Permeability evolution in sorbing media: analogies between organic‐rich shale and coal

Shale gas reservoirs like coalbed methane (CBM) reservoirs are promising targets for geological sequestration of carbon dioxide (CO₂). However, the evolution of permeability in shale reservoirs on injection of CO₂ is poorly understood unlike CBM reservoirs. In this study, we report measurements of permeability evolution in shales infiltrated separately by nonsorbing (He) and sorbing (CO₂) gases under varying gas pressures and confining stresses. Experiments are completed on Pennsylvanian shales containing both natural and artificial fractures under nonpropped and propped conditions. We use the models for permeability evolution in coal (Journal of Petroleum Science and Engineering, Under Revision) to codify the permeability evolution observed in the shale samples. It is observed that for a naturally fractured shale, the He permeability increases by approximately 15% as effective stress is reduced by increasing the gas pressure from 1 MPa to 6 MPa at constant confining stress of 10 MPa. Conversely, the CO₂ permeability reduces by a factor of two under similar conditions. A second core is split with a fine saw to create a smooth artificial fracture and the permeabilities are measured for both nonpropped and propped fractures. The He permeability of a propped artificial fracture is approximately 2‐ to 3fold that of the nonpropped fracture. The He permeability increases with gas pressure under constant confining stress for both nonpropped and propped cases. However, the CO₂ permeability of the propped fracture decreases by between one‐half to one‐third as the gas pressure increases from 1 to 4 MPa at constant confining stress. Interestingly, the CO₂ permeability of nonpropped fracture increases with gas pressure at constant confining stress. The permeability evolution of nonpropped and propped artificial fractures in shale is found to be similar to those observed in coals but the extent of permeability reduction by swelling is much lower in shale due to its lower organic content. Optical profilometry is used to quantify the surface roughness. The changes in surface roughness indicate significant influence of proppant indentation on fracture surface in the shale sample. The trends of permeability evolution on injection of CO₂ in coals and shales are found analogous; therefore, the permeability evolution models previously developed for coals are adopted to explain the permeability evolution in shales.     

Experimental study of the effect of variation in in‐situ stress on capillary residual trapping during CO2 geo‐sequestration in sandstone reservoirs

During a geo‐sequestration process, CO₂ injection causes an increase in reservoir pore pressure, which in turn decreases the reservoir net effective stress. Changes in effective stress can change all the reservoir and cap‐rock properties including residual saturations. This article presents the results of an experimental work carried out to understand the potential change in the volumes of residually trapped CO₂, while the porous medium tested underwent change in the net effective stress under in‐situ reservoir conditions of pore pressure and temperature. The experimental results obtained show that an initial 1725 psi (11.9 MPa) decrease in the net effective pressure caused 1.4% reduction in the volumes of residually trapped CO₂, while another 1500 psi (10.3 MPa) reduction caused a further 3.2% drop in the residual saturation of CO₂.     

Carbon dioxide controlled earthquake distribution pattern in the NW Bohemian swarm earthquake region,western Eger Rift,Czech Republic – gas migration in the crystalline basement

The ascent of magmatic carbon dioxide in the western Eger (Oh?e) Rift is interlinked with the fault systems of the Variscian basement. In the Cheb Basin, the minimum CO₂ flux is about 160 m³ h^?1, with a diminishing trend towards the north and ceasing in the main epicentral area of the Northwest Bohemian swarm earthquakes. The ascending CO₂ forms Ca‐Mg‐HCO₃ type waters by leaching of cations from the fault planes and creates clay minerals, such as kaolinite, as alteration products on affected fault planes. These mineral reactions result in fault weakness and in hydraulically interconnected fault network. This leads to a decrease in the friction coefficient of the Coulomb failure stress (CFS) and to fault creep as stress build‐up cannot occur in the weak segments. At the transition zone in the north of the Cheb Basin, between areas of weak, fluid conductive faults and areas of locked faults with frictional strength, fluid pressure can increase resulting in stress build‐up. This can trigger strike‐slip swarm earthquakes. Fault creep or movements in weak segments may support a stress build‐up in the transition area by transmitting fluid pressure pulses. Additionally to fluid‐driven triggering models, it is important to consider that fluids ascending along faults are CO₂‐supersaturated thus intensifying the effect of fluid flow. The enforced flow of CO₂‐supersaturated fluids in the transitional zone from high to low permeability segments through narrowings triggers gas exsolution and may generate pressure fluctuations. Phase separation starts according to the phase behaviour of CO₂‐H₂O systems in the seismically active depths of NW Bohemia and may explain the vertical distribution of the seismicity. Changes in the size of the fluid transport channels in the fault systems caused, or superimposed, by fault movements, can produce fluid pressure increases or pulses, which are the precondition for triggering fluid‐induced swarm earthquakes.     

The origin of overpressure in 'old' sedimentary basins: an example from the Cooper Basin, Australia

Overpressure in ‘old’ sedimentary basins that have not undergone rapid, recent sedimentation cannot be easily explained using traditional burial‐driven mechanisms. The last significant burial event in the Cooper Basin, Australia, was the Late Cretaceous deposition of the Winton Formation (98.5–90 Ma). Maximum temperature in the basin was attained during the Late Cretaceous, with cooling beginning prior to 75 Ma. Hence, overpressure related to rapid burial or palaeomaximum temperatures (e.g. hydrocarbon generation) must have developed prior to 75 Ma. Retaining overpressure for 75 Ma in ‘old’ basins such as the Cooper Basin requires extremely low seal permeabilities. An alternative explanation is that overpressure in the Cooper Basin has been generated because of an increase in mean stress associated with an increase in horizontal compressive stress since Late Cretaceous times. Structural observations and contemporary stress data indicate that there has been an increase in mean stress of approximately 50 MPa between Late Cretaceous times to that presently measured at 3780 m. The largest measured overpressure in the Cooper Basin is 14.5 MPa at 3780 m in the Kirby 1 well. Hence, disequilibrium compaction driven by increasing mean stress can explain the magnitude of the observed overpressure in the Cooper Basin. Increases in mean stress (tectonic loading) may be a feasible mechanism for overpressure generation in other ‘old’ basins that have undergone a recent increase in horizontal stress (e.g. Anadarko Basin).     

The October 2008 Nový Kostel earthquake swarm and its gas geochemical precursor

A gas geochemical precursor anomaly was identified prior to the October 2008 Nový Kostel (Czech Republic) earthquake swarm with a peak magnitude M_L of 3.8. This anomaly was observed as a deviation of CO₂ concentrations from the long‐term annual CO₂ concentration trend in the gas extracted from the scree at the Nový Kostel and Old?i?ská gas monitoring stations, which are directly above the Plesná valley‐Po?átky and Mariánské Lázně fault systems. Both sites are located within the major focal zone of the NW Bohemian swarm earthquake region at the northern edge of the Cheb Basin. A decrease in CO₂ concentration started at Nový Kostel in September 2008, 17 days before the swarm, opposite to the usually increasing annual trend in the autumn period, and ended with a nearly coseismic drop immediately prior to the onset of the first swarm. The CO₂ concentrations at Old?i?ská, deviating from the annual trend, did not further increase after August 2008. The calculated horizontal strain field, based on the data of two permanent Global Navigation Satellite Systems stations, proved there was horizontal compression in this period. The increasing compression along the Plesná valley‐Po?átky and Mariánské Lázně fault systems during the stress build‐up reduced the fault permeability prior to this earthquake swarm as indicated by the decrease in CO₂ concentration. The 17‐day duration of the earthquake precursor at Nový Kostel and about 65 days at Old?i?ská lie within the range of the precursor times that are hypothesized worldwide for an M_L = 3.8 earthquake. The nature of earthquake precursors and their origin are discussed, for example, as an indication of changed fault permeability by stress build‐up in the case of the Nový Kostel swarm earthquake precursor or as fault opening in other cases.     

Fluid effect on hydraulic fracture propagation behavior: a comparison between water and supercritical CO2‐like fluid

The initiation of hydraulic fractures during fluid injection in deep formations can be either engineered or induced unintentionally. Upon injection of CO₂, the pore fluids in deep formations can be changed from oil/saline water to CO₂ or CO₂ dominated. The type of fluid is important not only because the fluid must fracture the rock, but also because rocks saturated with different pore fluids behave differently. We investigated the influence of fluid properties on fracture propagation behavior by using the cohesive zone model in conjunction with a poroelasticity model. Simulation results indicate that the pore pressure fields are very different for different pore fluids even when the initial field conditions and injection schemes (rate and time) are kept the same. Low viscosity fluids with properties of supercritical CO₂ will create relatively thin and much shorter fractures in comparison with fluids exhibiting properties of water under similar injection schemes. Two significant times are recognized during fracture propagation: the time at which a crack ceases opening and the later time point at which a crack ceases propagating. These times are very different for different fluids. Both fluid compressibility and viscosity influence fracture propagation, with viscosity being the more important property. Viscosity can greatly affect hydraulic conductivity and the leak‐off coefficient. This analysis assumes the in‐situ pore fluid and injected fluid are the same and the pore space is 100% saturated by that fluid at the beginning of the simulation.     

Simulation of the impact of faults on CO2 injection into sandstone reservoirs

Numerical simulations of multiphase CO₂ behavior within faulted sandstone reservoirs examine the impact of fractures and faults on CO₂ migration in potential subsurface injection systems. In southeastern Utah, some natural CO₂ reservoirs are breached and CO₂‐charged water flows to the surface along permeable damage zones adjacent to faults; in other sites, faulted sandstones form barriers to flow and large CO₂‐filled reservoirs result. These end‐members serve as the guides for our modeling, both at sites where nature offers ‘successful’ storage and at sites where leakage has occurred. We consider two end‐member fault types: low‐permeability faults dominated by deformation‐band networks and high‐permeability faults dominated by fracture networks in damage zones adjacent to clay‐rich gouge. Equivalent permeability (k) values for the fault zones can range from <10^?14 m² for deformation‐band‐dominated faults to >10^?12 m² for fracture‐dominated faults regardless of the permeability of unfaulted sandstone. Water–CO₂ fluid‐flow simulations model the injection of CO₂ into high‐k sandstone (5 × 10^?13 m²) with low‐k (5 × 10^?17 m²) or high‐k (5 × 10^?12 m²) fault zones that correspond to deformation‐band‐ or fracture‐dominated faults, respectively. After 500 days, CO₂ rises to produce an inverted cone of free and dissolved CO₂ that spreads laterally away from the injection well. Free CO₂ fills no more than 41% of the pore space behind the advancing CO₂ front, where dissolved CO₂ is at or near geochemical saturation. The low‐k fault zone exerts the greatest impact on the shape of the advancing CO₂ front and restricts the bulk of the dissolved and free CO₂ to the region upstream of the fault barrier. In the high‐k aquifer, the high‐k fault zone exerts a small influence on the shape of the advancing CO₂ front. We also model stacked reservoir seal pairs, and the fracture‐dominated fault acts as a vertical bypass, allowing upward movement of CO₂ into overlying strata. High‐permeability fault zones are important pathways for CO₂ to bypass unfaulted sandstone, which leads to reduce sequestration efficiency. Aquifer compartmentalization by low‐permeability fault barriers leads to improved storativity because the barriers restrict lateral CO₂ migration and maximize the volume and pressure of CO₂ that might be emplaced in each fault‐bound compartment. As much as a 3.5‐MPa pressure increase may develop in the injected reservoir in this model domain, which under certain conditions may lead to pressures close to the fracture pressure of the top seal.     

Permeability of the Mercia Mudstone: suitability as caprock to carbon capture and storage sites

The Upper Triassic Mercia Mudstone is the caprock to potential carbon capture and storage (CCS) sites in porous and permeable Lower Triassic Sherwood Sandstone reservoirs and aquifers in the UK (primarily offshore). This study presents direct measurements of vertical (k_v) and horizontal (k_h) permeability of core samples from the Mercia Mudstone across a range of effective stress conditions to test their caprock quality and to assess how they will respond to changing effective stress conditions that may occur during CO₂ injection and storage. The Mercia samples analysed were either clay‐rich (muddy) siltstones or relatively clean siltstones cemented by carbonate and gypsum. Porosity is fairly uniform (between 7.4 and 10.7%). Porosity is low either due to abundant depositional illite or abundant diagenetic carbonate and gypsum cements. Permeability values are as low as 10^?20 m² (10nD), and therefore, the Mercia has high sealing capacity. These rocks have similar horizontal and vertical permeabilities with the highest k_h/k_v ratio of 2.03 but an upscaled k_h/k_v ratio is 39, using the arithmetic mean of k_h and the harmonic mean of k_v. Permeability is inversely related to the illite clay content; the most clay‐rich (illite‐rich) samples represent very good caprock quality; the cleaner Mercia Mudstone samples, with pore‐filling carbonate and gypsum cements, represent fair to good caprock quality. Pressure sensitivity of permeability increases with increasing clay mineral content. As pore pressure increases during CO₂ injection, the permeability of the most clay‐rich rocks will increase more than carbonate‐ and gypsum‐rich rocks, thus decreasing permeability heterogeneity. The best quality Mercia Mudstone caprock is probably not geochemically sensitive to CO₂ injection as illite, the cause of the lowest permeability, is relatively stable in the presence of CO₂–water mixtures.     

The stress regime of the Western Canadian Sedimentary Basin

All available information relevant to in situ stress orientations and magnitudes in the Western Canadian Sedimentary Basin (WCSB) were examined to provide a better understanding of how regional stress fields may affect geothermal development. The smallest principal stress is horizontal over most of the Western Canadian Sedimentary Basin, and it varies in magnitude across the region. Horizontal stress trajectories show that S_Hmax axes are generally aligned SW–NE. A total of 1643 measurements of microfracture and minifracture closure pressures, leak‐off pressures and fracture breakdown pressures have been harnessed to map S_Hmin gradients across the basin at depths of 156–500, 500–1000, 1000–4185 and 2000–4185 m. Vertical stress magnitudes, calculated in 91 wells, showed that at constant depth, S_V increases towards the Canadian Rocky Mountains. Resultant regional stress maps show consistent trends in orientation of stress axes. As a result, predictions can be made that propagation axes of subsurface hydraulic fractures will be dominantly SW–NE, except over the Peace River Arch area, where they will trend more towards SSW–NNE. Engineered geothermal systems in the WCSB can be optimised by drilling horizontal wells parallel to S_Hmin.     

Real‐time quadrupole mass spectrometer analysis of gas in borehole fluid samples acquired using the U‐tube sampling methodology

Sampling of fluids in deep boreholes is challenging because of the necessity of minimizing external contamination and maintaining sample integrity during recovery. The U‐tube sampling methodology was developed to collect large volume, multiphase samples at in situ pressures. As a permanent or semi‐permanent installation, the U‐tube can be used for rapidly acquiring multiple samples or it may be installed for long‐term monitoring applications. The U‐tube was first deployed in Liberty County, TX to monitor crosswell CO₂ injection as part of the Frio CO₂ sequestration experiment. Analysis of gases (dissolved or separate phase) was performed in the field using a quadrupole mass spectrometer, which served as the basis for determining the arrival of the CO₂ plume. The presence of oxygen and argon in elevated concentrations, along with reduced methane concentration, indicates sample alteration caused by the introduction of surface fluids during borehole completion. Despite producing the well to eliminate non‐native fluids, measurements demonstrate that contamination persists until the immiscible CO₂ injection swept formation fluid into the observation wellbore.     

Geometry‐coupled reactive fluid transport at the fracture scale: application to CO2 geologic storage

Water acidification follows CO₂ injection and leads to reactive fluid transport through pores and rock fractures, with potential implications to reservoirs and wells in CO₂ geologic storage and enhanced oil recovery. Kinetic rate laws for dissolution reactions in calcite and anorthite are combined with the Navier‐Stokes law and advection–diffusion transport to perform geometry‐coupled numerical simulations in order to study the evolution of chemical reactions, species concentration, and fracture morphology. Results are summarized as a function of two dimensionless parameters: the Damköhler number Da which is the ratio between advection and reaction times, and the transverse Peclet number Pe defined as the ratio between the time for diffusion across the fracture and the time for advection along the fracture. Reactant species are readily consumed near the inlet in a carbonate reservoir when the flow velocity is low (low transverse Peclet number and Da > 10^?1). At high flow velocities, diffusion fails to homogenize the concentration field across the fracture (high transverse Peclet number Pe > 10^?1). When the reaction rate is low as in anorthite reservoirs (Da < 10^?1), reactant species are more readily transported toward the outlet. At a given Peclet number, a lower Damköhler number causes the flow channel to experience a more uniform aperture enlargement along the length of the fracture. When the length‐to‐aperture ratio is sufficiently large, say l/d > 30, the system response resembles the solution for 1D reactive fluid transport. A decreased length‐to‐aperture ratio slows the diffusive transport of reactant species to the mineral fracture surface, and analyses of fracture networks must take into consideration both the length and slenderness of individual fractures in addition to Pe and Da numbers.     

Wettability alteration of caprock minerals by carbon dioxide

One of the critical factors that control the efficiency of CO₂ geological storage process in aquifers and hydrocarbon reservoirs is the capillary‐sealing potential of the caprock. This potential can be expressed in terms of the maximum reservoir overpressure that the brine‐saturated caprock can sustain, i.e. of the CO₂ capillary entry pressure. It is controlled by the brine/CO₂ interfacial tension, the water‐wettability of caprock minerals, and the pore size distribution within the caprock. By means of contact angle measurements, experimental evidence was obtained showing that the water‐wettability of mica and quartz is altered in the presence of CO₂ under pressures typical of geological storage conditions. The alteration is more pronounced in the case of mica. Both minerals are representative of shaly caprocks and are strongly water‐wet in the presence of hydrocarbons. A careful analysis of the available literature data on breakthrough pressure measurements in caprock samples confirms the existence of a wettability alteration by dense CO₂, both in shaly and in evaporitic caprocks. The consequences of this effect on the maximum CO₂ storage pressure and on CO₂ storage capacity in the underground reservoir are discussed. For hydrocarbon reservoirs that were initially close to capillary leakage, the maximum allowable CO₂ storage pressure is only a fraction of the initial reservoir pressure.     

The inclusion record of fluid evolution,crack healing and trapping from a heterogeneous system during rapid cooling of pegmatitic veins (Dronning Maud Land; Antarctica)

Granitoid (pegmatite and aplite) veins in metamorphic rocks and intrusive syenites of central Dronning Maud Land, Antarctica, are flanked by conspicuous light‐coloured alteration halos, which represent the damage zone of fracture propagation. The damage zone is characterized by a high density of sealed or healed microcracks, about 1 order of magnitude above background. Fluid inclusions along healed microcracks in quartz of both pegmatite and alteration halos are inspected by optical and scanning electron microscopy, and their composition is analysed by microthermometry and quadrupole mass spectrometry. The similar inclusion record in the granitoid vein and in the damaged host rock indicates the derivation of the fluids from the hydrous melt phase. The aqueous inclusions bear abundant daughter crystals, mainly silicates, and may represent a hydrous melt. The volatile composition is variable in the system H₂O–CO₂, with mostly subordinate amounts of N₂. Phase separation with partitioning of CO₂ into the fluid phase coexisting with the hydrous melt, and possibly immiscibility in the subsolidus range, govern fluid evolution during cooling. The variable CO₂/N₂ ratio suggests mixing with fluids from an external source in the host rock and vigorous circulation at an early stage of high transient permeability. Experiments have shown that healing of microcracks at high temperatures is a matter of hours to weeks, hence similar in time scale to the cooling of the cm‐ to dm‐thick granitoid veins. In this case, rapid cooling and concomitant crack healing in a system undergoing phase separation causes a broad compositional variability of the inclusions due to necking down, and the underpressure developing in closed compartments precludes a meaningful thermobarometric interpretation.     

Experimental investigation of carbon dioxide trapping due to capillary retention in saline aquifers

Capillary trapping is a physical mechanism by which carbon dioxide (CO₂) is naturally immobilized in the pore spaces of aquifer rocks during geologic carbon sequestration operations, and thus a key aspect of estimating geologic storage potential. Here, we studied capillary trapping of supercritical carbon dioxide (scCO₂), and the effect of initial scCO₂ saturation and flow rate on the storage/trapping potential of Berea sandstone. We performed two‐phase, scCO₂‐brine displacements in two samples, each subject to four sequential drainage–imbibition core‐flooding cycles to quantify end‐point saturations of scCO₂ with the aid of micro‐ and macro‐computed tomography imaging. From these experiments, we found that between 51% and 75% of the initial CO₂ injected can be left behind after the brine injection. We also observed that the initial scCO₂ saturation influenced the residual scCO₂ saturation to a greater extent than the rate of brine injection under the experimental conditions examined. In spite of differences in the experimental conditions tested, as well as those reported in the literature, initial and residual saturations were found to follow a consistent relationship.     

Changes in fluid pathways in a calcite vein mesh (Natih Formation,Oman Mountains): insights from stable isotopes

We present a structural, microstructural, and stable isotope study of a calcite vein mesh within the Cretaceous Natih Formation in the Oman Mountains to explore changes in fluid pathways during vein formation. Stage 1 veins form a mesh of steeply dipping crack‐seal extension veins confined to a 3.5‐m‐thick stratigraphic interval. Different strike orientations of Stage 1 veins show mutually crosscutting relationships. Stage 2 veins occur in the dilatant parts of a younger normal fault interpreted to penetrate the stratigraphy below. The δ¹⁸O composition of the host rock ranges from 21.8‰ to 23.7‰. The δ¹³C composition ranges from 1.5‰ to 2.3‰. This range is consistent with regionally developed diagenetic alteration at top of the Natih Formation. The δ¹⁸O composition of vein calcite varies from 22.5‰ to 26.2‰, whereas δ¹³C composition ranges from ?0.8‰ to 2.1‰. A first trend observed in Stage 1 veins involves a decrease of δ¹³C to compositions nearly 1.3‰ lower than the host rock, whereas δ¹⁸O remains constant. A second trend observed in Stage 2 calcite has δ¹⁸O values up to 3.3‰ higher than the host rock, whereas the δ¹³C composition is similar. Stable isotope data and microstructures indicate an episodic flow regime for both stages. During Stage 1, formation of a stratabound vein mesh involved bedding‐parallel flow, under near‐lithostatic fluid pressures. The ¹⁸O fluid composition was host rock‐buffered, whereas ¹³C composition was relatively depleted. This may reflect reaction of low ¹³C CO₂ derived by fluid interaction with organic matter in the limestones. Stage 2 vein formation is associated with fault‐controlled fluid flow accessing fluids in equilibrium with limestones about 50 m beneath. We highlight how evolution of effective stress states and the growth of faults influence the hydraulic connectivity in fracture networks and we demonstrate the value of stable isotopes in tracking changes in fluid pathways.     

Basin‐scale fluid movement patterns revealed by veins: Wessex Basin,UK

Calcite veins at outcrop in the Mesozoic, oil‐bearing Wessex Basin, UK, have been studied using field characterization, petrography, fluid inclusions and stable isotopes to help address the extent, timing and spatial and stratigraphic variability of basin‐scale fluid flow. The absence of quartz shows that veins formed at low temperature without an influence of hydrothermal fluids. Carbon isotopes suggest that the majority of vein calcite was derived locally from the host rock but up to one quarter of the carbon in the vein calcite came from CO₂ from petroleum source rocks. Veins become progressively enriched in source‐rock‐derived CO₂ from the outer margin towards the middle, indicating a growing influence of external CO₂. The carbon isotope data suggest large‐scale migration of substantial amounts of CO₂ around the whole basin. Fluid inclusion salinity data and interpreted water‐δ¹⁸O data show that meteoric water penetrated deep into the western part of the basin after interacting with halite‐rich evaporites in the Triassic section before entering fractured Lower and Middle Jurassic rocks. This large‐scale meteoric invasion of the basin probably happened during early Cenozoic uplift. A similar approach was used to reveal that, in the eastern part of the basin close to the area that underwent most uplift, uppermost Jurassic and Cretaceous rocks underwent vein formation in the presence of marine connate water suggesting a closed system. Stratigraphically underlying Upper Jurassic mudstone and Lower Cretaceous sandstone, in the most uplifted part of the basin, contain veins that resulted from intermediate behaviour with input from saline meteoric water and marine connate waters. Thus, while source‐rock‐derived CO₂ seems to have permeated the entire section, water movement has been more restricted. Oil‐filled inclusions in vein calcite have been found within dominant E‐W trending normal faults, suggesting that these may have facilitated oil migration.     

Fluidized sandstone intrusions as an indicator of Paleostress orientation, Santa Cruz, California

The late Miocene sandstone intrusions of northern Santa Cruz County, California, are the largest subaerial exposures of clastic intrusions on earth. The intrusions are sourced from a sandstone, underlying mudstone, accumulated in an outer shelf to upper slope environment. Dikes are the most frequent intrusion type, reach the greatest thickness and tend to strike north‐east and dip steeply. One giant dike is more than 150 m wide. Sills are least frequent, locally > 8 m thick and have no clear preferred geographical distribution. Clustered intrusions are commonly < 10 cm thick and mostly composed of dikes of various attitudes. The majority of the intrusions probably were injected shallowly as some extrude onto the seafloor. The local seafloor extrusion also indicates injection during the deposition of the Santa Cruz Mudstone (7–9 Ma). The intrusions are concentrated at the basin margin. Fluid pressure at the centre of the basin and perhaps hydrocarbons were communicated to the basin margin through the then sand, causing fluid overpressures that contributed to the fluidization and intrusion into the overlying mudstone. Primarily north‐east‐striking, steeply dipping dikes and secondarily, shallowly dipping sills are most significant in terms of regional connectivity of intrusions and physical dilation of the formation. The orientation of the dikes and sills indicates a regional stress field with a horizontal NE–SW maximum and a NW–SE minimum compressive direction. The simultaneous development of dikes and sills suggests similar magnitudes of the minimum and intermediate principal stresses. Preferential weakness along bedding contributed to the development of sills. Palaeomagnetic data indicate no significant block rotation around a vertical axis. The maximum principal stress direction indicated by the intrusions is about 55° to the San Gregorio Fault and about 70° to the San Andreas Fault during the late Miocene. This stress field is similar to the modern stress field and suggests moderate fault weakness.     

Migration of metamorphic CO2 into a coal seam: a natural analog study to assess the long‐term fate of CO2 in Coal Bed Carbon Capture,Utilization, and Storage Projects

This study assesses the displacement of coalbed methane by CO₂ migration along a fault into the coal seam in the Yaojie coalfield. Coal and gas samples were collected continuously at various distances in NO.2 coal seam from F19 fault. Vitrinite reflectance, maceral, and pore distributions and proximate analysis of fourteen coal samples were performed. Gas components, concentrations, carbon isotopes of 28 gas samples were determined. We examined the coal–gas trace characteristics of coalbed methane displaced away from the fault by CO₂ injection after geological ages. From east to west, away from the F19 fault, the CO₂ concentration decreased, whereas the CH₄ concentration increased gradually. The δ¹³C values for CO₂ varied between ?9.94‰ and 1.12‰, suggesting a metamorphic origin. A wider range of values (from ?9.94‰ to 20‰) was associated with the mixing of microbial carbon dioxide, isotopic fractionation during CO₂ migration through the microporous structures of coals, and/or carbon isotope fractionation during gas–water exchange and dissolution of CO₂. Away from the F19 fault, the volumes of micropores, mesopores and macropores decrease gradually. The Dubinin–Radushkevich (DR) micropore volume decreased from 0.0059 to 0.0037 cm³ g^‐1, and the mesopore and macropore volumes decreased from 0.066 to 0.026 cm³ g^‐1. The CO₂ injection can mobilize aromatic hydrocarbons and mineral matter from coal matrix, resulting in the decrease in the absorption peak intensity for coal samples after supercritical CO₂ treatment, which indicates that chemical reactions occur between coal and CO₂, not only physical adsorption.     

Characteristics of CO2‐driven cold‐water geyser,Crystal Geyser in Utah: experimental observation and mechanism analyses

Geologic carbon capture and storage (CCS) is an option for reducing CO₂ emissions, but leakage to the surface is a risk factor. Natural CO₂ reservoirs that erupt from abandoned oil and gas holes leak to the surface as spectacular cold geysers in the Colorado Plateau, United States. A better understanding of the mechanisms of CO₂‐driven cold‐water geysers will provide valuable insight about the potential modes of leakage from engineered CCS sites. A notable example of a CO₂‐driven cold‐water geyser is Crystal Geyser in central Utah. We investigated the fluid mechanics of this regularly erupting geyser by instrumenting its conduit with sensors and measuring pressure and temperature every 20 sec over a period of 17 days. Analyses of these measurements suggest that the timescale of a single‐eruption cycle is composed of four successive eruption types with two recharge periods ranging from 30 to 40 h. Current eruption patterns exhibit a bimodal distribution, but these patterns evolved during past 80 years. The field observation suggests that the geyser's eruptions are regular and predictable and reflect pressure and temperature changes resulting from Joule–Thomson cooling and endothermic CO₂ exsolution. The eruption interval between multiple small‐scale eruptions is a direct indicator of the subsequent large‐scale eruption.     

Bleached mudstone,iron concretions,and calcite veins: a natural analogue for the effects of reducing CO2‐bearing fluids on migration and mineralization of iron,sealing properties,and composition of mudstone cap rocks

This study investigates the Wangfu Depression of the Songliao Basin, China, as a natural analogue site for Fe migration (bleaching) and mineralization (formation of iron concretions) caused by reducing CO₂‐bearing fluids that leak along fractures after carbon capture, utilization, and storage. We also examined the origin of fracture‐filling calcite veins, the properties of self‐sealing fluids, the influence of fluids on the compositions of mudstone and established a bleaching model for the study area. Our results show that iron concretions are the oxidative products of precursor minerals (pyrite and siderite) during uplift and are linked to H₂S and CO₂ present in early stage fluids. The precipitation of calcite veins is the result of CO₂ degassing and is related to CO₂, CH₄, and minor heavy hydrocarbons in the main bleaching fluids. In our model, fluids preferentially enter high‐permeability fracture systems and result in the bleaching of surrounding rocks and precipitation of calcite veins. The infilling of calcite veins significantly decreases the permeability of fractures and forces the fluids to slowly enter and bleach the mudstone rocks. The Fe²⁺ released during bleaching migrates to elsewhere with the solutions or is reprecipitated in the calcite veins and iron concretions. The formation of calcite veins reduces the fracture space and effectively prevents fluid flow. The fluids have an insignificant effect on minerals within the mudstone. In terms of the chemistry of the mudstone, only the contents of Fe₂O₃, U, and Mo change significantly, with the content of U increasing in the mudstone and the contents of Fe₂O₃ and Mo decreasing during bleaching.