Neogene land-mammal localities are very rare in the northeastern U.S.; therefore, the late Miocene/early Pliocene Gray Fossil Site in eastern Tennessee can clarify paleoecological dynamics during a time of dramatic global change. In particular, the identification of ancient forests and past climate regimes will better our understanding of the environmental context of mammalian evolution during the late Cenozoic. Stable isotope analyses of bulk and serial samples of fossil tooth enamel from all ungulates present at the Gray site elucidate paleoecological reconstructions. The herbivorous megafauna include taxa of likely North American and Eurasian ancestry including: the tapir Tapirus polkensis, rhino Teleoceras cf. T. hicksi, camel cf. Megatylopus sp., peccary Tayassuidae, and proboscidean Gomphotheriidae. The tapir, rhino, camel, and peccary yield mean stable carbon isotope (δ13C) tooth enamel values of - 13.0‰, - 13.3‰, - 13.8‰, and - 13.1‰, respectively, suggesting forest-dwelling browsers. This range of δ13C values indicates the presence of a C3 dominated ancient local flora. Because δ13C values decline with increasing canopy density, the ancient temperate forests from the Gray site were moderately dense. The lack of significant C4 plant consumption (i.e., tooth enamel δ13C values < - 9‰) suggests the presence of forests large enough to independently support the continued browsing of sustainable populations of browsers from the Gray site. In contrast, bulk and serial δ13C values ranging from - 0.7‰ to 0.3‰ from a gomphothere tusk support a diet consisting of C4 grasses, suggesting the presence of C4 grasslands within the individuals home range. The rare earth element (REE) analyses of the gomphothere tusk and the teeth of Tapirus and Teleoceras indicates that these individuals shared similar depositional environments; thus, demonstrating the concurrent presence of C3 forests and C4 grasslands in the northeast. Stable carbon and oxygen serial sample variation of the tapir, rhino, peccary, and gomphothere is less than 1.5‰, suggesting minor differences in seasonal temperature and/or precipitation. These data support the possibility of a North American forest refugium in the southern Appalachians during a time typified by more open environments.

Rare earth elements (REEs) are a group of 15 elements in the lanthanide series along with scandium and yttrium. They are often grouped together because of their similar chemical properties. As a result of their increased application in advanced technologies and electronics including electric vehicles, the demand of REEs and other critical elements has increased in recent decades and is expected to significantly grow over the next decade. As the majority of REEs are produced and utilized within the manufacturing industry in China, concerns over future supplies to support national defense technologies and associated manufacturing industries has generated interest in the recovery of REEs from alternate sources such as coal and recycling. A solvent extraction (SX) process and circuit was developed to concentrate REEs from dilute pregnant leach solutions containing low concentrations of REEs and high concentrations of contaminant ions. The separation processes used for concentrating REEs from leachates generated by conventional sources are not directly applicable to the PLS generated from coal-based sources due to their substantially different composition. Parametric effects associated with the SX process were evaluated and optimized using a model test solution produced based on the composition of typical pregnant leach solution (PLS) generated from the leaching of pre-combustion, bituminous coal-based sources. Di-2(ethylhexyl) phosphoric acid (DEHPA) was used as the extractant to selectively transfer the REEs in the PLS from the aqueous phase to the organic phase. The tests performed on the model PLS found that reduction of Fe3+ to Fe2+ prior to introduction to the SX process provided a four-fold improvement in the rejection of iron during the first loading stage in the SX circuit. The performances on the model system confirmed that the SX process was capable of recovering and concentrating the REEs from a dilute PLS source. Subsequently, the process and optimized parametric values were tested on a continuous basis in a pilot-scale facility using PLS generated from coal coarse refuse. The continuous SX system was comprised of a train of 10 conventional mixer settlers having a volume of 10 liters each. A rare earth oxide (REO) concentrate containing 94.5% by weight REO was generated using a two- stage (rougher and cleaner) solvent extraction process followed by oxalic acid precipitation. The laboratory evaluations using the model PLS revealed issues associated with a third phase formation. Tributyl Phosphate (TBP) is commonly used as a phase modifier in the organic phase to improve the phase separation characteristics and prevent the formation of a third phase. The current study found that the addition of TBP affected the equilibrium extraction behavior of REE as well as the contaminant elements., The effect on each metal was found to be different which resulted in a significant impact on the separation efficiency achieved between individual REEs as well as for REEs and the contaminant elements. The effect of TBP was studied using concentrations of 1% and 2% by volume in the organic phase. A Fourier Transform Infrared (FTIR) analysis on the mixture of TBP and DEHPA and experimental data quantifying the change in the extraction equilibrium for each element provided insight into their interaction and an explanation for the change in the extraction behavior of each metal. The characteristic peak of P-O-C from 1033 cm-1 in pure DEHPA to 1049 cm-1 in the 5%DEHPA-1%TBP mixture which indicated that the bond P-O got shorter suggesting that the addition of TBP resulted in the breaking of the dimeric structure of the DEHPA and formation of a TBP-DEHPA associated molecule with hydrogen bonding. The experimental work leading to a novel SX circuit to treat dilute PLS sources was primarily focused on the separation of REEs from contaminant elements to produce a high purity rare earth oxide mix product. The next step in the process was the production of individual REE concentrates. To identify the conditions needed to achieve this objective, a thermodynamic model was developed for the prediction of distribution coefficients associated with each lanthanide using a cation exchange extractant. The model utilized the initial conditions of the system to estimate the lanthanide complexation and the non-idealities in both aqueous and organic phases to calculate the distribution coefficients. The non-ideality associated with the ions in the aqueous phase was estimated using the Bromley activity coefficient model, whereas the non-ideality in the organic phase was computed as the ratio of the activity coefficient of the extractant molecule and the metal extractant molecule in the organic phase which was calculated as a function of the dimeric concentration of the free extractant in the organic phase. To validate the model, distribution coefficients were predicted and experimentally determined for a lanthanum chloride solution using DEHPA as the extractant. The correlation coefficient defining the agreement of the model predictions with the experimental data was 0.996, which is validated the accuracy of the model. As such, the developed model can be used to design solvent extraction processes for the separation of individual metals without having to generate a large amount of experimental data for distribution coefficients under different conditions.

Mining activities, as essential as they are for our economy and our society, bring pollutants such as acid mine drainage (AMD) which contains dissolved metal(loid)s into the environment. There are different technologies currently being practiced to treat AMD, but many of these methods are prohibitive in industry due to high energy, material and labor requirements. This study investigated two emerging technologies to treat AMD with high removal rates of some metals. In addition, as AMD contains strategic metals such as rare earth elements (REEs), hydrometallurgical and biosorptive approaches were used to recover REEs from AMD, hydrometallurgical recovery method was also applied for coal by-products for the method developed. A two-chamber bioelectrochemical system (BES) was used to remove different types of metals from AMD. After 7 days, the pH of the cathode solution increased from 2.5 to 7.3. More than 99% of Al, Fe and Pb were removed, and removal rates of 93%, 91%, 89% and 69% were achieved for Cd, Zn, Mn, and Co, respectively, at the biocathode. Energy-dispersive X-ray spectroscopy (EDS) studies revealed the deposition of the various metals on the cathode surface, and some metals were detected in precipitates from the cathode chamber. During the BES operation, ~30-50 mV of closed circuit voltage was obtained for different conditions. A single-chambered BES study was conducted for the removal of Cd, Ni, and Mn in mine drainage. Compared to a double chamber, a single chamber BES is easier to design and operate. The removal process was studied with activated sludge from a local wastewater treatment plant. The effect of applied voltage, time, and initial concertation of these metals on their removal rate was studied. For Cd initial concentrations of 625 and 165 µg/L, 1.0 V showed the highest removal efficiency, and ~93 and 95% of Cd were removed, respectively. For a Ni initial concentration of 2,440 µg/L, 72% was removed under 1.0 V compared to the control of 77%. However, for a lower initial Ni concentration of 190 µg/L, 1.0 V was better compared than other conditions, and it removed 92% of Ni. For a Mn initial concentration of 1,800 µg/L, 1.0 V had a better result, however, only ~19% of the Mn was removed. For a lower Mn initial concentration of 390 µg/L, 1.0 V was favorable only at 24 h and the removal rate was ~37%. Nanoscale zerovalent iron (nZVI) was used to remove contaminants from AMD. These contaminants include transition metals (Co, Ni, Cu, Mn, and Zn), alkali and alkaline earth metals (Li, Mg, and Ca), metalloid (As), nonmetals (Se and S), and active metal (Al). Purchased nZVI in concentrations of 10-6500 mg/L was used for a reaction duration of up to 480 min. The pH of the AMD increased linearly with increasing concentrations of nZVI, with a maximum of 6.0±0.1 at 6500 mg/L of nZVI. Cu and Al had the highest removal rate among all other elements. With 10 mg/L of nZVI, ~100% of Cu was removed within 120 min. Up to ~98% of Al was removed with 5000 mg/L of nZVI in 480 min. Reuse of the purchased nZVI was studied for the first time for AMD treatment; however, after reuse in the second cycle, the nZVI was no longer effective. Lab-made nZVI by the precipitation method was tested for a longer time of 48 h. Removal rates for different elements did not change after ~8 h (e.g., 480 min), and in general, the lab-made nZVI had better removal efficiency compared to the purchased nZVI, with removal rate of ~28-79% when using 80 mg/L of the lab-made nZVI. Besides Cu, Al, Ni, and Co, successful removal of Mg and Ca, as well as S, Co, Li, As, and Se from AMD was reported for the first time by using nZVI. Different coal ranks were examined for REE concentration from coal ash. Maximum REE content of more than 700 mg/kg was observed for the highest-rank coal (anthracite) sample, and that was used for leaching and recovery studies. Hydrometallurgical processes including leaching, solvent extraction, stripping, and precipitation were performed to recover REEs from coal ash. Nitric acid leaching tests were conducted at 95 ℃ using a 4×2×2 factorial design. The results indicated that the highest rate of light REEs (LREEs) recovery was achieved at the highest molarity of the acid solution, lowest solids content and longest retention time. However, the highest rate of heavy REEs (HREEs) recovery needed only an intermediate level of acid molarity. The highest recovery rates of 90% for LREEs and 94% for HREEs were obtained. Recirculation of the leachate was conducted to prepare the REE-concentrated solution for the solvent extraction. After two stages of leaching, a 33 mg/L of TREE concentration was obtained in the leachate. Solvent extraction (SX) tests conducted using three different extractants, namely, TBP, D2EHPA and Cyanex 572, and their combinations showed that D2EHPA was the best extractant for recovering REEs from the nitric acid leachate solution with an extraction efficiency of 99%. Nitric acid and sulfuric acid and their mixture were used in the stripping tests. The effect of solvent concentration (in the SX process) was also studied in the stripping stage. When 50% solvent concentration was used, a maximum of 58% stripping recovery was obtained. Oxalic acid helped precipitate ~94% of total REEs (TREEs) from the above aqueous solution. Calcination of the product was performed to reach a final product of 0.8% rear earth oxides (REOs). The same process flowsheet was also successfully tested for another coal ash sample. To recover REEs from AMD, two different approaches were carried out including hydrometallurgical technique and more environmentally friendly approach- biosorptive recovery. A complete process flowsheet including either solvent extraction or biosorption, followed by stripping, and precipitation was developed to recover REEs from an unconventional source of AMD for the first time. At the natural pH of 2.5 almost all REEs were extracted from the solution. Metal-loaded organic solution was reused for three cycles, and it was shown that after three cycles, there was no major reduction in the capacity of the extractant. Striping with 6.0 M HNO3 recovered 23.9±0.7, 74.7±2.1, and 53.1±1.4% of LREEs, HREEs, and TREEs from the organic phase accordingly. Using oxalic acid, and for pH of 2.0, 92.9±2.8% of LREEs, 10±1.5% of HREEs, and 56.2±1.8% of TREEs were precipitated. In the biosorptive extraction, >99% of TREEs were extracted from the solution. The REE-bearing bacteria was also stripped with 6.0 M HNO3, 2871.3±114.8 µg/L (45.0±1.8%) LREEs, 3851.0±154.0 µg/L (65.0±2.6%) HREEs, and 6722.0±268.9 µg/L (50.0±2.0%) TREEs were obtained. Both hydrometallurgical and biosorptive methods extracted almost all of the REEs in the AMD, though pH was adjusted to 4.0 for the biosorptive method. After stripping, comparable amounts of TREEs were obtained by both methods.

Three phases of work were performed for this study. First a new form of liberation analysis was created and applied to two coal samples from separate formations. This new method of liberation analysis attempts to remove sources of error found in the traditional form of liberation analysis. This new method is capable of producing results comparable to multiple iterations of the traditional liberation analysis while using only one head sample. The new method relies on the mathematical reconstruction of the data to produce the resulting liberation profile. This allows the user to easily expand the method to include more liberation profiles without greatly increasing the amount of head weight needed. The results of this phase confirm that the products of each liberation profile reconstitute the correct feed ash. The second phase of work focused on the evaluation and concentration of rare earth elements (REEs) present in the refuse streams of coal processing plants found in the eastern United States. Twenty plants were sampled for the fleet study. Samples of these plants' refuse streams were collected and their REE and ash contents were determined. Coal from the Eagle seam, Fire Clay seam, and Fire Clay Rider were collected and tested during the concentration phase. Samples of a waste coal from the Pittsburgh seam and a coal combustion by prodcut were also provided by a third party. The separation methods investigated include multi-gravity separation, electrostatic separation, and selective oil agglomeration. Partition curves from x-ray sorting devices were also applied to REE float-sink data as well. The results of this work show that REEs tend to partition with low ash material when viewing the results on an ash basis. Finally, the third phase of this work involved the application of x-ray sorting technology on different coals. This work showed that the x-ray sorting technology in question is capable of effectively treating prescreened feed with a size range of 2" x 1/4". The work also shows that the x-ray sorting technology also has applications in the power generation field, where it can be used to eliminate elements of environmental concern. / Ph. D.

Concentrations of rare earth (REE), U, Th, and other trace elements (TE) were measured using LA-ICP-MS along transects across five Late Eocene brontothere bones from the terrestrial Late Eocene Chadron Formation of Nebraska and four Miocene marine mammals from the Atlantic Coastal Plain. Samples were analyzed to determine REE diffusion periods, and to determine if histological factors affect post mortem uptake of REE/TE. In terrestrial fossil bones, concentrations of REE are highest at the bone surface and decrease with depth into the trabecular bone, consistent with diffusion-limited models. Histology may affect REE incorporation. An outer circumferential layer (OCL) is preserved along the outer 1 mm of the brontothere rib (F08-10) and femur (F08-09). REE concentrations in the OCL are much lower than in the underlying bone, indicating either lower incorporation or post fossilization leaching. REE concentrations are sometimes elevated in trabecular bone and Haversian systems, which may act as secondary diffusion pathways. REE concentration gradients are generally steeper in marine fossils than in terrestrial fossil bones, indicating longer periods of REE uptake in terrestrial fossils. Calculated periods of diffusion in terrestrial environments are 2.2 +/- 0.5 to 54.8 +/- 1.5 ka (based on a wetness factor of 0.5 +/- 0.1). Periods of diffusion for marine environments range from ca. 0.9 +/- 0.2 to 2.8 +/- 0.6 ka. However, within some terrestrial samples U is introduced into the bone over a much longer time span, possibly as a function of fluctuating redox conditions. If these values are representative, diffusion-fossilization periods are shorter in marine/lacustrine/spring/channel environments due to constant water saturation. Saturation of a bone during diffusion may also affect the morphology of REE signatures within the bone. In terrestrial bones, REE are strongly fractionated with depth, producing signatures varying from light-REE enriched at the surface to middle-REE depleted at depth. However, depth fractionation of REE is much less pronounced in marine bones, which may result from the introduction of fluid unreactive. These differences in REE fractionation are consistent with a greater influence of multiple secondary REE/TE diffusion paths in marine samples. Periods of diffusion for terrestrial samples differed within a single bonebed accumulation (2.2 +/- 0.5 to 54.8 +/- 1.5 ka). However, REE signatures are internally consistent with one another within the bonebed indicating that groundwater chemistry did vary during fossilization. If groundwater chemistry changes during diffusion, bone could be recording different signals, which has implications for using post-mortem REE/TE/Isotopes for paleoenvironmental reconstruction. Previous studies of soft tissue preservation in fossilized bone have inferred shorter periods of diffusion and suggested that the rate of diffusion must outpace the rate of decay. Diffusion periods in bone from well drained terrestrial settings are too long to preserve soft tissue. However, periods of diffusion in marine fossil bones are much shorter, suggesting the possibility for bio-molecule preservation. / Geology

Rare earth elements (REE) exhibit particular and unique properties that render them essential to technological applications. Of particular interest is their involvement in the transition toward global sustainability and their military applications. The magnetic properties of the rare earth elements is of primordial importance to sustainable development. More specifically, terbium and dysprosium are two elements with no known substitutes in critical applications and with no domestic or allied sourcing available. These elements are currently mined by in-situ leaching of ion-absorbed clays, mostly from illegal operations in Myanmar financed by Chinese companies. The demand from both elements, and for the other magnet rare earths is projected to growth at very high rates through 2035 while the world undergoes a transition toward sustainability, and a drastic reduction in greenhouse gases emissions. Our team has been evaluating the potential of acid mine drainage (AMD) as a source of rare earth elements and critical materials (CM). Acid mine drainage is the result of in-situ generation of sulfuric acid due to the weathering of sulfide ores. It is a significant legacy environmental issue and one of the largest pollutants in many mining districts throughout the world. The objective of the present work is to provides a roadmap for the utilization of AMD as a critical material feedstock to preserve the independence of the United States of America with regards to these materials. To that effect, a fundamental economic assessment of REE/CM recovery from AMD using a network sourcing strategy in addition to a robust, flexible feedstock separations and refining facility was undertaken. A techno-economic analysis of the extraction, refining, separation and reduction to metal is presented along with a sensitivity analysis.The results of this analysis show that, with the exception of the minimum price scenario, all operational configurations have positive economic indicators with rates of return varying from 25% to 32% for the contemporary price scenario. This is primarily due to the very high enrichment in terbium and dysprosium of AMD. The optimal configuration was determined to be production of Co, Mn, and all REEs except for mischmetal, which is not recovered. Sensitivity analysis and Monte Carlo Simulation show that capital cost and HCl consumption are the two major factors influencing rate of return, thus indicating opportunities for future technology development and cost optimization. In order to reduce both the capital and operation cost of the facility, alternative ionic liquids extractants based on conventional acidic extractants where synthesized and investigated. The results show that the ionic liquids varied in performance, with [c101][D2EHP] and [c101][EHEHP] performing poorer than their conventional counterparts and [c101][c572] performing better. The performance of [c101][c572] was 13% superior to Cyanex 572, 20% superior to EHEHPA and 27% superior to D2EHPA the current commercially used extractants. Recommendations for further study on [c101][c572] include stripping tests, continuous pilot testing, and techno-economic analysis. The test work revealed that zinc and to a lesser extent calcium were significant deleterious elements in the solvent extraction circuit, and that selective removal would significantly reduce the acid-base consumption of the separation circuit. A process was developed to selectively remove calcium and zinc from AMD-derived feedstock and from REE products. The ammonium chloride leach process offer many advantages, including the possibility of closing the cycle by using carbon dioxide sequestration as a step to regenerate the ammonium chloride in a zero-discharge process. / Doctor of Philosophy / A younger me: - What are these elements in the bottom of the periodic table? My high school chemistry teacher: - "Don't waste time there, these are of no concern." Twenty years later, technological developments and the imperative to transition away from fossil energy to mitigate climate change have brought the rare earth elements, a series of 17 elements with unique properties to the forefront of the conversation. In addition to an organic increase in demand, the recent supply chain consolidation by China is adding a geopolitical risk to the equation. The magnetic properties of the rare earth elements is of primordial importance to sustainable development and to our military technology. More specifically, terbium and dysprosium are two elements with no known substitutes in critical applications and with no domestic or allied sourcing available. These elements are currently mined from illegal operations in Myanmar, with the support of Chinese companies. The demand from both elements, and for the other magnet rare earths is projected to growth at very high rates through 2035 while the world undergoes a transition toward sustainability, and a drastic reduction in greenhouse gases emissions. Given the important of the rare earth elements, and the absence of significant deposits in the united states, with the exception of the Bear Lodge and Elk Creek deposits, the Department of Energy has mandated academic institution of evaluating alternative sources of rare earth elements. Our team has been evaluating the potential of acid mine drainage as a source of rare earth elements and critical materials. Our team has surveyed many acid mine drainage sources and determined that many sites are highly enriched in terbium and dysprosium. Acid mine drainage is a legacy environmental issue related to past problematic mine development techniques. In the problematic mines. these acidic mine waters are permanently generated and if not treated can have severe impacts on water streams in which they flow. The toxicity of the acid mine drainage on the environment is due to its high acidity and significant levels of toxic metals. Acid mine drainage can be recognized by their yellow to red tint. It is treated by reacting it with a neutralization agent, which results in treated water and a sludge. The sludge is dewatered and stored in tailing impoundments. I have designed a process for the economical recovery of rare earth elements and critical materials from acid mine drainage. The cost to build and operate the facility was derived and it was determined that the project could be further enhanced by reducing the plant chemical reagent consumption. One specific category of chemical referred to as extractant, is central to the rare earth separation process. A novel variation on the standard extractants has been evaluated and promises to provide significant savings. While the extractants were investigated, it was noticed that some impurities such as zinc and calcium created issues in the circuit. I then developed a process for their selective removal. The process also provide a net carbon dioxide sequestration potential.

Several recent studies have shown that acid mine drainage (AMD) may be a promising source of rare earth elements (REEs), which are essential feedstocks for many high tech applications and defense products. AMD is a longstanding environmental challenge and is currently the primary pollutant of water in the Appalachian coal mining region. Acid generated during the coal mining process tends to leach several transition metals from the surrounding rock strata. While iron, aluminum, and manganese have traditionally been noted as the predominant metals in AMD, recent studies have also shown that REEs are also present, albeit in trace concentrations, often less than 5 μg/L. The recovery of REEs from AMD can be both an economic and environmental advantage; however, the low REE concentrations and high contamination from other metals makes the concentration and purification of REEs quite difficult. This research seeks to develop and optimize a process capable of producing mixed rare earth concentrates with purities exceeding 90% from an AMD feedstock. Parallel efforts by other members of the research team showed that a solid preconcentrate, nominally 0.1 to 2% REE, can be readily produced from AMD; however, that pre-concentration process cannot provide the further enrichment needed to generate high purity oxides suitable for downstream markets. In this project, solvent extraction was investigated as secondary process used to further enrich the low grade preconcentrate to a purity exceeding 90%. Initially, laboratory-scale batch solvent extraction tests were performed on synthetic REE solutions to determine the influence of various process parameters (e.g. pH, extractant dosage, diluent type, and feedstock concentration). Next, the separation of REEs from major AMD gangue elements was investigated using synthetic leachate solutions with concentrations similar to those expected from the pre-concentrate samples. This process showed that the grade targets could easily be met when combining optimal parameters from each step. From this preliminary work with synthetic solutions, an optimal SX process was developed and validated using a real leachate generated from a pre-concentrate sample. By integrating leachate preparation, solvent extraction, scrubbing, stripping, and oxalic acid precipitation, an oxide containing 90.5% rare earth oxides was generated. Details on the process development, experimental optimization, and opportunities for process improvement are described. / Master of Science / Rare earth elements (REEs) are essential for many modern industries, high-tech applications, and defense products. The U.S. consumes approximately 11% of the global REE demand; however, the US supply chain is heavily reliant on imported Chinese feedstocks. This lack of a domestic supply chain exposes the US to both price and supply volatility, which are prevalent in the international markets. This supply issue is further compounded by a lack of suitable domestic feedstocks. REEs are rarely concentrated into mineable ore deposits, and in some cases the extraction and processing of conventional REEs deposits entails considerable environmental risk. As a result of these challenges, numerous federal agencies and private companies have recently sought to identify promising alternative resources. One potential alternative resource is acid mine drainage (AMD), which is a common environmental challenge associated with coal and hard rock mining. Prior studies have shown that acid mine drainage contains REEs; however, other metals, such as iron, aluminum, and manganese, preclude REE recovery using conventional processing techniques. As such, the goal of this research is to develop and optimize a process capable of recovering and concentrating REEs from an AMD feedstock. The research conducted in this thesis predominantly included laboratory testing using synthetic AMD samples. The complexity of the synthetic AMD progressively increased from very simple, single element solutions to complex multi-component mixtures. Through this research, data and information from these controlled experiments was used to design a multi-step solvent extraction process capable of producing final REE products exceeding 90% purity. In the last stage of the research, the final process was validated using actual AMD recovered from an operating mine site. The validation test showed that the process was effective in meeting its initial objectives: the grade of the final rare earth oxide was determined to be 90.5%. This laboratory-scale experimental work represents the first step of process needed to develop and deploy a commercial technology capable of producing REE products from AMD feedstocks.

Niobium (Nb) and Rare Earth Elements (REE’s) have in recent years received considerable attention because of their importance to the modern technical industry, and more specifically the enhanced sustainability that comes with them. The main source for Nb and REE’s on Earth are carbonatites and associated alkaline silicate rocks. This report examines the magnetic properties of rocks from the Oldoinyo Dili carbonatite complex in northern Tanzania. Previous workers have suggested a link between the Fe-bearing mineralogy and the formation of Nb-mineralizations at Oldoinyo Dili. This hypothesis is further examined in this report by combining detailed petrographic observations and withnew measurements of magnetic susceptibility. The aim is to see if any correlation exists between occurrence of Nb-mineralizations and the types of Fe-minerals present at Oldoinyo Dili. Based on the magnetic susceptibility measurements, at least two different species of Fe-minerals arefound in the examined samples. These are characterized by different magnetic trends during heating/cooling and also by their separate Curie temperatures (Tc). In combination with the petrographic observations these minerals are interpreted to be magnetite (Fe2O4) with Tc ~580°C, and a mineral that most likely represents a solid solution between ilmenite (FeTiO3) and hematite (Fe2O3) with Tc ~300°C. Here, no clear link between the type of opaque mineral(s) present and the total Nb content of the carbonatites can be conclusively determined based on the petrography and the magnetic measurements alone. Although the results of this report provide an important first step towards understanding the relationship between Nb-mineralizations and the magnetic mineralogy at Oldoinyo Dili, more detailed analyses of the mineral chemistry is a necessity to fully understand their complex relations and the specific conditions under which they formed. / Niob (Nb) och sällsynta jordartsmetaller (REE’s) har på senare år fått stor uppmärksamhet för sin betydelse för den moderna tekniska industrin, och specifikt för den förhöjda hållbarhet som de bidrar med. Den huvudsakliga källan till Nb och REE’s på jorden är karbonatiter och associerade alkalisilikater. Denna rapport undersöker de magnetiska egenskaperna för karbonatit-komplexet Oldoinyo Dili i norra Tanzania. Forskare har tidigare anat att det finns en koppling mellan Fe-bärande mineralogi och bildandet av Nb-mineraliseringar vid Oldoinyo Dili. Denna hypotes undersöks vidare i denna rapport genom att kombinera detaljerade petrografiska observationer med nya mätningar av magnetisk susceptibilitet. Syftet är att undersöka om det finns någon korrelation mellan förekomst av Nb-mineraliseringar och de typer av järnmineral som finns vid Oldoinyo Dili. Baserat på de genomförda magnetiska susceptibilitets-mätningarna så finns det åtminstone två olika sorters järnmineral i de undersökta proverna. De karaktäriseras av olika magnetiska trender vid upphettning/nedkylning och även av sina olika Curietemperaturer (Tc). Kombinerat med petrografiska observationer uttolkas att dessa mineral är magnetit (Fe2O4) med Tc ~580°C, samt en mineral som troligen är en solid solution av ilmenit (FeTiO3) och hematit (Fe2O3) med Tc ~300°C. Det går inte att senågon tydlig koppling mellan förekommande opaka mineral och det totala Nb-innehållet i karbonatiterna med säkerhet enbart utifrån petrografin och de genomförda magnetiska mätningarna. Resultaten av denna rapport utgör ett bra första steg mot att förstå relationen mellan Nb-mineraliseringar och den magnetiska mineralogin för Oldoinyo Dili, men mer detaljerade analyser av mineralkemin är nödvändigt för att till fullo förstå de komplexa förhållanden som råder vid bildning av dessa.

Master of Science / Department of Geology / Sambhudas Chaudhuri / The exploration and development of unconventional shale plays provide an opportunity to study the hydrocarbon generation process. These unconventional plays allow one to investigate the interactions between the fluid, mineral, and organic material that occur in a hydrocarbon-generating source bed, before any changes in composition that may occur during secondary migration or post migration processes. Previous studies have determined the chemical constituents of formation waters collected from conventional reservoirs after secondary migration has occurred. This investigation targets formation waters collected from the Woodford shale that acts as both source and reservoir, therefore samples have yet to experience any changes in composition that occur during secondary migration. This investigation focuses on the major element and trace element chemistry of the formation water (Cl, Br, Na, K, Rb, Mg, Ca, Sr, and Rare Earth Elements), which has been compared to chemical constituents of the associated crude oil and kerogens. Analytical data for this investigation were determined by the following methods; Ion Chromatography, Inductively Coupled Plasma Mass Spectrometry (ICP-MS), and Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES). The information is used to assess the presence of different sources of water that constitute the formation water, and also to investigate interaction between different minerals and formation waters within the source beds. The formation water data also yields new insights into compartmentalization of oil-gas rich zones within the source beds.

With current energy demands globally and locally, nuclear energy remains one of the top competitors for cleaner and sustainable energy. The nuclear industry requires more inherent safety and proliferation resistance in reactor design. Thorium has therefore been identified as a possible fuel for future nuclear reactors that can comply with these requirements. However current extraction techniques are expensive, time consuming and generate large quantities of hazardous waste. A possible alternative to conventional solvent extraction of thorium is SFE (Supercritical Fluid Extraction). A monazite sample from the Steenkampskraal mine was investigated using SEM (Scanning Electron Microscope) analysis methods to determine the distribution of thorium in the grains that could potentially complicate the effectiveness of the SFE extraction method if zoning is present. The results show a homogeneous distribution with no discernable zonation in the grains. The concentration of Th, Ce and Nd was determined by quantitative MPA (Micro Probe Analysis). The results obtained from the MPA point analysis on several grains show average Th, Ce and Nd concentrations of 6.5 wt. %, 24.1 wt. % and 9.7 wt. % respectively. The extraction of Th+4 from a filter paper was conducted to verify the extraction procedure and extractability of transition elements employing SFE. The extraction was conducted using supercritical CO2 and methanol as co-solvent with TBP (Tributyl Phosphate) and HFA (Hexafluoroacetylacetone) added in situ as chelates. ICP-MS results for the Th+4 extraction procedure showed extraction efficiency of 53 % compared to 83 % in literature (Kumar et al. 2009). This marked difference in extraction efficiency is attributed to ineffective trapping methods employed and lack of prior maintenance and support on the extraction apparatus. Subsequently all further extracted samples of Th from monazite were tested using XRF analysis methods. Due to the lack of prior maintenance on the extraction apparatus several technical breakdowns were encountered and addressed from a mechanical engineering standpoint. The operational effectiveness of the modified apparatus was verified through the extraction of marula seed oil and compared with another supercritical fluid (SF) extractor to show 50 % extraction efficiency in each case. A review of the literature indicated that the crystal chemical requirements for substitution of trivalent (Ce+3) for tetravalent (Th+4) may be fulfilled during SFE processes. Experimental substitution extractions were conducted by addition of different chelates and were conducted by subjecting the monazite samples to 20 MPa pressure for 180 min static flow and 10 min continuous flow extraction times with a CO2 flow rate of 2 mL/min with 10 % co-solvent flow rate. The results of the two sets of substitution extractions namely α and β show no clear indication of Th extraction. The maximum theoretical efficiency obtainable under current extraction equipment limitations was calculated as 12%. The XRF analysis error margin was given by the analytical laboratory as 10 %. The literature has shown the substitution of trivalent cations for tetravalent cations in the monazite structure to be a valid reaction mechanism. The experimental results showed little or no success in extracting thorium from monazite. In order to prove the practical feasibility of thorium extraction several changes to the experimental operating conditions is required. / MIng (Mechanical Engineering), North-West University, Potchefstroom Campus, 2015