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Copper Sorption Mechanisms on Smectites

Published online by Cambridge University Press:  01 January 2024

Daniel G. Strawn ,
Noel E. Palmer ,
Luca J. Furnare ,
Carmen Goodell ,
James E. Amonette  and
Ravi K. Kukkadapu
Daniel G. Strawn*
Affiliation:
Department of Plant, Soil and Entomological Sciences, University of Idaho, Moscow, ID 83844-2339, USA
Noel E. Palmer
Affiliation:
Department of Plant, Soil and Entomological Sciences, University of Idaho, Moscow, ID 83844-2339, USA
Luca J. Furnare
Affiliation:
Department of Plant, Soil and Entomological Sciences, University of Idaho, Moscow, ID 83844-2339, USA
Carmen Goodell
Affiliation:
Department of Plant, Soil and Entomological Sciences, University of Idaho, Moscow, ID 83844-2339, USA
James E. Amonette
Affiliation:
Pacific Northwest National Laboratory, Richland, Washington, USA
Ravi K. Kukkadapu
Affiliation:
Pacific Northwest National Laboratory, Richland, Washington, USA
*
*E-mail address of corresponding author: dgstrawn@uidaho.edu
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Abstract

Due to the importance of clay minerals in metal sorption, many studies have attempted to derive mechanistic models that describe adsorption processes. These models often include several different types of adsorption sites, including permanent charge sites and silanol and aluminol functional groups on the edges of clay minerals. To provide a basis for development of adsorption models it is critical that molecular-level studies be done to characterize sorption processes. In this study we conducted X-ray absorption fine structure (XAFS) and electron paramagnetic resonance (EPR) spectroscopic experiments on copper (II) sorbed on smectite clays using suspension pH and ionic strength as variables. At low ionic strength, results suggest that Cu is sorbing in the interlayers and maintains its hydration sphere. At high ionic strength, Cu atoms are excluded from the interlayer and sorb primarily on the silanol and aluminol functional groups of the montmorillonite or beidellite structures. Interpretation of the XAFS and EPR spectroscopy results provides evidence that multinuclear complexes are forming. Fitting of extended X-ray absorption fine structure spectra revealed that the Cu-Cu atoms in the multinuclear complexes are 2.65 Å apart, and have coordination numbers near one. This structural information suggests that small Cu dimers are sorbing on the surface. These complexes are consistent with observed sorption on mica and amorphous silicon dioxide, yet are inconsistent with previous spectroscopic results for Cu sorption on montmorillonite. The results reported in this paper provide mechanistic data that will be valuable for modeling surface interactions of Cu with clay minerals, and predicting the geochemical cycling of Cu in the environment.

Keywords

CopperEPREXAFSMontmorilloniteSmectiteSorption
Type
Research Article
Information
Clays and Clay Minerals , Volume 52 , Issue 3 , June 2004 , pp. 321 - 333
Copyright
Copyright © 2004, The Clay Minerals Society

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References

Ankudinov, A.L. Ravel, B. Rehr, J.J. and Conradson, S.D., (1998) Real space multiple scattering calculation of XANES Physical Review B 58 7565 10.1103/PhysRevB.58.7565.Google Scholar
Baes, C.F. and Mesmer, R.E., (1986) The Hydrolysis of Cations Malabar, Florida Krieger Publishing Co..Google Scholar
Bradbury, M.H. and Baeyens, B., (1999) Modelling the sorption of Zn and Ni on Ca-montmorillonite Geochimica et Cosmochimica Acta 63 325–326 10.1016/S0016-7037(98)00281-6.Google Scholar
Burns, R.G., (1970) Mineralogical Applications of Crystal Field Theory Cambridge, UK Cambridge University Press.Google Scholar
Cheah, S.-F. Brown, G.E. Jr. and Parks, G.A., (1998) XAFS spectroscopy study of Cu(II) sorption on amorphous SiO2 and γ-Al2O3: Effect of substrate and time on sorption complexes Journal of Colloid and Interface Science 208 110–128 10.1006/jcis.1998.5678.Google Scholar
Cheah, S.-F. Brown, G.E. Jr. and Parks, G.A., (2000) XAFS study of Cu model compounds and Cu2+ sorption on amorphous SiO2, γ-Al2O3, and anatase American Mineralogist 85 118–132 10.2138/am-2000-0113.Google Scholar
Clementz, D.M. Pinnavaia, T.J. and Mortland, M.M., (1973) Stereochemistry of hydrated copper(II) ions on the interlamellar surfaces of layer silicates. An electron spin resonance study The Journal of Physical Chemistry 77 196–200 10.1021/j100621a010.Google Scholar
Dahn, R. Scheidegger, A.M. Manceau, A. Schlegel, M. Baeyens, B. Bradbury, M.H. and Morales, M., (2002) Neoformation of Ni phyllosilicate upon Ni uptake on montmorillonite: A kinetic study by powder and polarized extended X-ray absorption fine strucuture spectroscopy Geochimica et Cosmochimica Acta 66 2335–2347 10.1016/S0016-7037(02)00842-6.Google Scholar
Dahn, R. Scheidegger, A.M. Manceau, A. Schlegel, M.L. Baeyens, B. Bradbury, M.H. and Chateigner, D., (2003) Structural evidence for the sorption of Ni(II) atoms on the edges of montmorillonite clay minerals: A polarized X-ray absorption fine structure study Geochimica et Cosmochimica Acta 67 1–15 10.1016/S0016-7037(02)01005-0.Google Scholar
Di Leo, P. and O’Brien, P., (1999) Nuclear magnetic resonance (NMR) study of Cd2+ sorption on montmorillonite Clays and Clay Minerals 47 761–768 10.1346/CCMN.1999.0470611.Google Scholar
Evans, H.T. and Mrose, M.E., (1977) The crystal chemistry of the hydrous copper silicates, shattuckite and plancheite American Mineralogist 62 491–502.Google Scholar
Farquhar, M.L. Charnock, J.M. England, K.E.R. and Vaughan, D.J., (1996) Adsorption of Cu(II) on the (0001) plane of mica: A REFLEXAFS and XPS study Journal of Colloid and Interface Science 177 561–567 10.1006/jcis.1996.0070.Google Scholar
Farrah, H. and Pickering, W.F., (1976) The sorption of copper species Australian Journal of Chemistry 1976 29 1167–1176 10.1071/CH9761167.Google Scholar
Ford, R.G. and Sparks, D.L., (1998) The potential formation of secondary hydrotalcite-like precipitates during Zn and Cu sorption to pyrophyllite Mineralogical Magazine 62A 462–463 10.1180/minmag.1998.62A.1.245.Google Scholar
Helmy, A.K. Ferreiro, E.A. and deBussetti, S.G., (1994) Cation exchange capacity and condition of zero charge of hydroxyl-Al montmorillonite Clays and Clay Minerals 42 444–450 10.1346/CCMN.1994.0420410.Google Scholar
Hyun, S.P. Cho, Y.H. Kim, S.J. and Hahn, P.S., (2000) Cu(II) sorption mechanisms on montmorillonite: An electron paramagnetic resonance study Journal of Colloid and Interface Science 222 254–261 10.1006/jcis.1999.6632.Google Scholar
Kau, L.S. Spira-Solomon, D.J. Penner-Hahn, J.E. Hodgson, K.O. and Solomon, E.I., (1987) X-ray absorption edge determination of the oxidation state and coordination number of copper: Application to the Type 3 site in Rhus vernicifera Laccase and its reaction with oxygen Journal of the American Chemical Society 109 6433–6442 10.1021/ja00255a032.CrossRefGoogle Scholar
Lytle, F.W. Greegor, R.B. Sandstrom, D.R. Marques, E.C. Wong, J. Spiro, C.L. Huffman, G.P. and Huggins, F.E., (1984) Nuclear Instrumental Methods .Google Scholar
Marshal, C.E., (1935) Layer lattices and the base exchange clays Zeitschrift für Kristallographie und Mineralogie 91 443–449.Google Scholar
Martinez, C.E. and McBride, M.B., (2000) Aging of coprecipitated Cu in alumina: Changes in structural location, chemical form, and solubility Geochimica et Cosmochimica Acta 64 1729–1736 10.1016/S0016-7037(00)00344-6.Google Scholar
McBride, M.B., (1982) Cu2+ sorption characteristics of aluminum hydroxide and oxyhydroxides Clays and Clay Minerals 30 21–28 10.1346/CCMN.1982.0300103.Google Scholar
McBride, M.B., (1982) Hydrolysis and dehydration reactions of exchangeable Cu2+ on hectorite Clays and Clay Minerals 30 200–206 10.1346/CCMN.1982.0300306.Google Scholar
McBride, M.B. and Bouldin, D.R., (1984) Long-term reactions of copper(II) in a contaminated calcareous soil Soil Science Society of America Journal 48 56–59 10.2136/sssaj1984.03615995004800010010x.Google Scholar
McBride, M.B. Fraser, A.R. and McHardy, W.J., (1984) Cu2+ interaction with microcyrstalline gibbsite. Evidence for oriented chemisorbed copper ions Clays and Clay Minerals 32 12–18 10.1346/CCMN.1984.0320102.Google Scholar
Morton, J.D. Semrau, J.D. and Hayes, K.F., (2001) An X-ray absorption spectroscopy study of the structure and reversibility of copper adsorbed on montmorillonite clay Geochimica et Cosmochimica Acta 65 2709–2722 10.1016/S0016-7037(01)00633-0.Google Scholar
O’Day, P. Brown, G.E. Jr. and Parks, G.A., (1994) X-ray absorption spectroscopy of cobalt (II) multinuclear surface complexes and surface precipitates on kaolinite Journal of Colloid and Interface Science 165 269–289 10.1006/jcis.1994.1230.Google Scholar
Ozutsumi, K. Miyata, Y. and Kawashima, T., (1991) EXAFS and spectrophotometric studies on the structure of Mono and Bis(Aminocarboxylato) copper(II) complexes in aqueous solution Journal of Inorganic Biochemistry 1991 44 97–108 10.1016/0162-0134(91)84022-2.Google Scholar
Palladrino, L. Della Long, S. Reale, A. Belli, M. Scafati, A. Onori, G. and Santucci, A., (1993) X-ray absorption near edge structure (XANES) of Cu(II)-ATP and related compounds in solution: Quantitative determination of the distortion of the Cu site Journal of Physical Chemistry 98 2720–2726 10.1063/1.464153.Google Scholar
Papelis, C. and Hayes, K.F., (1996) Distinguishing between interlayer and external sorption sites of clay minerals using X-ray absorption spectroscopy Colloids and Surfaces 107 89 10.1016/0927-7757(95)03370-X.Google Scholar
Ravel, B., (2001) ATOMS: crystallography for the X-ray absorptions pectroscopist Journal of Synchrotron Radiation 8 314–316 10.1107/S090904950001493X.Google Scholar
Ressler, T., (1998) WinXAS: A program for X-ray absorption spectroscopy data analysis under MS-Windows Journal of Synchrotron Radiation 5 118–122 10.1107/S0909049597019298.Google Scholar
Savitzky, A. and Golay, M.J.E., (1964) Smoothing and differentiation of data by simplified least squares procedures Analytical Chemistry 36 1627–1639 10.1021/ac60214a047.Google Scholar
Schecher, W., (1998) Mineql+ version 4.5 Hallowell, Maine, USA Environmental Research Software.Google Scholar
Schindler, P.W. Liechti, P. and Westall, J.C., (1987) Adsorption of copper, cadmium and lead from aqueous solution to the kaolinite/water interface Netherlands Journal of Agricultural Science 35 219–230.Google Scholar
Schlegel, M.L. Manceau, A. Chateigner, D. and Charlet, L., (1999) Sorption of metal ions on clay minerals I. Polarized EXAFS evidence for the adsorption of Co on the edges of hectorite particles Journal of Colloid and Interface Science 215 140–158 10.1006/jcis.1999.6253.Google Scholar
Schlegel, M. Manceau, A. Charlet, L. Chatigner, D. and Hazemann, J., (2001) Sorption of metal ions on clay minerals. III. Nucleation and epitaxial growth of Zn phyllosilicate on the edge of hectorite Geochimica et Cosmochimica Acta 65 4155–4170 10.1016/S0016-7037(01)00700-1.Google Scholar
Sposito, G., (1989) The Chemistry of Soils New York Oxford University Press, Inc..Google Scholar
Stadler, M. and Schindler, P.W., (1993) Modeling of H+ and Cu2+ adsorption on calcium-montmorillonite Clays and Clay Minerals 41 288–296 10.1346/CCMN.1993.0410303.Google Scholar
Stern, E.A., Koningsberger, D.C. and Prins, R., (1988) Theory of EXAFS X-ray Absorption: Principles, Applications, and Techniques of EXAFS, SEXAFS, and XANES New York Wiley 3–51.Google Scholar
Strawn, D.G. and Sparks, D.L., (1999) The use of XAFS to distinguish between inner- and outer-sphere lead adsorption complexes on montmorillonite Journal of Colloid and Interface Science 216 257–269 10.1006/jcis.1999.6330.Google Scholar
Towle, S.N. Bargar, J.R. Brown, G.E. Jr. and Parks, G.A., (1997) Surface precipitation of Co(II)(aq) on Al2O3 Journal of Colloid and Interface Science 187 62–82 10.1006/jcis.1996.4539.Google Scholar
Undabeytia, T. Nir, S. Rytwo, G. Sereban, C. Morillo, E. and Maqueda, C., (2002) Modeling adsorption-desorption processes of Cu on edge and planar sites of montmorillonite Environmental Science and Technology 36 2677–2683 10.1021/es011154x.Google Scholar
Weesner, F.J. and Bleam, W.F., (1997) X-ray absorption and EPR spectroscopic characterization of the adsorbed copper(II) complexes at the boehmite (AlOOH) surface Journal of Colloid and Interface Science 196 79–86 10.1006/jcis.1997.5190.Google Scholar
Xia, K. Bleam, W. and Helmke, P.A., (1997) Studies of the nature of Cu2+ and Pb2+ binding sites in soil humic substances using X-ray absorption spectroscopy Geochimica et Cosmochimica Acta 61 2211–2221 10.1016/S0016-7037(97)00079-3.Google Scholar
Xia, K. Mehadi, A. Taylor, R.W. and Bleam, W.F., (1997) X-ray absorption and electron paramagnetic resonance studies of Cu(II) sorbed to silica: Surface-induced precipitation at low surface coverages Journal of Colloid and Interface Science 185 252–257 10.1006/jcis.1996.4590.Google Scholar
Zachara, J.M. and McKinley, J.P., (1993) Influences of hydrolysis on the sorption of metal cations by smectites: Importance of edge coordination reactions Aquatic Sciences 55 1015–1621 10.1007/BF00877270.Google Scholar
Zachara, J.M. Smith, S.C. McKinley, J.P. and Resch, C.T., (1993) Cadmium sorption on specimen and soil smectites in sodium and calcium electrolytes Soil Science Society of America 57 1491–1501 10.2136/sssaj1993.03615995005700060017x.Google Scholar