Browsing by Author "Phillips, Adrienne J."
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Item Beyond the Surface: Non-Invasive Low-Field NMR Analysis of Microbially-Induced Calcium Carbonate Precipitation in Shale Fractures(Springer Science and Business Media LLC, 2024-07) Willett, Matthew R.; Bedey, Kayla; Crandall, Dustin; Seymour, Joseph D.; Rutqvist, Jonny; Cunningham, Alfred B.; Phillips, Adrienne J.; Kirkland, Catherine M.Microbially-induced calcium carbonate precipitation (MICP) is a biological process in which microbially-produced urease enzymes convert urea and calcium into solid calcium carbonate (CaCO3) deposits. MICP has been demonstrated to reduce permeability in shale fractures under elevated pressures, raising the possibility of applying this technology to enhance shale reservoir storage safety. For this and other applications to become a reality, non-invasive tools are needed to determine how effectively MICP seals shale fractures at subsurface temperatures. In this study, two different MICP strategies were tested on 2.54 cm diameter and 5.08 cm long shale cores with a single fracture at 60 ℃. Flow-through, pulsed-flow MICP-treatment was repeatedly applied to Marcellus shale fractures with and without sand (“proppant”) until reaching approximately four orders of magnitude reduction in apparent permeability, while a single application of polymer-based “immersion” MICP-treatment was applied to an Eagle Ford shale fracture with proppant. Low-field nuclear magnetic resonance (LF-NMR) and X-Ray computed microtomography (micro-CT) techniques were used to assess the degree of biomineralization. With the flow-through approach, these tools revealed that while CaCO3 precipitation occurred throughout the fracture, there was preferential precipitation around proppant. Without proppant, the same approach led to premature sealing at the inlet side of the core. In contrast, immersion MICP-treatment sealed off the fracture edges and showed less mineral precipitation overall. This study highlights the use of LF-NMR relaxometry in characterizing fracture sealing and can help guide NMR logging tools in subsurface remediation efforts.Item Beyond the Surface: Non-Invasive Low-Field NMR Analysis of Microbially-Induced Calcium Carbonate Precipitation in Shale Fractures(Springer Science and Business Media LLC, 2024-07) Willet, Matthew R.; Bedey, Kayla; Crandall, Dustin; Seymour, Joseph D.; Rutqvist, Jonny; Cunningham, Alfred B.; Phillips, Adrienne J.; Kirkland, Catherine M.Microbially-induced calcium carbonate precipitation (MICP) is a biological process in which microbially-produced urease enzymes convert urea and calcium into solid calcium carbonate (CaCO3) deposits. MICP has been demonstrated to reduce permeability in shale fractures under elevated pressures, raising the possibility of applying this technology to enhance shale reservoir storage safety. For this and other applications to become a reality, non-invasive tools are needed to determine how effectively MICP seals shale fractures at subsurface temperatures. In this study, two different MICP strategies were tested on 2.54 cm diameter and 5.08 cm long shale cores with a single fracture at 60 ℃. Flow-through, pulsed-flow MICP-treatment was repeatedly applied to Marcellus shale fractures with and without sand (“proppant”) until reaching approximately four orders of magnitude reduction in apparent permeability, while a single application of polymer-based “immersion” MICP-treatment was applied to an Eagle Ford shale fracture with proppant. Low-field nuclear magnetic resonance (LF-NMR) and X-Ray computed microtomography (micro-CT) techniques were used to assess the degree of biomineralization. With the flow-through approach, these tools revealed that while CaCO3 precipitation occurred throughout the fracture, there was preferential precipitation around proppant. Without proppant, the same approach led to premature sealing at the inlet side of the core. In contrast, immersion MICP-treatment sealed off the fracture edges and showed less mineral precipitation overall. This study highlights the use of LF-NMR relaxometry in characterizing fracture sealing and can help guide NMR logging tools in subsurface remediation efforts.Item Biofilm detection in a model well-bore environment using low-field magnetic resonance(2015-09) Kirkland, Catherine M.; Hiebert, Dwight Randall; Phillips, Adrienne J.; Grunewald, Elliot; Walsh, David O.; Seymour, Joseph D.; Codd, Sarah L.This research addresses the challenges of the lack of non-invasive methods and poor spatiotemporal resolution associated with monitoring biogeochemical activity central to bioremediation of subsurface contaminants. Remediation efforts often include growth of biofilm to contain or degrade chemical contaminants, such as nitrates, hydrocarbons, heavy metals, and some chlorinated solvents. Previous research indicates that nuclear magnetic resonance (NMR) is sensitive to the biogeochemical processes of biofilm accumulation. The current research focuses on developing methods to use low-cost NMR technology to support in situ monitoring of biofilm growth and geochemical remediation processes in the subsurface. Biofilm was grown in a lab-scale radial flow bioreactor designed to model the near wellbore subsurface environment. The Vista Clara Javelin NMR logging device, a slim down-the-borehole probe, collected NMR measurements over the course of eight days while biofilm was cultivated in the sand-packed reactor. Measured NMR mean log T2 relaxation times decreased from approximately 710 to 389 ms, indicating that the pore environment and bulk fluid properties were changing due to biofilm growth. Destructive sampling employing drop plate microbial population analysis and scanning electron and stereoscopic microscopy confirmed biofilm formation. Our findings demonstrate that the NMR logging tool can detect small to moderate changes in T2 distribution associated with environmentally relevant quantities of biofilm in quartz sand.Item Biofilm enhanced subsurface sequestration of supercritical CO2(2009-01) Mitchell, Andrew C.; Phillips, Adrienne J.; Hiebert, Dwight Randall; Gerlach, Robin; Cunningham, Alfred B.In order to develop subsurface CO2 storage as a viable engineered mechanism to reduce the emission of CO2 into the atmosphere, any potential leakage of injected supercritical CO2 (SC-CO2) from the deep subsurface to the atmosphere must be reduced. Here, we investigate the utility of biofilms, which are microorganism assemblages firmly attached to a surface, as a means of reducing the permeability of deep subsurface porous geological matrices under high pressure and in the presence of SC-CO2, using a unique high pressure (8.9 MPa), moderate temperature (32 °C) flow reactor containing 40 millidarcy Berea sandstone cores. The flow reactor containing the sandstone core was inoculated with the biofilm forming organism Shewanella fridgidimarina. Electron microscopy of the rock core revealed substantial biofilm growth and accumulation under high-pressure conditions in the rock pore space which caused >95% reduction in core permeability. Permeability increased only slightly in response to SC-CO2 challenges of up to 71 h and starvation for up to 363 h in length. Viable population assays of microorganisms in the effluent indicated survival of the cells following SC-CO2 challenges and starvation, although S. fridgidimarina was succeeded by Bacillus mojavensis and Citrobacter sp. which were native in the core. These observations suggest that engineered biofilm barriers may be used to enhance the geologic sequestration of atmospheric CO2.Item Biomineralization of Plastic Waste to Improve the Strength of Plastic-Reinforced Cement Mortar(2021-04) Kane, Seth; Thane, Abby; Espinal, Michael; Lunday, Kendra; Armagan, Hakan; Phillips, Adrienne J.; Heveran, Chelsea M.; Ryan, Cecily A.The development of methods to reuse large volumes of plastic waste is essential to curb the environmental impact of plastic pollution. Plastic-reinforced cementitious materials (PRCs), such as plastic-reinforced mortar (PRM), may be potential avenues to productively use large quantities of low-value plastic waste. However, poor bonding between the plastic and cement matrix reduces the strength of PRCs, limiting its viable applications. In this study, calcium carbonate biomineralization techniques were applied to coat plastic waste and improved the compressive strength of PRM. Two biomineralization treatments were examined: enzymatically induced calcium carbonate precipitation (EICP) and microbially induced calcium carbonate precipitation (MICP). MICP treatment of polyethylene terephthalate (PET) resulted in PRMs with compressive strengths similar to that of plastic-free mortar and higher than the compressive strengths of PRMs with untreated or EICP-treated PET. Based on the results of this study, MICP was used to treat hard-to-recycle types 3–7 plastic waste. No plastics investigated in this study inhibited the MICP process. PRM samples with 5% MICP-treated polyvinyl chloride (PVC) and mixed type 3–7 plastic had compressive strengths similar to plastic-free mortar. These results indicate that MICP treatment can improve PRM strength and that MICP-treated PRM shows promise as a method to reuse plastic waste.Item Darcy-scale modeling of microbially induced carbonate mineral precipitation in sand columns(2012-07) Ebigbo, Anozie; Phillips, Adrienne J.; Gerlach, Robin; Helmig, Rainer; Cunningham, Alfred B.; Class, Holger; Spangler, Lee H.This investigation focuses on the use of microbially induced calcium carbonate precipitation (MICP) to set up subsurface hydraulic barriers to potentially increase storage security near wellbores of CO2 storage sites. A numerical model is developed, capable of accounting for carbonate precipitation due to ureolytic bacterial activity as well as the flow of two fluid phases in the subsurface. The model is compared to experiments involving saturated flow through sand-packed columns to understand and optimize the processes involved as well as to validate the numerical model. It is then used to predict the effect of dense-phase CO2 and CO2-saturated water on carbonate precipitates in a porous medium.Item Design of a meso-scale high pressure vessel for the laboratory examination of biogeochemical subsurface processes(2015-02) Phillips, Adrienne J.; Eldring, Joseph; Hiebert, Dwight Randall; Lauchnor, Ellen G.; Mitchell, Andrew C.; Cunningham, Alfred B.; Spangler, Lee H.; Gerlach, RobinBiocides are critical components of hydraulic fracturing (“fracking†) fluids used for unconventional shale gas development. Bacteria may cause bioclogging and inhibit gas extraction, produce toxic hydrogen sulfide, and induce corrosion leading to downhole equipment failure. The use of biocides such as glutaraldehyde and quaternary ammonium compounds has spurred a public concern and debate among regulators regarding the impact of inadvertent releases into the environment on ecosystem and human health. This work provides a critical review of the potential fate and toxicity of biocides used in hydraulic fracturing operations. We identified the following physicochemical and toxicological aspects as well as knowledge gaps that should be considered when selecting biocides: (1) uncharged species will dominate in the aqueous phase and be subject to degradation and transport whereas charged species will sorb to soils and be less bioavailable; (2) many biocides are short-lived or degradable through abiotic and biotic processes, but some may transform into more toxic or persistent compounds; (3) understanding of biocides’ fate under downhole conditions (high pressure, temperature, and salt and organic matter concentrations) is limited; (4) several biocidal alternatives exist, but high cost, high energy demands, and/or formation of disinfection byproducts limits their use. This review may serve as a guide for environmental risk assessment and identification of microbial control strategies to help develop a sustainable path for managing hydraulic fracturing fluids.Item Detecting Microbially Induced Calcite Precipitation in a Model Well-Bore Using Downhole Low-Field NMR(2017-02) Kirkland, Catherine M.; Zanetti, Sam; Grunewald, Elliot; Walsh, David O.; Codd, Sarah L.; Phillips, Adrienne J.Microbially induced calcite precipitation (MICP) has been widely researched recently due to its relevance for subsurface engineering applications including sealing leakage pathways and permeability modification. These applications of MICP are inherently difficult to monitor nondestructively in time and space. Nuclear magnetic resonance (NMR) can characterize the pore size distributions, porosity, and permeability of subsurface formations. This investigation used a low-field NMR well-logging probe to monitor MICP in a sand-filled bioreactor, measuring NMR signal amplitude and T2 relaxation over an 8 day experimental period. Following inoculation with the ureolytic bacteria, Sporosarcina pasteurii, and pulsed injections of urea and calcium substrate, the NMR measured water content in the reactor decreased to 76% of its initial value. T2 relaxation distributions bifurcated from a single mode centered about approximately 650 ms into a fast decaying population (T2 less than 10 ms) and a larger population with T2 greater than 1000 ms. The combination of changes in pore volume and surface minerology accounts for the changes in the T2 distributions. Destructive sampling confirmed final porosity was approximately 88% of the original value. These results indicate the low-field NMR well-logging probe is sensitive to the physical and chemical changes caused by MICP in a laboratory bioreactor.Item Engineered applications of ureolytic biomineralization: A review(2013-07) Phillips, Adrienne J.; Gerlach, Robin; Lauchnor, Ellen G.; Mitchell, Andrew C.; Cunningham, Alfred B.; Spangler, Lee H.Microbially induced calcium carbonate (CaCO3) precipitation (MICP) is a widely explored and promising technology for use in various engineering applications. In this review, CaCO3 precipitation induced via urea hydrolysis (ureolysis) is examined for improving construction materials, cementing porous media, hydraulic control, and remediating environmental concerns. The control of MICP is explored through the manipulation of three factors: (1) the ureolytic activity (of microorganisms), (2) the reaction and transport rates of substrates, and (3) the saturation conditions of carbonate minerals. Many combinations of these factors have been researched to spatially and temporally control precipitation. This review discusses how optimization of MICP is attempted for different engineering applications in an effort to highlight the key research and development questions necessary to move MICP technologies toward commercial scale applications.Item Enhancing wellbore cement integrity with microbially induced calcite precipitation (MICP): A field scale demonstration(2018-12) Phillips, Adrienne J.; Troyer, E.; Hiebert, R.; Kirkland, Catherine M.; Gerlach, Robin; Cunningham, Alfred B.; Spangler, Lee H.; Kirksey, J.; Rowe, W.; Esposito, R.The presence of delaminations, apertures, fractures, voids and other unrestricted flow channels in the wellbore environment substantially reduces wellbore integrity. Compromised cement may cause a loss of zonal isolation leading to deleterious flow of fluids between zones or to the surface with multiple potential negative impacts including: loss of resource production, reduction of sweep efficiency in EOR operations, and regulatory non-compliance. One potential solution to enhance wellbore integrity is microbially induced calcite precipitation (MICP) to plug preferential flow pathways. MICP is promoted with micrometer-sized organisms and low viscosity (aqueous) solutions thereby facilitating fluid transport into small aperture, potentially tortuous leakage flow paths within the cement column. In this study, MICP treatment of compromised wellbore cement was demonstrated at a depth interval of 310.0–310.57 m (1017–1019 feet) below ground surface (bgs) using conventional oil field subsurface fluid delivery technologies (packer, tubing string, and a slickline deployed bailer). After 25 urea/calcium solution and 10 microbial (Sporosarcina pasteurii) suspension injections, injectivity was reduced from the initial 0.29 cubic meters per hour (m3/h) (1.28 gallons per minute (gpm)) to less than 0.011 m3/h (0.05 gpm). The flow rate was decreased while maintaining surface pumping pressure below a maximum pressure of 81.6 bar (1200 psi) to minimize the potential for fracturing a shale formation dominant in this interval. The pressure decay immediately after each injection ceased decreased after MICP treatment. Comparison of pre- and post-test cement evaluation logs revealed substantial deposition of precipitated solids along the original flow channel. This study suggests MICP is a promising tool for enhancing wellbore cement integrity.Item Evaluation of the bonding properties between low-value plastic fibers treated with microbially-induced calcium carbonate precipitation and cement mortar(Elsevier BV, 2022-11) Espinal, Michael; Kane, Seth; Ryan, Cecily; Phillips, Adrienne J.; Heveran, ChelseaPlastic fiber reinforced cementitious materials offer the potential to increase the reusability of plastic waste and create lower-CO2 cementitious composites. However, the bonding properties of many plastic types with ordinary Portland cement (OPC) are largely unknown. This work employs single fiber pullout (SFPO) tests to quantify the interfacial bonding properties of polyvinyl chloride, low-density polyethylene, polypropylene, polystyrene, and acrylonitrile butadiene styrene embedded in OPC mortar. The interfacial bonding properties were compared for fibers either treated with microbially-induced calcium carbonate precipitation (MICP) or left untreated. SFPO tests revealed that plastic type had a large influence over bonding properties. Specifically, the fiber surface energy, as estimated from water contact angle measurements, was found to be the driving factor of bond strength. ABS had the highest surface energy and demonstrated the strongest bonding out of all plastic types studied. However, MICP treatment of fibers did not increase the interfacial bond strength for any of the plastics studied. The thick and inconsistent coverage of biomineral over the fiber surface from MICP is likely attributed to preventing an increase in bond strength. These results contribute to the design and application of plastic-reinforced mortars by comparing bonding properties for a range of typically low-value, unrecycled plastic types.Item Field-scale modeling of microbially induced calcite precipitation(2018-11) Cunningham, Alfred B.; Class, Holger; Ebigbo, Anozie; Gerlach, Robin; Phillips, Adrienne J.; Hommel, JohannesThe biogeochemical process known as microbially induced calcite precipitation (MICP) is being investigated for engineering and material science applications. To model MICP process behavior in porous media, computational simulators must couple flow, transport, and relevant biogeochemical reactions. Changes in media porosity and permeability due to biomass growth and calcite precipitation, as well as their effects on one another must be considered. A comprehensive Darcy-scale model has been developed by Ebigbo et al. (Water Resour. Res. 48(7), W07519, 2012) and Hommel et al. (Water Resour. Res. 51, 3695–3715, 2015) and validated at different scales of observation using laboratory experimental systems at the Center for Biofilm Engineering (CBE), Montana State University (MSU). This investigation clearly demonstrates that a close synergy between laboratory experimentation at different scales and corresponding simulation model development is necessary to advance MICP application to the field scale. Ultimately, model predictions of MICP sealing of a fractured sandstone formation, located 340.8 m below ground surface, were made and compared with corresponding field observations. Modeling MICP at the field scale poses special challenges, including choosing a reasonable model-domain size, initial and boundary conditions, and determining the initial distribution of porosity and permeability. In the presented study, model predictions of deposited calcite volume agree favorably with corresponding field observations of increased injection pressure during the MICP fracture sealing test in the field. Results indicate that the current status of our MICP model now allows its use for further subsurface engineering applications, including well-bore cement sealing and certain fracture-related applications in unconventional oil and gas production.Item Fracture Sealing with Microbially-Induced Calcium Carbonate Precipitation: A Field Study(2016-04) Phillips, Adrienne J.; Cunningham, Alfred B.; Gerlach, Robin; Hiebert, Dwight Randall; Hwang, Chiachi; Lomans, B. P.; Westrich, Joseph; Mantilla, C.; Kirksey, J.; Esposito, R.; Spangler, Lee H.A primary environmental risk from unconventional oil and gas development or carbon sequestration is subsurface fluid leakage in the near wellbore environment. A potential solution to remediate leakage pathways is to promote microbially induced calcium carbonate precipitation (MICP) to plug fractures and reduce permeability in porous materials. The advantage of microbially induced calcium carbonate precipitation (MICP) over cement-based sealants is that the solutions used to promote MICP are aqueous. MICP solutions have low viscosities compared to cement, facilitating fluid transport into the formation. In this study, MICP was promoted in a fractured sandstone layer within the Fayette Sandstone Formation 340.8 m below ground surface using conventional oil field subsurface fluid delivery technologies (packer and bailer). After 24 urea/calcium solution and 6 microbial (Sporosarcina pasteurii) suspension injections, the injectivity was decreased (flow rate decreased from 1.9 to 0.47 L/min) and a reduction in the in-well pressure falloff (>30% before and 7% after treatment) was observed. In addition, during refracturing an increase in the fracture extension pressure was measured as compared to before MICP treatment. This study suggests MICP is a promising tool for sealing subsurface fractures in the near wellbore environment.Item In Situ Enhancement and Isotopic Labeling of Biogenic Coalbed Methane(American Chemical Society, 2022-02) Barnhart, Elliott P.; Ruppert, Leslie; Hiebert, Randy; Smith, Heidi J.; Schweitzer, Hannah D.; Clark, Arthur C.; Weeks, Edwin P.; Orem, William H.; Varonka, Matthew S.; Platt, George; Shelton, Jenna L.; Davis, Katherine J.; Hyatt, Robert J.; McIntosh, Jennifer C.; Ashley, Kilian; Ono, Shuhei; Martini, Anna M.; Hackley, Keith C.; Gerlach, Robin; Spangler, Lee; Phillips, Adrienne J.; Barry, Mark; Cunningham, Alfred B.; Fields, Matthew W.Subsurface microbial (biogenic) methane production is an important part of the global carbon cycle that has resulted in natural gas accumulations in many coal beds worldwide. Laboratory studies suggest that complex carbon-containing nutrients (e.g., yeast or algae extract) can stimulate methane production, yet the effectiveness of these nutrients within coal beds is unknown. Here, we use downhole monitoring methods in combination with deuterated water (D2O) and a 200-liter injection of 0.1% yeast extract (YE) to stimulate and isotopically label newly generated methane. A total dissolved gas pressure sensor enabled real time gas measurements (641 days preinjection and for 478 days postinjection). Downhole samples, collected with subsurface environmental samplers, indicate that methane increased 132% above preinjection levels based on isotopic labeling from D2O, 108% based on pressure readings, and 183% based on methane measurements 266 days postinjection. Demonstrating that YE enhances biogenic coalbed methane production in situ using multiple novel measurement methods has immediate implications for other field-scale biogenic methane investigations, including in situ methods to detect and track microbial activities related to the methanogenic turnover of recalcitrant carbon in the subsurface.Item Kinetics of Calcite Precipitation by Ureolytic Bacteria under Aerobic and Anaerobic Conditions(2019-05) Mitchell, Andrew C.; Espinosa-Ortiz, Erika J.; Parks, Stacy L.; Phillips, Adrienne J.; Cunningham, Alfred B.; Gerlach, RobinThe kinetics of urea hydrolysis (ureolysis) and induced calcium carbonate (CaCO3) precipitation for engineering use in the subsurface was investigated under aerobic conditions using Sporosarcina pasteurii (ATCC strain 11859) as well as Bacillus sphaericus strains 21776 and 21787. All bacterial strains showed ureolytic activity inducing CaCO3 precipitation aerobically. Rate constants not normalized to biomass demonstrated slightly higher-rate coefficients for both ureolysis (kurea) and CaCO3 precipitation (kprecip) for B. sphaericus 21776 (kurea=0.10±0.03 h−1, kprecip=0.60±0.34 h−1) compared to S. pasteurii (kurea=0.07±0.02 h−1, kprecip=0.25±0.02 h−1), though these differences were not statistically significantly different. B. sphaericus 21787 showed little ureolytic activity but was still capable of inducing some CaCO3 precipitation. Cell growth appeared to be inhibited during the period of CaCO3 precipitation. Transmission electron microscopy (TEM) images suggest this is due to the encasement of cells and was reflected in lower kurea values observed in the presence of dissolved Ca. However, biomass regrowth could be observed after CaCO3 precipitation ceased, which suggests that ureolysis-induced CaCO3 precipitation is not necessarily lethal for the entire population. The kinetics of ureolysis and CaCO3 precipitation with S. pasteurii was further analyzed under anaerobic conditions. Rate coefficients obtained in anaerobic environments were comparable to those under aerobic conditions; however, no cell growth was observed under anaerobic conditions with NO−3, SO2−4 or Fe3+ as potential terminal electron acceptors. These data suggest that the initial rates of ureolysis and ureolysis-induced CaCO3 precipitation are not significantly affected by the absence of oxygen but that long-term ureolytic activity might require the addition of suitable electron acceptors. Variations in the ureolytic capabilities and associated rates of CaCO3 precipitation between strains must be fully considered in subsurface engineering strategies that utilize microbial amendments.Item Microbial CaCO3 mineral formation and stability in an experimentally simulated high pressure saline aquifer with supercritical CO2(2013-07) Mitchell, Andrew C.; Phillips, Adrienne J.; Schultz, Logan N.; Parks, Stacy L.; Spangler, Lee H.; Cunningham, Alfred B.; Gerlach, RobinThe use of microbiologically induced mineralization to plug pore spaces is a novel biotechnology to mitigate the potential leakage of geologically sequestered carbon dioxide from preferential leakage pathways. The bacterial hydrolysis of urea (ureolysis) which can induce calcium carbonate precipitation, via a pH increase and the production of carbonate ions, was investigated under conditions that approximate subsurface storage environments, using a unique high pressure (∼7.5 MPa) moderate temperature (32 °C) flow reactor housing a synthetic porous media core. The synthetic core was inoculated with the ureolytic organism Sporosarcina pasteurii and pulse-flow of a urea inclusive saline growth medium was established through the core. The system was gradually pressurized to 7.5 MPa over the first 29 days. Concentrations of NH4+, a by-product of urea hydrolysis, increased in the flow reactor effluent over the first 20 days, and then stabilized at a maximum concentration consistent with the hydrolysis of all the available urea. pH increased over the first 6 days from 7 to 9.1, consistent with buffering by NH4+ ⇔ NH3 + H+. Ureolytic colony forming units were consistently detected in the reactor effluent, indicating a biofilm developed in the high pressure system and maintained viability at pressures up to 7.5 MPa. All available calcium was precipitated as calcite. Calcite precipitates were exposed to dry supercritical CO2 (scCO2), water-saturated scCO2, scCO2-saturated brine, and atmospheric pressure brine. Calcite precipitates were resilient to dry scCO2, but suffered some mass loss in water-saturated scCO2 (mass loss 17 ± 3.6% after 48 h, 36 ± 7.5% after 2 h). Observations in the presence of scCO2 saturated brine were ambiguous due to an artifact associated with the depressurization of the scCO2 saturated brine before sampling. The degassing of pressurized brine resulted in significant abrasion of calcite crystals and resulted in a mass loss of approximately 92 ± 50% after 48 h. However dissolution of calcite crystals in brine at atmospheric pressure, but at the pH of the scCO2 saturated brine, accounted for only approximately 7.8 ± 2.2% of the mass loss over the 48 h period. These data suggest that microbially induced mineralization, with the purpose of reducing the permeability of preferential leakage pathways during the operation of GCS, can occur under high pressure scCO2 injection conditions.Item Microbially enhanced carbonate mineralization and the geologic containment of CO2(2008) Mitchell, Andrew C.; Phillips, Adrienne J.; Kaszuba, John P.; Hollis, W. Kirk; Cunningham, Alfred B.; Gerlach, RobinGeologic sequestration of CO2 involves injection into deep underground formations including oil beds, un-minable coal seams, and saline aquifers with temperature and pressure conditions such that CO2 will likely be in the supercritical state. Supercritical CO2 injection into the receiving formation will result in elevated pressure in the region surrounding the point of injection, and may result in an upward hydrodynamic pressure gradient and associated “leakage†of supercritical to gaseous CO2. Therefore mechanisms to reduce leakage and to mineralize CO2 in a solid form are extremely advantageous for the long-term geologic containment of CO2.This paper will focus on microbially-based strategies for controlling leakage and sequestrating supercritical CO2 during geologic injection. We will examine the concept of using engineered microbial barriers (Cunningham et al., in review; Mitchell et al., in review) which are capable of precipitating calcium carbonate (Mitchell and Ferris, 2005; 2006) under high-pressure subsurface conditions. These “biomineralization barriers†may provide a method for plugging preferential flow pathways in the vicinity of CO2 injection, thereby reducing the potential for unwanted upward migration of CO2, as well as mineralizing injected CO2. A summary of experiments investigating biofilm and associated calcium carbonate formation in porous media using a unique high pressure (8.9 MPa), moderate temperature (≥ 32 °C) flow reactor will be presented, and the potential for biomineralization enhanced CO2 sequestration discussed.Item NMR relaxation measurements of biofouling in model and geological porous media(2011-09) Codd, Sarah L.; Vogt, Sarah J.; Hornemann, Jennifer A.; Phillips, Adrienne J.; Maneval, James E.; Romanenko, K. R.; Hansen, L.; Cunningham, Alfred B.; Seymour, Joseph D.Recently 2D nuclear magnetic resonance (NMR) relaxation techniques have been able to access changes in pore structures through surface and diffusion based relaxation measurements. This research investigates the applicability of these methods for measuring pore and surface changes due to biofilm growth in various model porous systems and natural geological media. Model bead packs of various construction containing 100 lm borosilicate and soda lime glass beads were used to demonstrate how changes in the measured relaxation rates can be used to non-invasively verify and quantify biofilm growth in porous media. However significant challenges are shown to arise when trying to implement the same techniques to verify biofilm growth in a natural geological media.Item A Numerical Model for Enzymatically Induced Calcium Carbonate Precipitation(MDPI, 2020-06) Hommel, Johannes; Akyel, Arda; Frieling, Zachary; Phillips, Adrienne J.; Gerlach, Robin; Cunningham, Alfred B.; Class, HolgerEnzymatically induced calcium carbonate precipitation (EICP) is an emerging engineered mineralization method similar to others such as microbially induced calcium carbonate precipitation (MICP). EICP is advantageous compared to MICP as the enzyme is still active at conditions where microbes, e.g., Sporosarcina pasteurii, commonly used for MICP, cannot grow. Especially, EICP expands the applicability of ureolysis-induced calcium carbonate mineral precipitation to higher temperatures, enabling its use in leakage mitigation deeper in the subsurface than previously thought to be possible with MICP. A new conceptual and numerical model for EICP is presented. The model was calibrated and validated using quasi-1D column experiments designed to provide the necessary data for model calibration and can now be used to assess the potential of EICP applications for leakage mitigation and other subsurface modifications.Item Potential CO2 leakage reduction through biofilm-induced calcium carbonate precipitation(2013-01) Phillips, Adrienne J.; Lauchnor, Ellen G.; Eldring, Joseph; Esposito, R.; Mitchell, Andrew C.; Gerlach, Robin; Cunningham, Alfred B.; Spangler, Lee H.Mitigation strategies for sealing high permeability regions in cap rocks, such as fractures or improperly abandoned wells, are important considerations in the long term security of geologically stored carbon dioxide (CO2). Sealing technologies using low-viscosity fluids are advantageous in this context since they potentially reduce the necessary injection pressures and increase the radius of influence around injection wells. Using aqueous solutions and suspensions that can effectively promote microbially induced mineral precipitation is one such technology. Here we describe a strategy to homogenously distribute biofilm-induced calcium carbonate (CaCO3) precipitates in a 61 cm long sandfilled column and to seal a hydraulically fractured, 74 cm diameter Boyles Sandstone core. Sporosarcina pasteurii biofilms were established and an injection strategy developed to optimize CaCO3 precipitation induced via microbial urea hydrolysis. Over the duration of the experiments, permeability decreased between 2 and 4 orders of magnitude in sand column and fractured core experiments, respectively. Additionally, after fracture sealing, the sandstone core withstood three times higher well bore pressure than during the initial fracturing event, which occurred prior to biofilm-induced CaCO3 mineralization. These studies suggest biofilm-induced CaCO3 precipitation technologies may potentially seal and strengthen fractures to mitigate CO2 leakage potential.