Theses and Dissertations at Montana State University (MSU)
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Item Bio-trapping ureolytic bacteria on sand to improve the efficiency of biocementation(Montana State University - Bozeman, College of Engineering, 2023) Ugur, Gizem Elif; Chairperson, Graduate Committee: Chelsea M. Heveran; Adrienne J. Phillips (co-chair); This is a manuscript style paper that includes co-authored chapters.Microbially induced calcium carbonate precipitation (MICP) has emerged as a novel biocementation technique for its potential solution to sustainable construction. Although current MICP approaches have made significant progress, achieving spatial control over biomineralization is challenging due to its complexity, which is affected by many factors, such as microorganisms, reaction kinetics, and environmental factors. Spatially controlling biomineralization for building or targeted repair of materials can significantly improve efficiency and sustainability while achieving desired outcomes. The purpose of this thesis was to assess whether biomineralization can be enhanced through surface pre-treatment of sand using amino silanes, such as 3-aminopropyl-methyl-diethoxysilane (APMDES), which is one form of spatial control of biomineralization through prescribing the location of the microbes. Moreover, a preliminary study was conducted to assess whether biomineralized sand, with and without the APMDES treatment, can be recycled and reused for biomineralization of subsequent generations. The impact of APMDES treatment on bacterial adhesion on sand, growth, and urease activity was analyzed. Biocementation efficiency was evaluated by comparing compressive strength and calcium gain of APMDES-treated sand with untreated sand. APMDES treatment promotes abundant and immediate trapping of bacteria on sand surfaces through increased electrostatic interaction that attracts negatively charged walls of bacteria to positively charged amine groups. While APMDES treatment compromises microbial viability, it preserves the urease enzyme for catalyzing urea hydrolysis. APMDES-treated sand achieved comparable strength with fewer bacterial injections compared to untreated sand. APMDES-treated sand biocemented using three injections of bacteria and cementation media gained the same strength as seven injections. Biomineral gain of APMDES-treated sand was similar compared to untreated sand, which shows calcium accrual in the structure may be influenced by additional factors, such as the distribution of calcite, differences in the calcite precipitation patterns, and morphology. Overall, incorporating APMDES treatment can potentially improve the efficiency and sustainability of MICP by spatially controlling biomineralization.Item Investigation of microbially induced carbonate precipitation for mitigation of acid mine drainage from coal mining waste(Montana State University - Bozeman, College of Engineering, 2023) Delwiche, Jenna Anne; Chairperson, Graduate Committee: Ellen G. Lauchnor; Adrienne J. Phillips (co-chair); This is a manuscript style paper that includes co-authored chapters.Acid Mine Drainage (AMD) is a serious environmental concern associated with coal mining. Many of the existing methods for addressing AMD are costly and focus on clean-up rather than prevention. In this study, the feasibility of using microbially induced carbonate precipitation (MICP) as an alternative method for mitigating environmental impacts from coal mining waste rock was investigated using laboratory scale experiments. Flow-through column testing showed that MICP can be used to create a calcium carbonate coating on coal waste rock, acting as a barrier between the rock and water. This treatment increased leachate pH, and microscopic inspection indicated that the presence of live bacteria was important for creating a durable coating. The MICP treatment decreased concentrations of heavy metals such as aluminum, barium, beryllium, copper, nickel, zinc, and iron in the leachate, but increased concentrations of vanadium, selenium, molybdenum, uranium, and arsenic. These results indicate that MICP may be an effective technique for mitigating AMD, but additional laboratory and field testing is needed to assess the feasibility of this treatment technology.Item Feasibility study for field-scale use of Ureolysis-Induced Calcite Precipitation (UICP) for roadbed improvement(Montana State University - Bozeman, College of Engineering, 2023) Dorian, Hudson Thomas; Chairperson, Graduate Committee: Mohammad Khosravi; Adrienne J. Phillips (co-chair); This is a manuscript style paper that includes co-authored chapters.A series of tests were conducted to evaluate the feasibility of using ureolysis-induced calcium carbonate precipitation (UICP) to improve the strength of the soil layers used to in the construction of roads. This process involved three series of tests conducted on soil specimens of gradually increasing volume. The first series regarded the relative effect of treatment direction, comparing top-down treatment to bottom-upwards and alternating treatment methods on 50-by-100-millimeter soil columns. This was evaluated through unconfined compressive strength (UCS) and the calcium carbonate distribution over the length of the soil, finding that all methods generated a reliable increase in the strength of the soil specimen. This phase of research also included a batch study, evaluating the growth of the ureolytic bacteria Sporosarcina pasteurii in a solution composed of commercially available ingredients, showing that the bacteria could be cultured at a far lower cost (as low as 20 cents per liter) than with lab-grade ingredients ($2.66 per liter). The next series of tests compared the effect of applying treatment solutions to the soil surface directly and using a probe to inject solutions beneath the surface. This was done with 15-centimeter, cylindrical specimens, evaluated through the California bearing ratio (CBR) test. It was determined that the treatment process had the capacity to increase the CBR value substantially (from ~11% up to 188%), and it was suggested that each treatment mechanism resulted in a predictable distribution of calcium carbonate. There was also success in using alternative, commercially-sourced ingredients to facilitate the treatment and improve the CBR value. The last tests centered on the treatment of a 30-centimeter-by-30-centimeter mock road section, combining the treatment mechanisms used at the 15-centimeter-scale to facilitate an increase in the CBR of a soil layer under pavement. Through UICP, the CBR value of this layer was successfully increased.Item Microbially induced calcium carbonate precipitation: meso-scale optimization and micro-scale characterization(Montana State University - Bozeman, College of Engineering, 2020) Zambare, Neerja Milind; Chairperson, Graduate Committee: Robin Gerlach and Ellen G. Lauchnor (co-chair); Ellen Lauchnor and Robin Gerlach were co-authors of the article, 'Controlling the distribution of microbially precipitated calcium carbonate in radial flow environments' in the journal 'Environmental science and technology' which is contained within this dissertation.; Robin Gerlach and Ellen Lauchnor were co-authors of the article, 'Spatio-temporal dynamics of strontium partitioning with microbially induced calcium carbonate precipitation in porous media flow cells' submitted to the journal 'Environmental science & technology' which is contained within this dissertation.; Robin Gerlach and Ellen Lauchnor were co-authors of the article, 'Co-precipitation of strontium and barium' submitted to the journal 'Environmental science & technology' which is contained within this dissertation.; Nada Naser, Robin Gerlach and Connie Chang were co-authors of the article, 'Visualizing microbially induced mineral precipitation from single cells using drop-based microfluidics' submitted to the journal 'Nature methods' which is contained within this dissertation.Microorganisms have the potential to impact processes on a scale orders of magnitude larger than their size. For example, microbe-mineral interactions at the micro-scale can drive macro-scale processes such as rock formation and weathering. Many bioremediation technologies derive inspiration from microbial mineralization processes. Microbially induced calcium carbonate precipitation (MICP) can produce calcium carbonate (CaCO 3) precipitates which can be utilized as a biological cement to strengthen porous media by reducing fluid permeability in subsurface fractures or as an immobilization matrix to remove metal contaminants dissolved in groundwater. To make MICP a feasible and successful bioremediation technology in the world outside the lab, it is necessary to bridge the gap between the meso-scale research studies and macro-scale applications. This thesis focuses on such meso-scale studies but also contributes to bridging the gap in the other direction, i.e., meso-scale to micro-scale to gain a fundamental understanding of the cellular level processes behind MICP. The research presented here investigates two applications of MICP with a focus on controlling precipitate distribution and process efficiency in target environments. Subsurface precipitate distribution and metal partitioning during MICP were studied in novel reactive transport systems that mimic application-environment conditions. A radial flow reactor was used to study the spatial distribution of precipitates in conditions similar to subsurface injection well environments. The distribution and degree of metal partitioning during MICP was investigated in batch reactors and porous media flow cells to study kinetics and reactive transport effects on kinetics. In the radial flow environment, more precipitates formed away from the center injection zone. Results showed that longer reactant residence times and an equimolar ratio of calcium to urea were able to maximize precipitation efficiency. Metal partitioning could be maximized at low reactant flow rates and low metal concentrations. The novel flow cell set up used revealed a spatial decoupling between ureolysis and precipitation. A micro-scale investigation of the fundamental MICP process itself is presented wherein microbe-mineral interactions are observed at the cell level. A semi-correlative approach to investigating individual precipitates in microdroplets is presented, using a multitude of microscopy and microanalysis techniques. The presented studies capture MICP across a range of scales.Item Urease immobilization for advancing enzyme-induced calcium carbonate precipitation applications(Montana State University - Bozeman, College of Engineering, 2019) Frieling, Zachary James; Chairperson, Graduate Committee: Robin Gerlach and Adrienne Phillips (co-chair)Microbially induced calcium carbonate precipitation (MICP) is a widely studied field of research exploiting bacterial activity to form a calcium carbonate precipitate that has been used to modify porous media. MICP is an enzymatically driven process and uses the enzyme urease to change solution chemistry to favor calcium carbonate precipitation. An enzyme slurry can be used in lieu of microbial growth and can be applied in a similar fashion and is commonly referred to as enzymatically induced calcium carbonate precipitation (EICP). For some applications temperature can stunt microbial growth and EICP may be the preferred method. However, as the temperature increases further the urease enzyme is thermally inactivated inhibiting calcium carbonate precipitation. Thermal inactivation limits the potential use of EICP in higher temperature environments. To combat thermal inactivation, immobilization of the urease enzyme through entrapment in silica gel and adsorption on an internally porous ceramic proppant was evaluated, and the first order inactivation coefficient (kd) was determined for temperatures between 60°C and 90°C. It was found that immobilization of the urease enzyme drastically reduced the apparent k d when compared to the free, non-immobilized form. Column experiments were performed using the urease immobilized on the ceramic proppant at room temperature (~23°C) and at 60°C. It was found that the immobilized urease retained high activity for the duration of the experiments even when subjected to the elevated temperature condition. The immobilized form of the urease enzyme was indeed protected from thermal degradation. It also seemed that the immobilized form of the urease enzyme was shielded from inactivation from active calcium carbonate precipitation, as observed in previous EICP and MICP experiments, in which ureolytic activity decreased rapidly as calcium carbonate precipitated. As a result, the immobilized form of the urease enzyme showed promise for advancing EICP applications.Item Kinetics of thermally inactivated ureases and management of sand production through ureolysis-induced mineral precipitation(Montana State University - Bozeman, College of Engineering, 2018) Morasko, Vincent John; Chairperson, Graduate Committee: Robin Gerlach; Adrienne Phillips (co-chair)Biocement has the potential to seal subsurface hydraulic fractures, manipulate subsurface flow paths to enhance oil recovery, treat fractured cement, stabilize soil structures and minimize dust dispersal. Biocement can be formed using the urease enzyme from various sources (bacteria, plant, or fungi) to break down urea into carbonate, combining with calcium for use in engineering applications such as biocement production. Higher temperatures, pressures, and extreme pH conditions may be encountered as these engineering applications expand deeper into the subsurface. Temperatures beyond 1000 meters can exceed 80°C, potentially rapidly inactivating the enzyme. The first part of this study focused on monitoring urea hydrolysis catalyzed by jack bean urease at temperatures ranging from 20-80°C. An increasing rate of urease inactivation was observed with increasing temperatures and first-order models described the kinetics of urea hydrolysis and enzyme inactivation properly. The second part of this study focused on developing a technology to mitigate sand transport in oil and gas wells. This study addressed a method to cement sand in the subsurface so that it is not returned when oil or gas is extracted. As the sand leaves the formation, it can cause damage in the subsurface, leading to economic concerns, as well as reducing the lifespan of pumps, piping and other components on the well pad. A reactor system was developed to mimic a subsurface oil well that produces sand. Biocement production was promoted within the reactor, utilizing common sources of urease (Sporosarcina pasteurii and Canavalia ensiformis or jack bean meal). The resultant calcium carbonate/sand mass was subjected to elevated flowrates, simulating field conditions where sand is potentially fluidized and potentially transported into the wellbore. It was shown that biocement can reduce sand transport while allowing for higher flow rates than conditions without biocement. The findings from this study broaden the potential application range of biocementation technologies into higher temperature environments. Applying biocement specifically to sand mitigation may have significant environmental, economic, and safety implications within the natural resource industry.Item Ureolysis induced mineral precipitation material properties compared to oil and gas well cements(Montana State University - Bozeman, College of Engineering, 2018) Beser, Guneycan Dicle; Chairperson, Graduate Committee: Damon Fick; Adrienne Philips (co-chair)Novel methods are needed to prevent or mitigate subsurface fluid leakage, for example stored carbon dioxide, fuels during unconventional oil and gas resource development or nuclear waste disposal. Ureolysis-induced calcium carbonate precipitation (UICP) has been investigated as a method to plug leakage pathways in the near-wellbore environment and in fractures. The enzyme urease catalyzes the hydrolysis of urea to react with calcium to form solid calcium carbonate (similar to limestone). UICP test specimens were prepared in triplicate by filling 2.5 cm (diameter) x 5 cm (length) and 5 cm x 10 cm cylindrical molds with sand and injecting both microbial and plant-based enzymes with urea and calcium solutions to promote precipitation. Sources of urease included jack bean enzyme and S. pasteurii microbe, resulting in both enzyme and microbe induced calcite precipitation (EICP, MICP) specimens. For comparison, Class H well- and Type I-Portland specimens were made by mixing cement paste (API 10B) with sand (ASTM C305). Fine cement specimens were also included in the comparison and were made both by mixing and also injecting to match the process used to make the biocement specimens. For the 2.5 cm x 5 cm specimens, the addition of nutrient broth to the enzyme specimens (ENICP) resulted in increased compression strengths compared with specimens without nutrient (EICP). The average compression strengths of these ENICP specimens reached 77% and 66% of the compressive strength of the 28-day well cement and Type I cement mortars, respectively and were over two times larger than the 28-day strength of the fine cement specimens. For 5 cm x 10 cm specimens, compression strengths of MICP, ENICP, and EICP specimens reached 42%, 38%, and 16% of the 28-day injected fine cement specimens. The average modulus of elasticity of ENICP was 17,316 + or = 1,430 MPa with 8.3 + or = 1.8% CaCO3 content (g/g sand) and was approximately 30% larger than the average modulus measured for the fine cement specimens. The results of this study indicate that the UICP produced specimens may have adequate strength and stiffness for field applications.Item Nuclear magnetic resonance studies of biofilm - porous media systems(Montana State University - Bozeman, College of Engineering, 2017) Kirkland, Catherine Mullinnix; Chairperson, Graduate Committee: Sarah L. Codd; Joseph D. Seymour (co-chair); Sarah L. Codd was a co-author of the article, 'Low-field borehole NMR applications in the near subsurface environment' submitted to the journal 'Vadose zone journal' which is contained within this thesis.; Randy Hiebert, Adrienne Phillips, Elliot Grunewald, David O. Walsh, Joseph D. Seymour and Sarah L. Codd were co-authors of the article, 'Biofilm detection in a model well-bore environment using low-field NMR' in the journal 'Groundwater monitoring and remediation' which is contained within this thesis.; Maria P. Herrling, Randy Hiebert, Andrew T. Bender, Elliot Grunewald, David O. Walsh and Sarah L. Codd were co-authors of the article, 'In-situ detection of subsurface biofilm using low-field NMR - a field study' in the journal 'Environmental science and technology' which is contained within this thesis.; Sam Zanetti, Elliot Grunewald, David O. Walsh, Sarah L. Codd and Adrienne J. Phillips were co-authors of the article, 'Detecting microbially-induced calcite precipitation (MICP) in a model well-bore using downhole low-field NMR' in the journal 'Environmental science and technology' which is contained within this thesis.; Jessica Weisbrodt, Catherine M. Kirkland, Nathan H. Williamson, Susanne Lackner, Sarah L. Codd, Joseph D. Seymour, Gisela Guthausen and Harald Horn were co-authors of the article, 'NMR investigation of water diffusion in different biofilm structures' submitted to the journal 'Biotechnology and bioengineering' which is contained within this thesis.Nuclear magnetic resonance (NMR) allows for in-situ non-invasive studies of opaque systems over a wide range of length and time scales, making the method uniquely suited to studies of biofilms and porous media. The research comprising this thesis uses NMR to explore biophysical, chemical, and transport properties within heterogeneous porous media systems at both a macro- and micro-scale. The macro-scale projects validate a low-field borehole NMR instrument to monitor field-scale environmental engineering applications like subsurface biofilms and microbially-induced calcite precipitation (MICP). Subsurface biofilms are central to bioremediation of chemical contaminants in soil and groundwater whereby micro-organisms degrade or sequester environmental pollutants like nitrate, hydrocarbons, chlorinated solvents and heavy metals. When composed of ureolytic microbes, subsurface biofilms can also induce calcite precipitation. MICP has engineering applications that include soil stabilization and subsurface barriers, as well as sealing of cap rocks and well-bore regions for carbon dioxide sequestration. To meet the design goals of these beneficial applications, subsurface biofilms and MICP must be monitored over space and time - a challenging task with traditional methods. The low-field borehole NMR tool recorded changes in the T 2 relaxation distribution where enhanced relaxation indicated biofilm accumulation in a sand bioreactor and in subsurface soil. Additionally, the tool was able to detect MICP in a sand bioreactor. The changed mineral surface of the sand lead to an increase in T 2 relaxation times. The complementary high-field NMR project investigated micro-scale internal structures and mass transport within biofilm granules used for wastewater treatment. Granular sludge, composed of spherical aggregates of biofilm grown without a carrier, is an innovative biological treatment method with the potential to vastly reduce the cost of wastewater treatment without sacrificing efficiency. Large gaps remain, however, in our understanding of the fundamental formation mechanisms and the factors that control granule activity and stability. Magnetic resonance imaging (MRI) identified heterogeneous internal structures within aerobic granular sludge where relaxation rates and diffusion coefficients vary. Ultimately, these results will help improve modeling for optimization of granular sludge wastewater treatment process design.Item Stabilization of metallic catalyst microstructures against high-temperature thermal coarsening(Montana State University - Bozeman, College of Engineering, 2016) Driscoll, David Robert; Chairperson, Graduate Committee: Stephen W. Sofie; Clay D. Hunt, Julie E. Muretta and Stephen W. Sofie were co-authors of the article, 'Thermally stabilized nickel electro-catalyst introduced by infiltration for high temprature electrochemical energy conversion' in the journal 'Transactions of the Electrochemical Society' which is contained within this thesis.; Cameron H. Law and Stephen W. Sofie were co-authors of the article, 'Design and synthesis of metallic nanoparticle-ceramic support interfaces for enhancing thermal stability' in the journal 'Ceramic transactions' which is contained within this thesis.; Stephen W. Sofie was a co-author of the article, 'Stabilization of nano-scale metallic microstructure against thermal coarsening' in the journal 'Ceramic transactions' which is contained within this thesis.; Melissa D. McIntyre, Martha M. Welander, Stephen W. Sofie and Robert A. Walker were co-authors of the article, 'Enhancement of high temperature metallic catalysts : aluminum titanate in the nickel-zirconia system' in the journal 'Applied catalysis A: general' which is contained within this thesis.; Thesis contains two articles of which David Robert Driscoll is not the main author.; Melissa D. McIntyre, Martha M. Welander, Daniel E. Perea, Robert A. Walker and Stephen W. Sofie were co-authors of the article, 'Aluminum oxide processed as a beneficial additive in SOFC anodes' submitted to the journal 'Journal of the electrochemical society' which is contained within this thesis.; Clay D. Hunt, Daniel E. Perea, and Stephen W. Sofie were co-authors of the article, 'Diffusion caging : thermodynamic arrest of Ostwald ripening' submitted to the journal 'Advanced Materials' which is contained within this thesis.The size and shape of metal particulate at high temperature is dictated by surface energy. In systems containing very small metal particles, smaller particles shrink and disappear as they grow into larger particles in a process referred to as coarsening. Coarsening causes irreversible degradation in a number of important systems including automotive catalytic converters and solid oxide fuel cells (SOFC) through a loss of catalyst (metal) surface area. This phenomenon is exemplified by nickel metal catalyst that is supported on ytrria-stabilized zirconia (YSZ) which represents a materials system critical to the function of SOFCs. It has been demonstrated that additions of aluminum titanate (ALT) to the Ni-YSZ system with subsequent thermal treatment can act to stabilize the geometry of Ni on YSZ. In demonstration SOFCs, ALT has increased the time required for the first 10% of degradation by a factor of 115. This work has sought to elucidate the mechanisms by which ALT imparts increased stability. The work contained here demonstrates that ALT easily decomposes to Al 2O 3 and TiO 2. During thermal treatment, the alumina reacts with NiO to form nickel aluminate and the titania interacts with the YSZ where it can form Zr 5Ti 7O 24 -- a mixed ion electron conducting phase. In this way, the Al and Ti components of ALT have been determined to act independently where alumina appears to be dominant in microstructural stabilization. During cell operation, the nickel aluminate decomposes to nickel metal decorated with alumina nano-particulate. This geometry forms the basis of 'diffusion caging' as a stabilization mechanism which is the subject of Chapter 8. The role of titania appears to be less important except when processing occurs in a way that facilitates formation of the MIEC phase. However, Ni-YSZ cermets have also shown a strength enhancement when doped with ALT. This strength enhancement is likely due to the influence of titania (Chapter 7). Future work has the potential to extend concepts discussed here to a number of high temperature catalytic systems.Item Effect of monomeric binding affinity on scaffold mediated protein aggregation(Montana State University - Bozeman, College of Letters & Science, 2015) Goodman, Candace Kay; Chairperson, Graduate Committee: Mary J. CloningerThe intermolecular interactions that occur in a system determine the degree and duration of the contact. They govern processes from signaling and recognition to aggregation and tumor formation. The ability to control and affect intermolecular processes requires an understanding of the assembly process and factors modulating the assembly, such as the strength of individual interactions (binding affinity) and the number of interactions between molecules (valency). Functionalized PAMAM dendrimers were used as nucleating scaffolds to study the significance of intermolecular interactions on aggregate assembly. Dendrimers functionalized with biotin, lactose and mannose units spontaneously aggregated when added to the appropriate protein binding partner (streptavidin, galectin-3, and Concanavalin A, respectively). Aggregates were characterized to provide insight regarding the effects of binding affinity, protein valency and concentration on the average diameter, regularity (polydispersity) and kinetics of aggregate formation. A number of tools were used in this investigation, including dynamic light scattering (DLS), fluorescence microscopy (FM) and fluorescence lifetime spectroscopy (FLS). FLS instrumentation was reconfigured to enable high thoughput formats. A discussion of the validation and re-design of the FLS instrumentation is included.