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Foamed Cement Interactions with CO 2

Geologic carbon storage (GCS) is a potentially viable strategy to reduce greenhouse emissions. Understanding the risks to engineered and geologic structures associated with GCS is an important first step towards developing practices for safe and effective storage. The widespread utilization of foamed cement in wells may mean that carbon dioxide (CO 2 )/brine/foamed cement reactions may occur within these GCS sites. Characterizing the difference in alteration rates as well as the physical and mechanical impact of CO 2 /brine/foamed cement is an important preliminary step to ensuring offshore and onshore GCS is a prudent anthropogenic CO 2 mitigation choice. In a typical oil and gas well, cement is placed in the annulus between the steel casing and formation rock for both zonal isolation and casing support. The cement must have sufficient strength to secure the casing in the hole and withstand the stress of drilling, perforating, and fracturing (e.g. API, 1997, 2010 Worldwide Cementing Practices). As such, measuring the mechanical and properties of cement is an important step in predicting cement behavior under applied downhole stresses (Nelson, 2006). Zonal isolation is the prevention of fluids migrating to different zones outside of the casing and is strongly impacted by the permeability of the wellbore cement (Nelson, 2006). Zonal isolation depends on both the mechanical behavior and permeability (a physical property) of the cement (Mueller and Eid, 2006; Nelson, 2006). Long-term integrity of cement depends on the mechanical properties of the cement sheath, such as Young’s Modulus (Griffith et al., 2004). The cement sheath’s ability to withstand the stresses from changes in pressure and temperature is predominantly determined by the mechanical properties, including Young’s modulus, Poisson’s ratio, and tensile strength. Any geochemical alteration may impact both the mechanical and physical properties of the cement, thus ultimately impacting the structural integrity of the wellbore. In this study, atmospheric foamed cements were generated using a neat cement and three foam qualities (volume of entrained gas in the cement) - 10%, 20%, and 30 % gas volume. The samples were immersed in a 0.25 M NaCl brine followed by the injection of supercritical CO 2 at 28.9 MPa and 50°C. Petrophysical properties were examined for representative samples using computed tomography (CT) and scanning electron microscopy (SEM). CT scanning of representative samples across the range of reacted cements revealed macroscopic changes in structure due to brine/CO 2 /cement interactions. The high foam quality samples resulted in more CO 2 -saturated brine infiltrating radially deeper into the cement and thus were more susceptible to alteration. After 56 days of exposure, the 30% foam quality sample had the most reaction resulting in an alteration depth of 8.35 ± 0.13 mm with a calculated 34.6 ± 0.2% reacted area and 5.76 ± 0.2% reacted pore space area. The neat sample on the other hand, had a reaction depth of 0.31 ± 0.13 mm with a calculated 0.15 ± 0.08% reacted area and 0.57 ± 0.05% reacted pore area. Physical measurements of the exposed samples were consistent with this degree of alteration having 47.02% porosity and the highest permeability of 0.041 mD. These results indicate that the greater surface area provided by the increase of pore space in the higher quality foam coupled with carbonate diffusion reactions enabled greater alteration.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Recommended Practices for Managing Induced Seismicity Risk Associated with Geologic Carbon Storage

The geologic storage of carbon dioxide (CO 2 ) is one method to help reduce or eliminate atmospheric CO 2 emissions. The sequestered CO 2 is originally captured from the atmosphere or from a stationary industrial source and subsequently injected into a deep subsurface porous rock formation. To facilitate the successful deployment of field scale carbon storage projects, the U.S. Department of Energy (DOE) is developing tools and protocols for defensible, science-based frameworks to quantify and mitigate risks associated with the long-term storage of CO 2 . This protocol specifically addresses the risk of induced seismicity due to injection in a geologic carbon storage (GCS) site. This integrated and risk-based protocol is a product of the U.S. DOE Fossil Energy’s National Risk Assessment Partnership (NRAP), a multi-year collaborative research effort of Los Alamos National Laboratory (LANL), Lawrence Berkeley National Laboratory (LBNL), Lawrence Livermore National Laboratory (LLNL), National Energy Technology Laboratory (NETL), and Pacific Northwest National Laboratory (PNNL). These recommended practices describe a set of 7 steps to evaluate, manage, communicate, and mitigate the risk of induced seismicity at GCS sites. The base methodology of the recommended practices follows a framework similar to the Protocol for Addressing Induced Seismicity Associated with Enhanced Geothermal Systems (Majer et al., 2012), developed for the Geothermal Technology Office of the U.S. DOE. These recommended practices present a framework to systematically assess the induced seismicity risk and quantify the associated uncertainties. These recommendations are based on current research and are sufficiently general to allow for modification and application to a variety of different types of sites. The substance of the recommended practices contained herein includes both technical and non-technical issues, and covers all operational stages of the GCS project lifecycle. They start at the preliminary risk assessment phase, continue through site assessment and characterization, include best practice communication and seismic monitoring plan methodologies, discuss the evaluation and mitigation of seismic hazard and risk, and closes with an exploration of operational management plans, which conclude when the induced seismicity risk abates back to background level. The focus of these recommendations is on actively managing the risks associated with induced seismicity by developing an actionable risk management plan that starts at the project proposal stage and continues through site closure through an iterative assessment and improvement process. The audience of this document is expected to include all interested stakeholders (e.g., operators, project developers, regulators, and the general public) and is expressly written to be accessible to this broad range of partners. This document is intended to disseminate knowledge gained through recent advances in the science of induced seismicity hazard and risk assessments, to provide updates based on recent experience gained by similar corollary injection-induced seismicity cases, and most importantly to establish a uniform framework to carry out a successful induced seismicity risk management plan for carbon storage projects in the future. These recommendations do not directly address any domestic or international regulations or standards. A complementary NRAP report makes recommendations for the assessment and management of environmental subsurface risks associated with unwanted fluid migration at GCS sites (Thomas et al., 2021) and should be referred to in order to address those additional GCS site risks.

54 ENVIRONMENTAL SCIENCES↗

Probabilistic Geomechanical Analysis of Compartmentalization at the Snøhvit CO 2 Sequestration Project

Pressure build-up caused by large-scale CO 2 injection is one of the key concerns during a carbon sequestration project. Large overpressures can potentially compromise seal integrity, reactivate faults, and induce concerning seismicity, among other hazards. Furthermore, pressure build-up is directly related with storage capacity. In this work we study the geomechanical response to CO 2 injection in the Tubåen Fm at Snøhvit, with the objective of understanding the potential for fault reactivation, leakage, and contamination of the producing interval in an adjacent block through the bounding faults. Furthermore, we evaluate the potential contribution of a structural component to reservoir compartmentalization. We combine simplified analytical models, based on critically stressed fracture theory and a Mohr-Coulomb failure criterion, with a quantitative risk assessment methodology to perform a rigorous uncertainty quantification. Large stress uncertainties are present and are reflected in the modeling results. It was found that under the “most likely” stress state (Strike-Slip and North-South maximum horizontal stress (S Hmax ) azimuth) the faults are fairly stable, and tensile hydrofracturing of the caprock would be expected before fault reactivation. In most of the analyzed cases, the critical pressure perturbation needed for reactivation is above 13 MPa, which was the limiting pressure increase before reaching the fracture pressure. Faults were found to be ~ 20% less stable when considering plausible variations in the orientation of S Hmax . In those cases, fault reactivation could be expected before caprock failure if injection continued, posing risks of induced seismicity, CO 2 leakage and/or contamination of the gas producing reservoir. Finally, a potential structural component in the compartmentalization and fluid migration is difficult to assess due to stress orientation uncertainty.

54 ENVIRONMENTAL SCIENCES↗

Recommended Practices for Managing Induced Seismicity Risk Associated with Geologic Carbon Storage

The geologic storage of carbon dioxide (CO 2 ) is one method to help reduce or eliminate atmospheric CO 2 emissions. The sequestered CO 2 is originally captured from the atmosphere or from a stationary industrial source and subsequently injected into a deep subsurface porous rock formation. To facilitate the successful deployment of field scale carbon storage projects, the U.S. Department of Energy (DOE) is developing tools and protocols for defensible, science-based frameworks to quantify and mitigate risks associated with the long-term storage of CO 2 . This protocol specifically addresses the risk of induced seismicity due to injection in a geologic carbon storage (GCS) site. This integrated and risk-based protocol is a product of the U.S. DOE Fossil Energy’s National Risk Assessment Partnership (NRAP), a multi-year collaborative research effort of Los Alamos National Laboratory (LANL), Lawrence Berkeley National Laboratory (LBNL), Lawrence Livermore National Laboratory (LLNL), National Energy Technology Laboratory (NETL), and Pacific Northwest National Laboratory (PNNL). These recommended practices describe a set of 7 steps to evaluate, manage, communicate, and mitigate the risk of induced seismicity at GCS sites. The base methodology of the recommended practices follows a framework similar to the $\textit{Protocol for Addressing Induced Seismicity Associated with Enhanced Geothermal Systems}$ (Majer et al., 2012), developed for the Geothermal Technology Office of the U.S. DOE. These recommended practices present a framework to systematically assess the induced seismicity risk and quantify the associated uncertainties. These recommendations are based on current research and are sufficiently general to allow for modification and application to a variety of different types of sites. The substance of the recommended practices contained herein includes both technical and non-technical issues, and covers all operational stages of the GCS project lifecycle. They start at the preliminary risk assessment phase, continue through site assessment and characterization, include best practice communication and seismic monitoring plan methodologies, discuss the evaluation and mitigation of seismic hazard and risk, and closes with an exploration of operational management plans, which conclude when the induced seismicity risk abates back to background level. The focus of these recommendations is on actively managing the risks associated with induced seismicity by developing an actionable risk management plan that starts at the project proposal stage and continues through site closure through an iterative assessment and improvement process. The audience of this document is expected to include all interested stakeholders (e.g., operators, project developers, regulators, and the general public) and is expressly written to be accessible to this broad range of partners. This document is intended to disseminate knowledge gained through recent advances in the science of induced seismicity hazard and risk assessments, to provide updates based on recent experience gained by similar corollary injection-induced seismicity cases, and most importantly to establish a uniform framework to carry out a successful induced seismicity risk management plan for carbon storage projects in the future. These recommendations do not directly address any domestic or international regulations or standards. A complementary NRAP report makes recommendations for the assessment and management of environmental subsurface risks associated with unwanted fluid migration at GCS sites (Thomas et al., 2021) and should be referred to in order to address those additional GCS site risks

58 GEOSCIENCES↗

Mars weathering analogs - Secondary mineralization in Antarctic basalts

Alkalic basalt samples from Ross Island, Antarctica, are evaluated as terrestrial analogs to weathered surface materials on Mars. Secondary alteration in the rocks is limited to pneumatolytic oxidation of igneous minerals and glass, rare groundmass clay and zeolite mineralization, and hydrothermal minerals coating fractures and vesicle surfaces. Hydrothermal mineral assemblages consist mainly of K-feldspar, zeolites (phillipsite and chabazite), calcite, and anhydrite. Low alteration rates are attributed to cold and dry environmental factors common to both Antarctica and Mars. It is noted that mechanical weathering (aeolian abrasion) of Martian equivalents to present Antarctic basalts would yield minor hydrothermal minerals and local surface fines composed of primary igneous minerals and glass but would produce few hydrous products, such as palagonite, clay or micas. It is thought that leaching of hydrothermal vein minerals by migrating fluids and redeposition in duricrust deposits may represent an alternate process for incorporating secondary minerals of volcanic origin into Martian surface fines.

Berkley, J. L.↗

Impulsive Injection for Compressor Stator Separation Control

Flow control using impulsive injection from the suction surface of a stator vane has been applied in a low speed axial compressor. Impulsive injection is shown to significantly reduce separation relative to steady injection for vanes that were induced to separate by an increase in vane stagger angle of 4 degrees. Injected flow was applied to the airfoil suction surface using spanwise slots pitched in the streamwise direction. Injection was limited to the near-hub region, from 10 to 36 percent of span, to affect the dominant loss due to hub leakage flow. Actuation was provided externally using high-speed solenoid valves closely coupled to the vane tip. Variations in injected mass, frequency, and duty cycle are explored. The local corrected total pressure loss across the vane at the lower span region was reduced by over 20 percent. Additionally, low momentum fluid migrating from the hub region toward the tip was effectively suppressed resulting in an overall benefit which reduced corrected area averaged loss through the passage by 4 percent. The injection mass fraction used for impulsive actuation was typically less than 0.1 percent of the compressor through flow.

Culley, Dennis E.↗

Potentially Habitable Ancient Environments in Gusev Crater, Mars

Habitable environments must sustain liquid water at least intermittently and also provide both chemical building blocks and useful sources of energy for life. Observations by Spirit rover indicate that conditions have probably been too dry to sustain life, at least since the emplacement of the extensive basalts that underlie the plains around the Columbia Memorial Station landing site. Local evidence of relatively minor aqueous alteration [1] probably occurred under conditions where the activity of water was too low to sustain biological processes as we know them. In contrast, multiple bedrock units in West Spur and Husband Hill in the Columbia Hills have been extensively altered. Patterns of elemental abundances are consistent with aqueous processes involving migrating fluids [2]. Fe in several of these units has been extensively oxidized [3]. Conceivably any microbiota present during the aqueous alteration of these rocks might have obtained energy from Fe oxidation. Spirit discovered olivine-rich ultramafic rocks during her descent from Husband Hill southward into Inner Basin. Alteration of similar ultramafic rocks on Earth can yield H2 that can provide both energy and reducing power for microorganisms. Spirit's discovery of deposits rich in ferric sulfate is consistent with the aqueous dissolution and/or alteration of olivine under acidic conditions [2] such as those associated with hydrothermal activity. The oxidation of iron and sulfur that can accompany such activity can be an energy source for life. Hydrothermal systems on Earth that sustain either acidic [4] or neutral to alkaline fluids [5] have been shown to provide this energy. Collectively the observations by Spirit rover are consistent with the possibility that habitable environments existed in Gusev crater at least intermittently in the distant geologic past.

Fe oxidation↗

Project Methods to Enhance Wellbore Cement Integrity with Microbially-Induced Calcite Precipitation (MICP) (Final Scientific/Technical Report)

The goal of this project was to develop improved methods for sealing compromised wellbore cement in leaking oil and gas wells, thereby reducing the risk of unwanted upward fluid migration. Novel methods for improving wellbore integrity, such as microbially induced calcite precipitation (MICP), can reduce leakage potential, improve the safety of fossil fuel extraction, improve the public perception of hydraulic fracturing, and promote environmentally-prudent unconventional oil and gas development. Microbes, with the urease enzyme, can catalyze the chemical reaction of urea hydrolysis to induce the precipitation of calcium carbonate which can be used as a cementitious material to seal leakage pathways. In this project, methods to promote robust bio-composite cementitious materials were designed and tested in the laboratory. Scale-up of those methods were tested in meso-scale reactor systems and in field applications. In this report, in Section One, we describe laboratory efforts to develop injection strategies to promote precipitation in wellbore analogs and determine the strength of the bio-composite cements as compared to fine cement. In Section Two, we describe the efforts to scale up the work and study the use of materials that can be used in field application, for example exploring the use of calcium chloride ice melt or urea fertilizer as source chemicals. In Section Three, the three field trials (methods and results) performed as part of the project are described and summarized. At the end of the report is a comprehensive summary and conclusion section which highlights the key findings of the project. The work performed during this project significantly advanced the technology readiness level (TRL) of the MICP wellbore sealing strategy.

02 PETROLEUM↗

Methods to Enhance Wellbore Cement Integrity with Microbially-Induced Calcite Precipitation (MICP) (Final Scientific/ Technical Report)

The goal of this project was to develop improved methods for sealing compromised wellbore cement in leaking oil and gas wells, thereby reducing the risk of unwanted upward fluid migration. Novel methods for improving wellbore integrity, such as microbially induced calcite precipitation (MICP), can reduce leakage potential, improve the safety of fossil fuel extraction, improve the public perception of hydraulic fracturing, and promote environmentally-prudent unconventional oil and gas development. Microbes, with the urease enzyme, can catalyze the chemical reaction of urea hydrolysis to induce the precipitation of calcium carbonate which can be used as a cementitious material to seal leakage pathways. In this project, methods to promote robust bio-composite cementitious materials were designed and tested in the laboratory. Scale-up of those methods were tested in meso-scale reactor systems and in field applications. In this report, in Section One, we describe laboratory efforts to develop injection strategies to promote precipitation in wellbore analogs and determine the strength of the bio-composite cements as compared to fine cement. In Section Two, we describe the efforts to scale up the work and study the use of materials that can be used in field application, for example exploring the use of calcium chloride ice melt or urea fertilizer as source chemicals. In Section Three, the three field trials (methods and results) performed as part of the project are described and summarized. At the end of the report is a comprehensive summary and conclusion section which highlights the key findings of the project. The work performed during this project significantly advanced the technology readiness level (TRL) of the MICP wellbore sealing strategy.

03 NATURAL GAS↗

Multimodal Mass Spectrometry Imaging (MSI) of Archean and Jurassic Geologic Samples

Current geochemical analytical techniques such as gas chromatography-mass spectrometry (GC-MS and $G\acute{C}GC-MS$) can effectively determine the composition and structure of the organic biosignatures within a sample but cannot resolve the spatial distribution of organic biosignatures within rocks or sediments. The spatial distribution can be used to determine the character of the organic biosignatures [1], which can be indigenous (deposited with host rocks), non-indigenous (incorporated after deposition via fluid migration), or contaminant. Determining the character of organic biosignatures is critical for ancient samples [2] and will be critical if organics are observed in samples returned from Mars [3].Fs-LDPI-MS has the ability to map organic compounds across the surface of samples at 2 - 10 μm lateral resolution. Furthermore, fs-LDPI-MS can be used to carry out multiple analyses in the same location for micron-scale analysis of previously buried material [4]. We used fs-LDPI-MS to examine a ~164 million year old organic-rich mudstone from SW England (14.2 wt. % total organic carbon) [5] and determined the spatial distribution of likely indigenous components buried below potentially contaminated surface layers.We then used ToF-SIMS to re-analyze the mudstone to directly compare ToF-SIMS to fs-LDPI-MS datasets, and to analyze a series of ~2.7 billion year old geologic samples from Timmins, ON, CA [6]. Ref. [6] previously analyzed the Archean samples and observed a series of archaeal biomarkers, as well as hopanes and steranes. Using ToF-SIMS analysis, we were able to detect hopanes and steranes in the mudstone samples, but not in the Archean samples indicating that the hopanes and steranes are most likely contaminants in the Archean samples. We also did not observe the archaeal biomarkers; however, this may be from the lack of molecular ion preservation during ToF-SIMS.

Pasterski, Michael↗

Imaging of a fluid injection process using geophysical data — A didactic example

In many subsurface industrial applications, fluids are injected into or withdrawn from a geologic formation. It is of practical interest to quantify precisely where, when, and by how much the injected fluid alters the state of the subsurface. Routine geophysical monitoring of such processes attempts to image the way that geophysical properties, such as seismic velocities or electrical conductivity, change through time and space and to then make qualitative inferences as to where the injected fluid has migrated. The more rigorous formulation of the time-lapse geophysical inverse problem forecasts how the subsurface evolves during the course of a fluid-injection application. Using time-lapse geophysical signals as the data to be matched, the model unknowns to be estimated are the multiphysics forward-modeling parameters controlling the fluid-injection process. Properly reproducing the geophysical signature of the flow process, subsequent simulations can predict the fluid migration and alteration in the subsurface. The dynamic nature of fluid-injection processes renders imaging problems more complex than conventional geophysical imaging for static targets. This work intents to clarify the related hydrogeophysical parameter estimation concepts.

58 GEOSCIENCES↗

The Role of Capillary Hysteresis and Pore-Scale Heterogeneity in Limiting the Migration of Buoyant Immiscible Fluids in Porous Media

Understanding the main mechanisms affecting long-term migration and redistribution of injected CO 2 in geological carbon storage is needed for developing predictive models to assess environmental risks and designing monitoring schemes. Preparation of a postinjection site care plan is required for CO 2 injection wells, including monitoring of pressure changes and injected CO 2 plume. Knowledge gaps exist regarding assessment of postinjection monitoring timeframes for the CO 2 plume because the processes driving long-term CO 2 plume migration and trapping are not fully understood. In the postinjection stage of geological carbon storage, redistribution of CO 2 occurs mainly due to buoyancy and capillary forces. This work presents experimental and modeling studies to investigate processes contributing to postinjection plume distribution and stabilization. We conducted a flow cell experiments (0.5 m × 0.05 m × 0.01 m) with two immiscible fluid phases in a glass bead porous medium to study postinjection plume behavior. We employed a hysteretic macroscopic two-phase flow model to interpret the experimental results and to understand main processes leading to plume stabilization. Our findings show that capillary pressure hysteresis explains the experimentally observed plume shape and redistribution at early postinjection stages; however, the long-term plume migration and eventual plume stabilization can only be represented when in addition microscale heterogeneity is accounted for. Results also show that plume stabilization can be extremely slow and that the migration of the plume front can occur through multiple intermittent bursts over long times. Here, further studies are needed to understand implications of the results for more realistic porous media and large-scale storage reservoirs.

58 GEOSCIENCES↗

Unconventional Resources Annual FY13 Format

The objective of the UCR research portfolio was to develop research products that address safety and environmental concerns associated with shale gas development in four primary areas: (1) fugitive air emissions; (2) produced waste management; (3) subsurface migration of gas and fluids; and (4) ground motion associated with unconventional resource development. The UCR portfolio consisted of thirteen projects that leveraged a combination of field, experimental, modeling, and data mining and compilation approaches with the goal of building an understanding of how geologic and environmental systems respond to shale gas development.

03 NATURAL GAS↗

Environmental Impact Analysis on the Hydraulic Fracture Test Site (HFTS)

Objective The Hydraulic Fracture Test Site (HFTS) provided a platform to test new extraction and production techniques and technologies to understand fracture geometry and increase the efficiency of shale hydrocarbon production. Eleven test wells were drilled in the Upper and Middle Wolfcamp formations, hydraulically fractured, and produced. Air quality, groundwater quality, and produced water chemistry and microbiology were monitored through the duration of the field experiment and one year into production. Methods BTEX, methane, VOCs, SOx, NOx, and PM 10 were measured 1,000 ft up-wind and 1,000 ft down-wind of the HFTS experiment before operations began, during hydraulic fracturing, flowback, and several months into production to evaluate operational impact on local air quality. The underlying Edward-Trinity Plateau aquifer was monitored using 5 groundwater wells within 2 miles of the HFTS pad; BTEX, methane, petroleum hydrocarbons, and a comprehensive suite of anions and metals were analyzed from samples taken before operations began, during hydraulic fracturing, flowback, and one year after production. Water produced from 3 of the 11 HFTS wells was analyzed for chemical and microbiological properties 1.5 years into production. Observations There was no significant impact to air quality from HFTS operations, although elevated BTEX concentrations were measured 1,000 ft. away from the well-pads during the flowback period. We detected no migration of hydrocarbon or fracture fluid chemical migration into the Edward-Trinity Plateau aquifer. Source waters used for hydraulic fracturing contained naturally occurring high concentrations (~500ppm) of sulfate. Rapid microbially induced corrosion was detected in several wells, leading to biocide dosing. Microbiological populations were significantly altered by biocide treatment, but still continued to increase in population size six months after application. Significance After hydraulic fracturing, detailed chemical and microbiological analysis provides evidence for microbiologicallymediated sub-surface transformations of supplied sulfate and organic carbon into sulfides. This report discusses air quality, water quality, and produced water analytical results for the HFTS experiment and further implications for the unconventional oil and gas industry.

Eisenlord, Sarah↗

Multicomponent Equilibrium Models for Testing Geothermometry Approaches

Geothermometry is an important tool for estimating deep reservoir temperature from the geochemical composition of shallower and cooler waters. The underlying assumption of geothermometry is that the waters collected from shallow wells and seeps maintain a chemical signature that reflects equilibrium in the deeper reservoir. Many of the geothermometers used in practice are based on correlation between water temperatures and composition or using thermodynamic calculations based a subset (typically silica, cations or cation ratios) of the dissolved constituents. An alternative approach is to use complete water compositions and equilibrium geochemical modeling to calculate the degree of disequilibrium (saturation index) for large number of potential reservoir minerals as a function of temperature. We have constructed several “forward” geochemical models using The Geochemist’s Workbench to simulate the change in chemical composition of reservoir fluids as they migrate toward the surface. These models explicitly account for the formation (mass and composition) of a steam phase and equilibrium partitioning of volatile components (e.g., CO2, H2S, and H2) into the steam as a result of pressure decreases associated with upward fluid migration from depth. We use the synthetic data generated from these simulations to determine the advantages and limitations of various geothermometry and optimization approaches for estimating the likely conditions (e.g., temperature, pCO2) to which the water was exposed in the deep subsurface. We demonstrate the magnitude of errors that can result from boiling, loss of volatiles, and analytical error from sampling and instrumental analysis. The estimated reservoir temperatures for these scenarios are also compared to conventional geothermometers. These results can help improve estimation of geothermal resource temperature during exploration and early development.

15 GEOTHERMAL ENERGY↗

Depressurization-Induced Fines Migration in Sediments Containing Methane Hydrate: X-Ray Computed Tomography Imaging Experiments

Depressurization of hydrate-bearing sediments (HBS) can cause the movement of fine particles, and in turn, such fines migration affects fluid flow and mechanical behavior of sediments, ultimately affecting long-term hydrocarbon production and wellbore stability. In this work, we investigate how and to what extent depressurization of HBS causes fines migration using X-ray computed tomography (CT) imaging. Methane hydrate was synthesized in sediments with 10% fines content (FC), composed of sands with silt and/or clay, and the hydrate-bearing samples were stepwisely depressurized while acquiring CT images. The CT images were analyzed to quantify the spatial changes in FC in the host sediment and thus to capture the fines migration during depressurization. It was found that the FC changes began occurring from the hydrate dissociation regions. This confirms that the multiphase flow caused by depressurization accompanies fines migration. Depressurization of HBS with a hydrate saturation of ~20–40% caused FC reduction from ~10% to ~6–9%, and the extent of fines migration differed with the particle sizes of the host sands and the types of fines. It was found that fines migration was more pronounced with coarse sands and with silty fines. Such observed level of FC reduction is estimated to increase sediment permeability by several factors based on the Kozeny-type permeability model. In conclusion, our results support the notion that the extent of fines migration and its effect on fluid flow behavior need to be assessed in consideration of physical properties of host sediment and fine particles to identify optimum depressurization strategies.

42 ENGINEERING↗

Reactive Transport Simulation of Fracture Channelization and Transmissivity Evolution

Underground fractures serve as flow conduits, and they may produce unwanted migration of water and other fluids in the subsurface. An example is the migration and leakage of greenhouse gases in the context of geologic carbon sequestration. This study has generated new understanding about how acids erode carbonate fracture surfaces and the positive feedback between reaction and flow. A two-dimensional reactive transport model was developed and used to investigate the extent to which geochemical factors influence fracture permeability and transmissivity evolution in carbonate rocks. The only mineral modeled as reactive is calcite, a fast-reacting mineral that is abundant in subsurface formations. The X-ray computed tomography dataset from a previous experimental study of fractured cores exposed to carbonic acid served as a testbed to benchmark the model simulation results. The model was able to capture not only erosion of fracture surfaces but also the specific phenomenon of channelization, which produces accelerating transmissivity increase. Results corroborated experimental findings that higher reactivity of the influent solution leads to strong channelization without substantial mineral dissolution. Simulations using mineral maps of calcite in a specimen of Amherstburg limestone demonstrated that mineral heterogeneity can either facilitate or suppress the development of flow channels depending on the spatial patterns of reactive mineral. In these cases, fracture transmissivity may increase rapidly, increase slowly, or stay constant, and for all these possibilities, the calcite mineral continues to dissolve. Collectively, these results illustrate that fluid chemistry and mineral spatial patterns need to be considered in predictions of reaction-induced fracture alteration and risks of fluid migration.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Multiphase Fluid Flow in Deformable Variable-Aperture Fractures (Final Report, February 1, 2009 – January 31, 2014)

Fractures provide flow paths that can potentially lead to fast migration of fluids or contaminants. A number of energy-­related applications involve fluid injections that significantly perturb both the pressures and chemical composition of subsurface fluids. These perturbations can cause both mechanical deformation and chemical alteration of host rocks with potential for significant changes in permeability. In fractured rock subjected to coupled chemical and mechanical stresses, it can be difficult to predict the sign of permeability changes, let alone the magnitude. This project integrated experimental and computational studies to improve mechanistic understanding of these coupled processes and develop and test predictive models and monitoring techniques. The project involved three major components: (1) study of two-­phase flow processes involving mass transfer between phases and dissolution of minerals along fracture surfaces (Detwiler et al., 2009; Detwiler, 2010); (2) study of fracture dissolution in fractures subjected to normal stresses using experimental techniques (Ameli, et al., 2013; Elkhoury et al., 2013; Elkhoury et al., 2014) and newly developed computational models (Ameli, et al., 2014); (3) evaluation of electrical resistivity tomography (ERT) as a method to detect and quantify gas leakage through a fractured caprock (Breen et al., 2012; Lochbuhler et al., 2014). The project provided support for one PhD student (Dr. Pasha Ameli; 2009-­2013) and partially supported a post-­doctoral scholar (Dr. Jean Elkhoury; 2010-­2013). In addition, the project provided supplemental funding to support collaboration with Dr. Charles Carrigan at Lawrence Livermore National Laboratory in connection with (3) and supported one MS student (Stephen Breen; 2011-­2013). Major results from each component of the project include the following: (1) Mineral dissolution in fractures occupied by two fluid phases (e.g., oil-­water or water-­CO 2 ) causes changes in local capillary forces and redistribution of fluids. These coupled processes enhance channel formation and the potential for development of fast flow paths through fractures. (2) Dissolution in fractures subjected to normal stress can result in behaviors ranging from development of dissolution channels and rapid permeability increases to fracture healing and significant permeability decreases. The timescales associated with advective transport of dissolved ions in the fracture, mineral dissolution rates, and diffusion within the adjacent porous matrix dictate the sign and magnitude of the resulting permeability changes. Furthermore, a high--resolution mechanistic model that couples elastic deformation of contacts and aperture-­dependent dissolution rates predicts the range of observed behaviors reasonably well. (3) ERT has potential as a tool for monitoring gas leakage in deep formations. Using probabilistic inversion methods further enhances the results by providing uncertainty estimates of inverted parameters.

02 PETROLEUM↗