Direct Measurements of the Forces between Silver and Mica in Humic Substance-Rich Solutions.

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 NaNO3, Ca(NO3)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. Ca2+ 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.

Morphology of Shear-Induced Colloidal Aggregates in Porous Media: Consequences for Transport, Deposition, and Re-entrainment.

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.

Relating mechanistic fate with spatial positioning for colloid transport in surface heterogeneous porous media.

HYPOTHESES: The transport behavior of colloids in subsurface porous media is altered by surface chemical and physical heterogeneities. Understanding the mechanisms involved and distribution outcomes is crucial to assess and control groundwater contamination. The multi-scale processes that broaden residence time distribution for particles in the medium are here succinctly described with an upscaling model. Experiments/model: The spatial distribution of silver particles along glass bead-packed columns obtained from X-ray micro-computed tomography and a mechanistic upscaling model were used to study colloid retention across interface-, collector-, pore-, and Darcy-scales. Simulated energy profiles considering variable colloid-grain interactions were used to determine collector efficiencies from particle trajectories via full force-torque balance. Rate coefficients were determined from collector efficiencies to parameterize the advective-dispersive-reactive model that reports breakthrough curves and depth profiles. FINDINGS: Our results indicate that: (i) with surface heterogeneity, individual colloid-grain interactions are non-unique and span from repulsive to attractive extremes; (ii) experimentally observed spatial positioning of retention at grain-water interfaces and grain-to-grain contacts is governed respectively by mechanistic attachment to the grain surface and retention without contact at rear-flow stagnation zones, and (iii) experimentally observed non-monotonic retention profiles and heavy-tailed breakthrough curves can be modeled with explicit implementation of heterogeneity at smaller scales.