In alkaline media and at 70°C dilute suspensions of ferrihydrite transformed to goethite between pH 11.2 and 14 and to a mixture of goethite and hematite above and below this pH range. Increasing the temperature of the transformation or the concentration of the suspension reduced the pH range in which goethite alone formed. The morphology of goethite was chiefly a function of the pH of the system. Acicular crystals formed at all pHs and exclusively above pH 12.2. Epitaxial twinned crystals predominated at pHs below 11, and twins free from hematite formed at higher pHs. Increasing the suspension concentration, ionic strength, or temperature extended the pH range over which twinned crystals formed. Electron micrographs showed that twins formed mainly during the initial stage of the transformation, whereas acicular crystals formed over a longer period. Thus, the twins appeared to nucleate in the ferrihydrite; nucleation of acicular particles took place in solution.

The hydrolysis of aluminum-tri-(sec-butoxide), ASB, in ionic and nonionic media is shown to be a useful method for the synthesis of aluminum minerals. Infrared and X-ray analysis were used to identify the reaction products. Pseudoboehmite is formed at low water to aluminum ratios. At higher water content, transformation of pseudoboehmite occurs with bayerite as the final phase. Dawsonite-type minerals are produced when ASB is hydrolyzed in the presence of sodium, potassium, or ammonium bicarbonate. Infrared evidence suggests that the carbonate group is more perturbed than indicated by the proposed crystal structure. A compound with a structure like the pyoaurite-sjögrenite group was obtained when ASB reacted with a lithium carbonate solution. The infrared spectrum indicates the possible existence of bicarbonate and carbonate ions between the brucite-like layers.

Electron microscope microprobe analysis (EMMA) has been applied to the determination of the elemental compositions of the kaolinite particles (Mg, Al, Si, K, Ti and Fe) contained in the 0·2-0·3 µm e.s.d., the 0·9-1·0 µm e.s.d. and the 1·9-2·0 µm e.s.d. fractions of an English kaolin and an American kaolin. Particles with masses as small as 10-13 g were analysed. An EMMA-4 instrument (A.E.I. Ltd.) equipped with linear fully focussing spectrometers was used. The ratio method of analysis was employed. The operating procedures used to obtain the required high experimental precision in the measurement of Al:Si atom ratio are discussed.

Statistical analysis of the results gives the estimated mean and spread of the Al:Si atom ratios. In the English kaolin the mean Al:Si atom ratio differs from the ideal 1:1 at the 0·05 significance level. There is evidence for a variation in composition from kaolinite particle to kaolinite particle in the 1·9-2·0 µm fraction of each kaolin. In the 0·9-1·0 µm fractions, the mean Fe:Si atom ratio was close to 0·002 showing the presence of iron in the kaolinite structure. The mean K:Si ratio was about 0·002 which would be equivalent to 1 unit muscovite layer associated with a 0·175 µm thick kaolinite particle. In the American clay the Ti:Si atom ratio was 0·002 suggesting that some 12 per cent of the 'titania' found by conventional chemical analysis was associated with the kaolinite particles either as titania itself or as an isomorphous substituent.

Steamboat Springs, Nevada, an area of present-day hot springs, clearly illustrates the genetic dependence of some kaolin deposits on hot-spring activity. Andesite, granodiorite and arkosic sediments are locally altered at the land surface to siliceous residues consisting of primary quartz and anatase, plus opal from primary silicates. These siliceous residues commonly exhibit the textural and structural features of their unaltered equivalents. Beneath the siliceous residues, kaolin and alunite replace primary silicates and fill open spaces, forming a blanketlike deposit. Beneath the kaolin-alunite zone, montmorillonite, commonly accompanied by pyrite, replaces the primary silicates. On the ground surface, the same alteration mineral zones can be traced outward from the siliceous residue; however, hematite rather than pyrite accompanies montmorillonite.

Chemical analysis indicates that sulfuric acid is the active altering agent. The acid forms from hydrogen sulfide that exsolves from deep thermal water, rises above the water table and is oxidized by sulfur-oxidizing bacteria living near the ground surface. This acid dissolves in precipitation or condensed water vapor and percolates downward destroying most of the primary minerals producing a siliceous residue. Coincidence of the water table with the downward transition from siliceous residue to kaolin-alunite signifies decreasing hydrogen metasomatism because of dilution of descending acid by ground water.

In hot-spring areas, beds of siliceous sinter deposited at the surface by hypogene thermal water look, superficially, like areas of surficial acid alteration. Features diagnostic of a surficial alteration are the relict rock structures of a siliceous residue and a kaolin-alunite zone immediately beneath.

Interlayer K in muscovite, biotite, phlogopite, illite and vermiculite-hydrobiotite samples was replaced by cation exchange with Na. The rate and amount of exchange varied with the mineral and the level of K in solution.

Essentially, all the K in muscovite, biotite, phlogopite and vermiculite was exchangeable when the mass-action effect of the replaced KT was reduced by maintaining a very low level of K in solution. The time required for this exchange varied from < 10 hr with vermiculite to > 45 weeks with muscovite. Only 66% of the K in the illite was exchangeable under these conditions. When the replaced K was allowed to accumulate in the solution, the amount of exchange was determined by the level of K in solution required for equilibrium. These levels decreased with the degree of K-depletion and with the selectivity of the mica for K. The order of selectivity was muscovite > illite > biotite > phlogopite > vermiculite. Decreasing the K in solution from 10 to 7 ppm increased the exchangeable K in biotite from 30 to 100%. A K level of only 0.1 ppm restricted the exchange of K in muscovite to 17%.

A decrease in layer charge was not required for K exchange, but a decrease did occur in K-depleted biotite and vermiculite. Muscovite with the highest layer charge (247 meq/100 g), least expansion with Na (12.3Å), and least sensitivity to solution pH had the highest selectivity for K and the slowest rate of exchange. The K in vermiculite was the most readily exchangeable.

Due to the importance of clay minerals in metal sorption, many studies have attempted to derive mechanistic models that describe adsorption processes. These models often include several different types of adsorption sites, including permanent charge sites and silanol and aluminol functional groups on the edges of clay minerals. To provide a basis for development of adsorption models it is critical that molecular-level studies be done to characterize sorption processes. In this study we conducted X-ray absorption fine structure (XAFS) and electron paramagnetic resonance (EPR) spectroscopic experiments on copper (II) sorbed on smectite clays using suspension pH and ionic strength as variables. At low ionic strength, results suggest that Cu is sorbing in the interlayers and maintains its hydration sphere. At high ionic strength, Cu atoms are excluded from the interlayer and sorb primarily on the silanol and aluminol functional groups of the montmorillonite or beidellite structures. Interpretation of the XAFS and EPR spectroscopy results provides evidence that multinuclear complexes are forming. Fitting of extended X-ray absorption fine structure spectra revealed that the Cu-Cu atoms in the multinuclear complexes are 2.65 Å apart, and have coordination numbers near one. This structural information suggests that small Cu dimers are sorbing on the surface. These complexes are consistent with observed sorption on mica and amorphous silicon dioxide, yet are inconsistent with previous spectroscopic results for Cu sorption on montmorillonite. The results reported in this paper provide mechanistic data that will be valuable for modeling surface interactions of Cu with clay minerals, and predicting the geochemical cycling of Cu in the environment.

White saponite occurs in joints and open fracture zones in metamorphosed dolomitic limestone near Ballarat, California. The saponite appears to have formed by hydrothermal alteration, possibly during Pliocene times. The material shows a 06l X-ray powder diffraction peak at 1.529 Å, A12O3 and MgO contents of about 4.4 and 23.5%, respectively, and a half-cell octahedral atoms summation value of about 2.82. The saponite appears to consist of a single, uniform clay species; the main impurities are fine shards of diopside and tremolite. The infrared and thermal properties of the Ballarat saponite are similar to those of the Allt Ribhein saponite. It has a lower water-holding capacity than montmorillonite and is characterized by lower Atterberg limits and expansion pressures and higher compaction densities. The apparent density of the saponite, 2.865 g/cm3, is greater than that of montmorillonite. This saponite is available from the Source Clays Repository of The Clay Minerals Society.

The distribution of clay minerals in Recent sediments can be explained by the relative stability of the clays. The rates of particle aggregation for three clays were determined in the laboratory in synthetic estuarine solutions; from the kinetic studies stability values were calculated. The results indicate that illite is more stable than kaolinite which is more stable than montmorillonite. The distribution of the clays in the Pamlico River Estuary can be explained on the basis of relative clay stability where kaolinite which aggregates rapidly (relatively unstable clay) is found upstream of illite.

Saponite, hectorite, and laponite have been pillared with cationic Al clusters, and special attention has been given to the solution chemistry or Al. Pillared saponite is obtained after exchange with refluxed Al solutions; while for hectorite, Al solutions treated with ammonium acetate give a pillared product with 1.8–1.9 nm spacing and thermal stability up to 873 K. In both types of solutions, the Keggin ion Al cluster is a minority species or totally absent. The typical 1.8–1.9 nm spacing is only obtained after washing. The quality of the pillared material can be judged from its thermal stability, its surface area, and the width of the d001 line before and after pillaring. The width should not exceed 0.3 nm before calcination and 0.5 nm after calcination. The latter criterion reflects the importance of the crystallinity of the parent clay for successful pillaring. Pillaring in concentrated conditions occurs by a combination of ion exchange and precipitation of Al and gives materials that exhibit poor thermal stability.

The structural transformation of dioctahedral 2:1 layer silicates (illite, montmorillonite, glauconite, and celadonite) during a dehydoxylation-rehydroxylation process has been studied by X-ray diffraction. thermal analysis, and infrared spectroscopy. The layers of the samples differ in the distribution of the octahedral cations over the cis- and trans-sites as determined by the analysis of the positions and intensities of the 11l, 02l reflections, and that of the relative displacements of adjacent layers along the a axis (c cos ß/a), as well as by dehydroxylation-temperature values. One illite, glauconite, and celadonite consist of trans-vacant (tv) layers; Wyoming montmorillonite is composed of cis-vacant (cv) layers, whereas in the other illite sample tv and cv layers are interstratified. The results obtained show that the rehydroxylated Al-rich minerals (montmorillonite, illites) consist of tv layers whatever the distribution of octahedral cations over cis- and trans-sites in the original structure. The reason for this is that in the dehydroxylated state, both tv and cv layers are transformed into the same layer structure where the former trans-sites are vacant.

The dehydroxylation of glauconite and celadonite is accompanied by a migration of the octahedral cations from former cis-octahedra to empty trans-sites. The structural transformation of these minerals during rehydroxylation depends probably on their cation composition. The rehydroxylation of celadonite preserves the octahedral-cation distribution formed after dehydroxylation. Therefore, most 2:1 layers of celadonite that rehydroxylate (~75%) have cis-vacant octahedra and, only in a minor part of the layers, a reverse cation migration from former trans-sites to empty octahedra occurred. In contrast, for a glauconite sample with a high content in IVA1 and VIAl the rehydroxylation is accompanied by the reverse cation migration and most of the 2:1 layers are transformed into tv layers.

Hydrothermal syntheses were performed at various pH values and temperatures to induce variability in kaolinite defect density. Temperature of synthesis ranged from 200 to 240°C, for 21 d. Initial pH at room temperature ranged from 0.5 to 14. The starting material was a hydrothermally treated gel, with an atomic Si/Al ratio of 0.93, partly transformed into kaolinite.

Kaolinite was obtained for a wide range of pH. Although no influence of temperature on “crystallinity” (i.e., defect density) was observed, the effect of pH was important. A continuous series was obtained from a low-defect kaolinite, with high thermal stability and a hexagonal morphology for the most acidic final pH, to a high-defect kaolinite, with low thermal stability and lath shape for the most basic final pH. These variations of kaolinite properties appear related to the pH dependence of kaolinite surface speciation. Increasing pH value results in increased cation adsorption on the kaolinite external surfaces and increases in the elongation of particles.

The diffusion of exchanged Yb, Ho, and Eu from interlayer positions in montmorillonite was studied using infrared spectroscopy (IR), X-ray powder diffraction, and cation-exchange measurements. Dehydration of exchanged montmorillonite between 100° and 280°C caused the ions to diffuse into the hexagonal rings of surface oxygens. Subsequent migration into vacant octahedral sites was small regardless of the radius of the cation. Considerable ion fixation in excess of the cation-exchange capacity of the clay was observed at 20°C in both water and a 1:1 water:95% ethanol mixture. Evidence for hydrolysis as a possible mechanism for cation fixation was obtained by observing frequency shifts for deuterated hydroxyl groups using IR spectroscopy. A major IR band centered at 2680 cm−1 was observed for all three lanthanide-exchanged montmorillonites studied and assigned to the OH-stretching frequency of a lanthanide hydroxide. This band intensified on heating at 300°C for 1 hr. An IR band between 690 and 710 cm−1 also was observed for all three lanthanide-exchanged montmorillonites and was assigned to a lanthanide-hydroxyl deformation mode. No hydrolysis was observed for Na-montmorillonite, as expected from the very low hydration energy of Na+.

Micas are described from the kaolin type Tertiary weathering crusts formed on granites and gneisses of Lower Silesia, Poland. In the weathering crust, large scale processes of transformation of micas (muscovite, biotite) take place. Weathering of micas is a gradual transformation of their structures by removal of the mobile cations Mg2+ Fe2+ Fe3+ and finally K +. Muscovite transforms into kaolinite through the intergrowths of two phases, mica and kaolinite. A degradation series, muscovite → mica/montmorillonite → montmorillonite → kaolinite also is observed. Biotite passes directly into kaolinite, but at higher concentrations of K and Al one observes the following sequence of biotite degradation: biotite → dioctahedral mica rich in Fe → dioctahedral mica poor in Fe → kaolinite. This process involves the exchange of Mg2+ and then Fe2+ of octahedral layers by Al3+ less mobile under weathering conditions. In the next stage of degradation, K + removal and kaolinite formation takes place. The micas representing different stages of this transformation, dark green, light-green, and silver-white, have been separated and investigated.

Weathering products formed on surfaces of both potassium and plagioclase feldspar (An70), which were continuously leached in a Soxhlet extraction apparatus for 140 days with 7·21 of distilled water per day at a temperature of approximately 78°C, are morphologically identical to natural products developed on potassium feldspars weathered under conditions of good drainage in the humid tropics. The new products, which first appear as tiny bumps on the feldspar surface, start to develop mainly at exposed edges but also at apparently random sites on flat cleavage surfaces. As weathering continues, the bumps grow outward from the feldspar surface to form tapered projections, which then develop into wide-based thin films or sheets. The thin sheets of many projections merge laterally to form one continuous flame-shaped sheet. The sheets formed on potassium feldspars may then roll to form tubes that are inclined at a high angle to the feldspar surface. Etch pits of triangular outline on the artificially weathered potassium feldspars serve as sites for development of continuous, non-rolled, hollow tubes. It is inferred from its morphology that this weathering product is halloysite or its primitive form. The product of naturally weathered potassium feldspars is halloysite · 4H2O.

The flame-shaped films or sheets formed on artificially weathered plagioclase feldspar do not develop into hollow tubes, but instead give rise to a platy mineral that is most probably boehmite. These plates form within the flame-shaped films, and with continued weathering are released as the film deteriorates. There is no indication from this experiment that platy pseudohexagonal kaolinite forms from any of these minerals under the initial stage of weathering.

Clays have played an important role in medicine since the dawn of mankind and are still applied widely as active ingredients and/or excipients in pharmaceutical formulations. Due to their outstanding properties of large retention capacity, swelling and rheological properties, and relative low cost, they have been used widely as advanced carriers for the efficient delivery of drugs by modifying their release (rate and/or time), increasing the stability of the drug, improving the dissolution profile of a drug, or enhancing their intestinal permeability. In addition, recent studies have shed new light on the potential of clay minerals in the nanomedicine field due to their biocompatibility, beneficial effects of clay nanoparticles on cellular adhesion, proliferation, and differentiation. Use as active ingredients and excipients are exerted via the oral and topical administration pathways. Skin drug delivery represents an attractive alternative to the oral route, providing local and/or systemic drug delivery. Due to their complex structures, however, most drugs penetrate the human skin only with difficulty. Enormous efforts have been invested, therefore, in developing advanced drug delivery systems able to overcome the skin barrier. Most strategies require the use of singular materials with new properties. In particular, and on the basis of their inherent properties, clay minerals are ideal candidates for the development of intelligent skin drug delivery systems. In this article, the properties of clay materials and their use in the skin-addressed pharmaceutical field are reviewed. A brief introduction of skin physiology and biopharmaceutical features of penetration by a drug through the skin layers is also included and is designed to shed light on the optimum properties of ideal nanosystems for advanced skin drug delivery. Special attention is devoted to the pharmacological functions of clays and their biomedical applications in pelotherapy, wound healing, regenerative medicine, antimicrobial, and dermocosmetics.

Integrated intensities of the fundamental modes of vibrations of ammonium in heat-treated, NH4+-exchanged swelling minerals permits (1) a quantitative determination of the amount of tetrahedral substitutions of Si4+ by M3+ in dioctahedral smectites, and (2) an estimate of the degree of interlayer surface heterogeneity in trioctahedral minerals to be made. This is possible because NH4+ cations balancing the negative charge of tetrahedral sites that are not influenced by an excess positive charge of the octahedral layer have a symmetry lower (probably C3v) than the usual tetrahedral Td symmetry of NH4+. In C3v symmetry the ν1 band is infrared active whereas it is only Raman active in Td symmetry. Protons left after deammoniating dioctahedral smectites with tetrahedral substitutions form interlayer silanol groups, the stretching vibration of which give a band that is distinct from that of octahedral OH-stretching modes.

Pierre shale samples from a thin stratigraphic zone within the contact aureole of the lamprophyric Waisen dike record changes due to thermal effects that are not influenced by detrital differences. Analyses of fixed-NH4, mineralogy, and Rock-Eval pyrolysis indicators of organic matter maturity provide new insights on the fixation process. Fixed-NH4 increases with the quantity of authigenic illite formed from illite/smectite, but the maximum fixation per unit of illite formed occurs within the “oil window” where thermal breakdown of organic matter is rapid. Extrapolation of these results to the burial diagenetic regime supports the potential use of fixed-NH4 as an indicator of organic maturity and hydrocarbon migration pathways.

The objective of this work was to prepare series of reduced-charge materials from different parent Li-saturated dioctahedral smectites, to investigate the effects of temperature, chemical composition and charge location in smectites on the charge reduction and to characterize reduced-charge smectites (RCSs) using methylene blue (MB) adsorption. The layer charge decrease, induced by Li fixation, is correlated with the trends in the spectra of MB-RCS dispersions in the visible region (VIS) spectra. Distribution of the negative surface charge of the clay minerals controls the distance between the adsorbed MB cations and thus affects the formation of MB dimers and higher agglomerates. Because each form of MB (monomer, dimer, higher agglomerate, J-aggregates) absorbs light at a different wavelength, the VIS spectra of MB depend sensitively on the charge density at the clay surface. Both cation exchange capacity (CEC) values and spectra of MB-clay dispersions clearly detect extensive reduction of the layer-charge density in reduced-charge montmorillonites (RCMs) upon Li-thermal treatment. The extent of charge reduction depends on the temperature of the thermal treatment, as well as on the octahedral charge of the montmorillonite. Reduction of the layer charge proceeds to a much lesser extent for smectites with mainly tetrahedral charge and high Fe content (Fe-rich beidellite and ferruginous smectite). Both CEC data and MB spectra detect only a slight decrease of the layer charge density, which relates to the low octahedral charge of these minerals. Following heating at higher temperatures (120-160°C), slightly higher Li fixation is indicated by CEC values; however, no charge reduction is confirmed by MB spectra. Release of protons accompanying Li+ fixation in Fe-rich smectites heated at 180 or 200°C was detected in the spectra of MB-clay dispersions and confirmed by potentiometric titrations.

X-ray diffraction, FTIR, and chemical analyses were performed on clay fractions (1–2 µm, <0.1 µm), separated by means of size fractionations and high-gradient magnetic separation techniques, from a Cryorthod developed in a chlorite-mica schist saprolite. Weathering of large phyllosilicates pre-existing in the saprolite involves physical fragmentation and mineralogical transformations. Chloritic minerals in the coarse fractions were the most affected by physical breakdown, while micas were generally preserved. As a consequence, a concentration of mica layers occurred in the coarse clay fraction, while chloritic residues accumulated in the fine clays. These residues exhibited the typical XRD pattern of hydroxy-interlayered intergrade minerals, but the interlayered contaminants were found to be mainly hydroxy-Mg cations. Further mineralogical transformations of the intergrade minerals involved the progressive removal of the hydroxide interlayered sheet and dissolution of chloritic layers. Illite/smectite mixed-layers were formed in the surface horizon of the soil profile. These processes were associated with a strong decrease in Fe and Mg contents in the clay fractions.

Adsorption by synthetic 2-line ferrihydrite and hematite of glyphosate and phosphate, separately and together, was compared with adsorption results for goethite, gibbsite and two kaolinites in order to determine adsorption differences and similarities, in particular competition and phosphate preference, of these variable-charge minerals. Hematite rapidly adsorbed both compounds, while adsorption by ferrihydrite was slow, in particular of glyphosate, probably because of very slow diffusion of the bulky glyphosate molecules into interior sites in ferrihydrite particles. Accordingly, the Langmuir adsorption capacity of glyphosate (GAC) was considerably smaller (1.85 µmol m−2)than GAC for hematite (2.61 µmol m−2). The phosphate adsorption capacities (PAC) for ferrihydrite and hematite were more alike, 2.91 µmol m−2 and 2.85 µmol m−2, respectively. Differences between surface coordination (mono- or bidentate) may also contribute to the observed differences but conflicting information about the nature of the surface complexes makes this a difficult contributary factor to assess. The minerals were found to exhibit great variation in extent of competition and phosphate preference. Little competition and phosphate preference characterized hematite adsorption, while phosphate almost completely outcompeted glyphosate on goethite; ferrihydrite adsorption fell between these extremes. These differences may be attributed to different numbers of common (competitive) and specific (selective) adsorption sites on the three Fe oxides with a decreasing number of common sites in the order: goethite>>ferrihydrite>hematite, i.e. almost all goethite sites are common but with strong phosphate preference, while most hematite sites are specific for either glyphosate or phosphate. Alternatively, the result may be explained by adsorption in more planes, e.g. glyphosate adsorption onto the inner-Helmholtz-plane-adsorbed phosphate. For all six minerals compared, desorption of glyphosate following phosphate addition was found to be significantly correlated with the difference between the amounts of phosphate and glyphosate adsorbed indicating that this difference may be used as a competition index for predicting the influence of phosphate on glyphosate adsorption.