Dispersion stability and electrokinetic properties of intrinsic plutonium colloids: implications for subsurface transport.

Subsurface transport of plutonium (Pu) may be facilitated by the formation of intrinsic Pu colloids. While this colloid-facilitated transport is largely governed by the electrokinetic properties and dispersion stability (resistance to aggregation) of the colloids, reported experimental data is scarce. Here, we quantify the dependence of ζ-potential of intrinsic Pu(IV) colloids on pH and their aggregation rate on ionic strength. Results indicate an isoelectric point of pH 8.6 and a critical coagulation concentration of 0.1 M of 1:1 electrolyte at pH 11.4. The ζ-potential/pH dependence of the Pu(IV) colloids is similar to that of goethite and hematite colloids. Colloid interaction energy calculations using these values reveal an effective Hamaker constant of the intrinsic Pu(IV) colloids in water of 1.85 × 10(-19) J, corresponding to a relative permittivity of 6.21 and refractive index of 2.33, in agreement with first principles calculations. This relatively high Hamaker constant combined with the positive charge of Pu(IV) colloids under typical groundwater aquifer conditions led to two contradicting hypotheses: (a) the Pu(IV) colloids will exhibit significant aggregation and deposition, leading to a negligible subsurface transport or (b) the Pu(IV) colloids will associate with the relatively stable native groundwater colloids, leading to a considerable subsurface transport. Packed column transport experiments supported the second hypothesis.

Mobilization of colloidal particles by low-frequency dynamic stress stimulation.

Naturally occurring seismic events and artificially generated low-frequency (1 to 500 Hz) elastic waves have been observed to alter the production rates of oil and water wells, sometimes increasing and sometimes decreasing production, and to influence the turbidity of surface and well water. The decreases in production are of particular concern, especially when artificially generated elastic waves are applied as a method for enhanced oil recovery. The exact conditions that result in a decrease in production remain unknown. Although the underlying environment is certainly complex, the observed increase in water well turbidity after natural seismic events suggests the existence of a mechanism that can affect both the subsurface flow paths and the mobilization of in situ colloidal particles. This article explores the macroscopic and microscopic effects of low-frequency dynamic stress stimulations on the release of colloidal particles from an analog core representing an infinitesimal section along the propagation paths of an elastic wave. Experiments on a column packed with 1 mm borosilicate beads and loaded with polystyrene microparticles demonstrate that axial mechanical stress oscillations enhance the mobilization of captured microparticles. Increasing the amplitude of the oscillations increases the number of microparticles released and can also result in cyclical spikes in effluent microparticle concentration during stimulation. Under a prolonged period of stimulation, the cyclical effluent spikes coincided with fluctuations in the column pressure data and continued at a diminished level after stimulation. This behavior can be attributed to rearrangements of the beads in the column, resulting in possible changes in the void space and/or tortuosity of the packing. Optical microscopy observations of the beads during low-frequency oscillations reveal that individual beads rotate, thereby rubbing against each other and scraping away portions of the adsorbed microparticles. These results support the theory that mechanical interactions between porous matrix grains are important mechanisms in flow path alteration and the mobilization of naturally occurring colloidal particles during elastic wave stimulation. These results also point to both continuous and discrete en masse releases of colloidal particles, perhaps because of circulation cells within the packing material.

The structure and dynamics of microparticles at pickering emulsion interfaces.

We have employed a laser scanning confocal microscope (LSCM) to study the structure and dynamics of microparticles at Pickering emulsion interfaces. The microparticles can have rich morphology at the emulsion interfaces, ranging from an aggregated structure to colloidal lattices, with a possibility of involving heterogeneous particles. With a specific interest in colloidal lattices, we find that although the enhanced electrostatic repulsion explains the formation of colloidal lattices by sulfate-treated polystyrene (S-PS) particles, it fails to interpret the unsuccessfulness of assembling lattices containing single-species carboxylate-treated polystyrene (C-PS) particles. A small percentage of C-PS particles in the colloidal mixture does not disturb the formation of lattices made of S-PS particles. The LSCM also provides a meaningful way to probe dynamic information. The diffusion of single particles at the emulsion interfaces depends strongly on the oil phase viscosity, particle size, and particle wettability. A highly curved emulsion interface slows the motion of microparticles at oil-water interfaces but the interface curvature effect decreases with increasing oil phase viscosity. Although the confocal microscope was originally used as an imaging tool, we find that the thermodynamic equilibrium of colloidal lattices can be disturbed and even destroyed when increasing the output laser intensity.

Dynamics and collapse of two-dimensional colloidal lattices.

One interesting aspect of colloidal particles is the formation of colloidal crystals at the 2D and 3D levels. Here we report the dynamics and collapse of colloidal lattices at liquid-liquid interfaces using Pickering emulsions as an experimental template. The colloidal particles oscillate around their equilibrium positions. The short-time diffusion constant (<10 s) of single particles increases with increasing lattice spacing; the oil-phase viscosity has an effect on diffusion only at large interparticle distances. Strikingly, we observe that the equilibrium structure can be disturbed when increasing the output laser intensity in a confocal laser scanning microscope, which leads to the collapse of colloidal lattices in the presence of small laser powers.

Dynamics of charged microparticles at oil-water interfaces.

Solid-stabilized emulsions have been used as a model system to investigate the dynamics of charged microparticles with diameters of 1.1 microm at oil-water interfaces. Using confocal microscopy, we investigated the influences of interfacial curvature, cluster size, and temperature on the diffusion of solid particles. Our work suggests that a highly curved emulsion interface slows the motion of solid particles. This qualitatively supports the theoretical work by Danov et al. (Danov, K. D.; Dimova, R.; Pouligny, B. Phys. Fluids 2000, 12, 2711); however, the interfacial curvature effect decreases with increasing oil-phase viscosity. The diffusion of multiparticle clusters at oil-water interfaces is a strong function of cluster size and oil-phase viscosity and can be quantitatively related to fractal dimension. Finally, we report the influence of temperature and quantify the diffusion activation energy and friction factor of the particles at the investigated oil-water interfaces.

Mobility and in situ aggregation of charged microparticles at oil-water interfaces.

Particle mobility, aggregate structure, and the mechanism of aggregate growth at the two-dimensional level have been of long-standing interest. Here, we use solid-stabilized emulsions as a model system to investigate the mobility of charged microparticles at poly(dimethylsiloxane) (oil)-water interfaces using confocal laser scanning microscopy. Remarkably, the rate of diffusion of the charged colloidal-sized polystyrene particles at the oil-water interface is only moderately slower than that in the bulk water phase. The ambient diffusion constant of solid particles is significantly reduced from 1.1 x 10(-9) cm2/s to 2.1 x 10(-11) cm2/s when the viscosity of the oil phase increases from 5 cSt to 350 cSt. In addition, we successfully observe the in situ structural formation of solid particles at the oil-water interface.

Structure of microparticles in solid-stabilized emulsions.

Emulsions of oil and water stabilized by adsorbed solid particles are known as solid-stabilized emulsions (often referred to as Pickering emulsions). Using confocal microscopy, we have studied the assembly of colloidal-sized polystyrene particles in poly(dimethylsiloxane)-in-water solid-stabilized emulsions. Monodisperse polystyrene particles, when included in the emulsions at low concentrations, were found to form small patches with local "hexagonal" order, separated by other particle-free domains. Polystyrene particles with different sizes (1 and 4 microm) and different wettability could simultaneously segregate to the emulsion interface; even mixtures of hydrophobic and hydrophilic solid particles were found to simultaneously segregate to the same interface.