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Site Occupancy in Nontronite Studied by Acid Dissolution and Mössbauer Spectroscopy

Published online by Cambridge University Press:  28 February 2024

Vittorio Luca*
Affiliation:
Chemistry Department, Victoria University of Wellington, P.O. Box 600, Wellington, New Zealand
Dugald J. MacLachlan*
Affiliation:
Chemistry Department, Victoria University of Wellington, P.O. Box 600, Wellington, New Zealand
*
1Present address: Research School of Chemistry, The Australian National University, Canberra, ACT 2601, Australia
2Present address: Department of Biology, University College, London WC1E6BT, England.
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Abstract

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The dissolution of two Ca2+-exchanged nontronite samples has been studied in 10% HCl. Early acid-dissolution studies (Osthaus, 1954) have indicated that after two hours of dissolution most of the octahedral Fe3+ (VIFe3+) would be removed leaving mainly tetrahedral Fe3+ (IVFe3+) in the nontronite structure. In the present study, 57Fe Mössbauer spectra of acid-treated samples were recorded and fitted with two octahedral Fe3+ (2 × VIFe3+) and two octahedral and one tetrahedral (2 × VIFe3+, 1 × IVFe3+) doublet models. The Mössbauer spectra of acid-treated Garfield nontronite samples could be adequately fitted with two-doublet models but acid-treated Hohen Hagen nontronite samples could not. Isomer shift and quadrupole splitting values obtained from the two-doublet models corresponded to VIFe3+ and not IVFe3+, as was suggested by the Osthaus (1954) experiment. When an IVFe3+ doublet was included in the model used to fit the Mössbauer spectra of acid-treated Garfield nontronite samples, a slight increase in the intensity of the IVFe3+ doublet occurred with increasing dissolution, but this was much lower than indicated by Osthaus (1954). No trend in the intensity of the IVFe3+ doublet was observed for acid-treated Hohen Hagen nontronite. Therefore, acid treatment appears to remove VIFe3+ and IVFe3+ from the nontronite structure at about the same rate. Mössbauer spectroscopy, infrared spectroscopy and X-ray powder diffraction data indicate that the nontronite that remains undissolved following acid treatment is structurally similar to the untreated nontronite.

Type
Research Article
Copyright
Copyright © 1992, The Clay Minerals Society

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