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Infrared Study of Reduced and Reduced-Reoxidized Ferruginous Smectite

Published online by Cambridge University Press:  01 January 2024

Claire-Isabelle Fialips ,
Dongfang Huo ,
Laibin Yan ,
Jun Wu  and
Joseph W. Stucki
Claire-Isabelle Fialips
Affiliation:
Department of Natural Resources and Environmental Sciences, University of Illinois, 1102 South Goodwin Avenue, Urbana, Illinois 61801
Dongfang Huo
Affiliation:
Department of Natural Resources and Environmental Sciences, University of Illinois, 1102 South Goodwin Avenue, Urbana, Illinois 61801
Laibin Yan
Affiliation:
Department of Natural Resources and Environmental Sciences, University of Illinois, 1102 South Goodwin Avenue, Urbana, Illinois 61801
Jun Wu
Affiliation:
Department of Natural Resources and Environmental Sciences, University of Illinois, 1102 South Goodwin Avenue, Urbana, Illinois 61801
Joseph W. Stucki*
Affiliation:
Department of Natural Resources and Environmental Sciences, University of Illinois, 1102 South Goodwin Avenue, Urbana, Illinois 61801
*
*E-mail address of corresponding author: [email protected]
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Abstract

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Oxidation-reduction processes within natural systems greatly influence the properties of sediments, soils and clays. The objective of this experimental study was to gather new evidence for the effects of changes in redox conditions (reduction and reoxidation) on structural properties of ferruginous smectite and to understand better the mechanisms involved. The <2 µm fraction of a ferruginous smectite (sample SWa-1), which contains 17.3 wt.% of total structural Fe, was studied by infrared (IR) spectroscopy. The pure Na-saturated clay was reduced by Na dithionite for 10 to 240 min to obtain various Fe(II):(total Fe) ratios ranging from 0 to 1.0. Selected reduced samples were then reoxidized completely by bubbling O2 gas through the suspensions for up to 12 h. Infrared spectra of the initially unaltered, reduced and reduced-reoxidized samples were collected. Reduction generated changes in the three studied spectral regions (O-H stretching, M-O-H deformation, and Si-O stretching), indicating that major modifications occurred within the clay crystal beyond merely a change in Fe oxidation state. partial dehydroxylation and redistribution of Fe, and perhaps Al, cations occurred upon reduction of SWa-1, changing the structural properties of its tetrahedral and octahedral sheets. Water molecules, probably generated by dehydroxylation within the octahedral sheet upon reduction, were tightly bound to the clay surface and were possibly trapped within the clay structure. Except for dehydroxylation and the Fe oxidation state, all these modifications were largely irreversible. The tightly bound water was not completely removed upon reoxidation and the cationic rearrangements generated during reduction were not reversed: either they were preserved as in the reduced state or cations were redistributed into a different configuration from the unreduced clay.

Keywords

Cationic RearrangementInfrared SpectroscopyIronIrreversibilityOH StretchingOH DeformationReductionReoxidationSi-O StretchingSWa-1 Smectite
Type
Research Article
Information
Clays and Clay Minerals , Volume 50 , Issue 4 , August 2002 , pp. 455 - 469
Copyright
Copyright © 2002, The Clay Minerals Society

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