Bentonites are commonly used as chemical containment barriers to minimize liquid flow and contaminant transport. However, chemicals can adversely affect bentonite performance to the extent that modified bentonites have been developed to improve chemical resistance relative to traditional (unmodified) bentonites. The present study focused on the diffusion of potassium chloride (KCl) through a bentonite-polymer composite, or BPC, that was known to behave as a semipermeable membrane. Specifically, the effective diffusion coefficients, D*, for chloride (Cl−) and potassium (K+) were measured and correlated with previously measured membrane efficiency coefficients, ω, for the BPC. The values of D* at steady-state for chloride ($D_{ss,C{l}^{-}}^{*}$\$\end{document}) and potassium ($D_{ss,K^{+}}^{*}$\$\end{document}) decreased as the ω values increased. The decrease in $D_{ss,C{l}^{-}}^{*}$\$\end{document} and $D_{ss,K^{+}}^{*}$\$\end{document} was approximately a linear function of (1 − ω), which is consistent with previous research performed on unmodified Na-bentonite contained within a geosynthetic clay liner (GCL). In contrast to the previous GCL tests, however, $D_{ss,C{l}^{-}}^{*}$\$\end{document} values for the BPC generally were greater than the $D_{ss,K^{+}}^{*}$\$\end{document} values, and the differences between $D_{ss,C{l}^{-}}^{*}$\$\end{document} and $D_{ss,K^{+}}^{*}$\$\end{document} decreased as KCl concentration increased. The apparent discrepancy between $D_{ss,C{l}^{-}}^{*}$\$\end{document} and $D_{ss,K^{+}}^{*}$\$\end{document} is consistent with excess sodium (Na+) in the BPC prior to testing and the requirement for electroneutrality during testing. Also, despite an apparent linear trend in diffusive mass flux for K+, lack of agreement between the ratio of the diffusive mass flux of K+ relative to that for Cl− as required on the basis of electroneutrality at steady state suggested that steadystate diffusive mass flux for K+ had probably not been achieved due to continual K+-for-Na+ cation exchange. Nonetheless, the excess Na+ and bentonite modification did not affect the fundamental correlation between D* and ω, which requires that D* approaches zero as ω approaches unity (D* → 0 as ω → 1).

Widespread lateritized ultramafic rocks in the southern part of the Muratdağı region of Turkey constitute a significant source of Ni-Cr-bearing ore with economic potential. However, no mineralogical or geochemical characterizations of these important materials have been performed previously. The aim of the present study was to describe the mineralogy, geochemistry, and genesis of Ni-Cr-bearing smectite in garnierite and ferruginous saprolite associated with the lateritized ophiolite-related ultramafic rocks. The lateritic zones are well developed over serpentinized harzburgitic mantle peridotites. The lateritized units and related bedrocks were examined using polarized-light microscopy, X-ray diffraction, scanning and transmission electron microscopies, and chemical and isotopic methods. The garnierite-containing saprolites are enriched in smectite, Fe-(oxyhydr)oxide phases, and opal-CT. Micromorphological images revealed that flaky smectite and, locally, Fe-rich particles, alunite, gypsum, gibbsite, and sulfur crystals developed along the fractures and dissolution voids. The development of saprolite demonstrates chemical weathering. The presence of silicified and Fe-(oxyhydr)oxide phases associated with gypsum, alunite, and local native sulfur in vertical and/or subvertical fractures and fault infillings are indicative of hydrothermal processes along the extensional, tectonically related fault systems. Chemical weathering and hydrothermal processes, which probably started during the Oligocene and Miocene, led to the formation of nontronite, Fe-bearing montmorillonite, and local Fe-rich kaolinite. Nickel and Cr are concentrated significantly in the saprolite zone and are positively correlated with Fe2O3 content, which is controlled by the formation of nontronite, montmorillonite, and Fe-(oxyhydr)oxide phases. Nickel-Cr-bearing nontronite and montmorillonite precipitated from alkaline water as a result of the increasing (Fe2O3+Al2O3+Cr2O5+Ni+Co)/(MgO+SiO2) ratio under the control of both chemical weathering and hydrothermal processes. The Fe and Mg (associated with Ni and Cr) required for the formation of smectite were supplied by solutions from both chemical weathering and hydrothermal alteration of Ni-Cr-bearing olivine and pyroxene in the harzburgitic bedrock; the Al was supplied by schists, granite, and volcanic units.

Organic dyes such as methylene blue (MB) are often used in the characterization of clays and related minerals, but details of the adsorption mechanisms of such dyes are only partially understood from spectroscopic data, which indicate the presence of monomers, dimers, and higher aggregates for varying mineral surfaces. A combination of quantum (density functional theory) and classical molecular simulation methods was used to provide molecular detail of such adsorption processes, specifically the adsorption of MB onto kaolinite basal surfaces. Slab models with vacuum-terminated surfaces were used to obtain detailed structural properties and binding energies at both levels of theory, while classical molecular dynamics simulations of aqueous pores were used to characterize MB adsorption at infinite dilution and at higher concentration in which MB dimers and one-dimensional chains formed. Results for the neutral MB molecules are compared with those for the corresponding cation. Simulations of the aqueous pore indicate preferred adsorption on the hydrophobic siloxane surface, while charge-balancing chloride ions adsorb at the aluminol surface. At infinite dilution and in the gas-phase models, MB adsorbs with its primary molecular plane parallel to the siloxane surface to enhance hydrophobic interactions. Sandwiched dimers and chains are oriented perpendicular to the surface to facilitate the strong hydrophobic intermolecular interactions. Compared with quantum results, the hybrid force field predicts a weaker MB adsorption energy but a stronger dimerization energy. The structure and energetics of adsorbed MB at infinite dilution are consistent with the gas-phase binding results, which indicate that monomer adsorption is driven by strong interfacial forces rather than by the hydration properties of the dye. These results inform spectroscopic studies of MB adsorption on mineral surfaces while also revealing critical areas for development of improved hybrid force fields.

When clay minerals, notably smectites, intercalate organic cations, their interlayer surfaces change from hydrophilic to hydrophobic. The resultant intercalates, known as organo-clays (OCs), have a large affinity for hydrophobic organic contaminants (HOCs). Organo-clays are used as sorbents of HOCs in wastewater treatment and as sorptive barriers in landfill liners. The structural and sorptive characteristics of OCs with respect to HOCs have been studied extensively, and a large volume of literature has accumulated over the past few decades. The interactions of OCs with HOCs and the various approaches to improving the sorption capacity of OCs are reviewed here, with particular reference to the application of novel analytical techniques, such as molecular modeling, to characterizing the OC—HOC interaction.

The application of ceramic membranes is limited by the high cost of raw materials and the sintering process at high temperatures. To overcome these drawbacks, the present study investigated both the preparation of ceramic membranes using cost-effective raw materials and the possibility of recycling the membranes for the treatment of oily wastewater. Ceramic membranes with a pore size of 0.29–0.67 μm were prepared successfully at temperatures as low as 1000–1100°C by a simple pressing route using lowcost base materials including diatomite, kaolin, bentonite, talc, sodium borate, and barium carbonate. The typical steady-state flux, fouling resistance, and oil-rejection rate of the low-cost virgin membranes sintered at 1000°C were 2.5 × 10−5 m3m−2s−1 at 303 kPa, 63.5%, and 84.1%, respectively, with a feed oil concentration of 600 mg/L. A simple burn-out process of the used membranes at 600°C in air resulted in >95% recovery of the specific surface area (SSA) of the virgin membranes, a significantly increased steady-state flux, decreased fouling resistance, and increased oil-rejection rate. The typical steady-state flux, fouling resistance, and oil-rejection rate of the low-cost ceramic membrane sintered at 1000°C and subsequently heat treated at 600°C for 1 h in air after the first filtration were 5.4 × 10−5 m3m−2s−1 at 303 kPa, 27.1%, and 92.9%, respectively, with a feed oil concentration of 600 mg/L. The present results suggest that the low-cost ceramic membranes used for oily wastewater filtration can be recycled by simple heat-treatment at 600°C in air. As the fouling resistance of the low-cost ceramic membranes decreased with a decrease in pore size, the preferred pore size of the membranes for oily wastewater filtration is <0.4 μm.