Surface Hydroxylation-Induced Electrostatic Forces Thicken Water Films on Quartz.

Aqueous films on mineral surfaces control the physical, chemical, and biological transport processes in the atmosphere, soil, and rocks. Despite the importance of thin films for various research and engineering fields, there are still unanswered questions regarding the roles of the different forces affecting the nature of water films. One of these, the focus of this study, is the development of abnormally thick water films on quartz surfaces. In this study, we developed a density-functional-theory-based model to describe the time-dependent evolution of water films and identify the governing forces responsible for thickening films. We simulated the diffusion of water vapor from ambient air toward mineral surfaces and the formation and thickening of water films at various relative humidity values. Our model predicts an abnormal water film thickness on a hydroxylated quartz surface compared to a surface free of hydroxylation, which explains experimental observations. We further used the model to understand the key interaction forces at different stages of water film formation and thickening. Our model suggests that the attractive hydrogen bonding and van der Waals forces initiate a seed layer of water, and the electrostatic forces, generated by the hydroxylated and thus charged surface, lead to the thickening of water films. This generalizable model can provide insights into the peculiarities of water film development on various mineral surfaces.

Adsorption and Capillary Condensation-Induced Imbibition in Nanoporous Media.

Multiphase flow phenomena in nanoporous media are encountered in many science and engineering applications. Shales, for example, possessing complex nanopore networks, have considerable importance as source rocks for unconventional oil and gas production and as low-permeability seals for geologic carbon sequestration or nuclear waste disposal. This study presents a theoretical investigation of the processes controlling adsorption, capillary condensation, and imbibition in such nanoporous media, with a particular focus on understanding the effects of fluid-fluid and fluid-pore wall interaction forces in the interconnected nanopore space. Building on a new theoretical framework, we developed a numerical model for the multiphase nanoporous flow and tested it against water vapor uptake measurements conducted on a shale core sample. The model, which is based on the density functional approach, explicitly includes the relevant interaction forces among fluids and solids while allowing for a continuum representation of the porous medium. The experimental data include gravimetrically measured mass changes in an initially dry core sample exposed to varying levels of relative humidity, starting with a low relative humidity (rh = 0.31) followed by a period of a higher relative humidity (rh = 0.81). During this process, water vapor uptake in the dry core is recorded as a function of time. Our model suggests that, under low rh conditions, the flow within the shale sample is controlled by adsorption- and diffusion-type processes. After increasing the rh to 0.81, the uptake of water vapor becomes more significant, and according to our model, this can be explained by capillary condensation followed by immiscible displacement in the core sample. It appears that strong fluid-pore wall attractive forces cause condensation near the inlet, which then induces water imbibition further into sample.

Permeability Decline by Clay Fines Migration around a Low-Salinity Fluid Injection Well.

Migration of clay fines can be a concern when less saline fluids are injected into brine-saturated sandstone formations containing clays. If the salinity near fluid injection wells decreases below a critical value, the clay fines near the injection may detach, start migrating, and finally clog the pores. This effect can cause permeability decline near the well and may rapidly reduce the well injectivity. The focus of this work is on evaluating the impacts of clay fines migration on permeability decline in the field, using a numerical model and pressure buildup data collected during successive variable-rate water injections in a deep sandstone reservoir. The numerical model accounts for the mixing of low-salinity water with native brine and the migration of clay fines with the detachment and pore-clogging processes. The model interpretation of the pressure buildup data implies that the observed reduction in well injectivity is mainly associated with the clay fines migration and related pore clogging near the well. The model reasonably well represents the pressure buildup data during the injections. Our simulations demonstrate that the permeability near the well can rapidly decline within the first hour of injection. The measured pressure buildup in post-injection periods appears to decay more rapidly, compared to the simulation results of the model that assume irreversible permeability damage. This raises the question whether the permeability damage may be partly reversible near the well by backflow of brine after the injection of low-salinity water.

Transport and deposition of polymer-modified Fe0 nanoparticles in 2-D heterogeneous porous media: effects of particle concentration, Fe0 content, and coatings.

Concentrated suspensions of polymer-modified Fe(0) nanoparticles (NZVI) are injected into heterogeneous porous media for groundwater remediation. This study evaluated the effect of porous media heterogeneity and the dispersion properties including particle concentration, Fe(0) content, and adsorbed polymer mass and layer thickness which are expected to affect the delivery and emplacement of NZVI in heterogeneous porous media in a two-dimensional (2-D) cell. Heterogeneity in hydraulic conductivity had a significant impact on the deposition of NZVI. Polymer modified NZVI followed preferential flow paths and deposited in the regions where fluid shear is insufficient to prevent NZVI agglomeration and deposition. NZVI transported in heterogeneous porous media better at low particle concentration (0.3 g/L) than at high particle concentrations (3 and 6 g/L) due to greater particle agglomeration at high concentration. High Fe(0) content decreased transport during injection due to agglomeration promoted by magnetic attraction. NZVI with a flat adsorbed polymeric layer (thickness ∼30 nm) could not be transported effectively due to pore clogging and deposition near the inlet, while NZVI with a more extended adsorbed layer thickness (i.e., ∼70 nm) were mobile in porous media. This study indicates the importance of characterizing porous media heterogeneity and NZVI dispersion properties as part of the design of a robust delivery strategy for NZVI in the subsurface.

Examining Developmental Patterns of Prison Misconduct: An Integrated Model Approach.

Recent prison scholarship has employed an integrated model of the developmental/life-course perspectives and importation model to examine prison misconduct. Using longitudinal data from a large sample of inmates incarcerated in a U.S. prison system, this study attempts to validate and expand recent prison research by systematically examining the relationship among inmate characteristics and misconduct trajectories, particularly for the higher/chronic pattern of misconduct relative to other identified clusters. The results show that smaller groups of inmates have persistent criminal careers and continually engaged in high level of misconduct. In addition, several inmate characteristics associated with prison misconduct can also be useful to distinguishing high-risk inmates/persistent offenders from groups that offend at low rates over time. These findings could provide vital information to prison officials in developing and designing alternative prison services, assistance, and rehabilitation programs based on the misconduct trajectories.

Multiphase modeling of geologic carbon sequestration in saline aquifers.

Geologic carbon sequestration (GCS) is being considered as a climate change mitigation option in many future energy scenarios. Mathematical modeling is routinely used to predict subsurface CO2 and resident brine migration for the design of injection operations, to demonstrate the permanence of CO2 storage, and to show that other subsurface resources will not be degraded. Many processes impact the migration of CO2 and brine, including multiphase flow dynamics, geochemistry, and geomechanics, along with the spatial distribution of parameters such as porosity and permeability. In this article, we review a set of multiphase modeling approaches with different levels of conceptual complexity that have been used to model GCS. Model complexity ranges from coupled multiprocess models to simplified vertical equilibrium (VE) models and macroscopic invasion percolation models. The goal of this article is to give a framework of conceptual model complexity, and to show the types of modeling approaches that have been used to address specific GCS questions. Application of the modeling approaches is shown using five ongoing or proposed CO2 injection sites. For the selected sites, the majority of GCS models follow a simplified multiphase approach, especially for questions related to injection and local-scale heterogeneity. Coupled multiprocess models are only applied in one case where geomechanics have a strong impact on the flow. Owing to their computational efficiency, VE models tend to be applied at large scales. A macroscopic invasion percolation approach was used to predict the CO2 migration at one site to examine details of CO2 migration under the caprock.

Pressure buildup and brine migration during CO2 storage in multilayered aquifers.

Carbon dioxide injection into deep saline formations may induce large-scale pressure increases and migration of native fluid. Local high-conductivity features, such as improperly abandoned wells or conductive faults, could act as conduits for focused leakage of brine into shallow groundwater resources. Pressurized brine can also be pushed into overlying/underlying formations because of diffuse leakage through low-permeability aquitards, which occur over large areas and may allow for effective pressure bleed-off in the storage reservoirs. This study presents the application of a recently developed analytical solution for pressure buildup and leakage rates in a multilayered aquifer-aquitard system with focused and diffuse brine leakage. The accuracy of this single-phase analytical solution for estimating far-field flow processes is verified by comparison with a numerical simulation study that considers the details of two-phase flow. We then present several example applications for a hypothetical CO2 injection scenario (without consideration of two-phase flow) to demonstrate that the new solution is an efficient tool for analyzing regional pressure buildup in a multilayered system, as well as for gaining insights into the leakage processes of flow through aquitards, leaky wells, and/or leaky faults. This solution may be particularly useful when a large number of calculations needs to be performed, that is, for uncertainty quantification, for parameter estimation, or for the optimization of pressure-management schemes.