The lower Mount Rogers Formation (LMRF) is described by Rankin (1993) as a sequence of intercalated metabasalts and volcanogenic sediments with minor metarhyolite. We have chosen to examine the sequence of the LMRF units exposed along Elk Garden Ridge, a high shoulder between the summits of Whitetop Mountain and Mount Rogers in the Mount Rogers National Recreation Area in SW Virginia. This sequence represents an uplifted block of LMRF units enclosed by exposures of Whitetop and Wilburn metarhyolites. In the field, progressive lithologic changes can be observed walking up-section along Elk Garden ridge that are indicative of changes in lava compositions and eruptive environments. From the bottom of the section, massive basalts with distinctive 1-2 cm long swallowtail plagioclase phenocrysts grade into vesicular basalts, then into sheet flow basalts, followed by a thick sequence of aphyric and amygdaloidal pillow basalts. Further up section, eruptive products transition into rhyolitic ignimbrites and ash and lapilli tuffs. Boulders of cobble conglomerates near the middle of the sequence and sedimentary layers in between individual sheet flows suggest short periods of relative eruptive quiescence. The only unit broken out in the LMRF by Rankin (1993), Fees Rhyolite, is not observed in the field area, suggesting local differences in topography, eruptive products and eruptive styles across the outcrop area during the deposition of these eruptive products. Petrographically, the rocks reflect the regional greenschist facies metamorphic conditions with chlorite and epidote as primary metamorphic minerals, and unakite-like zones of mineralization. Relict plagioclase and pyroxene phenocrysts persist, as do primary igneous textures and structures. Compositionally, all of the rocks in the Elk Garden Ridge sequence are strongly enriched in alkali metals, with elevated Na2O and K2O contents, and high TiO2 in the basalts. Major and trace element systematics suggest that the chemical signatures of the metabasalts are primary controlled by shallow-level crystallization processes. The LMRF metabasalts share many compositional affinities with later (~570 Ma) rift-related basalts preserved in the Appalachians, suggesting that all of these lavas were formed by melting of a compositionally uniform mantle source, followed by shallow crystallization, despite being separated from one another by large stretches of time and space.

<p>Rare earth elements (REEs) are 15 elements in the lanthanide series plus scandium and yttrium. They are essential for clean energy, defense, and other high-tech industries. Production of high-purity REEs, however, is limited to a few countries, posing great supply risks. Separation of crude REE mixtures into individual REEs is the most challenging step because of similar physical and chemical properties of the REEs. Conventional REE purification processes are based on solvent extraction methods, which are inefficient, require thousands of separator units, and produce large amounts of waste. Chromatography methods are inherently more efficient than solvent extraction methods because of orders of magnitude higher interfacial area per unit volume. Low-cost chromatography sorbents, however, do not have sufficient selectivity for REE purification. </p><p>In this dissertation, ligand-assisted displacement (LAD) chromatography was developed for the separation and purification of REEs from complex mixtures. A ligand, which is selective for REEs, can be added in the mobile phase or immobilized in the sorbent to achieve REE separation and purification. Constant-pattern design methods and a general zone splitting strategy were developed for producing high-purity REEs with high yields and high productivities from complex mixtures. The new methods were tested for producing three high-value REEs, called the magnets REEs, which are the key ingredients in permanent magnets, neodymium (Nd), praseodymium (Pr), and dysprosium (Dy), from waste magnets, bastnäsite concentrates, and monazite concentrates. </p><p>A two-zone LAD was designed and tested for recovering high-purity <a>neodymium (Nd), praseodymium (Pr), and dysprosium (Dy) </a>from waste magnets. Three-zone LAD was designed to recover high purity Nd and Pr from bastnäsite and monazite concentrates. High purity REEs (>99.5%) were produced with high yields (>99%) and high productivities (>100 kg REEs/m³/day). </p><p>Compared to conventional solvent extraction methods, the LAD methods are inherently safer and greener, since they do not require flammable organic solvents or toxic extractants and generate much less waste. LAD methods require only a few zones with a small number of columns. They have more than 10 times higher productivity, or less than10 time the footprint, than solvent extraction. The LAD methods are also versatile and adaptable to a wide range of product purity requirement, feedstock composition, or production scale. </p><p>The LAD methods have the potential to transform the conventional solvent extraction methods with low efficiency and high environmental impact into more efficient and environmentally friendly chromatography methods. They can enable the production of the magnet REEs domestically and provide a driving force to change the current linear path of the REEs, from ores to permanent magnets, to landfills, into a more sustainable circular REE economy.</p>

The dissertation is comprised of three manuscripts presenting rare earth element (REE) and neodymium (Nd) isotopic analyses for the groundwaters, surface waters, sediments, and bedrocks of two estuaries along the eastern coast of the United States: Indian River Lagoon, Florida, and Pettaquamscutt Estuary, Rhode Island. This research was performed to understand the behavior of REEs in subterranean estuaries, the REE SGD fluxes, and the Nd isotopic composition of SGD. The selection of these sites offers contrasting geology (carbonate/sand matrix aquifer versus glacial till aquifer sourced from granitoids) and contrasting subterranean estuary structure. In the first site, the flux of REEs to the Indian River Lagoon, FL is comprised of a nearshore source of terrestrial SGD displaying a HREE-enriched fractionation pattern, and LREE- and MREE-enriched sources that originate from the reductive dissolution of Fe (III) oxide/hydroxides in the subterranean estuary and transported by bioirrigation to the overlying lagoon. The εNd(0) value the Indian River Lagoon groundwater is much more radiogenic than those of the surface water and sediments which could be due to the use of fertilizers in adjacent communities. The surface waters Nd isotopic composition appears to be a mixture of weathering of the Anastasia Formation and dissolution of eolian-transported Saharan Dust. In contrast at the second site, phosphate minerals control the surface and groundwaters of the Pettaquamscutt estuary, RI. The weathering of apatite and precipitation of secondary REE phosphate minerals most likely produce the MREE-enriched fractionation patterns of the Pettaquamscutt groundwaters. The further precipitation of the secondary REE phosphates in the surface waters of the Pettaquamscutt yields HREE-enriched fractionation patterns. The radiogenic Nd isotopic ratios of the Pettaquamscutt waters relative to the bedrock further suggest that apatite is the source of REEs. The Nd flux of SGD for both sites is roughly equal to the respective river fluxes; however, the Nd flux of SGD to the Pettaquamscutt is approximately 3 times greater than the SGD flux to the Indian River Lagoon. More research is needed in both environments to evaluate the impact of SGD on the Nd isotopic budget of the oceans. / acase@tulane.edu

Microbes exert extensive control on redox element cycles. They participate directly orindirectly in the concentration and fractionation of elements by influencing the partitioningbetween soluble and insoluble species. Putative microbially mediated manganese (Mn) oxidesof the birnessite-type, enriched in rare earth elements (REE) + yttrium (Y) were recentlyfound in the Ytterby mine, Sweden. A poorly crystalline birnessite-type phyllomanganate isregarded as the predominant initial phase formed during microbial Mn oxidation. Owing to ahigher specific surface area, this biomineral also enhances the known sorption property of Mnoxides with respect to heavy metals (e.g. REE) and therefore has considerable environmentalimpact.The concentration of REE + Y (2±0.5% of total mass, excluding oxygen, carbon and silicon)in the Ytterby Mn oxide deposit is among the highest ever observed in secondary precipitateswith Mn and/or iron. Sequential extraction provides evidence of a mineral structure where theREE+Y are firmly included, even at pH as low as 1.5. Concentration ratios of Mn oxideprecipitates to fracture water indicate a strong preference for the trivalent REE+Y overdivalent and monovalent metals. A culture independent molecular phylogenetic approach wasadopted as a first step to analyze the processes that microbes mediate in this environment andspecifically how the microbial communities interact with the Mn oxides. Plausible players inthe formation of the investigated birnessite-type Mn oxides are mainly found within theferromanganese genera Hyphomicrobium and Pedomicrobium and a newly identified YtterbyBacteroidetes cluster most closely related to the Terrimonas. Data also indicate that thedetected microorganisms are related to the environmental constraints of the site including lowconstant temperature (8°C), absence of light, high metal content and possibly proximity to theformer storage of petroleum products.

No description available.

Froth flotation has long been regarded as the best available technology for ultrafine particles separation. However, froth flotation has extreme deficiencies for recovering ultrafine particles that are less than 30-50 μm in size for coal and 10-20 μm for minerals. Furthermore, dewatering of flotation products is difficult and costly using currently available technologies. Due to these problems, coal and mineral fines are either lost to tailings streams inadvertently or discarded purposely prior to flotation. In light of this, researchers at Virginia Tech have developed a process called hydrophobic-hydrophilic separation (HHS), which is based originally on a concept known as dewatering by displacement (DbD). The process uses non-polar solvents (usually short-chain alkanes) to selectively displace water from particle surfaces and to agglomerate fine coal particles. The resulting agglomerates are subsequently broken (or destabilized) mechanically in the next stage of the process, whereby hydrophobic particles are dispersed in the oil phase and water droplets entrapped within the agglomerates coalesce and exit by gravity along with the hydrophilic particles dispersed in them. In the present work, further laboratory-scale tests have been conducted on various coal samples with the objective of commercial deployment of the HHS process. Test work has also been conducted to explore the possibility of using this process for the recovery of ultrafine minerals such as copper and rare earth minerals. Ultrafine streams produced less than 10% ash and moisture consistently, while coarse coal feed had no observable degradation to the HHS process. Middling coal samples were upgraded to high-value coal products when micronized by grinding. All coal samples performed better with the HHS process than with flotation in terms of separation efficiency. High-grade rare earth mineral concentrates were produced with the HHS process ranging from 600-2100 ppm of total rare earth elements, depending on the method and reagent. Additionally, the HHS process produced copper concentrates assaying greater than 30% Cu for both artificial and real feed samples, as well as, between 10-20% Cu for waste samples, which all performed better than flotation. / Master of Science / Froth flotation has long been regarded as the best available technology for separating fine particles. Due to limitations in particle size with froth flotation, and high downstream dewatering costs, a new process has been developed called the hydrophobic-hydrophilic separation (HHS) process. This process was originally based on a concept known as dewatering by displacement (DbD) which was developed by researchers at Virginia Tech in 1995. The process uses hydrocarbon oils, like pentane or heptane, to selectively collect hydrophobic particles, such as coal, for which it was originally developed. In coal preparation plants, a common practice is to purposefully discard the ultrafine stream that flotation cannot recover and has an increased dewatering cost. The HHS process can effectively recovery this waste stream and produce highgrade salable product, with significantly reduced cost of dewatering. In the work presented, laboratory-scale tests have been conducted on various coal samples with the objective of commercial deployment of the HHS process. In this respect, several varying plant streams have been tested apart from the traditional discard stream. Additionally, test work has expanded into mineral commodities such as copper and rare earth minerals. In this work, salable high-value coal products were achievable with the HHS process. Ultrafine streams consistently produced less than 10% ash and moisture. Coarse coal feeds had no observable degradation to the HHS process and were able to produce single digit ash and moisture values. Middling coal samples were upgraded to high-value coal products when micronized by grinding. All coal samples performed better with the HHS process than with flotation in terms of separation efficiency. High-grade rare earth mineral concentrates were produced with the HHS process ranging from 600- 2100 ppm of total rare earth elements depending on the method and reagent. Additionally, the HHS process produced copper concentrates assaying greater than 30% Cu for an artificial and feed samples, as well as, between 10-20% Cu for waste samples, which all performed better than flotation.

The field of analytical chemistry is very important to today's society as more and more regulations and legislations emerge regarding trace elements in food, consumer products, medicines, and the environment. Like many areas of science, the current goals of trace elemental measurements and speciation are to increase knowledge on the subject and to improve upon current techniques by enhancing the figures of merit, such as accuracy and reproducibility, meanwhile balancing with the cost and time of analysis. The topics covered in this work were investigated primarily through the use of inductively coupled plasma mass spectrometry (ICP-MS) and inductively coupled plasma optical emission spectrometry (ICP-OES). The phenomenon of compound-dependent responses in plasma spectrometry is discussed, seeking possible causes of it and offering some advice on how to prevent it. A new method was developed for the speciation of selenium in dietary supplements using anion-exchange chromatography ICP-MS. A novel method for the determination of total mercury at trace concentrations in rice was developed for use with conventional ICP-MS. Inductively coupled plasma mass spectrometry was also used for fingerprinting the rare earth elements in Maya archaeological pottery for provenance studies.

Rare earth elements (REEs) are critically important for high-tech, renewable energy and defense industries. However, rare earth minerals (REMs) are stable compounds, requiring aggressive conditions to decompose them for their extraction and use. One exception is the ion-adsorption clays (IACs) that are mined in South China. They were formed in nature via the adsorption of the REE ions on clay minerals; therefore, they can be readily extracted into solution under mild conditions using the ion-exchange leaching process using (NH4)2SO4 as lixiviant. It also happens that IACs are the largest source of the heavy rare earth elements (HREEs) that are critical, especially for the defense industry. At present, more than 80% of the HREEs are produced commercially from the IACs mined in Southeast Asia. The objective of the present research was to study the fundamental mechanisms involved in the formation and processing of IACs using the ion-change leaching process. The first part of the project was the synthesis of IACs by contacting kaolinite samples with known concentrations of rare earth chloride (REECl3) solutions at different pHs and analyzing the synthetic IACs for XPS studies. It was found that the REE adsorption on kaolinite stays constant in acidic pHs. At pH 7 and above, adsorption density increases sharply, possibly due to the formation of REE(OH)3 and/or REE(OOH). The IACs formed under these conditions responded well to the ion-exchange leaching process by reducing the pH to below 7. In the second part of the study, the effect of iron (Fe3+) species co-adsorbing with REEs on the kaolinite surface was studied. Unlike the colloidal phases of IACs formed at pH > 7, the synthetic IACs formed in the presence of iron did not respond to the ion-exchange leaching process using (NH4)2SO4 as lixiviant. This problem has been solved by subjecting the synthetic IACs to a reducing condition to convert the Fe3+ to soluble Fe2+ species at pH < 7. The driving force for the standard exchange leaching process is the large differences between the hydration enthalpies of the Ln3+ ions that are in the range of -3,400 kJ/mole and that of the NH4+ ions (-320 kJ/mole). In the present work, alkylammonium ions (CnH2nNH4+) of varying chain lengths were used as novel lixiviants and obtained excellent results. Since these are surface active species, their concentrations in the vicinity of the clay minerals that are negatively charged would be substantially higher than in the bulk. As a result, it was possible to achieve the same level of leaching efficiencies as obtained using ammonium sulfate at approximately ten times lower reagent dosages. One of the problems associated with extracting REEs from coal-based clays is that the REE concentrations are typically in the range of 300 to 600 ppm, which makes it difficult to extract the critical materials economically using ion-exchange leaching and other processes. As a means to overcome this issue, the REE-bearing particles, including IACs and REMs, were liberated by blunging and subsequently upgraded using the hydrophobic-hydrophilic separation (HHS) process. The results showed that blunging outperformed grinding in liberating the REE-bearing particles from the clayey materials in coal. It was shown that one can improve blunging by increasing the disjoining in the thin liquid films present between clay and other minerals by controlling the double-layer (EDL) forces. These findings should enhance our understanding of the fundamental mechanisms involved in upgrading critical materials and thereby increase the economic viability of REE recovery from coal-based materials. / Doctor of Philosophy / Rare earth elements (REEs) play a vital role in numerous modern industries, advanced technological applications, and defense industries. The United States accounts for about 15 % of the global demand for REEs. However, the country heavily relies on imported Chinese raw materials, creating vulnerability in the U.S. supply chain. REEs are rarely found in concentrations suitable for mining, and in certain cases, extracting and processing conventional REE deposits come with significant environmental hazards. The limited availability of rare earth elements (REEs) raises concerns regarding their production despite their critical role in high-tech industries. Consequently, various federal agencies and private enterprises have recently attempted to identify promising alternative resources due to these complex challenges. REEs have been found in several major coal basins and are evidenced to be associated with coal byproducts such as kaolinite clays–one of the major host materials of IACs. This research investigates the recovery of rare earth elements (REEs) from clayey materials through various processes. Emphasis is placed on the synthesis of ion-adsorption clays from kaolinite, and the factors influencing the ion-exchange leaching process are being studied. Furthermore, the impact of iron co-adsorption on REE binding to kaolinite is being examined, and reductive leaching is being evaluated as a means to overcome the hindrance caused by iron passivating layers. Novel lixiviants are being tested as alternatives to conventional lixiviant ((NH4)2SO4) for REE extraction. The application of hydrophobic-hydrophilic separation techniques for extracting REE-bearing particles from coal clay samples is also being explored, with a comparison made between grinding and blunging processes. Overall, valuable insights into the efficient recovery of REEs from clay minerals are being obtained, contributing to the development of cost-effective and novel approaches for their extraction.

The rapid development of advanced technologies has led to an increase in demand for critical elements that are essential in the manufacturing of high-tech products. Among these critical elements, manganese (Mn), cobalt (Co), and nickel (Ni) are used in the production of batteries, electronics, and other advanced applications. The demand for these elements has been growing exponentially in recent years, driven by the rise of electric vehicles, renewable energy, and other emerging technologies. However, the United States is heavily dependent on foreign sources of critical minerals and on foreign supply chains, resulting in the potential for strategic vulnerabilities to both economy and military. To address this problem and reduce the Nation's vulnerability to disruptions in the supply of critical minerals, it is important to develop critical minerals recycling technologies. A systematic study was conducted to develop a process for producing high-purity Mn, Co, and Ni products from an acid mine drainage (AMD). As major contaminants, Fe and Al in the solution were sequentially precipitated and eliminated by elevating the pH. After that, a pre-concentrated slurry containing Mn, Co, Ni, and Zn was obtained by collecting the precipitates formed in the pH range of 6.50 to 10.00. The pre-concentrated slurry was redissolved for further purification. Sodium sulfide was added into the redissolved solution to precipitate Co, Ni, and Zn selectively while retaining Mn in the solution. Almost 100% of Co, Ni, and Zn but only around 15% of Mn were precipitated using a sulfur-to-metal molar ratio of 1 at pH 4.00. The sulfide precipitate was calcined and then completely dissolved. The critical elements existing in the dissolved solution were efficiently separated using a two-stage solvent extraction process. Ultimately, Co and Ni products with almost 94% and 100% purity were obtained by sulfide and alkaline precipitation, respectively. AMD also contains rare earth elements (REEs), which can be recovered through selective chemical precipitation. REE removal improved at pH 4.0 after converting ferrous to ferric ions with H2O2. Aluminum species in the solution hindered REE adsorption on ferric precipitates, and ferrous ions reduced REE adsorption on aluminum precipitates at lower pH, but at higher pH, REE removal increased due to ferrous ion precipitation. Various tests and analyses were conducted to understand the partitioning mechanisms of REE during the precipitation process of AMD. Sulfide precipitation is crucial to separate Mn from other elements, but the presence of contaminants like Fe and Al can affect sulfide precipitation efficiency. The effects of Al3+ iii and Fe2+ on the precipitation characteristics of four valuable metals, including Mn2+, Ni2+, Co2+, and Zn2+, were investigated by conducting solution chemistry calculations, sulfide precipitation tests, and mineralogy characterizations. It was found that the ability of the valuable metals to form sulfide precipitates followed an order of Zn2+ > Ni2+ > Co2+ > Mn2+. The sulfide precipitate of Zn2+ was the most stable and did not re-dissolve under the acidic condition (pH 4.00 ± 0.05). In addition, the sulfide precipitation of Zn2+ was barely affected by the contaminant metal ions. However, in the presence of Al3+, the precipitation recoveries of Mn2+, Ni2+, and Co2+ in a solution containing all the valuable metals were noticeably reduced due to simultaneous hydrolysis and competitive adsorption. The precipitation recoveries of Ni2+ and Co2+ in solutions containing individual valuable metals also reduced when Fe2+ was present, primarily due to competitive precipitation. However, the recovery of Mn2+ was enhanced due to the formation of ferrous sulfide precipitate, providing abundant active adsorption sites for Mn species. In the solution containing all the valuable metals, Fe2+ promoted the recoveries of the valuable metals due to the higher concentration of Na2S and the formation of ferrous sulfide precipitate. / Doctor of Philosophy / The rapid development of advanced technologies has increased the demand for critical elements essential in manufacturing high-tech products. In this study, a process was developed for producing high-purity Mn, Co, and Ni products from an acid mine drainage (AMD). A product with around 30 wt.% Mn was produced. Co and Ni products with 94% and 100% purity were also obtained. However, when developing the process, it was found that a portion of the REEs is often lost to the precipitates of the dominant metal contaminant ions (Fe and Al) in the staged precipitation. It was found that the REE removal increase was realized through adsorption onto the surfaces of the ferric precipitates. In sulfide precipitation, the presence of Fe and Al in the solution can significantly influence the separation efficiency of the critical elements. The effect of Al3+ on the sulfide precipitation is due to the simultaneous hydrolysis of aluminum and sulfur ions. The reduction of the recovery of valuable metals caused by the Fe2+ is due to the form of iron sulfides.

No description available.