrossRefGoogle Scholar
Barbier, F., Duc, G., & Petit-Ramel, M. (2000). Adsorption of lead and cadmium ions from aqueous solution to the montmorillonite/water interface. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 166, 153159.CrossRefGoogle Scholar
Bloom, P. R., McBride, M. B., & Chadbourne, B. (1977). Adsorption of aluminum by a smectite: I. Surface hydrolysis during Ca2+-Al3+ exchange. Soil Science Society of America Journal, 41, 10681073.CrossRefGoogle Scholar
Bourg, I. C., Bourg, A. C., & Sposito, G. (2003). Modeling diffusion and adsorption in compacted bentonite: A critical review. Journal of Contaminant Hydrology, 61, 293302.CrossRefGoogle ScholarPubMed
Bradbury, M. H., & Baeyens, B. (1997). A mechanistic description of Ni and Zn sorption on Na-montmorillonite Part II: Modelling. Journal of Contaminant Hydrology, 27, 223248.CrossRefGoogle Scholar
Bradbury, M. H., & Baeyens, B. (2005). Experimental measurements and modeling of sorption competition on montmorillonite. Geochimica et Cosmochimica Acta, 69, 41874197.CrossRefGoogle Scholar
Chatterjee, A., Iwasaki, T., Ebina, T., & Miyamoto, A. (1999). A DFT study on clay-cation-water interaction in montmorillonite and beidellite. Computational Materials Science, 14, 119124.CrossRefGoogle Scholar
Chipera, S. J., & Bish, D. L. (2001). Baseline studies of the clay minerals society source clays: Powder X-ray diffraction analyses. Clays and Clay Minerals, 49, 398409.CrossRefGoogle Scholar
Chorom, M., & Rengasamy, P. (1996). Effect of heating on swelling and dispersion of different cationic forms of a smectite. Clays and Clay Minerals, 44, 783790.CrossRefGoogle Scholar
Cornell, R. (1993). Adsorption of cesium on minerals: A review. Journal of Radioanalytical and Nuclear Chemistry, 171, 483500.CrossRefGoogle Scholar
Coulter, B. S. (1969). The equilibria of K: Al exchange in clay minerals and acid soils. Journal of Soil Science, 20(1), 7283.CrossRefGoogle Scholar
Coulter, B. S., & Talibudeen, O. (1968). Calcium: aluminum exchange equilibria in clay minerals and acid soils. Journal of Soil Science, 19, 237250.CrossRefGoogle Scholar
Davies, C. W. (1938). The extent of dissociation of salts in water. Part VIII. An equation for the mean ionic activity coefficient of an electrolyte in water, and a revision of the dissociation constants of some sulphates. Journal of the Chemical Society, Part II, 20932098.Google Scholar
Dzene, L., Tertre, E., Hubert, F., & Ferrage, E. (2015). Nature of the sites involved in the process of cesium desorption from vermiculite. Journal of Colloid and Interface Science, 455, 254260.CrossRefGoogle ScholarPubMed
Dzene, L., Ferrage, E., Hubert, F., Delville, A., & Tertre, E. (2016). Experimental evidence of the contrasting reactivity of external vs. 0 interlayer adsorption sites on swelling clay minerals: The case of Sr2+-for-Ca2+ exchange in vermiculite. Applied Clay Science, 132, 205215.CrossRefGoogle Scholar
Efron, B. (1978). Regression and ANOVA with zero-one data: Measures of residual variation. Journal of the American Statistical Association, 73, 113121.CrossRefGoogle Scholar
Fernandes, M. M., & Baeyens, B. (2019). Cation exchange and surface complexation of lead on montmorillonite and illite including competitive adsorption effects. Applied Geochemistry, 100, 190202.CrossRefGoogle Scholar
Ferrage, E., Lanson, B., Sakharov, B. A., & Drits, V. A. (2005). Investigation of smectite hydration properties by modeling experimental X-ray diffraction patterns: Part I. Montmorillonite hydration properties. American Mineralogist, 90, 13581374.Google Scholar
Ferreira, D. R., & Schulthess, C. P. (2011). The nanopore inner sphere enhancement effect on cation adsorption: Sodium, potassium, and calcium. Soil Science Society of America Journal, 75, 389396.CrossRefGoogle Scholar
Ferreira, D. R., Schulthess, C. P., & Giotto, M. V. (2012). An investigation of strong sodium retention mechanisms in nanopore environments using nuclear magnetic resonance spectroscopy. Environmental Science and Technology, 46, 300306.CrossRefGoogle ScholarPubMed
Galamboš, M., Kufčáková, J., & Rajec, P. (2009). Adsorption of cesium on domestic bentonites. Journal of Radioanalytical and Nuclear Chemistry, 281, 485492.CrossRefGoogle Scholar
Galamboš, M., Paučová, V., Kufčáková, J., Rosskopfová, O., Rajec, P., & Adamcová, R. (2010). Cesium sorption on bentonites and montmorillonite K10. Journal of Radioanalytical and Nuclear Chemistry, 284, 5564.CrossRefGoogle Scholar
Halliwell, D. J., Barlow, K. M., & Nash, D. M. (2001). A review of the effects of wastewater sodium on soil physical properties and their implications for irrigation systems. Soil Research, 39, 12591267.CrossRefGoogle Scholar
Iijima, K., Tomura, T., & Shoji, Y. (2010). Reversibility and modeling of adsorption behavior of cesium ions on colloidal montmorillonite particles. Applied Clay Science, 49, 262268.CrossRefGoogle Scholar
Jacquier, P., Ly, J., & Beaucaire, C. (2004). The ion-exchange properties of the Tournemire argillite: I. Study of the H, Na, K, Cs, Ca and Mg behaviour. Applied Clay Science, 26, 163170.CrossRefGoogle Scholar
Klika, Z., Kraus, L., & Vopálka, D. (2007). Cesium uptake from aqueous solutions by bentonite: A comparison of multicomponent sorption with ion-exchange models. Langmuir, 23, 12271233.CrossRefGoogle ScholarPubMed
Li, W. Y., Schulthess, C. P., Co, K., Sahoo, S., & Alpay, S. P. (2020). Influence of octahedral cation distribution in montmorillonite on interlayer hydrogen counter-ion retention strength by DFT simulation. Clays and Clay Minerals, 110.Google Scholar
Long, H., Wu, P., & Zhu, N. (2013). Evaluation of Cs+ removal from aqueous solution by adsorption on ethylamine-modified montmorillonite. Chemical Engineering Journal, 225, 237244.CrossRefGoogle Scholar
Manning, D. A. (2010). Mineral sources of potassium for plant nutrition. A review. Agronomy for Sustainable Development, 30, 281294.CrossRefGoogle Scholar
Martin, L. A., Wissocq, A., Benedetti, M. F., & Latrille, C. (2018). Thallium (Tl) sorption onto illite and smectite: Implications for Tl mobility in the environment. Geochimica et Cosmochimica Acta, 230, 116.CrossRefGoogle Scholar
McKinley, J. P., Zachara, J. M., Smith, S. C., & Turner, G. D. (1995). The influence of uranyl hydrolysis and multiple site-binding reactions on adsorption of U (VI) to montmorillonite. Clays and Clay Minerals, 43, 586598.CrossRefGoogle Scholar
Missana, T., & García-Gutiérrez, M. (2007). Adsorption of bivalent ions (Ca (II), Sr(II) and Co (II)) onto FEBEX bentonite. Physics and Chemistry of the Earth, Parts A/B/C, 32, 559567.CrossRefGoogle Scholar
Missana, T., Benedicto, A., García-Gutiérrez, M., & Alonso, U. (2014). Modeling cesium retention onto Na-, K-and Ca-smectite: Effects of ionic strength, exchange and competing cations on the determination of selectivity coefficients. Geochimica et Cosmochimica Acta, 128, 266277.CrossRefGoogle Scholar
Moore, D. M., & Reynolds, R. C. (1989). X-ray Diffraction and the Identification and Analysis of Clay Minerals. New York: Oxford University Press.Google Scholar
Morodome, S., & Kawamura, K. (2011). In situ X-ray diffraction study of the swelling of montmorillonite as affected by exchangeable cations and temperature. Clays and Clay Minerals, 59, 165175.CrossRefGoogle Scholar
Motellier, S., Ly, J., Gorgeon, L., Charles, Y., Hainos, D., Meier, P., & Page, J. (2003). Modelling of the ion-exchange properties and indirect determination of the interstitial water composition of an argillaceous rock. Application to the Callovo-Oxfordian low-water-content formation. Applied Geochemistry, 18, 15171530.CrossRefGoogle Scholar
Nash, V. E. & Marshall, C. E. (1956). The Surface Reactions of Silicate Minerals: The Reactions of Feldspar Surfaces with Acidic Solutions. University of Missouri, College of Agriculture, Agricultural Experiment Station, Bulletin 613.Google Scholar
Nolin, D. (1997). Rétention de radioéléments à vie longue par des matériaux argileux. Influence d'anions contenus dans les eaux naturelles. Ph.D. Thesis, Universite Pierre et Marie Curie, Paris 6.Google Scholar
Odom, I. E. (1984). Smectite clay minerals: Properties and uses. Philosophical Transactions of the Royal Society of London. Series A, Mathematical and Physical Sciences, 311, 391409.Google Scholar
Ohkubo, T., Okamoto, T., Kawamura, K., Guégan, R., Deguchi, K., Ohki, S., Shimizu, T., Tachi, Y., & Iwadate, Y. (2018). New insights into the Cs adsorption on montmorillonite clay from 133Cs solid–state NMR and density functional theory calculations. The Journal of Physical Chemistry A, 122, 93269337.CrossRefGoogle Scholar
Park, Y., Shin, W., & Choi, S. J. (2011). Sorptive removal of cobalt, strontium and cesium onto manganese and iron oxide-coated montmorillonite from groundwater. Journal of Radioanalytical and Nuclear Chemistry, 292, 837852.CrossRefGoogle Scholar
Poinssot, C., Baeyens, B., & Bradbury, M. H. (1999). Experimental and modelling studies of caesium sorption on illite. Geochimica et Cosmochimica Acta, 63, 32173227.CrossRefGoogle Scholar
Robin, V., Tertre, E., Beaufort, D., Regnault, O., Sardini, P., & Descostes, M. (2015). Ion exchange reactions of major inorganic cations (H+, Na+, Ca2+, Mg2+ and K+) on beidellite: Experimental results and new thermodynamic database. Toward a better prediction of contaminant mobility in natural environments. Applied Geochemistry, 59, 7484.CrossRefGoogle Scholar
Robin, V., Tertre, E., Beaucaire, C., Regnault, O., & Descostes, M. (2017). Experimental data and assessment of predictive modeling for radium ion-exchange on beidellite, a swelling clay mineral with a tetrahedral charge. Applied Geochemistry, 85, 19.CrossRefGoogle Scholar
Rotenberg, B., Morel, J. P., Marry, V., Turq, P., & 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, 40344044.CrossRefGoogle Scholar
Rozalén, M. L., Huertas, F. J., Brady, P. V., Cama, J., García-Palma, S., & Linares, J. (2008). Experimental study of the effect of pH on the kinetics of montmorillonite dissolution at 25oC. Geochimica et Cosmochimica Acta, 72, 42244253.CrossRefGoogle Scholar
Sadri, S., Johnson, B. B., Ruyter-Hooley, M., & Angove, M. J. (2018). The adsorption of nortriptyline on montmorillonite, kaolinite and gibbsite. Applied Clay Science, 165, 6470.CrossRefGoogle Scholar
Salles, F., Bildstein, O., Douillard, J. M., Jullien, M., & Van Damme, H. (2007). Determination of the driving force for the hydration of the swelling clays from computation of the hydration energy of the interlayer cations and the clay layer. The Journal of Physical Chemistry C, 111, 1317013176.CrossRefGoogle Scholar
Salles, F., Douillard, J. M., Bildstein, O., El Ghazi, S., Prélot, B., Zajac, J., & Van Damme, H. (2015). Diffusion of interlayer cations in swelling clays as a function of water content: Case of montmorillonites saturated with alkali cations. The Journal of Physical Chemistry C, 119, 1037010378.CrossRefGoogle Scholar
Savoye, S., Beaucaire, C., Grenut, B., & Fayette, A. (2015). Impact of the solution ionic strength on strontium diffusion through the Callovo-Oxfordian clayrocks: An experimental and modeling study. Applied Geochemistry, 61, 4152.CrossRefGoogle Scholar
Schulthess, C. P., & Dey, D. K. (1996). Estimation of Langmuir constants using linear and nonlinear. Soil Science Society of America Journal, 60, 433442.CrossRefGoogle Scholar
Schulthess, C. P., & Huang, C. P. (1990). Adsorption of heavy metals by silicon and aluminum oxide surfaces on clay minerals. Soil Science Society of America Journal, 54, 679688.CrossRefGoogle Scholar
Schulthess, C. P., & Sparks, D. L. (1991). Equilibrium-based modeling of chemical sorption on soils and soil constituents. Advances in Soil Science, 16, 121163.CrossRefGoogle Scholar
Schulthess, C. P., Taylor, R. W., & Ferreira, D. R. (2011). The nanopore inner sphere enhancement effect on cation adsorption: Sodium and nickel. Soil Science Society of America Journal, 75, 378388.CrossRefGoogle Scholar
Shi, J., Liu, H., Lou, Z., Zhang, Y., Meng, Y., Zeng, Q., & Yang, M. (2013). Effect of interlayer counterions on the structures of dry montmorillonites with Si4+/Al3+ substitution. Computational Materials Science, 69, 9599.CrossRefGoogle Scholar
Siroux, B., Beaucaire, C., Tabarant, M., Benedetti, M. F., & Reiller, P. E. (2017). Adsorption of strontium and caesium onto an Na-MX80 bentonite: Experiments and building of a coherent thermodynamic modelling. Applied Geochemistry, 87, 167175.CrossRefGoogle Scholar
Sposito, G., Skipper, N. T., Sutton, R., Park, S. H., Soper, A. K., & Greathouse, J. A. (1999). Surface geochemistry of the clay minerals. Proceedings of the National Academy of Sciences, 96, 33583364.CrossRefGoogle ScholarPubMed
Srinivasan, R. (2011). Advances in application of natural clay and its composites in removal of biological, organic, and inorganic contaminants from drinking water. Advances in Materials Science and Engineering, 2011, 117.CrossRefGoogle Scholar
Stul, M. S., & Van Leemput, L. (1982). Particle-size distribution, cation exchange capacity and charge density of deferrated montmorillonites. Clay Minerals, 17, 209216.CrossRefGoogle Scholar
Teppen, B. J., & Miller, D. M. (2006). Hydration energy determines isovalent cation exchange selectivity by clay minerals. Soil Science Society of America Journal, 70, 3140.CrossRefGoogle Scholar
Tertre, E., Beaucaire, C., Coreau, N., & Juery, A. (2009). Modelling Zn (II) sorption onto clayey sediments using a multi-site ion-exchange model. Applied Geochemistry, 24, 18521861.CrossRefGoogle Scholar
Tertre, E., Prêt, D., & Ferrage, E. (2011). Influence of the ionic strength and solid/solution ratio on Ca (II)-for-Na+ exchange on montmorillonite. Part 1: Chemical measurements, thermodynamic modeling and potential implications for trace elements geochemistry. Journal of Colloid and Interface Science, 353, 248256.CrossRefGoogle ScholarPubMed
The Clay Minerals Society (2020). Physical and chemical data of source clays,, viewed 7 January 2020.Google Scholar
Tournassat, C., Neaman, A., Villiéras, F., Bosbach, D., & Charlet, L. (2003). Nanomorphology of montmorillonite particles: Estimation of the clay edge sorption site density by low-pressure gas adsorption and AFM observations. American Mineralogist, 88, 19891995.CrossRefGoogle Scholar
Wanger, T. C. (2011). The Lithium future-resources, recycling, and the environment. Conservation Letters, 4, 202206.CrossRefGoogle Scholar
Way, J. T. (1850). On the power of soils to absorb manure. Journal of the Royal Agricultural Society of England, 11, 313379.Google Scholar
Wissocq, A., Beaucaire, C., & Latrille, C. (2018). Application of the multi-site ion exchanger model to the sorption of Sr and Cs on natural clayey sandstone. Applied Geochemistry, 93, 167177.CrossRefGoogle Scholar
Yamashita, S., & Suzuki, S. (2013). Risk of thyroid cancer after the Fukushima nuclear power plant accident. Respiratory Investigation, 51, 128133.CrossRefGoogle ScholarPubMed
Yang, S., Han, C., Wang, X., & Nagatsu, M. (2014). Characteristics of cesium ion sorption from aqueous solution on bentonite-and carbon nanotube-based composites. Journal of Hazardous Materials, 274, 4652.CrossRefGoogle ScholarPubMed