One montmorillonite, STx-1 (Texas, USA), was activated with different amounts of Al and tetramethylammonium (TMA+) cations to obtain materials with a combined Al3+ and TMA+ content equal to its cation exchange capacity. The adsorption capacity of these samples was studied saturating them with hept-1-ene at room temperature. The samples were heated and the evolved gases analyzed by Fourier transform infrared spectroscopy and gas chromatography-mass spectrometry. Hept-1-ene reacted with the clays via proton transfer and resulted in the formation of a variety of reaction products (>60 hydrocarbons). In general, the presence of TMA+ cations significantly reduced the population of protons to selectively produce isomerization and hydration products.

Sorption of the herbicide isoxaflutole and its main degradate, diketonitrile (DKN), to natural clays, SAz-1, SWy-2 and SHCa-1, and the organoclay derivatives (octadecylammonium (ODA) and hexadecyltrimethylammonium (HDTMA)) of these clays was investigated. Isoxaflutole hydrolysis to DKN was too rapid in aqueous solutions with organoclays to characterize sorption. No measurable DKN sorption was observed for the natural clays. Sorption of DKN was greater on organoclays with an interlayer paraffin-like complex that were prepared from the high-charge SAz-1 clay than on organoclays with a bilayer or monolayer interlayer complex prepared using lower-charge SWy-2 or SHCa-1 clays. Desorption isotherms indicated that sorption was irreversible. For SAz-1 with HDTMA at ∼100% of the clay CEC, the d001 values suggest that DKN enters the interlamellar space of the organoclay and dissociates into the anion. The DKN anion forms a very stable chelate complex with the residual cations and/or partially-coordinated structural cations. This strong interaction supports the irreversibility of the sorptive process.

Thermally induced lamellar structure changes due to phase transition and degradation in organoclays based on a synthetic ‘Somasif’ mineral and two organic surfactants, di-methyl dihydro-ditallow ammonia chloride (DMDTA) and tri-butyl-hexadecyl phosphonium bromide (HTBP) were investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), Fourier transform infrared (FTIR) spectroscopy, in situ simultaneous small-angle X-ray scattering (SAXS) and wide-angle X-ray diffraction (WAXD) over the temperature range 30–280°C. Results indicated that the surfactant layer in ‘Somasif’-based organoclays underwent thermally induced melting-like order-disorder transition followed by desorption of surfactant molecules, resulting in drastic changes in the character of the layer periodicity. The transition temperature (Ttr), determined from the endothermic transition in DSC, was found to depend strongly on the type and the content of surfactant incorporated. Temperature-resolved SAXS indicated complex intercalated layered structures, containing multiple lamellar stack populations of two different organic layer thicknesses. A weak scattering peak (s0), located at exactly the half angular position of the strong first scattering maximum s1 (s0 = 0.5s1), was found in all tested ‘Somasif’ clays. The presence of this peak can be attributed to a slight breaking of the translational symmetry in the layered structure, causing the 1D repeat period in real space to be doubled. In other words, some portions of layers are grouped into pairs and a single pair forms the new repeat unit. This arrangement is reminiscent of the Peierls-like distortion.

The sorption of two sulfonylurea herbicides (SU), metsulfuron methyl and nicosulfuron, on pure clays and organoclays was investigated. Three clays (Arizona smectite, SAz-1, Wyoming smectite, SWy-2, and hectorite, SHCa-1), were treated with amounts of octadecylammonium (ODA) or dioctadecyldimethylammonium (DODMA) cations equal to ∼50 and 100% of the clays’ cation exchange capacity (CEC). Sorption isotherms were fitted to the Freundlich equation. While no measurable sorption was found on the pure clays (Kf = 0), organoclays prepared using both primary and quaternary amines were effective as SU sorbents. The metsulfuron methyl Kf values ranged between 196 and 1498 µmol1−1/n kg−1 L1/n, and Kf values for nicosulfuron, which were lower than those of metsulfuron methyl, ranged from 35 to 198 umol1−1/n kg−1 L1/n. As shown by sorption coefficients, Kd and KOC, SWy-2 treated with DODMA at ∼100% of the CEC was the most effective sorbent for metsulfuron, Kd = 684 L kg−1 and KOC = 2138 L kg−1. For nicosulfuron the most effective sorbent was SAz-1 with ODA at ∼ 50% of the CEC (Kd = 147 L kg−1 and KOC = 1233 L kg−1). In contrast to other weak-acid herbicides, such as phenoxy and picolinic acids, no clear relationships were found between sorption and layer charge, organic carbon content, and basal spacing of the organoclays for both sulfonylurea herbicides. Sorption of both herbicides on organoclays was assumed to involve hydrophobic and polar interactions for which the availability of interlayer room between organocations was a very important factor.

Because of their large potential for agricultural, industrial and medicinal applications, nanomaterials have been the focus of much research during the past few decades. Nanoclays are natural nanomaterials that occur in the clay fraction of soil, among which montmorillonite and allophane are the most important species. Montmorillonite is a crystalline hydrous phyllosilicate (layer silicate). Organically-modified montmorillonites or ‘organoclays’, formed by intercalation of quaternary ammonium cations, have long been used as rheological modifiers and additives in paints, inks, greases and cosmetics and as carriers and delivery systems for the controlled release of drugs. Perhaps the largest single usage of organoclays over recent years has been in the manufacture of polymer-clay nanocomposites. These organic–inorganic hybrid materials show superior mechanical, thermal and gas-barrier properties. Organoclays are also useful in pollution control and water treatment. Allophane is a non-crystalline aluminosilicate derived from the weathering of volcanic ash. A large proportion of the agricultural land in Chile is covered by volcanic soils,the clay fraction of which is dominated by allophane. Consisting of nanosize (3.5–5.0 nm) hollow spherules, allophane is a suitable support material for enzyme immobilization. Allophane is also effective at adsorbing phenolic compounds and colour from kraft mill effluents and phosphate from water and wastewater.

The synthesis of clay composites modified with magnetite and Co ferrite magnetic nanoparticles is described. The synthetic method relies on the adsorption of colloidal magnetite or Co ferrite particles onto the external surfaces of a Na-saturated clay mineral to give magnetic clay composites that can be converted easily, through ion exchange reactions, to valuable clay derivatives, e.g. organoclays, which maintain the magnetic properties of the parent composite. The magnetic solids were characterized by XRD, EPR, Mössbauer, magnetic measurement and TEM techniques.

The use of organoclays as adsorbents in the remediation of polluted water has been the subject of many recent studies. In the present work, a Tunisian smectite modified with two cationic surfactants was used as an adsorbent to examine the adsorption kinetics, isotherms and thermodynamic parameters of fluoride ions from aqueous solution. Various pH values, initial concentrations and temperatures have been tested. Two simplified kinetic models, first-order and pseudo-second-order, were used to predict the adsorption rate constants. It was found that the adsorption kinetics of fluoride onto modified smectites at different operating conditions can best be described by the pseudo-second-order model. Adsorption isotherms and equilibrium adsorption capacities were determined by the fitting of the experimental data to well known isotherm models including those of Langmuir and Freundlich. The results showed that the Langmuir model appears to fit the adsorption better than the Freundlich adsorption model for the adsorption of fluoride ions onto modified smectites. The equilibrium constants were used to calculate thermodynamic parameters, such as the change of free energy, enthalpy and entropy. Results of this study demonstrated the effectiveness and feasibility of organoclays for the removal of fluoride ions from aqueous solution.

Organo-bentonites were prepared using a bentonite and an aqueous cetyltrimethylammonium hydroxide solution. The ratio of the surfactant (in mmoles) to the cation exchange capacity varied from 0.5 to 20, with 20 being the highest ratio ever reported in the literature. At high surfactant to cation exchange capacity ratios, the interlayer spacing increased to 3.75 nm due to the formation of a paraffin-type bilayer of surfactant cations, which was shown to be mainly in gauche conformations using solid state 13C CP/NMR. When the exchange reaction was carried out in a methanol-water mixture, the expansion of the organo-bentonites depended on the concentration of methanol (% by volume). The decomposition temperatures of the organic cations depended on the basal spacing of the organo-bentonites, and in situ X-ray diffraction revealed that the basal spacing of our organo-bentonites was stable up to 210°C. Above this temperature, the basal spacing shrunk to 1.47 nm due to decomposition of the surfactants.