Browsing by Author "Kirkland, Catherine M."

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Addressing wellbore integrity and thief zone permeability using microbially-induced calcium carbonate precipitation (MICP): A field demonstration
(Elsevier BV, 2020-02) Kirkland, Catherine M.; Thane, Abby; Hiebert, Randy; Hyatt, Robert; Kirksey, Jim; Cunningham, Alfred B.; Gerlach, Robin; Spangler, Lee; Philips, Adrienne J.
Microbially-induced calcium carbonate precipitation (MICP) is an emerging biotechnology for wellbore integrity applications including sealing defects in wellbore cement and modifying the permeability of rock formations. The goal of this field demonstration was to characterize a failed waterflood injection well and provide proof of principle that MICP can reduce permeability in the presence of oil using conventional oilfield fluid delivery methods. We compared well logs performed at the time the well was drilled with ultrasonic logs, sonic cement evaluation, and temperature logs conducted after the well failed. Analysis of these logs suggested that, rather than entering the target waterflood formation, injectate was traveling through defects in the well cement to a higher permeability sandstone layer above the target formation. Sporosarcina pasteurii cultures and urea-calcium media were delivered 2290 ft (698 m) below ground surface using a 3.75 gal (14.2 L) slickline dump bailer to promote mineralization in the undesired flow paths. By Day 6 and after 25 inoculum and 49 calcium media injections, the injectivity [gpm/psi] had decreased by approximately 70%. This demonstration shows that 1) common well logs can be used to identify scenarios where MICP can be employed to reduce system permeability, remediate leakage pathways, and improve waterflood efficiency, and 2) MICP can occur in the presence of hydrocarbons.
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.
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.
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.
Characterizing the structure of aerobic granular sludge using ultra-high field magnetic resonance
(IWA Publishing, 2020-08) Kirkland, Catherine M.; Krug, Julia R.; Vergeldt, Frank J.; van den Berg, Lenno; Velders, Aldrik H.; Seymour, Joseph D.; Codd, Sarah L.; Van As, Henk; de Kreuk, Merle K.
Despite aerobic granular sludge wastewater treatment plants operating around the world, our understanding of internal granule structure and its relation to treatment efficiency remains limited. This can be attributed in part to the drawbacks of time-consuming, labor-intensive, and invasive microscopy protocols which effectively restrict samples sizes and may introduce artefacts. Timedomain nuclear magnetic resonance (NMR) allows non-invasive measurements which describe internal structural features of opaque, complex materials like biofilms. NMR was used to image aerobic granules collected from five full-scale wastewater treatment plants in the Netherlands and United States, as well as laboratory granules and control beads. T1 and T2 relaxation-weighted images reveal heterogeneous structures that include high- and low-density biofilm regions, waterlike voids, and solid-like inclusions. Channels larger than approximately 50 μm and connected to the bulk fluid were not visible. Both cluster and ring-like structures were observed with each granule source having a characteristic structural type. These structures, and their NMR relaxation behavior, were stable over several months of storage. These observations reveal the complex structures within aerobic granules from a range of sources and highlight the need for non-invasive characterization methods like NMR to be applied in the ongoing effort to correlate structure and function.
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.
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.
Heterogeneous diffusion in aerobic granular sludge
(Wiley, 2020-08) van den Berg, Lenno; Kirkland, Catherine M.; Seymour, Joseph D.; Codd, Sarah L.; Van Loosdrecht, Mark C. M.; de Kreuk, Merle K.
Aerobic granular sludge (AGS) technology allows simultaneous nitrogen, phosphorus, and carbon removal in compact wastewater treatment processes. To operate, design, and model AGS reactors, it is essential to properly understand the diffusive transport within the granules. In this study, diffusive mass transfer within full‐scale and lab‐scale AGS was characterized with nuclear magnetic resonance (NMR) methods. Self‐diffusion coefficients of water inside the granules were determined with pulsed‐field gradient NMR, while the granule structure was visualized with NMR imaging. A reaction‐diffusion granule‐scale model was set up to evaluate the impact of heterogeneous diffusion on granule performance. The self‐diffusion coefficient of water in AGS was ∼70% of the self‐diffusion coefficient of free water. There was no significant difference between self‐diffusion in AGS from full‐scale treatment plants and from lab‐scale reactors. The results of the model showed that diffusional heterogeneity did not lead to a major change of flux into the granule (<1%). This study shows that differences between granular sludges and heterogeneity within granules have little impact on the kinetic properties of AGS. Thus, a relatively simple approach is sufficient to describe mass transport by diffusion into the granules.
In situ detection of subsurface biofilm using low-field NMR: A field study
(2015-09) Kirkland, Catherine M.; Herrling, M. P.; Hiebert, Dwight Randall; Bender, A. T.; Grunewald, Elliot; Walsh, David O.; Codd, Sarah L.
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. Current methods to monitor subsurface biofilm growth in situ are indirect. Previous laboratory research conducted at MSU has indicated that low-field nuclear magnetic resonance (NMR) is sensitive to biofilm growth in porous media, where biofilm contributes a polymer gel-like phase and enhances T2 relaxation. Here we show that a small diameter NMR well logging tool can detect biofilm accumulation in the subsurface using the change in T2 relaxation behavior over time. T2 relaxation distributions were measured over an 18 day experimental period by two NMR probes, operating at approximately 275 kHz and 400 kHz, installed in 10.2 cm wells in an engineered field testing site. The mean log T2 relaxation times were reduced by 62% and 43%, respectively, while biofilm was cultivated in the soil surrounding each well. Biofilm growth was confirmed by bleaching and flushing the wells and observing the NMR signal’s return to baseline. This result provides a direct and noninvasive method to spatiotemporally monitor biofilm accumulation in the subsurface.
Low-Field Borehole NMR Applications in the Near-Surface Environment
(2018-01) Kirkland, Catherine M.; Codd, Sarah L.
The inherent heterogeneity of the near subsurface (<200 m below the ground surface) presents challenges for agricultural water management, hydrogeologic characterization, and engineering, among other fields. Borehole nuclear magnetic resonance (NMR) has the potential not only to describe this heterogeneity in space nondestructively but also to monitor physical and chemical changes in the subsurface with time. Nuclear magnetic resonance is sensitive to parameters of interest like porosity and permeability, saturation, fluid viscosity, and formation mineralogy. Borehole NMR tools have been used to measure soil moisture in model soils, and recent advances in lowfield borehole NMR instrumentation allow estimation of hydraulic properties of unconsolidated aquifers. We also demonstrate the potential for low-field borehole NMR tools to monitor field-relevant biogeochemical processes like biofilm accumulation and microbially induced calcite precipitation at laboratory and field scales. Finally, we address some remaining challenges and areas of future research, as well as other possible applications where borehole. NMR could provide valuable complementary data.
NMR investigation of water diffusion in different biofilm structures
(2017-09) Herrling, M. P.; Weisbrodt, Jessica; Kirkland, Catherine M.; Williamson, Nathan H.; Lackner, S.; Codd, Sarah L.; Seymour, Joseph D.; Guthausen, G.; Horn, H.
Mass transfer in biofilms is determined by diffusion. Different mostly invasive approaches have been used to measure diffusion coefficients in biofilms, however, data on heterogeneous biomass under realistic conditions is still missing. To non-invasively elucidate fluid–structure interactions in complex multispecies biofilms pulsed field gradient-nuclear magnetic resonance (PFG-NMR) was applied to measure the water diffusion in five different types of biomass aggregates: one type of sludge flocs, two types of biofilm, and two types of granules. Data analysis is an important issue when measuring heterogeneous systems and is shown to significantly influence the interpretation and understanding of water diffusion. With respect to numerical reproducibility and physico-chemical interpretation, different data processing methods were explored: (bi)-exponential data analysis and the Γ distribution model. Furthermore, the diffusion coefficient distribution in relation to relaxation was studied by D-T2 maps obtained by 2D inverse Laplace transform (2D ILT). The results show that the effective diffusion coefficients for all biofilm samples ranged from 0.36 to 0.96 relative to that of water. NMR diffusion was linked to biofilm structure (e.g., biomass density, organic and inorganic matter) as observed by magnetic resonance imaging and to traditional biofilm parameters: diffusion was most restricted in granules with compact structures, and fast diffusion was found in heterotrophic biofilms with fluffy structures. The effective diffusion coefficients in the biomass were found to be broadly distributed because of internal biomass heterogeneities, such as gas bubbles, precipitates, and locally changing biofilm densities. Thus, estimations based on biofilm bulk properties in multispecies systems can be overestimated and mean diffusion coefficients might not be sufficiently informative to describe mass transport in biofilms and the near bulk.
Pharmaceutical impacts on aerobic granular sludge morphology and potential implications for abiotic removal
(Elsevier, 2024-02) Bodle, Kylie B.; Kirkland, Catherine M.
The goal of this study was to investigate abiotic pharmaceutical removal and abiotic pharmaceutical effects on aerobic granular sludge morphology. For 80 days, a pharmaceutical mixture containing approximately 150 μg/L each of diclofenac, erythromycin, and gemfibrozil was fed to an aerobic granular sludge sequencing batch reactor and granule characteristics were compared with those from a control reactor. Aqueous and solid phase pharmaceutical concentrations were monitored and staining was used to assess changes in biofilm structures. Solid phase pharmaceutical concentrations were elevated over the first 12 days of dosing; however, they then dropped, indicative of desorption. The lipid content in pharmaceutical-exposed granules declined by approximately half over the dosing period, though the relative concentrations of other key biofilm components (proteins, alpha-, and beta-polysaccharides) did not change. Batch experiments were conducted to try to find an explanation for the desorption observed, but reduced solid phase pharmaceutical concentrations could not be linked with the presence of common wastewater constituents such as ammonia or phosphate. Sorption of all three compounds was modeled best by the Henry isotherm, indicating that, even at 150 μg/L, granules’ sorption site coverage was incomplete. Altogether, this study demonstrates that simplified batch systems may not accurately represent the complex abiotic processes occurring in flow-through, biotic systems.
Pharmaceutical Sorption to Lab Materials May Overestimate Rates of Removal in Lab-Scale Bioreactors
(Springer Science and Business Media LLC, 2022-11) Bodle, Kylie B.; Pernat, Madeline R.; Kirkland, Catherine M.
Environmental contamination from pharmaceuticals has received increased attention from researchers in the past 20 years. As such, numerous lab-scale studies have sought to characterize the effects of these contaminants on various targets, as well as determine improved removal methods. Many studies have used lab-scale bioreactors to investigate pharmaceutical effects on wastewater bacteria, as wastewater treatment plants often act as reservoirs for pharmaceuticals. However, few—if any—of these studies report the specific lab materials used during testing, such as tubing or pipette tip type. In this study, the pharmaceuticals erythromycin, diclofenac, and gemfibrozil were exposed to different micropipette tips, syringe filters, and tubing types, and losses over time were evaluated. Losses to tubing and syringe filters were particularly significant and neared 100%, depending on the pharmaceutical compound and length of exposure time. Results discussed herein indicate that pharmaceutical sorption to various lab supplies results in decreases to both dosed and quantified pharmaceutical concentrations. Studies that fail to consider this source of loss may therefore draw inaccurate conclusions about pharmaceutical effects or removal efficiencies.
Simultaneous Gaussian and exponential inversion for improved analysis of shales by NMR relaxometry
(2015-01) Washburn, K. E.; Anderssen, E.; Vogt, Sarah J.; Seymour, Joseph D.; Birdwell, J. E.; Kirkland, Catherine M.; Codd, Sarah L.
Nuclear magnetic resonance (NMR) relaxometry is commonly used to provide lithology-independent porosity and pore-size estimates for petroleum resource evaluation based on fluid-phase signals. However in shales, substantial hydrogen content is associated with solid and fluid signals and both may be detected. Depending on the motional regime, the signal from the solids may be best described using either exponential or Gaussian decay functions. When the inverse Laplace transform, the standard method for analysis of NMR relaxometry results, is applied to data containing Gaussian decays, this can lead to physically unrealistic responses such as signal or porosity overcall and relaxation times that are too short to be determined using the applied instrument settings. We apply a new simultaneous Gaussian-Exponential (SGE) inversion method to simulated data and measured results obtained on a variety of oil shale samples. The SGE inversion produces more physically realistic results than the inverse Laplace transform and displays more consistent relaxation behavior at high magnetic field strengths. Residuals for the SGE inversion are consistently lower than for the inverse Laplace method and signal overcall at short T2 times is mitigated. Beyond geological samples, the method can also be applied in other fields where the sample relaxation consists of both Gaussian and exponential decays, for example in material, medical and food sciences.
Treatment performance and microbial community structure in an aerobic granular sludge sequencing batch reactor amended with diclofenac, erythromycin, and gemfibrozil
(Frontiers Media SA, 2023-09) Bodle, Kylie B.; Mueller, Rebecca C.; Pernat, Madeline R.; Kirkland, Catherine M.
This study characterizes the effects of three commonly detected pharmaceuticals—diclofenac, erythromycin, and gemfibrozil—on aerobic granular sludge. Approximately 150 µg/L of each pharmaceutical was fed in the influent to a sequencing batch reactor for 80 days, and the performance of the test reactor was compared with that of a control reactor. Wastewater treatment efficacy in the test reactor dropped by approximately 30-40%, and ammonia oxidation was particularly inhibited. The relative abundance of active Rhodocyclaceae, Nitrosomonadaceae, and Nitrospiraceae families declined throughout exposure, likely explaining reductions in wastewater treatment performance. Pharmaceuticals were temporarily removed in the first 12 days of the test via both sorption and degradation; both removal processes declined sharply thereafter. This study demonstrates that aerobic granular sludge may successfully remove pharmaceuticals in the short term, but long-term tests are necessary to confirm if pharmaceutical removal is sustainable.
Ureolysis-induced calcium carbonate precipitation (UICP) in the presence of CO2-affected brine: A field demonstration
(Elsevier BV, 2021-07) Kirkland, Catherine M.; Akyel, Arda; Hiebert, Randy; McCloskey, Jay
Biomineralization is an emerging biotechnology for subsurface engineering applications like remediating leaky wellbores. The process relies on ureolysis to induce precipitation of calcium carbonate in undesired flow paths. In geologic storage of CO2, there is a potential for leakage and low pH conditions, thus, ureolysis-induced calcium carbonate precipitation (UICP) was tested at field scale to seal a channel in the wellbore cement annulus in the presence of CO2-affected brine. Conventional oil field methods were used to deliver UICP-promoting fluids downhole to the treatment zone approximately 1000 feet (305 m) below ground surface (bgs). Over 4 days, 242 L (64 gal) of heat-treated Sporosarcina pasteurii cultures (22 bailers) and 329 L (87 gal) of urea – calcium chloride solution (30 bailers) were injected. The UICP treatment resulted in a 94% reduction of injectivity and ultrasonic well logging showed a noticeable increase in the percentage of solids in the channel outside the casing, including more than 30 m (100 ft) above the injection point. Subsequent well logging 11 months after the field demonstration showed that a significant portion of the new solids remained but the seal was compromised following sustained pumping. The results of this experiment suggest that UICP can be promoted in the presence of CO2-affected brine to seal leakage pathways. Additional research is required to optimize long term seal integrity to ensure storage of CO2 in geologic carbon sequestration scenarios.