Transport of kaolinite colloids through quartz sand: influence of humic acid, Ca(2+), and trace metals

To evaluate the risk of contaminant transport by mobile colloids, it seems essential to understand how colloids and associated pollutants behave during their migration through uncontaminated soil or groundwater. In this study, we investigated at pH 4 the influence of flow velocity, humic acid, solution Ca(2+) concentrations, and trace metals (Pb(2+), Cu(2+)) on the transport and deposition of kaolinite particles through a pure crystalline quartz sand as porous medium. A short-pulse chromatographic technique was used to measure colloid deposition. Adsorption of humic acid to the kaolinite increase its negative surface charge and then decrease colloid deposition. Experiments with different flow rates showed that humic-coated kaolinite colloid deposition followed a first-order kinetic rate law. The deposition rate coefficients of humic-coated kaolinite colloids increase with increasing Ca(2+) concentration in the suspension. The effect of trace metals on the mobility is studied by injecting two suspensions with different concentrations of Pb(2+) and Cu(2+). At very low cation concentration, the fraction of colloids retained is low and roughly independent of the nature of divalent cations. At high concentration, the deposition is higher and depends on the affinity of divalent cations toward humic-coated kaolinite colloids.     

Modelling colloid transport in groundwater; the prediction of colloid stability and retention behaviour

The association of contaminants with mobile colloidal particles present in groundwaters has been recognised as a potentially important mass transfer mechanism for contaminant migration in the environment. To predict the fate of environmental contaminants there is a need to develop numerical models which include colloid-mediated transport. The mobility of groundwater colloids is controlled by their stability towards aggregation and attachment to rock surfaces. For inorganic particles, the conceptual framework for predicting their stability and deposition behaviour is provided by the DLVO theory. However, under conditions unfavourable to coagulation or surface attachment (ie. when particles and surfaces are of like charge) there are significant discrepancies between theory and experimentally measured coagulation and deposition rates.Predictive shortcomings of the DLVO theory arise from the simplicity of the original model, which was formulated for smooth bodies with ideal geometries and uniform surface properties. However, surfaces are by nature rough, non-uniform and heterogeneous in composition. In addition, the theory does not consider the dynamics of particle interactions. Furthermore, the presence of additional forces, which may be either attractive or repulsive, acting at short range, which arise from interactions between surfaces and water, are not accounted for. Significant developments have been made to extend and modify the DLVO model to account for the discrepancies between theory and experiment. In this paper the prediction of colloid stability and deposition behaviour under unfavourable conditions is reviewed. Emphasis is placed on the phenomenological behaviour of inorganic colloids in aqueous systems that may need to be accounted for in a transport model.     

Surface and bulk sorption of uranium(VI) onto granite rock

Surface and bulk sorption of U(VI) onto granite rock with different types of surfaces were carried out and the results were compared for the different surfaces such as crushed granite, machined core granite, and core granite with fractured surface. The sorption behavior of U(VI) dependent on surface types was investigated and discussed for contacting time, pH, constituent minerals, and surface area. Results from the sorption experiments were also compared each other in order to analyze the differences in sorption behaviors of U(VI) and to correlate the surface sorption coefficient K_a and the bulk sorption coefficient K_d. The effect of contact time and pH on the sorption of U(VI) onto fractured surfaces was larger than that onto the machined fresh surfaces but smaller than that onto the crushed surfaces. As expected, it was noticed that the surface sorption coefficients of U(VI) for the natural fracture surfaces were greater than those of the machined fresh surfaces due to the higher content of secondary minerals such as calcite and chlorite which acted as stronger sorbents. It is presumed that there are many micro-fractures or micro-pores available for the uranium sorption on the granite surfaces, even on the machined fresh surfaces, and there can be an intrinsic difference between the surface and the bulk sorption due to the different types of surfaces.     

Sorption of U(VI) onto granite surfaces: A kinetic approach

Surface sorption experiments of U(VI) onto the surfaces of a Korean granite rock are carried out in order to investigate the kinetics and reversibility of U(VI) sorption as a function of pH and surface types such as fresh intact surfaces and natural fracture surfaces. It was shown that the effect of pH is significant in the sorption of U(VI) onto both types of the granite surfaces. However the sorption rates do not greatly depend upon the pH regardless of the surface types. A two-step first order kinetic behavior dominates onto both the intact surfaces and natural fracture surfaces of granite and that the linearization approach of the kinetic model agrees well with experimental sorption data. The desorption results showed that the sorption process of U(VI) was a little irreversible for the two types of granite surfaces regardless of pH and surface types. This kinetic approach could give a better understanding of U(VI) sorption onto granite surfaces depending on pH and surface types. This revised version was published online in July 2006 with corrections to the Cover Date.     

Surface charge property governing co-transport of illite colloids and Eu(III) in saturated porous media

The transport of colloids and radionuclides is sophisticated because of the variety of charge properties between colloidal particles and host subsurface media, which causes great difficulty in establishing a reliable model of radionuclides migration by taking the colloid phase into consideration. In this work, the co-transport of illite colloids (IC) and Eu(III) in the quartz sand and iron-coated sand porous media was investigated by column experiments to address the predominant mechanism of charge properties on co-transport. Results showed that Eu(III) transport was driven by the illite colloids and electrostatic interaction was critical in governing the co-transport patterns. The promotion of Eu(III) transport by IC was attenuated in the iron-coated sand systems; more IC-Eu(III) complexes were retained uniformly in the column. The pore throat shrinkage caused by electrostatic attachment between aggregated IC and iron oxides exacerbated the physical straining and size exclusion effect of IC-Eu(III) complexes. An aggravated irreversible retention of IC-Eu(III) was detected in iron-coated sand column due to the electrostatic attraction of IC-Eu(III) to host media. The findings are essential for improving the understanding on the potential transport, retention and release risk of colloids associated radionuclides, and imply that the positively charged permeable reactive barrier is an effective strategy to reduce the transport risk of colloid associated radionuclides.     

Model analysis of the colloid and radionuclide retardation experiment at the Grimsel Test Site

The colloid and radionuclide retardation experiments performed at NAGRA's Grimsel Test Site in Switzerland are part of an international collaboration program designed to collect in situ data on the impacts of colloids on radionuclide transport. In this work, breakthrough behaviors of trivalent americium (i.e., 241Am and 243Am) both in the absence and presence of bentonite colloids are analyzed with COLFRAC--a code that models colloid-facilitated solute transport in discretely-fractured, porous media. Model fits to the experimental results indicate that Am sorbed onto mobile colloids, which enhance Am transport relative to a non-sorbing tracer, 131I. Modelling results suggest that Am is kinetically sorbed onto both naturally occurring and exogenous bentonite colloids. Results also indicate that desorption of Am from colloids is slow with respect to the duration of the experiment. In addition, early colloid breakthrough compared to a conservative tracer suggests the effects of hydrodynamic chromatography. Overall, Am breakthrough curves suggest enhanced mobility due to co-transport with both naturally occurring and bentonite colloids.     

Blocking and ripening of colloids in porous media and their implications for bacterial transport

A model accounting for the dynamics of colloid deposition in porous media was developed and applied to systems containing similarly charged particles and collectors. Colloid breakthrough and intracolumn retention data confirmed that blocking reduced overall colloidal adhesion to soil. The surface coverage at which blocking occurred varied for the type of colloid, as shown by changes in the clean-bed collision efficiency, _0, and the excluded area parameter, β. Excluded area parameters were relatively high due to unfavorable interactions between particles and collectors, and ranged from 11.5 for one bacterium (Pseudomonas putida KT2442) to 13.7 and 24.1 for carboxylated latex microspheres with differing degrees of charged groups on their surfaces. Differences in β values for the three colloids were correlated with electrophoretic mobility, with the most negatively charged colloid (carboxylated latex; CL microspheres) having the highest β. No correlation between hydrophobicity and ₀ or β was found. Besides using colloidal particles capable of blocking, the addition of chemical additives to the soil has been suggested as a means for reducing attachment of colloids to porous media. Dextran addition caused an order-of-magnitude reduction in the overall (for carboxylated-modified latex; CMLs). This reduction was not attributed to blocking, but to the sorption of dextran to the soil which lowered ₀. The filtration-based numerical model used to fit the ₀ and β parameters was used to demonstrate that blocking could result in significantly enhanced bacterial transport in field situations.     

Detachment of colloids from a solid surface by a moving air-water interface

Colloid attachment to liquid–gas interfaces is an important process used in industrial applications to separate suspended colloids from the fluid phase. Moving gas bubbles can also be used to remove colloidal dust from surfaces. Similarly, moving liquid–gas interfaces lead to colloid mobilization in the natural subsurface environment, such as in soils and sediments. The objective of this study was to quantify the effect of moving air–water interfaces on the detachment of colloids deposited on an air-dried glass surface, as a function of colloidal properties and interface velocity. We selected four types of polystyrene colloids (positive and negative surface charge, hydrophilic and hydrophobic). The colloids were deposited on clean microscope glass slides using a flow-through deposition chamber. Air–water interfaces were passed over the colloid-deposited glass slides, and we varied the number of passages and the interface velocity. The amounts of colloids deposited on the glass slides were visualized using confocal laser scanning microscopy and quantified by image analysis. Our results showed that colloids attached under unfavorable conditions were removed in significantly greater amounts than those attached under favorable conditions. Hydrophobic colloids were detached more than hydrophilic colloids. The effect of the air–water interface on colloid removal was most pronounced for the first two passages of the air–water interface. Subsequent passages of air–water interfaces over the colloid-deposited glass slides did not cause significant additional colloid removal. Increasing interface velocity led to decreased colloid removal. The force balances, calculated from theory, supported the experimental findings, and highlight the dominance of detachment forces (surface tension forces) over the attachment forces (DLVO forces).     

Resolving the coupled effects of hydrodynamics and DLVO forces on colloid attachment in porous media

Transport of colloidal particles in porous media is governed by the rate at which the colloids strike and stick to collector surfaces. Classic filtration theory has considered the influence of system hydrodynamics on determining the rate at which colloids strike collector surfaces, but has neglected the influence of hydrodynamic forces in the calculation of the collision efficiency. Computational simulations based on the sphere-in-cell model were conducted that considered the influence of hydrodynamic and Derjaguin-Landau-Verwey-Overbeek (DLVO) forces on colloid attachment to collectors of various shape and size. Our analysis indicated that hydrodynamic and DLVO forces and collector shape and size significantly influenced the colloid collision efficiency. Colloid attachment was only possible on regions of the collector where the torque from hydrodynamic shear acting on colloids adjacent to collector surfaces was less than the adhesive (DLVO) torque that resists detachment. The fraction of the collector surface area on which attachment was possible increased with solution ionic strength, collector size, and decreasing flow velocity. Simulations demonstrated that quantitative evaluation of colloid transport through porous media will require nontraditional approaches that account for hydrodynamic and DLVO forces as well as collector shape and size.     

Technetium(VII) sulfide colloid growing observed by laser-induced photoacoustic spectroscopy

Particle growing processes were investigated for technetium(VII) sulfide (Tc₂S₇) colloids produced in a mixture of Na₂S and TcO₄ ^- solutions by laser-induced photoacoustic spectroscopy (LPAS). Analysis of the LPAS signal intensities indicated that the particle size increased in the solution with an increase of standing time, while the number of particles remained constant. It was revealed that the size of colloid particles increased by deposition of Tc₂S₇ on the particle surfaces, not by coagulation of colloid particles. The formation mechanism and growing process of the colloids are discussed based on the LaMer model, which deals with nucleation processes.     

Colloid dispersion in a uniform-aperture fracture

This research investigates the dispersion of colloids through fracture systems by exploring experimentally and numerically the transport and dispersion of 1.0-, 0.11-, and 0.043-mum diameter fluorescent carboxylate-modified microspheres and chloride at various flow rates through variable-length, synthetic Plexiglas fractures (flow cells). A dimensionless number describing each experiment is varied by changing the colloid size, flow rate, and fracture length. Surface characteristics of the microspheres and Plexiglas favor repulsive interactions, thereby minimizing the chance of colloid filtration and remobilization. Full recovery of the colloids is typically observed, thereby supporting the assumption of negligible colloid filtration. In comparison to chloride transport, there is increased tailing for colloid plumes traveling through the flow cell. This increased tailing is attributed to Taylor dispersion phenomena (dispersion due to an advection gradient). In the synthetic fractures investigated here, colloid dispersion due to the velocity gradient is evident, but fully developed Taylor conditions are not realized. A particle-tracking algorithm is run inversely to estimate the effective dispersion rate for the colloid plume in each experiment as a function of the experimental parameters (flow rate, fracture length, and colloid size). Results suggest that the log of the effective dispersion rate of the colloid plume increases linearly with the log of the dimensionless number comprising experimental parameters.     

Dense colloid transport in a bifurcating fracture

In this work, the transport of dense colloids through a water-saturated, bifurcating fracture is investigated using a constant spatial step particle tracking technique. The size of the constituents of a colloid plume is an important factor affecting the partitioning of dense colloids at the bifurcation. While neutrally buoyant colloids partition between daughter fractures in proportion to flow rates, dense colloids will preferentially exit fractures that are gravitationally downgradient, notwithstanding that the majority of the interstitial fluid may flow through the upper fracture. Comparison of the partitioning ratio between daughter fractures with the ratios of characteristic settling, diffusion, and advection time reveal that these parameters control how colloids behave at fracture bifurcations.     

土壤胶体迁移行为及其介导污染物迁移模拟与研究进展

本文综述了土壤多孔介质中胶体迁移的释放与沉积机制、影响胶体迁移的多种因素以及土壤中胶体与各种污染物的协同迁移作用,总结了模拟胶体迁移的数学模型以及计算机软件的应用。研究表明,胶体在土壤中的迁移主要受应变、附着、薄膜应变等迁移机制的影响,多孔介质的性质、流体的性质以及胶体自身的性质也会影响胶体的迁移。此外,胶体能有效吸附地下水多孔介质中的有机或无机污染物,并对其在地下环境中的迁移产生显著影响。目前已有许多学者通过数学模型来模拟胶体在土壤中的迁移过程,而计算机技术的进步也将促进更加先进的软件模型应用到胶体迁移的模拟中。     

Controlled electrophoretic patterning of polyaniline from a colloidal suspension

We present a method for controlled deposition of polyaniline from colloidal suspensions. Stable suspensions of polyaniline colloids (approximately 115 nm in diameter) were formed by dispersing polyaniline/formic acid solution into acetonitrile. It was demonstrated that the positively charged polyaniline colloids can be electrophoretically deposited onto various substrate materials such as platinum and ITO, forming continuous ultrathin films. We examined the film morphology, as well as the effects of process parameters, such as deposition time, colloid concentration, and applied voltage, on the deposition efficiency. Furthermore, the efficacy of the technique was illustrated by electrophoretically patterning polyaniline thin films onto selected individual micrometer-scale sensing elements within a microfabricated sensor array, and by further demonstrating its sensitivity to gaseous analytes including water and methanol.     

Perforated, freely suspended layer-by-layer nanoscale membranes

Ultrathin, perforated, and freely suspended membranes with uniform nanopores in the range of tens of nanometers have been fabricated using a fast, simple method of spin-assisted layer-by-layer assembly on hydrophobic substrates. Membranes with thicknesses down to 20 nm were robust enough to be released from the sacrificial substrates, transferred onto various surfaces, and suspended over microscopic openings. The nanopore size can be controlled by tuning the number of polyelectrolyte bilayers, spinning speed, and a proper selection of hydrophobic substrates. We demonstrate that the formation of nanopores is caused by the partial dewetting of polyelectrolyte layers in the course of their deposition on the underlying hydrophobic surfaces. The nanoscale thickness of perforated membranes with relatively uniform size and a high concentration of nanopores provides perspectives for higher rates of transport through freely suspended LbL membranes. The highly perforated LbL membranes introduced here can serve as a novel platform for ultrafine separation considering an intriguing combination of nanopores, nanoscale membrane thickness, and easy functionalization.     

Sulfonic Acid-functionalized gold nanoparticles: a colloid-bound catalyst for soft lithographic application on self-assembled monolayers

In this report, we present a new lithographic approach to prepare patterned surfaces. Self-assembled monolayers (SAMs) of the acid-labile trimethylsilyl ether (TMS-OC(11)H(22)S)(2) (TMS adsorbate) was formed on gold. 5-Mercapto-2-benzimidazole sulfonic acid sodium salt (MBS-Na(+)) was used as a ligand for gold nanoparticles. These monolayer-protected gold colloids (MPCs) were transformed into the catalytically active H(+)-form by ion exchange. This colloid-bound catalyst hydrolyzed the TMS adsorbate (TMS-OC(11)H(22)S)(2) both in solution and when self-assembled on gold surfaces. Microcontact printing of the active colloid-bound catalyst on the preformed TMS SAM led to the deposition of the colloid onto the SAMs. After the catalyst nanoparticles were rinsed off, a patterned surface was created as shown by AFM.     

Differential transport and dispersion of colloids relative to solutes in single fractures

This work employed numerical experiments simulating colloid and solute transport in single parallel-plate fractures, using the random walk particle tracking method, to demonstrate that (1) there exists an aspect ratio of the colloid radius to half the fracture aperture, δ_o, where the average velocities of colloids and solutes are similar. When δ > δ_o, the velocity distribution assumption is satisfied, and the fact that the ratio of the colloid transport velocity to the solute transport velocity, τ_p, decreases as δ increases is well documented in the literature. However, when δ < δ_o, the velocity distribution assumption is violated, and τ_p increases as δ increases and (2) the Taylor dispersion coefficient and its extension by James and Chrysikopoulos [S.C. James, C. V. Chrysikopoulos, J. Colloid Interface Sci. 263 (2003) 288] will overestimate the colloid dispersion coefficient significantly. Additionally, numerical experiments simulating colloid and solute transport in variable-aperture fractures demonstrated that τ_p and D_L,coll/D_L,solute decrease with increasing CoV, and the anisotropy ratio only plays a minor role compared to the CoV. These observations have important implications towards the interpretation of colloid transport in both porous and fractured media.     

Size dispersion and colloid mediated radionuclide transport in a synthetic porous media

Size dispersion effects during the migration of natural submicron bentonite colloids (<200 nm) through a ceramic column are observed for the first time by laser-induced breakdown detection (LIBD) at ppm (parts per million) mass concentration. Larger size fractions ( approximately 200 nm) arrive prior to smaller size fractions (<100 nm) at the column outlet in agreement with model predictions and earlier findings with carboxylated polystyrene spheres. By addition of trace amounts of americium(III) and plutonium(IV), colloid mediated transport of these radionuclides is studied. The peak arrival times of Pu-244 and Am-241, as measured by ICP-MS, match the bentonite colloid breakthrough and occur significantly prior to the conservative tracer (HTO) indicating the colloid-borne migration of tri- and tetravalent radionuclides.     

Kolloide: Die Welt der vernachlässigten Dimensionen

Aquatic colloids are abundant in all natural aquatic systems. Aquatic colloids consist of clay minerals, micro‐organisms, humic substances, and anthropogenic colloids like soot and platinum (from catalysts in motor vehicles). Colloids may enhance contaminant transport due to sorption of hydrophobic organic compounds. They can have negative effects on water quality, especially micro‐organisms like pathogens or viruses. Colloids also can cause pore blocking and subsequent head loss in groundwater production wells. However, colloids can be useful in groundwater remediation or waster water treatment (e.g. tensides, flocculation, catalysts). The origin of colloids is due to weathering, degradation of organic compounds, dissolution or precipitation as well as hydrochemical or hydraulic gradients. Colloid stability is dominated by surface properties. New analytical tools like field flow fractionation, laser induced breakdown detection and scanning x‐ray microscopy will provide new insight into the behaviour of aquatic colloids.