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.

Understanding fluid flow in rocks is crucial to quantify many natural processes such as ground water flow and naturally triggered seismicity, as well as engineering questions such as displacement of contaminants, the eligibility of subsurface waste storage, geothermal energy usage, oil and gas recovery and artificially induced seismicity. Two key parameters that control the variability of fluid flow and the movement of dissolved chemical species are (i) the local hydraulic conductivity, and (ii) the local sorption properties of the dissolved chemical species by the solid matrix. These parameters can be constrained through tomography imaging of rock samples subjected to fluid injection under constrained flow rate and pressure. The neutron imaging technique is ideal to explore fluid localization in porous materials due to the high but variable sensitivity of neutrons to the different hydrogen isotopes. However, until recently, this technique was underused in geology because of its large acquisition time. With the improved acquisition times of newly set-up neutron beamlines, it has become easier to study fluid flow. In the current set of experiments, we demonstrate the feasibility of in-situ 2D and 3D time-lapse neutron imaging of fluid and pollutant percolation in rocks, in particular that of cadmium salt. Cadmium is a hazardous compound that is found in many electronic devices, including batteries and is a common contaminant in soil and groundwater. It also exhibits higher contrast in neutron attenuation with respect to heavy water, and is therefore an ideal tracer. Time-lapse 2D radiographies and 3D neutron tomographies of the samples were acquired on two neutron beamlines (ILL, France and SINQ, Switzerland). We performed two sets of experiments, imbibition and injection experiments, where we imaged in-situ flow properties, such as local permeability and interactions between cadmium and the solid rock matrix. Our results indicate that even within these cm-scale porous rocks, cadmium transport follows preferential pathways, and locally interacts within the limestone samples. Our results demonstrate that the use of neutron imaging provides additional insights on subsurface transport of pollutants.

We present an experimental method to study time-dependent, CO₂-induced, local topography changes in mm-sized composite samples, plus results showing heterogeneous swelling of coal and shale on the nano- to micrometer scale. These results were obtained using high resolution interferometry measurements of sample topography, combined with a new type of experimental microfluidic device. This device is a custom-built pressure vessel, which can contain any impermeable sample type and can be placed under any microscope. The pressure vessel itself has been tested to handle pressures up to 100 bar at room temperature conditions. For the experiments reported here we used three sample types: i) epoxy and dolomite, ii) coal, epoxy and dolomite and iii) shale. These model systems (thicknesses between 2 and 10 mm) were exposed to pressurized CO₂ (20–35 bars) and subsequently deformation over time was monitored with a white light interferometer. This provided a lateral spatial resolution of 979 nm and a vertical spatial resolution of 200 nm, i.e. sufficient resolution so that coal and shale constituents can be tracked individually. Within 72 h epoxy swells homogeneously up to 11 μm, coal swells 4 ± 1 μm and dolomite is unreactive with the dry CO₂ injected here, and as such is used as a reference surface. The differential swelling of coal can be correlated in space with the macerals, where macerals with an initial higher topography swell more. The average or bulk swelling exhibits an approximate t^½ relation, indicative of diffusion-controlled adsorption of CO₂ on the organic matter. Measurements of the differential swelling of both shale samples enabled tracking of individual patches of organic matter within the shale (max. 20 × 20 μm). These patches exhibit finite swelling of on average 250 nm in 4 h (in the Pomeranian shale) and 850 μm in 20 h (in the Green River shale), where total swelling is assumed to be related to the volume of the patches of organic matter.