Hostname: page-component-cd9895bd7-jkksz Total loading time: 0 Render date: 2024-12-27T13:03:06.405Z Has data issue: false hasContentIssue false
  • English
  • Français

The Effect of Surface Charge and Wettability on H2O Self Diffusion in Compacted Clays

Published online by Cambridge University Press:  01 January 2024

Birgit Schampera  and
Stefan Dultz
Birgit Schampera*
Affiliation:
Institute of Soil Science, Leibniz University Hannover, Herrenhäuser Str. 2, D-30419, Hannover, Germany
Stefan Dultz
Affiliation:
Institute of Soil Science, Leibniz University Hannover, Herrenhäuser Str. 2, D-30419, Hannover, Germany ZFM - Center for Solid State Chemistry and New Materials, Leibniz University Hannover, Germany
*
* E-mail address of corresponding author: schampera@ifbk.uni-hannover.de
Rights & Permissions [Opens in a new window]

Abstract

Core share and HTML view are not available for this content. However, as you have access to this content, a full PDF is available via the ‘Save PDF’ action button.

Organo-clays are of interest in the modification of anion transport properties in engineered barriers. In the present study, surface charge and wettability were assessed for tracking changes in the effective diffusion coefficient (Deff) by the formation or suppression of bound H2O layers on the external surfaces of clays. Bentonite samples modified with three different organic cations in amounts of 0 to 400% of the cation exchange capacity were used. Diffusive transport was determined in H2O→D2O exchange experiments in a newly constructed cell adapted to the attenuated total reflectance (ATR) accessory of a Fourier-transform infrared (FTIR) spectrometer at two different dry bulk densities and various degrees of water saturation.

All organo-clay combinations showed changes in surface charge after the addition of organic cations, from a negative value of 99 mmolc/kg for the original bentonite to a maximum positive value of 230.5 mmolc/kg for hexadecylpyridinium (HDPy)-montmorillonite. The positive charge resulted from adsorption of the organic cation in excess of the CEC. Hydrophobic surface properties with contact angles >90° were obtained for HDPy-montmorillonite samples with monolayers of organic cations on the external surfaces only. Here, where hydrophobicity suppressed the formation of bound H2O layers, the largest Deff o f 2.7×10−10 m2/s was observed in the high dry bulk density range (1.0–1.5 g/cm3) under water-saturated conditions. In the low dry bulk density range (0.6–0.9 g/cm3) this effect was weakened significantly because, with increasing pore size, the effect of bound H2O layers was reduced. In the high dry bulk density range at partial water saturation (40%), diffusive transport was hindered by the small water volume. Previous work found that, in the high dry bulk density range and water-saturated state, Deff was 2.4×10−11 m2/s for the original bentonite. Deff for all hydrophilic organo-clay samples was ⩽2.1×10−11 m2/s, somewhat less than for the hydrophobic sample. In hydrophilic organo-clay samples, retardation factors that retard the value for Deff, up toa magnitude of 0.5, include an increase in dry bulk density and a decrease in water saturation. In the water-saturated state at high dry bulk densities, hydrophobic surface properties suppressing the formation of bound H2O layers can increase Deff by one order of magnitude.

Keywords

BentoniteBound H2ODiffusive TransportOrgano-claysSurface ChargeWettability
Type
Article
Information
Clays and Clay Minerals , Volume 59 , Issue 1 , February 2011 , pp. 42 - 57
Copyright
Copyright © The Clay Minerals Society 2011

References

An, J.-H. and Dultz, S., 2007 Adsorption of tannic acid on chitosan-montmorillonite as a function of pH and surface charge properties Applied Clay Science 36 256–264 10.1016/j.clay.2006.11.001.CrossRefGoogle Scholar
Bachmann, J., Woche, S.K., Goebel, M.-O., Kirkham, M.B., and Horton, R. (2003) Extended methodology for determining wetting properties of porous media. Water Resources Research, 39, article no. 1353.CrossRefGoogle Scholar
Böckenhoff, K. and Fischer, W.R., 2001 Determination of electrokinetic charge with a particle-charge detector and its relationship to the total charge Fresenius Journal of Analytical Chemistry 371 670–674 10.1007/s002160100897.CrossRefGoogle Scholar
Bors, J. Gorny, A. and Dultz, S.t., 1997 Iodide, caesium and strontium adsorption by organophilic vermiculite Clay Minerals 32 21–28 10.1180/claymin.1997.032.1.04.CrossRefGoogle Scholar
Bors, J. Dultz, S. and Riebe, B., 2000 Organophilic bentonites as adsorbents for radionuclides I Adsorption of ionic fission products. Applied Clay Science 16 1–13.CrossRefGoogle Scholar
Bourg, I.C. Sposito, G. and Bourg, A.C.M., 2006 Tracer diffusion in compacted, water-saturated bentonite Clays and Clay Minerals 54 363–374 10.1346/CCMN.2006.0540307.CrossRefGoogle Scholar
Boving, T.B. and Grathwohl, P., 2001 Tracer diffusion coefficient in sedimentary rocks: correlation to porosity and hydraulic conductivity Journal of Contaminant Hydrology 53 85–100 10.1016/S0169-7722(01)00138-3.CrossRefGoogle ScholarPubMed
Chatterjee, A. Iwasaki, T. Ebina, T. and Hayashi, H., 1997 Quantum chemical calculation on clay-water interface Applied Surface Science 121/122 167–170 10.1016/S0169-4332(97)00280-8.CrossRefGoogle Scholar
Delage, P. Marcial, D. Cui, Y.J. and Ruiz, X., 2006 Ageing effects in compacted bentonite: a microstructure approach Géotechnique 56 291–304 10.1680/geot.2006.56.5.291.CrossRefGoogle Scholar
Duval, F.P. Porion, P. Faugère, A.-M. and Van Damme, H., 2001 An NMR investigation of water self-diffusion and relaxation rates in controlled ionic strength laponite sols and gels Journal of Colloid and Interface Science 242 319–326 10.1006/jcis.2001.7806.CrossRefGoogle Scholar
Fielderson, G.T. and Barbari, T.A., 1993 The use of FTi.r.- a.t.r spectroscopy to characterize penetrant diffusion in polymers Polymer 34 1146–1153 10.1016/0032-3861(93)90765-3.CrossRefGoogle Scholar
Garcia-Gutierrez, M. Mingarro, M. Missana, T. Martin, P.L. Sedano, L.A. and Cormenzana, J.L., 2004 Diffusion experiments with compacted powder/pellets clay mixtures Applied Clay Science 26 57–64 10.1016/j.clay.2003.09.014.CrossRefGoogle Scholar
Gillham, R.W. Robin, M.J.L. Dytynyshyn, D.J. and Johnston, H.M., 1984 Diffusion of nonreactive and reactive solutes through fine-grained barrier material Canadian Geotechnical Journal 23 541–550 10.1139/t84-056.CrossRefGoogle Scholar
Guegan, R. Gautier, M. Beny, J.-M. and Mueller, F., 2009 Adsorption of a C10E3 non-ionic surfactant on a Casmectite Clays and Clay Minerals 57 502–509 10.1346/CCMN.2009.0570411.CrossRefGoogle Scholar
Hicher, P.Y. Wahyudi, H. and Tessier, D., 2000 Microstructural analysis of inherent and induced anisotropy in clay Mechanics of Cohesive-Frictional Materials 5 341–371 10.1002/1099-1484(200007)5:5<341::AID-CFM99>3.0.CO;2-C.3.0.CO;2-C>CrossRefGoogle Scholar
Hunt, A.G. and Ewing, R.P., 2003 On the vanishing of solute diffusion in porous media at a threshold moisture content Soil Science Society of America Journal 67 1701–1702 10.2136/sssaj2003.1701.CrossRefGoogle Scholar
Hunter, R., 1993 Introduction to Modern Colloid Science Oxford, UK Oxford University Press.Google Scholar
Ichikawa, Y. Kawamura, K. Nakano, M. Kitayama, K. and Kawamura, H., 1999 Unified molecular and homogenization analysis for bentonite behaviour: current results and future possibilities Engineering Geology 54 21–32 10.1016/S0013-7952(99)00058-7.CrossRefGoogle Scholar
Ichikawa, Y. Kawamura, K. Nakano, M. Kitayama, K. Seiki, T. and Theramast, N., 2001 Seepage and consolidation of bentonite saturated with pure- or salt water by method of unified molecular dynamics and homogenization analysis Engineering Geology 60 127–138 10.1016/S0013-7952(00)00095-8.CrossRefGoogle Scholar
Imai, Y. Nishimura, S. Inukai, Y. and Tateyama, H., 2003 Differences in quasicrystals of smectite-cationic surfactant complexes due to head group structures Clays and Clay Minerals 51 162–167 10.1346/CCMN.2003.0510205.CrossRefGoogle Scholar
Jeschke, F. and Meleshyn, A., 2010 A Monte Carlo study of interlayer and surface structures of tetraphenyl-phosphonium- modified Na-montmorillonite Geoderma .CrossRefGoogle Scholar
Johnston, C.T. Tombacz, E., Dixon, J.B. Schulze, D.G., 2002 Surface chemistry of minerals Soil Mineralogy with Environmental Applications Madison, Wisconsin, USA Soil Science Society of America 37–67.Google Scholar
Jougnot, D. and Revil, A., 2007 Diffusion of ions in unsaturated clay-rocks: theory and application to the Callovo-Oxfordian argillite International Meeting on Clay in Natural and Engineered Barriers for Radioactive Waste Confinement, Lille, France 247–248.Google Scholar
Koh, S.M. Song, M.S. and Takagi, T., 2005 Mineralogy, chemical characteristics and stabilities of Cetylpyridiniumexchange smectite Clay Minerals 40 213–222 10.1180/0009855054020167.CrossRefGoogle Scholar
Kozaki, T. Inada, K. Sato, S. and Ohashi, H., 2001 Diffusion mechanism of chloride ions in sodium montmorillonite Journal of Contaminant Hydrology 47 159–170 10.1016/S0169-7722(00)00146-7.CrossRefGoogle ScholarPubMed
Kung, K-HS and Hayes, K.F., 1993 Fourier transform infrared spectroscopic study of adsorption of cetyltrimethylammonium bromide and cetylpyridinium chloride on silica Langmuir 9 263–267 10.1021/la00025a050.CrossRefGoogle Scholar
Li, Y.-H. and Gregory, S., 1974 Diffusion of ions in sea water and in deep-sea sediments Geochimica et Cosmochimica Acta 38 703–714 10.1016/0016-7037(74)90145-8.Google Scholar
Li, Z.H. and Bowman, R.S., 1998 Sorption of chromate and PCE by surfactant modified clay minerals Environmental Engineering Science 15 237–245 10.1089/ees.1998.15.237.CrossRefGoogle Scholar
Longsworth, L.G., 1960 The mutual diffusion of light and heavy water Journal of Chemical Physics 64 1914–1917 10.1021/j100841a027.CrossRefGoogle Scholar
Lorenzetti, R.L. Shannon, L. Bartelt-Hunt, Burns, S.E. and Smith, J.A., 2005 Hydraulic conductivities and effective diffusion coefficients of geosynthetic clay liners with organobentonite amendments Geotextiles and Geomembranes 23 385–400 10.1016/j.geotexmem.2005.02.002.CrossRefGoogle Scholar
Marry, V. Rotenberg, B. and Turq, P., 2008 Structure and dynamics of water at a clay surface from molecular dynamics simulation Physical Chemistry Chemical Physics 10 4802–4813 10.1039/b807288d.CrossRefGoogle Scholar
Mazo, M.A. Manevitch, L.I. Gusarova, E.B. Berlin, A.A. Balabaev, N.K. and Rutledge, G.C., 2008 Molecular dynamics simulation of thermomechanical properties of montmorillonite crystal. II. Hydrated montmorillonite crystal The Journal of Chemical Physics C 112 17056–17062 10.1021/jp711188u.CrossRefGoogle Scholar
Meleshyn, A., 2009 Cetylpyridinium aggregates at montmorillonite- and muscovite-water interface: a Monte Carlo study of surface charge effect Langmuir 25 6250–6259 10.1021/la804311w.CrossRefGoogle ScholarPubMed
Meleshyn, A. and Bunnenberg, C., 2006 Interlayer expansion and mechanisms of anion sorption of Na-montmorillonite modified by Cetylpyridinium chloride: A Monte Carlo study Journal of Physical Chemistry B 110 2271–2277 10.1021/jp056178v.CrossRefGoogle ScholarPubMed
Michot, L.J. Villieras, F. Francois, M. Bihannic, I. Pelletier, M. and Cases, J.-M., 2002 Water organisation at solidaqueous solution interface Geoscience 334 611–631 10.1016/S1631-0713(02)01801-1.CrossRefGoogle Scholar
Mills, R., 1973 Self-diffusion in normal and heavy water in the range 1–45°C Journal of Physical Chemistry 77 685–689 10.1021/j100624a025.CrossRefGoogle Scholar
Nakashima, Y., 2003 Diffusion of H2O in smectite gels: obstruction effects of bound H2O layer Clays and Clay Minerals 51 9–22 10.1346/CCMN.2003.510102.CrossRefGoogle Scholar
Nakashima, Y. and Mitsumori, F., 2005 H2O self-diffusion restricted by clay platelets with immobilized bound H2O layers: PGSE NMR study of water-rich saponite gels Applied Clay Science 28 209–221 10.1016/j.clay.2004.01.017.CrossRefGoogle Scholar
Oyanedel-Craver, V.A. Fuller, M. and Smith, J.A., 2007 Simultaneous sorption of benzene and heavy metals onto two organoclays Journal of Colloid and Interface Science 309 485–492 10.1016/j.jcis.2006.10.001.CrossRefGoogle ScholarPubMed
Patel, H.A. Somani, R.S. Bajaj, H.C. and Jasra, R.V., 2007 Preparation and characterization of phosphonium montmorillonite with enhance thermal stability Applied Clay Science 35 194–200 10.1016/j.clay.2006.09.012.CrossRefGoogle Scholar
Revil, A. and Jougnot, D., 2008 Diffusion of ions in unsaturated porous materials Journal of Colloid and Interface Science 319 226–235 10.1016/j.jcis.2007.10.041.CrossRefGoogle ScholarPubMed
Rytwo, G. Huterer-Harari, R. Dultz, S. and Gonen, Y., 2006 Adsorption of fast green and erythrosine-B to montmorillonite modified with crystal violet Journal of Thermal Analysis and Calorimetry 84 225–231 10.1007/s10973-005-7187-5.CrossRefGoogle Scholar
Rytwo, G. Kohavi, Y. Botnick, I. and Gonen, Y., 2007 Use of CV- and TPP-montmorillonite for the removal of priority pollutants from water Applied Clay Science 36 182–190 10.1016/j.clay.2006.04.016.CrossRefGoogle Scholar
Schampera, B. and Dultz, S., 2009 Determination of diffusive transport in HDPy-montmorillonite by H2O-D2O exchange using in situ ATR-FTIR spectroscopy Clay Minerals 44 249–266 10.1180/claymin.2009.044.2.249.CrossRefGoogle Scholar
Shackelford, C.D. and Daniel, E.D., 1991 Diffusion in saturated soil I: Background. Journal of Geotechnical Engineering 117 467–484.Google Scholar
Simonyan, A.V. Behrens, H. and Dultz, S., 2009 Diffusive transport of water in porous feldspars from granitic saprolites: In situ experiments using FTIR spectroscopy Geochimica et Cosmochimica Acta 73 7019–7033 10.1016/j.gca.2009.08.031.CrossRefGoogle Scholar
Soule, N.M. and Burns, S.E., 2001 Effect of organic cation structure on behaviour of organobentonites Journal of Geotechnical and Geoenvironmental Engineering 127 363–370 10.1061/(ASCE)1090-0241(2001)127:4(363).CrossRefGoogle Scholar
Tanaka, R. and Hirayama, N., 2008 Crystal structure of benzethonium chloride monohydrate Analytical Sciences 24 163–164.Google Scholar
Van Loon, L.R. Glaus, M.A. and Müller, W., 2007 Anion exclusion effects in compacted bentonites: towards a better understanding of anion diffusion Applied Geochemistry 22 2536–2552 10.1016/j.apgeochem.2007.07.008.CrossRefGoogle Scholar
Van Reeuwijk, L.P., 2003 Procedures for Soil Analysis 6th edition.Google Scholar
Woche, S.K. Goebel, M.-O. Kirkham, M.B. Horton, R. van der Ploeg, R.R. and Bachmann, J., 2005 Contact angle of soils as affected by depth, texture, and land management European Journal of Soil Science 56 239–251 10.1111/j.1365-2389.2004.00664.x.CrossRefGoogle Scholar
Yllera, A. Hernandez, M. Mingarro, A. Quejido, L.A. Sedano, J.M. Soler, J. Samper, J. Molinero, J.M. Barcala, P.L. Martýn, M. Fernandez, P. Wersin, P. Rivas, P. and Hernan, P., 2004 DI-B experiment: planning, design and performance of an in situ diffusion experiment in the Opalinus Clay formation Applied Clay Science 26 181–196 10.1016/j.clay.2003.12.007.CrossRefGoogle Scholar
Zhu, J. Zhu, L. Zhu, R. and Chen, B., 2008 Microstructure of organo-bentonites in water and effect of steric hindrance on the uptake of organic compounds Clays and Clay Minerals 56 144–154 10.1346/CCMN.2008.0560202.CrossRefGoogle Scholar