3D Quantification of Pore Networks and Anthropogenic Carbon Mineralization in Stacked Basalt Reservoirs.

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.

Facile Metal Release from Pore-Lining Phases Enables Unique Carbonate Zonation in a Basalt Carbon Mineralization Demonstration.

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.

Exotic Carbonate Mineralization Recovered from a Deep Basalt Carbon Storage Demonstration.

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.

Reactive Transport Simulation of Fracture Channelization and Transmissivity Evolution.

Underground fractures serve as flow conduits, and they may produce unwanted migration of water and other fluids in the subsurface. An example is the migration and leakage of greenhouse gases in the context of geologic carbon sequestration. This study has generated new understanding about how acids erode carbonate fracture surfaces and the positive feedback between reaction and flow. A two-dimensional reactive transport model was developed and used to investigate the extent to which geochemical factors influence fracture permeability and transmissivity evolution in carbonate rocks. The only mineral modeled as reactive is calcite, a fast-reacting mineral that is abundant in subsurface formations. The X-ray computed tomography dataset from a previous experimental study of fractured cores exposed to carbonic acid served as a testbed to benchmark the model simulation results. The model was able to capture not only erosion of fracture surfaces but also the specific phenomenon of channelization, which produces accelerating transmissivity increase. Results corroborated experimental findings that higher reactivity of the influent solution leads to strong channelization without substantial mineral dissolution. Simulations using mineral maps of calcite in a specimen of Amherstburg limestone demonstrated that mineral heterogeneity can either facilitate or suppress the development of flow channels depending on the spatial patterns of reactive mineral. In these cases, fracture transmissivity may increase rapidly, increase slowly, or stay constant, and for all these possibilities, the calcite mineral continues to dissolve. Collectively, these results illustrate that fluid chemistry and mineral spatial patterns need to be considered in predictions of reaction-induced fracture alteration and risks of fluid migration.

An integrated experimental-modeling approach to identify key processes for carbon mineralization in fractured mafic and ultramafic rocks.

Controlling atmospheric warming requires immediate reduction of carbon dioxide (CO2) emissions, as well as the active removal and sequestration of CO2 from current point sources. One promising proposed strategy to reduce atmospheric CO2 levels is geologic carbon sequestration (GCS), where CO2 is injected into the subsurface and reacts with the formation to precipitate carbonate minerals. Rapid mineralization has recently been reported for field tests in mafic and ultramafic rocks. However, unlike saline aquifers and depleted oil and gas reservoirs historically considered for GCS, these formations can have extremely low porosities and permeabilities, limiting storage volumes and reactive mineral surfaces to the preexisting fracture network. As a result, coupling between geochemical interactions and the fracture network evolution is a critical component of long-term, sustainable carbon storage. In this paper, we summarize recent advances in integrating experimental and modeling approaches to determine the first-order processes for carbon mineralization in a fractured mafic/ultramafic rock system. We observe the critical role of fracture aperture, flow, and surface characteristics in controlling the quantity, identity, and morphology of secondary precipitates and present where the influence of these factors can be reflected in newly developed thermo-hydro-mechanical-chemical models. Our findings provide a roadmap for future work on carbon mineralization, as we present the most important system components and key challenges that we are overcoming to enable GCS in mafic and ultramafic rocks.

New insights into the dolomitization and dissolution mechanisms of dolomite-calcite (104)/(110) crystal boundary: An implication to geologic carbon sequestration process.

Geologic carbon sequestration (GCS) is a promising strategy to reduce the harm of CO2 due to the rapidly increased fossil fuel combustion. Dolomitization and dissolution processes of deeply buried carbonate reservoirs significantly impact the potential of GCS. However, previous investigations mainly focus on the macroscopic batch experiments, the mechanisms at atomic level are still unclear especially for crystal boundary, but urgently required. Herein, the GCS potential and the effects of boundary dissolution on calcite and dolomite were investigated based on both analytical and simulation methods such as molecular dynamics simulation (MDS) and density functional theory (DFT) calculations, to deeply unveil the mechanisms of dolomitization and formation of intergranular secondary pores from the atomic perspective. The morphology results indicated that the dissolution of calcite and dolomite in carbonic acid solution started via the edges and corners. In addition, the simulated results showed that the carbon sequestration potential presented an order in dolomite (PMg50%) > PMg40% > PMg30% > PMg20% > PMg10% > calcite by dolomitization due to the reduced bulk volume but increased lattice stress. Furthermore, both electrons transfer and diffusion coefficients results suggested that the (104)/(110) boundary was preferentially dissolved as compared to the (104) and (110) planes, indicating that crystal boundary was beneficial to the formation of pores for the oil and gas storage, but harmful to the stability of long-term GCS. Therefore, this study, for the first time, provides new insights into uncovering the mechanisms of the GCS process in depth, from an atomic level focusing on the crystal boundary, thereby promoting the understand of the long-term evolution for both calcite and dolomite in deep reservoirs.

Improved Vinegar & Wellington calibration for estimation of fluid saturation and porosity from CT images for a core flooding test under geologic carbon storage conditions.

X-ray computed tomography (CT) of fluid flow in formation rocks is an important characterization technique in geologic carbon sequestration research to provide insight into the migration and capillary trapping of CO2 under reservoir conditions. An improved calibration method adapted from traditional Vinegar & Wellington calibration is proposed to map the 3D pore and fluid distributions from the CT images of CO2/brine displacement flooding. Similar to Vinegar & Wellington calibration, the proposed method adopts the linear scaling law of CT number transformation to mass density. However, different from Vinegar & Wellington calibration that uses a 100% brine-saturated core image and a 100% CO2-saturated core image as references to calculate CO2 and brine saturations at all time steps, the proposed method uses the CT numbers of CO2 and brine to calculate the incremental of CO2 and brine saturations from time step i to time step i +1. The method is intended for cases in which the two 100% brine saturation and 100% CO2 saturation images can not be successfully obtained. Overall, the improved calibration proposed by this study presents more reasonable results of CO2 and brine distribution in a Berea sandstone core, as compared to traditional Vinegar & Wellington calibration. The reconstructed porosity image agrees with the laminated structure of the Berea sandstone core, and the average porosity evaluated over the entire core (0.176) is comparable to the physical porosity (0.165). Furthermore, the reconstructed saturation images using the improved calibration reveal a flat piston-like flooding front from a homogeneous longitudinal-section of the 3D orthogonal view and preferential fingerings from another non-homogeneous longitudinal-section, which are not present in the reconstructed saturation images using traditional Vinegar & Wellington calibration. Concerns and causes with respect to the uncertainty of linear CT number calibration are also explained, and approaches to alleviate the uncertainty are suggested.