This study was conducted in the framework of the PILOT CO₂-DISSOLVED project, which provides an additional approach for CO₂ sequestration, with the aims of capturing, injecting, and locally storing the CO₂ after being dissolved in brine. The brine acidity is expected to induce chemical reactions with the mineral phase of the host reservoir. A set of continuous radial CO₂ flow experiments was performed on cylindrical carbonate rock samples under geological storage conditions. The objective was to interpret the dissolution network morphology and orientation involved. To explore the three-dimensional architecture of dissolution arrays and their connection integrity within core samples, we used computed tomography. A structural investigation at different scales revealed the impact of the rock heterogeneity on the dissolution pathways. The initial strike of the observed mesoscopic wormholes appears to be parallel to dilatational fractures, with a subsequent change in major trends of dissolution along master shears or, more specifically, a combination of synthetic shears and secondary synthetic shears. Antithetic shears organize themselves as slickolitic surfaces, which may be fluid-flow barriers due to different mineralogy, thus affecting the permeability distribution-wormhole growth geometry induced by CO₂-rich solutions. Full article

The risk of CO₂ leakage from damaged wellbore is identified as a critical issue for the feasibility and environmental acceptance of CO₂ underground storage. For instance, Portland cement can be altered if flow of CO₂-rich water occurs in hydraulic discontinuities such as cement-tubing or cement-caprock interfaces. In this case, the raw cement matrix is altered by diffusion of the solutes. This fact leads to the formation of distinctive alteration fronts indicating the dissolution of portlandite, the formation of a carbonate-rich layer and the decalcification of the calcium silicate hydrate, controlled by the interplay between the reaction kinetics, the diffusion-controlled renewing of the reactants and products, and the changes in the diffusion properties caused by the changes in porosity induced by the dissolution and precipitation mechanisms. In principle, these mass transfers can be easily simulated using diffusion-reaction numerical models. However, the large uncertainties of the parameters characterizing the reaction rates (mainly the kinetic and thermodynamic coefficients and the evolving reactive surface area) and of the porosity-dependent diffusion properties prevent making reliable predictions required for risk assessment. In this paper, we present the results of a set of experiments consisting in the alteration of a holed disk of class-G cement in contact with a CO₂-rich brine at reservoir conditions (P = 12 MPa and T = 60 °C) for various durations. This new experimental protocol allows producing time-resolved data for both the spatially distributed mass transfers inside the cement body and the total mass transfers inferred from the boundary conditions mass balance. The experimental results are used to study the effect of the fluid salinity and the pCO₂ on the overall reaction efficiency. Experiments at high salinity triggers more portlandite dissolution, thinner carbonate layers, and larger alteration areas than those at low salinity. These features are accompanied with different spatial distribution of the alteration layers resulting from a complex interplay between salinity-controlled dissolution and precipitation mechanisms. Conversely, the effect of the pCO₂ is more intuitive: Increasing pCO₂ results in increasing the overall alteration rate without modifying the relative distribution of the reaction fronts. Full article

Investigation into geological storage of CO₂ is underway at Hontomín (Spain). The storage reservoir is a deep saline aquifer formed by naturally fractured carbonates with low matrix permeability. Understanding the processes that are involved in CO₂ migration within these formations is key to ensure safe operation and reliable plume prediction. A geological model encompassing the whole storage complex was established based upon newly-drilled and legacy wells. The matrix characteristics were mainly obtained from the newly drilled wells with a complete suite of log acquisitions, laboratory works and hydraulic tests. The model major improvement is the integration of the natural fractures. Following a methodology that was developed for naturally fractured hydrocarbon reservoirs, the advanced characterization workflow identified the main sets of fractures and their main characteristics, such as apertures, orientations, and dips. Two main sets of fracture are identified based upon their mean orientation: North-South and East-West with different fracture density for each the facies. The flow capacity of the fracture sets are calibrated on interpreted injection tests by matching their permeability and aperture at the Discrete Fracture Network scale and are subsequently upscaled to the geological model scale. A key new feature of the model is estimated permeability anisotropy induced by the fracture sets. Full article

The full-scale deployment of underground storage of CO₂ in permeable sedimentary reservoirs depends strongly on the sealing capacity of the caprocks and wellbore cement that may be degraded leading to hydraulic discontinuities. Remediation technologies consisting in rebuilding the sealing capacity of the degraded material, or adding a new sealing layer, is a critical issue as part of the risk mitigation procedure required for underground CO₂ storage. Actually, engineered Portland cement injection is the foremost available industrial technique; however, alternative products offering, for instance, better injection properties, are currently investigated with variable success so far. In this study, a new technique aimed at using a low viscosity hydrated solgel as sealant product in case of leakage is presented. Its low cost, high injectivity capacity and low density of the hydrated product (hydrogel) makes this technique attractive. The solgel synthesis was optimized for (1) reducing energetic and material costs; (2) improving the chemical and mechanical properties of the emplaced product and (3) controlling the duration of the aging process in order to form a solid hydrogel after a few days. Permeability tests that consisted of injecting the synthesized solgel in different porous media confirmed the sealant capacity of the emplaced hydrogel to significantly reduce rock permeability. Full article

The aim of this article is to provide a qualitative and quantitative description of Lower–Upper Cretaceous detrital rocks (Escucha and Utrillas sandstones) in order to explore their potential use as CO₂ reservoirs based on their petrographic and petrophysical characteristics. Optical microscopy (OpM) and scanning electron microscopy (SEM) aided by optical image analysis (OIA) were used to get qualitative and quantitative information about mineralogy, texture and pore network structure. Complementary analyses by X-ray fluorescence (XRF) and X-ray diffraction (XRD) were performed to refine the mineralogical information and to obtain whole rock geochemical data. Furthermore, mercury injection capillary pressure analysis (MICP), the gas permeameter test (GPT) and the hydraulic test (HT) were applied to assess the potential storage capacity and the facility of fluid flow through the rocks. Both of these factors have an outstanding importance in the determination of CO₂ reservoir potential. The applied petrophysical and petrographic methods allowed an exhaustive characterization of the samples and a preliminary assessment of their potential as a CO₂ reservoir. The studied conglomerates and sandstones have a porosity range of 8–26% with a dominant pore size range of 80–500 μm. The grain skeleton consists of quartz (95%), very minor potassium feldspars (orthoclase) and a small amount of mica (muscovite and chlorite). According to these preliminary results, among the studied varieties, the Escucha sandstones have the most favorable properties for CO₂ geological storage at the rock matrix scale. Full article

Cap-rock integrity is an important consideration for geological storage of CO₂. While CO₂ bearing fluids are known to have reactivity to certain rock forming minerals, impurities including acid gases such as SOx, NOx, H₂S or O₂ may be present in injected industrial CO₂ streams at varying concentrations, and may induce higher reactivity to cap-rock than pure CO₂. Dissolution or precipitation of minerals may modify the porosity or permeability of cap-rocks and compromise or improve the seal. A calcite cemented cap-rock drill core sample (Evergreen Formation, Surat Basin) was experimentally reacted with formation water and CO₂ containing SO₂ and O₂ at 60 °C and 120 bar. Solution pH was quickly buffered by dissolution of calcite cement, with dissolved ions including Ca, Mn, Mg, Sr, Ba, Fe and Si released to solution. Dissolved concentrations of several elements including Ca, Ba, Si and S had a decreasing trend after 200 h. Extensive calcite cement dissolution with growth of gypsum in the formed pore space, and barite precipitation on mineral surfaces were observed after reaction via SEM-EDS. A silica and aluminium rich precipitate was also observed coating grains. Kinetic geochemical modelling of the experimental data predicted mainly calcite and chlorite dissolution, with gypsum, kaolinite, goethite, smectite and barite precipitation and a slight net increase in mineral volume (decrease in porosity). To better approximate the experimental water chemistry it required the reactive surface areas of: (1) calcite cement decreased to 1 cm²/g; and, (2) chlorite increased to 7000 cm²/g. Models were then up-scaled and run for 30 or 100 years to compare the reactivity of calcite cemented, mudstone, siderite cemented or shale cap-rock sections of the Evergreen Formation in the Surat Basin, Queensland, Australia, a proposed target for future large scale CO₂ storage. Calcite, siderite, chlorite and plagioclase were the main minerals dissolving. Smectite, siderite, ankerite, hematite and kaolinite were predicted to precipitate, with SO₂ sequestered as anhydrite, alunite, and pyrite. Predicted net changes in porosity after reaction with CO₂, CO₂-SO₂ or CO₂-SO₂-O₂ were however minimal, which is favourable for cap-rock integrity. Mineral trapping of CO₂ as siderite and ankerite however was only predicted in the CO₂ or CO₂-SO₂ simulations. This indicates a limit on the injected O₂ content may be needed to optimise mineral trapping of CO₂, the most secure form of CO₂ storage. Smectites were predicted to form in all simulations, they have relatively high CO₂ sorption capacities and provide additional storage. Full article

In the framework of CO₂ geological storage, one of the critical points leading to possible important CO₂ leakage is the behaviour of the different interfaces between the rocks and the injection wells. This paper discussed the results from an experimental modelling of the evolution of a caprock/cement interface under high pressure and temperature conditions. Batch experiments were performed with a caprock (Callovo-Oxfordian claystone of the Paris Basin) in contact with a cement (Portland class G) in the presence of supercritical CO₂ under dry or wet conditions. The mineralogical and mechanical evolution of the caprock, the Portland cement, and their interface submitted to the attack of carbonic acid either supercritical or dissolved in a saline water under geological conditions of pressure and temperature. This model should help to better understand the behaviour of interfaces in the proximal zone at the injection site and to prevent risks of leakage from this critical part of injection wells. After one month of ageing at 80 °C under 100 bar of CO₂ pressure, the caprock, the cement, and the interface between the caprock and cement are investigated with Scanning Electron Microscopy (SEM) and cathodoluminescence (CL). The main results reveal (i) the influence of the alteration conditions: with dry CO₂, the carbonation of the cement is more extended than under wet conditions; (ii) successive phases of carbonate precipitation (calcite and aragonite) responsible for the loss of mechanical cohesion of the interfaces; (iii) the mineralogical and chemical evolution of the cement which undergoes successive phases of carbonation and leaching; (iv) the limited reactivity of the clayey caprock despite the acidic attack of CO₂; and (v) the influence of water on the transport mechanisms of dissolved species and thus on the location of mineral precipitations. Full article