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Spectroscopic (ESR, EXAFS) evidence of Cu for (Al-Mg) substitution in octahedral sheets of smectites

Published online by Cambridge University Press:  09 July 2018

C. Mosser ,
M. Mestdagh ,
A. D'Ecarreau  and
A. J. Herbillon
C. Mosser
Affiliation:
Centre de Géochimie de la Surface, 1 rue Blessig, 67084 Strasbourg Cedex, France
M. Mestdagh
Affiliation:
Laboratoire de Chimie des Interfaces, Université Catholique de Louvain, Place Croix du Sud 1, 1348 Louvain la Neuve, Belgique
A. D'Ecarreau
Affiliation:
Laboratoire de Pétrologie de la Surface, Université de Poitiers, 40 Avenue du Recteur Pineau, 86022 Poitiers Cedex, France
A. J. Herbillon
Affiliation:
Centre de Pédologie Biologique, 17 rue Notre Dame des Pauvres BP.5, 54500 Vandoeuvre Les Nancy, France
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Abstract

ESR has been used to obtain information on the octahedral or interlamellar position of Cu(II) in natural smectites from Burkina Faso (West Africa). On the basis of 060 XRD reflections and chemical data, these smectites were found to be Al-rich and dioctahedral. After both Mehra & Jackson, and De Endredy deferrification treatments, the Cu contents remained high (4500 and 22000 p.p.m., respectively). The Cu(II) ESR spectra of these deferrated smectites were compared to those of two reference smectites for which the structural position of Cu(II) was precisely known. The interlayer Cu(II) signal was obtained on a Cu-saturated Camp Berteau montmorillonite, while the octahedral Cu(II) signal was obtained on a synthetic Cu-rich smectite. For this latter reference sample, EXAFS spectroscopy provided evidence that Cu was in six-fold coordination in the octahedral sheet only, and was not exchangeable. In agreement with the experiments by Clementz, Pinnavaia and Mortland, a shift in the g⊥ ESR signal was observed when the air-dried Cu-saturated Camp Berteau montmorillonite (g⊥ = 2·05) was soaked in water for 48 h (g⊥ = 2·13). A small shift in the opposite sense was observed for the synthetic Cu smectite (g⊥ = 2·05 for the air-dried sample, g⊥ = 2·02 for the water-soaked sample). For the two natural smectites a small shift similar to that for the synthetic Cu-smectite was observed. These results indicate that up to 10% of the Cu atoms substitute for Al-Mg-Fe atoms in the octahedral sheets of the smectites studied.

Type
Research Article
Information
Clay Minerals , Volume 25 , Issue 3 , September 1990 , pp. 271 - 282
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 1990

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