The increasing concentrations of CO2 in the atmosphere are attributed to the rising consumption of fossil fuels for energy generation around the world. One of the most stable and environmentally benign methods of reducing atmospheric CO2 is by storing it as thermodynamically stable carbonate minerals. Olivine ((Mg,Fe)2SiO4) is an abundant mineral that reacts with CO2 to form Mg-carbonate. The carbonation of olivine can be enhanced by injecting solutions containing CO2 at high partial pressure into olivine-rich formations at high temperatures, or by performing ex situ mineral carbonation in a reactor system with temperature and pressure control. In this study, the effects of NaHCO3 and NaCl, whose roles in enhanced mineral carbonation have been debated, were investigated in detail along with the effects of temperature, CO2 partial pressure and reaction time for determining the extent of olivine carbonation and its associated chemical and morphological changes. At high temperature and high CO2 pressure conditions, more than 70% olivine carbonation was achieved in 3 hours in the presence of 0.64 M NaHCO3. In contrast, NaCl did not significantly affect olivine carbonation. As olivine was dissolved and carbonated, its pore volume, surface area and particle size were significantly changed and these changes influenced subsequent reactivity of olivine. Thus, for both long-term simulation of olivine carbonation in geologic formations and the ex situ reactor design, the morphological changes of olivine during its reaction with CO2 should be carefully considered in order to accurately estimate the CO2 storage capacity and understand the mechanisms for CO2 trapping by olivine.

In the past few years, experimental studies have shown that CO 2 is roughly 5 times more soluble in watersaturated clay interlayer water than in bulk liquid water. The fundamental basis of this selectivity remains unknown, as does its relevance to other gases. Here, we use molecular dynamics (MD) simulations and gravimetric adsorption experiments to determine the solubilities of CO 2 , CH 4 , H 2 , and noble gases in clay interlayer water. Our results confirm that clay minerals, despite their well-known hygroscopic nature, have a significant hydrophobic character at the atomistic scale. The affinity of dissolved gases for the clay surface shows significant variations related to the size and shape of the adsorbing molecules and the structuring of interfacial water by clay surfaces. Our results indicate that dissolved gases likely do not behave as inert tracers in fine-grained sedimentary rocks such as shale and mudstone, as routinely assumed in groundwater hydrology studies. Our results have implications for the fundamental science of hydrophobic adsorption, for the use of dissolved gases as tracers of fluid migration in the subsurface, and for low-carbon energy technologies that rely on fine-grained sedimentary rocks, such as carbon capture and storage, nuclear energy, and the transition from coal to natural gas.

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Carbon mineralization is a versatile and thermodynamically downhill process that can be harnessed for capturing, storing, and utilizing CO 2 to synthesize products with enhanced properties. Here the author discusses the advances in and challenges of carbon mineralization, and concludes that tuning the chemical interactions involved will allow us to unlock its potential for advancing low carbon energy and resource conversion pathways.

Understanding the changes in the microstructures and structures of clays with varying intercalated metal ions at elevated temperatures is of importance for many applications ranging from the recovery of shale gas from unconventional formations to developing effective nuclear waste containment technologies, and engineering materials such as ceramics for fuel cell applications. In this study, synchrotron-based in-operando multi-scale X-ray scattering analyses are used to determine dynamic microstructural and crystal structural changes in Na- and Ca-montmorillonite on heating from 30 °C to 1150 °C. Larger cations such as Ca2+ confer more defined morphological regimes compared to Na+ ions in compacted clays, as evident from the ultra-small-angle X-ray scattering results. The hierarchical morphology of clays is characterized to distinguish between nano-scale interlayer swelling porosity, meso-scale porosity, and intergranular pore spaces between powdered clay grains. On heating from ambient temperature to 200 °C, the removal of interlayer water reduced the basal distances to 9.6 Å. On further heating to 800 °C, gradual dehydroxylation of the clay sheets is evident from the structural changes. The effects of sintering at temperatures greater than 800 °C are evident from significant reductions in the intrinsic porosities of the clay sheets, and the formation of newer phases such as mullite. By connecting the in-operando microstructural and structural changes across spatial scales ranging from micrometers to Angstroms, the possibility of engineering high temperature processes for achieving morphologies and chemical compositions of interest is presented.

Silicate minerals such as olivine (Mg2SiO4) and serpentine [Mg3(OH)4(Si3O5)] can react with CO2 to form mineral carbonates to permanently store CO2. Despite significant advancements in carbon mineralization, major discrepancies in the reported kinetics exist because of inconsistencies among various experimental methodologies, the heterogeneity and aging of the minerals, and inadequate fast kinetics and morphological data to probe the reaction mechanisms. In this work, it was found that aged and freshly ground olivine produce very different carbonation yields. A new mineral cleaning protocol to remove fines (<5 μm) was developed. Fast and slow serpentine dissolution regimes were distinguished using a custom-built differential-bed reactor. Mineral carbonate formation using a bubble-column reactor was described. Different carbon analyses were evaluated for accurate estimation of the extent of carbon mineralization. Therefore, this study focused on the development of an experimental framework and a data analysis method for the systematic investigation of mineral dissolution and carbonation behaviors.

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