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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: [email protected]
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Abstract

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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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