Hydrogeochemical controls on uranium in aquifers of the Jacobsville Sandstone

The occurrence of elevated uranium (U) in sandstone aquifers was investigated in the Upper Peninsula of Michigan, focusing on aquifers of the Jacobsville Sandstone. The hydrogeochemical controls on groundwater U concentrations were characterized using a combination of water sampling and spectral gamma-ray logging of sandstone cliffs and residential water wells. 235U/238U isotope ratios were consistent with naturally occurring U. Approximately 25% of the 270 wells tested had U concentrations above the U.S. Environmental Protection Agency Maximum Contaminant Level (MCL) of 30 μg/L, with elevated U generally occurring in localized clusters. Water wells were logged to determine whether groundwater U anomalies could be explained by the heterogeneous distribution of U in the sandstone. Not all wells with relative U enrichment in the sandstone produced water with U above the MCL, indicating that the effect of U enrichment in the sandstone may be modified by other hydrogeochemical factors. Well water had high redox, indicating U is in its highly soluble (VI) valence. Equilibrium modeling indicated that aqueous U is complexed with carbonates. In general, wells with elevated U concentrations had low 235U/238U activity ratios. However, in some areas U concentrations and 235U/238U activity ratios were simultaneously high, possibly indicating differences in rock-water interactions. Limited groundwater age dating suggested that residence time may also help explain variations in well water U concentrations. Low levels of U enrichment (4 to 30 ppm) in the Jacobsville sandstone may make wells in its oxidized aquifers at risk for U concentrations above the MCL. On average, U concentrations were highest in heavy mineral and clay layers and rip up conglomerates. Uranium concentrations above 4 ppm also occurred in siltstones, sandstones and conglomerates. Uranium enrichment was likely controlled by deposition processes, sorption to clays, and groundwater flow, which was controlled by permeability variations in the sandstone. Low levels of U enrichment were found at deltaic, lacustrine and alluvial fan deposits and were not isolated to specific depositional environments.

BENEFICIATION OF HIGH-MgO SEDIMENTARY PHOSPHATE ORES

Dolomite [CaMg(CO3)2] is an intolerable impurity in phosphate ores due to its MgO content. Traditionally, the Florida phosphate industry has avoided mining high-MgO phosphate reserves due to the lack of an economically viable process for removal of dolomite. However, as the high grade phosphate reserves become depleted, more emphasis is being put on the development of a cost effective method for separating dolomite from high-MgO phosphate ores. In general, the phosphate industry demands a phosphate concentrate containing less than 1%MgO. Dolomite impurities have mineralogical properties that are very similar to the desired phosphate minerals (francolite), making the separation of the two minerals very difficult. Magnesium is primarily found as distinct dolomite-rich pebbles, very fine dolomite inclusions in predominately francolite pebbles, and magnesium substituted into the francolite structure. Jigging is a gravity separation process that attempts to take advantage of the density difference between the dolomite and francolite pebbles. A unique laboratory scale jig was designed and built at Michigan Tech for this study. Through a series of tests it was found that a pulsation rate of 200 pulse/minute, a stroke length of 1 inch, a water addition rate of 0.5gpm, and alumina ragging balls were optimum for this study. To investigate the feasibility of jigging for the removal of dolomite from phosphate ore, two high-MgO phosphate ores were tested using optimized jigging parameters: (1) Plant #1 was sized to 4.00x0.85mm and contained 1.55%MgO; (2) Plant #2 was sized to 3.40mmx0.85mm and contained 3.07% MgO. A sample from each plant was visually separated by hand into dolomite and francolite rich fractions, which were then analyzed to determine the minimum achievable MgO levels. For Plant #1 phosphate ore, a concentrate containing 0.89%MgO was achieved at a recovery of 32.0%BPL. For Plant #2, a phosphate concentrate containing 1.38%MgO was achieved at a recovery of 74.7%BPL. Minimum achievable MgO levels were determined to be 0.53%MgO for Plant #1 and 1.15%MgO for Plant #2.

Shear band evolution in Zr/Hf-based bulk metallic glasses under static and dynamic indentations

Bulk metallic glasses (BMGs) exhibit superior mechanical properties as compared with other conventional materials and have been proposed for numerous engineering and technological applications. Zr/Hf-based BMGs or tungsten reinforced BMG composites are considered as a potential replacement for depleted uranium armor-piercing projectiles because of their ability to form localized shear bands during impact, which has been known to be the dominant plastic deformation mechanism in BMGs. However, in conventional tensile, compressive and bending tests, limited ductility has been observed because of fracture initiation immediately following the shear band formation. To fully investigate shear band characteristics, indentation tests that can confine the deformation in a limited region have been pursued. In this thesis, a detailed investigation of thermal stability and mechanical deformation behavior of Zr/Hf-based BMGs is conducted. First, systematic studies had been implemented to understand the influence of relative compositions of Zr and Hf on thermal stability and mechanical property evolution. Second, shear band evolution under indentations were investigated experimentally and theoretically. Three kinds of indentation studies were conducted on BMGs in the current study. (a) Nano-indentation to determine the mechanical properties as a function of Hf/Zr content. (b) Static Vickers indentation on bonded split specimens to investigate the shear band evolution characteristics beneath the indention. (c) Dynamic Vickers indentation on bonded split specimens to investigate the influence of strain rate. It was found in the present work that gradually replacing Zr by Hf remarkably increases the density and improves the mechanical properties. However, a slight decrease in glass forming ability with increasing Hf content has also been identified through thermodynamic analysis although all the materials in the current study were still found to be amorphous. Many indentation studies have revealed only a few shear bands surrounding the indent on the top surface of the specimen. This small number of shear bands cannot account for the large plastic deformation beneath the indentations. Therefore, a bonded interface technique has been used to observe the slip-steps due to shear band evolution. Vickers indentations were performed along the interface of the bonded split specimen at increasing loads. At small indentation loads, the plastic deformation was primarily accommodated by semi-circular primary shear bands surrounding the indentation. At higher loads, secondary and tertiary shear bands were formed inside this plastic zone. A modified expanding cavity model was then used to predict the plastic zone size characterized by the shear bands and to identify the stress components responsible for the evolution of the various types of shear bands. The applicability of various hardness—yield-strength ( H −σγ ) relationships currently available in the literature for bulk metallic glasses (BMGs) is also investigated. Experimental data generated on ZrHf-based BMGs in the current study and those available elsewhere on other BMG compositions were used to validate the models. A modified expanding-cavity model, employed in earlier work, was extended to propose a new H −σγ relationship. Unlike previous models, the proposed model takes into account not only the indenter geometry and the material properties, but also the pressure sensitivity index of the BMGs. The influence of various model parameters is systematically analyzed. It is shown that there is a good correlation between the model predictions and the experimental data for a wide range of BMG compositions. Under dynamic Vickers indentation, a decrease in indentation hardness at high loading rate was observed compared to static indentation hardness. It was observed that at equivalent loads, dynamic indentations produced more severe deformation features on the loading surface than static indentations. Different from static indentation, two sets of widely spaced semi-circular shear bands with two different curvatures were observed. The observed shear band pattern and the strain rate softening in indentation hardness were rationalized based on the variations in the normal stress on the slip plane, the strain rate of shear and the temperature rise associated with the indentation deformation. Finally, a coupled thermo-mechanical model is proposed that utilizes a momentum diffusion mechanism for the growth and evolution of the final spacing of shear bands. The influence of strain rate, confinement pressure and critical shear displacement on the shear band spacing, temperature rise within the shear band, and the associated variation in flow stress have been captured and analyzed. Consistent with the known pressure sensitive behavior of BMGs, the current model clearly captures the influence of the normal stress in the formation of shear bands. The normal stress not only reduces the time to reach critical shear displacement but also causes a significant temperature rise during the shear band formation. Based on this observation, the variation of shear band spacing in a typical dynamic indentation test has been rationalized. The temperature rise within a shear band can be in excess of 2000K at high strain rate and high confinement pressure conditions. The associated drop in viscosity and flow stress may explain the observed decrease in fracture strength and indentation hardness. The above investigations provide valuable insight into the deformation behavior of BMGs under static and dynamic loading conditions. The shear band patterns observed in the above indentation studies can be helpful to understand and model the deformation features under complex loading scenarios such as the interaction of a penetrator with armor. Future work encompasses (1) extending and modifying the coupled thermo-mechanical model to account for the temperature rise in quasistatic deformation; and (2) expanding this model to account for the microstructural variation-crystallization and free volume migration associated with the deformation.

Reflection, refraction, and rejection : copper smelting heritage and the execution of environmental policy

This dissertation examines the global technological and environmental history of copper smelting and the conflict that developed between historic preservation and environmental remediation at major copper smelting sites in the United States after their productive periods ended. Part I of the dissertation is a synthetic overview of the history of copper smelting and its environmental impact. After reviewing the basic metallurgy of copper ores, the dissertation contains successive chapters on the history of copper smelting to 1640, culminating in the so-called German, or Continental, processing system; on the emergence of the rival Welsh system during the British industrial revolution; and on the growth of American dominance in copper production the late 19th and early 20th centuries. The latter chapter focuses, in particular, on three of the most important early American copper districts: Michigan’s Keweenaw Peninsula, Tennessee’s Copper Basin, and Butte-Anaconda, Montana. As these three districts went into decline and ultimately out of production, they left a rich industrial heritage and significant waste and pollution problems generated by increasingly more sophisticated technologies capable of commercially processing steadily growing volumes of decreasingly rich ores. Part II of the dissertation looks at the conflict between historic preservation and environmental remediation that emerged locally and nationally in copper districts as they went into decline and eventually ceased production. Locally, former copper mining communities often split between those who wished to commemorate a region’s past importance and develop heritage tourism, and local developers who wished to clear up and clean out old industrial sites for other purposes. Nationally, Congress passed laws in the 1960s and 1970s mandating the preservation of historical resources (National Historic Preservation Act) and laws mandating the cleanup of contaminated landscapes (CERCLA, or Superfund), objectives sometimes in conflict – especially in the case of copper smelting sites. The dissertation devotes individual chapters to the conflicts that developed between environmental remediation, particularly involving the Environmental Protection Agency and the heritage movement in the Tennessee, Montana, and Michigan copper districts. A concluding chapter provides a broad model to illustrate the relationship between industrial decline, federal environmental remediation activities, and the growth of heritage consciousness in former copper mining and smelting areas, analyzes why the outcome varied in the three areas, and suggests methods for dealing with heritage-remediation issues to minimize conflict and maximize heritage preservation.

THE DISPERSION AND SELECTIVE FLOCCULATION OF HEMATITE ORE

Iron ore is one of the most important ores in the world. Over the past century, most mining of iron ore has been focused on magnetite (Fe3O4). As the name suggests, magnetite is magnetic in nature and is easily separated from gangue (unwanted) minerals through magnetic separation processes. Unfortunately, the magnetite ore bodies are diminishing. Because of this, there has been a recent drive to pursue technology that can economically separate hematite (Fe2O3) from its gangue minerals as hematite is a much more abundant source of iron. Most hematite ore has a very small liberation size that is frequently less than 25μm. Beneficiation of any ore with this fine of a liberation size requires advanced processing methods and is seldom pursued. A single process, known as selective flocculation and dispersion, has been successfully implemented at a plant scale for the beneficiation of fine liberation size hematite ore. Very little is known about this process as it was discovered by the U.S. Bureau of Mines by accident. The process is driven by water chemistry and surface chemistry modifications that enhance the separation of the hematite from its gangue minerals. This dissertation focuses on the role of water chemistry and process reagents in this hematite beneficiation process. It has been shown that certain ions, including calcium and magnesium, play a significant role in the process. These ions have a significant effect on the surface chemistry as reported by zeta potential studies. It was shown that magnesium ions within the process water have a more significant impact on surface chemistry than calcium ions due to steric hindrance effects at the hematite surface. It has also been shown that polyacrylic acid dispersants, if used in the process, can increase product quality (increase iron content, decrease phosphorus content, decrease silica content) substantially. Water, surface and reagent chemistry experiments were performed at a laboratory, pilot, and full plant scale during the course of this work. Many of the conclusions developed in the laboratory and pilot scale were found to be true at the full plant scale as well. These studies are the first published in history to develop theories of water chemistry and surface chemistry interactions at a full plant scale.