Intercalation and exchange reactions of clay minerals and non-clay layer compounds

Presently, a large variety of layered materials are synthesized that are able to intercalate neutral guest molecules or to exchange inorganic and organic ions for interlayer ions. Several of these materials are also found as minerals.The intracrystalline reactivity of a few selected compounds will be described and compared to clay minerals:

Laser microprobe mass analysis (LAMMA) of pyridine adsorbed on some clay minerals from Turkey

Using laser microproble mass analysis (LAMMA), it is possible to characterize the inorganic composition of clays and to study adsorption phenomena. Natural sepiolite, (Na-sepiolite), montmorillonite and saponite samples from Anatolia (Turkey) have been investigated. All the clays gave different fingerprint mass spectra which allowed a quick estimation of the relative amounts of exchangeable cations as well as the trace contaminants and the homogeneity of their distribution. The adsorption behaviour of these clays for pyridine was also studied and it appeared that pyridine molecules penetrated the inner layers, as well as being adsorbed on the external surface.     

Release of cationic drugs from loaded clay minerals

The adsorption of promethazine chloride [10-(2-dimethylammonium propyl) fenothiazine chloride] and buformin hydrochloride (1-butylbiguanidine chloride) on montmorillonite was studied in previous work. The present article focuses on the desorption of these molecules from their organocomplexes in a medium of artificial intestinal juice (pH 7.0 ± 0.1) at the temperature of the human body (37 ± 0.5 °C). The desorption was investigated by kinetic studies, basal spacing measurements and Fourier transform IR studies. Important quantitative differences were observed: buformin, which adsorbed in a monolayer coverage, exhibited a very high desorption rate, whereas promethazine formed a pseudotrilayer arrangement and showed a lower dissolution rate. Received: 20 January 2001 Accepted: 8 March 2001     

Removal of diphenhydramine from water by swelling clay minerals

Frequent detection of pharmaceuticals in surface water and wastewater attracted renewed attention on studying interactions between pharmaceuticals and sludge or biosolids generated from wastewater treatment. Less attention was focused on studying interactions between pharmaceuticals and clay minerals, important soil and sediment components. This research targeted on investigating interactions between diphenhydramine (DPH), an important antihistamine drug, and a montmorillonite, a swelling clay, in aqueous solution. Stoichiometric desorption of exchangeable cations accompanying DPH adsorption confirmed that cation exchange was the most important mechanism of DPH uptake by the swelling clay. When the solution pH was below the pK(a) of DPH, its adsorption on the swelling clay was less affected by pH. Increasing solution pH above the pK(a) value resulted in a decrease in DPH adsorption by the clay. An increase in d(001) spacing at a high DPH loading level suggested interlayer adsorption, thus, intercalation of DPH. The results from this study showed that swelling clays are a good environmental sink for weak acidic drugs like DPH. In addition, the large cation exchange capacity and surface area make the clay a good candidate to remove cationic pharmaceuticals from the effluent of wastewater treatment facilities.     

Polarographic reduction behaviour of clay minerals

Suspensions of the clay minerals bentonite, kaolinite illite and chlorite have been examined polarographically and reduction waves found. The differences in their behaviour, with and without the addition of surface active reagents, are reported.     

Ultrathin hybrid films of clay minerals

Smectites or swelling clay minerals are naturally occurring nanomaterials that can be fully delaminated to elementary clay mineral platelets in dilute aqueous dispersion. This review article gives an overview of the recent progress on how the elementary clay mineral platelets can be reorganized in monolayered or multilayered hybrid nanofilms by layer-by-layer assembly or the Langmuir-Blodgett technique. In the latter case one hybrid layer consists of one layer of elementary clay mineral platelets with a theoretical thickness of 0.96 nm, covered on one side by amphiphilic cations. The organization of the elementary clay mineral platelets and that of the adsorbed amphiphilic cations in the nanofilms has been studied in great detail by ATR-FTIR, UV-Vis and fluorescence spectroscopy, XRD and AFM. The nanofilms carry functional properties, such as chirality, optical nonlinearity and magnetism, which are due to the nature of the amphiphilic cations and to the organization of both the amphiphilic molecules and the elementary clay mineral platelets.     

Thermal investigation of acid-activated clay minerals

Samples of the clay mineral from the Çanakkale reserve in Turkey were activated with sulphuric acid under three different sets of conditions. DTA and TG curves of both natural and activated samples were then obtained and compared with one other.     

Adsorption of nitrobenzene andn-pentanol from aqueous solution on hydrophilic and hydrophobic clay minerals

The sorption of nitrobenzene andn-pentanol from dilute aqueous solution on swelling clay minerals and their organophilized derivatives (organo clays) was studied. Adsorption excess isotherms were obtained by the immersion method. The basal spacings of the clay minerals were determined by X-ray diffraction measurements. By combining these two independent methods, composition and structure of the interlamellar space could be calculated. On the hydrophilic surface of montmorillonite negative adsorption of the organic component was observed at low molar fractions of nitrobenzene or pentanol, i.e., water was preferentially adsorbed. On organophilized montmorillonite and vermiculite adsorption of nitrobenzene and pentanol was positive over the whole range of liquid composition. The amount of interlamellar alkyl chains which is determined by the surface charge of clay mineral inversely affected the adsorption of both solutes.     

Infrared study of influence of temperature on clay minerals

The effect of temperature on the infrared absorption bands of different clay minerals has been investigated with a view to identify the thermal transformation occurring between 30 and 1000°C.     

An x-ray diffraction study of some clay minerals of the eastern caribbean,west indies

X-Ray diffraction patterns were run on 12 soil-clays from Antigua, Dominica, Grenada, Trinidad and St. Vincent, West Indies. The d spacings of the diffraction maxima of these soil-clays saturated with Mg²⁺ and K⁺ cations were used for identification of the clay minerals present. The criteria for species differentiation was obtained by diagnostic diffraction maxima from clays specially treated with ethylene glycol and heat treatment up to 550°C.     

Sorption and immobilization of cellulase on silicate clay minerals

The interaction of organic molecules with mineral surfaces is a subject of interest in a variety of disciplines. Enzymes are able to be sorbed and immobilized by clay minerals and humic colloids in soil environment. The present study was done to elucidate some aspects of sorption and immobilization of cellulase on soil components by analysis of the sorption, and immobilization of cellulase on Avicel, a soil sample, illite, kaolinite, montmorillonite, and palygorskite. Palygorskite displayed the highest sorption capacity. Sorbents coated with hydroxyaluminum displayed significantly higher capacity than uncoated sorbents. The positive effects of Al(OH)(x) coating on sorption capacities of the different sorbents were not equal. The effect decreased in the order soil > palygorskite > kaolinite > Avicel > montmorillonite > illite. The amount of sorbed cellulase desorbed from external surfaces of soil was quite low (about 16%), especially in coated samples (about 6%). X-ray diffraction analysis of K-montmorillonite and Ca-montmorillonite showed that Al(OH)(x) was intercalated between the montmorillonite layers. Immobilization of cellulase on the sorbents did not result in expansion of their crystal structures. Therefore, it may be concluded that the amount of cellulase immobilized on internal surfaces of the sorbents was negligible.     

Preferential adsorption of extracellular polymeric substances from bacteria on clay minerals and iron oxide

The adsorption of extracellular polymeric substances (EPS) from Bacillus subtilis on montmorillonite, kaolinite and goethite was investigated as a function of pH and ionic strength using batch studies coupled with Fourier transform infrared (FTIR) spectroscopy. The adsorption isotherms of EPS on minerals conformed to the Langmuir equation. The amount of EPS-C and -N adsorbed followed the sequence of montmorillonite>goethite>kaolinite. However, EPS-P adsorption was in the order of goethite>montmorillonite>kaolinite. A marked decrease in the mass fraction of EPS adsorption on minerals was observed with the increase of final pH from 3.1 to 8.3. Calcium ion was more efficient than sodium ion in promoting EPS adsorption on minerals. At various pH values and ionic strength, the mass fraction of EPS-N was higher than those of EPS-C and -P on montmorillonite and kaolinite, while the mass fraction of EPS-P was the highest on goethite. These results suggest that proteinaceous constituents were adsorbed preferentially on montmorillonite and kaolinite, and phosphorylated macromolecules were absorbed preferentially on goethite. Adsorption of EPS on clay minerals resulted in obvious shifts of infrared absorption bands of adsorbed water molecules, showing the importance of hydrogen bonding in EPS adsorption. The highest K values in equilibrium adsorption and FTIR are consistent with ligand exchange of EPS phosphate groups for goethite surface. The information obtained is of fundamental significance for understanding interfacial reactions between microorganisms and minerals.     

Effect of grinding on thermal reactivity of ceramic clay minerals

The effect of grinding on thermal behavior of pyrophyllite and talc as commonly used ceramic clay minerals was investigated by DTA, TG, emanation thermal analysis (ETA), B.E.T. surface area (s.a.) measurements, X-ray diffraction (XRD) and scanning electron microscopy (SEM). A vibratory mill was used in this study, grinding time was 5 min. It was found that the grinding caused an increase in surface area and a grain size reduction of the samples. From TG and DTA results it followed that grinding caused a decrease of the temperature at which the structure bound OH groups released. The formation of high temperature phases was enhanced with the ground samples. For the ground talc sample the crystallization of non-crystalline phase into orthorhombic enstatite was observed in the range of 800°C. For ground pyrophyllite a certain agglomeration of grains was observed in the range above 950°C. Moreover, for both clays the ETA characterized a closing up of subsurface irregularities caused by grinding as a decrease of the emanation rate in the range 250–400°C. The comparison of thermal analysis results with the results of other methods made it possible to better understand the effect of grinding on the ceramic clays.     

Adsorption of Pseudomonas putida on clay minerals and iron oxide

Adsorption of Pseudomonas putida on minerals including montmorillonite, kaolinite and goethite was studied. The adsorption isotherms of P. putida on the examined minerals conformed to the Langmuir equation. The amount of P. putida adsorbed followed the order: goethite > kaolinite > montmorillonite. A greater extent of P. putida adsorption on minerals was observed in the range of temperature from 15 to 35 °C. The adsorption of P. putida on minerals decreased with the increase of pH from 3.0 to 10.0. Magnesium ion was more efficient than sodium ion in promoting P. putida adsorption on minerals. The results suggest that electrostatic interactions play a vital role in P. putida adsorption by soil colloidal factions. The information obtained in this study is of fundamental significance for the understanding of the survival and transport of bacteria in soil systems.     

Sorption of Cs,Pu and Am on clay minerals

Performance assessment of radioactive waste disposal requires modeling of long-term migration of radionuclides through the engineered barriers and the geological environment. The chemical complexity of sorption-desorption processes is usually reduced to integrated parameter distribution coefficients (K _d ). There are a great number of publications on K _d determination, however, the existing data on K _d of radionuclides on different geological materials are for general understanding only and are not very useful for performance assessment, since changes of the geological conditions result in variability of K _d values by two orders of magnitude. In order to obtain realistic sorption data sets for safety relevant radionuclides present in a cement/concrete based repository some preliminary studies were carried out. The development of sorption database for the near-surface repository was started with measurements of cesium, plutonium and americium K _d values. Several experiments were performed in order to determine the chemical composition of cement water which could originate from infiltration of precipitation and from contact of groundwater with concrete. More than 100 batch sorption experiments were conducted with two clay samples. Cs, Pu and Am K _d values were determined for rainwater, groundwater and cement-water of different chemical compositions. Cs, Pu, Am K _d values ranged from 450 to 9700, from 15000 to 21000 and 15000 to 80000 ml/g, respectively. Changes in the geochemical conditions resulted in the variability of Cs, Pu and Am K _d values.     

Electrodeposition of mercury film on electrodes modified with clay minerals

A new type of carbon paste electrode modified with clay mineral and covered with a mercury film is presented in this work. Electrodeposition of the mercury film was performed on the carbon paste electrode modified with montmorillonite. The mercury film was deposited by both electrodeposition in situ and a preliminary electrodeposition. The pre-deposited film of mercury showed to be suitable for anodic stripping voltammetry. An open-circuit sorption of Cd, Pb, and Cu with subsequent anodic stripping voltammetry exhibited higher current responses of metals. Besides the enhanced sensitivity superior separation of the current responses during a simultaneous stripping of metals is expected to be achieved by means of the newly prepared electrode. Presented at the 57th Congress of Chemical Societies, Tatranské Matliare, 4–8 September 2005.     

Ion exchange of some transition metal cations on hydrated titanium dioxide in aqueous ammonia solutions

The adsorption of transition metal cations on hydrated titanium dioxide in complexing ammonia and amine solutions has been studied as a function of ammonia (amine) concentration. The relationships between the distribution coefficients and ammonia concentration as well as the effects of various amines on sorption of transition metals indicate that a coordinate bond is formed between the metal ions and the hydroxy groups of the sorbent. The distribution coefficients of silver(I) and cobalt(III), which form strong ammonia complexes in aqueous solutions, decrease with increasing concentration of ammonia already at concentrations exceeding 10^–3. mol·dm^–3. Cations of zinc, manganese and mercury which form much weakerammonia complexes do not exhibit any effect of ammonia concentration in the whole range investigated. In the case of sorption of macroamounts of ammonia or amine complexes of silver, the molecular sieve effect plays an important role. The differences in the affinity of hydrated titanium dioxide for ammonia solvates of various transition metal ions can serve as a tool for effective separation of these ions in ammonia solutions.