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Structural properties of reduced Upton montmorillonite

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Abstract

Reduction of octahedral Fe in the crystalline structure of smectites influences, possibly controls, surface-sensitive physical and chemical properties. The purpose of this study was to investigate if reduction of structural Fe by Na-dithionite or bacteria affects the chemical environment of constituent cations in montmorillonite, employing solid state multinuclear (29Si and 27Al) magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy. Reduction of structural Fe resulted in a positive (down field) chemical shift of the main Si Q3 (Q3(0Al)) site which was strongly correlated with Fe(II) content and inferred that distortions in Si-OT (T=Si, Al) bond angles and Si-O bond lengths occur with increasing layer charge. The line width (W) of the 29Si Q3 signal also increased with increasing levels of reduction. No change occurred in the position of the peak maximum for the octahedral Al (27AlVI) signal; however, an increased W was observed for this peak with increasing Fe(II) content. These results are attributed to decreases in Si-O-T bond angles and Si-O bond distances, corresponding to a better fit between the tetrahedral and octahedral sheets brought about by the presence of Fe(II) in the clay structure. The increased 27AlVI signal width (W) may also be due to a lessening of the paramagnetic influence of Fe(III) nuclei and enhancement of 27AlVI signals with different quadrupole coupling constants (QCC). Multinuclear MAS NMR analyses of dithioniteand microbially-reduced montmorillonite indicate that reduction of structural Fe caused reversible changes in the smectite structure, at least as far as this method could discern.

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  1. W. P. Gates

    Present address: Savannah River Ecology Laboratory, University of Georgia, Drawer E, 29802, Aiken, SC, USA

Authors and Affiliations

  1. Department of Natural Resources and Environmental Sciences, University of Illinois, 1102 South Goodwin, 61801, Urbana, IL, USA

    W. P. Gates & J. W. Stucki

  2. Department of Geology, University of Illinois, 1301 West Green, 61801, Urbana, IL, USA

    R. J. Kirkpatrick

Authors
  1. W. P. Gates
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  2. J. W. Stucki
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  3. R. J. Kirkpatrick
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Gates, W.P., Stucki, J.W. & Kirkpatrick, R.J. Structural properties of reduced Upton montmorillonite. Phys Chem Minerals 23, 535–541 (1996). https://doi.org/10.1007/BF00242003

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