Hostname: page-component-848d4c4894-ndmmz Total loading time: 0 Render date: 2024-05-26T05:32:17.765Z Has data issue: false hasContentIssue false

Influence of Cations on Aggregation Rates in Mg-Montmorillonite

Published online by Cambridge University Press:  01 January 2024

Al. Katz
Department of Physics, City College of New York, NY 10031, USA
Min Xu
Department of Physics, Fairfield University, Fairfield, CT 06824, USA
Jeffrey C. Steiner
Department of Earth and Atmospheric Science, City College of New York, New York, NY 10031, USA
Adrianna Trusiak
Department of Earth and Atmospheric Science, City College of New York, New York, NY 10031, USA
Alexandra Alimova
Sophie Davis School of Biomedical Education, City College of New York, NY 10031, USA
Paul Gottlieb
Sophie Davis School of Biomedical Education, City College of New York, NY 10031, USA
Karin Block*
Department of Earth and Atmospheric Science, City College of New York, New York, NY 10031, USA
*E-mail address of corresponding author:


Critical-zone reactions involve inorganic and biogenic colloids in a cation-rich environment. The present research defines the rates and structure of purified Mg-montmorillonite aggregates formed in the presence of monovalent (K+) and divalent (Ca2+, Mg 2+) cations using light-extinction measurements. Time evolution of turbidity was employed to determine early-stage aggregation rates. Turbidity spectra were used to measure the fractal dimension at later stages. The power law dependence of the stability ratios on cation concentration was found to vary with the reciprocal of the valence rather than the predicted reciprocal of valence-squared, indicating that the platelet structure may be a factor influencing aggregation rates. The critical coagulation concentrations (CCC) (3 mM for CaCl2, 4 mM for MgCl2, and 70 mM for KCl) were obtained from the stability ratios. At a later time and above a minimal cation concentration, turbidity reached a quasi-stable state, indicating the formation of large aggregates. Under this condition, an approximate turbidity forward-scattering correction factor was applied and the fractal dimension was determined from the extinction spectra. For the divalent cations, the fractal dimensions were 1.65 ± 0.3 for Ca2+ and 1.75 ± 0.3 for Mg2+ and independent of cation concentrations above the CCC. For the monovalent cation, the fractal dimension increased with K+ concentration from 1.35 to 1.95, indicating a transition to a face-to-face geometry from either an edge-to-edge or edge-to-face orientation.

Research Article
Copyright © The Clay Minerals Society 2013

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)


Alimova, A. Katz, A. Orozco, J. Wei, H. Gottlieb, P. Rudolph, E. Steiner, J.C. and Xu, M., 2009.Time evolution of smectite fractal dimension measured by broadband light scattering Journal of Optics A: Pure and Applied OpticsGoogle Scholar
Banin, A. and Lahav, N., 1968 Optical study of particle size of montmorillonite with various adsorbed cations Nature 217 11461147.CrossRefGoogle Scholar
Berka, M. and Rice, J.A., 2004 Absolute aggregation rate constants in aggregation of kaolinite measured by simultaneous static and dynamic light scattering Langmuir 20 61526157.CrossRefGoogle ScholarPubMed
Berka, M. and Rice, J.A., 2005 Relation between aggregation kinetics and the structure of kaolinite aggregates Langmuir 21 12231229.CrossRefGoogle ScholarPubMed
Berry, M.V. and Wills, H.H., 1986 Optics of fractal clusters such as smoke Optica Acta 33 577591.CrossRefGoogle Scholar
Bouchelaghem, F. and Jozja, N., 2009 Multi-scale study of permeability evolution of a bentonite clay owing to pollutant transport: Part I. Model derivation Engineering Geology 108 119132.CrossRefGoogle Scholar
Czigany, S. Flury, M. and Harsh, J.B., 2005 Colloid stability in vadose zone Hanford sediments Environmental Science & Technology 39 15061512.CrossRefGoogle Scholar
Derjaguin, B. and Landau, L., 1941 Theory of the stability of strongly charged lyophobic sols and of the adhesion of strongly charged particles in solution of electrolytes Acta Physicochimica 14 633662.Google Scholar
Derrendinger, L. and Sposito, G., 2000 Flocculation kinetics and cluster morphology in illite/NaCl suspensions Journal of Colloid and Interface Science 222 111.CrossRefGoogle ScholarPubMed
Elimelech, M. Gregory, J. Jia, X. and Williams, R., 1998.Particle Deposition and Aggregation: Measurement, Modelling and SimulationGoogle Scholar
Ferreiro, E.A. and Helmy, A.K., 1974 Flocculation of Na-montmorillonite by electrolytes Clays and Clay Minerals 10 203213.CrossRefGoogle Scholar
García-García, S. Jonsson, M. and Wold, S., 2006 Temperature effect on the stability of bentonite colloids in water Journal of Colloid and Interface Science 298 694705.CrossRefGoogle Scholar
García-García, S. Wold, S. and Jonsson, M., 2007 Kinetic determination of critical coagulation concentrations for sodium- and calcium-montmorillonite colloids in NaCl and CaCl2 aqueous solutions Journal of Colloid and Interface Science 315 512519.CrossRefGoogle ScholarPubMed
Goldberg, S. Forster, H.S. and Heick, E.L., 1991 Flocculation of illite/kaolinite and illite/montmorillonite mixtures as affected by sodium adsorption ratio and pH Clays and Clay Minerals 39 375380.CrossRefGoogle Scholar
Goldberg, S. and Glaubig, R.A., 1987 Effect of saturating cation, pH, and aluminum and iron oxide on the flocculation of kaolinite and montmorillonite Clays and Clay Minerals 35 220227.CrossRefGoogle Scholar
Hunter, R.J., 1993 Introduction to Modern Colloid Science New York Oxford University Press.Google Scholar
Keren, R. and Sparks, D.L., 1995 The role of edge surfaces in flocculation of 2:1 clay minerals Soil Science Society of America Journal 59 430435.CrossRefGoogle Scholar
Kobayashi, M. and Ishibashi, D., 2011 Absolute rate of turbulent coagulation from turbidity measurement Colloid & Polymer Science 289 831836.CrossRefGoogle Scholar
Kornilovich, B. Mishchuk, N. Abbruzzese, K. Pshinko, G. and Klishchenko, R., 2005 Enhanced electrokinetic remediation of metals-contaminated clay Colloids and Surfaces A: Physicochemical and Engineering Aspects 265 114123.CrossRefGoogle Scholar
Lagaly, G., Bergaya, F. Theng, B.K.G. and Lagaly, G., 2006 Colloid Clay Science Handbook of Clay Science Amsterdam Elsevier 141246.CrossRefGoogle Scholar
Lagaly, G. and Ziesmer, S., 2003 Colloid chemistry of clay minerals: the coagulation of montmorillonite dispersions Advances in Colloid and Interface Science 100 105128.CrossRefGoogle Scholar
Lin, M.Y. Lindsay, H.M. Weitz, D.A. Ball, R.C. Klein, R. and Meakin, P., 1989 Universality in colloid aggregation Nature 339 360362.CrossRefGoogle Scholar
Lin, M.Y. Lindsay, H.M. Weitz, D.A. Ball, R.C. Klein, R. and Meakin, P., 1990 Universal reaction-limited colloid aggregation Physical Review A 41 20052030.CrossRefGoogle ScholarPubMed
Lin, M.Y. Lindsay, H.M. Weitz, D.A. Klein, R. Ball, R.C. and Meakin, P., 1990 Universal diffusion-limited colloid aggregation Journal of Physics: Condensed Matter 2 30933113.Google Scholar
Luckham, P.F. and Rossi, S., 1999 The colloidal and rheological properties of bentonite suspensions Advances in Colloid and Interface Science 82 4392.CrossRefGoogle Scholar
Meakin, P., 1983 Formation of fractal clusters and networks by irreversible diffusion-limited aggregation Physical Review Letters 51 11191122.CrossRefGoogle Scholar
Missana, T. and Adell, A., 2000 On the applicability of DLVO theory to the prediction of clay colloids stability Journal of Colloid and Interface Science 230 150156.CrossRefGoogle Scholar
Moore, D. Reynolds, R.C. Jr., 1997 X-ray Diffraction and the Identification and Analysis of Clay Minerals 2 New York Oxford University Press.Google Scholar
Morris, G.E. and Zbik, M.S., 2009 Smectite suspension structural behaviour International Journal of Mineral Processing 93 2025.CrossRefGoogle Scholar
Nasser, M.S. and James, A.E., 2009 The effect of electrolyte concentration and pH on the flocculation and rheological behaviour of kaolinite suspensions Journal of Engineering Science and Technology 4 430446.Google Scholar
Novich, B.E. and Ring, T.A., 1984 Colloid stability of clays using photon correlation spectroscopy Clays and Clay Minerals 32 400406.CrossRefGoogle Scholar
Pierre, A.C. and Ma, K., 1999 DLVO theory and clay aggregate architectures formed with AlCl3 Journal of the European Ceramic Society 19 16151622.CrossRefGoogle Scholar
Plaschke, M. Schäfer, T. Bundschuh, T. Ngo Manh, T. Knopp, R. Geckeis, H. and Kim, J.I., 2001 Size characterization of bentonite colloids by different methods Analytical Chemistry 73 43384347.CrossRefGoogle ScholarPubMed
Ploehn, H.J. and Liu, C., 2006 Quantitative analysis of montmorillonite platelet size by atomic force microscopy Industrial & Engineering Chemistry Research 45 70257034.CrossRefGoogle Scholar
Puertas, A.M. and Nieves, FJdl, 1997 A new method for calculating kinetic constants within the Rayleigh — Gans — Debye approximation from turbidity measurements Journal of Physics: Condensed Matter 9 3313.Google Scholar
Ravera, M. Ciccarelli, C. Gastaldi, D. Rinaudo, C. Castelli, C. and Osella, D., 2006 An experiment in the electro-kinetic removal of copper from soil contaminated by the brass industry Chemosphere 63 950955.CrossRefGoogle Scholar
Reerink, H. and Overbeek, J.T.G., 1954 The rate of coagulation as a measure of the stability of silver iodide sols Discussions of the Faraday Society 18 7484.CrossRefGoogle Scholar
Schramm, L.L. and Kwak, J.C.T., 1982 Influence of exchangeable cation composition on the size and shape of montmorillonite particles in dilute suspension Clays and Clay Minerals 30 4048.CrossRefGoogle Scholar
Sorensen, C.M., 2001 Light scattering by fractal aggregates: a review Aerosol Science & Technology 35 648687.CrossRefGoogle Scholar
Spinrad, R.W. Zaneveld, J.R.V. and Pak, H., 1978 Volume scattering function of suspended particulate matter at near-forward angles: a comparison of experimental and theoretical values Applied Optics 17 11251130.CrossRefGoogle Scholar
Srodon, J., 2006 Identification and quantitative analysis of clay minerals Handbook of Clay Science 765788.CrossRefGoogle Scholar
Stawinski, J. Wierzchos, J. and Garcia-Gonzalez, M.T., 1990 Influence of calcium and sodium concentration on the microstructure of bentonite and kaolin Clays and Clay Minerals 38 617622.CrossRefGoogle Scholar
Tawari, S.L. Koch, D.L. and Cohen, C., 2001 Electrical double-layer effects on the Brownian diffusivity and aggregation rate of Laponite clay particles Journal of Colloid and Interface Science 240 5466.CrossRefGoogle ScholarPubMed
Tombácz, E. and Szekeres, M., 2004 Colloidal behavior of aqueous montmorillonite suspensions: the specific role of pH in the presence of indifferent electrolytes Applied Clay Science 27 7594.CrossRefGoogle Scholar
Tournassat, C. Neaman, A. Villiéras, F. Bosbach, D. and 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
van Olphen, H., 1977.Introduction to Clay Colloid ChemistryCrossRefGoogle Scholar
van Oss, C.J. Giese, R.F. and Costanzo, P.M., 1990 DLVO and non-DLVO interactions in hectorite Clays and Clay Minerals 38 151159.CrossRefGoogle Scholar
Verwey, E.J.W. and Overbeek, J.T.G., 1948.Theory of the Stability of Lyophobic ColloidsGoogle Scholar
von Wachenfeldt, E. Bastviken, D. and Tranvik, L.J., 2009 Microbially induced flocculation of allochthonous dissolved organic carbon in lakes Limnology and Oceanography 54 18111818.CrossRefGoogle Scholar
Whalley, W.R. and Mullins, C.E., 1991 Effect of saturating cation on tactoid size distribution in bentonite suspensions Clay Minerals 26 1117.CrossRefGoogle Scholar
Wind, L. and Szymanski, W.W., 2002 Quantification of scattering corrections to the Beer-Lambert law for transmit-tance measurements in turbid media Measurement Science and Technology 13 270.CrossRefGoogle Scholar