Nano zero-valent iron (nZVI) has been used for in situ groundwater remediation due to its strong adsorption and reaction characteristics. However, oxyanion contaminants in groundwater can ready adsorbed onto the surface of nZVI. This can potentially alter the mobility of nZVI and create a secondary pollution source, but these issues have not yet been systematically investigated. In this study, polyaniline-supported nZVI (PnZVI) and phosphate-sorbed PnZVI (PS-PnZVI) were synthesized in the laboratory. The sedimentation and transport behavior of these two nZVI particles were investigated, compared, and mathematically modeled to better understand the impact of phosphate adsorption on these processes. Results showed that phosphate adsorption can enhance the stability and mobility of PnZVI. Interaction energy calculations that considered van der Waals and magnetic attraction, electrostatic double layer and Born repulsion, and the influence of nanoscale roughness and binary charge heterogeneity were conducted to better infer mechanisms causing nZVI particle sedimentation and retention. Nanoscale roughness and binary charge heterogeneity were found to significantly decrease the energy barrier, but not to low enough levels to explain the observed behavior. The rapid settling of PnZVI was attributed to strong magnetic attraction between particles, which produced rapid aggregation and retention due to straining and/or hydrodynamic bridging. Phosphate adsorption enhanced the mobility of PS-PnZVI in comparison with PnZVI due to a decrease in particle size and aggregation, and an increase in the energy barrier with the porous media. A potential risk of nZVI particles to facilitate oxyanion contaminant transport was demonstrated for phosphate.

The permeability of shale is a significant and important design parameter for shale gas extraction. The shale gas permeability is usually obtained based on Darcy flow using standard laboratory permeability tests done on core samples, that do not account for different transport mechanisms at high pressures and anisotropic effects in shales due to nano-scale pore structure. In this study, the permeability of shale is predicted using a pore network model. The characteristics of pore structure can be described by specific parameters, including porosity, pore body and pore throat sizes and distributions and coordination numbers. The anisotropy was incorporated into the model using a coordination number ratio, and an algorithm that was developed for connections of pores in the shale formation. By predicting hydraulic connectivity and comparing it with several high-pressure permeability tests, the proposed three-dimensional pore network model was verified. Results show that the prediction from the anisotropic pore network model is closer to the test results than that based on the isotropic pore network model. The predicted permeability values from numerical simulation using anisotropic pore network model for four shales from Qaidam Basin, China are quite similar to those measured from laboratory tests. This study confirmed that the developed anisotropic three-dimensional pore network model could reasonably represent the natural gas flow in the actual shale formation so that it can be used as a prediction tool.

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Colloid transport and retention in porous media is a common phenomenon in both nature and industry. However, many questions remain on how to obtain colloid transport and retention parameters. Previous work usually assumed constant transport parameters in a medium under a given physicochemical condition. In this study, pore‐network modeling is employed to upscale colloid transport and retention from the pore‐scale to the macro‐scale. The pore‐scale transport parameters including the collection efficiency (η), the sticking efficiency (α), and the fraction of the solid‐water interface that contributes to the colloid attachment (Sf) are obtained using numerical simulation and probability analysis for each pore throat. The influence of roughness and charge heterogeneity on the distribution of pore‐scale parameters is discussed. Breakthrough curves and the retention profiles under different roughness and charge heterogeneity conditions are also analyzed. Results show that pore‐scale parameters η, α, and Sf have various distributions in porous media that may not be accurately described using single‐valued effective parameters. The value of η decreases with velocity and exhibits a wide distribution under low‐velocity conditions. The parameter α tends to decrease with the colloid size and the pore water velocity and increased with the charge heterogeneity fraction. Nanoscale roughness alters α in a non‐monotonic fashion but tends to increase for lower roughness fractions and zeta potential. Microscopic roughness increases values of α for colloids that would otherwise be susceptible to hydrodynamic removal. Breakthrough curves and retention profiles show that more retention occurs for smaller particles, which reflects the influence of blocking.