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Capturing Carbonation: Understanding Kinetic Complexities through a New Era of Electron Microscopy

Deitz, Julia D.; Dewers, Thomas D.; Heath, Jason; Polonsky, Andrew P.; Perry, Daniel L.

Cryogenic plasma focused ion beam (PFIB) electron microscopy analysis is applied to visualizing ex situ (surface industrial) and in situ (subsurface geologic) carbonation products, to advance understanding of carbonation kinetics. Ex situ carbonation is investigated using NIST fly ash standard #2689 exposed to aqueous sodium bicarbonate solutions for brief periods of time. In situ carbonation pathways are investigated using volcanic flood basalt samples from Schaef et al. (2010) exposed to aqueous CO2 solutions by them. The fly ash reaction products at room temperature show small amounts of incipient carbonation, with calcite apparently forming via surface nucleation. Reaction products at 75° C show beginning stages of an iron carbonate phase, e.g., siderite or ankerite, common phases in subsurface carbon sequestration environments. This may suggest an alternative to calcite in carbonation low calcium-bearing fly ashes. Flood basalt carbonation reactions show distinct zonation with high calcium and calcium-magnesium bearing zones alternating with high iron-bearing zones. The calcium-magnesium zones are notable with occurrence of localized pore space. Oscillatory zoning in carbonate minerals is distinctly associated with far-from-equilibrium conditions where local chemical environments fluctuate via a coupling of reaction with transport. The high porosity zones may reflect a precursor phase (e.g., aragonite) with higher molar volume that then “ripens” to the high-Mg calcite phase-plus-porosity. These observations reveal that carbonation can proceed with evolving local chemical environments, formation and disappearance of metastable phases, and evolving reactive surface areas. Together this work shows that future application of cryo-PFIB in carbonation studies would provide advanced understanding of kinetic mechanisms for optimizing industrial-scale and commercial-scale applications.

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FY2022 Progress on Imbibition Testing in Containment Science

Kuhlman, Kristopher L.; Good, Forest T.; LaForce, Tara; Heath, Jason

Estimation of two-phase fluid flow properties is important to understand and predict water and gas movement through the vadose zone for agricultural, hydrogeological, and engineering applications, such as for vapor-phase contaminant transport and/or containment of noble gases in the subsurface. In this second progress report of FY22, we present two ongoing activities related to imbibition testing on volcanic rock samples. We present the development of a new analytical solution predicting the temperature response observed during imbibition into dry samples, as discussed in our previous first progress report for FY22. We also illustrate the use of a multi-modal capillary pressure distribution to simulate both early- and late-time imbibition data collected on tuff core that can exhibit multiple pore types. These FY22 imbibition tests were conducted for an extended period (i.e., far beyond the time required for the wetting front to reach the top of the sample), which is necessary for parameter estimation and characterization of two different pore types within the samples.

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FY22 Progress on Multicontinuum Methods in Containment

Kuhlman, Kristopher L.; Mills, Melissa M.; Heath, Jason; Paul, Matthew J.

Estimation of two-phase fluid flow properties is important to understand and predict water and gas movement through the vadose zone for agricultural, hydrogeological, and engineering applications, such as containment transport and/or containment of gases in the subsurface. To estimate rock fluid flow properties and subsequently predict physically realistic processes such as patterns and timing of water, gas, and energy (e.g., heat) movement in the subsurface, laboratory spontaneous water imbibition with simultaneous temperature measurement and numerical modeling methods are presented in the FY22 progress report. A multiple-overlapping-continua conceptual model is used to explain and predict observed complex multi-phenomenological laboratory test behavior during spontaneous imbibition experiments. This report primarily addresses two complexities that arise during the experiments: 1) capturing the late-time behavior of spontaneous imbibition tests with dual porosity; and 2) understanding the thermal perturbation observed at or ahead of the imbibing wetting front, which are associated with adsorption of water in initially dry samples. We use numerical approaches to explore some of these issues, but also lay out a plan for further laboratory experimentation and modeling to best understand and leverage these unique observations.

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Parameter estimation from spontaneous imbibition into volcanic tuff

Vadose Zone Journal

Kuhlman, Kristopher L.; Mills, Melissa M.; Heath, Jason; Paul, Matthew J.; Wilson, Jennifer E.; Bower, John E.

Two-phase fluid flow properties underlie quantitative prediction of water and gas movement, but constraining these properties typically requires multiple time-consuming laboratory methods. The estimation of two-phase flow properties (van Genuchten parameters, porosity, and intrinsic permeability) is illustrated in cores of vitric nonwelded volcanic tuff using Bayesian parameter estimation that fits numerical models to observations from spontaneous imbibition experiments. The uniqueness and correlation of the estimated parameters is explored using different modeling assumptions and subsets of the observed data. The resulting estimation process is sensitive to both moisture retention and relative permeability functions, thereby offering a comprehensive method for constraining both functions. The data collected during this relatively simple laboratory experiment, used in conjunction with a numerical model and a global optimizer, result in a viable approach for augmenting more traditional capillary pressure data obtained from hanging water column, membrane plate extractor, or mercury intrusion methods. This method may be useful when imbibition rather than drainage parameters are sought, when larger samples (e.g., including heterogeneity or fractures) need to be tested that cannot be accommodated in more traditional methods, or when in educational laboratory settings.

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Multiscale assessment of caprock integrity for geologic carbon storage in the pennsylvanian farnsworth unit, Texas, USA

Energies

Trujillo, Natasha; Rose-Coss, Dylan; Heath, Jason; Dewers, Thomas D.; Ampomah, William; Mozley, Peter S.; Cather, Martha

Leakage pathways through caprock lithologies for underground storage of CO2 and/or enhanced oil recovery (EOR) include intrusion into nano-pore mudstones, flow within fractures and faults, and larger-scale sedimentary heterogeneity (e.g., stacked channel deposits). To assess multiscale sealing integrity of the caprock system that overlies the Morrow B sandstone reservoir, Farnsworth Unit (FWU), Texas, USA, we combine pore-to-core observations, laboratory testing, well logging results, and noble gas analysis. A cluster analysis combining gamma ray, compressional slowness, and other logs was combined with caliper responses and triaxial rock mechanics testing to define eleven lithologic classes across the upper Morrow shale and Thirteen Finger limestone caprock units, with estimations of dynamic elastic moduli and fracture breakdown pressures (minimum horizontal stress gradients) for each class. Mercury porosimetry determinations of CO2 column heights in sealing formations yield values exceeding reservoir height. Noble gas profiles provide a “geologic time-integrated” assessment of fluid flow across the reservoir-caprock system, with Morrow B reservoir measurements consistent with decades-long EOR water-flooding, and upper Morrow shale and lower Thirteen Finger limestone values being consistent with long-term geohydrologic isolation. Together, these data suggest an excellent sealing capacity for the FWU and provide limits for injection pressure increases accompanying carbon storage activities.

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Spontaneous Imbibition Tests and Parameter Estimation in Volcanic Tuff

Kuhlman, Kristopher L.; Mills, Melissa M.; Heath, Jason; Paul, Matthew J.; Wilson, Jennifer E.; Bower, John E.

We present a dynamic laboratory spontaneous imbibition test and interpretation method, demonstrated on volcanic tuff samples from the Nevada National Security Site. The method includes numerical inverse modeling to quantify uncertainty of estimated two-phase fluid flow properties. As opposed to other approaches requiring multiple different laboratory instruments, the dynamic imbibition method simultaneously estimates capillary pressure and relative permeability from one test apparatus.

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Multicontinuum Flow Models for Assessing Two-Phase Flow in Containment Science

Kuhlman, Kristopher L.; Heath, Jason

We present a new pre-processor tool written in Python that creates multicontinuum meshes for PFLOTRAN to simulate two-phase flow and transport in both the fracture and matrix continua. We discuss the multicontinuum modeling approach to simulate potentially mobile water and gas in the fractured volcanic tuffs at Aqueduct Mesa, at the Nevada National Security Site.

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Heterogeneous multiphase flow properties of volcanic rocks and implications for noble gas transport from underground nuclear explosions

Vadose Zone Journal

Heath, Jason; Kuhlman, Kristopher L.; Broome, Scott T.; Wilson, Jennifer E.; Malama, Bwalya

Of interest to the Underground Nuclear Explosion Signatures Experiment are patterns and timing of explosion-generated noble gases that reach the land surface. The impact of potentially simultaneous flow of water and gas on noble gas transport in heterogeneous fractured rock is a current scientific knowledge gap. This article presents field and laboratory data to constrain and justify a triple continua conceptual model with multimodal multiphase fluid flow constitutive equations that represents host rock matrix, natural fractures, and induced fractures from past underground nuclear explosions (UNEs) at Aqueduct and Pahute Mesas, Nevada National Security Site, Nevada, USA. Capillary pressure from mercury intrusion and direct air–water measurements on volcanic tuff core samples exhibit extreme spatial heterogeneity (i.e., variation over multiple orders of magnitude). Petrographic observations indicate that heterogeneity derives from multimodal pore structures in ash-flow tuff components and post-depositional alteration processes. Comparisons of pre- and post-UNE samples reveal different pore size distributions that are due in part to microfractures. Capillary pressure relationships require a multimodal van Genuchten (VG) constitutive model to best fit the data. Relative permeability estimations based on unimodal VG fits to capillary pressure can be different from those based on bimodal VG fits, implying the choice of unimodal vs. bimodal fits may greatly affect flow and transport predictions of noble gas signatures. The range in measured capillary pressure and predicted relative permeability curves for a given lithology and between lithologies highlights the need for future modeling to consider spatially distributed properties.

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First-Round Testing of the Brine Availability Test in Salt (BATS) at the Waste Isolation Pilot Plant (WIPP)

Kuhlman, Kristopher L.; Mills, Melissa M.; Jayne, Richard S.; Herrick, Courtney G.; Choens, Robert C.; Nemer, Martin N.; Heath, Jason; Matteo, Edward N.; Xiong, Yongliang X.; Otto, Shawn O.; Dozier, Brian D.; Weaver, Doug W.; Stauffer, Phil S.; Guiltinan, Eric J.; Boukhalfa, Hakim B.; Rahn, Thom R.; Wu, Yuxin W.; Rutqvist, Jonny R.; Hu, Mengsu H.; Crandall, Dustin C.

Abstract not provided.

An Experimental Method to Measure Gaseous Diffusivity in Tight and Partially Saturated Porous Media via Continuously Monitored Mass Spectrometry

Transport in Porous Media

Paul, Matthew J.; Broome, Scott T.; Kuhlman, Kristopher L.; Feldman, Joshua D.; Heath, Jason

Detection of radioxenon and radioargon produced by underground nuclear explosions is one of the primary methods by which the Comprehensive Nuclear-Test–Ban Treaty (CTBT) monitors for nuclear activities. However, transport of these noble gases to the surface via barometric pumping is a complex process relying on advective and diffusive processes in a fractured porous medium to bring detectable levels to the surface. To better understand this process, experimental measurements of noble gas and chemical surrogate diffusivity in relevant lithologies are necessary. However, measurement of noble gas diffusivity in tight or partially saturated porous media is challenging due to the transparent nature of noble gases, the lengthy diffusion times, and difficulty maintaining consistent water saturation. Here, the quasi-steady-state Ney–Armistead method is modified to accommodate continuous gas sampling via effusive flow to a mass spectrometer. An analytical solution accounting for the cumulative sampling losses and induced advective flow is then derived. Experimental results appear in good agreement with the proposed theory, suggesting the presence of retained groundwater reduces the effective diffusivity of the gas tracers by 10–1000 times. Furthermore, by using a mass spectrometer, the method described herein is applicable to a broad range of gas species and porous media.

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Verification of a rapid mooring and foundation design tool

Proceedings of the Institution of Mechanical Engineers Part M: Journal of Engineering for the Maritime Environment

Weller, Sam D.; Hardwick, Jon; Gomez, Steven P.; Heath, Jason; Jensen, Richard P.; Mclean, Niall; Johanning, Lars

Marine renewable energy devices require mooring and foundation systems that suitable in terms of device operation and are also robust and cost effective. In the initial stages of mooring and foundation development a large number of possible configuration permutations exist. Filtering of unsuitable designs is possible using information specific to the deployment site (i.e. bathymetry, environmental conditions) and device (i.e. mooring and/or foundation system role and cable connection requirements). The identification of a final solution requires detailed analysis, which includes load cases based on extreme environmental statistics following certification guidance processes. Static and/or quasi-static modelling of the mooring and/or foundation system serves as an intermediate design filtering stage enabling dynamic time-domain analysis to be focused on a small number of potential configurations. Mooring and foundation design is therefore reliant on logical decision making throughout this stage-gate process. The open-source DTOcean (Optimal Design Tools for Ocean Energy Arrays) Tool includes a mooring and foundation module, which automates the configuration selection process for fixed and floating wave and tidal energy devices. As far as the authors are aware, this is one of the first tools to be developed for the purpose of identifying potential solutions during the initial stages of marine renewable energy design. While the mooring and foundation module does not replace a full design assessment, it provides in addition to suitable configuration solutions, assessments in terms of reliability, economics and environmental impact. This article provides insight into the solution identification approach used by the module and features the verification of both the mooring system calculations and the foundation design using commercial software. Several case studies are investigated: a floating wave energy converter and several anchoring systems. It is demonstrated that the mooring and foundation module is able to provide device and/or site developers with rapid mooring and foundation design solutions to appropriate design criteria.

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Heterogeneity, pore pressure, and injectate chemistry: Control measures for geologic carbon storage

International Journal of Greenhouse Gas Control

Dewers, Thomas D.; Eichhubl, Peter; Ganis, Ben; Gomez, Steven P.; Heath, Jason; Jammoul, Mohamad; Kobos, Peter H.; Liu, Ruijie; Major, Jonathan; Matteo, Edward N.; Newell, Pania; Rinehart, Alex; Sobolik, Steven R.; Stormont, John; Reda Taha, Mahmoud; Wheeler, Mary; White, Deandra

Desirable outcomes for geologic carbon storage include maximizing storage efficiency, preserving injectivity, and avoiding unwanted consequences such as caprock or wellbore leakage or induced seismicity during and post injection. To achieve these outcomes, three control measures are evident including pore pressure, injectate chemistry, and knowledge and prudent use of geologic heterogeneity. Field, experimental, and modeling examples are presented that demonstrate controllable GCS via these three measures. Observed changes in reservoir response accompanying CO2 injection at the Cranfield (Mississippi, USA) site, along with lab testing, show potential for use of injectate chemistry as a means to alter fracture permeability (with concomitant improvements for sweep and storage efficiency). Further control of reservoir sweep attends brine extraction from reservoirs, with benefit for pressure control, mitigation of reservoir and wellbore damage, and water use. State-of-the-art validated models predict the extent of damage and deformation associated with pore pressure hazards in reservoirs, timing and location of networks of fractures, and development of localized leakage pathways. Experimentally validated geomechanics models show where wellbore failure is likely to occur during injection, and efficiency of repair methods. Use of heterogeneity as a control measure includes where best to inject, and where to avoid attempts at storage. An example is use of waste zones or leaky seals to both reduce pore pressure hazards and enhance residual CO2 trapping.

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Statistical Inference for Porous Materials using Persistent Homology

Moon, Chul M.; Heath, Jason; Mitchell, Scott A.

We propose a porous materials analysis pipeline using persistent homology. We rst compute persistent homology of binarized 3D images of sampled material subvolumes. For each image we compute sets of homology intervals, which are represented as summary graphics called persistence diagrams. We convert persistence diagrams into image vectors in order to analyze the similarity of the homology of the material images using the mature tools for image analysis. Each image is treated as a vector and we compute its principal components to extract features. We t a statistical model using the loadings of principal components to estimate material porosity, permeability, anisotropy, and tortuosity. We also propose an adaptive version of the structural similarity index (SSIM), a similarity metric for images, as a measure to determine the statistical representative elementary volumes (sREV) for persistence homology. Thus we provide a capability for making a statistical inference of the uid ow and transport properties of porous materials based on their geometry and connectivity.

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Modeling Dynamic Helium Release as a Tracer of Rock Deformation

Journal of Geophysical Research: Solid Earth

Gardner, W.P.; Bauer, Stephen J.; Kuhlman, Kristopher L.; Heath, Jason

We use helium released during mechanical deformation of shales as a signal to explore the effects of deformation and failure on material transport properties. A dynamic dual-permeability model with evolving pore and fracture networks is used to simulate gases released from shale during deformation and failure. Changes in material properties required to reproduce experimentally observed gas signals are explored. We model two different experiments of 4He flow rate measured from shale undergoing mechanical deformation, a core parallel to bedding and a core perpendicular to bedding. We find that the helium signal is sensitive to fracture development and evolution as well as changes in the matrix transport properties. We constrain the timing and effective fracture aperture, as well as the increase in matrix porosity and permeability. Increases in matrix permeability are required to explain gas flow prior to macroscopic failure, and the short-term gas flow postfailure. Increased matrix porosity is required to match the long-term, postfailure gas flow. Our model provides the first quantitative interpretation of helium release as a result of mechanical deformation. The sensitivity of this model to changes in the fracture network, as well as to matrix properties during deformation, indicates that helium release can be used as a quantitative tool to evaluate the state of stress and strain in earth materials.

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The Gothic shale of the Pennsylvanian Paradox Formation Greater Aneth Field (Aneth Unit) Southeastern Utah U.S.A.: Seal for Hydrocarbons and Carbon Dioxide Storage

Heath, Jason; Dewers, Thomas D.; Chidsey, Thomas C.; Carney, Stephanie M.; Bereskin, S.R.

Greater Aneth oil field, Utah’s largest oil producer, was discovered in 1956 and has produced over 483 million barrels of oil. Located in the Paradox Basin of southeastern Utah, Greater Aneth is a stratigraphic trap producing from the Pennsylvanian (Desmoinesian) Paradox Formation. Because Greater Aneth is a mature, major oil field in the western U.S., and has a large carbonate reservoir, it was selected to demonstrate combined enhanced oil recovery and carbon dioxide storage. The Aneth Unit in the northwestern part of the field has produced over 160 million barrels of the estimated 386 million barrels of original oil in place—a 42% recovery rate. The large amount of remaining oil made the Aneth Unit ideal to enhance oil recovery by carbon dioxide flooding and demonstrate carbon dioxide storage capacity.

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Deep Borehole Field Test Laboratory and Borehole Testing Strategy

Kuhlman, Kristopher L.; Brady, Patrick V.; MacKinnon, R.J.; Heath, Jason; Herrick, Courtney G.; Jensen, Richard P.; Gardner, W.P.; Sevougian, Stephen D.; Bryan, Charles R.; Jang, Jay J.; Stein, Emily S.; Bauer, Stephen J.; Daley, Tom D.; Freifeld, Barry M.; Birkholzer, Jens T.; Spane, Frank A.

Deep Borehole Disposal (DBD) of high-level radioactive wastes has been considered an option for geological isolation for many years (Hess et al. 1957). Recent advances in drilling technology have decreased costs and increased reliability for large-diameter (i.e., ≥50 cm [19.7”]) boreholes to depths of several kilometers (Beswick 2008; Beswick et al. 2014). These advances have therefore also increased the feasibility of the DBD concept (Brady et al. 2009; Cornwall 2015), and the current field test design will demonstrate the DBD concept and these advances. The US Department of Energy (DOE) Strategy for the Management and Disposal of Used Nuclear Fuel and High-Level Radioactive Waste (DOE 2013) specifically recommended developing a research and development plan for DBD. DOE sought input or expression of interest from States, local communities, individuals, private groups, academia, or any other stakeholders willing to host a Deep Borehole Field Test (DBFT). The DBFT includes drilling two boreholes nominally 200m [656’] apart to approximately 5 km [16,400’] total depth, in a region where crystalline basement is expected to begin at less than 2 km depth [6,560’]. The characterization borehole (CB) is the smaller-diameter borehole (i.e., 21.6 cm [8.5”] diameter at total depth), and will be drilled first. The geologic, hydrogeologic, geochemical, geomechanical and thermal testing will take place in the CB. The field test borehole (FTB) is the larger-diameter borehole (i.e., 43.2 cm [17”] diameter at total depth). Surface handling and borehole emplacement of test package will be demonstrated using the FTB to evaluate engineering feasibility and safety of disposal operations (SNL 2016).

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Controls on Incomplete Mixing of Injected Raw Water and Brine in Strategic Petroleum Reserve Salt Caverns

Heath, Jason; Nemer, Martin N.; Chojnicki, Kirsten C.

Mixing of injected raw (undersaturated) water with brine in Strategic Petroleum Reserve (SPR) salt caverns affects the shape of cavern walls due to leaching. Cavern shape impacts cavern geomechanical stability and available volume for oil storage. Raw water injection occurs during initial solution mining of caverns, remedial leaching of caverns, and oil drawdown. Of interest are factors that control the degree of raw water-brine mixing and thereby the concentration of the aqueous fluid mixture that contacts the salt cavern walls. It is hypothesized that poorly-mixed fresh water could potentially cause undesirable and non-uniform leaching , for example, if buoyant poorly-mixed fresh water collects and preferentially leaches under the oil-brine interface . This report presents current understanding of controls on incomplete-to-complete mixing of raw water and brine, focusing on implications for SPR cavern leaching. In the context of mixing, we review the following: SPR leaching operations; models of leaching; field measurements of leaching and cavern shapes; and previous laboratory experiments of mixing and /or leaching performed at Sandia National Laboratories. We present recent laboratory experiments in 2014-2016 that focused explicitly on understanding controls of poor-to-well mixed conditions. We find that well-mixed conditions are expected for typical operating conditions of the SPR.

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An investigation of DTOcean foundation and anchor systems

Gomez, Steven P.; Jensen, Richard P.; Heath, Jason

This memo documents the mechanical loading analysis performed on the second set of DTOcean program WP4 foundation and anchor systems submodule design iterations [4]. Finite Element Analysis (FEA) simulations were performed to validate design requirements defined by Python based analytic simulations of the WP4 program Naval Facilities Engineering Command (NAVFAC) tool. This FEA procedure focuses on worst case loading scenarios on shallow gravity foundation and pile anchor designs produced by WP4. These models include a steel casing and steel anchor with soft clay surrounding the steel components respectively.

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An investigation of DTOcean foundation and anchor systems

Gomez, Steven P.; Jensen, Richard P.; Heath, Jason

This memo documents the mechanical loading analysis performed to date for the DTOcean program WP4 foundation and anchor systems submodule. FEA simulations were performed to validate design requirements defined by Python based analytic simulations of the WP4 program Naval Facilities Engineering Command (NAVFAC) tool. This FEA procedure focuses on worst case loading scenarios on direct mbedment anchor and suction caisson designs produced by WP4. These models include a steel casing and steel anchor with soft clay and dense sand surrounding the steel components respectively.

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Origin and heterogeneity of pore sizes in the Mount Simon Sandstone and Eau Claire Formation: Implications for multiphase fluid flow

Geosphere

Mozley, Peter S.; Heath, Jason; Dewers, Thomas D.; Bauer, Stephen J.

The Mount Simon Sandstone and Eau Claire Formation represent a potential reservoir-caprock system for wastewater disposal, geologic CO2 storage, and compressed air energy storage (CAES) in the Midwestern United States. A primary concern to site performance is heterogeneity in rock properties that could lead to nonideal injectivity and distribution of injected fluids (e.g., poor sweep efficiency). Using core samples from the Dallas Center domal structure, Iowa, we investigate pore characteristics that govern flow properties of major lithofacies of these formations. Methods include gas porosimetry and permeametry, mercury intrusion porosimetry, thin section petrography, and X-ray diffraction. The lithofacies exhibit highly variable intraformational and interformational distributions of pore throat and body sizes. Based on pore-throat size, there are four distinct sample groups. Micropore-throat-dominated samples are from the Eau Claire Formation, whereas the macropore-dominated, mesopore-dominated, and uniform-dominated samples are from the Mount Simon Sandstone. Complex paragenesis governs the high degree of pore and pore-throat size heterogeneity, due to an interplay of precipitation, nonuniform compaction, and later dissolution of cements. The cement dissolution event probably accounts for much of the current porosity in the unit. Mercury intrusion porosimetry data demonstrate that the heterogeneous nature of the pore networks in the Mount Simon Sandstone results in a greater than normal opportunity for reservoir capillary trapping of nonwetting fluids, as quantified by CO2 and air column heights that vary over three orders of magnitude, which should be taken into account when assessing the potential of the reservoir-caprock system for waste disposal (CO2 or produced water) and resource storage (natural gas and compressed air). Our study quantitatively demonstrates the significant impact of millimeter-scale to micron-scale porosity heterogeneity on flow and transport in reservoir sandstones.

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FY:15 Transport Properties of Run-of-Mine Salt Backfill ? Unconsolidated to Consolidated

Dewers, Thomas D.; Heath, Jason; Leigh, Christi D.

The nature of geologic disposal of nuclear waste in salt formations requires validated and verified two-phase flow models of transport of brine and gas through intact, damaged, and consolidating crushed salt. Such models exist in other realms of subsurface engineering for other lithologic classes (oil and gas, carbon sequestration etc. for clastics and carbonates) but have never been experimentally validated and parameterized for salt repository scenarios or performance assessment. Models for waste release scenarios in salt back-fill require phenomenological expressions for capillary pressure and relative permeability that are expected to change with degree of consolidation, and require experimental measurement to parameterize and validate. This report describes a preliminary assessment of the influence of consolidation (i.e. volume strain or porosity) on capillary entry pressure in two phase systems using mercury injection capillary pressure (MICP). This is to both determine the potential usefulness of the mercury intrusion porosimetry method, but also to enable a better experimental design for these tests. Salt consolidation experiments are performed using novel titanium oedometers, or uniaxial compression cells often used in soil mechanics, using sieved run-of-mine salt from the Waste Isolation Pilot Plant (WIPP) as starting material. Twelve tests are performed with various starting amounts of brine pore saturation, with axial stresses up to 6.2 MPa (~900 psi) and temperatures to 90°C. This corresponds to UFD Work Package 15SN08180211 milestone “FY:15 Transport Properties of Run-of-Mine Salt Backfill – Unconsolidated to Consolidated”. Samples exposed to uniaxial compression undergo time-dependent consolidation, or creep, to various degrees. Creep volume strain-time relations obey simple log-time behavior through the range of porosities (~50 to 2% as measured); creep strain rate increases with temperature and applied stress as expected. Mercury porosimetry is used to determine characteristic capillary pressure curves from a series of consolidation tests and show characteristic saturation-capillary pressure curves that follow the common van Genuchten (1978, 1980) formulation at low stresses. Higher capillary pressure data are suspect due to the large potential for sample damage, including fluid inclusion decrepitation and pore collapse. Data are supportive of use of the Leverett “J” function (Leverett, 1941) to use for scaling characteristic curves at different degrees of consolidation, but better permeability determinations are needed to support this hypothesis. Recommendations for further and refined testing are made with the goal of developing a self- consistent set of constitutive laws for granular salt consolidation and multiphase (brine-air) flow.

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Conceptual Design and Requirements for Characterization and Field Test Boreholes: Deep Borehole Field Test

Kuhlman, Kristopher L.; Brady, Patrick V.; MacKinnon, R.J.; Heath, Jason; Herrick, Courtney G.; Jensen, Richard P.; Rigali, Mark J.; Hadgu, Teklu H.; Sevougian, Stephen D.; Birkholzer, Jens T.; Freifeld, Barry M.; Daley, Tom D.

Deep Borehole Disposal (DBD) of high-level radioactive wastes has been considered an option for geological isolation for many years (Hess et al. 1957). Recent advances in drilling technology have decreased costs and increased reliability for large-diameter (i.e., ≥50 cm [19.7”]) boreholes to depths of several kilometers (Beswick 2008; Beswick et al. 2014). These advances have therefore also increased the feasibility of the DBD concept (Brady et al. 2009; Cornwall 2015), and the current field test, introduced herein, is a demonstration of the DBD concept and these advances.

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Appraisal of transport and deformation in shale reservoirs using natural noble gas tracers

Heath, Jason; Kuhlman, Kristopher L.; Robinson, David G.; Bauer, Stephen J.; Gardner, W.P.

This report presents efforts to develop the use of in situ naturally-occurring noble gas tracers to evaluate transport mechanisms and deformation in shale hydrocarbon reservoirs. Noble gases are promising as shale reservoir diagnostic tools due to their sensitivity of transport to: shale pore structure; phase partitioning between groundwater, liquid, and gaseous hydrocarbons; and deformation from hydraulic fracturing. Approximately 1.5-year time-series of wellhead fluid samples were collected from two hydraulically-fractured wells. The noble gas compositions and isotopes suggest a strong signature of atmospheric contribution to the noble gases that mix with deep, old reservoir fluids. Complex mixing and transport of fracturing fluid and reservoir fluids occurs during production. Real-time laboratory measurements were performed on triaxially-deforming shale samples to link deformation behavior, transport, and gas tracer signatures. Finally, we present improved methods for production forecasts that borrow statistical strength from production data of nearby wells to reduce uncertainty in the forecasts.

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Uniaxial creep as a control on mercury intrusion capillary pressure in consolidating rock salt

Dewers, Thomas D.; Heath, Jason; Leigh, Christi D.

The nature of geologic disposal of nuclear waste in salt formations requires validated and verified two - phase flow models of transport of brine and gas through intact, damaged, and consolidating crushed salt. Such models exist in oth er realms of subsurface engineering for other lithologic classes (oil and gas, carbon sequestration etc. for clastics and carbonates) but have never been experimentally validated and parameterized for salt repository scenarios or performance assessment. Mo dels for waste release scenarios in salt back - fill require phenomenological expressions for capillary pressure and relative permeability that are expected to change with degree of consolidation, and require experimental measurement to parameterize and vali date. This report describes a preliminary assessment of the influence of consolidation (i.e. volume strain or porosity) on capillary entry pressure in two phase systems using mercury injection capillary pressure (MICP). This is to both determine the potent ial usefulness of the mercury intrusion porosimetry method, but also to enable a better experimental design for these tests. Salt consolidation experiments are performed using novel titanium oedometers, or uniaxial compression cells often used in soil mech anics, using sieved run - of - mine salt from the Waste Isolation Pilot Plant (WIPP) as starting material. Twelve tests are performed with various starting amounts of brine pore saturation, with axial stresses up to 6.2 MPa (%7E900 psi) and temperatures to 90 o C. This corresponds to UFD Work Package 15SN08180211 milestone "FY:15 Transport Properties of Run - of - Mine Salt Backfill - Unconsolidated to Consolidated". Samples exposed to uniaxial compression undergo time - dependent consolidation, or creep, to various deg rees. Creep volume strain - time relations obey simple log - time behavior through the range of porosities (%7E50 to 2% as measured); creep strain rate increases with temperature and applied stress as expected. Mercury porosimetry is used to determine characteri stic capillary pressure curves from a series of consolidation tests and show characteristic saturation - capillary pressure curves that follow the common van Genuchten (1978, 1980) formulation at low stresses. Higher capillary pressure data are suspect due t o the large potential for sample damage, including fluid inclusion decrepitation and pore collapse. Data are supportive of use of the Leverett "J" function (Leverett, 1941) to use for scaling characteristic curves at different degrees of consolidation, but better permeability determinations are needed to support this hypothesis. Recommendations for further and refined testing are made with the goal of developing a self - consistent set of constitutive laws for granular salt consolidation and multiphase (brin e - air) flow.

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Multiporosity flow in fractured low-permeability rocks

Water Resources Research

Kuhlman, Kristopher L.; Malama, Bwalya; Heath, Jason

A multiporosity extension of classical double and triple-porosity fractured rock flow models for slightly compressible fluids is presented. The multiporosity model is an adaptation of the multirate solute transport model of Haggerty and Gorelick (1995) to viscous flow in fractured rock reservoirs. It is a generalization of both pseudo steady state and transient interporosity flow double-porosity models. The model includes a fracture continuum and an overlapping distribution of multiple rock matrix continua, whose fracture-matrix exchange coefficients are specified through a discrete probability mass function. Semianalytical cylindrically symmetric solutions to the multiporosity mathematical model are developed using the Laplace transform to illustrate its behavior. The multiporosity model presented here is conceptually simple, yet flexible enough to simulate common conceptualizations of double and triple-porosity flow. This combination of generality and simplicity makes the multiporosity model a good choice for flow modelling in low-permeability fractured rocks. Key Points: New conceptual model generalizing dual porosity flow in fractured rocks Multiporosity model is generalization of existing well-known models Semianalytical radially symmetric solutions presented for new conceptual model

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The Water, Energy, and Carbon Dioxide Sequestration Simulation Model (WECSsim). A user's manual

Kobos, Peter H.; Roach, Jesse D.; Klise, Geoffrey T.; Heath, Jason; Dewers, Thomas D.; Malczynski, Leonard A.; Borns, David J.

The Water, Energy, and Carbon Sequestration Simulation Model (WECSsim) is a national dynamic simulation model that calculates and assesses capturing, transporting, and storing CO2 in deep saline formations from all coal and natural gas-fired power plants in the U.S. An overarching capability of WECSsim is to also account for simultaneous CO2 injection and water extraction within the same geological saline formation. Extracting, treating, and using these saline waters to cool the power plant is one way to develop more value from using saline formations as CO2 storage locations. WECSsim allows for both one-to-one comparisons of a single power plant to a single saline formation along with the ability to develop a national CO2 storage supply curve and related national assessments for these formations. This report summarizes the scope, structure, and methodology of WECSsim along with a few key results. Developing WECSsim from a small scoping study to the full national-scale modeling effort took approximately 5 years. This report represents the culmination of that effort. The key findings from the WECSsim model indicate the U.S. has several decades' worth of storage for CO2 in saline formations when managed appropriately. Competition for subsurface storage capacity, intrastate flows of CO2 and water, and a supportive regulatory environment all play a key role as to the performance and cost profile across the range from a single power plant to all coal and natural gas-based plants' ability to store CO2. The overall system's cost to capture, transport, and store CO2 for the national assessment range from $74 to $208 / tonne stored ($96 to 272 / tonne avoided) for the first 25 to 50% of the 1126 power plants to between $1,585 to well beyond $2,000 / tonne stored ($2,040 to well beyond $2,000 / tonne avoided) for the remaining 75 to 100% of the plants. The latter range, while extremely large, includes all natural gas power plants in the U.S., many of which have an extremely low capacity factor and therefore relatively high system's cost to capture and store CO2.

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Fundamental study of CO2-H2O-mineral interactions for carbon sequestration, with emphasis on the nature of the supercritical fluid-mineral interface

Bryan, Charles R.; Dewers, Thomas D.; Heath, Jason; Wang, Yifeng; Matteo, Edward N.; Meserole, Stephen M.

In the supercritical CO2-water-mineral systems relevant to subsurface CO2 sequestration, interfacial processes at the supercritical fluid-mineral interface will strongly affect core- and reservoir-scale hydrologic properties. Experimental and theoretical studies have shown that water films will form on mineral surfaces in supercritical CO2, but will be thinner than those that form in vadose zone environments at any given matric potential. The theoretical model presented here allows assessment of water saturation as a function of matric potential, a critical step for evaluating relative permeabilities the CO2 sequestration environment. The experimental water adsorption studies, using Quartz Crystal Microbalance and Fourier Transform Infrared Spectroscopy methods, confirm the major conclusions of the adsorption/condensation model. Additional data provided by the FTIR study is that CO2 intercalation into clays, if it occurs, does not involve carbonate or bicarbonate formation, or significant restriction of CO2 mobility. We have shown that the water film that forms in supercritical CO2 is reactive with common rock-forming minerals, including albite, orthoclase, labradorite, and muscovite. The experimental data indicate that reactivity is a function of water film thickness; at an activity of water of 0.9, the greatest extent of reaction in scCO2 occurred in areas (step edges, surface pits) where capillary condensation thickened the water films. This suggests that dissolution/precipitation reactions may occur preferentially in small pores and pore throats, where it may have a disproportionately large effect on rock hydrologic properties. Finally, a theoretical model is presented here that describes the formation and movement of CO2 ganglia in porous media, allowing assessment of the effect of pore size and structural heterogeneity on capillary trapping efficiency. The model results also suggest possible engineering approaches for optimizing trapping capacity and for monitoring ganglion formation in the subsurface.

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Petrologic and petrophysical evaluation of the Dallas Center Structure, Iowa, for compressed air energy storage in the Mount Simon Sandstone

Heath, Jason; Bauer, Stephen J.; Broome, Scott T.; Dewers, Thomas D.; Rodriguez, Marko A.

The Iowa Stored Energy Plant Agency selected a geologic structure at Dallas Center, Iowa, for evaluation of subsurface compressed air energy storage. The site was rejected due to lower-than-expected and heterogeneous permeability of the target reservoir, lower-than-desired porosity, and small reservoir volume. In an initial feasibility study, permeability and porosity distributions of flow units for the nearby Redfield gas storage field were applied as analogue values for numerical modeling of the Dallas Center Structure. These reservoir data, coupled with an optimistic reservoir volume, produced favorable results. However, it was determined that the Dallas Center Structure cannot be simplified to four zones of high, uniform permeabilities. Updated modeling using field and core data for the site provided unfavorable results for air fill-up. This report presents Sandia National Laboratories petrologic and petrophysical analysis of the Dallas Center Structure that aids in understanding why the site was not suitable for gas storage.

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Expanding the potential for saline formations : modeling carbon dioxide storage, water extraction and treatment for power plant cooling

Kobos, Peter H.; Roach, Jesse D.; Klise, Geoffrey T.; Krumhansl, James L.; Heath, Jason; Dewers, Thomas D.; Borns, David J.

The National Water, Energy and Carbon Sequestration simulation model (WECSsim) is being developed to address the question, 'Where in the current and future U.S. fossil fuel based electricity generation fleet are there opportunities to couple CO{sub 2} storage and extracted water use, and what are the economic and water demand-related impacts of these systems compared to traditional power systems?' The WECSsim collaborative team initially applied this framework to a test case region in the San Juan Basin, New Mexico. Recently, the model has been expanded to incorporate the lower 48 states of the U.S. Significant effort has been spent characterizing locations throughout the U.S. where CO{sub 2} might be stored in saline formations including substantial data collection and analysis efforts to supplement the incomplete brine data offered in the NatCarb database. WECSsim calculates costs associated with CO{sub 2} capture and storage (CCS) for the power plant to saline formation combinations including parasitic energy costs of CO{sub 2} capture, CO{sub 2} pipelines, water treatment options, and the net benefit of water treatment for power plant cooling. Currently, the model can identify the least-cost deep saline formation CO{sub 2} storage option for any current or proposed coal or natural gas-fired power plant in the lower 48 states. Initial results suggest that additional, cumulative water withdrawals resulting from national scale CCS may range from 676 million gallons per day (MGD) to 30,155 MGD depending on the makeup power and cooling technologies being utilized. These demands represent 0.20% to 8.7% of the U.S. total fresh water withdrawals in the year 2000, respectively. These regional and ultimately nation-wide, bottom-up scenarios coupling power plants and saline formations throughout the U.S. can be used to support state or national energy development plans and strategies.

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Micropillar compression technique applied to micron-scale mudstone elasto-plastic deformation

Dewers, Thomas D.; Boyce, Brad B.; Buchheit, Thomas E.; Heath, Jason; Michael, Joseph R.

Mudstone mechanical testing is often limited by poor core recovery and sample size, preservation and preparation issues, which can lead to sampling bias, damage, and time-dependent effects. A micropillar compression technique, originally developed by Uchic et al. 2004, here is applied to elasto-plastic deformation of small volumes of mudstone, in the range of cubic microns. This study examines behavior of the Gothic shale, the basal unit of the Ismay zone of the Pennsylvanian Paradox Formation and potential shale gas play in southeastern Utah, USA. Precision manufacture of micropillars 5 microns in diameter and 10 microns in length are prepared using an ion-milling method. Characterization of samples is carried out using: dual focused ion - scanning electron beam imaging of nano-scaled pores and distribution of matrix clay and quartz, as well as pore-filling organics; laser scanning confocal (LSCM) 3D imaging of natural fractures; and gas permeability, among other techniques. Compression testing of micropillars under load control is performed using two different nanoindenter techniques. Deformation of 0.5 cm in diameter by 1 cm in length cores is carried out and visualized by a microscope loading stage and laser scanning confocal microscopy. Axisymmetric multistage compression testing and multi-stress path testing is carried out using 2.54 cm plugs. Discussion of results addresses size of representative elementary volumes applicable to continuum-scale mudstone deformation, anisotropy, and size-scale plasticity effects. Other issues include fabrication-induced damage, alignment, and influence of substrate.

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Dual FIB-SEM 3D imaging and lattice boltzmann modeling of porosimetry and multiphase flow in chalk

Rinehart, Alex R.; Yoon, Hongkyu Y.; Heath, Jason; Dewers, Thomas D.

Mercury intrusion porosimetry (MIP) is an often-applied technique for determining pore throat distributions and seal analysis of fine-grained rocks. Due to closure effects, potential pore collapse, and complex pore network topologies, MIP data interpretation can be ambiguous, and often biased toward smaller pores in the distribution. We apply 3D imaging techniques and lattice-Boltzmann modeling in interpreting MIP data for samples of the Cretaceous Selma Group Chalk. In the Mississippi Interior Salt Basin, the Selma Chalk is the apparent seal for oil and gas fields in the underlying Eutaw Fm., and, where unfractured, the Selma Chalk is one of the regional-scale seals identified by the Southeast Regional Carbon Sequestration Partnership for CO2 injection sites. Dual focused ion - scanning electron beam and laser scanning confocal microscopy methods are used for 3D imaging of nanometer-to-micron scale microcrack and pore distributions in the Selma Chalk. A combination of image analysis software is used to obtain geometric pore body and throat distributions and other topological properties, which are compared to MIP results. 3D data sets of pore-microfracture networks are used in Lattice Boltzmann simulations of drainage (wetting fluid displaced by non-wetting fluid via the Shan-Chen algorithm), which in turn are used to model MIP procedures. Results are used in interpreting MIP results, understanding microfracture-matrix interaction during multiphase flow, and seal analysis for underground CO2 storage.

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Storing carbon dioxide in saline formations : analyzing extracted water treatment and use for power plant cooling

Kobos, Peter H.; Roach, Jesse D.; Klise, Geoffrey T.; Krumhansl, James L.; Dewers, Thomas D.; Heath, Jason; Dwyer, Brian P.; Borns, David J.

In an effort to address the potential to scale up of carbon dioxide (CO{sub 2}) capture and sequestration in the United States saline formations, an assessment model is being developed using a national database and modeling tool. This tool builds upon the existing NatCarb database as well as supplemental geological information to address scale up potential for carbon dioxide storage within these formations. The focus of the assessment model is to specifically address the question, 'Where are opportunities to couple CO{sub 2} storage and extracted water use for existing and expanding power plants, and what are the economic impacts of these systems relative to traditional power systems?' Initial findings indicate that approximately less than 20% of all the existing complete saline formation well data points meet the working criteria for combined CO{sub 2} storage and extracted water treatment systems. The initial results of the analysis indicate that less than 20% of all the existing complete saline formation well data may meet the working depth, salinity and formation intersecting criteria. These results were taken from examining updated NatCarb data. This finding, while just an initial result, suggests that the combined use of saline formations for CO{sub 2} storage and extracted water use may be limited by the selection criteria chosen. A second preliminary finding of the analysis suggests that some of the necessary data required for this analysis is not present in all of the NatCarb records. This type of analysis represents the beginning of the larger, in depth study for all existing coal and natural gas power plants and saline formations in the U.S. for the purpose of potential CO{sub 2} storage and water reuse for supplemental cooling. Additionally, this allows for potential policy insight when understanding the difficult nature of combined potential institutional (regulatory) and physical (engineered geological sequestration and extracted water system) constraints across the United States. Finally, a representative scenario for a 1,800 MW subcritical coal fired power plant (amongst other types including supercritical coal, integrated gasification combined cycle, natural gas turbine and natural gas combined cycle) can look to existing and new carbon capture, transportation, compression and sequestration technologies along with a suite of extracting and treating technologies for water to assess the system's overall physical and economic viability. Thus, this particular plant, with 90% capture, will reduce the net emissions of CO{sub 2} (original less the amount of energy and hence CO{sub 2} emissions required to power the carbon capture water treatment systems) less than 90%, and its water demands will increase by approximately 50%. These systems may increase the plant's LCOE by approximately 50% or more. This representative example suggests that scaling up these CO{sub 2} capture and sequestration technologies to many plants throughout the country could increase the water demands substantially at the regional, and possibly national level. These scenarios for all power plants and saline formations throughout U.S. can incorporate new information as it becomes available for potential new plant build out planning.

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Mechanical-chemical coupling and self-organization in mudstones

Heath, Jason

Shales and other mudstones are the most abundant rock types in sedimentary basins, yet have received comparatively little attention. Common as hydrocarbon seals, these are increasingly being targeted as unconventional gas reservoirs, caprocks for CO{sub 2} sequestration, and storage repositories for waste. The small pore and grain size, large specific surface areas, and clay mineral structures lend themselves to rapid reaction rates accompanying changes in stress, pressure, temperature and chemical conditions. Under far from equilibrium conditions, mudrocks display a variety of spatio-temporal self-organized phenomena arising from the nonlinear coupling of mechanics with chemistry. Beginning with a detailed examination of nano-scale pore network structures in mudstones, we discuss the dynamics behind such self-organized phenomena as pressure solitons, chemically-induced flow self focusing and permeability transients, localized compaction, time dependent well-bore failure, and oscillatory osmotic fluxes as they occur in clay-bearing sediments. Examples are draw from experiments, numerical simulation, and the field. These phenomena bear on the ability of these rocks to serve as containment barriers.

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Natural helium as a screening tool for assessing caprock imperfections at geologic CO2 storage sites

Energy Procedia

Heath, Jason; McPherson, Brian; Phillips, Fred; Cooper, Scott; Dewers, Thomas D.

Natural helium is a screening tool for identifying the presence or absence of caprock imperfections. Imperfections can be manifested as a variety of features or processes, including insufficiently low permeability, preferential flowpaths such as fractures and faults, and the propensity for capillary breakthrough. Theory and simulations detail how various types of imperfections affect the spatial distribution of natural helium above, within, and below caprock in a single-phase, brine-saturated system. Specifically, the distribution of natural helium can reveal the presence of preferential flowpaths through formations with low matrix permeability. The distribution patterns of helium shed insight on the size, shape, location, and connectedness of imperfections in caprock. We show how imperfections associated with characteristic distributions of natural helium will affect the retention of CO2. We discuss the advantages of natural helium, together with temperature distributions, for revealing imperfections and the optimum locations for sampling the natural tracers. This research is being carried out to support design and interpretation of ongoing field-testing by the Southwest Regional Partnership on Carbon Sequestration. Specifically, we are evaluating seal integrity of the Partnership's Pump Canyon Enhanced Coalbed Methane- CO2 Storage Demonstration, located in the San Juan Basin, New Mexico. The caprock at this site is the Kirtland Formation. This formation is composed of a variety of continental deposits (sandstones, siltstones, mudrocks, and shales) and is ideal for investigating the capability of helium to characterize sealing integrity of a very heterogeneous caprock. We present results of analyses of noble gases and a variety of petrological and petrophysical analyses on core through this caprock. These results are used to investigate the presence of imperfections and their potential impact on CO2 migration and the overall viability of utilizing natural helium as a screening tool. The authors gratefully acknowledge the U.S. Department of Energy and the National Energy Technology Laboratory for sponsoring this project. © 2009 Elsevier Ltd. All rights reserved.

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136 Results
136 Results