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A study of adsorption and absorption mechanisms of copper in palygorskite

Published online by Cambridge University Press:  09 July 2018

Y. F. Cai  and
J. Y. Xue
Y. F. Cai*
Affiliation:
State Key Laboratory of Mineral Deposits Research, Nanjing University, Nanjing, 210093, P. R. China Department of Earth Sciences, School of Earth Sciences and Engineering, Nanjing University, Nanjing, 210093, P. R. China
J. Y. Xue
Affiliation:
Department of Earth Sciences, School of Earth Sciences and Engineering, Nanjing University, Nanjing, 210093, P. R. China
*
*E-mail: caiyf@nju.edu.cn
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Abstract

Desorption experiments performed on four Cu-adsorbed palygorskites suggest that the leached Cu2+ ion originates at the surface and/or net-like interstice of the palygorskite fibres. The leached fraction, calculated from the quantities of adsorbed Cu2+ before and after desorption, is <1%. This may indicate that the majority of Cu is in inaccessible structural sites. X-ray diffraction, X-ray photoelectron spectroscopy, Fourier transform infrared (FTIR) spectroscopy and electron spin resonance (ESR) were used to determine the mineralogical character of the Cu-adsorbed palygorskite. Two photoelectron lines at 932.5 and/or 933.7 eV in the narrow scan Cu 2p3/2 spectra show that Cu adsorbed on the surface of palygorskite is in the Cu+ and Cu2+ state. The stretching vibrations of the octahedral cation shift ~3–5 cm–1 towards a greater wavenumber in the FTIR spectra of Cu-adsorbed palygorskite. It can be deduced that the Cu2+ is trapped in the channel of the palygorskite structure. The ESR spectra of the palygorskite give g values of 2.34, 2.12, 2.08 and 2.05, suggesting that some Cu ions cannot be reached by H+. These results confirm that Cu is adsorbed by palygorskite via three possible mechanisms: (1) the Cu is adsorbed onto the surface or in a net-like interstice, and its oxidation states are +1 and +2; (2) Cu forms a complex ion – [Cu(H2O)4]2+ or [Cu(H2O)6]2+, and is trapped in the channel; or (3) Cu enters into the hexagonal channel of the tetrahedral sites or the unoccupied octahedral sites of palygorskite.

Keywords

palygorskiteCuadsorbed siteadsorptionabsorptionXPSFTIRESRXRD
Type
Research Article
Information
Clay Minerals , Volume 43 , Issue 2 , June 2008 , pp. 195 - 203
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2008

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References

Álvarez-Ayuso, E. & García-Sánchez, A. (2003) Palygorskite as a feasible amendment to stabilize heavy metal polluted soils. Environmental Pollution, 125, 337–344.Google Scholar
Bahranowski, K., Dula, R., Lambanowska, M. & Serwicka, E.M. (1996) ESR study of Cu centers supported on Al-, Ti- and Zr-pillared montmorillonite clays. Applied Spectroscopy, 50, 1439–1445.Google Scholar
Barrer, R.M., Mackenzie, N. & MacLeod, D.M. (1954) Sorption by attapulgite. The Journal of Physical Chemistry, 58, 560–572.Google Scholar
Bradley, W.F. (1940) The structure scheme of attapulgite. American Mineralogist, 25, 405–410.Google Scholar
Cai, Y.F. & Xue, J.Y. (2004) Dissolution behavior and dissolution mechanism of palygorskite in HCl solution. Progress in Natural Sciences, 14, 235–240.Google Scholar
Cai, Y.F., Xue, J.Y. & Polya, D.A. (2007) A Fourier transform infrared spectroscopic study of Mg-rich, Mg-poor and acid-leached palygorskites. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 66, 282–288.Google Scholar
Chastain, J. & King, R.C. Jr. (1995) Handbook of X-ray Photoelectron Spectroscopy. Perkin-Elmer Corporation, Eden Prairie, Minnesota, USA. Pp. 86–87.Google Scholar
Clementz, D.M., Pinnavaia, T.J. & Mortland, M.M. (1973) Stereochemistry of hydrated copper (II) ions on the interlamellar surface of layer silicates: an electron spin resonance study. The Journal of Physical Chemistry, 77, 196–200.Google Scholar
Corma, A., Mifsud, A. & Sanz, E. (1990) Kinetics of the acid leaching of palygorskite: influence of the octahedral sheet composition. Clay Minerals, 25, 197–205.Google Scholar
Davison, N. & McWhinnie, W.R. (1991) X-ray photo-electron spectroscopic study of cobalt(II) and nickel(II) sorbed on hectorite and montmorillonite. Clays and Clay Minerals, 39, 22–27.Google Scholar
Daza, L., Mendioroz, S. & Pajares, J.A. (1991) Mercury adsorption by sulfurized fibrous silicates. Clays and Clay Minerals, 39, 14–21.Google Scholar
Farmer, V.C. (1974) The layer silicates. Pp. 331–343 in: The Infrared Spectra of Minerals (Farmer, V.C., editor). Monograph 4, Mineralogical Society, London.Google Scholar
Farquhar, M.L., Charnock, J.M., England, K.E.R. & Vaughan, D.J. (1996) Adsorption of Cu(II) on the (001) plane of mica: a REFLEXAFS and XPS study. Journal of Colloid and Interface Science, 177, 561–567.CrossRefGoogle Scholar
García-Sánchez, A., Alastuey, A. & Querol, X. (1999) Heavy metal adsorption by different minerals: application to the remediation of polluted soils. The Science of the Total Environment, 242, 179–188.Google Scholar
Gier, S. & Johns, W.D. (2000) Heavy metal-adsorption on micas and clay minerals studied by X-ray photo-electron spectroscopy. Applied Clay Science, 16, 289–299.Google Scholar
He, H.P., Guo, J.G., Xie, X.D. & Peng, J.L. (2001) Location and migration of cations in Cu2+-adsorbed montmorillonite. Environment International, 26, 347–352.CrossRefGoogle ScholarPubMed
Heller-Kallai, L. & Mosser, C. (1995) Migration of Cu ions in Cu montmorillonite heated with and without alkali halides. Clays and Clay Minerals, 43, 738–743.Google Scholar
Heller-Kallai, L. & Rozenson, I. (1981) Mössbauer studies of palygorskite and some aspects of paly-gorskite mineralogy. Clays and Clay Minerals, 29, 226–232.CrossRefGoogle Scholar
Holland, T.J.B. & Redfern, S.A.T. (1997) Unit-cell refinement from powder diffraction data: the use of regression diagnostics. Mineralogical Magazine, 61, 65–77.Google Scholar
Klein, J.C., Li, C.P., Hercules, D.M. & Black, J.F. (1984) Decomposition of copper compounds in X-ray photoelectron spectrometers. Applied Spectroscopy, 38(5), 729–734.Google Scholar
Koppelman, M.H. & Dillard, J.G. (1977) A study of the adsorption of Ni(II) and Cu(II) by clay minerals. Clays and Clay Minerals, 25, 457–462.Google Scholar
McBride, M.B. & Martínez, C.E. (2000) Copper phytotoxicity in a contaminated soil: remediation tests with adsorptive materials. Environmental Science and Technology, 34, 4386–4391.Google Scholar
McIntyre, N.S., Sunder, S., Shoesmith, D.W. & Stanchell, F.W. (1981) Chemical information from XPS —applications to the analysis of electrode surfaces. Journal of Vacuum Science and Technology, 18, 714–721.Google Scholar
Mosser, C., Mestdagh, M., Decarreau, A. & Herbillon, A.J. (1990) Spectroscopic (ESR, EXAFS) evidence of Cu for (Al-Mg) substitution in octahedral sheets of smectites. Clay Minerals, 25, 271–282.Google Scholar
Mosser, C., Mosser, A., Romeo, M., Petit, S. & Decarreau, A. (1992) Natural and synthetic copper phyllosilicates studied by XPS. Clays and Clay Minerals, 40, 593–599.Google Scholar
Mosser, C. , Michot, L.J., Villieras, F. & Romeo, M. (1997) Migration of cations in copper(II) exchanged montmorillonite and saponite upon heating. Clays and Clay Minerals, 45, 789–802.Google Scholar
Petit, S., Decarreau, A., Mosser, C. , Ehret, G. & Grauby, O. (1995) Hydrothermal synthesis (250°C) of copper-substituted kaolinites. Clays and Clay Minerals, 43, 482–494.Google Scholar
Potgieter, J.H., Potgieter-Vermaak, S.S. & Kalibantonga, P.D. (2006) Heavy metals removal from solution by palygorskite clay. Minerals Engineering, 19, 463–470.Google Scholar
Shariatmadari, H., Mermut, A.R. & Benke, M.B. (1999) Sorption of selected cationic and neutral organic molecules on palygorskite and sepiolite. Clays and Clay Minerals, 47, 44–53.CrossRefGoogle Scholar
Shirvani, M., Shariatmadari H, Kalbasi, M., Nourbakhsh, F. & Najafi, B. (2006a) Sorption of cadmium on palygorskite, sepiolite and calcite: equilibria and organic ligand affected kinetics. Colloids and Surfaces A: Physicochemical Engineering Aspects, 287, 182–190.CrossRefGoogle Scholar
Shirvani, M., Shariatmadari, H., Kalbasi, M., Nourbakhsh, F. & Najafi, B. (2006b) Sorption-desorption of cadmium on palygorskite, sepiolite and calcite: isotherm hysteresis. Chemosphere, 65, 2178–2184.Google Scholar
Strens, R.G.J., (1974) The common chain, ribbon and ring silicates. Pp. 313–318 in: The Infrared Spectra of Minerals (Farmer, V.C., editor). Monograph 4, Mineralogical Society, London.Google Scholar
Wen, L. (1989) FTIR Spectra of Minerals. 1 st Edition, Press of Chongqing University, China. 89–104 pp.Google Scholar
Yariv, S. (1986) Infrared evidence for the occurrence of SiO groups with double-bond character in antigorite, sepiolite and palygorskite. Clay Minerals, 21, 925–936.Google Scholar