RESUMEN
Despite the advantageous resolution of electron tomography (ET), reconstruction of three-dimensional (3D) images from multiple two-dimensional (2D) projections presents several challenges, including small signal-to-noise ratios, and a limited projection range. This study evaluates the capabilities of ET for thin sections of shale, a complex nanoporous medium. A numerical phantom with 1.24 nm pixel size is constructed based on the tomographic reconstruction of a Barnett shale. A dataset of 2D projection images is numerically generated from the 3D phantom and studied over a range of conditions. First, common reconstruction techniques are used to reconstruct the shale structure. The reconstruction uncertainty is quantified by comparing overall values of storage and transport metrics, as well as the misclassification of pore voxels compared to the phantom. We then select the most robust reconstruction technique and we vary the acquisition conditions to quantify the effect of artifacts. We find a strong agreement for large pores over the different acquisition workflows, while a wider variability exists for nanometer-scale features. The limited projection range and reconstruction are identified as the main experimental bottlenecks, thereby suggesting that sample thinning, advanced holders, and advanced reconstruction algorithms offer opportunities for improvement.
RESUMEN
Deep subsurface stimulation processes often promote fluid-rock interactions that can lead to the formation of small colloidal particles that are suspected to migrate through the rock matrix, partially or fully clog pores and microfractures, and promote the mobilization of contaminants. Thus, the goal of this work is to understand the geochemical changes of the host rock in response to reservoir stimulation that promote the formation and migration of colloids. Two different carbonate-rich shales were exposed to different solution pHs (pH = 2 and 7). Iron and other mineral transformations at the shale-fluid interface were first characterized by synchrotron-based XRF mapping. Then, colloids that were able to migrate from the shale into the bulk fluid were characterized by synchrotron-based extended X-ray absorption structure (EXAFS), scanning electron microscopy (SEM), and single-particle inductively coupled plasma time-of-flight mass spectrometry (sp-icpTOF-MS). When exposed to the pH = 2 solution, extensive mineral dissolution and secondary precipitation was observed; iron-(oxyhydr)oxide colloids colocated with silicates were observed by SEM at the fluid-shale interfaces, and the mobilization of chromium and nickel with these iron colloids into the bulk fluid was detected by sp-icpTOF-MS. Iron EXAFS spectra of the solution at the shale-fluid interface suggests the rapid (within minutes) formation of ferrihydrite-like nanoparticles. Thus, we demonstrate that the pH neutralization promotes the mobilization of existing silicate minerals and the rapid formation of new iron colloids. These Fe colloids have the potential to migrate through the shale matrix and mobilize other heavy metals (such as Cr and Ni, in this study) and impacting groundwater quality, as well produced waters from these hydraulic fracturing operations.
RESUMEN
Characterization of microscopic details of the fabric of mudstones and shales (i.e., structure and composition) is important to understand their storage and transport properties. Current characterization methods struggle to probe reliably multiple scales of interest (e.g., pore and fracture) and measure properties at the finest resolution under representative in situ conditions. Micro X-ray fluorescence (µXRF) is a high-performance imaging technique that produces elemental images at sub-10 µm spatial resolution and could offer insight into a diversity of shale properties, such as mineral composition, porosity, and in situ pressure gradients. This study designed and carried out a porosity mapping protocol using model and real-rock microfluidic devices and contrast fluids. Etched silicon micromodels with real-rock pore network patterns served as ideal models to establish a proof of concept. Measurements were performed on a novel µXRF microscope not powered by synchrotron radiation. We registered the µXRF datasets with the binary rock masks used for micromodel fabrication and applied segmentation algorithms to compare porosities. We assessed expected advantages and limitations through a sensitivity analysis and beam study. µXRF is an important new imaging technique for microfluidic applications.
