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.

Urban, agriculture and coal mining land use/cover impacts upon aquatic habitat, toxicity and biodiversity were investigated in Leading Creek, a 388 km2 watershed in southeastern Ohio. Abandoned strip mine land (ASML) and active deep underground mines were examined along with abandoned near-surface underground mine land (AUML). The work focused on assessment of aquatic toxicity, water quality, and biodiversity through investigation of associated ecological responses for both treated and untreated AMD. Relations were examined among land use/cover, chemistry, and various ecological and toxicological endpoints. Sources of data (scale 1:24000) included Landsat5 imaging from 1988 and 1994, and directly digitized extents of underground mining activities dating to the 19th century, with more recently created strip mines. USEPA and Ohio EPA qualitative habitat scoring protocols were used. Land use/cover thresholds were established using ASML=3%, AUML=2% to 10%, Urban=3% to 5%, and Bare Soil=3%. Biodiversity was assessed using qualitative benthic macroinvertebrate taxon richness and abundance, for total and EPT groups, respectively. A better understanding of acid mine drainage (AMD) was demonstrated linking land use/cover, coal bed, sediment, and water column chemistry to aquatic ecotoxicity through examination of the origin and fate of sulfate, magnesium, iron, manganese, and zinc. Key findings in risk assessment of Leading Creek indicated that (1) abandoned near-surface underground mine lands (AUML) were associated with >90% of untreated AMD reaching Leading Creek; (2) degradation to aquatic ecology was primarily associated with water quality degradation due to AMD, not with sediment quality degradation; (3) modest habitat destruction, especially sedimentation effects, were observed for ASML>3%, and urbanization>5% in small subsheds; (4) unique chemical signatures differentiated mining techniques instream; and (5) in situ Corbicula fluminea growth rates were dependent upon drainage area. Sporadic signs of agricultural and urban impacts were indicated from acute toxicity with Ceriodaphnia dubia and chronic in situ toxicity testing with C. fluminea. Both the ecotoxicological tests were shown to be reliable indicators of AMD impact from AUML, on watershed and subwatershed scales. AMD was strongly associated with depressed biodiversity, low pH, and elevated zinc. Ecotoxicity monitoring supported interconnections found between sediment and water chemistry, land use/cover, and biodiversity. / Ph. D.

This dissertation reports the design of a process (patent pending) to remove iron from acid mine drainage (AMD) without the formation of metal hydroxide sludge. The system includes the oxidation of ferrous iron in a packed bed bioreactor, the precipitation of iron within a fluidized bed, the removal of manganese and heavy metals (Cu, Ni, Zn) in a trickling filter at high (>9) pH, with final neutralization in a carbonate bed. The technique avoided the generation of iron oxyhydroxide sludge. In the packed bed bioreactor, maximum substrate oxidation rate (R_,max) was 1500 mg L⁻¹ h⁻¹ at dilution rates of 2 h⁻¹, with oxidation efficiency at 98%. The half-saturation constant (similar to a Ks) was 6 mg L⁻¹. The oxidation rate was affected by dissolved oxygen below 2 mg L⁻¹, with a Monod-type Ko for DO of 0.33 mg L⁻¹. Temperature had a significant effect on oxidation rate, but pH (2.0 to 3.25) and supplemental CO₂ did not affect oxidation rates. Iron hydroxide precipitation was not instantaneous when base was added at a OH/Fe ratio of less than 3. Induction time was found to be a function of pH, sulfate concentration and iron concentration, with a multiple R² of 0.84. Aqueous [Al (III)] and [Mn (II)] did not significantly (α = 0.05) affect induction time over the range of concentrations investigated. When specific loading to the fluidized bed reactor exceeded 0.20 mg Fe m⁻² h⁻¹, dispersed iron particulates formed leading to a turbid effluent. Reactor pH determined the minimum iron concentration in the effluent, with an optimal at pH 3.5. Total iron removals of 98% were achieved in the fluidized bed with effluent [Fe] below 10 mg L⁻¹. Further iron removal occurred within the calcium carbonate bed. Heavy metals were removed both in the fluidized bed reactor as well as in the trickling filter. Oxidation at pH >9 caused manganese to precipitate (96% removal); removals of copper, nickel, and zinc were due primarily to sorption onto oxide surfaces. Removals averaged 97% for copper, 70% for nickel and 94% for zinc. The treatment strategy produced an effluent relatively free of iron (< 3 mg/L), without the formation of iron sludge and may be suitable for AMD seeps, drainage from acidic tailings ponds, active mine effluent, and acidic iron-rich industrial wastewater. / Ph. D.

Although mining is essential to life in our modern society, it generates huge amounts of waste that can lead to acid mine drainage (AMD). Most of these mine wastes occur as large piles that are open to the atmosphere so that air and water vapor can circulate through them. This study addresses the reactions and transformations of the minerals that occur in humid air in the pore spaces in the waste piles. The rate of pyrite oxidation in moist air was determined by measuring over time the change in pressure between a sealed chamber containing pyrite plus oxygen and a control. The experiments carried out at 25?C, 96.8% fixed relative humidity, and oxygen partial pressures of 0.21, 0.61, and 1.00 showed that the rate of oxygen consumption is a function of oxygen partial pressure and time. The rates of oxygen consumption fit the expression (dn/dt=(3.31x10^-7)(P^0.5)(t^-0.5) It appears that the rate slows with time because a thin layer of ferrous sulfate + sulfuric acid solution grows on pyrite and retards oxygen transport to the pyrite surface. The transformation of efflorescent sulfate minerals (the reaction products of iron sulfide oxidation) from a pyrrhotite-rich massive sulfide is explained using a systematic analysis of their stoichiometry and thermodynamics. Their stabilities are controlled by oxygen partial pressure, relative humidity, and activity of sulfuric acid and can be visualized using log activity of oxygen-log activity of water and log acitvity of sulfuric acid-log activity of water diagrams developed during this study. Samples from the field site were analyzed in the laboratory to determine mineralogy, equilibrium relative humidity, chemical composition, and acid generation potential. Dissolution experiments showed that fibroferrite-rich samples had the highest acid producing potential, followed by copiapite-rich samples and then halotrichite-rich samples. The most abundant metals in solutions produced by dissolving the salts were magnesium, aluminum, zinc, copper, calcium, and lead. The molar concentrations of the metals varied with mineralogy. However, all of these minerals release metals and acid when they dissolve and therefore represent a significant environmental threat. / Ph. D.

Schwertmannite, a ferric oxyhydroxysulfate mineral typically found under acidic, high sulfate and iron aqueous conditions, such as acid mine drainage environments, was studied using analytical high resolution transmission electron microscopy (HRTEM). HRTEM offers advantages over bulk techniques such as powder x-ray diffraction and pair distribution function (PDF) analysis of synchrotron data, in its ability to discern multiple phases within poorly crystalline nanominerals. Based on extensive HRTEM observations of both natural and synthetic schwertmannite samples, the authors suggest that schwertmannite should not be described as a single phase mineral with a repeating unit cell, but as a polyphasic nanomineral with crystalline areas spanning less than a few nanometers within an amorphous matrix. The few visible lattice fringes observable in both natural and synthetic schwertmannite agree well with d-spacings of goethite (and jarosite in natural samples) implying that the transformation from schwertmannite to these phases occurs as a gradual structural reordering at the nanoscale. In the synthetic study, the complete transformation from schwertmannite to goethite nanorods and nanoparticles within 24 hours at 75°C was observed, indicating a low energetic barrier to schwertmannite's phase transformation. We also found that amorphous silica can be intimately entrained within natural schwertmannite, and that high concentrations of arsenic can be held in close association of nanocrystalline regions of the mineral. / Ph. D.

The production of acid mine drainage (AMD) is catalyzed by iron-oxidizing bacteria primarily of the species Thiobacillus ferrooxidans. By inhibiting these bacteria, the production of AMD can be greatly reduced. One compound found to be effective in the inhibition of T. ferrooxidans is nitrapyrine. N-Serve, a product of Dow Chemical, Inc., is the commercially available form of nitrapyrine. This compound has been widely used in agriculture for nitrification inhibition. The purpose of this study was to determine the effectiveness of N-Serve in reducing the production of AMD under simulated field conditions. A column study was completed using a coal mine waste and a hard-rock mine waste. Eight columns containing 7kg of rock were established for each substrate. Three doses of NServe (22% nitrapyrine) were applied once at the beginning of this study: a high dose 2200 mg/kg, a medium dose 220 mg/kg, and a low dose 22 mg/kg. Duplicate columns were included for each N-Serve dose including two untreated columns to serve as a control for each substrate. Beginning the week after treatment, the columns were leached once a week for 29 weeks with deionized, distilled water (equivalent to 2.5 cm precipitation). Only the highest NServe dose produced a column leachate of significantly better quality than that of the controls. The acidity in the high-dose coal mine columns averaged less than 50 percent of the acidity in the control effluent from week 6 through the end of the study. A monolithic controlled release system utilizing acrylonitrile rubber was successfully developed and tested for use with nitrapyrine. This formulation should withstand the rigors of the environment and with minor modification could produce a variety of release rates. / Master of Science

Alkaline fly ash has been studied as a liming agent within coal refuse fills to reclaim acid-forming refuse. Previous studies focused on bulk blending ash with acid-forming (pyritic) refuse. A better representation of field conditions is a "pancake layer" of ash above the refuse. A column study was initiated to evaluate the leachate chemistry from acid-forming refuse-ash bulk blends vs. ash over refuse layers. An acidic and an alkaline ash were blended with, or layered over, acid-forming refuse and sandstone and packed into columns which were leached with deionized water twice a week for 24 weeks under unsaturated conditions. Leachates were analyzed for pH, electrical conductivity, and a suite of elements with a focus on the oxyanions of As, Cr, Mo, and Se. A sequential extraction procedure revealed a significant portion of the elements in the residual fraction for the refuse/spoil substrates and in metal-oxide bound fractions for the ashes prior to leaching, and a general trend for a greater proportion of oxyanion elements to be associated with metal oxide fractions after leaching. Bulk-blended treatments maintained higher leachate pH than corresponding layered treatments. The acidic ash and refuse pancaked treatments exhibited relatively high initial concentrations of most elements analyzed. Pancake layers of ash over refuse are an inadequate co-disposal method to prevent and mitigate acid mine drainage. Blending alkaline ash with refuse to acid-base accounting specifications should improve leachate quality overall, but there may be water quality concerns for loss of Se and other soluble ions during initial leaching events. / Master of Science

Acid mine drainage (AMD) results from the oxidation of pyretic mineralogy, exposed by mining operations to oxygen and water. This reaction produces sulfuric acid and liberates heavy metals from the surrounding mineralogy and impairs water quality and freshwater communities. The U.S. Army Corps of Engineers has begun an ecosystem restoration project to remediate the abandoned mine land (AML) impacts to the North Fork Powell River (NFP) and is utilizing the ecotoxicological rating (ETR) system to delineate these affects to focus restoration efforts. The ETR was developed to summarize the integrative data into a single number ranging from 0 to 100, which is descriptive of the environmental integrity of a sampling station. The ETR is conceptualized to work as an academic grading scale (0 through 100), rating reference stations with A's (90-100) and B's (80-89) and impacted stations with C's (70-80), D's (60-70) and failures (F = 60). Two rounds of ETR investigations have evaluated seven headwater tributaries to the NFP including investigations of Ely and Puckett's Creek from 1997 and 1998. This thesis contains the results of the second series of ETR investigations at 41 stations in Cox Creek, Jone's Creek, Reed's Creek, Summers Fork, Straight Creek, and areas in the NFP. Eight stations were recommended for reclamation; CC 03, JCRF2 02, JCRF2 01, RCPS 09B, RCPS 11B, SULF 01, SU 02, and SU 01. Summers Fork was the most severely impacted watershed of the second round of ETR investigations. An effort to streamline the ETR to the most ecologically predictive parameters was successful in creating a system more time and cost efficient then the initial ETRs and exclusive of benthic macroinvertebrate surveys. The Modified ETR streamlined the ETR to just 5 parameters including; mean conductivity, mean Asian clam survival, mean aluminum (Al) and manganese (Mn) in the water column, and mean habitat score to describe the AMD impacts to small headwater streams. Also, an investigation was conducted to determine the mode of toxicity, (i.e., exposures to metal contaminated surface waters or sediments) by which Al and iron (Fe) dominated AMD impairs benthic macroinvertebrate communities. It was found that water column exposures both within and beyond the zone of pH depression are the most likely mode by which AMD impairs the benthic macroinvertebrate communities of the NFP. / Master of Science

M. Tech. (Chemical Engineering, Faculty of Engineering and Technology), Vaal University of Technology / Acid mine drainage (AMD) is a serious problem associated with mining activities, and it has the potential to contaminate surface and ground water. The aim of this study was to evaluate the performance of constructed wetland and photocatalysis in treating AMD. Three identical unvegetated upflow constructed wetlands packed with natural zeolite (clinoptilolite) and coarse silica sand were made of a cylindrical plastic pipe, and the slurry photocatalyst was prepared using quartz material. A hydro-alcohol thermal method was used to prepare an anatase core-void-shell TiO2 photocatalyst. The results showed that the three unvegetated upflow constructed wetlands (CW) had relatively similar percentage removal of heavy metals despite their varying concentrations within the AMD. The removals were: Fe (86.54 - 90.4%); Cr (56.2 - 64.5%); Mg (56.2 - 67.88%); Ca (77.1 - 100%); and 100% removal was achieved for Be, Zn, Co, Ni, and Mn. The removal of sulphate was also 30%. Heavy metals concentration in CW packing material was significantly higher in the outlet of the constructed wetlands than in the inlet. The adsorption isotherms revealed that the experimental data fitted the Langmuir Isotherms better, which suggested a monolayer coverage of heavy metals on the surface of the adsorbents; thermodynamic studies showed that the nature of adsorption taking place was physical; the kinetics models showed that the adsorption was first order reaction. A higher photocatalytic reduction (62%) of Cr(VI) was obtained at pH 2, 30 mg/l Cr(VI) initial concentration, and three hours of irradiation time. It was also found that the presence of Fe(III) enhanced the reduction of Cr(VI). The core-void-shell TiO2 photocatalyst showed a better activity than the commercial P25 Degussa for the reduction of Cr(VI) to Cr(III). The kinetic studies showed that the reduction of Cr(VI) was first order reaction. Photocatalytic reduction of Cr(VI) in real AMD sample was achieved only for the Douglas North Discharge (DND) sample (68%), and the Fe(III) reduction was found to be 83%. Therefore it was concluded that the combination of constructed wetland and UV/ TiO2 photocatalysis employing anatase core-void-shell TiO2 as a photocatalyst has a potential to reduce the toxicity of Cr(VI)-laden acid mine drainage.

[Truncated abstract] The influence of environmental conditions and properties of pyritic shale in the mining waste from Mt. Whaleback in Western Australia, in particular the inclusions and encapsulation of pyrite on the oxidation of pyritic shale and its subsequent acid mine drainage, was studied by employing an isothermal batch reactor system and QEMSCAN technique. The experimental technique was validated by comparing the experimental results obtained in this study with the literature data. It was found that the presence of water significantly accelerates the rate of shale oxidation. Weathering of the shale samples was found to influence the O2 consumption rate. It was also found that shale properties have a major effect on the oxidation rate and thereby affect the acid generation. Static test methods (Sobek and Lawrence) were employed to test the Neutralisation Potential (NP) of more than 100 actual and composite samples including pyritic shale samples, rock samples, mineral samples, various pyrite-mineral, pyrite-shale, and pseudo-shale blends. The influence of sample properties (bulk elemental composition, and mineralogy), test technique (Sobek and Lawrence) and associated variables (acid strength and volume) on the acid neutralisation potential of the samples was studied. It was found that the Sobek method produced consistently higher NP results under comparable acid conditions to those obtained with the Lawrence method. The theoretical NP values of individual minerals were calculated based on the mineral composition combined with the acid neutralising equations and ideal chemical formula. ... To experimentally model the major mineral phases, 11 minerals were used to produce pyrite-mineral blends and pseudo-shales, whose compositions mimic those of the actual shales studied. Mineral blends were employed to evaluate and contrast their individual acid generation or neutralisation behaviour with binary and higher order interactions. Blends of pyrite with some selected shales were also employed in this study. It was found that interactions can occur between the multiple mineral components which can enhance the rate of acid generation beyond that of the individual behaviour. It was found that the products from the pre-oxidation of shales, the properties and morphology of a sample such as the surface area, encapsulation, the mineralogy and pH all play a significant role in the acid generation and neutralisation rates. However, the absolute rate of acid generation appears to be most sensitive to the components such as Fe3+, which contribute to its reaction mechanisms. This investigation has provided a scientific insight into the acid generation and neutralisation behaviour of pyritic shale in relation to its mineralogy. It was found that the relative instantaneous rates of acid generation and consumption for individual minerals can be significantly different to that of their total potentials for acid generation and neutralisation. The significantly different behaviour of the actual and pseudo shales suggests that at low pH, there may be other mechanisms underlying the net capacity and rates of shales to generate or consume acid than bulk mineralogy. These findings have significant implications to the mining industry operating in reactive grounds.