The transition towards green energy requires both carbon dioxide removal and consistent supplies of energy-critical minerals. Injection and mineralization of supercritical CO2 at active mafic and ultramafic-hosted mines provides a potential avenue to achieve both, through the stable geologic storage of carbon and subsequent mobilization of critical metals. A sample from the Eagle occurrence, an ultramafic-hosted sulfide deposit in Michigan, USA that is the only active Ni mine in the United States, was characterized both before and after reaction with supercritical CO2 at elevated pressure and temperature. We present the changes in mineralogy, feature relocation, and potential for carbon mineralization and critical mineral recovery based on the comparison of pre- and post-reaction datasets. Herein, we present evidence of dissolution-precipitation reactions leading to carbon mineralization and critical mineral mobilization driven by water-saturated supercritical CO2 fluids, including the formation of aragonite and dissolution-reprecipitation of Ni phases Collectively, these results will improve fate and transport models for carbon storage in ultramafic rocks, increase understanding of new unconventional sources for critical minerals, and provide a foundation for future studies on CO2 enhanced mineral recovery (CO2-EMR).

Carbonate minerals are important carbon sinks that have acted to regulate Earth's climate throughout geologic history. Developing the ability to accelerate their formation is a promising approach to help mitigate global climate disruption from anthropogenic CO2 emissions. Here we compiled and analyzed a diffraction database to examine relationships between the structures and compositions of natural and synthetic double carbonates from the dolomite-ankerite-kutnohorite series. Data was carefully curated from both the International Centre for Diffraction Data powder diffraction file database and the broad literature, whereby lattice spacings, cell parameters and volumes were plotted against composition. Theoretical structures generated using density functional theory (DFT) energy minimizations were used to assess the impact of cation ordering on cell parameters. The collective findings reveal structural distinctions between natural and synthetic samples likely arising from the extent of cation ordering, a characteristic promoted during slow growth of natural samples versus the relatively fast growth of synthetic samples. They also highlight structural parameters that can be used as a basis to predict composition, and vice versa. The insights help advance a fundamental understanding of double carbonate minerals common in nature that also comprise compelling targets for accelerated carbon mineralization.

Olivine is a dynamic and important mineral in the crust and mantle with relevance to processes that are important to climate change technology, such as geologic carbon storage and critical mineral recovery. In this work, we critically evaluated and compiled a new database of olivine diffraction data, lattice parameters, and compositions to enable rapid Ni-Mg-Fe olivine composition determination. A compilation of olivine X-ray diffraction data and chemical compositions from both the literature and the International Centre for Diffraction Data (ICDD) powder database was assembled to plot both the forsterite-fayalite and forsterite-liebenbergite solid-solution lines. We present an expanded data set to delineate equations and relationships used for quantifying the correlations between olivine lattice parameters and chemical compositions in Mg2SiO4-Fe2SiO4 (forsterite-fayalite) and Mg2SiO4-Ni2SiO4 (forsterite-liebenbergite) olivine solid-solution series.

Locating and developing ideal sites for large-scale capture and storage of carbon dioxide has become increasingly necessary due to increasing global emissions and warming. Mafic-ultramafic rocks present a unique geologic setting as they can trap injected CO2 in pore space, mineralize that CO2 to permanently store it as carbonate minerals, and simultaneously release critical minerals. However, these reservoirs are undercharacterized relative to sedimentary carbon storage settings. In this study, we execute a methodology for determining carbonation and critical mineral recovery potential in mafic-ultramafic reservoirs. Using an olivine-rich basalt from the island of Hawai'i, we performed petrologic and geochemical analyses to determine its chemistry, mineralogy, and pore network architecture. We use this data to first quantify the nonreactive storage resource potential and determine the bulk storage of 50 MMT of CO2 in the pore space of a basalt volume test case, along with realistic P10, P50, and P90 scenarios for that same volume. Then, using the chemistry and mineralogy, we both estimate the total mineralization and critical mineral recovery potential, as well as more realistic values based on dissolution-precipitation reactions at the surface areas of pores. This storage resource estimate methodology can assist in accelerating the global commercialization of geologic carbon storage and critical mineral recovery.

This work presents a detailed supercritical CO2 storage resource estimation for the stacked basalt reservoirs in the Grande Ronde Basalt of the Columbia River Basalt Group in eastern Washington and Oregon. The assessment aims to derisk the commercialization potential of geologic carbon storage in basalt by leveraging both structural and mineralization trapping of CO2 in basalt. The structural closures formed by anticlinal ridges and synclinal valleys in Yakima Fold Belt are excellent physical traps to accommodate injected supercritical CO2. Rigorous hydraulic testing, well logs and simulation results from the Wallula Basalt Pilot #1 well showed the occurrence of 17 suitable permeable injection zones (up to 2,496 mD) intercalated with dense seals (similar to 2.6E-10 mD) in the Grand Ronde Basalt. In addition, geochemical studies showed fast reactions between supercritical CO2 and dissolved basalt minerals to form stable carbonates. Our calculation indicates up to 40 gigatons (P90) of mineralization storage resources exist in the Grande Ronde Basalt reservoirs.

Mitigating the deleterious effects of climate change requires the development and implementation of carbon capture and storage technologies. To expand the monitoring, verification, and reporting (MRV) capabilities of geologic carbon mineralization projects, we developed a thermogravimetric analysis-mass spectrometry (TGA-MS) methodology to enable quantification of <100 ppm calcite (CaCO3) in complex samples. We extended TGA-MS calcite calibration curves to enable a higher measurement resolution and lower limits of quantification for evolved CO2 from a calcite-corundum mixture. We demonstrated <100 ppm carbonate mineral quantification with TGA-MS for the first time, an outcome applicable across earth, environmental, and materials science fields. We applied this carbonate quantification method to a suite of Columbia River Basalt Group (CRBG) well cuttings recovered in 2009 from Pacific Northwest National Laboratory's Wallula #1 Well. Our execution of this new combined calcite and calcite-corundum calibration curve TGA-MS method on our CRBG sample suite indicated average carbonate contents of 0.050 wt % in flow interiors (caprocks) and 0.400 wt % in interflow zones (reservoirs) in the upper 1250 m of the Wallula #1 Well. By advancing our knowledge of continental flood basalt-hosted carbonates in the mafic subsurface and reaching new TGA-MS quantification limits for carbonate minerals, we expand MRV capabilities and support the commercial-scale deployment of carbon mineralization projects in the Pacific Northwest United States and beyond.

Basalt formations are promising candidates for the geologic storage of anthropogenic CO2 due to their storage capacity, porosity, permeability, and reactive geochemical trapping ability. The Wallula Basalt Carbon Storage Pilot Project demonstrated that supercritical CO2 injected into >800 m deep Columbia River Basalt Group stacked reservoir flow tops mineralizes to ankerite-siderite-aragonite on month-year time scales, with 60% of the 977 metric tons of CO2 converted within 2 years. The potential impacts of mineral precipitation and consequent changes in the rock porosity, pore structure, pore size, and pore size distributions have likely been underestimated hitherto. Herein, we address these knowledge gaps using X-ray microcomputed tomography (XMT) to evaluate the pore network architecture of sidewall cores recovered 2 years after CO2 injection. In this study, we performed a detailed quantitative analysis of the CO2-reacted basalt cores by XMT imaging. Reconstructed 3D images were analyzed to determine the distribution and volumetric details of porosity and anthropogenic carbonate nodules in the cores. Additional mineralogic quantification provided insight into the overall paragenesis and carbonate growth mechanisms, including mineralogic/chemical zonation. These findings are being used to parametrize multiphase reactive transport models to predict the fate and transport of subsurface CO2, enabling scale-up to commercial-scale geologic carbon storage in basalts and other reactive mafic-ultramafic formations.

EDITORIAL article Front. Clim., 10 January 2023Sec. Negative Emission Technologies Volume 4 - 2022 | https://doi.org/10.3389/fclim.2022.1128721

Complex carbon mineralization at nanoscale mineral interfaces resolved with in situ X-ray diffraction and molecular simulations.

ConspectusIn the mid 2010s, high-pressure diffraction and spectroscopic tools opened a window into the molecular-scale behavior of fluids under the conditions of many CO2 sequestration and shale/tight gas reservoirs, conditions where CO2 and CH4 are present as variably wet supercritical fluids. Integrating high-pressure spectroscopy and diffraction with molecular modeling has revealed much about the ways that supercritical CO2 and CH4 behave in reservoir components, particularly in the slit-shaped micro- and mesopores of layered silicates (phyllosilicates) abundant in caprocks and shales. This Account summarizes how supercritical CO2 and CH4 behave in the slit pores of swelling phyllosilicates as functions of the H2O activity, framework structural features, and charge-balancing cation properties at 90 bar and 323 K, conditions similar to a reservoir at ∼1 km depth. Slit pores containing cations with large radii, low hydration energy, and large polarizability readily interact with CO2, allowing CO2 and H2O to adsorb and coexist in these interlayer pores over a wide range of fluid humidities. In contrast, cations with small radii, high hydration energy, and low polarizability weakly interact with CO2, leading to reduced CO2 uptake and a tendency to exclude CO2 from interlayers when H2O is abundant. The reorientation dynamics of confined CO2 depends on the interlayer pore height, which is strongly influenced by the cation properties, framework properties, and fluid humidity. The silicate structural framework also influences CO2 uptake and behavior; for example, smectites with increasing F-for-OH substitution in the framework take up greater quantities of CO2. Reactions that trap CO2 in carbonate phases have been observed in thin H2O films near smectite surfaces, including a dissolution-reprecipitation mechanism when the edge surface area is large and an ion exchange-precipitation mechanism when the interlayer cation can form a highly insoluble carbonate. In contrast, supercritical CH4 does not readily associate with cations, does not react with smectites, and is only incorporated into interlayer slit mesopores when (i) the pore has a z-dimension large enough to accommodate CH4, (ii) the smectite has low charge, and (iii) the H2O activity is low. The adsorption and displacement of CH4 by CO2 and vice versa have been studied on the molecular scale in one shale, but opportunities remain to examine behavioral details in this more complicated, slit-pore inclusive system.

Increased penetration of renewables for power generation has negatively impacted the dynamics of conventional fossil fuel-based power plants. The power plants operating on the base load are forced to cycle, to adjust to the fluctuating power demands. This results in an inefficient operation of the coal power plants, which leads up to higher operating losses. To overcome such operational challenge associated with cycling and to develop an optimal process control, this work analyzes a set of models for predicting power generation. Moreover, the power generation is intrinsically affected by the state of the power plant components, and therefore our model development also incorporates additional power plant process variables while forecasting the power generation. We present and compare multiple state-of-the-art forecasting data-driven methods for power generation to determine the most adequate and accurate model. We also develop an interpretable attention-based transformer model to explain the importance of process variables during training and forecasting. The trained deep neural network (DNN) LSTM model has good accuracy in predicting gross power generation under various prediction horizons with/without cycling events and outperforms the other models for long-term forecasting. The DNN memory-based models show significant superiority over other state-of-the-art machine learning models for short, medium and long range predictions. The transformer-based model with attention enhances the selection of historical data for multi-horizon forecasting, and also allows to interpret the significance of internal power plant components on the power generation. This newly gained insights can be used by operation engineers to anticipate and monitor the health of power plant equipment during high cycling periods.

Mitigating climate change requires transformational advances for carbon dioxide removal, including geologic carbon sequestration in reactive subsurface environments. The Wallula Basalt Carbon Storage Pilot Project demonstrated that CO2 injected into >800 m deep Columbia River Basalt Group flow top reservoirs mineralizes on month-year timescales. Herein, we present new optical petrography, micro-computed X-ray tomography, and electron microscopy results obtained from sidewall cores collected two years after CO2 injection. As no other anthropogenic carbonates from geologic carbon storage field studies have been recovered, this world-unique sample suite provides unparalleled insight for subsurface carbon mineralization products and paragenesis. Chemically zoned nodules with Ca/Mn-rich cores and Fe-dominant outer rims are prominent examples of the neoformed carbonate assemblages with ankerite-siderite compositions and exotic divalent cation correlations. Paragenetic insights for the timing of aragonite, silica, and fibrous zeolites are clarified based on mineral texture and spatial relationships, along with time-resolved downhole fluid sampling. Collectively, these results clarify the mineralogy, chemistry, and paragenesis of carbon mineralization, providing insight into the ultimate fate and transport of CO2 in reactive mafic-ultramafic reservoirs.

Carbon-negative strategies such as geologic carbon sequestration in continental flood basalts offers a promising route to the removal of greenhouse gases, such as CO2, via safe and permanent storage as stable carbonates. This potential has been successfully demonstrated at a field scale at the Wallula Basalt Carbon Storage Pilot Project where supercritical CO2 was injected into the Columbia River Basalt Group (CRBG). Here, we analyze recovered post-injection sidewall core cross-sections containing carbonate nodules using μ-XRF chemical mapping techniques that revealed compositional zonation within the nodules. The unique nature of the subsurface anthropogenic carbonates is highlighted by the near absence of Mg in an ankerite-like composition. Furthermore, a comparison between pre- and post-injection sidewall cores along with an in-depth chemical mapping of basalt pore lining cements provides a better understanding into the source and fate of critical cationic species involved in the precipitation of carbon mineralization products. Collectively, these results provide crucial insights into carbonate growth mechanisms under a time-dependent pore fluid composition. As such, these findings will enable parameterization of predictive models for future CO2 sequestration efforts in reactive reservoirs around the world.

Basalt reservoirs offer the potential for carbon mineralization, aiding in achieving net-zero emissions. However, debates persist about microscopic crystallization mechanisms due to limited characterization techniques under high-temperature and pressure conditions. By using Identical Location Transmission Electron Microscopy (IL-TEM) and cryo-TEM, this study reveals nanoscale interfacial carbonation processes of forsterite and diopside nanoparticles in water-saturated supercritical carbon dioxide under realistic reservoir conditions. Both minerals undergo preferential metal cation dissolution into a thin water film, forming porous Si-rich amorphous layers, supporting the leached layer mechanism as the dominant mineral reactivity process. Diopside's amorphous layer has lower porosity and growth rate relative to forsterite, likely related to the connectivity of silicate tetrahedra. Kinetically favorable nesquehonite and aragonite nanocrystals form on the amorphous layers. These findings support the development of accurate reservoir simulations and help enable commercial-scale carbon storage deployment.

Several strategies for mitigating the build-up of atmospheric carbon dioxide (CO2) bring wet supercritical CO2 (scCO2) in contact with phyllosilicates such as illites and smectites. While some work has examined the role of the charge-balancing cation and smectite framework features on CO2/smectite interactions, to our knowledge no one has examined how the polarizability of the charge-balancing cation influences these behaviors. In this paper, the scCO2 adsorption properties of Pb2+, Rb+, and NH4+ saturated smectite clays at variable relative humidity are studied by integrating in situ high-pressure X-ray diffraction (XRD), infrared spectroscopic titrations, and magic angle spinning nuclear magnetic resonance (MAS NMR) methods. The results are combined with previously published data for Na+, Cs+, and Ca2+ saturated versions of the same smectites to isolate the roles of the charge-balancing cations and perform two independent tests of the role of charge-balancing cation polarizability in determining the interlayer fluid properties and smectite expansion. Independent correlations developed for (i) San Bernardino hectorite (SHCa-1) and (ii) Wyoming montmorillonite (SWy-2) both show that cation polarizability is important in predicting the interlayer composition (mol% CO2 in the interlayer fluid and CO2/cation ratio in interlayer) and the expansion behavior for smectites in contact with wet and dry scCO2. In particular, this study shows that the charge-balancing cation polarizability is the most important cation-associated parameter in determining the expansion of the trioctahedral smectite, hectorite, when in contact with dry scCO2. While both independent tests show that cation polarizability is an important factor in smectite-scCO2 systems, the correlations for hectorite are different from those determined for montmorillonite. The root of these differences is likely associated with the roles of the smectite framework on adsorption, warranting follow-up studies with a larger number of unique smectite frameworks. Overall, the results show that the polarizability of the charge-balancing cation should be considered when preparing smectite clays (or industrial processes involving smectites) to capture CO2 and in predicting the behavior of caprocks over time.

Thin sections and hand samples from 50 sidewall cores from the stration, provided the opportunity for the in-depth analysis of carbon mineralization induced by the injection of supercritical CO2. In this study, we used optical petrography and scanning electron microscopy to characterize the physical and chemical characteristics of the basalt components influenced by carbon mineralization reactions from all available hand samples and thin sections within the three CO2 injection zones and caprock flow interiors. We found extensive carbonate mineralization, mostly in the form of nodules that were shown to be chemically zoned: Ca-dominant in the core regions and Ca-bearing Fe-dominant in the outer regions. Carbonate mineralization also took the form of fracture-filling carbonate cement, and acicular aragonite was also observed. Overall, we clarified the structural and paragenetic relationships between newly formed minerals, identifying a new fibro-palagonite-like, poorly crystalline silicate phase that grew on the carbonate nodules and pore-lining zeolites. We observed Fe-dominant carbonate precipitates surrounding acicular aragonite and rhombohedral Ca-carbonate cores, whereas previous studies of these zoned nodules did not observe these structures. A comprehensive accounting of the carbon mineralization products is vital to understand and predict the behavior of supercritical CO2 in the subsurface given both the diversity of the host rock between and within injection zones, especially considering that the morphology and chemistry of the diverse precipitates are influenced by the pore-scale microenvironments of the basalt.

Injecting fluids into deep underground geologic structures is a critical component to development of long-term strategies for managing greenhouse gas emissions and facilitating energy extraction operations. Recently, we reported that metal-organic frameworks are low-frequency absorptive acoustic metamaterial that may be injected into the subsurface enhancing geophysical monitoring tools used to track fluids and map complex structures. A key requirement for this nanotechnology deployment is transportability through porous geologic media without being retained by mineral-fluid interfaces. Flow-through column studies were used to estimate transport and retention properties of five different polymer-coated MIL-101(Cr) nanoparticles in siliceous porous media. Nanoparticle transport experiments revealed that nanoparticle surface characteristics play a critical role in nanoparticle colloidal stability and as well the transport.

Two new activation energies for olivine transformation to magnesite improves understanding of subsurface carbon mineralization, critical for aiding development of carbon-management technologies.