Masters Degrees (Soil Science)

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Browsing Masters Degrees (Soil Science) by Author "Dowding, Catherine Elaine"

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    Morphology, mineralogy and surface chemistry of manganiferous oxisols near Graskop, Mpumalanga Province, South Africa
    (Stellenbosch : University of Stellenbosch, 2004-12) Dowding, Catherine Elaine; Fey, M. V.; University of Stellenbosch. Faculty of Agrisciences. Dept. of Soil Science.
    ENGLISH ABSTRACT: In the humid Graskop region of Mpumalanga Province, South Africa, there is an anomalous body of highly weathered black, manganiferous oxisols derived from dolomite. With Mn contents as high as 17%, potential large-scale Mn release is an environmental concern under current, acid generating, forestry practices. This study aims at establishing the factors which may affect the stability of the manganiferous oxisols of Graskop and in the process, investigating some of the morphological, mineralogical and chemical properties of these unique soils. Typically, the soils show a reddish, nodule-rich horizon, containing 3-4% Mn, grading through a red and black mottled zone into a black (5YR 2.5/1) apedal subsoil with >7% Mn. The Mn gradient down the profile as well as the abundant nodule content of the upper subsoil horizons implies that Mn mobilization and redistribution are active pedogenic processes. The exceptional Mn content of these soils is complemented with Fe and Al concentrations of up to 10 and 8%, respectively, and anomalously high trace element levels in particular Ni and Zn (as high as 541 and 237 mg kg-1, respectively) which are at the upper limit of cited world natural maxima for soils. The Mn mineral lithiophorite [(Al,Li)MnO2(OH)2], dominates the mineralogy of the soils with accessory amounts of birnessite, gibbsite, goethite, hematite, maghemite, kaolinite, aluminous chlorite and mica - a mineral suite reflecting that of well weathered soils. With the pH of the soil being at or close to the point of zero charge (4.5-5.5) the soils show isoelectric equilibrium. The very low buffer capacity results in metal dissolution commencing with the first increment of titrated acidity. Manganese dissolution is relatively minor considering the large potential for release and is highly overshadowed by Al release. The apparent resilience of the Mn phase to added acidity may relate to the overwhelming poise of the soils which maintains robust, oxic conditions despite the usual instability of Mn oxides at low pH. Manganese release and soil redox properties are substantially affected by drying especially in the organic rich topsoils. Using various redox analyses, evidence is shown for involvement of Mn(III)-organic complexes in the drying reactions. Using this and information gained in a real time, attenuated total reflectance Fourier transform infrared(ATR-FTIR) spectroscopic study, a mechanism is suggested which may account for the observed Mn release and the loss of Cr oxidising capacity commonly observed in dried soils. The information provided by the ATR-FTIR study showed the decrease in surface pH of a clay film, from 5 to below 2, as well as the shift in coordination nature of sorbed oxalate from a more outer-sphere association to a more inner-sphere association concomitant with the removal of free water from the clay surface. This spectroscopic evidence for these chemical changes which accompany surface drying not only provides further insight into the reactions involving Mn oxides in soils but also highlights the suitability of ATR-FTIR for real time, in situ investigation into the chemistry of the drying water interface. From these results it is concluded that Mn release from the manganiferous oxisols, under acid generation of the kind known to occur in pine plantations, is less that anticipated. On the other hand, desiccation of the topsoil results in substantial Mn release with a suggested mechanism which involves a Mn(III) intermediate.