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  • 1
    Electronic Resource
    Electronic Resource
    Oxford, UK : Blackwell Science Ltd
    European journal of soil science 53 (2002), S. 0 
    ISSN: 1365-2389
    Source: Blackwell Publishing Journal Backfiles 1879-2005
    Topics: Geosciences , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: The long-term effects of intermittent flooding on soil properties were studied in field experiments on a Vertisol cropped with rice in Senegal. The dominant clay minerals were smectite and kaolinite. When the soil was reduced after flooding, its cation exchange capacity (CEC) increased to twice that of its oxidized, unflooded state. Mössbauer spectroscopy showed an increase in smectite structural FeII upon reduction, which explained a part of the increase in CEC. The rest of the increase was attributed to the removal of iron oxyhydroxide coatings by reductive dissolution. The reduction and dissolution of oxides under the field conditions were substantiated by analysis of the surfaces of vermiculites buried in the Ap horizons of the cropped and the non-cropped soils. The redox-induced CEC changes were found to be reversible after 22 cycles of rice cropping. Nevertheless, the structural Fe and free Fe contents of the rice field Ap horizon were less than those of soil in uncropped neighbouring land, suggesting that inundation induced weathering and eluviation of the minerals. The observed changes in CEC and related redox reactions may substantially modify proton, anion and cation balances in intermittently flooded soils.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Physics and chemistry of minerals 23 (1996), S. 535-541 
    ISSN: 1432-2021
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences , Physics
    Notes: 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.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 1432-2021
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences , Physics
    Notes: Abstract  This paper reports on the new application of polarized extended X-ray absorption fine structure (P-EXAFS) spectroscopy to fine-grained layer silicates taking the Garfield nontronite as a case study. Up to now application of P-EXAFS to structural studies of layer silicates has been restricted to single phyllosilicate crystals (Manceau et al. 1988; Manceau et al. 1990), but we show here that P-EXAFS can rigorously be applied to self-supporting clay films without loss of spatial resolution. The quantitative analysis of P-EXAFS requires however the preparation of highly oriented clay films, the orientation distribution of which can be assessed by texture goniometry. The Fe K-edge linear dichroism measurements were simulated by ab initio EXAFS modeling performed on a nontronite cluster whose structure was refined by distance-valence least-squares calculations. It is shown that ab initio modeling quantitatively accounts for the angular dependence of experimental EXAFS spectra. These calculations allowed for the identification of the fundamental character of single- and multiple-scattering paths of the photoelectron, and the structural interpretation of all spectral features observed up to 6.5 Å for the in-plane and out-of-plane radial structure functions of nontronite. In practice, P-EXAFS measurements allow the determination of the flattening angle of Fe(O,OH)6 octahedra, cations distribution in the octahedral sheet with an enhanced sensitivity, and differentiation between dioctahedral and trioctahedral structures.
    Type of Medium: Electronic Resource
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