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Reliable estimations of the relative permeability of gas and water in hydrate-bearing sediments (HBS) and the dependency of the relative permeability on hydrate saturation are critical to predict the productivity of a hydrate reservoir. Yet, this remains poorly estimated owing to lack of experimental data associated with difficulties in conducting multiphase flow experiments in HBS. Recognizing the experimental challenges, this study intends to develop and validate a new experimental system and procedure of unsteady-state relative permeability test that can generate reliable and reproducible flow measurements in HBS. Gas hydrate is considered as a part of solid matrix in the sediment, so one of the challenges is to maintain a constant hydrate saturation, which is achieved in this experimental study using tight pressure-temperature (P-T) control near the hydrate stability boundary. The measured differential pressure across the specimen, methane injection flow rate, and volume of displaced brine are used to calculate the relative permeability by adopting a conventional Buckley-Leverett theory-based interpretation method. Residual brine saturation calculated for the hydrate-bearing specimen is higher than that of hydrate-free specimen, presumably due to decrease in pore size, increase in heterogeneity of solid matrix, and increase in size distribution of solid matrix and pore in the presence of hydrates. Further studies are necessary to represent the results of the unsteady-state flow experiment in HBS with a gas hydrate-dependent relative permeability model.

We investigate the influence of foliation orientation and fine-scale folding on the static and dynamic elastic properties and unconfined strength of the Poorman schist. Measurements from triaxial and uniaxial laboratory experiments reveal a significant amount of variability in the static and dynamic Young’s modulus depending on the sample orientation relative to the foliation plane. Dynamic P-wave modulus and S-wave modulus are stiffer in the direction parallel to the foliation plane as expected for transversely isotropic mediums with average Thomsen parameters values 0.133 and 0.119 for epsilon and gamma, respectively. Static Young’s modulus varies significantly between 21 and 117 GPa, and a peculiar trend is observed where some foliated sample groups show an anomalous decrease in the static Young’s modulus when the symmetry axis (x3-axis) is oriented obliquely to the direction of loading. Utilizing stress and strain relationships for transversely isotropic medium, we derive the analytical expression for Young’s modulus as a function of the elastic moduli E1, E3, ν31, and G13 and sample orientation to fit the static Young’s modulus measurements. Regression of the equation to the Young’s modulus data reveals that the decrease in static Young’s modulus at oblique symmetry axis orientations is directly influenced by a low shear modulus, G13, which we attribute to shear sliding along foliation planes during static deformation that occurs as soon as the foliation is subject to shear stress. We argue that such difference between dynamic and static anisotropy is a characteristic of near-zero porosity anisotropic rocks. The uniaxial compressive strength also shows significant variability ranging from 21.9 to 194.6 MPa across the five sample locations and is the lowest when the symmetry axis is oriented 45° or 60° from the direction of loading, also a result of shear sliding along foliation planes during static deformation.

Geologic reservoirs containing gas hydrate occur beneath permafrost environments and within marine continental slope sediments, representing a potentially vast natural gas source. Numerical simulators provide scientists and engineers with tools for understanding how production efficiency depends on the numerous, interdependent (coupled) processes associated with potential production strategies for these gas hydrate reservoirs. Confidence in the modeling and forecasting abilities of these gas hydrate reservoir simulators (GHRSs) grows with successful comparisons against laboratory and field test results, but such results are rare, particularly in natural settings. The hydrate community recognized another approach to building confidence in the GHRS: comparing simulation results between independently developed and executed computer codes on structured problems specifically tailored to the interdependent processes relevant for gas hydrate-bearing systems. The United States Department of Energy, National Energy Technology Laboratory, (DOE/NETL), sponsored the first international gas hydrate code comparison study, IGHCCS1, in the early 2000s. IGHCCS1 focused on coupled thermal and hydrologic processes associated with producing gas hydrates from geologic reservoirs via depressurization and thermal stimulation. Subsequently, GHRSs have advanced to model more complex production technologies and incorporate geomechanical processes into the existing framework of coupled thermal and hydrologic modeling. This paper contributes to the validation of these recent GHRS developments by providing results from a second GHRS code comparison study, IGHCCS2, also sponsored by DOE/NETL. IGHCCS2 includes participants from an international collection of universities, research institutes, industry, national laboratories, and national geologic surveys. Study participants developed a series of five benchmark problems principally involving gas hydrate processes with geomechanical components. The five problems range from simple geometries with analytical solutions to a representation of the world's first offshore production test of methane hydrates, which was conducted with the depressurization method off the coast of Japan. To identify strengths and limitations in the various GHRSs, study participants submitted solutions for the benchmark problems and discussed differing results via teleconferences. The GHRSs evolved over the course of IGHCCS2 as researchers modified their simulators to reflect new insights, lessons learned, and suggested performance enhancements. The five benchmark problems, final sample solutions, and lessons learned that are presented here document the study outcomes and serve as a reference guide for developing and testing gas hydrate reservoir simulators.

Geological carbon storage (GCS) involves unstable drainage processes, the formation of patterns in a morphologically unstable interface between two fluids in a porous medium during drainage. The unstable drainage processes affect CO2 storage efficiency and plume distribution and can be greatly complicated by the mixed-wet nature of rock surfaces common in hydrocarbon reservoirs where supercritical CO2 (scCO2) is used in enhanced oil recovery. We performed scCO2 injection (brine drainage) experiments at 8.5 MPa and 45°C in heterogeneous micromodels, two mixed-wet with varying water- and intermediate-wet patches, and one water-wet. The flow regime changes from capillary fingering through crossover to viscous fingering in the micromodels of the same pore geometry but different wetting surfaces at displacement rates with logCa (capillary number) increasing from −8.1 to −4.4. While the mixed-wet micromodel with uniformly distributed intermediate-wet patches yields ~0.15 scCO2 saturation increase at both capillary fingering and crossover flow regimes (−8.1 ≤ logCa ≤ − 6.1), the one heterogeneous wetting to scCO2 results in ~0.09 saturation increase only at the crossover flow regime (−7.1 ≤ logCa ≤ − 6.1). The interconnected flow paths in the former are quantified and compared to the channelized scCO2 flow through intermediate-wet patches in the latter by topological analysis. At logCa > − 6.1 (near well), the effects of wettability and pore geometry are suppressed by strong viscous force. Both scCO2 saturation and distribution suggest the importance of wettability on CO2 storage efficiency and plume shape in reservoirs and capillary leakage through caprock at GCS conditions.

Compacted bentonite is commonly considered for use as backfill material in emplacement tunnels of nuclear waste repositories because of its low permeability, high swelling pressure, and retardation capacity of radionuclide. To assess whether this material can maintain its favorable features when undergoing heating from the waste package and hydration from the host rock, we need a thorough understanding of the thermal, hydrological, mechanical, and chemical evolution under disposal conditions. Laboratory and field tests integrated with THMC modeling have provided an effective way to deepen such understanding; however, most of this work has been conducted for maximum temperatures around 100°C. In contrast, some international disposal programs have recently started investigations to understand whether local temperatures in the bentonite of up to 200°C could be tolerated with no significant changes in safety relevant properties. For example, the United States disposal program is evaluating the feasibility of geological disposal of large spent nuclear fuel canisters that are currently in dry storage. Direct disposal of these canisters is attractive for economical and safety reasons, but faces the challenge of exposing the bentonite to significant temperatures increases. As a result, strong thermal gradients may induce complex moisture transport processes and bentonite-rock interactions while cementation and perhaps also illitization effects may occur, all of which could  strongly affect the bentonite properties.Here, we present initial investigations of bentonite behavior exposed to strongly elevated temperatures. We first show results from coupled thermal, hydrological, mechanical and chemical (THMC) simulations of a generic nuclear waste repository in a clay formation with a bentonite-based buffer exposed to a maximum temperature of 200°C. Modeling results illustrate possible performance impacts, such as the time frame and condition of the early unsaturated phase during bentonite hydration, the porosity and permeability after the bentonite becomes fully saturated, and changing in swelling properties. We then discuss preliminary data from a bench-scale laboratory mockup experiment which was designed to represents the strong THMC gradients occurring in a “hot” repository, and we briefly touch on a full-scale field experiment to be conducted soon in the Grimsel Test Site underground research laboratory in Switzerland (referred to as HotBENT, with bentonite exposure from up to 200oC).

Ice-wedge polygons are common Arctic landforms. The future of these landforms in a warming climate depends on the bidirectional feedback between the rate of ice-wedge degradation and changes in hydrological characteristics. This work aims to better understand the relative roles of vertical and horizontal water fluxes in the subsurface of polygonal landscapes, providing new insights and data to test and calibrate hydrological models. Field-scale investigations were conducted at an intensively instrumented location on the Barrow Environmental Observatory (BEO) near Utqiagvik, AK, USA. Using a conservative tracer, we examined controls of microtopography and the frost table on subsurface flow and transport within a low-centered and a high-centered polygon. Bromide tracer was applied at both polygons in July 2015 and transport was monitored through two thaw seasons. Sampler arrays placed in polygon centers, rims, and troughs were used to monitor tracer concentrations. In both polygons, the tracer first infiltrated vertically until encountering the frost table and was then transported horizontally. Horizontal flow occurred in more locations and at higher velocities in the low-centered polygon than in the high-centered polygon. Preferential flow, influenced by frost table topography, was significant between polygon centers and troughs. Estimates of horizontal hydraulic conductivity were within the range of previous estimates of vertical conductivity, highlighting the importance of horizontal flow in these systems. This work forms a basis for understanding complexity of flow in polygonal landscapes.

The primary objective of the EGS Collab Project sponsored by DOE is to increase the understanding needed to efficiently implement enhanced geothermal systems (EGS). The EGS Collab project is a collaborative research environment studying stimulation of crystalline rock at the 10-meter scale. High-quality characterization and monitoring data are collected during stimulation and flow tests to allow comparison to numerical coupled process models in an effort to build confidence in the codes and improve modeling techniques. The Experiment 1 test bed, located at the Sanford Underground Research Facility (SURF) in Lead, SD at a depth of approximately 1.5 km is being used to examine hydraulic fracturing. The testbed was characterized using numerous field-based geophysical and geologic techniques and laboratory testing, and a well-instrumented test bed was created to allow us to carefully monitor fracture stimulation events and flow tests. A number of hydraulic stimulation tests at several locations in one well were performed, creating new fractures that connect to existing fractures between the injection and production boreholes. Long-term ambient and chilled water injection tests have been performed as an analog to EGS, and system changes resulting from these water injections have been monitored using geophysical monitoring, flow, temperature, and pressure measurements, tracer tests, and microbiology. Here, we summarize the tests performed, issues identified including poroelastic and thermoelastic effects, Joule-Thomson effects, restarting effects, indications of flow channeling, and the scientific findings to date from Experiment 1. We are currently designing a second test bed aimed at investigating shear stimulation (Experiment 2).

Flow in natural media with nanoporous regions is very complicated, with many governing processes. Welldeveloped numerical codes to integrate and model flow through these media are available. A great deal of very creative work has been done to understand individual processes governing flow in natural media with nanoporous regions, and both simple and elaborate tools have been used to gain process understanding. The complications in understanding and predicting flow in these rocks, particularly with multiscale heterogeneities, anisotropies, and the presence of multiple phases and large gradients are enormous. Here, we examine factors governing flow through natural porous media containing nanoporous regions. We present a conceptual model of the media, touch on the flow physics, and describe the techniques used to examine pore space in these rocks. In addition, we briefly describe some modeling of flow through these media. A number of processes which need better description are identified.

Geological carbon storage in deep aquifers involves displacement of resident brine by supercritical CO2 (scCO2), which is an unstable drainage process caused by the invasion of less viscous scCO2. The unstable drainage is greatly complicated by aquifer heterogeneity and anisotropy and regarded as one of the key factors accounting for the uncertainty in storage capacity estimates. The impacts of pore-scale characteristics on the unstable drainage remain poorly understood. In this study, scCO2 drainage experiments were conducted at 40 °C and 9 MPa using a homogeneous elliptical micromodel with low or high anisotropy, a homogeneous/isotropic hexagonal micromodel, and a heterogeneous sandstone-analog micromodel. Each initially water-saturated micromodel was invaded by scCO2 at different rates with logCa (the capillary number)ranging from −7.6 to −4.4, and scCO2/water images were obtained. The measured CO2 saturations in these centimeter-scale micromodels vary considerably from 0.08 to 0.93 depending on the pore-scale characteristics and capillary number. It was also observed that scCO2 drainage follows the classic flow-regime transition from capillary fingering through crossover to viscous fingering for either of the low-anisotropy elliptical and heterogeneous micromodels, but with disparate crossover zones. The crossover zones of scCO2 saturation were then unified with the minimum scCO2 saturation occurring at logCa*=-4.0 using the complete capillary number (Ca*)that considers pore characteristics. For the hexagonal and the high-anisotropy elliptical micromodels, a monotonic increase in scCO2 saturation with increasing Ca* (without crossover)was observed. It appears that the complete capillary number is more appropriate than the classic capillary number when characterizing flow regimes and CO2 saturation in different pore networks.

Geological carbon storage in deep aquifers involves displacement of resident brine by supercritical CO2 (scCO2), which is an unstable drainage process caused by the invasion of less viscous scCO2. The unstable drainage is greatly complicated by aquifer heterogeneity and anisotropy and regarded as one of the key factors accounting for the uncertainty in storage capacity estimates. The impacts of pore-scale characteristics on the unstable drainage remain poorly understood. In this study, scCO2 drainage experiments were conducted at 40 °C and 9 MPa using a homogeneous elliptical micromodel with low or high anisotropy, a homogeneous/isotropic hexagonal micromodel, and a heterogeneous sandstone-analog micromodel. Each initially water-saturated micromodel was invaded by scCO2 at different rates with logCa (the capillary number)ranging from −7.6 to −4.4, and scCO2/water images were obtained. The measured CO2 saturations in these centimeter-scale micromodels vary considerably from 0.08 to 0.93 depending on the pore-scale characteristics and capillary number. It was also observed that scCO2 drainage follows the classic flow-regime transition from capillary fingering through crossover to viscous fingering for either of the low-anisotropy elliptical and heterogeneous micromodels, but with disparate crossover zones. The crossover zones of scCO2 saturation were then unified with the minimum scCO2 saturation occurring at logCa*=-4.0 using the complete capillary number (Ca*)that considers pore characteristics. For the hexagonal and the high-anisotropy elliptical micromodels, a monotonic increase in scCO2 saturation with increasing Ca* (without crossover)was observed. It appears that the complete capillary number is more appropriate than the classic capillary number when characterizing flow regimes and CO2 saturation in different pore networks.

Describing the pore habit of methane hydrate in sediment matrices is essential for understanding natural distribution of methane hydrate, methane trace (transport and solidification) in the hydrate stability zone, physical properties of hydrate-bearing sediments, and the associated influence on potential gas production. Pore habit visualization in natural media at pore scale even with laboratory synthesized cores has been challenging due to the similar densities of methane hydrate from pore liquid. In this work, we used phase-contrast assisted micro-CT with potassium iodine-doped brine to visualize four phases: sand particles, pore fluid, methane hydrate and methane gas. This study visualizes the pore habit of methane hydrate at various stages including during hydrate formation in excess-gas systems, its evolution after brine injection to replace pore fluid, and hydrate formation in excess-water systems. Hydrate tends to adopt round and smooth surfaces when in contact with water while exhibits relatively angular interfaces when in contact with methane gas. Hydrate formation in excess-gas systems results in a partial cementing and partial mineral-coating pore habit, while hydrate in excess-water systems develops mainly as pore-filling, and locally cementing or mineral-coating where big gas pockets exist at the initial state. Pore liquid replacement from methane gas to brine triggers a shift of hydrate pore habit towards pore-filling. Methane hydrate evolution over time produces bigger hydrate particles but with less contact area with sand particles. The effects of hydrate pore habit become less important as hydrate particle size exceeds the pore size. Additionally, hydrate formation could trap residual methane gas and brine as inclusions.

Describing the pore habit of methane hydrate in sediment matrices is essential for understanding natural distribution of methane hydrate, methane trace (transport and solidification) in the hydrate stability zone, physical properties of hydrate-bearing sediments, and the associated influence on potential gas production. Pore habit visualization in natural media at pore scale even with laboratory synthesized cores has been challenging due to the similar densities of methane hydrate from pore liquid. In this work, we used phase-contrast assisted micro-CT with potassium iodine-doped brine to visualize four phases: sand particles, pore fluid, methane hydrate and methane gas. This study visualizes the pore habit of methane hydrate at various stages including during hydrate formation in excess-gas systems, its evolution after brine injection to replace pore fluid, and hydrate formation in excess-water systems. Hydrate tends to adopt round and smooth surfaces when in contact with water while exhibits relatively angular interfaces when in contact with methane gas. Hydrate formation in excess-gas systems results in a partial cementing and partial mineral-coating pore habit, while hydrate in excess-water systems develops mainly as pore-filling, and locally cementing or mineral-coating where big gas pockets exist at the initial state. Pore liquid replacement from methane gas to brine triggers a shift of hydrate pore habit towards pore-filling. Methane hydrate evolution over time produces bigger hydrate particles but with less contact area with sand particles. The effects of hydrate pore habit become less important as hydrate particle size exceeds the pore size. Additionally, hydrate formation could trap residual methane gas and brine as inclusions.

The EGS Collab project was initiated in March 2017 to enable the subsurface modelling and researchcommunity to establish validations against controlled, small-scale, in-situ experiments focused on rockfracture behavior and permeability enhancement. The EGS Collab project is to provide the opportunityfor reservoir model prediction and validation, in coordination with in depth analysis of geophysical andother fracture characterization data with an ultimate goal of further elucidating the basic relationshipbetween stress, seismicity and permeability enhancement. In addition, the project is to identify andquantify other key governing parameters that impact permeability as well as understanding how theseparameters change throughout the three EGS development phases (identify/characterize site, createreservoir, operate power plant). The project is to use comprehensive instrumentation and datacollection effort to inform baseline, predictive, and post stimulation reservoir modeling is essential.This report describes the activities performed in Phase 1 of the project. The work done to date isextensive, and a large number of participants have contributed significant effort to enable projectsuccess. From planning to execution, we have stayed on track to address the objectives established bythe Department of Energy in the paragraph above.

Abstract. Ice-wedge polygons are common Arctic landforms. The future of these landforms in a warming climate depends on the bidirectional feedback between the rate of ice-wedge degradation and changes in hydrological characteristics. This work aims to better understand the relative roles of vertical and horizontal water fluxes in the subsurface of polygonal landscapes, providing new insights and data to test and calibrate hydrology models. Field-scale investigations were conducted at an intensively-instrumented location on the Barrow Environmental Observatory (BEO) near Utqiaġvik, AK, USA. Using a conservative tracer, we examined controls of microtopography and the frost table on subsurface flow and transport within a low-centered and a high-centered polygon. Bromide tracer was applied at both polygons in July 2015 and transport was monitored through two thaw seasons. Samplers arrays placed in polygon centers, rims, and troughs were used to monitor tracer concentrations. In both polygons, the tracer first infiltrated vertically until encountering the frost table, then was transported horizontally. Horizontal flow occurred in more locations and at higher velocities of fluxes in the low-centered polygon than in the high-centered polygon. Preferential flow, influenced by frost table topography, was significant between polygon centers and troughs. Estimates of horizontal hydraulic conductivity were within the range of previous estimates of vertical conductivity, highlighting the importance of horizontal flow in these systems. This work forms a basis for understanding complexity of flow in polygonal landscapes.

Dissolution trapping is one of the most important mechanisms for geological carbon storage (GCS). Recent laboratory and field experiments have shown non-equilibrium dissolution of supercritical CO2 (scCO2) and coupled scCO2 dissolution and water flow, i.e., scCO2 dissolution at local pores/pore throats creating new water-flow paths, which in turn enhance dissolution by increased advection and interfacial area. However, the impacts of pore-scale characteristics on these coupled processes have not been investigated. In this study, imbibition and dissolution experiments were conducted under 40 °C and 9 MPa using a homogeneous/isotropic hexagonal micromodel, two homogeneous elliptical micromodels with low or high anisotropy, and a heterogeneous sandstone-analog micromodel. The four micromodels, initially saturated with deionized (DI)-water, were drained by injecting scCO2 to establish a stable scCO2 saturation. DI water was then injected at different rates with logCa (the capillary number) ranging from −6.56 to −4.34. Results show that bypass of scCO2 by displacing water is the dominant mechanism contributing to the residual CO2 trapping, triggered by heterogeneity in pore characteristics or pore-scale scCO2-water distribution. Bypass can be enhanced by pore heterogeneity or reduced by increasing transverse permeability, resulting in relatively low (

Copyright 2019 ARMA, American Rock Mechanics Association. The EGS (Enhanced Geothermal Systems) Collab project is performing stimulation and flow experiments in highly-monitored and well-characterized intermediate-scale (approximately10 to 20 meter) field test beds at a depth of approximately 1,500 meters in the Sanford Underground Research Facility (SURF) in the Black Hills of South Dakota. Our fracture stimulation and interwell flow tests are performed to better understand processes that control formation of effective subsurface heat exchangers that are critical to the development and success of EGS. Different EGS Collab stimulations will be performed under dissimilar stress conditions to produce data for model comparisons that better differentiate stimulation mechanisms and the evolution of permeability enhancement in crystalline rock. EGS Collab experiments provide a means of testing tools, concepts, and strategies that could later be employed under geothermal reservoir conditions at DOE’s Frontier Observatory for Research in Geothermal Energy (FORGE) and other enhanced geothermal systems. Key to the project is using numerical simulations in the experiment design and interpretation of

Dissolution trapping is one of the most important mechanisms for geological carbon storage (GCS). Recent laboratory and field experiments have shown non-equilibrium dissolution of supercritical CO2 (scCO2) and coupled scCO2 dissolution and water flow, i.e., scCO2 dissolution at local pores/pore throats creating new water-flow paths, which in turn enhance dissolution by increased advection and interfacial area. However, the impacts of pore-scale characteristics on these coupled processes have not been investigated. In this study, imbibition and dissolution experiments were conducted under 40 °C and 9 MPa using a homogeneous/isotropic hexagonal micromodel, two homogeneous elliptical micromodels with low or high anisotropy, and a heterogeneous sandstone-analog micromodel. The four micromodels, initially saturated with deionized (DI)-water, were drained by injecting scCO2 to establish a stable scCO2 saturation. DI water was then injected at different rates with logCa (the capillary number) ranging from −6.56 to −4.34. Results show that bypass of scCO2 by displacing water is the dominant mechanism contributing to the residual CO2 trapping, triggered by heterogeneity in pore characteristics or pore-scale scCO2-water distribution. Bypass can be enhanced by pore heterogeneity or reduced by increasing transverse permeability, resulting in relatively low (

Thawing permafrost can stimulate microbial activity, leading to faster decomposition of formerly preserved organic matter and CO2 release. Detailed knowledge about the vertical distribution of the responsible microbial community that is changing with increasing soil depth is limited. In this study, we determined the microbial community composition from cores sampled in a high Arctic heath at Svalbard, Norway; spanning from the active layer (AL) into the permafrost layer (PL). A special aim has been on identifying a layer of recently thawed soil, the transition zone (TZ), which might provide new insights into the fate of thawing permafrost. A unique sampling strategy allowed us to observe a diverse and gradually shifting microbial community in the AL, a Bacteroidetes dominated community in the TZ and throughout the PL, a community strongly dominated by a single Actinobacteria family (Intrasporangiaceae). The contrasting abundances of these two taxa caused a community difference of about 60%, just within 3 cm from TZ to PL. We incubated subsamples at about 5°C and measured highest CO2 production rates under aerobic incubations, yet contrasting for five different layers and correlating to the microbial community composition. This high resolution strategy provides new insights on how microbial communities are structured in permafrost and a better understanding of how they respond to thaw.

A laboratory study of cryogenic fracturing was performed to test its ability to improve oil/gas recovery from low-permeability reservoirs. Our objective is to develop well-stimulation technologies using cryogenic fluids [e.g., liquid nitrogen (LN)] to increase permeability in a large reservoir volume surrounding wells. The new technology has the potential to reduce formation damage caused by current stimulation methods and minimize or eliminate water usage. The concept of cryogenic fracturing is that a sharp thermal gradient (thermal shock) created at the surfaces of formation rocks by applying cryogenic fluid can cause strong local tensile stress and start fractures. We developed a laboratory system for cryogenic fracturing under true-triaxial loading, with LN-delivery/control and -measurement systems. The loading system simulates confining stresses by independently loading each axis up to approximately 5,000 psi on 888-in. cubes. Temperature in boreholes and at block surfaces and fluid pressure in boreholes were continuously monitored. Acoustic and pressure-decay measurements were obtained before and at various stages of stimulations. Cubic blocks (8 88-in.) of Niobrara shale, concrete, and sandstones were tested, and stress levels and anisotropies varied. Three schemes were considered: Gas fracturing without cryo-stimulation, gas fracturing after low-pressure cryogen flow-through, and gas fracturing after high-pressure cryogen flow-through. Results from pressure-decay tests show that LN stimulation clearly increases permeability, and repeated stimulations further increase the permeability. Acoustic velocities and amplitudes decreased significantly after cryo-stimulation, indicating fracture creation. In the gas fracturing without the stimulation, breakdown (complete fracturing) occurs suddenly without any initial leaking, and major fracture planes form along the plane containing principal-stress and intermediate-stress directions, as expected theoretically. However, in the gas fracturing after cryogenic stimulations, breakdown occurred gradually and with massive leaking because of thermal fractures created during stimulation. In addition, the major fracture direction does not necessarily follow the plane containing the principal-stress direction, especially at low confining-stress levels. In tests, we observed that cryogenic stimulation seems to disrupt the internal stress field. The increase in borehole temperature after stimulation affects the permeability of the specimen. When a stimulated specimen is still cold, it maintains high permeability because fractures remain open and local thermal tension is maintained near the borehole. When the rock warms back, fractures close and permeability decreases. In these tests, we have not used proppants. Overall, fractures are clearly generated by low- and high-pressure thermal shocks. The added pressure of the high-pressure thermal shocks helps to further propagate cryogenic fractures generated by thermal shock. Breakdown pressure is significantly lowered by LN stimulation, with observed breakdown-pressure reductions up to approximately 40%.

A laboratory study of cryogenic fracturing was performed to test its ability to improve oil/gas recovery from low-permeability reservoirs. Our objective is to develop well-stimulation technologies using cryogenic fluids [e.g., liquid nitrogen (LN)] to increase permeability in a large reservoir volume surrounding wells. The new technology has the potential to reduce formation damage caused by current stimulation methods and minimize or eliminate water usage. The concept of cryogenic fracturing is that a sharp thermal gradient (thermal shock) created at the surfaces of formation rocks by applying cryogenic fluid can cause strong local tensile stress and start fractures. We developed a laboratory system for cryogenic fracturing under true-triaxial loading, with LN-delivery/control and -measurement systems. The loading system simulates confining stresses by independently loading each axis up to approximately 5,000 psi on 888-in. cubes. Temperature in boreholes and at block surfaces and fluid pressure in boreholes were continuously monitored. Acoustic and pressure-decay measurements were obtained before and at various stages of stimulations. Cubic blocks (8 88-in.) of Niobrara shale, concrete, and sandstones were tested, and stress levels and anisotropies varied. Three schemes were considered: Gas fracturing without cryo-stimulation, gas fracturing after low-pressure cryogen flow-through, and gas fracturing after high-pressure cryogen flow-through. Results from pressure-decay tests show that LN stimulation clearly increases permeability, and repeated stimulations further increase the permeability. Acoustic velocities and amplitudes decreased significantly after cryo-stimulation, indicating fracture creation. In the gas fracturing without the stimulation, breakdown (complete fracturing) occurs suddenly without any initial leaking, and major fracture planes form along the plane containing principal-stress and intermediate-stress directions, as expected theoretically. However, in the gas fracturing after cryogenic stimulations, breakdown occurred gradually and with massive leaking because of thermal fractures created during stimulation. In addition, the major fracture direction does not necessarily follow the plane containing the principal-stress direction, especially at low confining-stress levels. In tests, we observed that cryogenic stimulation seems to disrupt the internal stress field. The increase in borehole temperature after stimulation affects the permeability of the specimen. When a stimulated specimen is still cold, it maintains high permeability because fractures remain open and local thermal tension is maintained near the borehole. When the rock warms back, fractures close and permeability decreases. In these tests, we have not used proppants. Overall, fractures are clearly generated by low- and high-pressure thermal shocks. The added pressure of the high-pressure thermal shocks helps to further propagate cryogenic fractures generated by thermal shock. Breakdown pressure is significantly lowered by LN stimulation, with observed breakdown-pressure reductions up to approximately 40%.

We form methane hydrate by injecting methane gas into a brine-saturated, coarse-grained sample under hydrate-stable thermodynamic conditions. Hydrate forms to a saturation of 11%, which is much lower than that predicted assuming three-phase (gas-hydrate-brine) thermodynamic equilibrium (67%). During hydrate formation, there are temporary flow blockages. We interpret that a hydrate skin forms a physical barrier at the gas-brine interface. The skin fails periodically when the pressure differential exceeds the skin strength. Once the skin is present, further hydrate formation is limited by the rate that methane can diffuse through the solid skin. This process produces distinct thermodynamic states on either side of the skin that allows gas to flow through the sample. This study illuminates how gas can be transported through the hydrate stability zone and thus provides a mechanism for the formation of concentrated hydrate deposits in sand reservoirs. It also illustrates that models that assume local equilibrium at the core-scale and larger may not capture the fundamental behaviors of these gas flow and hydrate formation processes.

For better understanding of frequency dependence (dispersion) of seismic wave velocities caused by stress-induced fluid flow, broadband laboratory measurements were performed on a suite of synthetic glass media containing both equant pores and thermal cracks. Complementary forced oscillation, resonant bar, and ultrasonic techniques provided access to millihertz-hertz frequencies, ~1 kHz frequency, and ~1 MHz frequency, respectively. The wave speeds or effective elastic moduli and associated dissipation were measured on samples under dry, argon- or nitrogen-saturated, and water-saturated conditions in sequence. The elastic moduli, in situ permeability, and crack porosity inferred from in situ X-ray computed tomography all attest to strong pressure-induced crack closure for differential (confining-minus-pore) pressures

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. This study investigated 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. 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.

Permafrost physicochemical parameters play a key role in controlling the response of permafrost carbon to climate change. We studied the physicochemical parameters of permafrost in an Arctic tundra region to evaluate (1) how soil parameters vary with depth and whether and how they are interrelated, (2) whether and how permafrost soil differs from its overlaying active layer, and (3) whether soil property-depth relationships are different across geomorphic features (e.g., low, flat, and high centered polygons). We also explored the possible biogeochemical processes that led to these soil characteristics and how they may affect biogeochemical reactions upon permafrost thaw. We observed (1) consistent relationships between soil property and depth and between major parameters, (2) large contrasts of key soil parameters between active layer and permafrost, indicative of potentially different response of the permafrost carbon to warming when compared to the active layer, and (3) a correlation between soil hydraulic conductivity and topographic features that impacts soil hydrologic processes. Our analysis suggests that the permafrost has a marine-derived chemical signature that differs from the active layer and shapes the physicochemical fingerprints of the different geomorphic features. Specifically, we revealed the unique signatures of the high center polygons, indicative of possible microbial activity at depth (>1 m). Our study suggested consistent key soil parameter-depth correlations while demonstrating complex lateral and vertical variabilities. These results are valuable for identifying approaches to upscale point-based measurements and for improving model parameterization to predict permafrost carbon behavior and feedback under future climate.

In the Arctic, environmental factors governing microbial degradation of soil carbon (C) in active layer and permafrost are poorly understood. Here we determined the functional potential of soil microbiomes horizontally and vertically across a cryoperturbed polygonal landscape in Alaska. With comparative metagenomics, genome binning of novel microbes, and gas flux measurements we show that microbial greenhouse gas (GHG) production is strongly correlated to landscape topography. Active layer and permafrost harbor contrasting microbiomes, with increasing amounts of Actinobacteria correlating with decreasing soil C in permafrost. While microbial functions such as fermentation and methanogenesis were dominant in wetter polygons, in drier polygons genes for C mineralization and CH4 oxidation were abundant. The active layer microbiome was poised to assimilate N and not to release N2O, reflecting low N2O flux measurements. These results provide mechanistic links of microbial metabolism to GHG fluxes that are needed for the refinement of model predictions.

The organic and mineralogical heterogeneity in shale at micrometer and nanometer spatial scales contributes to the quality of gas reserves, gas flow mechanisms and gas production. Here, we demonstrate two molecular imaging approaches based on infrared spectroscopy to obtain mineral and kerogen information at these mesoscale spatial resolutions in large-sized shale rock samples. The first method is a modified microscopic attenuated total reflectance measurement that utilizes a large germanium hemisphere combined with a focal plane array detector to rapidly capture chemical images of shale rock surfaces spanning hundreds of micrometers with micrometer spatial resolution. The second method, synchrotron infrared nano-spectroscopy, utilizes a metallic atomic force microscope tip to obtain chemical images of micrometer dimensions but with nanometer spatial resolution. This chemically "deconvoluted" imaging at the nano-pore scale is then used to build a machine learning model to generate a molecular distribution map across scales with a spatial span of 1000 times, which enables high-throughput geochemical characterization in greater details across the nano-pore and micro-grain scales and allows us to identify co-localization of mineral phases with chemically distinct organics and even with gas phase sorbents. This characterization is fundamental to understand mineral and organic compositions affecting the behavior of shales.

The Special Issue “Water and Solute Transport in Vadose Zone” in the journal Water is dedicated to the memory of Dr. Gudmundur “Bo” Bodvarsson, the former director of the Earth Sciences Division of Lawrence Berkeley National Laboratory (http://eesa.lbl.gov/profiles/gudmundur-bo-sbodvarsson/).[...]

Niobrara shale cubes of 20 cm from Colorado were employed to investigate gas and supercritical CO2 injection-induced fracturing in naturally fractured caprocks of deep aquifers/depleted reservoirs and fractured shale reservoirs. Under tri-axial stresses, gas or supercritical CO2 was injected into the center of the cubes to induce fracturing. Real-time pressure and temperature, acoustic wave, pressure decay, fracture coloring, and gas fracturing were used to characterize the fracturing process and fracture morphology. Without pore pressure, CO2 injection-induced fracturing occurred and completed instantly, accompanied by an evident temperature drop. Strongly bonded fractures barely affected transverse fracture propagation, whereas weakly bonded or open fractures arrested the injected fluid first and then allowed it to generate new fractures perpendicular to the minimum horizontal stress. Breakdown pressures for cubes with preexisting fractures using gas and supercritical CO2 are much lower than both poroelastic predictions and slick-water fracturing pressure, and some are even lower than the minimum horizontal stress. This is attributed to unconformable preexisting fractures and the low viscosity of CO2. Moreover, decreasing tri-axial stress levels and increasing stress differences tend to lower the breakdown pressure. This study is instructive for understanding and tackling geomechanical issues related to CO2 geological storage and fracturing of shale reservoirs.

The performance of geologic CO2 sequestration (GCS) can be affected by CO2 mineralization and changes in the permeability of geologic formations resulting from interactions between water-bearing supercritical CO2 (scCO2) and silicates in reservoir rocks. However, without an understanding of the size effects, the findings in previous studies using nanometer- or micrometer-size particles cannot be applied to the bulk rock in field sites. In this study, we report the effects of particle sizes on the carbonation of wollastonite (CaSiO3) at 60 °C and 100 bar in water-bearing scCO2. After normalization by the surface area, the thickness of the reacted wollastonite layer on the surfaces was independent of particle sizes. After 20 h, the reaction was not controlled by the kinetics of surface reactions but by the diffusion of water-bearing scCO2 across the product layer on wollastonite surfaces. Among the products of reaction, amorphous silica, rather than calcite, covered the wollastonite surface and acted as a diffusion barrier to water-bearing scCO2. The product layer was not highly porous, with a specific surface area 10 times smaller than that of the altered amorphous silica formed at the wollastonite surface in aqueous solution. These findings can help us evaluate the impacts of mineral carbonation in water-bearing scCO2.

Niobrara shale cubes of 20 cm from Colorado were employed to investigate gas and supercritical CO2 injection-induced fracturing in naturally fractured caprocks of deep aquifers/depleted reservoirs and fractured shale reservoirs. Under tri-axial stresses, gas or supercritical CO2 was injected into the center of the cubes to induce fracturing. Real-time pressure and temperature, acoustic wave, pressure decay, fracture coloring, and gas fracturing were used to characterize the fracturing process and fracture morphology. Without pore pressure, CO2 injection-induced fracturing occurred and completed instantly, accompanied by an evident temperature drop. Strongly bonded fractures barely affected transverse fracture propagation, whereas weakly bonded or open fractures arrested the injected fluid first and then allowed it to generate new fractures perpendicular to the minimum horizontal stress. Breakdown pressures for cubes with preexisting fractures using gas and supercritical CO2 are much lower than both poroelastic predictions and slick-water fracturing pressure, and some are even lower than the minimum horizontal stress. This is attributed to unconformable preexisting fractures and the low viscosity of CO2. Moreover, decreasing tri-axial stress levels and increasing stress differences tend to lower the breakdown pressure. This study is instructive for understanding and tackling geomechanical issues related to CO2 geological storage and fracturing of shale reservoirs.

© 2017 We conducted laboratory studies on the geophysical signals from Arctic saline permafrost soils to help understand the physical and mechanical processes during freeze-thaw cycles. Our results revealed low electrical resistivity (< 20 Ωm) and elastic moduli (7.7 GPa for Young's modulus and 2.9 GPa for shear modulus) at temperatures down to ~− 10 °C, indicating the presence of a significant amount of unfrozen saline water under the current field conditions. The spectral induced polarization signal showed a systematic shift during the freezing process, affected by concurrent changes of temperature, salinity, and ice formation. An anomalous induced polarization response was first observed during the transient period of supercooling and the onset of ice nucleation. Seismic measurements showed a characteristic maximal attenuation at the temperatures immediately below the freezing point, followed by a decrease with decreasing temperature. The calculated elastic moduli showed a non-hysteric response during the freeze – thaw cycle, which was different from the concurrently measured electrical resistivity response where a differential resistivity signal is observed depending on whether the soil is experiencing freezing or thawing. The differential electrical resistivity signal presents challenges for unfrozen water content estimation based on Archie's law. Using an improved formulation of Archie's law with a variable cementation exponent, the unfrozen water content estimation showed a large variation depending on the choice of the resistivity data during either a freezing or thawing cycle. Combining the electrical and seismic results, we suggest that, rather than a large hysteresis in the actual unfrozen water content, the shift of the resistivity response may reflect the changes of the distribution pattern of the unfrozen water (or ice) in the soil matrix during repeated freeze and thaw processes. Collectively, our results provide an improved petrophysical understanding of the physical and mechanical properties of saline permafrost during freeze – thaw transitions, and suggest that large uncertainty may exist when estimating the unfrozen water content using electrical resistivity data.

Leakage risk assessment is an inevitable procedure in permanent sequestration and storage of CO2 in deep saline aquifers and depleted oil and gas reservoirs, where the integrity of caprock is most critical. Low porosity and low permeability concrete cubes were employed as caprock analogs to investigate the supercritical CO2 injection-induced fracturing processes under true tri-axial stress conditions. A systematic experimental procedure, consisting of active acoustic emission measurement, pressure decay, injection pressure and temperature monitoring, fracture coloring, and gas fracturing, is formulated to qualitatively and quantitatively characterize the injection-induced fracturing processes and fracture morphology. Occurrence of injection-induced fracturing can be directly identified from peaks of borehole pressure profiles as well as sharp drops on temperature profiles due to CO2 expansion, but generally there was no fracture propagation plateau appearing for the 20 cm rock cubes with zero pore pressure. Acoustic wave signatures, including both waveform change and arrival time delay, can effectively capture the extension of induced fractures inside the opaque rock. Initiation and propagation of supercritical CO2 injection-induced fractures are highly dominated by the tri-axial stresses, following the general trend of continuum mechanics at high stress levels with large stress difference. As the stress difference decreases, induced fractures branch off in relatively arbitrary directions. For these supercritical CO2 injection-induced fracturing experiments, poroelastic mechanics model makes a decent fit with the measured breakdown pressure of the caprock analogs. Findings in this study are valuable for risk analysis and operation optimization of geological CO2 sequestration and storage as well as for CO2 fracturing design and implementation in shale and tight reservoirs.

The concept of cryogenic fracturing is that a sharp thermal gradient developed by applying a cryogenic fluid on a rock surface causes a strong local tensile stress that initiates fractures. Prior field tests suggest that field application with special equipment rated for cryogenic temperatures may deliver potential benefits. The tests did not, however, identify the fracture mechanisms at work in downhole conditions. In this study, we present our laboratory designs and procedures developed for studying cryogenic fracturing mechanisms in a well environment, and examine typical data indicative of the performance of the system. The experimental apparatus and procedures were specifically designed to conduct cryogenic fracturing tests in specimens under confining stress, with integrated cryogen transport, measurements, and fracture characterization. A true-triaxial loading system was built to simulate reservoir stress levels and anisotropic stress application, and was designed to avoid thermal stresses in tests involving cryogen by arranging discrete components in an open chamber. To maximize thermal shock on the wellbore surface, tubing and wellhead are configured so that liquid nitrogen enters the borehole and flow out after contributing to thermal shock. The temperature at boreholes and along flow lines, borehole pressure, and liquid nitrogen consumption are monitored throughout treatments. Acoustic transmission and pressure-decay measurements are used to characterize fractures before and after the experiments. Breakdown tests performed on un-stimulated specimens and stimulated specimens compare breakdown pressures of the two groups and thus evaluate the performance of thermal fracturing. The laboratory design was able to effectively apply cryogenic stimulations to laboratory rock specimens. The characterization methods were able to capture fracture creation and rock property changes due to cryogenic fracturing.

Gas flow through the vadose zone from sources at depth involves fractionation effects that can obscure the nature of transport and even the identity of the source. Transport processes are particularly complex in low permeability media but as shown in this study, can be elucidated by measuring the atmospheric noble gases. A series of laboratory column experiments was conducted to evaluate the movement of noble gas from the atmosphere into soil in the presence of a net efflux of CO2, a process that leads to fractionation of the noble gases from their atmospheric abundance ratios. The column packings were designed to simulate natural sedimentary deposition by interlayering low permeability ceramic plates and high permeability beach sand. Gas samples were collected at different depths at CO2 fluxes high enough to cause extreme fractionation of the noble gases (4He/36Ar > 20 times the air ratio). The experimental noble gas fractionation-depth profiles were in good agreement with those predicted by the dusty gas (DG) model, demonstrating the applicability of the DG model across a broad spectrum of environmental conditions. A governing equation based on the dusty gas model was developed to specifically describe noble gas fractionation at each depth that is controlled by the binary diffusion coefficient, Knudsen diffusion coefficient and the ratio of total advection flux to total flux. Finally, the governing equation was used to derive the noble gas fractionation pattern and illustrate how it is influenced by soil CO2 flux, sedimentary sequence, thickness of each sedimentary layer and each layer's physical parameters. Three potential applications of noble gas fractionation are provided: evaluating soil attributes in the path of gas flow from a source at depth to the atmosphere, testing leakage through low permeability barriers used to isolate buried waste, and tracking biological methanogenesis and methane oxidation associated with hydrocarbon degradation.

The rates of mineral dissolution reactions in porous media are difficult to predict, in part because of a lack of understanding of mineral reactive surface area in natural porous media. Common estimates of mineral reactive surface area used in reactive transport models for porous media are typically ad hoc and often based on average grain size, increased to account for surface roughness or decreased by several orders of magnitude to account for reduced surface reactivity of field as opposed to laboratory samples. In this study, accessible mineral surface areas are determined for a sample from the reservoir formation at the Nagaoka pilot CO2 injection site (Japan) using a multi-scale image analysis based on synchrotron X-ray microCT, SEM QEMSCAN, XRD, SANS, and FIB-SEM. This analysis not only accounts for accessibility of mineral surfaces to macro-pores, but also accessibility through connected micro-pores in smectite, the most abundant clay mineral in this sample. While the imaging analysis reveals that most of the micro- and macro-pores are well connected, some pore regions are unconnected and thus inaccessible to fluid flow and diffusion. To evaluate whether mineral accessible surface area accurately reflects reactive surface area a flow-through core experiment is performed and modeled at the continuum scale. The core experiment is performed under conditions replicating the pilot site and the evolution of effluent solutes in the aqueous phase is tracked. Various reactive surface area models are evaluated for their ability to capture the observed effluent chemistry, beginning with parameter values determined as a best fit to a disaggregated sediment experiment (Beckingham et al., 2016) described previously. Simulations that assume that all mineral surfaces are accessible (as in the disaggregated sediment experiment) over-predict the observed mineral reaction rates, suggesting that a reduction of RSA by a factor of 10–20 is required to match the core flood experimental data. While the fit of the effluent chemistry (and inferred mineral dissolution rates) greatly improve when the pore-accessible mineral surface areas are used, it was also necessary to include highly reactive glass phases to match the experimental observations, in agreement with conclusions from the disaggregated sediment experiment. It is hypothesized here that the 10–20 reduction in reactive surface areas based on the limited pore accessibility of reactive phases in core flood experiment may be reasonable for poorly sorted and cemented sediments like those at the Nagaoka site, although this reflects pore rather than larger scale heterogeneity.

Gas flow through the vadose zone from sources at depth involves fractionation effects that can obscure the nature of transport and even the identity of the source. Transport processes are particularly complex in low permeability media but as shown in this study, can be elucidated by measuring the atmospheric noble gases. A series of laboratory column experiments was conducted to evaluate the movement of noble gas from the atmosphere into soil in the presence of a net efflux of CO2, a process that leads to fractionation of the noble gases from their atmospheric abundance ratios. The column packings were designed to simulate natural sedimentary deposition by interlayering low permeability ceramic plates and high permeability beach sand. Gas samples were collected at different depths at CO2 fluxes high enough to cause extreme fractionation of the noble gases (4He/36Ar > 20 times the air ratio). The experimental noble gas fractionation-depth profiles were in good agreement with those predicted by the dusty gas (DG) model, demonstrating the applicability of the DG model across a broad spectrum of environmental conditions. A governing equation based on the dusty gas model was developed to specifically describe noble gas fractionation at each depth that is controlled by the binary diffusion coefficient, Knudsen diffusion coefficient and the ratio of total advection flux to total flux. Finally, the governing equation was used to derive the noble gas fractionation pattern and illustrate how it is influenced by soil CO2 flux, sedimentary sequence, thickness of each sedimentary layer and each layer's physical parameters. Three potential applications of noble gas fractionation are provided: evaluating soil attributes in the path of gas flow from a source at depth to the atmosphere, testing leakage through low permeability barriers used to isolate buried waste, and tracking biological methanogenesis and methane oxidation associated with hydrocarbon degradation.

The rates of mineral dissolution reactions in porous media are difficult to predict, in part because of a lack of understanding of mineral reactive surface area in natural porous media. Common estimates of mineral reactive surface area used in reactive transport models for porous media are typically ad hoc and often based on average grain size, increased to account for surface roughness or decreased by several orders of magnitude to account for reduced surface reactivity of field as opposed to laboratory samples. In this study, accessible mineral surface areas are determined for a sample from the reservoir formation at the Nagaoka pilot CO2 injection site (Japan) using a multi-scale image analysis based on synchrotron X-ray microCT, SEM QEMSCAN, XRD, SANS, and FIB-SEM. This analysis not only accounts for accessibility of mineral surfaces to macro-pores, but also accessibility through connected micro-pores in smectite, the most abundant clay mineral in this sample. While the imaging analysis reveals that most of the micro- and macro-pores are well connected, some pore regions are unconnected and thus inaccessible to fluid flow and diffusion. To evaluate whether mineral accessible surface area accurately reflects reactive surface area a flow-through core experiment is performed and modeled at the continuum scale. The core experiment is performed under conditions replicating the pilot site and the evolution of effluent solutes in the aqueous phase is tracked. Various reactive surface area models are evaluated for their ability to capture the observed effluent chemistry, beginning with parameter values determined as a best fit to a disaggregated sediment experiment (Beckingham et al., 2016) described previously. Simulations that assume that all mineral surfaces are accessible (as in the disaggregated sediment experiment) over-predict the observed mineral reaction rates, suggesting that a reduction of RSA by a factor of 10–20 is required to match the core flood experimental data. While the fit of the effluent chemistry (and inferred mineral dissolution rates) greatly improve when the pore-accessible mineral surface areas are used, it was also necessary to include highly reactive glass phases to match the experimental observations, in agreement with conclusions from the disaggregated sediment experiment. It is hypothesized here that the 10–20 reduction in reactive surface areas based on the limited pore accessibility of reactive phases in core flood experiment may be reasonable for poorly sorted and cemented sediments like those at the Nagaoka site, although this reflects pore rather than larger scale heterogeneity.

Fine-grained sedimentary rocks – namely mudrocks, including their laminated fissile variety — shales – make up about two thirds of all sedimentary rocks in the Earth's crust and a quarter of the continental land mass. Organic-rich shales and mudstones are the source rocks and reservoirs for conventional and unconventional hydrocarbon resources. Mudrocks are relied upon as natural barriers for geological carbon storage and nuclear waste disposal. Consideration of mudrock multi-scale physics and multi-scale spatial and temporal behavior is vital to address emergent phenomena in shale formations perturbed by engineering activities. Unique physical characteristics of shales arise as a result of their layered and highly heterogeneous and anisotropic nature, low permeability fabric, compositional complexity, and nano-scale confined chemical environments. Barriers of lexicon among geoscientists and engineers impede the development and use of conceptual models for the coupled thermal-hydraulic-mechanical-chemical-biological (THMCB) processes in mudrock formations. This manuscript reviews the THMCB process couplings, resulting emergent behavior, and key modeling approaches. We identify future research priorities, in particular fundamental knowledge gaps in understanding the phase behavior under nano-scale confinement, coupled chemo-mechanical effects on fractures, the interplay between physical and chemical processes and their rates, and issues of non-linearity and heterogeneity. We develop recommendations for future research and integrating multi-disciplinary conceptual models for the coupled multi-scale multi-physics behavior of mudrocks. Consistent conceptual models across disciplines are essential for predicting emergent processes in the subsurface, such as self-focusing of flow, time-dependent deformation (creep), fracture network development, and wellbore stability.

Fine-grained sedimentary rocks – namely mudrocks, including their laminated fissile variety — shales – make up about two thirds of all sedimentary rocks in the Earth's crust and a quarter of the continental land mass. Organic-rich shales and mudstones are the source rocks and reservoirs for conventional and unconventional hydrocarbon resources. Mudrocks are relied upon as natural barriers for geological carbon storage and nuclear waste disposal. Consideration of mudrock multi-scale physics and multi-scale spatial and temporal behavior is vital to address emergent phenomena in shale formations perturbed by engineering activities. Unique physical characteristics of shales arise as a result of their layered and highly heterogeneous and anisotropic nature, low permeability fabric, compositional complexity, and nano-scale confined chemical environments. Barriers of lexicon among geoscientists and engineers impede the development and use of conceptual models for the coupled thermal-hydraulic-mechanical-chemical-biological (THMCB) processes in mudrock formations. This manuscript reviews the THMCB process couplings, resulting emergent behavior, and key modeling approaches. We identify future research priorities, in particular fundamental knowledge gaps in understanding the phase behavior under nano-scale confinement, coupled chemo-mechanical effects on fractures, the interplay between physical and chemical processes and their rates, and issues of non-linearity and heterogeneity. We develop recommendations for future research and integrating multi-disciplinary conceptual models for the coupled multi-scale multi-physics behavior of mudrocks. Consistent conceptual models across disciplines are essential for predicting emergent processes in the subsurface, such as self-focusing of flow, time-dependent deformation (creep), fracture network development, and wellbore stability.

Recently, both core- and pore-scale imbibition experiments have shown non-equilibrium dissolution of supercritical CO2 (scCO2) and a prolonged depletion of residual scCO2. In this study, pore-scale scCO2 dissolution and mass transfer under drainage conditions were investigated using a two-dimensional heterogeneous micromodel and a novel fluorescent water dye with a sensitive pH range between 3.7 and 6.5. Drainage experiments were conducted at 9 MPa and 40 °C by injecting scCO2 into the sandstone-analogue pore network initially saturated by water without dissolved CO2 (dsCO2). During the experiments, time-lapse images of dye intensity, reflecting water pH, were obtained. These images show non-uniform pH in individual pores and pore clusters, with average pH levels gradually decreasing with time. Further analysis on selected pores and pore clusters shows that (1) rate-limited mass transfer prevails with slowly decreasing pH over time when the scCO2-water interface area is low with respect to the volume of water-filled pores and pore clusters, (2) fast scCO2 dissolution and phase equilibrium occurs when scCO2 bubbles invade into water-filled pores, significantly enhancing the area-to-volume ratio, and (3) a transition from rate-limited to diffusion-limited mass transfer occurs in a single pore when a medium area-to-volume ratio is prevalent. The analysis also shows that two fundamental processes – scCO2 dissolution at phase interfaces and diffusion of dsCO2 at the pore scale (10–100 µm) observed after scCO2 bubble invasion into water-filled pores without pore throat constraints – are relatively fast. The overall slow dissolution of scCO2 in the millimeter-scale micromodel can be attributed to the small area-to-volume ratios that represent pore-throat configurations and characteristics of phase interfaces. This finding is applicable for the behavior of dissolution at pore, core, and field scales when water-filled pores and pore clusters of varying size are surrounded by scCO2 at narrow pore throats.

Recently, both core- and pore-scale imbibition experiments have shown non-equilibrium dissolution of supercritical CO2 (scCO2) and a prolonged depletion of residual scCO2. In this study, pore-scale scCO2 dissolution and mass transfer under drainage conditions were investigated using a two-dimensional heterogeneous micromodel and a novel fluorescent water dye with a sensitive pH range between 3.7 and 6.5. Drainage experiments were conducted at 9 MPa and 40 °C by injecting scCO2 into the sandstone-analogue pore network initially saturated by water without dissolved CO2 (dsCO2). During the experiments, time-lapse images of dye intensity, reflecting water pH, were obtained. These images show non-uniform pH in individual pores and pore clusters, with average pH levels gradually decreasing with time. Further analysis on selected pores and pore clusters shows that (1) rate-limited mass transfer prevails with slowly decreasing pH over time when the scCO2-water interface area is low with respect to the volume of water-filled pores and pore clusters, (2) fast scCO2 dissolution and phase equilibrium occurs when scCO2 bubbles invade into water-filled pores, significantly enhancing the area-to-volume ratio, and (3) a transition from rate-limited to diffusion-limited mass transfer occurs in a single pore when a medium area-to-volume ratio is prevalent. The analysis also shows that two fundamental processes – scCO2 dissolution at phase interfaces and diffusion of dsCO2 at the pore scale (10–100 µm) observed after scCO2 bubble invasion into water-filled pores without pore throat constraints – are relatively fast. The overall slow dissolution of scCO2 in the millimeter-scale micromodel can be attributed to the small area-to-volume ratios that represent pore-throat configurations and characteristics of phase interfaces. This finding is applicable for the behavior of dissolution at pore, core, and field scales when water-filled pores and pore clusters of varying size are surrounded by scCO2 at narrow pore throats.

The few prethaw observations of tundra carbon fluxes suggest that there may be large spring releases, but little is known about the scale and underlying mechanisms of this phenomenon. To address these questions, we combined ecosystem eddy flux measurements from two towers near Barrow, Alaska, with mechanistic soil-core thawing experiment. During a 2 week period prior to snowmelt in 2014, large fluxes were measured, reducing net summer uptake of CO2 by 46% and adding 6% to cumulative CH4 emissions. Emission pulses were linked to unique rain-on-snow events enhancing soil cracking. Controlled laboratory experiment revealed that as surface ice thaws, an immediate, large pulse of trapped gases is emitted. These results suggest that the Arctic CO2 and CH4 spring pulse is a delayed release of biogenic gas production from the previous fall and that the pulse can be large enough to offset a significant fraction of the moderate Arctic tundra carbon sink.