Clay minerals are layer type aluminosilicates that figure in terrestrial biogeochemical cycles, in the buffering capacity of the oceans, and in the containment of toxic waste materials. They are also used as lubricants in petroleum extraction and as industrial catalysts for the synthesis of many organic compounds. These applications derive fundamentally from the colloidal size and permanent structural charge of clay mineral particles, which endow them with significant surface reactivity. Unraveling the surface geochemistry of hydrated clay minerals is an abiding, if difficult, topic in earth sciences research. Recent experimental and computational studies that take advantage of new methodologies and basic insights derived from the study of concentrated ionic solutions have begun to clarify the structure of electrical double layers formed on hydrated clay mineral surfaces, particularly those in the interlayer region of swelling 2:1 layer type clay minerals. One emerging trend is that the coordination of interlayer cations with water molecules and clay mineral surface oxygens is governed largely by cation size and charge, similarly to a concentrated ionic solution, but the location of structural charge within a clay layer and the existence of hydrophobic patches on its surface provide important modulations. The larger the interlayer cation, the greater the influence of clay mineral structure and hydrophobicity on the configurations of adsorbed water molecules. This picture extends readily to hydrophobic molecules adsorbed within an interlayer region, with important implications for clay–hydrocarbon interactions and the design of catalysts for organic synthesis.

https://www.pnas.org/content/pnas/96/7/3358.full.pdf

Surface geochemistry of the clay minerals.

This review intends to deepen our understanding of mechanisms by which molecules with aromatic moieties attach to organic and mineral components of terrestrial environments. We present published evidence for the existence of specific, sorptive interactions of aromatic moieties with environmental sorbents. We find that aromatic pi-systems within organic compounds have the capacity to adsorb to minerals and organic soil and sediment components such as natural organic matter (NOM) and fire-derived black carbon (BC) through specific sorptive forces other than hydrophobic interactions. Polar interactions of aromatic pi-donor and -acceptor compounds show adsorption energies between 4 and 167 kJ mol(-1). Bonding strengths of cation-pi interactions and pi-pi electron donor-acceptor (EDA) interactions appear to be larger than H bonding strengths and comparable to inner- and outer-sphere complex formation. We conclude that, in analogy to polar and ionizable functional groups, components with aromatic pi-donor and -acceptor systems equip organic molecules with a substantial sorptive potential. This observation has important implications for the fate and transport of aromatic contaminants. The resulting sorptive interactions might also play a yet-overlooked functional role in the complex chain of processes which preserve NOM against decomposition.

Molecular-Level Interactions in Soils and Sediments: The Role of Aromatic π-Systems

The interactions of oxytetracycline with model clay adsorbents were investigated as a function of suspension pH. The clay adsorbents used were native montmorillonite (SWy-2), Na-montmorillonite (Na-SWy-2), and hexadecyl trimethylammonium-montmorillonite (HDTMA-montmorillonite). The adsorption of oxytetracycline to the clay could be described by Freundlich-type adsorption isotherms. It was observed that the adsorption of oxytetracycline in the native and sodium forms of montmorillonite decreases with increasing pH in the order pH 1.5 > 5.0 > 8.7 > 11.0. This trend is consistent with cationic exchange interactions that are dominant at lower pH values when oxytetracycline has a net positive charge. On the other hand, hydrophobic interactions when oxytetracycline is zwitterionic (at pH 5.0) are predominant over other mechanisms, as evident from the FT-IR spectrum of the HDTMA-montmorillonite and humic acid-montmorillonite adsorbed with oxytetracycline. The presence of a large amount of dissolved organic matter (DOM) was also found to decrease the sorption of oxytetracycline to clay, suggesting that DOM may increase its mobility in the natural environment. Several mechanisms of interaction of oxytetracycline in clay are proposed based on the adsorption isotherms and the results from X-ray diffraction (XRD) and Fourier transform-infrared (FT-IR) analyses.

Investigating the Molecular Interactions of Oxytetracycline in Clay and Organic Matter: Insights on Factors Affecting Its Mobility in Soil

Organic compounds can interact with clay minerals by i) adsorption at the external surfaces, ii) adsorption at the external and internal surfaces, iii) by exchange of exchangeable ions at the external surfaces, iv) by exchange of exchangeable ions at the external and internal surfaces, and v) by grafting reactions with silanol and aluminol groups leading to covalent bonds. Kaolin minerals intercalate only are a limited number of compounds whereas the reactions of 2:1 clay minerals, in particular smectites and vermiculites, are very manifold. Special attention is given to the interaction with neutral organic molecules such as alcohols, fatty acids, amines, amino acids, aromatic compounds, macrocyclic compounds, and nuclein bases. The interaction with complexes and dyes also provides the basis of advanced applications of clay minerals. Binding of long chain alkylammonium ions is a fundamental reaction for hydrophobising clay mineral particles as needed in many applications. The interaction of clay minerals with polymers including proteins is not only an actual field of research but also of practical importance. Organo-clay minerals are used as effective adsorbents. As these materials also adsorb solvent molecules together with the adsorptive, the adsorption process must be considered as adsorption from binary solution which, therefore, is also described in this chapter.

Clay mineral-organic interactions

Recent developments in the study of the intercalation of organoammonium ions into layered silicates are reviewed. The new developments of the applications of the organoammonium-exchanged layered silicates include the selective adsorption of toxic compounds from water, the immobilization of photo and electroactive species to construct novel photo and electrofunctional materials, and the complexation with organic polymers for the enhancement of the mechanical properties. The conversion of the layered solids to three dimensional nanoporous solids with novel microstructures and adsorptive properties has also been successfully done. The novel controlled properties achieved by the modification with the adsorption of organoammonium ions open new opportunities to tailor the properties of the inorganic-organic nanostructured materials.

Preparation of Inorganic–Organic Nanocomposites through Intercalation of Organoammonium Ions into Layered Silicates

The nature of the siloxane surface in smectites was investigated by measuring the adsorption of aromatic hydrocarbons from water by organo-clays. The organo-clays were prepared by replacing the hydrophilic, inorganic exchange cations of a series of smectites with the small, hydrophobic organic cation, trimethylphenylammonium (TMPA). Smectites with a range in charge densities were used that resulted in different TMPA contents in the organo-clays. Adsorption isotherms of benzene, alkylbenzenes, and naphthalene from water by the TMPA-smectites indicated that sorption was inversely related to TMPA content. The Langmuir form of the isotherms suggests that the aromatic compounds adsorb to the clay surface. Possible adsorptive sites in TMPA-smectites are limited to the TMPA cations and the siloxane oxygen surfaces. Because sorption increased as layer charge and TMPA content decreased, the organic compounds must adsorb to the siloxane surfaces. Calculations based on an adsorbed compound monolayer, which was estimated by fitting adsorption data to the Langmuir equation, and the N2 specific surface area of each TMPA-clay, indicate that the surface area occupied by each adsorbed molecule increases as the planar area of the molecule increases. This strongly indicates that the planar surfaces of the compounds adsorb directly to the clay surface. Apparently, the TMPA cations function to keep the smectite interlayers open. Interactions between the phenyl groups of TMPA cations on opposing interlayer clay surfaces may act to increase the size of the adsorptive regions. These results show that the siloxane surfaces of smectites can effectively adsorb aromatic hydrocarbons from water if the hydrophilic, inorganic exchange cations are replaced with small, hydrophobic organic cations. The strong adsorption of hydrophobic organic molecules from water demonstrates the hydrophobicity of the siloxane surfaces in smectites.

Hydrophobicity of siloxane surfaces in smectites as revealed by aromatic hydrocarbon adsorption from water

Homoionic trimethylphenylammonium (TMPA)- and tetramethylammonium (TMA)-clays were prepared by ion-exchange reactions using two smectite clays that differed in their cation exchange capacities and surface charge densities. These clays are referred to as a low-charge (SAC) and high-charge (SWa)-smectite. The organo-clays were evaluated as adsorbents of water soluble aromatic hydrocarbons including benzene, toluene, ethylbenzene, p-xylene, butylbenzene, and naphthalene. All of the aromatic hydrocarbons tested were effectively removed from water by the low-charge TMPA-smectite. The low-charge TMA-smectite was an effective adsorbent for benzene but was ineffective in the removal of the alkylbenzenes and naphthalene from water. The effect of surface charge on the adsorption properties of TMPA-smectite was pronounced. The uptake of benzene and toluene by the high-charge TMPA-smectite was greatly reduced as compared to the low-charge TMPA-smectite. These results suggest the utility of TMPA-smectite as a liner material for petroleum storage containers and waste disposal reservoirs. The use of TMPA-smectite in conjunction with Na-smectite would provide a barrier with the ability to impede the flow of water and to effectively adsorb dissolved organic contaminants.

William F. Jaynes

Papers

Hydrophobicity of siloxane surfaces in smectites as revealed by aromatic hydrocarbon adsorption from water

Trimethylphenylammonium-smectite as an effective adsorbent of water soluble aromatic hydrocarbons.

Role of Layer Charge in Organic Contaminant Sorption by Organo-Clays