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Bacterial biofilms can form in porous media that are of interest in industrial applications ranging from medical implants to biofilters as well as in environmental applications such as in situ groundwater remediation, where they can be critical locations for biogeochemical reactions. The presence of biofilms modifies porous media topology and hydrodynamics by clogging pores and consequently solutes transport and reactions kinetics. The interplay between highly heterogeneous flow fields found in porous media and microbial behavior, including biofilm growth, results in a spatially heterogeneous biofilm distribution in the porous media as well as internal heterogeneity across the thickness of the biofilm. Our study leverages highly resolved three-dimensional X-ray computed microtomography images of bacterial biofilms in a tubular reactor to numerically compute pore-scale fluid flow and solute transport by considering multiple equivalent stochastically generated internal permeability fields for the biofilm. We show that the internal heterogeneous permeability mainly impacts intermediate velocities when compared with homogeneous biofilm permeability. While the equivalent internal permeability fields of the biofilm do not impact fluid-fluid mixing, they significantly control a fast reaction. For biologically driven reactions such as nutrient or contaminant uptake by the biofilm, its internal permeability field controls the efficiency of the process. This study highlights the importance of considering the internal heterogeneity of biofilms to better predict reactivity in industrial and environmental bioclogged porous systems.

Deposition of engineered nanoparticles onto porous media from flowing suspensions is important for soil and groundwater quality. The deposition mechanism is controlled by interaction forces between particles and collectors. We investigated the origin and magnitude of opposing forces between silver and mica surfaces (representing nanosilver and sand grains) in solutions relevant to agricultural soils with direct measurements using a surface force apparatus. Solutions of variable NaNO 3 , Ca(NO 3 ) 2 , and humic acid (HA) concentrations were used to differentiate individual contributing forces and quantify surface properties. The measured Hamaker constant for silver-water-mica was consistent with Lifshitz theory. Our results indicate that HA forms an adsorbed surface layer, but its charge, thicknesses, compressibility, and mass are significantly larger on mica than silver. Ca 2+ primarily reduced the differences between the initially adsorbed HA layer properties on each surface, making them more similar. Force-distance profiles indicate that, when silver-mica systems were exposed to HA, osmotic-steric, electrostatic, and van der Waals forces dominate. Soft particle theory was deemed inappropriate for this system. Derjaguin's approximation was utilized to translate force measurements into interaction energy between nanosilver particles and mica collectors. We propose attachment efficiency estimates from measured surface properties, which suggest high particle mobility when nanosilver is applied to HA-rich agricultural soils with modest ionic strength.

Colloid deposition in granular media is relevant to numerous environmental problems. Classic filtration models assume a homogeneous pore space and largely ignore colloid aggregation. However, substantial evidence exists on the ubiquity of aggregation within porous media, suggesting that deposition is enhanced by it. This work studies the deposition process in relation to aggregate size and structure. We demonstrate that aggregation is induced at typical groundwater velocities by comparing the repulsive DLVO force between particle pairs to the hydrodynamic shear force opposing it. Column experiments imaged with high-resolution X-ray computed tomography are used to measure aggregate structure and describe their morphology probability distribution and spatial distribution. Aggregate volume and surface area are found to be power-law distributed, while Feret diameter is exponentially distributed with some flow rate dependencies caused by erosion and restructuring by the fluid shear. Furthermore, size and shape of aggregates are heterogeneous in depth, where a small number of large aggregates control the concentration versus depth profile shape. The range of aggregate fractal dimensions found (2.22-2.42) implies a high potential for restructuring or breaking during transport. Shear-induced aggregation is not currently considered in macroscopic models for particle filtration, yet is critical to consider in the processes that control deposition.

Hydraulic fracturing is expanding rapidly in the US to meet increasing energy demand and requires high volumes of hydrofracking fluid to displace natural gas from shale. Accidental spills and deliberate land application of hydrofracking fluids, which return to the surface during hydrofracking, are common causes of environmental contamination. Since the chemistry of hydrofracking fluids favors transport of colloids and mineral particles through rock cracks, it may also facilitate transport of in situ colloids and associated pollutants in unsaturated soils. We investigated this by subsequently injecting deionized water and flowback fluid at increasing flow rates into unsaturated sand columns containing colloids. Colloid retention and mobilization was measured in the column effluent and visualized in situ with bright field microscopy. While <5% of initial colloids were released by flushing with deionized water, 32-36% were released by flushing with flowback fluid in two distinct breakthrough peaks. These peaks resulted from 1) surface tension reduction and steric repulsion and 2) slow kinetic disaggregation of colloid flocs. Increasing the flow rate of the flowback fluid mobilized an additional 36% of colloids, due to the expansion of water filled pore space. This study suggests that hydrofracking fluid may also indirectly contaminate groundwater by remobilizing existing colloidal pollutants.

The prediction of colloid transport in unsaturated porous media in the presence of large energy barrier is hampered by scant information of the proportional retention by straining and attractive interactions at surface energy minima. This study aims to fill this gap by performing saturated and unsaturated column experiments in which colloid pulses were added at various ionic strengths (ISs) from 0.1 to 50 mM. Subsequent flushing with deionized water released colloids held at the secondary minimum. Next, destruction of the column freed colloids held by straining. Colloids not recovered at the end of the experiment were quantified as retained at the primary minimum. Results showed that net colloid retention increased with IS and was independent of saturation degree under identical IS and Darcian velocity. Attachment rates were greater in unsaturated columns, despite an over 3-fold increase in pore water velocity relative to saturated columns, because additional retention at the readily available air-associated interfaces (e.g., the air-water-solid [AWS] interfaces) is highly efficient. Complementary visual data showed heavy retention at the AWS interfaces. Retention by secondary minima ranged between 8% and 46% as IS increased, and was greater for saturated conditions. Straining accounted for an average of 57% of the retained colloids with insignificant differences among the treatments. Finally, retention by primary minima ranged between 14% and 35% with increasing IS, and was greater for unsaturated conditions due to capillary pinning.

Naturally occurring polymers such as organic matter have been known to inhibit aggregation and promote mobility of suspensions in soil environments by imparting steric stability. This increase in mobility can significantly reduce the water filtering capacity of soils, thus jeopardizing a primary function of the vadose zone. Improvements to classic filtration theory have been made to account for the known decrease in attachment efficiency of electrostatically stabilized particles, and more recently, of sterically stabilized particles traveling through simple and saturated porous media. In the absence of an established unsaturated transport expression, and in the absence of applicable theoretical approaches for suspensions with asymmetric and nonindifferent electrolytes, this study presents an empirical correlation to predict attachment efficiency (α) for electrosterically stabilized suspensions in unsaturated systems in the presence of nonideal electrolytes. We show that existing models fall short in estimating polymer-coated colloid deposition in unsaturated media. This deficiency is expected given that the models were developed for saturated conditions where the mechanisms controlling colloid deposition are significantly different. A new correlation is derived from unsaturated transport data and direct characterization of microspheres coated with natural organic matter over a range of pH and CaCl(2) concentrations. The improvements to existing transport models include the following: adjustment for a restricted liquid-phase in the medium, development of a quantitative term to account for unsaturated transport phenomena, and adjustments in the relative contribution of steric stability parameters based on direct measurements of the adsorbed polymer layer characteristics. Differences in model formulation for correlations designed for saturated systems and the newly proposed correlation for unsaturated systems are discussed, and the performance of the new model against a comprehensive set of experimental observations is evaluated.

Colloids play an important role in facilitating transport of adsorbed contaminants in soils. Recent studies showed that under saturated conditions colloid retention was a function of its concentration. It is unknown if this is the case under unsaturated conditions. In this study, the effect of colloid concentration on colloid retention was investigated in unsaturated columns by increasing concentrations of colloid influents with varying ionic strength. Colloid retention was observed in situ by bright field microscopy and quantified by measuring colloid breakthrough curves. In our unsaturated experiments, greater input concentrations resulted in increased colloid retention at ionic strength above 0.1 mM, but not in deionized water (i.e., 0 mM ionic strength). Bright field microscope images showed that colloid retention mainly occurred at the solid-water interface and wedge-shaped air-water-solid interfaces, whereas the retention at the grain-grain contacts was minor. Some colloids at the air-water-solid interfaces were rotating and oscillating and thus trapped. Computational hydrodynamic simulation confirmed that the wedge-shaped air-water-solid interface could form a "hydrodynamic trap" by retaining colloids in its low velocity vortices. Direct visualization also revealed that colloids once retained acted as new retention sites for other suspended colloids at ionic strength greater than 0.1 mM and thereby could explain the greater retention with increased input concentrations. Derjaguin-Landau-Verwey-Overbeek (DLVO) energy calculations support this concept. Finally, the results of unsaturated experiments were in agreement with limited saturated experiments under otherwise the same conditions.