In carbon storage activities, and in shale oil and gas extraction (SOGE) with carbon dioxide (CO₂) as stimulation fluid, CO₂ comes into contact with shale rock and its pore fluid. As a reactive fluid, the injected CO₂ displays a large potential to modify the shale’s chemical, physical, and mechanical properties, which need to be well studied and documented. The state of the art on shale–CO₂ interactions published in several review articles does not exhaust all aspects of these interactions, such as changes in the mechanical, petrophysical, or petrochemical properties of shales. This review paper presents a characterization of shale rocks and reviews their possible interaction mechanisms with different phases of CO₂. The effects of these interactions on petrophysical, chemical and mechanical properties are highlighted. In addition, a novel experimental approach is presented, developed and used by our team to investigate mechanical properties by exposing shale to different saturation fluids under controlled temperatures and pressures, without modifying the test exposure conditions prior to mechanical and acoustic measurements. This paper also underlines the major knowledge gaps that need to be filled in order to improve the safety and efficiency of SOGE and CO₂ storage.

Shales have a complex mineralogy with structural features spanning several length scales, making them notoriously difficult to fully understand. Conventional attenuation-based X-ray computed tomography (CT) measures density differences, which, owing to the heterogeneity and sub-resolution features in shales, makes reliable interpretation of shale images a challenging task. CT based on X-ray diffraction (XRD-CT), rather than intensity attenuation, is becoming a well established technique for non-destructive 3D imaging, and is especially suited for heterogeneous and hierarchical materials. XRD patterns contain information about the mineral crystal structure, and crucially also crystallite orientation. Here, we report on the use of orientational imaging using XRD-CT to study crystallite-orientation distributions in a sample of Pierre shale. Diffraction-contrast CT data for a shale sample measured with its bedding-plane normal aligned parallel to a single tomographic axis perpendicular to the incoming X-ray beam are discussed, and the spatial density and orientation distribution of clay minerals in the sample are described. Finally, the scattering properties of highly attenuating inclusions in the shale bulk are studied, which are identified to contain pyrite and clinochlore. A path forward is then outlined for systematically improving the structural description of shales.

Carbon capture and storage (CCS) by geological sequestration comprises a permeable formation (reservoir) for CO₂ storage topped by an impermeable formation (caprock). Time-lapse (4D) seismic is used to map CO₂ movement in the subsurface: CO₂ migration into the caprock might change its properties and thus impact its integrity. Simultaneous forced-oscillation and pulse-transmission measurements are combined to quantify Young’s modulus and Poisson’s ratio as well as P- and S-wave velocity changes in the absence and in the presence of CO₂ at constant seismic and ultrasonic frequencies. This combination is the laboratory proxy to 4D seismic because rock properties are monitored over time. It also improves the understanding of frequency-dependent (dispersive) properties needed for comparing in-situ and laboratory measurements. To verify our method, Draupne Shale is monitored during three consecutive fluid exposure phases. This shale appears to be resilient to CO₂ exposure as its integrity is neither compromised by notable Young’s modulus and Poisson’s ratio nor P- and S-wave velocity changes. No significant changes in Young’s modulus and Poisson’s ratio seismic dispersion are observed. This absence of notable changes in rock properties is attributed to Draupne being a calcite-poor shale resilient to acidic CO₂-bearing brine that may be a suitable candidate for CCS.

Despite the abundance of shales in the Earth's crust and their industrial and environmental importance, their microscale physical properties are poorly understood, owing to the presence of many structurally related mineral phases and a porous network structure spanning several length scales. Here, the use of coherent X-ray diffraction imaging (CXDI) to study the internal structure of microscopic shale fragments is demonstrated. Simultaneous wide-angle X-ray diffraction (WAXD) measurement facilitated the study of the mineralogy of the shale microparticles. It was possible to identify pyrite nanocrystals as inclusions in the quartz–clay matrix and the volume of closed unconnected pores was estimated. The combined CXDI–WAXD analysis enabled the establishment of a correlation between sample morphology and crystallite shape and size. The results highlight the potential of the combined CXDI–WAXD approach as an upcoming imaging modality for 3D nanoscale studies of shales and other geological formations via serial measurements of microscopic fragments.

Cement nanocomposites with carbon nanofibers (CNFs) are electrically conductive and sensitive to mechanical loads. These features make them useful for sensing applications. The conductive and load sensing properties are well known to be dependent on carbon nanofiber content; however, much less is known about how the conductivity of hybrid cement–CNF depend on other parameters (e.g., water to cement ratio (w/c), water saturation of pore spaces and temperatures above ambient temperature). In this paper we fill-in these knowledge gaps by: (1) determining a relationship between the cement–CNF bulk resistivity and w/c ratio; (2) determining the effect of water present in the pores on bulk resistivity; (3) describing the resistivity changes upon temperature changes up to 180 °C. Our results show that the increase in the water to cement ratio results in increased bulk resistivity. The decrease in nanocomposite resistivity upon a stepwise temperature increase up to 180 °C was found to be related to free water release from cement pores and the dry materials were relatively insensitive to temperature changes. The re-saturation of pores with water was not reversible with respect to electrical resistivity. The results also suggest that the change in the type of electrical connection can lead to two orders of magnitude different bulk resistivity results for the same material. It is expected that the findings from this paper will contribute to application of cement–CNF-based sensors at temperatures higher than ambient temperature.