Hostname: page-component-848d4c4894-xm8r8 Total loading time: 0 Render date: 2024-06-19T22:49:46.239Z Has data issue: false hasContentIssue false
  • English
  • Français

Stability of Iron in Clays Under Different Leaching Conditions

Published online by Cambridge University Press:  01 January 2024

Barbora Dousova ,
Lucie Fuitova ,
David Kolousek ,
Miloslav Lhotka ,
Tomas Matys Grygar  and
Petra Spurna
Barbora Dousova*
Affiliation:
Institute of Chemical Technology in Prague, Technicka 5, 166 28, Prague 6, Czech Republic
Lucie Fuitova
Affiliation:
Institute of Chemical Technology in Prague, Technicka 5, 166 28, Prague 6, Czech Republic
David Kolousek
Affiliation:
Institute of Chemical Technology in Prague, Technicka 5, 166 28, Prague 6, Czech Republic
Miloslav Lhotka
Affiliation:
Institute of Chemical Technology in Prague, Technicka 5, 166 28, Prague 6, Czech Republic
Tomas Matys Grygar
Affiliation:
Institute of Inorganic Chemistry AS CR, 250 68, Řež, Czech Republic
Petra Spurna
Affiliation:
Institute of Chemical Technology in Prague, Technicka 5, 166 28, Prague 6, Czech Republic
*
*E-mail address of corresponding author: Barbora.Dousova@vscht.cz
Get access Rights & Permissions [Opens in a new window]

Abstract

The iron chemistry of aluminosilicates can markedly affect their adsorption properties due to possible changes in surface charge upon exposure to a variety of processes in the environment. One of these processes is chemical leaching, but to date little has been reported on the susceptibility of structural Fe to chemical leaching. The purpose of the current study was to determine the effects of solution pH on the stability of structural Fe in kaolinites, illite, and bentonite and the potential for formation of ancillary (oxyhydr)oxides. Structurally bound Fe does not participate in sorption properties but Fe that is released and phase transformed during leaching could take part in adsorption processes and form complexes and/or covalent bonds via Fe ions. Five different Fe-bearing clay minerals were treated in 0.5 M and 2 M HCl, distilled H2O, 0.1MKCl, and 0.5MKHCO3 for 24 h. The amount of Fe leached varied from 10 μg g-1 (for 0.1 M KCl) to 104 μg g-1 (for 2 M HCl) depending on the leaching agents. Acidic and water treatments indicated a relative independence of leached Fe on the initial Fe content in the clay and, conversely, a heavy dependence on the crystallinity of initial Fe phases. Well crystallized Fe(III) was stable during the leaching process, while poorly crystallized and amorphous Fe(III) phases were less stable, forming new ion-exchangeable Fe3+ particles. Under alkaline conditions, no relation between Fe crystallinity and mobility was found. The structural and surface changes resulting from leaching processes were identified by equilibrium adsorption isotherms. In kaolinite, the specific surface area (SBET) and porosity changed independently of Fe leaching due to the stability and crystallinity of Fe. In bentonite, the number of micropores was reduced by their partial saturation with Fe3+ particles caused by poorly crystallized and more reactive Fe forms during the leaching process. Potential phase transformations of Fe were characterized by the voltammetry of microparticles; well crystallized Fe(III) oxides remained stable under leaching conditions, while poorly crystallized and amorphous Fe(III) phases were partially dissolved and transformed to reactive Fe3+ forms.

Keywords

ClaysIronLeaching StabilityStructureSurface Properties
Type
Article
Information
Clays and Clay Minerals , Volume 62 , Issue 2 , April 2014 , pp. 145 - 152
Copyright
Copyright © Clay Minerals Society 2014

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.)

References

Alvarez Querol, M.C., 1952 Manganometric microtitration of iron Microchimica Acta 39 2 126–132.CrossRefGoogle Scholar
Barret, E.P. Joyer, L.G. and Halenda, P.P., 1951 The determination of pore volume and area distributions in porous substances. I. Computations from nitrogen isotherms Journal of the American Chemical Society 73 373–380.CrossRefGoogle Scholar
Bonnin, D. Miller, S. and Calas, G., 1982 Iron in kaolins: studies by EPR, Mössbauer, X-ray absorption, EXAFS Bulletin de Mineralogie 105 467–475.CrossRefGoogle Scholar
Brunauer, S. Emmet, P.H. and Teller, F., 1938 Adsorption of gases in multimolecular layers Journal of the American Chemical Society 60 309–319.CrossRefGoogle Scholar
Burleson, D.J. and Penn, R.L., 2006 Two-step growth of goethite from ferrihydrite Langmuir 22 402–409.CrossRefGoogle ScholarPubMed
Cepriá, G. Usón, A. Pérez-Arantegui, J. and Castillo, J.R., 2003 Identification of iron(III) oxides and hydroxy-oxides by voltammetry of immobilised microparticles Analytica Chimica Acta 477 157–168.CrossRefGoogle Scholar
Dávila-Jiménez, M.M. Elizade-González, M.P. Mattusch, J. Morgenstern, P. Pérez-Cruz, M.A. Reyes-Ortega, Y. Wennrich, R. and Hee-Madeira, H., 2008 In situ and ex situ study of the enhanced modification with iron of clinoptilolite-rich zeolitic tuff for arsenic sorption from aqueous solutions Journal of Colloid and Interface Science 322 527–536.CrossRefGoogle ScholarPubMed
Doménech, A. Lastras, M. Rodrígues, F. and Osete, L., 2013 Mapping of corrosion products of highly altered archeological iron using voltammetry of microparticles Microchemical Journal 106 41–50.CrossRefGoogle Scholar
Doušová, B. Fuitová, L. Grygar, T. Machovič, V. Koloušek, D. Herzogová, L. and Lhotka, M., 2009 Modified aluminosilicates as low-cost sorbents of As(III) from anoxic groundwater Journal of Hazardous. Materials 165 134–140.CrossRefGoogle ScholarPubMed
Doušová, B. Lhotka, M. Grygar, T. Machovič, V. and Herzogová, L., 2011 In situ co-adsorption of arsenic and iron/manganese ions on raw clays Applied Clay Science 54 166–171.CrossRefGoogle Scholar
Favre, F. Bogdal, C. Gavillet, S. and Stucki, J.W., 2006 Changes in the CEC of a soil smectite-kaolinite clay fraction as induced by structural iron reduction and iron coatings dissolution Applied Clay Science 34 95–104.CrossRefGoogle Scholar
Ferris, A.P. and Jepson, W.B., 1975 The exchange capacities of kaolinite and the preparation of homoionic clays Journal of Colloid and Interface Science 51 245–259.CrossRefGoogle Scholar
Gil, B. and Adamski, A., 2010 Complementary use of IR and EPR spectroscopies for characterization of iron species in thermally treated MFI-type zeolites Microporous and Mesoporous Materials 127 82–89.CrossRefGoogle Scholar
Grygar, T. Bezdička, P. Hradil, D. Doménech-Carbó, A, M. F, P ^L and Cepriá, G., 2002 Voltammetric analysis of iron oxide pigments Analyst 127 1100.CrossRefGoogle ScholarPubMed
Grygar, T. Hradil, D. Bezdička, P. Doušová, B. Čapek, L. and Schneeweiss, O., 2007 Fe(III) modified montmorillonite and bentonite: Synthesis, chemical and UV-VIS spectral characterization, arsenic sorption, and catalysis of oxidative dehydrogenation of propane Clays and Clay Minerals 55 165–176.CrossRefGoogle Scholar
Hassan, M.S. and Salem, S.M., 2002 Distribution and influence of iron phases on the physico-chemical properties of phyllosilicates Chinese Journal of Geochemistry 21 29–39.CrossRefGoogle Scholar
Izumi, Y. Masih, D. Aika, K. and Seida, Y., 2005 Characterization of intercalated iron(III) nanoparticles and oxidative adsorption of arsenite on them monitored by X-ray absorption fine structure combined with fluorescence spectrometry The Journal of Physical Chemistry B 109 3227–3232.CrossRefGoogle ScholarPubMed
Komadel, P. Madejová, J. and Stucki, J.W., 2006 Structural Fe(III) reduction in smectites Applied Clay Science 34 88–94.CrossRefGoogle Scholar
Lhotka, M. Machovič, V. and Doušová, B., 2012 Preparation of modified sorbents from rehydrated clay minerals Clay Minerals 47 251–258.CrossRefGoogle Scholar
Malat, M., 1973 Absorption Inorganic Photometry Prague (in Czech) Academia 684–709.Google Scholar
Madejová, J. Pentrák, M. Pálková, H. and Komadel, P., 2009 Near-infrared spectroscopy: A powerful tool in studies of acid-treated clay minerals Vibrational Spectroscopy 49 211–218.CrossRefGoogle Scholar
Manceau, A. Drits, V.A. Lanson, B. Chateigner, D. Wu, J. Huo, D. Gates, W.P. and Stucki, J.W., 2000 Oxidation-reduction mechanism of iron in dioctahedral smectites: 2. Crystal chemistry of reduced Garfield nontronite American Mineralogist 85 153–172.CrossRefGoogle Scholar
Maqueda, C. Santas Romero, A. Morillo, E. Pérez-Rodríguez, J.L. Lerf, A. and Wagner, F.E., 2008 The behavior of Fe in ground and acid-treated vermiculite from Santa Olalla, Spain Clays and Clay Minerals 56 380–388.CrossRefGoogle Scholar
Pentráková, L. Su, K. Pentrák, M. and Stucki, W., 2013 A review of microbial redox interactions with structural Fe in clay minerals Clay Minerals 48 543–560.CrossRefGoogle Scholar
Sei, J. Jumas, J.C. Olivier-Fourcade, J. Quiquampoix, H. and Staunton, S., 2002 Role of iron oxides in the phosphate adsorption properties of kaolinites from the Ivory Coast Clays and Clay Minerals 50 217–222.CrossRefGoogle Scholar
Stucki, J.W. Goodman, B.A. and Schwertmann, U., 1988 Iron in Soils and Clay Minerals Dordrecht, The Netherlands D. Riedel Publishing Company 447–480.Google Scholar
Sultana, U.K. Gulshan, F. and Kurny, A.S.W., 2014 Kinetics of leaching of iron oxide in clay in oxalic acid and hydrochloric acid solutions Materials Science and Metallurgy Engineering 2 5–10.Google Scholar
van Oorschot, I.H.M. Grygar, T. and Dekkers, M.J., 2001 Detection of low concentrations of fine-grained iron oxides by voltammetry of microparticles Earth and Planetary Science Letters 193 631–642.CrossRefGoogle Scholar
Webb, P.A. and Orr, C., 1997 Analytical Methods in Fine Particle Technology Georgia, USA Micromeritics Instrument Corporation, Norcross.Google Scholar
Yang, L. Donahoe, R.J. and Redwine, J.C., 2007 In situ chemical fixation of arsenic contaminated soils: An experimental study Science of the Total Environment 387 28–41.CrossRefGoogle ScholarPubMed
Žák, T. and Jirásková, Y., 2006 CONFIT: Mössbauer spectra fitting program Surface and Interface Analysis 38 710–714.CrossRefGoogle Scholar