Monochloroanilines and dichloroanilines are important reagents or chemical intermediates in the production of dyes, pharmaceuticals, and agricultural chemicals. These toxic compounds have a large tendency to accumulate in the environment and a low natural biodegradability, so improved methods to remove or sequester them are needed. Halloysite is used as an efficient adsorbent to remove toxic compounds, such as aniline, from aqueous solutions. The purpose of this study was to evaluate whether acid-activated halloysites from the “Dunino” (Poland) strip mine could be effective in the removal of not just aniline but also of its chloro-substituted forms from aqueous solutions. The composition, structure, and morphology of activated halloysites were characterized using the following methods: wavelength dispersive X-ray fluorescence analysis (WDXRF), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), Fourier-transform infrared spectroscopy (FTIR), and N2 adsorption-desorption analysis. The acidactivated halloysites had an increased ability to remove aniline and chloroanilines from aqueous solutions as the acid activation temperature was increased. This suggests that the acid activation temperature is an important factor that influences the ability of acid activated halloysites to adsorb aromatic amines (anilines) from water. The efficiency of aniline and chloroaniline removal by halloysite activated at 80°C reached maximum levels, especially for the removal of aniline and 4-chloroaniline. The adsorption isotherm data were best described by the Langmuir adsorption model. The values of the Langmuir adsorption constants were calculated using the inverse liquid chromatography method.

Layers of volcanic ash and Andosol soils derived from the ash may play an important role in preserving snow and ice as well as in the development of permafrost conditions in (a) the immediate vicinity of volcanoes at high elevations or at high latitudes and (b) land areas that are often distant from volcanic activity and are either prone to permafrost or covered by snow and ice, but have been affected by subaerial ash deposition. The special properties of volcanic ash are critically reviewed, particularly in relation to recent research in Kamchatka in the Far East of Russia. Of special importance are the thermal properties, the unfrozen water contents of ash layers, and the rate of volcanic glass weathering.Weathering of volcanic glass results in the development of amorphous clay minerals (e.g. allophane, opal, palagonite), but occurs at a much slower rate under cold compared to warm climate conditions. Existing data reveal (1) a strong correlation between the thermal conductivity, the water/ice content, and the mineralogy of the weathered part of the volcanic ash, (2) that an increase in the amounts of amorphous clay minerals (allophane, palagonite) increases the proportion of unfrozen water and decreases the thermal conductivity, and (3) that amorphous silica does not alter to halloysite or other clay minerals, even in the Early Pleistocene age (Kamchatka) volcanic ashes or in the Miocene and Pliocene deposits of Antarctica due to the cold temperatures. The significance of these findings are discussed in relation to past climate reconstruction and the influence of volcanic ash on permafrost aggradation and degradation, snow and ice ablation, and the development of glaciers.

The adsorption properties of clay minerals (e.g. montmorillonite and palygorskite) have been improved through chemical treatment methods. However, the addition of extra chemicals is often not friendly to the environment and powdered clay-mineral adsorbents are inconvenient for some applications. To overcome these drawbacks in the present study, granular montmorillonite-palygorskite adsorbents (GMPA) were successfully prepared using Na-alginate and thermal treatments to improve heavy metal removal from water. The properties of GMPA samples under different calcination temperatures were examined using thermogravimetric (TG) analysis, scanning electron microscopy (SEM), X-ray diffraction (XRD), and specific surface area (BET). The results indicated that loss of mass by GMPA relative to the untreated montmorillonite-palygorskite was due to the loss of water, adsorbed Na-alginate, and mineral decomposition during thermal treatment. Changes in the morphology and crystallinity were significant at calcination temperatures from 500°C to 1000°C. The layered morphology totally disappeared after calcination at 1000°C, while transformation of the montmorillonite and palygorskite to a non-crystalline material was almost complete at 800°C and new crystalline phases appeared. Calcination temperature had a significant influence on the specific surface areas and pore volumes of GMPA. Both the changes in texture and chemical structure affected Pb2+ and Cu2+ removal. The GMPA sample produced at a 600°C calcination temperature was the most promising adsorbent for heavy metal removal from water.

To control a vast spectrum of applications and processes, an understanding of the morphologies of clay mineral assemblies dispersed in aqueous or non-aqueous media is important. As such, the objective of this study was to verify the relationship between dispersion medium type and the size and morphology of the clay aggregates that are formed, which can increase knowledge on the assembly formation process. Scanning electron microscopy (SEM), X-ray diffraction (XRD), and Fourier-transform infrared (FTIR) spectroscopy were used in an attempt to describe kaolinite platelet organization in non-aqueous media and to compare it to the organization in aqueous media or in media with or without a selection of dissolved organic polymers. The SEM images indicated that the kaolinite platelet assembly process occurs during slow evaporation of the solvent. Because the experimental procedure was rigorously identical for all cases in this study, the SEM images compared how the effects of various media and environments on kaolinite platelet interactions can lead to different morphologies. Quite spectacular morphological differences were indeed observed between samples dispersed in aqueous and non-aqueous media, particularly when the kaolinite platelets were dispersed in an organic solvent with dissolved organic polymers. For kaolinite dispersed in water, only small aggregates were observed after slow evaporation. In contrast, large kaolinite booklets or vermiform aggregates were formed by slow solvent evaporation when kaolinite was first dispersed into some organic solvents. The aggregates were particularly large when an organic polymer was dissolved in the organic solvent. For example, kaolinite aggregates dispersed in a binary cyclohexane/toluene mixture with dissolved ethyl cellulose (EC) had top apparent surface areas (i.e. stacking length × width) of more than 3,000 µm2. Other dissolved polymers, such as polystyrene or the polysaccharide, guar gum, gave similar results. Kaolinite platelet aggregation resulted from face-to-face interactions as well as edge-to-face and edge-to-edge interactions. The XRD results showed that ethyl cellulose led to the formation of smaller kaolinite platelets with an increased tendency to form larger aggregates, which is due to the ability of EC to chemically interact with silanol and/or the aluminol groups of kaolinite.

Nuclear magnetic resonance (NMR) provides a powerful tool to describe local nuclear environments. In this work, unique structural information on kaolinite and on kaolinite dimethylsulfoxide (DMSO) intercalate were provided by solid-state 1H and 27Al magic-angle spinning (MAS) NMR. The interlayer chemistry of kaolinite (K) was examined by intercalating a select group of highly polar organic molecules or salts into kaolinite as a first step. Once the interlayer space is expanded, the intercalated compounds can be replaced in a second step. Intercalating DMSO into kaolinite to form the DMSO-K intercalate is, thus, a particularly useful first step toward the intercalation of a large variety of molecules, including polymers and ionic liquids. Well developed characterization methods are essential to define the structural modifications of kaolinite, and MAS NMR is a useful complement to other techniques. The use of 1H and 27Al MAS NMR for this purpose has been relatively rare. 1H NMR, nevertheless, can give unique information about kaolinite hydroxyls. Because quadrupolar interactions are sensitive to the local octahedral Al(III) geometry, solid-state 27Al NMR can follow subtle structural modifications in the octahedral sheet. In the present work, the 1H MAS NMR chemical shifts of KGa-1b were unambiguously attributed to the internal surface hydroxyls at 2.7 ppm and to the internal hydroxyls at 1.7 ppm. The 1H MAS NMR chemical shifts of the two methyl groups in DMSO-K are not equivalent and can be attributed to the 2.9 and 4.2 ppm peaks. The 27Al MAS NMR spectra of KGa-1b obtained under different magnetic fields revealed that most of the quadrupolar effects were highly reduced at 21.1 T, whereas the spectra at lower field, 4.7 T, were dominated by quadrupolar effects. The two octahedral Al(III) sites are not equivalent and can be distinguished in the low-field spectral simulation. Increased quadrupolar constants were observed and showed the major perturbations of the local Al symmetry that resulted from DMSO intercalation. Both the 1H and 27Al MAS NMR studies at different magnetic fields afforded important information about the local environments of the kaolinite hydroxyl groups and structural Al(III).