The Permian Basin is one of the most prolific oil and gas-producing geologic basins in the United States. The Permian Basin is located in West Texas and Southeastern New Mexico. It has supplied more than 33.4 billion barrels of oil and 118 Tcf of natural gas during a 100-year period (EIA 2022). The ever-increasing water production and usage (e.g., hydraulic fracture stimulation) in the Permian Basin requires produced water management by the operators. Oil recovery from shale reservoirs is a very slow process because of the extremely low permeability of oil-containing pores, with the ultimate oil recovery of around 3 to 8%. Classical waterflooding or gas flooding in unconventional reservoirs is not plausible because of the small pore size and low permeability of the shale matrices. Therefore, creative approaches are needed to increase oil production without relying on large quantities of water injection to enhance oil production, which became the motivation for my research with the objective to integrate geology, fluid flow theory, experimental data, and reservoir modeling to assess production performance and enhance hydrocarbon recovery in the Permian basin. Injecting rich gas or CO2 in such formations in a cyclic fashion (the huff-n-puff process) increases oil recovery substantially but is expensive because of gas compression and injection equipment. Another alternative is to use solvent-containing water in a cyclic fashion (e.g., solutions of ketones and ethoxylated alcohols). Using brine-containing 3-pentanone or surfactant-based solutions results in much additional oil recoveries by cleaning the micro- and macro-fracture flow paths in the stimulated reservoir volume. In this study, the efficacy of injecting a brine solution containing a very small amount of 3-pentanone or a non-ionic surfactant (0.5 to 1.5 percent) determined to enhance oil recovery (EOR). The aqueous EOR huff-n-puff method is more cost-effective and easier to apply than the gas injection huff-n-puff process for the Wolfcamp formation in the Permian Basin. As an initial review of Wolfcamp formation, the production data for wells drilled into the Wolfcamp Formation of the Delaware Basin between 2012 and 2021 was reviewed and organized. A set of bubble maps to identify and visualize cumulative oil, gas, and water production changes was created. The maps showed the maturity of the basin where gas-prone wells are the majority in the northern and northwestern parts, and the southern area is more oil-prone. The wells drilled in Lea, Loving, and East-Reeves counties show the most oil production in one year of production. The gas production is highest in Culberson, North Reeves, and Loving counties. Furthermore, water production is significant throughout the region regardless of the produced hydrocarbon type. Wettability measurements (i.e., contact angles and wettability indices) and the associated water-rock capillary pressures reflect the interactions between the reservoir rock and the pore fluids, which, in turn, strongly affects the distribution of fluids in the reservoir pores. Consequently, I conducted contact angle experiments on five different unconventional reservoir formations across the US and measured interfacial tension (IFT) between oil and brine from the associated formations. Furthermore, I conducted contact angle experiments on the Wolfcamp formation rock samples using ketone and surfactant solutions. For engineering analysis, first, a static geologic model utilizing well-logs and core data was built on Petrel. Subsequently, the aforementioned static model was used to construct a compositional dual-porosity reservoir model using the CMG-GEM commercial reservoir modeling software in conjunction with the experiments. Second, Rate Transient Analysis (RTA) to determine the stimulated permeabilities associated with the hydraulic fracture stimulation was conducted. Next, Wolfcamp PVT report were evaluated and used to build a reservoir fluid model with CMG’s Winprop module. Finally, the compositional reservoir model was history match the field production data to validate the model. After the numerical model was ascertained by history matching, three distinct enhanced oil recovery (EOR) techniques, the huff-n-puff gas injection, ketone solution injection, and surfactant solution injection were implemented for the selected well. Afterward, a sensitivity analysis was conducted to determine the characteristics that had the most significant influence on the reservoir performance of the well in the three enhanced oil recovery (EOR) scenarios. A broad conclusion is that the use of ketone solutions resulted in a significant increase in oil production, while injection rate magnitude and period, soaking period, and solvent concentration affected the magnitude of the incremental oil recovery outcome.

Cobalt is a critical material as designated by the United States Department of Energy. It is used in electric vehicles as a cathode material and in high strength steels as an alloying addition. The United States currently relies nearly 100% on imports and secondary scrap materials for refined cobalt consumption. Because of this, efforts to establish a domestic supply for cobalt are being pursued. This thesis describes research into sortation and flotation to improve one such effort by Electra Battery Materials through the Iron Creek, ID deposit. Coarse material sortation was tested in order to determine its viability, specifically the viability of XRT sensor-based sorting on Iron Creek material. The sortation testing was successful as low-grade material was able to be separated from rocks that had higher cobalt and copper grades. Rougher flotation testing was used to ascertain the most appropriate conditions for particle size, collector type, and collector dosage. A cobalt grade of approximately 1.8% was achieved with a recovery of nearly 92.0% using rougher flotation. Differential flotation testing was undergone to obtain separate copper and cobalt concentrates by depressing the pyrite at a PH of 11.5. Separate cobalt and copper concentrates were obtained with the copper concentrate having a cobalt recovery of 3.98% and a copper recovery of nearly 20%. Cleaner flotation at high PH was undergone to further recovery cobalt from the differential flotation copper concentrate. Re-grinding to a particle size P80=80 microns aided in the recovery of cobalt to the cobalt concentrate as the final copper concentrate from cleaner flotation had only 0.27% cobalt recovery. Locked cycle testing was also conducted to simulate an industrial flotation operation with results supporting the implementation of an industrial flotation circuit for the recovery of cobalt and copper as separate products. An overall economic analysis incorporating sortation, flotation, thermal degradation, and magnetic separation was constructed. The economic analysis showed that the process was economical and a positive NPV of $35.2 million (+ or – 35%) indicated that the project should be pursued at the industrial level.

The numerical solution of partial differential equations can be very challenging, and while different numerical methods have their own advantages, there is no single numerical method without drawbacks. For example, data arising from Particle-In-Cell (PIC) methods have noise in their numerical solutions owing to the use of finitely many particles. The underlying mesh and corresponding approximation in Discontinuous Galerkin (DG) methods may not be of sufficient spatial resolution to capture localized solution features. Lastly, additional conservation equations such as entropy conditions satisfied by analytic solutions to PDEs are often not satisfied by their discrete counterparts. These deficiencies can be ameliorated by auxiliary techniques and method augmentations. It is the purpose of this thesis to detail three such improvements making use of Smoothness-Increasing Accuracy-Conserving (SIAC) filters, proceeding in order of increasing embedment of SIAC methodologies within the underlying numerical process. First, we detail the application of SIAC filters as denoisers of data arising from PIC simulations and demonstrate how careful tuning of these filters enables noise-reduction in the presence of non-periodic boundaries. Furthermore, in the computation of Bohm speed estimates from PIC data, we show that SIAC filters enable a dramatic reduction in the quantity of PIC data needed. Having applied SIAC filters to the equivalent of finite volume data, we next consider higher-order piecewise polynomial data. Here we show that SIAC filtering can be used to increase the resolution of coarse mesh polynomial data in multiple dimensions and over nonuniform meshes. The resulting enhancement procedure can be viewed within the framework of multiresolution analysis (MRA), making it a natural candidate for application in mesh adaptive DG schemes, where it provides a means of providing more accurate approximations with reduced degrees of freedom as compared to uniformly refined data. To conclude, we break the requirement of applying SIAC methodologies to effectively stationary data by fully integrating SIAC filters with DG numerical methods in the context of entropy-correction schemes. In this application, SIAC filters are applied to ensure that approximations produced by the baseline DG method satisfy additional physically motivated conservation conditions, namely energy conservation, for the duration of a simulation.

The use of Carbon Capture and Storage (CCS) as a climate mitigation tool envisions the permanent underground storage of CO₂. The prospects for large scale adoption of geological storage has raised concerns regarding the risks — of property damage, environmental degradation, and to human health — if stored CO₂ were to leak to the surface or into shallow water resources.

Triazine hydrolase (TrzN) from Arthrobacter aurescens TC1 is a Zn(II) dependent hydrolytic dehalogenase from the amidohydrolase super family. TrzN has 22 unique substrates. Most notably, TrzN can hydrolytically dechlorinate atrazine (2-chloro-4-ethylamino-6-isopropylamino-s-triazine) to its less toxic derivative hydroxyatrazine. Atrazine is a widely used synthetic herbicide which has an extensive list of potential environmental and health concerns. TrzN is a prime target for use in the engineering of biocatalysts for atrazine remediation. However, its catalytic and biochemical properties are not fully understood. This research project provides insight into the catalytic mechanism of TrzN as well as explores the enzymes use in biomaterials for atrazine degradation. Insight into the catalytic mechanism of TrzN has been provided in chapter 2. Three amino acids (Thr325, Glu241, and His274) showed significant catalytic importance. Thr325 is essential for catalysis and data agreed that an essential bond is formed between the Thr325 oxygen and the Zn(II)-bound water moiety which likely stabilizes the water moiety for nucleophilic attack. The mechanism functions based on a two proton transfer system. First the His274 residue removes a proton form the Zn(II)-bound water moiety. The proton is shuttle from His274 to Glu241 which can then form a hydrogen bond with the triazole nitrogen on the atrazine ring positioning it for nucleophilic attack. In chapters 3 and 4, TrzN was immobilized in alginate, sol-gel, and mesoporous nanoparticle (MSN) biomaterials. All of the biomaterials were catalytically active and could degrade atrazine to hydroxyatrazine. Using enzymes as biocatalyst can traditionally be tricky, the inability to recover the catalyst and the enzymes inherent unstable nature makes the process costly and inefficient. Often, the solution to these short comings has been to immobilize enzymes in functional biomaterials. The biomaterials tested in these chapters were all able to be recovered and reused cyclically and over several weeks while maintaining or improving TrzN’s stability. This research herein provides insight into a new avenue to design bioremediation methodologies for the removal of atrazine utilizing TrzN.

The Perseverance volcanogenic massive sulfide (VMS) deposit is a past producing Zn deposit of the Matagami camp, located in the Neoarchean Abitibi greenstone belt of Quebec, Canada. Matagami and the deposits within are known to be significantly enriched in tellurium, a critical element necessary for production of advanced photovoltaic panels. However, little is known on the occurrence, distribution, and deportment of tellurium at Perseverance. The goal of this study is to characterize the mineralogy of tellurium and telluride minerals within the Perseverance VMS deposit to better understand their occurrence at Perseverance and in the VMS environment in general. Scanning electron microscopy based automated mineralogy, field-emission scanning electron microscopy imaging and semi-quantitative analysis, and electron probe microanalysis were used to characterize the tellurium occurrence at Perseverance including mineral chemistry, grain size distribution, spatial relationships, modal abundance, and a conservative estimate of the tellurium grade. Seventeen different tellurium-bearing minerals were identified, including altaite, cervelleite, frohbergite, hessite, kochkarite, lingbaoite, mattagamite, melonite, montbrayite, pilsenite, poubaite, rucklidgeite, tellurantimony, tellurium, tellurobismuthite, tsumoite, volynskite, and native tellurium. Tellurium minerals occur as discrete free grains, inclusions, fracture fills, along grain boundaries, and as large composite aggregates. Grains vary in size from submicron inclusions to coarse aggregates, with over 50 volume% of the tellurides being hosted in grains 15 µm to 150 µm across. A conservative grade calculation based on automated mineralogy data revealed average Te concentrations of 42.5 ppm in high-grade ore samples, with the highest grade sample measuring 305 ppm Te. Tellurium minerals are most frequently associated with sphalerite and pyrite, and to a lesser extent with alteration minerals chlorite, talc, dolomite, and quartz. The close association with ore minerals such as sphalerite is promising for future Te production at similar deposits. Metamorphic overprinting of the Perseverance deposit to greenschist facies is interpreted to have a role in the formation and coarsening of tellurium mineral grains. Sulfides in the deposit are recrystallized and may have purged significant quantities of tellurium and other trace elements from their crystal structure, resulting in the formation of discrete tellurium mineralization and the coarsening of any primary tellurium minerals which might have precipitated during primary ore formation.

Cyanide is widely used in the gold mining industry to extract gold from different gold-bearing ores and as a result gold cyanidation process wastewater can contain high amounts of cyanide as well as other heavy metals that can pose risks if released to the environment. Electrochemical methods such as electrooxidation have been shown to effectively treat cyanide contaminated wastewater. However, past studies have largely focused on cyanide oxidation and metal recovery using synthetic solutions which may not accurately represent conditions of mining process waters. In the present study, the electrochemical destruction of cyanide and simultaneous removal of heavy metals using a graphite anode and copper cathode under alkaline conditions was investigated. Batch experiments were conducted on synthetic and real gold process wastewaters. First, the kinetics of cyanide electrooxidation were studied by examining the effects of applied voltage, electrolyte composition, and copper concentration. The effects of electrolyte composition were of particular interest as several gold cyanidation facilities have shifted towards using partially desalinized and even raw seawater for their processes. Results indicated that cyanide follows a first order reaction with respect to CN- ions for most wastewater samples examined. In addition, increased voltage and NaCl concentrations lead to an increase in the rate of cyanide oxidation. The effect of applied voltage, NaCl concentration and initial cyanide concentration on heavy metal removal was then evaluated for synthetic wastewater samples. Results showed that lower applied voltages and lower NaCl concentrations led to an increased removal of copper. For real process wastewater samples, only the effects of applied voltage and conductivity on metal removal were studied. Results indicated that a higher applied voltage and higher conductivity lead to increased removal of copper and zinc. The variation in results between real and synthetic wastewaters can be attributed to the higher amount and stability of metal-cyanide complexes measured in real process wastewaters. Although optimal conditions for an electrochemical system can vary depending on the water’s composition, results indicate that an applied voltage of 5V and addition of NaCl can help increase the rate of cyanide oxidation as well as metal removal. Overall, this study shows that electrochemical treatment of gold cyanidation process water can be an effective method for cyanide oxidation and simultaneous metal recovery.

The ability to produce hydrocarbons from low permeability shale reservoirs has been unlocked by advancements in horizontal drilling and hydraulic fracturing stimulation techniques. Hydrocarbon production in the Delaware Basin within the Permian Basin has been increased as unconventional reservoirs have begun to be infilled with multiple horizontal wells. The differences between conventional reservoirs and unconventional shale reservoirs have necessitated changes in asset evaluation and the deployment of new technologies to analyze the production behavior of unconventional wells at the time of stimulation and throughout the production lifetime. Fiber optic technology has been utilized to characterize and visualize the production from unconventional shale reservoirs. Distributed acoustic signals (DAS) and distributed temperature signals (DTS) can be collected and analyzed through the fiber optic line installed permanently into the well. DAS/DTS can be used to evaluate flow behavior and reservoir properties during completions and over the production lifetime of the well. In this thesis, production and fiber optic data were used to analyze hydraulic fracture performance, flow behavior, and communication between wells. The data was sourced from seven horizontal wells located in the Wolfcamp shale lithology within the Delaware Basin operated by Coterra Energy. Commercial software is used to build a seven-well multistage hydraulic fracturing model and to perform rate transient analysis (RTA). Petrophysical logs, geosteering data, and petrophysical data provided on the fiber optic well were used to build the model and place the seven wellbores within the grid. The model showed that wells located in two different Wolfcamp A landing zones were communicating with each other both vertically between landing zones and within the same landing zone. The proppant and fluid pumped down into the stimulated well traveled through the reservoir into the near-wellbore region of the other wells in the development. The final model results showed that there was little uncontacted rock existing between the hydraulically fractured wellbores. The 4H well within the development had a temperature and acoustic fiber optic line permanently installed behind the casing. The DAS and DTS data from this line was used to evaluate how many of the fracturing stages are contributing to production in isolation from one another. The DAS data was taken only during the time of completions and flowback, but the DTS data was taken for two years of production. Communication between the stages in the 4H lateral was seen in the DAS/DTS data that suggested that stages were communicating with each other through failed plugs, annular channels, and through the rock and natural fractures of the formation. 45 percent of the nominal stages were shown to be in communication with other stages in the lateral. The DAS/DTS data also showed that the 4H fiber optic monitoring well was in communication with each of the five wells that were being stimulated around the same time. Hydraulic fracture order and proximity to the 4H fiber optic monitor well were determined to be causes for different types of communication and the number of communication events detected. RTA was used to evaluate reservoir properties including permeability, area of reservoir drained, and hydraulic fracture effective length. Two sets of RTA were performed. An initial RTA was performed using the nominal number of stages. After evaluating the fiber optic data from the time of completions and the long term DTS data, the RTA was re-done with the effective number of stages. The effective number of stages was derived from the DAS/DTS data showing communication events between 45 percent of stages within the 4H lateral. The RTA completed with the effective number of stages was more accurate and better matched with the known reservoir permeability gathered from the DFITs performed on the wells within the development. The permeabilities calculated from the effective stage RTA range from 0.0016 - 0.0727 md. The drainage area of the wells ranged from 110 acres to 890 acres as determined by the effective stage RTA. The effective stage RTA results on permeability better matched the Delaware Basin permeabilities for other developments. Fiber data taken during the time of completions and throughout the production life of the well was determined to be beneficial in evaluating flow behavior and reservoir properties in horizontally drilled and hydraulically fractured wells.

In the face of dwindling economic mineral resources, this study addresses the critical need for reliable characterization of the mineral resources for improved extraction methods and safer, more profitable mining operations. Current resource modeling techniques are time-consuming, and prone to errors due to manual interpretation of detailed data leading to economic viability issues due to uncertainties associated with the estimates. Geostatistics, while a predominant method in resource modeling, depends on assumptions that may not always hold true, and common practices, such as variogram interpretations, and data filtering, can introduce errors early in the modeling process. Supervised Machine learning (ML) offers a promising alternative, capable of handling complex data sets for domain analysis and grade estimation. This research introduces novel geospatial estimation methods, validated through a case study on geological domains using Supervised Machine Learning methods. A comprehensive comparison analysis of various modeling and grade estimation methods is presented, highlighting the potential of supervised ML algorithms as an alternative to traditional geostatistical methods. However, the study also acknowledges the limitations of ML, emphasizing the importance of geographic validation and visualization, apart from statistical analysis, in ensuring methodological rigor. Recommendations for future work include enhancing ML algorithms through specific data feeding, improving sample relationships with variable orientation data, anisotropy, and anisotropy ratio, and integrating geochemical data to enhance predictability. The thesis serves as a foundational guide for future resource estimation endeavors using not only ML algorithms but also geostatistical methods, underscoring the necessity of methodological rigor and validation in both geostatistical and machine-learning applications.

Porous materials have demonstrated to be profoundly applicable for decades. There are several classes of porous materials which are defined by their pore size: microporous (< 2 nm), mesoporous (2-50 nm), and macroporous (> 50 nm). Each have specific areas where their utility dominates. While all classes of porous materials are heavily studied and used, mesoporous materials demonstrate incredible versatility and applicability. The ability to tune the surface area, pore size, morphology, etc., make mesoporous materials highly functional for applications in catalysis and water purification. The properties mentioned above can be adjusted through relatively small changes in synthetic methods. Different mesoshapes, pore arrangements, and pore volumes can be achieved by incorporating different surfactants and adjusting the duration and temperature at which hydrolysis and condensation occur. Considering the variety of mesoporous materials, mesoporous metal oxides and mesoporous silica nanomaterials (MSN) are heavily investigated for various applications. Direct air capture (DAC) is currently a method at the forefront for capturing dilute concentrations of CO2 from the atmosphere. Composite porous materials consisting of chemisorbent amines such as polyethyleneimine supported in solid mesoporous oxides like γ- A2O3 are the state-of-the-art sorbent for DAC technology. In this work, a fluorescent probe was incorporated into the sorbent to elucidate the effects of moisture on polymer mobility and CO2 adsorption using photoluminescence spectroscopy in the above mentioned composite systems. A well-controlled, systematic method was developed to examine sorbent behavior in various environments. Polymer mobility was better retained in the presence of moisture allowing greater CO2 uptake. This work demonstrated the development of novel characterization techniques to qualitatively assess material behavior under various conditions. With the current transition away from carbon-based fossil fuels, hydrogen has received a lot of attention to serve as a potential new source of energy. One of the main challenges and motivations for hydrogen research is the low volumetric energy density of molecular hydrogen. The technology and methodology behind liquid organic hydrogen carriers (LOHC) is one solution to this problem. Although LOHC technology has been commercialized, improvements are needed in the process for both hydrogenation, and dehydrogenation for increased global usage. Frustrated Lewis pairs (FLPs) and light-responsive catalysts were examined and synthesized as alternatives to the current state-of-the-art catalysts. Given the activity and synthetic flexibility of FLPs, if successful, their use in this area could reduce the quantity of precious metals used by this industry. After unsuccessful synthetic attempts of a novel FLP catalyst, a commercially available FLP was examined for its ability to hydrogenate benzyl toluene. The commercial FLP was found to be partially successful, indicating these catalysts may be viable for further applications. A secondary area of research focused on reducing the energy (heat) requirement of (de)hydrogenation of LOHCs through the use of the designed-light responsive catalysts. We designed, synthesized, and examined these mesoporous silica based catalysts for the dehydrogenation of formic acid. The results showed preliminary success and provided valuable insight and information regarding these photo-catalysts and their activity. Atrazine is a commonly used herbicide which has shown to be toxic to some species. Triazine hydrolase (TrzN) can catalyze the irreversible dechlorination of atrazine to its non-toxic hydrogenated derivative. There are, however, separation and recovery issues that arise with the use of TrzN for water remediation. Fortunately, there are numerous examples of synthesized biomaterials that utilize MSN to protect enzymes from non-native conditions. Various biocatalysts were synthesized and analyzed for atrazine degradation, and it was determined that a medium pore sized MSN with a chitosan coating demonstrated the highest (retained) activity when exposed to non-native conditions (co-solvent, pH, high temperature). This materials activity was also preliminarily examined in water samples from Clear Creek to ensure the biocatalyst retained its activity when exposed to components found in natural water sources. While the motivation, research, and goals of these projects are individually quite different, the commonality is the utilization of mesoporous materials to investigate various properties related to the given application. This collection of work further demonstrates the diverse applicability of this class of materials. As mesoporous materials continue to be used and uniquely designed for a given application, structure-function relationships will become better understood which will influence and encourage the use of these materials in industries.