Mixing-limited reactions are central to a wide range of processes in natural and engineered porous media. Recent advances have shown that concentration gradients sustained by flow at the pore-scale influence macroscopic reaction rates over a large range of reactive transport regimes. Yet, resolving concentration gradients driven by fluid mixing at the pore-scale is challenging with current simulation methods. Here, we introduce a computational methodology to resolve concentration gradients at the pore scale in mixing-limited reactions. We consider a steady-state reactive transport problem characterized by reactive fluids flowing in parallel in a porous material. Given a mesh representation of the pore space and a steady velocity field, we solve the steady advection-diffusion equation for conservative scalar transport using a stabilized finite-element method combined with mesh refinement adapted to local scalar gradients. Based on this solution and assuming instantaneous reaction kinetics in the fluid, we infer the distribution of species involved in an irreversible bi-molecular reaction. We validate the method by comparing our results for uniform flow with analytical solutions and then apply it to simulate mixing-limited reactions in a three-dimensional random bead pack and Berea sandstone sample. Chaotic flow within the pore space leads to sustained concentration gradients, which are captured by our numerical framework. The results underscore the ability of the methodology to simulate transverse mixing and mixing-limited reactions in complex porous media and to provide bottom-up numerical data to improve the prediction of effective reaction rates at larger scales.

In many geological systems, the porosity of rock or soil may evolve during mineral precipitation, a process that controls fluid transport properties. Here, we investigate the use of 4D neutron imaging to image flow and transport in Bentheim sandstone core samples before and after in-situ calcium carbonate precipitation. First, we demonstrate the applicability of neutron imaging to quantify the solute dispersion along the interface between heavy water and a cadmium aqueous solution. Then, we monitor the flow of heavy water within two Bentheim sandstone core samples before and after a step of in-situ mineral precipitation. The precipitation of calcium carbonate is induced by reactive mixing of two solutions containing CaCl2 and Na2CO3, either by injecting these two fluids one after each other (sequential experiment) or by injecting them in parallel (co-flow experiment). We use the contrast in neutron attenuation from time-resolved tomograms to derive three-dimensional fluid velocity field by using an inversion technique based on the advection-dispersion equation. Results show mineral precipitation induces a wider distribution of local flow velocities and leads to alterations in the main flow pathways. The flow distribution appears to be independent of the initial distribution in the sequential experiment, while in the co-flow experiment, we observed that higher initial local fluid velocities tended to increase slightly following precipitation. The outcome of this study contributes to progressing the knowledge in the domain of reactive solute and contaminant transport in the subsurface using the promising technique of neutron imaging. Flow and mixing processes in porous media control many natural and industrial systems, such as microbial clogging, oil extraction, and effluent disposal. In many systems, the porosity may evolve during mineral precipitation, such as in rocks, and control fluid transport properties. Here, we use time-lapsed three-dimensional neutron imaging to explore fluid transport into Berea sandstone core samples during in-situ carbonate precipitation. Neutron imaging can track fluid flow inside the rock, whereas X-ray imaging illuminates the regions where mineral precipitation occurs. We control the precipitation of calcium carbonate in the rock through reactive mixing between solutions containing CaCl2 and Na2CO3. By solving the adverse advection-diffusion equation using the contrast in neutron attenuation from time-lapse images, we derive the 3D velocity field of the injected fluids. Results show that under the effect of mineral precipitation, a wide range of local flow velocities develop in the sample, and we quantify the distribution of flow velocities in the sample. The finding of this experimental study is useful in progressing the knowledge in the domain of reactive solute and contaminant transport in the subsurface. 4D neutron imaging is used to image flow and transport in porous rock and investigate the effect of carbonate precipitation The velocity field of injected fluid is estimated by solving the advection-dispersion equation using the contrast in neutron attenuation Carbonate precipitation widens the distribution of fluid velocities due to local pore-clogging

Advances in micro-scale imaging techniques, such as X-ray microtomography, have provided new insights into a broad range of porous media processes. However, direct imaging of flow and transport processes remains challenging due to spatial and temporal resolution limitations. Here, we investigate the use of dynamic three-dimensional neutron imaging to image flow and transport in Bentheim sandstone core samples before and after in-situ calcium carbonate precipitation. First, we demonstrate the applicability of neutron imaging to quantify the solute dispersion along the interface between heavy water and a cadmium aqueous solution. Then, we monitor the flow of heavy water within two Bentheim sandstone core samples before and after a step of in-situ mineral precipitation. The precipitation of calcium carbonate is induced by reactive mixing of two solutions containing CaCl2 and Na2CO3, either by injecting these two fluids one after each other (sequential experiment) or by injecting them in parallel (co-flow experiment). We use the contrast in neutron attenuation from time-lapse tomograms to derive three-dimensional fluid velocity field by using an inversion technique based on the advection-dispersion equation. Results show mineral precipitation induces a wider distribution of local flow velocities and leads to alterations in the main flow pathways. The flow distribution appears to be independent of the initial distribution in the sequential experiment, while in the co-flow experiment, we observed that higher initial local fluid velocities tended to increase slightly following precipitation. These findings suggest that neutron imaging is a promising technique to investigate dynamics processes in porous media.

<p>Flow and mixing processes in porous media control many natural and industrial systems, such as microbial clogging, oil extraction, and effluent disposal. In many systems, the porosity may evolve during mineral precipitation, such as in rocks, and control fluid mixing and fluid transport properties. Here, we use three-dimensional in situ dynamic neutron and X-ray micro-tomography imaging to explore fluid transport into Berea sandstone core samples during in-situ carbonate precipitation. Neutron imaging can track fluid flow inside the rock, whereas X-ray imaging illuminates the regions where mineral precipitation occurs. We control the precipitation of calcium carbonate in the rock through reactive-mixing between solutions containing CaCl<sub>2</sub> and Na<sub>2</sub>CO<sub>3</sub>. By solving the advection-diffusion equation using the contrast in neutron attenuation from time-lapse images, we derive the 3D velocity field of the injected fluids and characterize the evolution of the permeability field into the rock during mineral precipitation. We also investigate the mixing between heavy water and a cadmium solution under the influence of mineral precipitation. Results show that, under the effect of mineral precipitation, a wide range of local flow velocities develop in the sample, under the same fluid injection rate, and we quantify the distribution of flow velocities in the sample. Moreover, we observe more efficient mixing between heavy water and a cadmium solution after mineral precipitation. The finding of this experimental study is useful in progressing the knowledge in the domain of reactive solute and contaminant transport in the subsurface.</p>

Carbon dioxide (CO2) storage in geologic formations is an attractive means of reducing greenhouse gas emissions. The main processes controlling the migration of CO2 in geological formations are related to convective mixing and geochemical reactions. The effects of heterogeneity on these coupled processes have been widely discussed in the literature. Recently, special attention has been devoted to fractured geological formations that can be found in several storage reservoirs. However, existing studies on the effect of fractures on the fate of CO2 neglect the key processes of geochemical reactions. This work aims at addressing this gap. Based on numerical simulations of a hypothetical reservoir, we explore the effect of fracture properties and topology on the domain's storage capacity at different rates of CO2 mineral dissolution. It is found that the fractures not only can help the mixing convection and reaction process in the domain but also may play a restrictive role in entering dissolved CO2 and hinder the plume fingers from growing. The hypothetical case is relevant in providing preliminary understanding but can show varying degrees of geological realism. For more representative geology, we investigate the migration-dissolution of buoyant CO2 on a large-scale outcrop of a volcanic basalt rock formation. The results show that neglecting thin fractures can significantly affect the predicted amount of trapped CO2. The storage capacity is more sensitive to heterogeneity at low dissolution rates. The findings are useful for the management of CO2 sequestration in fractured domains.

The Elder problem is one of the well-known examples of an unstable density-driven flow (DDF) and solute transport in porous media. The goal of this research is to investigate the influence of fracture networks on this benchmark problem due to the great importance of the fractured heterogeneity effect on unstable DDF. For this aim, the fractured Elder problem is solved using COMSOL Multiphysics, which is a finite element method simulator. Uniform and orthogonal fracture networks are embedded to analyze free convective flow and development of unstable salt plumes. The results indicate that the mesh sensitivity of the fractured Elder problem is greater than the homogeneous case. Furthermore, it has been shown that in the fractured cases, the onset of instability and free convection occur with lower critical Rayleigh number, which means that fracture networks have a destabilizing effect. Also, we examined the structural properties of fracture networks that control convective flow patterns, and the simulation results show that the strength of convection and instability at the beginning of the intrusion is proportional to the aperture size of the fractures. Moreover, the increase of the fracture's density leads different modes of transient convective modes, until a specific fracture density after which the transient convective modes become similar to the homogenous case.