The Bear Lodge alkaline complex in northeastern Wyoming (USA) is host to potentially economic rare-earth mineralization in carbonatite and carbonatite-related veins and dikes that intrude heterolithic diatreme breccias in the Bull Hill area of the Bear Lodge Mountains. The deposit is zoned and consists of pervasively oxidized material at and near the surface, which passes through a thin transitional zone at a depth of ~120-183m, and grades into unaltered carbonatites at depths greater than ~183-190m. Carbonatites in the unoxidized zone consist of coarse and fine-grained calcite that is Sr-, Mn- and inclusion-rich and are characterized by the presence of primary burbankite, early-stage parisite and synchysite with minor bastnäsite that have high (La/Nd)cn and (La/Ce)cn values. The early minerals are replaced with polycrystalline pseudomorphs consisting of secondary rare-earth fluorocarbonates and ancylite with minor monazite. Different secondary parageneses can be distinguished on the basis of the relative abundances and composition of individual minerals. Variations in key element ratios, such as (La/Nd)cn, and chondrite-normalized profiles of the rare-earth minerals and calcite record multiple stages of hydrothermal deposition involving fluids of different chemistry. A single sample of primary calcite shows mantle-like δ18O V-SMOW and δ13C V-PDB values, whereas most other samples are somewhat depleted in 13C (δ13C V-PDB ≈ –8 to –10‰) and show a small positive shift in δ18O V-SMOW due to degassing and wall-rock interaction. Isotopic re-equilibration is more pronounced in the transitional and oxidized zones; large shifts in δ18O V-SMOW (to ~ 18‰) reflect input of meteoric water during pervasive hydrothermal and supergene oxidation. The textural relations, mineral chemistry, and C and O stable-isotopic variations record a polygenetic sequence of rare-earth mineralization in the deposit. With the exception of one Pb-poor sample showing an appreciable positive shift in 208Pb/204Pb value (~39.2), the Bear Lodge carbonatites are remarkably uniform in their Nd, Sr and Pb isotopic composition: (143Nd/144Nd)i=0.512591-0.512608; εNd=0.2-0.6; (87Sr/86Sr)i=0.704555-0.704639; εSr=-1.5-2.7; (206Pb/204Pb)i=18.071-18.320; (207Pb/204Pb)i=15.543-15.593; (208Pb/204Pb)i=38.045-39.165. These isotopic characteristics indicate that the source of the carbonatitic magma was in the subcontinental lithospheric mantle, and modified by subduction-related metasomatism. Carbonatites are interpreted to be generated from small degrees of partial melt that may have been produced via interaction of upwelling asthenosphere giving a small depleted MORB component, with an EM1 component likely derived from subducted Farallon crust.

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archives@tulane.edu / This dissertation combines laboratory experiments with analysis of field samples and geochemical modeling to examine rare earth elements (REEs) geochemistry. The Mississippi River estuary, Louisiana and the Pettaquamscutt River estuary, Rhode Island provided ideal study sites to investigate the effects of salinity and redox gradients, respectively, on the cycling of the REEs in natural environments. Similar to the REE behavior in major estuaries such as the Amazon estuary, the REEs in the Mississippi River undergo salt-induced coagulation removal during mixing with the saline Gulf of Mexico seawater. However, unlike the Amazon estuary in which dissolved REE removal of up to 90% has been reported, only ca. 50% removal is observed in the Mississippi River estuary. The closed-system batch reaction experiment which followed showed that interactions with the Mississippi River particulate material substantially alter the dissolved REE concentrations of the Gulf of Mexico seawater. Combined effects of dissolution of the labile phases on the riverine particles and secondary mineral precipitation of likely REE phosphate phases result in a 24 ± 12 folds (mean ± 1σ) net increase in the REE concentrations of the seawater. Less than 1% of the REE contents in the operationally defined “exchangeable” phase of the sediments was mobilized at the maximum REE concentrations in the reacted seawater. The behavior of the REEs in the Pettaquamscutt River estuary is coupled with the cycling of Fe and Mn oxides/oxyhydroxides in the oxic surface waters and across the chemocline. Reaction path modeling suggests that the REE content of the oxic surface waters depicts a combined effect of mixing of 3 water masses and surface complexation with hydrous manganese oxides to achieve the cerium depleted pattern that characterizes the entire water column. / 1 / Segun Adebayo

In the Mojave Pegmatite district, located in northwestern AZ, numerous pegmatites intrude syn- to post-collisional Paleoproterozoic granitic rocks. The slightly older Cerbat plutons are associated with the suturing of the Mojave and Yavapai terranes whereas Aquarius granites were emplaced during the Yavapai Orogeny as the sutured terranes docked with North America. A detailed study of 5 pegmatites shows that they are zoned with composite cores and contain REE minerals characteristic of NYF pegmatites. However, they exhibit characteristics atypical for NYF pegmatites including F depletion, white microcline, an absence of columbite and, in the Rare Metals pegmatite, have muscovite and beryl. With the exception of the Kingman pegmatite, they exhibit normal LREE-HREE distributions. The Kingman pegmatite is extremely LREE enriched, HREE depleted and exhibits an unusual Nd enrichment which, in some cases, is sufficiently high that allanite is Nd dominant, thus a new mineral species, allanite-Nd.

Many of the world's economic rare earth element (REE) deposits are formed from, or have been subsequently upgraded by, hydrothermal fluids. Some of the most important REE minerals are the light REE (LREE) enriched fluorocarbonates and carbonates, which are commonly found in carbonatites. Textural and mineralogical evidence from these and other sites point towards wall rock composition as a major control on the observed REE mineralisation, with the supply of carbonate, and possibly fluoride, thought to be the limiting factor. Despite theoretical and experimental studies focussed on REE speciation in hydrothermal fluids, and a few on REE mineral solubility, there remains a lack of understanding of the processes occurring at the uid-rock interface during REE carbonate and fluorocarbonate mineralisation. Many of the issues surrounding this topic stem from the difficulty of working at elevated temperatures, low REE concentrations, and with the corrosive fluoride ion. The synthesis of REE carbonates under simple, low temperature conditions is a useful starting point for understanding REE mineralisation, and as such has been the focus of research for decades. Despite this, cross-series trends are rarely assessed together under the same conditions, and multi-REE-bearing systems - useful for assessing REE fractionation - have scarcely been explored. Furthermore, wall rock experiments, whereby REE-rich fluids are reacted directly with carbonate rocks, are absent from the literature. The same is true for systems containing fluoride, necessary for studying the formation of fluorocarbonates. A fuller understanding of REE mineralisation cannot be achieved until empirical experimental results can be compared with theoretical data and field observations. This thesis documents the laboratory synthesis of single- and multiple-REE-bearing carbonates and fluorocarbonates, and compares the findings with a mineralogical and textural study of two REE-bearing carbonatite deposits. The REEs La, Nd, Gd, Er and Yb were investigated as representatives of the entire series. The experiments constituted titrations of REE chloride solutions with sodium carbonate, and `wall rock reactions' of REE chloride with dolomite, or dolomite plus fluorite. Batch and flow-through setups were used, and the experiments were performed, or the products aged, at temperatures ranging from ambient to 200 °C. Products were characterised by techniques such as PXRD and SEM to document their structure and morphology as a function of temperature, and assess the influence of single vs multiple REE on the final material (whether mixed or separate phases formed). Results showed that in titration experiments, the LREEs crystallised easily and at low temperatures (as low as room temperature), HREEs either do not crystallise (in some cases even at 200 °C) or are more diffcult to crystallise, and mixed LREE + HREE precipitates behaved more like HREE-only examples. The HREEs and LREEs + HREEs mostly produced X-ray amorphous materials, identified as carbonates using FTIR. These were analysed by XAS (XANES and EXAFS) to assess whether they possessed the same short-range structure as the crystalline phase into which are known to form, thus adding to the non-classical nucleation pathway argument as previously suggested for these materials. Results suggested the short-range order of most phases analysed were similar to known bulk phases, but that these were probably different to the earlier precipitates formed in solution. Additionally, in the mixed LREE + HREE systems (Nd+Er), REEs were well dispersed (as opposed to Nd- and Er-rich clusters). In contrast to the titration results were those of wall rock reactions, in which excellent crystallisation was observed for almost every REE configuration (single- or up to five- REE mix), or ageing duration. All but three of the phases produced were previously described natural or synthetic minerals. When fluorite was included in batch reactions the results were more varied: REE carbonates, fluorides and fluorocarbonates were all observed, but never together in the same sample (except in one example). A textural and mineralogical assessment of two carbonatite deposits, Bayan Obo, China and Tundulu, Malawi, which were analysed by EMPA, revealed multiple stages of hydrothermal activity, some of which related to REE fluorocarbonate mineralisation. REE fluorocarbonates, identified at both sites, were typically LREE enriched. No REE carbonates or fluorides were observed, despite the presence of fluorite (REE-barren) and carbonates at Bayan Obo, and carbonates (low REE content) at Tundulu. However, at both sites apatite contained considerable REE. The REE fluorocarbonates were not solely associated with carbonate wall rocks, although the Ca-REE fluorocarbonate synchysite was only observed in the significantly more carbonate-rock-rich Tundulu samples. At Bayan Obo, bastnasite and huanghoite (Ba-REE fluorocarbonate) were observed, the latter of which is reportedly replacing earlier Ca-REE fluorocarbonates. The results demonstrate the varying behaviour of REEs during precipitation under different conditions, and highlights the influence of dissolved carbonate supply rate to morphology, structure and crystallinity of the products. The occurrence of only one class of REE mineral (carbonate, fluoride or fluorocarbonate) in the synthetic experiments with fluoride may help explain the lack of natural REE carbonates and fluorides - and predominance of REE fluorocarbonates - in hydrothermal systems, as was observed in the natural samples studied. In addition, the lack (absence?) of naturally occurring HREE carbonates and fluorocarbonates in the studied carbonatites (and the literature) is suggested to result not from factors such as structural constraints, but instead from the relative crustal abundances of the individual REEs. It is shown that HREE carbonates and fluorocarbonates are valid species under certain conditions, but that these are not likely to occur naturally.

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 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. / text

Rare Earth Elements (REEs: La–Lu, Y, and Sc) are critical components for technological innovations, therefore more effective methods for the domestic extraction and purification of REEs are in ever-increasing demand. Metal-chelating polymers have great potential in these applications due to their relatively low cost and high affinity for target elements. However, while much research has focused on specific ligands attached to polymers, little is known about the effect of polymer architecture itself on metal chelation. This dissertation reports recent progress in the design, synthesis, and application of polymers for the chelation of various REEs. In addition to synthesizing a series of metal-chelating polymers, we elucidated the thermodynamics of binding using isothermal titration calorimetry (ITC) to gain insight into the specific relationship between polymer structure and metal binding. ITC enables the direct measurement of the binding affinity (Ka), enthalpy changes (ΔH), and stoichiometry of the interactions between macromolecules and metal ions in solution. The thermodynamics of metal chelation underpins many technologies for REE extraction. Consequently, elucidating these parameters enables the rational design of future materials. / Doctor of Philosophy / Rare-Earth Elements (REEs) are critical metals used in many modern technologies, therefore more effective methods for the recovery and purification of REEs are in ever-increasing demand. Metal-chelating polymers—materials that can bind metals—have great potential in these applications due to their relatively low cost and high affinity for target elements. However, while much research has focused on the specific metal-binding group attached to the polymer, little is known about the effect of polymer architecture itself on metal chelation. This dissertation reports recent progress in the design, synthesis, and application of materials that bind to various REEs. In addition to synthesizing a series of metal-binding polymers, we measured the heat absorbed or produced during metal-binding interactions. These experiments produced fundamental insights into the interactions between the polymers, metals ions, and water molecules in solution. Overall, this work produces a depiction of the polymer–metal binding process, which enables insight into each polymer's properties as a metal-binding material. Future researchers can use these guidelines to develop the next generation of materials for the extraction of these critical metals.

Master of Science / Department of Geology / Sambhudas Chaudhuri / Rare earth element (REE) concentrations were measured in a source (reference) clay Ca-smectite standard and in the roots, stems, and leaves of a species of poplar plant (Populus eugenei). The poplar plant was grown in the clay standard under controlled laboratory conditions during a period of about three months. REEs were shown to fractionate in the clay mineral and plant materials with greater fractionation observed in plant materials. The REE data provide insight into the process of weathering of clay minerals such as a Ca-bearing smectite and provide insight into the degradation of and the composition of clay minerals in the plant environment. The degradation process is not followed by significant interlayer ion exchange effect on remaining clay minerals in the root environment. REEs were found to be transported into complex forms, potentially as REE-carboxylic anion pair complexes. The plant materials in this study were in general heavy REE (HREE) enriched relative to the source clay minerals due to the complexation effect. The REE anomalies observed in this study, in addition to the Ce and Eu anomalies, may be explained by the selective uptake by the plant by an enzyme effect rather than due to the influence of oxidation-reduction. The enzyme influence was more evident in the REE distribution when compared among the plant organs. These REE characteristics described for the plants may eventually be incorporated with data from numerous other studies and also used as a guide in the assessment of the contribution of plant materials to dissolved REE content in surface water and groundwater.