Colloid Transport Research Articles

Diffusiophoretic Transport of Charged Colloids in Ionic Surfactant Gradients Entirely below versus Entirely above the Critical Micelle Concentration.

When placed in an ionic surfactant gradient, charged colloids will undergo diffusiophoresis at a velocity, uDP = MDP∇ ln S, where MDP is the diffusiophoretic mobility and S is the surfactant concentration. The diffusiophoretic mobility depends in part on the charges and diffusivities of the surfactants and their counterions. Since micellization decreases surfactant diffusivity and alters charge distributions in a surfactant solution, MDP of charged colloids in ionic surfactant gradients may differ significantly when surfactant concentrations are above or below the critical micelle concentration (CMC). The role of micelles in driving diffusiophoresis is unclear, and a previously published model that accounts for micellization suggests the possibility of a change in the sign of MDP above the CMC [Warren, P. B.; . Soft Matter 2019, 15, 278-288]. In the current study, microfluidic channels were used to measure the transport of negatively charged polystyrene colloids in sodium dodecyl sulfate (SDS) surfactant gradients established at SDS concentrations that are either fully above or fully below the CMC. Interpretation of diffusiophoresis was aided by measurements of the colloid electrophoretic mobility as a function of SDS concentration. A numerical transport model incorporating the prior diffusiophoretic mobility model for ionic surfactant gradients was implemented to elucidate signatures of positive and negative diffusiophoretic mobilities and compare with experiments. The theoretically predicted sign of the diffusiophoretic mobility below the CMC was determined to be particularly sensitive to uncertainty in colloid and surfactant properties, while above the CMC, the mobility was consistently predicted to be positive in the SDS concentration range considered in the experiments conducted here. In contrast, experiments only showed signatures of a negative diffusiophoretic mobility for these negatively charged colloids with no change of sign. Colloid diffusiophoretic transport measured in micellar solutions was more extensive than that below the CMC with the same ∇ ln S.

The formation of multi-metal(loid)s contaminated groundwater at smelting site: Critical role of natural colloids

The occurrence and migration of colloids at smelting sites are crucial for the formation of multi-metal(loid)s pollution in groundwater. In this study, the behavior of natural colloids (1 nm-0.45 µm) at an abandoned smelting site was investigated by analyzing groundwater samples filtered through progressively decreasing pore sizes. Smelting activities in this site had negatively impacted the groundwater quality, leading to elevated concentrations of zinc (Zn), lead (Pb), arsenic (As), and cadmium (Cd). The results showed that heavy metal(loid)-bearing colloids were ubiquitous in the groundwater with the larger colloidal fractions (∼75 −450 nm) containing higher abundances of pollutants. It was also observed that the predominant colloids consisted of Zn-Al layered double hydroxide (LDH), sphalerite, kaolinite, and hematite. By employing multiple analytical techniques, including leaching experiments, soil colloid characterization, and Pb stable isotope measurements, the origin of groundwater colloids was successfully traced to the topsoil colloids. Most notably, our findings highlighted the increased risk of heavy metal(loid)s migration from polluted soils into adjacent sites through the groundwater because of colloid-mediated transport of contaminants. This field-scale investigation provides valuable insights into the geochemical processes governing heavy metal(loid) behavior as well as offering pollution remediation strategies specifically tailored for contaminated groundwater.

Out-of-equilibrium interactions and collective locomotion of colloidal spheres with squirming of nematoelastic multipoles

Many living and artificial systems show similar emergent behavior and collective motions on different scales, starting from swarms of bacteria to synthetic active particles, herds of mammals, and crowds of people. What all these systems often have in common is that new collective properties like flocking emerge from interactions between individual self-propelled or driven units. Such systems are naturally out-of-equilibrium and propel at the expense of consumed energy. Mimicking nature by making self-propelled or externally driven particles and studying their individual and collective motility may allow for deeper understanding of physical underpinnings behind collective motion of large groups of interacting objects or beings. Here, using a soft matter system of colloids immersed into a liquid crystal, we show that resulting so-called nematoelastic multipoles can be set into a bidirectional locomotion by external oscillating electric fields. Out-of-equilibrium elastic interactions between such colloidal objects lead to collective flock-like behaviors emerging from time-varying elasticity-mediated interactions between externally driven propelling particles. Repulsive elastic interactions in the equilibrium state can be turned into attractive interactions in the out-of-equilibrium state under applied external electric fields. We probe this behavior at different number densities of colloidal particles and show that particles in dense dispersions collectively select the same direction of a coherent motion due to elastic interactions between near neighbors. In our experimentally implemented design, their motion is highly ordered and without clustering or jamming often present in other colloidal transport systems, which is promising for technological and fundamental-science applications, like nano-cargo transport, out-of-equilibrium assembly, and microrobotics.

Dual roles of goethite coating on the transport of plastic nanoparticles in heterogeneous porous media: The significance of collector surface roughness

This study systematically examines the roles of positive goethite on the retention and release of negative plastic nanoparticles (PSNPs) with different surface functional groups (Blank, -COOH, and -NH2). It provides the first evidence for the dual roles of goethite coatings on colloid transport; e.g., increased transport caused by surface morphology modification or decreased transport due to increased surface roughness and charge heterogeneity. Although previous work has shown that goethite-coated sand increases the retention of negative colloids, this work demonstrates that collector surface roughness can also reduce the retention of PSNPs due to increased interaction energy profiles. Nonmonotonic retention of all the different functionalized PSNPs was observed in goethite-coated rough sand, and the magnitude of variations was contingent on the PSNP functionalization, the solution ionic strength (IS), and the goethite coating. The release of PSNPs with IS decrease (phase I) and pH increase (phase II) varied significantly due to differences in energy barriers to detachment, e.g., release in phase I was inhibited in both goethite-coated sands, whereas release in phase II was enhanced in coated smooth sand but completely inhibited in rough sand. The findings of this study provide innovative insight into transport mechanisms for colloidal and colloid-associated contaminants.

A Critical Look at Colloid Generation, Stability, and Transport in Redox-Dynamic Environments: Challenges and Perspectives.

Colloid generation, stability, and transport are important processes that can significantly influence the fate and transport of nutrients and contaminants in environmental systems. Here, we critically review the existing literature on colloids in redox-dynamic environments and summarize the current state of knowledge regarding the mechanisms of colloid generation and the chemical controls over colloidal behavior in such environments. We also identify critical gaps, such as the lack of universally accepted cross-discipline definition and modeling infrastructure that hamper an in-depth understanding of colloid generation, behavior, and transport potential. We propose to go beyond a size-based operational definition of colloids and consider the functional differences between colloids and dissolved species. We argue that to predict colloidal transport in redox-dynamic environments, more empirical data are needed to parametrize and validate models. We propose that colloids are critical components of element budgets in redox-dynamic systems and must urgently be considered in field as well as lab experiments and reactive transport models. We intend to bring further clarity and openness in reporting colloidal measurements and fate to improve consistency. Additionally, we suggest a methodological toolbox for examining impacts of redox dynamics on colloids in field and lab experiments.

A screening model for predicting the potential of soil colloids-enhanced leaching of hydrophobic organic contaminants to groundwater at contaminated sites

Modeling the fate and transport of organic pollutants at contaminated sites is critical for risk assessment and management practices, such as establishing realistic cleanup standards or remediation endpoints. Against the conventional wisdom that highly hydrophobic persistent organic pollutants (POPs) (e.g., polybrominated diphenyl ethers and polycyclic aromatic hydrocarbons) in surface soils are essentially immobile, mounting evidence has demonstrated the potential of these contaminants leaching into the groundwater, due to enhanced transport by soil colloids. Here, we develop a Colloids-Enhanced Transport (CET) model, which can be used as a simple screening tool to predict the leaching potential of POPs into groundwater, as mediated by soil colloids. The CET model incorporates several processes, including the release of POPs-bearing colloids into the porewater, the vertical transport of colloids and associated POPs in the vadose zone, the mixing of POPs-containing soil leachate with groundwater, and the migration of POPs-bearing colloids in saturated zone. Thus, using parameters that can be easily obtained (e.g., annual rainfall, soil type, and common hydrogeological properties of the subsurface porous media), the CET model can estimate the concentrations of POPs in the saturated zone from the observed POPs concentrations in surface or shallow subsurface zones. The CET model can also be used to derive soil quality standards or cleanup endpoints by back-calculating soil concentrations based on groundwater protection limits.

4D microvelocimetry reveals multiphase flow field perturbations in porous media

Many environmental and industrial processes depend on how fluids displace each other in porous materials. However, the flow dynamics that govern this process are still poorly understood, hampered by the lack of methods to measure flows in optically opaque, microscopic geometries. We introduce a 4D microvelocimetry method based on high-resolution X-ray computed tomography with fast imaging rates (up to 4 Hz). We use this to measure flow fields during unsteady-state drainage, injecting a viscous fluid into rock and filter samples. This provides experimental insight into the nonequilibrium energy dynamics of this process. We show that fluid displacements convert surface energy into kinetic energy. The latter corresponds to velocity perturbations in the pore-scale flow field behind the invading fluid front, reaching local velocities more than 40 times faster than the constant pump rate. The characteristic length scale of these perturbations exceeds the characteristic pore size by more than an order of magnitude. These flow field observations suggest that nonlocal dynamic effects may be long-ranged even at low capillary numbers, impacting the local viscous-capillary force balance and the representative elementary volume. Furthermore, the velocity perturbations can enhance unsaturated dispersive mixing and colloid transport and yet, are not accounted for in current models. Overall, this work shows that 4D X-ray velocimetry opens the way to solve long-standing fundamental questions regarding flow and transport in porous materials, underlying models of, e.g., groundwater pollution remediation and subsurface storage of CO2 and hydrogen.

Mechanisms of Pore-Clogging Using a High-Resolution CFD-DEM Colloid Transport Model

Colloidal transport and clogging in porous media is a phenomenon of critical importance in many branches of applied sciences and engineering. It involves multiple types of interactions that span from the sub-colloid scale (electrochemical interactions) up to the pore-scale (bridging), thus challenging the development of representative modelling. So far published simulation results of colloidal or particulate transport are based on either reduced set of forces or spatial dimensions. Here we present an approach enabling to overcome both computational and physical limitations posed by a problem of 3D colloidal transport in porous media. An adaptive octree mesh is introduced to a coupled CFD and DEM method while enabling tracking of individual colloids. Flow fields are calculated at a coarser scale throughout the domain, and at fine-scale around colloids. The approach accounts for all major interactions in such a system: elastic, electrostatic, and hydrodynamic forces acting between colloids, as well as colloids and the collector surface. The method is demonstrated for a single throat model made of four spherical segments, and the impact of clogging is reported in terms of the evolution of the critical path diameter for percolation and permeability. We identified four stages of clogging development depending on position and time of individual colloid entrapment, which in turn correlates to a cluster evolution and local transport.

Visualization of phenanthrene effect on biochar colloids transport in porous media

Biochar colloids (BCs) can be used as adsorbent materials for remediation of phenanthrene due to their high specific surface area and other characteristics. Understanding the effects of phenanthrene on the transport of BCs contributes to facilitate the removal of phenanthrene in soil and water habitats. In this work, the influence of phenanthrene on the transport of BCs under different environmental factors (pH, ionic strength (IS), media size) in a one-dimensional sand column was firstly explored together with a real-time visualization system to explore the transport mechanism of BCs in two-dimensional sand tank. The results show that phenanthrene adsorbed on the surface of BCs, shielded its surface charge and reduced the mobility of BCs in porous media. Acidic conditions promoted the agglomeration of BCs and adsorption of phenanthrene, resulting in a 51.03 % decrease in the maximum breakthrough rate of BCs compared to alkaline conditions. The same was true for the high IS condition, where the maximum breakthrough rate of BCs was only 0.95 % at IS = 50. Additionally, there was a substantial and positive correlation between media particle size and BCs mobility. As the quartz sand particle size increased, the maximum breakthrough rates of BCs were 2.67 %, 33.28 %, and 52.27 % in the 1-D experiment, and 0, 13.88 %, and 13.10 % in the 2-D experiment, respectively. The contact area of BCs with the medium expands under the fine particle size condition, leading to a significant decrease in the mobility of BCs at low potentials influenced by phenanthrene. This finding is significant for biochar application in phenanthrene contaminated soil and groundwater remediation.

Colloids facilitate transport of cadmium and uranium in arable soils, which is undetected by suction cups in the field

AbstractColloids can facilitate the transport of trace elements in soil, but earlier studies fell short either because of sampling artefacts or because no contrasting soils were used; both factors hamper a better understanding of where this occurs. Here, leaching in undisturbed and unsaturated soil columns was observed to identify colloidal transport of cadmium (Cd) and uranium (U) in soils with contrasting properties. Crucially, it was examined how such column data relate to more traditional in situ data obtained with porous suction cups. Soils were collected from three agricultural fields in Switzerland (soil pH 5.1–7.3), leached during 36 days (0.6 pore volumes, ~1.6 mm day−1), and elements trapped in the PTFE suction plates were recovered and were ascribed to colloids. Of the total mobile mass (sum percolate and plate), 18%–53% (Cd) or 8–89% (U) was retained by plates, the range depending on the field where soil was sampled and that fraction depends on soil pH and for U also on dissolved inorganic carbon. The total mobile Cd or U mass divided by the percolated volume indicates the metal concentration in the average leachate and was logically highest for Cd in the most acidic soil and for U in the most alkaline soil. The concentrations of Cd and U in these column leachates were >10‐fold higher than corresponding concentrations in the suction cups in the field for those soils and elements where colloids dominated leaching. In contrast, they were within a factor of two where colloids are <20% of the mobile mass. Flow Field‐Flow Fractionation (FlFFF) analyses showed an association of colloidal U with oxyhydroxides, clays and organic matter and, for colloidal Cd, an association with organic matter. These data show that suction cups or filtered percolates can underestimate the leaching of Cd and U by up to an order of magnitude.

Effect of coupled physical and chemical heterogeneity on the transport of pristine and aged pyrogenic carbon colloids in unsaturated porous media

Due to extensive application and recurrent wildfires, an increasing number of pyrogenic carbon (PyC) colloids are present in the environment, experiencing processes of environmental aging. Subsurface environments are typically heterogeneous in unsaturated conditions, which may affect the transport of PyC colloids. This study focused on the transport of both pristine and aged PyC colloids in physically (clean coarse and fine sand) and physicochemically (iron oxides-coated coarse and clean fine sand) heterogeneous porous media at three different water saturations (100 %, 70 %, and 40 %). In physically heterogeneous porous media, the decrease in water saturation from 100 % to 40 % led to a shift in the main water flow from the clean coarse sand to the clean fine sand domain, resulting in a continuous decrease in the transport of PyC colloids. In physicochemically heterogeneous porous media, the primary water flow shifted from the iron oxides-coated coarse sand to the clean fine sand domain, resulting in an initial increase and subsequent decrease in PyC colloid transport. Aging enhanced the transport of PyC colloids, attributed to the increasingly negative and hydrophilic surface. Retention profiles revealed substantial PyC colloid retention at the interface between coarse and fine sand domains. The release of retained PyC colloids exhibited two peaks at 100 % and 70 % water saturations, along with a single peak at 40 % water saturation. Additionally, the increased irreversible retention was observed at lower water saturation. This study underscores the significance of water content, environmental aging, and heterogeneity in PyC colloid transport. It provides essential insights into the environmental fate of PyC colloids in natural field conditions.

Competition between drift and topological transport of colloidal particles in twisted magnetic patterns

We simulate the motion of paramagnetic particles between two magnetic patterns with hexagonal symmetry that are twisted at a magic angle. The resulting Morié pattern develops flat channels in the magnetic potential along which colloidal particles can be transported via a drift force of magnitude larger than a critical value. Colloidal transport is also possible via modulation loops of a uniform external field with time varying orientation, in which case the transport is topologically protected. Drift and topological transport compete or cooperate giving rise to several transport modes. Cooperation makes it possible to move particles at drift forces weaker than the critical force. At supercritical drift forces the competition between the transport modes results e.g. in an increase of the average speed of the particles in integer steps and in the occurrence of subharmonic responses. We characterize the system with a dynamical phase diagram of the average particle speed as a function of the direction of the topological transport and the magnitude of the drift force.

Insight into the effects of low-molecular-weight aromatic acids on biochar colloid-assisted transport of Cd2+ through saturated porous media

Biochar colloids are likely to control the environmental fate of heavy metals because of the widespread application of this carbon-based material in environmental remediation. Low-molecular-weight aromatic acids (LWMAAs), a class of common organic substances in the environment, are critical in affecting biochar colloid-mediated transport of heavy metals in aquifer media. Nevertheless, thus far, little is known about the effects of LWMAAs on their co-mobility behaviors. Herein, the influences of two aromatic acids, including cinnamic acid and caffeic acid, on the biochar colloid-assisted mobility of Cd2+ in quartz sand were examined. Generally, LMWAAs promoted biochar colloid mobility because of the enhanced electrostatic repulsion, competitive retention between LMWAAs and colloids, and steric hindrance. More importantly, biochar colloids could act as carriers for contaminants to considerably facilitate Cd2+ transport, mainly due to the strong binding affinities of colloids toward Cd2+ and the high mobility of colloids. Intriguingly, although the presence of LMWAAs inhibited Cd2+ adsorption onto biochar colloids, the two aromatic acids enhanced the contaminant-mobilizing transport capacity of colloids, owing to the increased colloid mobility and the formation of stable Cd-LMWAA complexes. Furthermore, the promotion effects of caffeic acid on colloid mobility or colloid-mediated transport of Cd2+ were greater than those of cinnamic acid. This pattern was related to the different chemical properties (e.g., molecular size and/or hydrophobicity) of the two LMWAAs. The observations of this paper provide useful information for understating the effects of coexisting LMWAAs on the co-mobility behaviors of carbonaceous materials and heavy metals in the groundwater environment.

Colloid Transport and Retention in Constricted Tube Pore Spaces With Diverse Geometries and Orientations

AbstractColloidal contaminants infiltrate and can be attached onto grain surfaces of soils and aquifers, where they may persist. In this study, Lagrangian particle tracking is used to investigate particle trajectories and attachment in pore and fracture spaces modeled as three‐dimensional constricted tubes with diverse geometries and orientations relative to gravity. A comprehensive force balance arising from hydrodynamic drag and lift, gravitational settling, Brownian motion, and attractive DLVO interactions is simulated. Results show that the collection efficiency η is primarily governed by the dimensionless settling number 𝑆, representing the relative dominance of gravitational over hydrodynamic forces experienced by the particles. High‐𝑆 scenarios have larger η and are more sensitive to pore orientation, while low‐𝑆 scenarios are more sensitive to pore geometry. For all scenarios but especially low‐S scenarios, the majority of colloid attachment occurs near pore extremities, where fluid velocities are low, such that mechanical remobilization of particles attached is improbable. In low‐𝑆 scenarios, particles may spread and become immobilized at greater distances from the contamination source owing to lower η, are harder to mechanically remobilize as they attach more disproportionately at pore extremities, and have trajectories more sensitive to minor forces, rendering their environmental fates complex. Characterizing the collection efficiency and deposition morphology for various pore space geometries and orientations is crucial in understanding particle fate and developing continuum‐scale models of colloid transport in real soils, where pore spaces are heterogeneous and advection paths are tortuous.

Delineating the role of surface grafting density of organic coatings on the colloidal stability, transport, and sorbent behavior of engineered nanoparticles

Aqueous stability and sorption affinity (towards target environmental contaminants) of engineered nanoparticles, composed of inorganic nanoparticles and surface stabilizers, are dependent on surface grafting density.

Co-transport of ferrihydrite–organic matter colloids with Sb(v) in saturated porous media: implications for antimony mobility

Schematic diagram of the mechanism of Fe–NOM–Sb(v) colloids formation and transport in the natural environment.

Unveiling colloidal transport and deposition: Exploring pore network and random forest models for insights

The transport and deposition of colloids in porous media are common phenomena in nature and industry. In this study, a pore network model (PNM) was used to model the geometry, flow field, and colloidal mass transfer of porous media. The finite element method (FEM) was utilized to establish a database of the contact efficiency ηt of the pore-scale collectors, and a random forest model (RFM) was trained. Reasonable prediction of ηt shows that the developed RFM greatly improves the computational efficiency and frees users from repeated numerical simulations. The effects of the colloidal size and seepage velocity on colloidal transport and the surface deposition behavior were studied, the ηt distribution in the PNM was determined, and breakthrough and retention curves were calculated. The results show that the ηt distribution width and mean value increase with the increase in the colloidal particle size and decrease with the increase in the seepage velocity in the range of colloidal particle sizes and seepage velocities considered in this paper. The peak concentration of the breakthrough curve decreases with increasing colloidal particle size and increases with increasing seepage velocity. Surface deposition produces exponential or uniformly shaped retention curves, with retention concentrations increasing with increasing colloidal particle size and decreasing with increasing seepage velocity. The evolution analysis of the retention curve revealed notable detachment and reattachment effects of the colloids in porous media. The results of this study have potential applications in various fields such as environmental remediation, groundwater management, and filtration technology optimization.

Cotransport of fullerene nanoparticles and montmorillonite colloids in porous media: Critical role of divalent cations of montmorillonite

While the cotransport of carbon nanoparticles (CNPs) and clay colloids in porous media has been widely studied, the influence of the cation exchange capacity (CEC) of clay colloids on the transport process remains unclear. In this study, batch adsorption and column transport experiments were conducted to investigate the fate and transport of CNPs and clay colloids in quartz sand, with respect to the effect of monovalent-cation exchange capacity (mono-CEC), divalent-cation exchange capacity (di-CEC) and total CEC of clays. Fullerene nanoparticles (nC60) and six types of montmorillonite (ML) with different CEC were selected as modeled CNPs and clay colloids, respectively. Transport behavior of nC60 and ML was characterized using breakthrough curves (BTCs) and fitted with two-kinetic-sites colloid transport model. Results of the adsorption experiments showed a good linear correlation between the deposition of nC60 on the sand surface and the di-CEC of ML. Transport of ML and nC60 was inhibited by each other. The calculated mass recovery of nC60, as well as the fitted maximum deposition capacity and attachment rate coefficients of nC60 exhibited a strong linear relationship with the di-CEC of ML. These results indicate that divalent cations in ML interlayers play a significant role in aggregation between nC60 and ML and their cotransport. Through measurements of the particle size and zeta potentials of sole nC60 and mixtures of ML and nC60, FTIR and XPS analysis of nC60 under different conditions, and a release experiment of nC60 in a sand column, it demonstrated cation bridging (Ca2+-π) between nC60 and ML mediated by the divalent cations in ML interlayers. The study highlighted the potential of using di-CEC of clays as an indicator to predict the mobility of nC60 in clay-containing porous media and added insights to the transport behavior of CNPs in porous media.

Microplastic and Silica Colloid Transport in a Saturated Porous Medium Under Various Flow Directions: the Effect of Gravity

Microplastic and Silica Colloid Transport in a Saturated Porous Medium Under Various Flow Directions: the Effect of Gravity

Three-dimensional X-ray imaging of macropore flow

Macropores are known to be important pathways for the rapid transport of water, solutes and colloids in soil. Nevertheless, we still know very little about how the topology and geometry of macropore networks govern water flow configurations and velocities in natural soil. In this study, we aimed at gaining more insight into macropore flow by using X-ray tomography to quantify air–water distributions in the macropore networks of undisturbed topsoil and subsoil columns of a clay soil at varying steady-state flow rates. We observed that while large fractions of the macropore network remained air-filled, the air phase only became entrapped when the irrigation rate was very close to the saturated hydraulic conductivity of the soil. The data enabled us to parameterize a kinematic wave model for water flow following the approach proposed in Jarvis et al. (2017a). Follow-up experiments would be required to evaluate whether these kinematic wave parameters derived by X-ray imaging match with those obtained from outflow measurements. We found that quantitative X-ray imaging of macropore flow through soils still remains a challenging task. We recommend that future experiments are conducted on smaller soil samples to improve image resolution and minimize experimental time spans as well as X-ray image noise and illumination bias. Such experiments could also include 3-D tracer imaging to identify the imaged macropore networks transporting most of the water (i.e. the backbone) at varying steady irrigation rates.