We discuss the charging behavior of clays and clay minerals in aqueous electrolyte solutions. Clay platelets exhibit different charging mechanisms on the various surfaces they expose to the solution. Thus, the basal planes have a permanent charge that is typically considered to be independent of pH, whereas the edge surfaces exhibit the amphoteric behavior and pH-dependent charge that is typical of oxide minerals. Background electrolyte concentration and composition may affect these two different mechanisms of charging in different ways. To guide and to make use of these unique properties in technical application, it is necessary to understand the effects of the various master variables (i.e. pH and background salt composition and concentration). However, how to disentangle the various contributions to the charge that is macroscopically measurable via conventional approaches (i.e. electrokinetics, potentiometric titrations, etc.) remains a challenge. The problem is depicted by discussing in detail the literature data on kaolinite obtained with crystal face specificity. Some results from similar experiments on related substrates are also discussed. As an illustration of the complexity, we have carried out extensive potentiometric mass and electrolyte titrations on artificial clay samples (Na-, Ca-, and Mgmontmorillonite). A wide variety of salts was used, and it was found that the different electrolytes had different effects on the end point of mass titrations. In the case of a purified sample (i.e. no acid-base impurities), the end point of a mass titration (the plateau of pH achieved for the highest concentrations of solid), in principle, corresponds to the point of zero net proton and hydroxide consumption, at which in ideal systems, such as oxide minerals, the net proton surface charge density is zero. To such concentrated (dense) suspensions of clay particles, aliquots of salts can be added and the resulting pH indicates the specificity of a given salt for a given clay particle system. In the experimental data, some ambiguity remains, which calls for further detailed and comprehensive studies involving the application of all the available techniques to one system. Although, right now, the overall picture appears to be clear from a generic point of view (i.e. concerning the trends), clearly, in a quantitative sense, huge differences occur for nominally identical systems and only such a comprehensive study will allow to proof the current phenomenological picture and allow the next step to be taken to understand the fine details of the complex clay-electrolyte solution interfaces.

The spatial deposition of polystyrene latex colloids (d = 1 μm) at rough mineral and rock surfaces was investigated quantitatively as a function of Eu(III) concentration. Granodiorite samples from Grimsel test site (GTS), Switzerland, were used as collector surfaces for sorption experiments. At a scan area of 300 × 300 μm(2), the surface roughness (rms roughness, Rq) range was 100-2000 nm, including roughness contribution from asperities of several tens of nanometers in height to the sample topography. Although, an increase in both roughness and [Eu(III)] resulted in enhanced colloid deposition on granodiorite surfaces, surface roughness governs colloid deposition mainly at low Eu(III) concentrations (≤5 × 10(-7) M). Highest deposition efficiency on granodiorite has been found at walls of intergranular pores at surface sections with roughness Rq = 500-2000 nm. An about 2 orders of magnitude lower colloid deposition has been observed at granodiorite sections with low surface roughness (Rq < 500 nm), such as large and smooth feldspar or quartz crystal surface sections as well as intragranular pores. The site-specific deposition of colloids at intergranular pores is induced by small scale protrusions (mean height = 0.5 ± 0.3 μm). These protrusions diminish locally the overall DLVO interaction energy at the interface. The protrusions prevent further rolling over the surface by increasing the hydrodynamic drag required for detachment. Moreover, colloid sorption is favored at surface sections with high density of small protrusions (density (D) = 2.6 ± 0.55 μm(-1), asperity diameter (φ) = 0.6 ± 0.2 μm, height (h) = 0.4 ± 0.1 μm) in contrast to surface sections with larger asperities and lower asperity density (D = 1.2 ± 0.6 μm(-1), φ = 1.4 ± 0.4 μm, h = 0.6 ± 0.2 μm). The study elucidates the importance to include surface roughness parameters into predictive colloid-borne contaminant migration calculations.

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Deposition of latex colloids on a structured silicon surface was investigated. The surface with well-defined roughness and topography pattern served as an analogue for rough mineral surfaces with half-pores in the submicrometer size. The silicon topography consists of a regular pit pattern (pit diameter = 400 nm, pit spacing = 400 nm, pit depth = 100 nm). Effects of hydrodynamics and colloidal interactions in transport and deposition dynamics of a colloidal suspension were investigated in a parallel plate flow chamber. The experiments were conducted at pH ∼ 5.5 under both favorable and unfavorable adsorption conditions using carboxylate functionalized colloids to study the impact of surface topography on particle retention. Vertical scanning interferometry (VSI) was applied for both surface topography characterization and the quantification of colloidal retention over large fields of view. The influence of particle diameter variation (d = 0.3-2 μm) on retention of monodisperse as well as polydisperse suspensions was studied as a function of flow velocity. Despite electrostatically unfavorable conditions, at all flow velocities, an increased retention of colloids was observed at the rough surface compared to a smooth surface without surface pattern. The impact of surface roughness on retention was found to be more significant for smaller colloids (d = 0.3, 0.43 vs. 1, 2 μm). From smooth to rough surfaces, the deposition rate of 0.3 and 0.43 μm colloids increased by a factor of ∼2.7 compared to a factor of 1.2 or 1.8 for 1 and 2 μm colloids, respectively. For a substrate herein, with constant surface topography, the ratio between substrate roughness and radius of colloid, Rq/rc, determined the deposition efficiency. As Rq/rc increased, particle-substrate overall DLVO interaction energy decreased. Larger colloids (1 and 2 μm) beyond a critical velocity (7 × 10(-5) and 3 × 10(-6) m/s) (when drag force exceeds adhesion force) tend to detach from the surface irrespective of the impact of roughness. For polydisperse solutions, an increase in the polydispersity and flow velocity resulted in a reduction of colloid deposition efficiency due to the resulting enhanced double-layer repulsion. Quantification of surface topography variations of two endmembers of natural grain surfaces showed that half-pore depths and roughness of sedimentary quartz grains are mainly in the micrometer range. Grains with diagenetically formed quartz overgrowths, however, show surface roughness mainly in the submicrometer range. Thus, surface topography features applied in the here presented analogue study and resulting variation in particle retention can serve as quantitative analogue for particle reactions in diagenetically altered quartz sands and sandstones. The reported impact of particle polydispersity can have an important application for quantitative prediction of retention of varying types of minerals, such as different clay minerals in the environment under prevailing unfavorable conditions.