Doctoral Degrees (Earth Sciences)

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Browsing Doctoral Degrees (Earth Sciences) by Subject "Biogeochemical cycles"

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    Distribution and characterization of marine iron-rich particles
    (Stellenbosch : Stellenbosch University, 2013-12) Von Der Heyden, Bjorn Phillip; Roychoudhury, Alakendra N.; Myneni, Satish C. B.; Stellenbosch University. Faculty of Science. Dept. of Earth Sciences.
    ENGLISH ABSTRACT: This thesis investigates questions surrounding the role that iron-rich colloids (nominally sized between 0.02 μm and 0.2 μm) and particulates (>0.2-0.45 μm) play in the context of the greater iron biogeochemical cycle. To this end, this study complements a review of reported size-fractionated iron (Fe) measurements with chemical and mineralogical data derived from synchrotron-based xray measurements. From an extensive literature review, the global surface ocean colloidal iron (cFe) pool is found to be highly dynamic, frequently exhibiting seasonal trends and nutrient-like behaviour. Spatial variability in surface ocean colloidal iron concentration is primarily a function of total iron supply, although the concentration and strength of iron-binding ligands, and inorganic thermodynamic constraints are additional influential factors. The size-fractionated study of colloidal Fe has rendered considerable evidence pointing towards direct or indirect biological utilization of this cFe pool; however, a more complete understanding of cFe-biological interaction necessarily requires better knowledge of cFe chemistry and mineralogy. To address these issues, this thesis documents the development of a novel x-ray microscopy and spectroscopy technique for determining the Fe speciation of individual Fe-rich particles under environmental conditions. Variations in the peak splitting in iron L3-edge XANES (X-ray Absorption Near-Edge Structure) spectra reflect changes in the local coordination environment surrounding the metal centre. Specifically, the energy splitting ( ΔeV) and intensity ratio of the split peaks at the L3-edge vary as a function of the Fe valence state, the number and chemistry of coordinating ligands and polyhedral distortion effects; and combinations of the two parameters are found to be characteristic of individual Fe minerals. To understand Fe speciation, the Δ eV versus intensity ratio plot was successfully applied to a variety of environmental Fe particles (greater than 20 nm diameter) collected from two ocean basins; the Southern Ocean and the south western Pacific Ocean. Speciation differences in Fe particles collected from the Southern Ocean show distinct compositional trends between the coasts of South Africa and Antarctica, with different Fe pools associated with the different oceanographic frontal zones. Despite the oxygenated nature of the seawater sampled, the presence of significant particle-hosted Fe(II) was observed in both the Southern Ocean at high latitudes, and at sampling sites proximal to the Kermadec Ridge in the Pacific Ocean. Ferrous iron particles at the latter study area were shown to be strongly associated with carbon functional groups, notably alcohol and carboxamine moieties. These findings, relating to particle chemical differences and associations with organic matter, have significant implications for our understanding of particle behaviour, their surface interactions and the role that they play in primary productivity and global elemental cycles.