This study considered the geology, mineralogy, geochemistry, formation and evolution of the heavy rare earth element (HREE) mineralised Lofdal alkaline carbonatite complex (LACC), which is located on the Bergville and Lofdal farms northwest of Khorixas, in the Kunene Region of the Republic of Namibia. . Field methods used included mapping, ground and hyperspectral airborne geophysics, and sampling. Analytical techniques used were optical petrography and CL, XRF, ICP-AES, backscattered and secondary electron imaging, electron microprobe, LA-ICP-MS, leaching, as well as carbon and oxygen stable isotope determination. The LACC comprises a swarm of dykes, mainly calcite carbonatite but also dolomite and ankerite carbonatite dykes (classified into five types) and two newly discovered plugs of calcite carbonatite (‘Main’ and ‘Emanya’), with associated dykes and plugs of phonolites, syenites and rare mafic rocks. These all intrude into the Huab Metamorphic Complex basement rocks within a NE-SW shear zone over 30 km long. The main HREE host mineral is xenotime-(Y). It occurs in highly oxidised iron-rich calcite carbonatite dykes mantling and replacing zircon, associated with hematite, thorite and apatite, or associated with monazite-(Ce), synchysite-(Ce), and parisite-(Ce), replacing the fluorocarbonates; it also forms aggregates in ankerite carbonatite. Although xenotime-(Y) occurs throughout the paragenetic sequence, there is much evidence for hydrothermal fluid activity at Lofdal, altering the dykes, and taking xenotime-(Y) into brecciated carbonate veins in albitised country rock (fenite). Radiogenic (Sr, Nd-Sm, U-Pb) and C and O stable isotope studies confirm that the carbonatite, derived from an enriched mantle, is the source of the REE. Mineralisation was contemporaneous with carbonatite emplacement at 765 ±16 Ma. Magmatic fluids >300°C were diluted with cool meteoric fluids. Abundant fluorite and carbonate indicate roles for F- and CO32- in addition to Cl- in REE transport. These ligands form the most stable complexes with HREE and since xenotime is soluble in concentrated alkali halide solutions, they could have preferentially transported and then deposited xenotime. Many of the features of Lofdal are common to other REE-rich carbonatite complexes but the xenotime-(Y) abundance is so far unique. The high amount of fluid activity in shear zones around the dyke swarm and probably a higher proportion of HREE in the original magmas seem to be the main differentiating features.

Niobium and rare earth elements (REE) are considered as strategic metals in industrialised countries, and are mainly derived from carbonatite-related deposits. Indicator mineral methods for carbonatites using of portable XRF and Quantitative Evaluation of Materials by Scanning Electron Microscopy (QEMSCAN®), shows promise in exploration for Nb and REE. Portable XRF analysis of stream sediments from the Aley, Lonnie, and Wicheeda carbonatites identified 125-250 μm as the ideal size fraction for indicator mineral studies. QEMSCAN® provides (with no additional processing) detection and characterisation of indicator minerals (when found in high concentrations) from carbonatite deposits. Preconcentration by Mozley C800 separator is recommended for sediment samples with low concentrations of indicator minerals. Discrimination diagrams for pyrochlore supergroup and columbite-tantalite series minerals show that minerals from carbonatites occupy the pyrochlore field and extend slightly into the betafite field. Columbite-tantalite series minerals from carbonatites have Mn/(Mn+Fe) atomic ratios ≤0.25 and Ta/(Ta+Nb) ≤0.20. The compositional fields for pyrochlore supergroup and colubmite-tanatlite series minerals from different deposit types partially overlap. / Graduate / 0996 / 0411 / 0372

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This dissertation focuses on two areas of garnet porphyroblast crystallization that have until now remained largely uninvestigated: epitaxial nucleation of garnet porphyroblasts and yttrium and rare earth (Y+REE) uptake in metamorphic garnet. The mechanism of epitaxial nucleation is explored as a step towards determining which aspects of interfaces are significant to interfacial energies and nucleation rates. Garnet from the aureole of the Vedrette di Ries tonalite, Eastern Alps, shows a clear case of epitaxial nucleation in which garnet nucleated on biotite with (110)grt || (001)bt with [100]grt || [100]bt. The occurrence is remarkable for the clear genetic relationships revealed by the microstructures and for its preservation of the mica substrate, which allows unambiguous determination of the coincident lattice planes and directions involved in the epitaxy. Not all epitaxial nucleation is conspicuous; to increase the ability to document epitaxial relationships between garnet and micas, I develop and apply a method for determining whether evidence for epitaxial nucleation of garnet is present in porphyroblasts containing an included fabric. Although the magnitude of uncertainties in orientation measurements for garnets from Passo del Sole (Switzerland), the Nevado Filabride Complex (Spain), and Harpswell Neck (USA) preclude definitive identification of epitaxial relationships, the method has potential to become a viable technique for creating an inventory of instances and orientations of epitaxial nucleation with appropriate sample selection. Using lattice-dynamics simulations, I explore the most commonly documented epitaxial relationship, (110)grt || (001)ms. The range of interfacial energies resulting from variations in the intracrystalline layer within garnet at the interface, the initial atomic arrangement at the interface, and the rotational orientation of the garnet structure relative to the muscovite structure shows that the intracrystalline layer within garnet has the greatest effect on interfacial energy. A complete understanding of the role of intergranular diffusion for yttrium and rare-earth-element uptake in porphyroblastic garnet is critical because the complexities of Y+REE zoning in garnets and the mechanisms of Y+REE uptake have implications for petrologic interpretations and garnet-based geochronology. Y+REE distributions in garnets from the Picuris Mountains (USA), Passo del Sole (USA), and the Franciscan Complex (USA) imply diverse origins linked to differing degrees of mobility of these elements through the intergranular medium during garnet growth.

This dissertation focuses on two areas of garnet porphyroblast crystallization that have until now remained largely uninvestigated: epitaxial nucleation of garnet porphyroblasts and yttrium and rare earth (Y+REE) uptake in metamorphic garnet. The mechanism of epitaxial nucleation is explored as a step towards determining which aspects of interfaces are significant to interfacial energies and nucleation rates. Garnet from the aureole of the Vedrette di Ries tonalite, Eastern Alps, shows a clear case of epitaxial nucleation in which garnet nucleated on biotite with (110)grt || (001)bt with [100]grt || [100]bt. The occurrence is remarkable for the clear genetic relationships revealed by the microstructures and for its preservation of the mica substrate, which allows unambiguous determination of the coincident lattice planes and directions involved in the epitaxy. Not all epitaxial nucleation is conspicuous; to increase the ability to document epitaxial relationships between garnet and micas, I develop and apply a method for determining whether evidence for epitaxial nucleation of garnet is present in porphyroblasts containing an included fabric. Although the magnitude of uncertainties in orientation measurements for garnets from Passo del Sole (Switzerland), the Nevado Filabride Complex (Spain), and Harpswell Neck (USA) preclude definitive identification of epitaxial relationships, the method has potential to become a viable technique for creating an inventory of instances and orientations of epitaxial nucleation with appropriate sample selection. Using lattice-dynamics simulations, I explore the most commonly documented epitaxial relationship, (110)grt || (001)ms. The range of interfacial energies resulting from variations in the intracrystalline layer within garnet at the interface, the initial atomic arrangement at the interface, and the rotational orientation of the garnet structure relative to the muscovite structure shows that the intracrystalline layer within garnet has the greatest effect on interfacial energy. A complete understanding of the role of intergranular diffusion for yttrium and rare-earth-element uptake in porphyroblastic garnet is critical because the complexities of Y+REE zoning in garnets and the mechanisms of Y+REE uptake have implications for petrologic interpretations and garnet-based geochronology. Y+REE distributions in garnets from the Picuris Mountains (USA), Passo del Sole (USA), and the Franciscan Complex (USA) imply diverse origins linked to differing degrees of mobility of these elements through the intergranular medium during garnet growth.

This thesis focuses on the geochemistry of secondary minerals, mainly calcite but also others such as fluorite and Ca/Al silicates, precipitated throughout the last 1.5 billion years in fractures of crystalline rock, SE Sweden. The work was based on previous reconnaissance studies and has been possible thanks to access to high-quality drill cores and associated mapping data provided by the Swedish Nuclear Fuel and Waste Management Co (SKB). Concentrations of rare earth elements (REEs) and occasionally other metals were determined in a variety of secondary minerals from fractures (mainly open systems) and veins (mainly sealed systems) and in primary minerals from the bedrock. Stable-isotope composition was measured in the secondary minerals. The overall aim was to define the sources, uptake and fractionation of REEs in calcite, and a few other co-genetic minerals, precipitated throughout the geological history under conditions ranging from hydrothermal to low temperatures. Collectively, the findings of the individual studies show that there is no easy and straightforward control of REE abundance and fractionation in calcite and other minerals in fractures and veins in crystalline bedrock settings. For example, the REE features in calcite vary extensively within sub-generations of single vein-precipitating events, on micro scale in transects across individual veins, and unsystematically over the geological history characterised by successively decreasing temperatures of mineral formation. Although the REE content in, and release from, the crystalline bedrock can have an influence on REE distribution in calcite and other minerals, it is of overall minor importance within a given bedrock domain. The main advantage of determining REEs in secondary minerals in fractures and veins in crystalline rock is therefore, as revealed in this work, to assess the character and evolution of the conditions (including features of the paleofluids) during confined mineral-precipitating events.

M.Sc. / Aspects of electron-electron correlations have for the past few decades been at the forefront of research in Solid State Physics. More traditional concepts under this topic have been phenomena such as superconductivity, and magnetic ordering in its many forms including long-range ordering and spin-glass freezing. The class of so-called strongly correlated electron systems has been a particularly active field of study, as witnessed by for instance the series of annual international conferences held under this topic since 1992. Compounds and alloys of strong electronic correlations have proved a very rich field of new and anomalous physical behaviours in metallic and semiconducting compounds and alloys of especially 4f- and 5f-electron systems, together with ceramics characterized as the so-called ¡§high-TC¡¨ superconductors. The f-electron systems have revealed a variety of behaviours such as ~ 1000-fold enhanced effective electron masses at low temperature, coexistence of superconductivity and magnetic ordering in systems where the magnetic interactions are far too strong to allow for Cooper-pair formation within the well-established BCS-interpretation, and electron transport and thermodynamic behaviour at low temperatures that completely defy our conventional Fermi-liquid paradigm of understanding the ground states of metals. The series of pseudo-ternary compounds Ce1-xLaxRu4Sn6 that were synthesized and characterized in this work for the first time are formed by substituting La for Ce in CeRu4Sn6, the parent compound. CeRu4Sn6 exhibits a number of properties which have been associated with a special class, the Kondo semiconductors of strongly correlated electron systems. CeRu4Sn6 has very recently been shown [A. M. Strydom et al. (2004)] to comprise an intriguing combination of characteristics that are thus far unique among the Kondo semiconductors: At low temperature (T 10 K) the specific heat proves the development of very strong electronic correlation out of an already low density of charge carriers (as shown by Hall-effect, resistivity, and the Sommerfeld coefficient of the specific heat). Furthermore, the specific heat follows a logarithmic increase as temperature is decreased below ~ 2 K, in a range where thermal transport shows the presence of an energy gap in the electronic density of states. The aim of this work was to investigate the intermediate and higher temperature (4.01 K „T T „T 300 K) behaviour of the electrical resistivity of the Ce1-xLaxRu4Sn6 series of compounds in which the concentration of the 4f-electron magnetic ion Ce is progressively being reduced. A steady but slow decrease of the energy gap with increasing La concentration was found in this work in contrast with what is usually the case in Kondo semiconductors. Both the presence of an energy gap and the low density of charge carriers are found to be connected to the presence of Ce in the unit cell, and are therefore not an artefact of the peculiar filledƒ{cageƒ{like tetragonal crystal structure of these compounds. An interesting strong anisotropy was found in the way in which the tetragonal unit cell expands preferentially within the aƒ{b plane, compared to the elongation along the cƒ{axis, upon moving from CeRu4Sn6 to LaRu4Sn6. / Prof. A.M. Strydom

Biosurfactants are compounds that exhibit surface activity (e.g., reduce surface and interfacial tension) and are derived from natural, biological sources. They are considered green substances due to their natural derivation, biodegradability, and relatively low toxicity. Biosurfactants from multiple classes have been shown to interact with metals, and a review of these interactions is provided. Rhamnolipids produced by Pseudomonas aeruginosa are attracting attention for metal remediation applications. The purpose of this dissertation is to evaluate rhamnolipids' ability to complex rare earth elements, determine the environmental compatibility of novel rhamnolipid diastereomers, and assess the efficacy of rhamnolipid as a collector in ion flotation. Previous research shows rhamnolipids selectively bind elements of environmental concern over common soil and water cations, but there had been no examination of transition metals from the f-block of the periodic table. The f-block elements include the rare earth elements, which are a vital component of nearly every modern technology and subject to supply risk. The interaction between monorhamnolipids and the rare earth elements was investigated by determining conditional stability constants using a resin-based ion exchange method. For the 27 metals examined, the conditional stability constants could be divided into three groups, albeit somewhat subjectively: weakly, moderately, and strongly bound. UO22+, Eu3+, Nd3+, Tb3+, Dy3+, La3+, Cu2+, Al3+, Pb2+, Y3+, Pr3+, and Lu3+are strongly bound with conditional stability constants ranging from 9.82 to 8.20; Cd2+, In3+, Zn2+, Fe3+, Hg2+, and Ca2+ are moderately bound with stability constants ranging from 7.17 to 4.10; and Sr2+, Co2+, Ni2+, UO22+, Cs+, Ba2+, Mn2+, Mg2+, Rb+, and K+ are weakly bound with stability constants ranging from 3.95 to 0.96. The uranyl ion is reported twice due to the ion demonstrating two distinct binding regions. The conditional stability constants were demonstrated to be an effective predictor of metal removal order. The metal parameters of enthalpy of hydration and ionic charge to radius ratio were shown to be determinants of complexation strength. Naturally produced rhamnolipids are a mixture of congeners. Synthetic rhamnolipid synthesis has recently enabled production of four monorhamnolipid diastereomers of a single congener. The biodegradability, acute toxicity (Microtox assay), embryo toxicity (Zebrafish assay), and metal binding capacity of the diastereomers was investigated and compared to natural monorhamnolipid. Biodegradability testing showed all the diastereomers were inherently biodegradable. By the Microtox assay, all of the monorhamnolipids were categorized as slightly toxic by Environmental Protection Agency ecotoxicity categories. Out of 22 parameters tested, the zebrafish toxicity assay showed only diastereomer toxicity for the mortality parameter, except for diastereomer R,R which showed no toxic effects. All the monorhamnolipids interacted with both Cd2+ and Pb2+. Ion flotation is one possible technology for metal recovery and remediation of metal contaminated waters. Ion flotation utilizes charged surfactants to collect and concentrate non-surface active ions at the surface of an aerated solution. Rhamnolipid's suitability as a collector in ion flotation was investigated. A flotation column was designed to test monorhamnolipid efficacy as a collector. Monorhamnolipids form foams and effectively remove Cs+, Cd2+, and La3+ from solution. The efficacy of the flotation process relies on the collector:colligend ratio and valency of the colligend. Flotation of metal solutions showed a removal order of Cd2+>La3+>>Cs+ when the metals were present individually and mixed at equimolar concentrations. When mixed at order of magnitude different concentrations, the flotation order was Cd2+>>Cs+>>La3+. These studies show rhamnolipid has potential to be used for environmentally-compatible metal recovery and metalliferous water remediation, especially for the rare earth elements.

This Thesis describes the synthesis and characterisation of a series ofbisphenolate supported samarium borohydride, amide and zwitterionic rare earth complexes and their ability to effect the ring opening polymerisation (ROP) of cyclic esters and methylmethacrylate (MMA). Chapter 1 introduces ROP from both an industrial and an academic perspective and describes in detail the research in this area, with emphasis on rare earth initiators. The lanthanide elements and the bisphenolate ligand are also introduced. Chapter 2 describes the synthesis and characterisation ofbisphenolate supported samarium borohydride and silylamide complexes. Chapter 3 describes the ability of a selection of samarium borohydride and amide complexes to effect the ROP of the cyclic esters s-caprolactone (f-CL) and rac- lactide (rac-LA). Emphasis is placed on the effect that the nature of the bisphenolate pendant arm and the initiating moiety has on the polymerisation process. Chapter 4 describes the synthesis and characterisation of rare earth zwitterionic complexes and the ability ofa range of these complexes to effect the ROP of s-Cl. and rac-lactide. Mechanistic aspects ofthe ROP process will be discussed, as will the ability of these complexes to yield amide functionalised poly(rac-LA). Chapter 5 describes the ability ofbisphenolate samarium borohydride complexes to initiate the polymerisation of MMA. The experimental work conducted as part of this study is further supported computationally by calculations at the DFT level, both aspects will be described. Aspects concerning the synthesis and characterisation of the related borohydride derivative [Sm(N2siMe3NNPY)(BH4)2Li]oo will also be emphasised. Chapter 6 contains full experimental and characterising data for all 0 f the new compounds reported in this Thesis. Appendices A- T contain tables of selected crystallographic data for all new crystallographically characterised complexes described in this Thesis (partially on CD).