Hostname: page-component-cd9895bd7-gxg78 Total loading time: 0 Render date: 2024-12-26T06:48:17.908Z Has data issue: false hasContentIssue false
  • English
  • Français

Effect of Cd(II) on the Ripening of Ferrihydrite in Alkaline Media

Published online by Cambridge University Press:  01 January 2024

Mariana Alvarez ,
María Fernanda Horst ,
Elsa E. Sileo  and
Elsa H. Rueda
Mariana Alvarez*
Affiliation:
INQUISUR, Departamento de Química, Universidad Nacional del Sur, Av. Alem 1253, B8000CPB, Bahía Blanca, Argentina
María Fernanda Horst
Affiliation:
INQUISUR, Departamento de Química, Universidad Nacional del Sur, Av. Alem 1253, B8000CPB, Bahía Blanca, Argentina
Elsa E. Sileo
Affiliation:
INQUIMAE, Departamento de Química Inorgánica, Analítica y Química Física, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Pabellón II, Ciudad Universitaria, C1428EHA, Buenos Aires, Argentina
Elsa H. Rueda
Affiliation:
INQUISUR, Departamento de Química, Universidad Nacional del Sur, Av. Alem 1253, B8000CPB, Bahía Blanca, Argentina
*
*E-mail address of corresponding author: alvarezm@criba.edu.ar
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.

To acquire a better understanding of the influence exerted by the presence of Cd2+ during the process of transforming ferrihydrite to goethite, the morphological and structural changes of several samples obtained by the addition of Cd2+ to a suspension of nascent goethite were explored, and their chemical reactivity in acid media assessed. The samples (series Gi) were obtained by adding, at different times during the synthesis process, Cd2+ ions to ferrihydrite (Fe5HO8.4H2O) formed in alkaline media. The suspensions were aged for 5 days at 70°C, and the amorphous materials were extracted using a HCl solution (series GHCl-i). The X-ray diffraction (XRD) patterns showed that a goethite-like phase was formed, and chemical analyses indicated that the Cd content, xCd, increased with the earlier addition of the Cd2+ ions to the Fe oxyhydroxide suspension. Lattice parameters and cell volume, obtained by the Rietveld simulation of XRD data, indicated an enlargement of the cell parameters of goethite in line with the Cd-for-Fe substitution. In order to determine the influence of oxalate ions on the non-extracted solids, a second set of samples was also prepared that was kept in contact with an ammonium oxalate solution for 4 h (series Gox-i). The dissolution behavior of two series of Cd goethites and of a third series, obtained from coprecipitation of Fe3+ and Cd2+ ions in alkaline media, was observed. Kinetics measurements in 4 M HCl showed that the initial dissolution rate of samples Gox-i decreased with aging time, while the opposite effect was observed for series GHCl-i. Dissolution–time curves were well described by the Kabai equation, and activation energies were calculated using the Arrhenius equation. The results indicate that the presence of Cd during the crystallization process of goethite leads to the formation of a Cd goethite with modified morphology, structural parameters, and chemical reactivity.

Keywords

Acid ReactivityAgingCadmium IncorporationGoethiteHCl ExtractionOxalate Extraction
Type
Article
Information
Clays and Clay Minerals , Volume 60 , Issue 2 , April 2012 , pp. 99 - 107
Copyright
Copyright © Clay Minerals Society 2012

References

Alvarez, M. Sileo, E.E. and Rueda, E.H., 2005 Effect of Mn(II) incorporation on the transformation of ferrihydrite to goethite Chemical Geology 216 89–97.CrossRefGoogle Scholar
Alvarez, M. Rueda, E.H. and Sileo, E.E., 2007 Simultaneous incorporation of Mn and Al in the goethite structure Geochimica et Cosmochimica Acta 71 1009–1020.CrossRefGoogle Scholar
Alvarez, M. Sileo, E.E. and Rueda, E.H., 2008 Structure and reactivity of synthetic Co-substituted goethites American Mineralogist 93 584–590.CrossRefGoogle Scholar
Benjamin, M.M. Sletten, R.S. Bailey, R.P. and Bennett, T., 1996 Sorption and filtration of metals using iron-oxide coated sand Water Research 30 2609–2620.10.1016/S0043-1354(96)00161-3CrossRefGoogle Scholar
Cornell, R.M. and Giovanoli, R., 1987 Effect of manganese on the transformation of ferrihydrite into goethite and jacobsite in alkaline media Clays and Clay Minerals 35 11–20.CrossRefGoogle Scholar
Cornell, R.M. Posner, A.M. and Quirk, J.P., 1974 Crystal morphology and the dissolution of goethite Journal of Inorganic and Nuclear Chemistry 36 1937–1946.10.1016/0022-1902(74)80705-0CrossRefGoogle Scholar
Cornell, R.M. and Schwertmann, U., 2003 The Iron Oxides 2nd edition New York Wiley-VCH 664.10.1002/3527602097CrossRefGoogle Scholar
Dollase, W.A., 1986 Corrections of intensities for preferred orientations in powder diffractometry: Applications of the March model Journal of Applied Crystallography 19 267–272.10.1107/S0021889886089458CrossRefGoogle Scholar
Filius, J.D. Hiemstra, T. and van Riemsdijk, W.H., 1997 Adsorption of small weak organic acids on goethite: Modeling of mechanisms Journal of Colloid and Interface Science 195 368–380.10.1006/jcis.1997.5152CrossRefGoogle ScholarPubMed
Finger, L.W. Cox, D.E. and Jephcoat, A.P., 1994 A correction for powder diffraction peak asymmetry due to axial divergence Journal of Applied Crystallography 27 892–900.CrossRefGoogle Scholar
Ford, R.G. Bertsch, P.M. and Farley, K.J., 1997 Changes in transition and heavy metal partitioning during hydrous iron oxide aging Environmental Science & Technology 31 2028–2033.CrossRefGoogle Scholar
Gabal, M.A., 2007 Non-isothermal kinetics and characterization studies for the decomposition course of CuC2O4-CdC2O4 mixture in air Journal of Physics and Chemistry of Solids 68 1610–1616.CrossRefGoogle Scholar
Goldschmidt, V.M., 1937 The principles of distribution of chemical elements in minerals and rocks Journal of Chemical Society 655–673.10.1039/JR9370000655CrossRefGoogle Scholar
Hem, J.D., 1972 Chemistry and occurrence of cadmium and zinc in surface and ground water Water Resources Research 8 661–679.10.1029/WR008i003p00661CrossRefGoogle Scholar
Huynh, T. Tong, A.R. Singh, B. and Kennedy, B.J., 2003 Cd-substituted goethites–A structural investigation by synchrotron X-ray diffraction Clays and Clay Minerals 51 397–402.10.1346/CCMN.2003.0510405CrossRefGoogle Scholar
Jones, D.L., 1998 Organic acids in the rhizosphere — a critical review Plant Soil 205 25–44.CrossRefGoogle Scholar
Jones, D.L. and Brassington, D.S., 1998 Sorption of organic acids in acid soils and its implications in the rhizosphere European Journal of Soil Science 49 447–455.CrossRefGoogle Scholar
Kabai, J., 1973 Determination of specific activation energies of metal oxides and metal oxide hydrates by measurement of the rate of dissolution Acta Chimica Academiae Scientarium Hungaricae 78 57–73.Google Scholar
Kaur, N. Singh, B. and Kennedy, B., 2009 Copper substitution alone and in the presence of chromium, zinc, cadmium and lead in goethite (α-FeOOH) Clay Minerals 44 293–310.10.1180/claymin.2009.044.3.293CrossRefGoogle Scholar
Kaur, N. Gräfe, M. Singh, B. and Kennedy, B., 2009 Simultaneous incorporation of Cr, Zn, Cd, and Pb in the goethite structure Clays and Clay Minerals 57 234–250.CrossRefGoogle Scholar
Krehula, S. and Musić, S., 2007 The influence of Cd-dopant on the properties of α-FeOOH and α-Fe2O3 particles precipitated in highly alkaline media Journal of Alloys and Compounds 431 56–64.CrossRefGoogle Scholar
Larson, A.C. and Von Dreele, R.B., 1994.General Structure Analysis System (GSAS)Google Scholar
Lundtorp, K. Jensen, D.L. Sørensen, M.A. Christensen, T.H. and Mogensen, E.P.B., 2002 Treatment of waste incinerator air-pollution-control residues with FeSO4: Concept and product characterisation. Waste Management & Research, 20 1, 69–79.10.1177/0734242X0202000108CrossRefGoogle ScholarPubMed
Martínez, C.E. and McBride, M., 1998 Coprecipitates of Cd, Cu, Pb and Zn in iron oxides: solid phase transformation and metal solubility after aging and thermal treatment Clays and Clay Minerals 46 537–545.CrossRefGoogle Scholar
Posselt, H.S. Weber, W.J. Jr., 1971 Environmental chemistry of cadmium in aqueous systems Tech Rept. T-71-1 Ann Arbor, Michigan, USA University of Michigan.Google Scholar
Rietveld, H.M., 1969 A profile refinement method for nuclear and magnetic structures Journal of Applied Crystallography B 25 925–46.Google Scholar
Ruan, H.D. Frost, R.L. and Kloprogge, J.T., 2001 The behavior of hydroxyl units of synthetic goethite and its dehydroxylated product hematite Spectrochimica Acta Part A 57 2575–2586.10.1016/S1386-1425(01)00445-0CrossRefGoogle ScholarPubMed
Sadiq, M., 1992 Toxic Metal Chemistry in Marine Environments New York Marcel Dekker Inc. 390.Google Scholar
Schultz, M.F. Benjamin, M.M. and Ferguson, J.F., 1987 Adsorption and desorption of metals on ferrihydrite: Reversibility of the reaction and sorption properties of the regenerated solid Environmental Science & Technology 21 863–869.CrossRefGoogle Scholar
Schwertmann, U., 1984 The influence of aluminium on iron oxides: IX Dissolution of Al-goethites in 6 M HCl. Clay Minerals 19 9–19.Google Scholar
Schwertmann, U. Cambier, P. and Murad, E., 1985 Properties of goethites of varying crystallinity Clays and Clay Minerals 33 369–378.10.1346/CCMN.1985.0330501CrossRefGoogle Scholar
Schwertmann, U. and Cornell, R.M., 2000 Iron Oxides in the Laboratory. Preparation and Characterization 2nd edition New York Wiley, VCH 188.Google Scholar
Schwertmann, U. and Latham, M., 1986 Properties of iron oxides in some New Caledonian oxisols Geoderma 39 105–123.10.1016/0016-7061(86)90070-4CrossRefGoogle Scholar
Sileo, E.E. Solís, P.S. and Paiva-Santos, C.O., 2003 Structural study of a series of synthetic goethites obtained in aqueous solutions containing cadmium (II) ions Powder Diffraction 18 49–55.10.1154/1.1538188CrossRefGoogle Scholar
Sileo, E.E. Ramos, A.Y. Magaz, G.E. and Blesa, M.A., 2004 Long-range vs short-range ordering in synthetic Crsubstituted goethites. Geochimica et Cosmochimica Acta 68 3053–3063.10.1016/j.gca.2004.01.017CrossRefGoogle Scholar
Stephens, P.W., 1999 Phenomenological model of anisotropic bradening in powder diffraction Journal of Applied Crystallography 32 281–289.10.1107/S0021889898006001CrossRefGoogle Scholar
Sulzberger, B. and Laubscher, H., 1995 Reactivity of various types of iron (III) (hydr)oxides towards light-induced dissolution Marine Chemistry 50 103–115.10.1016/0304-4203(95)00030-UCrossRefGoogle Scholar
Szytula, A. Burewicz, A. Dimitrijewic, Z. Krasnicki, S. Rzany, H. Todorovic, J. Wanic, A. and Wolski, W., 1968 Neutron diffraction studies of α-FeOOH Physica Status Solidi 26 429–434.10.1002/pssb.19680260205CrossRefGoogle Scholar
Thompson, P. Cox, D.E. and Hastings, J.B., 1987 Rietveld refinement of Debye-Scherrer synchrotron X-ray data from Al2O3 Journal of Applied Crystallography 20 79–83.10.1107/S0021889887087090CrossRefGoogle Scholar
Toby, B.H., 2001 EXPGUI, a graphical user interface for GSAS Journal of Applied Crystallography 34 210–213.10.1107/S0021889801002242CrossRefGoogle Scholar
Vogel, A.I., 1960 Química Analítica Cuantitativa Volumen II. Química Analítica Aplicada, Análisis Instrumental y Análisis de Gases. Editorial Kapelusz, Buenos Aires, Argentina, 1173 pp.Google Scholar
Wells, M.A. Gilkes, R.J. and Fitzpatrick, R.W., 2001 Properties and acid dissolution of metal-substituted hematites Clays and Clay Minerals 49 60–72.CrossRefGoogle Scholar
Wells, M.A. Fitzpatrick, R.W. and Gilkes, R.J., 2006 Thermal and mineral properties of Al-, Cr-, Mn-, Ni- and Ti-substituted goethite Clays and Clay Minerals 54 176–194.10.1346/CCMN.2006.0540204CrossRefGoogle Scholar