Hostname: page-component-586b7cd67f-vdxz6 Total loading time: 0 Render date: 2024-12-01T01:38:06.909Z Has data issue: false hasContentIssue false
  • English
  • Français

Characterization of Natural Clays from Italian Deposits with Focus on Elemental Composition and Exchange Estimated by EDX Analysis: Potential Pharmaceutical and Cosmetic Uses

Published online by Cambridge University Press:  01 January 2024

Valentina Iannuccelli ,
Eleonora Maretti ,
Francesca Sacchetti ,
Marcello Romagnoli ,
Alessia Bellini ,
Eleonora Truzzi ,
Paola Miselli  and
Eliana Leo
Valentina Iannuccelli*
Affiliation:
Department of Life Sciences, University of Modena and Reggio Emilia, via G. Campi 103, 41125, Modena, Italy Department of Engineering Enzo Ferrari, University of Modena and Reggio Emilia, via P. Vivarelli 10, 41125, Modena, Italy
Eleonora Maretti
Affiliation:
Department of Life Sciences, University of Modena and Reggio Emilia, via G. Campi 103, 41125, Modena, Italy Department of Engineering Enzo Ferrari, University of Modena and Reggio Emilia, via P. Vivarelli 10, 41125, Modena, Italy
Francesca Sacchetti
Affiliation:
Department of Life Sciences, University of Modena and Reggio Emilia, via G. Campi 103, 41125, Modena, Italy Department of Engineering Enzo Ferrari, University of Modena and Reggio Emilia, via P. Vivarelli 10, 41125, Modena, Italy
Marcello Romagnoli
Affiliation:
Department of Life Sciences, University of Modena and Reggio Emilia, via G. Campi 103, 41125, Modena, Italy Department of Engineering Enzo Ferrari, University of Modena and Reggio Emilia, via P. Vivarelli 10, 41125, Modena, Italy
Alessia Bellini
Affiliation:
Department of Life Sciences, University of Modena and Reggio Emilia, via G. Campi 103, 41125, Modena, Italy Department of Engineering Enzo Ferrari, University of Modena and Reggio Emilia, via P. Vivarelli 10, 41125, Modena, Italy
Eleonora Truzzi
Affiliation:
Department of Life Sciences, University of Modena and Reggio Emilia, via G. Campi 103, 41125, Modena, Italy Department of Engineering Enzo Ferrari, University of Modena and Reggio Emilia, via P. Vivarelli 10, 41125, Modena, Italy
Paola Miselli
Affiliation:
Department of Life Sciences, University of Modena and Reggio Emilia, via G. Campi 103, 41125, Modena, Italy Department of Engineering Enzo Ferrari, University of Modena and Reggio Emilia, via P. Vivarelli 10, 41125, Modena, Italy
Eliana Leo
Affiliation:
Department of Life Sciences, University of Modena and Reggio Emilia, via G. Campi 103, 41125, Modena, Italy Department of Engineering Enzo Ferrari, University of Modena and Reggio Emilia, via P. Vivarelli 10, 41125, Modena, Italy
*
*E-mail address of corresponding author: [email protected]
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.

Purification processes performed on natural clays to select specific clay minerals are complex and expensive and can lead to over-exploitation of some deposits. The present study aimed to examine physicochemical (mineralogy, morphology, size, surface charge, chemical composition, cation exchange capacity [CEC], and pH) and hydration (swelling, wettability, water sorption, and rheological behavior) properties of three native clays from Italian deposits for potential pharmaceutical and cosmetic uses due to the presence of phyllosilicate minerals. Particular emphasis was placed on energy dispersive X-ray (EDX) microanalysis coupled with the ‘cesium method’ to assay clay elemental composition and CEC. One bentonite of volcanic origin (BNT) and two kaolins, one of hydrothermal origin (K-H) and another of lacustrine-fluvial origin (K-L), were evaluated in comparison with a commercial, purified bentonite. The CEC assay revealed the complete substitution of exchangeable cations (Na+ and Ca2+) by Cs+ in BNT samples and CEC values consistent with those of typical smectites (100.64 ± 7.33 meq/100 g). For kaolins, partial substitution of Na+ cations occurred only in the K-L samples because of the interstratified mineral component which has small CEC values (11.13 ± 5.46 meq/100 g for the K-H sample and 14.75 ± 6.58 meq/100 g for the K-L sample). The degree of isomorphous substitution of Al3+ by Mg2+ affected the hydration properties of BNT in terms of swelling, water sorption, and rheology, whereas both of the poorly expandable kaolins exhibited significant water-adsorption properties. The EDX microanalysis has proved to be of considerable interest in terms of providing more information about clay properties in comparison with other commonly used methods and to identify the role played by both chemical and mineralogical composition of natural clays for their appropriate use in pharmaceutical and cosmetic fields.

Keywords

BentoniteCation Exchange CapacityEnergy Dispersive X-ray AnalysisKaolinRheologyWater Sorption
Type
Article
Information
Clays and Clay Minerals , Volume 64 , Issue 6 , December 2016 , pp. 719 - 731
Copyright
Copyright © Clay Minerals Society 2016

Footnotes

An erratum to this article is available online at https://doi.org/10.1007/BF03406058.

References

Abu-Jdayil, B., 2011 Rheology of sodium and calcium bentonite-water dispersions: effect on electrolytes and aging time International Journal of Mineral Processing 98 208–213.CrossRefGoogle Scholar
Adeyinka, O.B. Samiei, S. Xu, Z. and Masliyah, J.H., 2009 Effect of particle size on the rheology of Athabasca clay suspensions The Canadian Journal of Chemical Engineering 87 422–434.CrossRefGoogle Scholar
Aguzzi, C. Cerezo, P. Viseras, C. and Caramella, C., 2007 Use of clays as drug delivery systems: possibilities and limitations Applied Clay Science 36 22–36.CrossRefGoogle Scholar
Alkan, M. Demirbas, O. and Dogan, M., 2005 Elektrokinetic properties of kaolinite in mono- and multivalent electrolyte solutions Microporous and Mesoporous Materials 83 51–59.CrossRefGoogle Scholar
Alves, J.L. Zanini, A.E. de Souza, M.E. and Nascimento, M.L.F., 2016 Study of selection and purification of Brazilian bentonite clay by elutriation: an XRF, SEM and Rietveld analysis Cerâmica 62 1–8.CrossRefGoogle Scholar
Anthony, J.W. Bideaux, R.A. Bladh, K.W. and Nichols, M.C., 1995 Handbook of Mineralogy II (Silica, Silicates) Arizona, USA. Mineral Data Publishing, Tucson.Google Scholar
Au, P.I. and Leong, Y.K., 2013 Rheological and zeta potential behaviour of kaolin and bentonite composite slurries Colloids and Surface A: Physicochemical and Engineering Aspect 436 530–541.CrossRefGoogle Scholar
Benea, M. and Gorea, M., 2004 Mineralogy and technological properties of some kaolin types used in the ceramic industry Studia UBB Geologia 49 33–39.CrossRefGoogle Scholar
Bergaya, F. Lagaly, G., Bergaya, F. and Lagaly, G., 2013 Purification of natural clays Handbook of Clay Science Amsterdam Elsevier 213–221.CrossRefGoogle Scholar
Bergaya, F. Jaber, M. Lambert, J.-F., Avérous, L. and Pollet, E., 2012 Clays and clay minerals as layered nanofillers for (bio) polymers Environmental Silicate Nano-Biocomposites London Springer-Verlag 41–76.CrossRefGoogle Scholar
Bloodworth, A.J. Highley, D.E. and Mitchell, C.J., 1993 Industrial Minerals Laboratory Manual: Kaolin. Bgs Technical Report Wg/93/1 Nottingham, UK British Geological Survey.Google Scholar
Carretero, M.I., 2002 Clay minerals and their beneficial effects upon human health A review. Applied Clay Science 21 155–163.CrossRefGoogle Scholar
Chemani, H., 2015 Correlation between milling time, particle size for stabilizing rheological parameters of clay suspensions in ceramic tiles manufacture International Journal of Physical Sciences 10 46–53.Google Scholar
Delgado, A. Conzalez-Caballero, F. and Bruque, J.M., 1986 On the zeta potential and surface charge density of montmorillonite in aqueous electrolyte solutions Journal of Colloid and Interface Science 113 203–211.CrossRefGoogle Scholar
de Paiva, L.B. Morales, A.R. and Valenzuela-Díaz, F.R., 2008 Organoclays: properties, preparation and applications Applied Clay Science 42 8–24.CrossRefGoogle Scholar
Dohnalova, Z. Svoboda, L. and Sulcova, P., 2008 Characterization of kaolin dispersion using acoustic and electroacoustic spectroscopy Journal of Mining and Metallurgy 44B 63–72.CrossRefGoogle Scholar
Donahue, R.L. Miller, R.W. and Shickluna, J.C., 1977 Soils: an Introduction to Soils and Plant Growth New Jersey, USA Prentice-Hall.Google Scholar
Dontsova, K.M. Norton, L.D. Johnston, C.I. and Bigham, J.M., 2004 Influence of exchangeable cations on water adsorption by soil clays Soil Science Society of America Journal 68 1218–1227.CrossRefGoogle Scholar
Enslin, O., 1933 Úber einen apparat zur messung der fl—ssigkeitsaufnahme von quellbaren und porósen stoffen und sur charakterisierung der benetzbarkeit Die Chemische Fabrik 6 147–148.Google Scholar
Foster, M.D., 1954 The relation between composition and swelling in clays Clays and Clay Minerals 3 205–220.CrossRefGoogle Scholar
Furukawa, Y. Watkins, J.L. Kim, J. Curry, K.J. and Bennett, R.H., 2009 Aggregation of montomorillonite and organic matter in aqueous media containing artificial seawater Geochemical Transactions 10 2.CrossRefGoogle Scholar
GALINDOROSALES, F. and RUBIOHERNANDEZ, F., 2006 Structural breakdown and build-up in bentonite dispersions Applied Clay Science 33 2 109–115.CrossRefGoogle Scholar
Grim, R.E., 1968 Clay Mineralogy New York McGraw-Hill.Google Scholar
He, H. Ma, Y. Zhu, J. Yuan, P. and Qing, Y., 2010 Organoclays prepared from montmorillonites with different cation exchange capacity and surfactant configuration Applied Clay Science 48 67–72.CrossRefGoogle Scholar
Heller, H. and Keren, R., 2001 Rheology of Na-rich montmorillonite suspension as affected by electrolyte concentration and shear rate Clays and Clay Minerals 49 286–291.CrossRefGoogle Scholar
Hillier, S., 1992 Cation exchange staining of clay minerals in thin-section for electron microscopy Clay Minerals 27 379–384.CrossRefGoogle Scholar
Holtz, R.D. and Kovacs, W.D., 1981 An Introduction to Geotechnical Engineering New Jersey, USA Prentice-Hall.Google Scholar
Hosterman, J.W. and Patterson, S.H., 1992 entonite and Fuller’s Earth Resources of the United States Washington United States Government Printing Office.Google Scholar
Huertas, F.J. Chou, L. and Wollast, R., 1998 Mechanism of kaolinite dissolution at room temperature and pressure: Part 1. Surface speciation Geochimica et Cosmochimica Acta 62 417–431.CrossRefGoogle Scholar
Iannuccelli, V. Maretti, E. Montorsi, M. Rustichelli, C. Sacchetti, F. and Leo, E., 2015 Gastroretentive montmorillonite-tetracycline nanoclay for the treatment of Helicobacter pylori infection International Journal of Pharmaceutics 493 295–304.CrossRefGoogle ScholarPubMed
Jin, H. Wie, J.J. and Kim, S.C., 2010 Effect of organoclays on the properties of polyurethane/clay nanocomposite coatings Journal of Applied Polymer Science 117 2090–2100.CrossRefGoogle Scholar
Katti, K.S. Ambre, A.H. Peterka, N. and Katti, D.R., 2010 Use of unnatural amino acids for design of novel organomodified clays as components of nanocomposite biomaterials Philosophical Transactions of the Royal Society A 368 1963–1980.CrossRefGoogle ScholarPubMed
Kaufhold, S. Dohrmann, R. and Houben, G., 2008 The pH of aqueous bentonite suspensions Clays and Clay Minerals 56 338–343.CrossRefGoogle Scholar
Kennedy, R.A. and Kennedy, M.L., 2007 Effect of selected non-ionic surfactants on the flow behavior of aqueous veegum suspensions AAPS PharmSciTech 8 E171–E176.CrossRefGoogle ScholarPubMed
Lloyd, M.K. and Conley, R.F., 1970 Adsorption studies on kaolinites Clays and Clay Minerals 18 37–46.CrossRefGoogle Scholar
Lopez-Galindo, A. Viseras, C. and Cerezo, P., 2007 Compositional, technical and safety specifications of clays to be used as pharmaceutical and cosmetic products Applied Clay Science 36 51–63.CrossRefGoogle Scholar
Low, P.F., 1981 The swelling of clay: III Dissociation of exchangeable cations. Soil Science Society of America Journal 45 1074–1078.CrossRefGoogle Scholar
Luckham, P.F. and Rossi, S., 1999 The colloidal and rheological properties of bentonite suspensions Advances in Colloid and Interface Science 82 43–92.CrossRefGoogle Scholar
Ma, C. and Eggleton, R.A., 1999 Cation exchange capacity of kaolinite Clays and Clay Minerals 47 174–180.Google Scholar
Miranda-Trevino, J.C. and Coles, C.A., 2003 Kaolinite properties, structure and influence of metal retention on pH Applied Clay Science 23 133–139.CrossRefGoogle Scholar
Motokawa, R. Endo, H. Yokoyama, S. Nishitsuji, S. Kobayashi, T. Suzuki, S. and Yaita, T., 2014 Collective structural changes in vermiculite clay suspensions induced by cesium ions Scientific Reports 4 6585.CrossRefGoogle ScholarPubMed
Murray, H.H., 1991 Overview — clay mineral applications Applied Clay Science 5 379–395.CrossRefGoogle Scholar
Nones, J. Riella, H.G. Trentin, A.G. and Nones, J., 2015 Effects of bentonite on different cell types: A brief review Applied Clay Science 105-106 225–230.CrossRefGoogle Scholar
Packter, A., 1956 Studies in the rheology of clay-water systems. Part I. The viscosity of sodium montmorillonite sols Kolloid-Zeitschrift und Zeitschrift fúr Polymere 149 109–115.CrossRefGoogle Scholar
Patterson, S.H. Murray, H.H., Lefond, S.J., 1983 Clays Industrial Minerals and Rocks New York American Institute of Mining, Metallurgical, and Petroleum Engineers 585–651.Google Scholar
Pecini, E.M. and Avena, M.J., 2013 Measuring the isoelectric point of the edges of clay mineral particles: the case of montmorillonite Langmuir 29 14926–14934.CrossRefGoogle ScholarPubMed
Pusch, R., 2015 Pharmacology and cosmetics Bentonite Clay — Environmental Properties and Applications Boca Raton, Florida, USA CRC Press, Taylor & Francis Group 381–308.CrossRefGoogle Scholar
Rajkumar, M. Meenakshisundaram, N. and Rajendran, V.R., 2011 Development of nanocomposites based on hydroxyapatite/sodium alginate: synthesis and characterisation Materials Characterization 62 469–479.CrossRefGoogle Scholar
Rieder, M. Cavazzini, G. D’Yakonov, Y.S. Frank-Kamenetskii, V.A. Gottardi, G. Guggenheim, S. Koval’, P.V. Múller, G. Neiva, A.M.R. Radoslovich, E.W. Robert, J.-L. Sassi, F.P. Takeda, H. Weiss, Z. and Wones, D.R., 1998 Nomenclature of the micas The Canadian Mineralogist 36 41–48.Google Scholar
Rodrigues, L.A.S. Figueiras, A. Veiga, F. de Freitas, R.M. Nunes, L.C. da Silva Filho, E.C. and da Silva Leite, C.M., 2013 The systems containing clays and clay minerals from modified drug release: A review Colloids and Surfaces B: Biointerfaces 103 642–651.CrossRefGoogle ScholarPubMed
Salles, F. Bildstein, O. Douillard, J.M. Jullien, M. Raynal, J. and Van, D. H., 2010 On the cation dependence of interlamellar and interparticular water and swelling in smectite clays Langmuir 26 5028–5037.CrossRefGoogle ScholarPubMed
Segad, M. Jónsson, B. Akesson, T. and Cabane, B., 2010 Ca/Na montmorillonite: structure, forces and swelling properties Langmuir 26 5782–5790.CrossRefGoogle ScholarPubMed
Sharma, A.L. and Thakur, A.K., 2010 Improvement in voltage, thermal, mechanical stability and ion transport properties in polymer-clay nanocomposites Journal of Applied Polymer Science 118 2743–2753.CrossRefGoogle Scholar
Singh, B. and Gilkes, R.J., 1991 Concentration of iron oxides from soil clays by 5 M NaOH treatment: the complete removal of sodalite and kaolin Clay Minerals 26 463–472.CrossRefGoogle Scholar
Stepkowska, E.T. Pérez-Rodríuez, J.L. de Haro, M.C.J. Sánchez-Soto, P.J. and Maqueda, C., 2001 Effect of grinding and water vapour on the particle size of kaolinite and pyrophyllite Clay Minerals 36 105–114.CrossRefGoogle Scholar
van Stul, MS L ^L, 1982 Particle-size distribution, cation exchange capacity and charge density of deferrated montmorillonites Clay Minerals 17 209–215.CrossRefGoogle Scholar
Tateo, F. and Summa, V., 2007 Element mobility in clays for healing use Applied Clay Science 36 64–76.CrossRefGoogle Scholar
Taylor, R.K. and Smith, T.J., 1986 The engineering geology of clay minerals: swelling, shrinking and mudrock breakdown Clay Minerals 21 235–260.CrossRefGoogle Scholar
Thomas, G.W., Page, A.L., 1982 Exchangeable cations Method of Soil Analysis, Part 2. Chemical and Microbiological Properties Madison, Wisconsin, USA American Society of Agronomy 159–165.Google Scholar
Tran, N.H. Wilson, M.A. Milev, A.S. Dennis, G.R. Kannangara, G.S.K. and Lamb, R.N., 2006 Dispersion of silicate nano-plates within poly(acrylic acid) and their interfacial interactions Science and Technology of Advanced Materials 7 786–791.CrossRefGoogle Scholar
Van Olphen, H., 1977 An Introduction to Clay Colloid Chemistry for Clay Technologists, Geologists, and Soil Scientists New York Wiley.Google Scholar
Velde, B., 1992 Introduction to Clay Minerals — Chemistry, Origins, Uses and Environmental Significance London Chapman & Hall.CrossRefGoogle Scholar
Veniale, F. Bettero, A. Jobstraibizer, P.G. and Setti, M., 2007 Thermal muds: perspectives of innovations Applied Clay Science 36 141–147.CrossRefGoogle Scholar
Viseras, C. Cerezo, P. Sanchez, R. Salcedo, I. and Aguzzi, C., 2010 Current challenges in clay minerals for drug delivery Applied Clay Science 48 291–295.CrossRefGoogle Scholar
White, J.L. and Hem, S.L., 1983 Pharmaceutical aspects of clay-organic interactions Industrial & Engineering Chemistry Product Research and Development 22 665–671.CrossRefGoogle Scholar
World Health Organization, 2005 Bentonite, kaolin, and selected clay minerals. Environmental Health Criteria 231 Geneva World Health Organization.Google Scholar