A numerical study of mineral alteration and self-sealing efficiency of a caprock for CO2 geological storage

Geochemical interactions of brine–rock–gas have a significant impact on the stability and integrity of the caprock for long-term CO₂ geological storage. Invasion of CO₂ into the caprock from the storage reservoir by (1) molecular diffusion of dissolved CO₂, (2) CO₂-water two-phase flow after capillary breakthrough, and (3) CO₂ flow through existing open fractures may alter the mineralogy, porosity, and mechanical strength of the caprock due to the mineral dissolution or precipitation. This determines the self-enhancement or self-sealing efficiency of the caprock. In this paper, two types of caprock, a clay-rich shale and a mudstone, are considered for the modeling analyses of the self-sealing and self-enhancement phenomena. The clay-rich shale taken from the Jianghan Basin of China is used as the base-case model. The results are compared with a mudstone caprock which is compositionally very different than the clay-rich shale. We focus on mineral alterations induced by the invasion of CO₂, feedback on medium properties such as porosity, and the self-sealing efficiency of the caprock. A number of sensitivity simulations are performed using the multiphase reactive transport code TOUGHREACT to identify the major minerals that have an impact on the caprock’s self-sealing efficiency. Our model results indicate that under the same hydrogeological conditions, the mudstone is more suitable to be used as a caprock. The sealing distances are barely different in the two types of caprock, both being about 0.6 m far from the interface between the reservoir and caprock. However, the times of occurrence of sealing are considerably different. For the mudstone model, the self-sealing occurs at the beginning of simulation, while for the clay-rich shale model, the porosity begins to decline only after 100 years. At the bottom of the clay-rich shale column, the porosity declines to 0.034, while that of mudstone declines to 0.02. The sensitive minerals in the clay-rich shale model are calcite, magnesite, and smectite-Ca. Anhydrite and illite provide Ca²⁺ and Mg²⁺ to the sensitive minerals for their precipitation. The mudstone model simulation is divided into three stages. There are different governing minerals in different stages, and the effect of the reservoir formation water on the alteration of sensitive minerals is significant.     

Evaluating the impact of caprock and reservoir properties on potential risk of CO2 leakage after injection

Numerical models are essential tools in fully understanding the fate of injected CO₂ for commercial-scale sequestration projects and should be included in the life cycle of a project. Common practice involves modeling the behavior of CO₂ during and after injection using site-specific reservoir and caprock properties. Little has been done to systematically evaluate and compare the effects of a broad but realistic range of reservoir and caprock properties on potential CO₂ leakage through caprocks. This effort requires sampling the physically measurable range of caprock and reservoir properties, and performing numerical simulations of CO₂ migration and leakage. In this study, factors affecting CO₂ leakage through intact caprocks are identified. Their physical ranges are determined from the literature from various field sites. A quasi-Monte Carlo sampling approach is used such that the full range of caprock and reservoir properties can be evaluated without bias and redundant simulations. For each set of sampled properties, the migration of injected CO₂ is simulated for up to 200 years using the water–salt–CO₂ operational mode of the STOMP simulator. Preliminary results show that critical factors determining CO₂ leakage rate through caprocks are, in decreasing order of significance, the caprock thickness, caprock permeability, reservoir permeability, caprock porosity, and reservoir porosity. This study provides a function for prediction of potential CO₂ leakage risk due to permeation of intact caprock and identifies a range of acceptable seal thicknesses and permeability for sequestration projects. The study includes an evaluation of the dependence of CO₂ injectivity on reservoir properties.     

Chemical effects of sulfur dioxide co-injection with carbon dioxide on the reservoir and caprock mineralogy and permeability in depleted gas fields

The most suitable candidates for subsurface storage of CO₂ are depleted gas fields. Their ability to retain CO₂ can however be influenced by the effect which impurities in the CO₂ stream (e.g. H₂S and SO₂) have on the mineralogy of reservoir and seal. In order to investigate the effects of SO₂ we carried out laboratory experiments on reservoir and cap rock core samples from gas fields in the northeast of the Netherlands. The rock samples were contained in reactor vessels for 30 days in contact with CO₂ and 100 ppm SO₂ under in-situ conditions (300 bar, 100 °C). The vessels also contained brine with the same composition as in the actual reservoir. Furthermore equilibrium modeling was carried out using PHREEQC software in order to model the experiments on caprock samples.After the experiments the permeability of the reservoir samples had increased by a factor of 1.2–2.2 as a result of dissolution of primary reservoir minerals. Analysis of the associated brine samples before and after the experiments showed that concentrations of K, Si and Al had increased, indicative of silicate mineral dissolution.In the caprock samples, composed of carbonate and anhydrite minerals, permeability changed by a factor of 0.79–23. The increase in permeability is proportional to the amount of carbonate in the caprock. With higher carbonate content in comparison with anhydrite the permeability increase is higher due to the additional carbonate dissolution. This dependency of permeability variations was verified by the modeling study. Hence, caprock with a higher anhydrite content in comparison with carbonate minerals has a lower risk of leakage after co-injection of 100 ppmv SO₂ with CO₂.     

鄂尔多斯盆地伊金霍洛旗附近二叠系石千峰组岩石学、地球化学特征及其固碳能力分析

鄂尔多斯盆地是我国CO2地下埋藏的潜在目标区,位于伊金霍洛旗附近的中神监X井与CO2地下注入井中神注1井相邻,两者钻遇地层系统和岩石组合一致。为对示范区储层的固碳潜力和泥岩改造状况做出预测,为CO2地质储存的数值模拟研究提供基础地质信息和相关数据,通过偏光显微镜、扫描电镜、X射线衍射、X射线荧光等多种技术手段,开展了中神监X井石千峰组的岩石学和地球化学特征研究。结果表明石千峰组的砂岩岩石类型主要为长石岩屑砂岩和岩屑长石砂岩;泥岩主要由石英、粘土矿物和长石组成,其中,粘土矿物主要为伊利石,其次为蒙皂石、高岭石和绿泥石。预测在CO2注入后的流体-砂岩长期相互作用过程中,石千峰组砂岩可以通过形成片钠铝石、方解石、铁白云石和菱铁矿等固碳矿物,形成对CO2泄露而言的矿物圈闭,进而实现CO2的长期和安全封存;红色泥岩夹层将发生金属离子活化,导致泥岩褪色。     

Experimental investigation into the sealing capability of naturally fractured shale caprocks to supercritical carbon dioxide flow

Geological storage of CO₂ is considered a solution for reducing the excess CO₂ released into the atmosphere. Low permeability caprocks physically trap CO₂ injected into underlying porous reservoirs. Injection leads to increasing pore pressure and reduced effective stress, increasing the likelihood of exceeding the capillary entry pressure of the caprocks and of caprock fracturing. Assessing on how the different phases of CO₂ flow through caprock matrix and fractures is important for assessing CO₂ storage security. Fractures are considered to represent preferential flow paths in the caprock for the escape of CO₂. Here we present a new experimental rig which allows 38 mm diameter fractured caprock samples recovered from depths of up to 4 km to be exposed to supercritical CO₂ (scCO₂) under in situ conditions of pressure, temperature and geochemistry. In contrast to expectations, the results indicate that scCO₂ will not flow through tight natural caprock fractures, even with a differential pressure across the fractured sample in excess of 51 MPa. However, below the critical point where CO₂ enters its gas phase, the CO₂ flows readily through the caprock fractures. This indicates the possibility of a critical threshold of fracture aperture size which controls CO₂ flow along the fracture.     

Mobilization and transport of organic compounds from reservoir rock and caprock in geological carbon sequestration sites

Supercritical CO₂ (scCO₂) is a good solvent for organic compounds such as benzene, toluene, ethyl-benzene, and xylene (BTEX), phenols, and polycyclic aromatic hydrocarbons (PAHs). Monitoring results from geological carbon sequestration (GCS) field tests have shown that organic compounds are mobilized following CO₂ injection. Such results have raised concerns regarding the potential for groundwater contamination by toxic organic compounds mobilized during GCS. Knowledge of the mobilization mechanism of organic compounds and their transport and fate in the subsurface is essential for assessing risks associated with GCS. Extraction tests using scCO₂ and methylene chloride (CH₂Cl₂) were conducted to study the mobilization of volatile organic compounds (VOCs, including BTEX), the PAH naphthalene, and n-alkanes by scCO₂ from representative reservoir rock and caprock obtained from depleted oil reservoirs and coal from an enhanced coal-bed methane recovery site. Results showed that the extent of mobilization for the organic compounds was a function of the source rock. In fate and transport sand column experiments, moisture content was found to have an important influence on the transport of the organic compounds. In dry sand columns the majority of the compounds were retained in the column except benzene and toluene. In wet sand columns the mobility of the BTEX was much higher than that of naphthalene. Based upon the results determined for the reservoir rock, caprock, and coal samples studied here, the risk to aquifers from contamination by organic compounds appears to be relatively low; however, further work is necessary to fully evaluate the risks.     

Determining effective wellbore permeability from a field pressure test: a numerical analysis of detection limits

We propose a simple pressure test that can be used in the field to determine the effective permeability of existing wellbores. Such tests are motivated by the need to understand and quantify leakage risks associated with geological storage of CO₂ in mature sedimentary basins. If CO₂ is injected into a deep geological formation, and the resulting CO₂ plume encounters a wellbore, leakage may occur through various pathways in the “disturbed zone” surrounding the well casing. The effective permeability of this composite zone, on the outside of the well casing, is an important parameter for models of leakage. However, the data that exist on this key parameter do not exist in the open literature, and therefore specific field tests need to be done in order to reduce the uncertainty inherent in the leakage estimates. The test designed and analyzed herein is designed to measure effective wellbore permeability within a low-permeability caprock, bounded above and below by permeable reservoirs, by pressurizing the reservoir below and measuring the response in the reservoir above. Alternatively, a modified test can be performed within the caprock without directly contacting the reservoirs above and below. We use numerical simulation to relate pressure response to effective well permeability and then evaluate the range of detection of the effective permeability based on instrument measurement error and limits on fracture pressure. These results can guide field experiments associated with site characterization and leakage analysis.     

Sealing efficiency analysis for shallow-layer caprocks in CO<Subscript>2</Subscript> geological storage

The CO₂ migrated from deeper to shallower layers may change its phase state from supercritical state to gaseous state (called phase transition). This phase transition makes both viscosity and density of CO₂ experience a sharp variation, which may induce the CO₂ further penetration into shallow layers. This is a critical and dangerous situation for the security of CO₂ geological storage. However, the assessment of caprock sealing efficiency with a fully coupled multi-physical model is still missing on this phase transition effect. This study extends our previous fully coupled multi-physical model to include this phase transition effect. The dramatic changes of CO₂ viscosity and density are incorporated into the model. The impacts of temperature and pressure on caprock sealing efficiency (expressed by CO₂ penetration depth) are then numerically investigated for a caprock layer at the depth of 800 m. The changes of CO₂ physical properties with gas partial pressure and formation temperature in the phase transition zone are explored. It is observed that phase transition revises the linear relationship of CO₂ penetration depth and time square root as well as penetration depth. The real physical properties of CO₂ in the phase transition zone are critical to the safety of CO₂ sequestration. Pressure and temperature have different impact mechanisms on the security of CO₂ geological storage.     

Impacts of mineralogical compositions on different trapping mechanisms during long-term CO<Subscript>2</Subscript> storage in deep saline aquifers

Deep saline aquifers in sedimentary basins are considered to have the greatest potential for CO₂ geological storage in order to reduce carbon emissions. CO₂ injected into a saline sandstone aquifer tends to migrate upwards toward the caprock because the density of the supercritical CO₂ phase is lower than that of formation water. The accumulated CO₂ in the upper portions of the reservoir gradually dissolves into brine, lowers pH and changes the aqueous complexation, whereby induces mineral alteration. In turn, the mineralogical composition could impose significant effects on the evolution of solution, further on the mineralized CO₂. The high density of aqueous phase will then move downward due to gravity, give rise to “convective mixing,” which facilitate the transformation of CO₂ from the supercritical phase to the aqueous phase and then to the solid phase. In order to determine the impacts of mineralogical compositions on trapping amounts in different mechanisms for CO₂ geological storage, a 2D radial model was developed. The mineralogical composition for the base case was taken from a deep saline formation of the Ordos Basin, China. Three additional models with varying mineralogical compositions were carried out. Results indicate that the mineralogical composition had very obvious effects on different CO₂ trapping mechanisms. Specific to our cases, the dissolution of chlorite provided Mg²⁺ and Fe²⁺ for the formation of secondary carbonate minerals (ankerite, siderite and magnesite). When chlorite was absent in the saline aquifer, the dominant secondary carbon sequestration mineral was dawsonite, and the amount of CO₂ mineral trapping increased with an increase in the concentration of chlorite. After 3000 years, 69.08, 76.93, 83.52 and 87.24 % of the injected CO₂ can be trapped in the solid (mineral) phase, 16.05, 11.86, 8.82 and 6.99 % in the aqueous phase, and 14.87, 11.21, 7.66 and 5.77 % in the gas phase for Case 1 through 4, respectively.     

Numerical modelling of the hydro‐chemo‐mechanical behaviour of geomaterials in the context of CO2 injection

Safety assessment of geosequestration of CO₂ into deep saline aquifers requires a precise understanding of the study of hydro‐chemo‐mechanical couplings occurring in the rocks and the cement well. To this aim, a coupled chemo‐poromechanical model has been developed and implemented into a research code well‐suited to the resolution of fully coupled problems. This code is based on the finite volume methods. In a 1D axisymmetrical configuration, this study aims to simulate the chemo‐poromechanical behaviour of a system composed by the cement well and the caprock during CO₂ injection. Major chemical reactions of carbonation occurring into cement paste and rocks are considered in order to evaluate the consequences of the presence of CO₂ on the amount of dissolved matrix and precipitated calcium carbonates. The dissolution of the solid matrix is taken into account through the use of a chemical porosity. Matrix leaching and carbonation lead, as expected, to important variations of porosity, permeability and to alterations of transport properties and mechanical stiffness. These results justify the importance of considering a coupled analysis accounting for the main chemical reactions. It is worth noting that the modelling framework proposed in the present study could be extended to model the chemo‐poromechanical behaviour of the reservoir rock and the caprock when subjected to the presence of an acidic pore fluid (CO₂‐rich brine). Copyright © 2013 John Wiley & Sons, Ltd.     

Alteration processes of cement induced by CO2-saturated water and its effect on physical properties: Experimental and geochemical modeling study

The objective of this study is to understand cement alteration processes with the evolution of porosity and hardness under geologic CO₂ storage conditions. For this study, the cylindrical cement cores (class G) were reacted with CO₂–saturated water in a vessel (40 °C and 8 MPa) for 10 and 100 days. After the experiment, the CO₂ concentration and Vickers hardness were measured in the hydrated cement core to estimate the carbonation depth and to identify the change in hardness, respectively. Diffusive-reactive transport modeling was also performed to trace the alteration processes and subsequent porosity changes. The results show that cement alteration mainly results from carbonation. With alteration processes, four different reaction zones are developed: degradation zone, carbonation zone, portlandite depletion zone, and unreacted zone. In the degradation zone, the re-dissolution of calcite formed in the carbonation zone leads to the increase of porosity. In contrast, the carbonation zone is characterized by calcite formation resulting mainly from the dissolution of portlandite. The carbonation zone acts as a barrier to CO₂ intrusion by consuming dissolved CO₂. Especially in this zone, although the porosity decreases, the Vickers hardness increases. Our results show that cement alteration processes can affect the physical and hydrological properties of the hydrated cement under CO₂-saturated conditions. Further long-term observation is required to confirm our results under in-situ fluid chemistry of a CO₂ storage reservoir. Nonetheless, this study would be helpful to understand alteration processes of wellbore cements under CO₂ storage conditions.     

Simulation of CO2 plume movement in multilayered saline formations through multilayer injection technology in the Ordos Basin,China

Deep saline aquifers still remain a significant option for the disposal of large amounts of CO₂ from the atmosphere as a means of mitigating global climate change. The small scale Carbon Capture and Sequestration demonstration project in Ordos Basin, China, operated by the Shenhua Group, is the only one of its kind in Asia, to put the multilayer injection technology into practice. This paper aims at studying the influence of temperature, injection rate and horizontal boundary effects on CO₂ plume transport in saline formation layers at different depths and thicknesses, focusing on the variations in CO₂ gas saturation and mass fraction of dissolved CO₂ in the formation of brine in the plume’s radial three-dimensional field around the injection point, and interlayer communication between the aquifer and its confining beds of relatively lower permeability. The study uses the ECO2N module of TOUGH2 to simulate flow and pressure configurations in response to small-scale CO₂ injection into multilayer saline aquifers. The modelling domain involves a complex multilayer reservoir–caprock system, comprising of a sequence of sandstone aquifers and sealing units of mudstone and siltstone layers extending from the Permian Shanxi to the Upper Triassic Liujiagou formation systems in the Ordos Basin. Simulation results indicate that CO₂ injected for storage into deep saline aquifers cause a significant pressure perturbation in the geological system that may require a long duration in the post-injection period to establish new pressure equilibrium. The multilayer simultaneous injection scheme exhibits mutual interference with the intervening sealing layers, especially when the injection layers are very close to each other and the corresponding sealing layers are thin. The study further reveals that injection rate and temperature are the most significant factors for determining the lateral and vertical extent that the CO₂ plume reaches and which phase and amount will exist at a particular time during and after the injection. In general, a large number of factors may influence the CO₂–water fluid flow system considering the complexity in the real geologic sequence and structural configurations. Therefore, optimization of a CO₂ injection scheme still requires pursuance of further studies.     

Characterization of deep saline aquifers in the Bécancour area,St. Lawrence Lowlands,Québec,Canada: implications for CO2 geological storage

The present paper provides a case study of the assessment of the potential for CO₂ storage in the deep saline aquifers of the Bécancour region in southern Québec. This assessment was based on a hydrogeological and petrophysical characterization using existing and newly acquired core and well log data from hydrocarbon exploration wells. Analyses of data obtained from different sources provide a good understanding of the reservoir hydrogeology and petrophysics. Profiles of formation pressure, temperature, density, viscosity, porosity, permeability, and net pay were established for Lower Paleozoic sedimentary aquifers. Lateral hydraulic continuity is dominant at the regional scale, whereas vertical discontinuities are apparent for most physical and chemical properties. The Covey Hill sandstone appears as the most suitable saline aquifer for CO₂ injection/storage. This unit is found at a depth of more than 1 km and has the following properties: fluid pressures exceed 14 MPa, temperature is above 35 °C, salinity is about 108,500 mg/l, matrix permeability is in the order of 3 × 10^?16 m² (0.3 mDarcy) with expected higher values of formation-scale permeability due to the presence of natural fractures, mean porosity is 6 %, net pay reaches 282 m, available pore volume per surface area is 17 m³/m², rock compressibility is 2 × 10^?9 Pa^?1 and capillary displacement pressure of brine by CO₂ is about 0.4 MPa. While the containment for CO₂ storage in the Bécancour saline aquifers can be ensured by appropriate reservoir characteristics, the injectivity of CO₂ and the storage capacity could be limiting factors due to the overall low permeability of aquifers. This characterization offers a solid basis for the subsequent development of a numerical hydrogeological model, which will be used for CO₂ injection capacity estimation, CO₂ injection scenarios and risk assessment.     

A sensitivity analysis of factors affecting in geologic CO2 storage in the Ordos Basin and its contribution to carbon neutrality

To accelerate the achievement of China’s carbon neutrality goal and to study the factors affecting the geologic CO₂ storage in the Ordos Basin, China’s National Key R&D Programs propose to select the Chang 6 oil reservoir of the Yanchang Formation in the Ordos Basin as the target reservoir to conduct the geologic carbon capture and storage (CCS) of 100000 t per year. By applying the basic theories of disciplines such as seepage mechanics, multiphase fluid mechanics, and computational fluid mechanics and quantifying the amounts of CO₂ captured in gas and dissolved forms, this study investigated the effects of seven factors that influence the CO₂ storage capacity of reservoirs, namely reservoir porosity, horizontal permeability, temperature, formation stress, the ratio of vertical to horizontal permeability, capillary pressure, and residual gas saturation. The results show that the sensitivity of the factors affecting the gas capture capacity of CO₂ decreases in the order of formation stress, temperature, residual gas saturation, horizontal permeability, and porosity. Meanwhile, the sensitivity of the factors affecting the dissolution capture capacity of CO₂ decreases in the order of formation stress, residual gas saturation, temperature, horizontal permeability, and porosity. The sensitivity of the influencing factors can serve as the basis for carrying out a reasonable assessment of sites for future CO₂ storage areas and for optimizing the design of existing CO₂ storage areas. The sensitivity analysis of the influencing factors will provide basic data and technical support for implementing geologic CO₂ storage and will assist in improving geologic CO₂ storage technologies to achieve China’s carbon neutralization goal.©2022 China Geology Editorial Office.     

Effect of injected CO2 on geochemical alteration of the Altmark gas reservoir in Germany

Capturing CO₂ from point sources and storing it in geologic formations is a potential option for allaying the CO₂ level in the atmosphere. In order to evaluate the effect of geological storage of CO₂ on rock-water interaction, batch experiments were performed on sandstone samples taken from the Altmark reservoir, Germany, under in situ conditions of 125 °C and 50 bar CO₂ partial pressure. Two sets of experiments were performed on pulverized sample material placed inside a closed batch reactor in (a) CO₂ saturated and (b) CO₂ free environment for 5, 9 and 14 days. A 3M NaCl brine was used in both cases to mimic the reservoir formation water. For the “CO₂ free” environment, Ar was used as a pressure medium. The sandstone was mainly composed of quartz, feldspars, anhydrite, calcite, illite and chlorite minerals. Chemical analyses of the liquid phase suggested dissolution of both calcite and anhydrite in both cases. However, dissolution of calcite was more pronounced in the presence of CO₂. In addition, the presence of CO₂ enhanced dissolution of feldspar minerals. Solid phase analysis by X-ray diffraction and Mössbauer spectroscopy did not show any secondary mineral precipitation. Moreover, Mössbauer analysis did not show any evidence of significant changes in redox conditions. Calculations of total dissolved solids’ concentrations indicated that the extent of mineral dissolution was enhanced by a factor of approximately 1.5 during the injection of CO₂, which might improve the injectivity and storage capacity of the targeted reservoir. The experimental data provide a basis for numerical simulations to evaluate the effect of injected CO₂ on long-term geochemical alteration at reservoir scale.     

Geomechanical and geochemical effects on sandstones caused by the reaction with supercritical CO2: an experimental approach to in situ conditions in deep geological reservoirs

The geochemical and geomechanical behaviour of reservoir rocks from deep saline aquifers during the injection and geological storage of CO₂ is studied in laboratory experiments. A combination of geochemical and geomechanical studies was carried out on various sandstones from the North German Basin. After the mineralogical, geochemical and petrophysical characterization, a set of sandstone samples was exposed to supercritical (sc)CO₂ and brine for 2–4 weeks in an autoclave system. One sample was mineralogically and geochemically characterised and then loaded in a triaxial cell under in situ pressure and temperature conditions to study the changes of the geomechanical rock properties. After treatment in the autoclaves, geochemical alterations mainly in the carbonate, but also in the sheet silicate cements as well as in single minerals of the sandstones were observed, affecting the rocks granular structure. In addition to partial solution effects during the geochemical experiments, small grains of secondary carbonate and other mineral precipitations were observed within the pore space of the treated sandstones. Results of additional geomechanical experiments with untreated samples show that the rock strength is influenced by the saturation degree, the confining pressure, the pore fluid pressure and temperature. The exposure to pure scCO₂ in the autoclave system induces reduced strength parameters, modified elastic deformation behaviour and changes of the effective porosity in comparison to untreated sandstone samples. Experimental results show that the volume of pore fluid fluxing into the pore space of the sandstones clearly depends on the saturation level of the sample.     

Wellbore cement fracture evolution at the cement–basalt caprock interface during geologic carbon sequestration

Composite Portland cement–basalt caprock cores with fractures, as well as neat Portland cement columns, were prepared to understand the geochemical and geomechanical effects on the integrity of wellbores with defects during geologic carbon sequestration. The samples were reacted with CO₂–saturated groundwater at 50 °C and 10 MPa for 3 months under static conditions, while one cement–basalt core was subjected to mechanical stress at 2.7 MPa before the CO₂ reaction. Micro-XRD and SEM–EDS data collected along the cement–basalt interface after 3-month reaction with CO₂–saturated groundwater indicate that carbonation of cement matrix was extensive with the precipitation of calcite, aragonite, and vaterite, whereas the alteration of basalt caprock was minor. X-ray microtomography (XMT) provided three-dimensional (3-D) visualization of the opening and interconnection of cement fractures due to mechanical stress. Computational fluid dynamics (CFD) modeling further revealed that this stress led to the increase in fluid flow and hence permeability. After the CO₂-reaction, XMT images displayed that calcium carbonate precipitation occurred extensively within the fractures in the cement matrix, but only partially along the fracture located at the cement–basalt interface. The 3-D visualization and CFD modeling also showed that the precipitation of calcium carbonate within the cement fractures after the CO₂-reaction resulted in the disconnection of cement fractures and permeability decrease. The permeability calculated based on CFD modeling was in agreement with the experimentally determined permeability. This study demonstrates that XMT imaging coupled with CFD modeling represent a powerful tool to visualize and quantify fracture evolution and permeability change in geologic materials and to predict their behavior during geologic carbon sequestration or hydraulic fracturing for shale gas production and enhanced geothermal systems.     

Review: The potential impact of underground geological storage of carbon dioxide in deep saline aquifers on shallow groundwater resources

Underground geological storage of CO₂ in deep saline aquifers is considered for reducing greenhouse gases emissions into the atmosphere. However, some issues were raised with regard to the potential hazards to shallow groundwater resources from CO₂ leakage, brine displacement and pressure build-up. An overview is provided of the current scientific knowledge pertaining to the potential impact on shallow groundwater resources of geological storage of CO₂ in deep saline aquifers, identifying knowledge gaps for which original research opportunities are proposed. Two main impacts are defined and discussed therein: the near-field impact due to the upward vertical migration of free-phase CO₂ to surficial aquifers, and the far-field impact caused by large-scale displacement of formation waters by the injected CO₂. For the near-field, it is found that numerical studies predict possible mobilization of trace elements but concentrations are rarely above the maximum limit for potable water. For the far-field, numerical studies predict only minor impacts except for some specific geological conditions such as high caprock permeability. Despite important knowledge gaps, the possible environmental impacts of geological storage of CO₂ in deep saline aquifers on shallow groundwater resources appears to be low, but much more work is required to evaluate site specific impacts.     

Numerical simulation of CO2 disposal by mineral trapping in deep aquifers

Carbon dioxide disposal into deep aquifers is a potential means whereby atmospheric emissions of greenhouse gases may be reduced. However, our knowledge of the geohydrology, geochemistry, geophysics, and geomechanics of CO₂ disposal must be refined if this technology is to be implemented safely, efficiently, and predictably. As a prelude to a fully coupled treatment of physical and chemical effects of CO₂ injection, the authors have analyzed the impact of CO₂ immobilization through carbonate mineral precipitation. Batch reaction modeling of the geochemical evolution of 3 different aquifer mineral compositions in the presence of CO₂ at high pressure were performed. The modeling considered the following important factors affecting CO₂ sequestration: (1) the kinetics of chemical interactions between the host rock minerals and the aqueous phase, (2) CO₂ solubility dependence on pressure, temperature and salinity of the system, and (3) redox processes that could be important in deep subsurface environments. The geochemical evolution under CO₂ injection conditions was evaluated. In addition, changes in porosity were monitored during the simulations. Results indicate that CO₂ sequestration by matrix minerals varies considerably with rock type. Under favorable conditions the amount of CO₂ that may be sequestered by precipitation of secondary carbonates is comparable with and can be larger than the effect of CO₂ dissolution in pore waters. The precipitation of ankerite and siderite is sensitive to the rate of reduction of Fe(III) mineral precursors such as goethite or glauconite. The accumulation of carbonates in the rock matrix leads to a considerable decrease in porosity. This in turn adversely affects permeability and fluid flow in the aquifer. The numerical experiments described here provide useful insight into sequestration mechanisms, and their controlling geochemical conditions and parameters.     

Identifying geochemical reactions on wellbore cement/caprock interface under sequestration conditions

The integrity of wells, which are key components for CO₂ sequestration, depends mainly on the seal between the wellbore cement and the geologic formation. To identify the reaction products that may alter the cement/caprock interface, batch experiments and computer modelling were conducted and analysed. Over time, the dissolution and precipitation of minerals alters the physical properties of the interface, including its tightness. One main objective of the simulation was thus to analyse the evolution of the porosity of cement and caprock over time. The alteration of the cement/caprock interface was identified as a complex problem and differentiated depending on rock type. The characteristic feature of a cement/shale contact zone is the occurrence of a highly carbonated, compacted layer within the shale, which in turn causes cement/shale detachment. In the case of a cement/anhydrite interface, the most important reaction is severe anhydrite dissolution. Secondary calcite precipitation takes place in deeper parts of the rock. The cement/rock contact zone is prone to rapid mineral dissolution, which contributes to increased porosity and may alter the well integrity. Comparison of computer simulations with autoclave experiments enabled the adjustment of unknown parameters. This enhances the knowledge of these particular assemblages. Overall, a good match was obtained between experiments and simulations, which enhances confidence in using models to predict longer-term evolution.