Organic matter present in clayey sediments may act as a cement between the clay particles as well as a blocking agent for the swelling of clay minerals like montmorillonite.

Removal of the organic matter is important when a clay sample is to be characterized by X-ray powder diffraction, or when it is to be separated into the composing minerals on the basis of differences in density.

Eight different methods for the removal of organic matter from a North Sea clay sample have been studied. Of all methods tried bromine oxidation was found to be the most effective.

The rates of release of Al by M NH4NO3 (pH 3) from minerals saturated with Al ions at pH 3 suggest that Al ions migrated from the surface layers and the matrix cores of kaolinite, montmorillonite, illite, and biotite, but only from the matrix core of muscovite mica. From the 0.25–0.5 μm kaolinite and montmorillonite, part of the ‘surface’ Al is released ‘instantaneously’ and the rest by first order kinetics, but the coarse 1.5–2.5 μm kaolinite has only the former component. From illite and biotite, ‘surface’ Al is released by ‘bulk diffusion’ kinetics suggesting the existence of disturbed peripheral layers of finite thickness. The diffusion coefficients, Dm, for the matrix core follow the trend: mica ≃ biotite > illite > montmorillonite > kaolinite.

Based on models proposed in previous work, the ionic composition of the ‘surface’ Al is calculated. This shows that (1) this composition varies according to the mineral from 3 to 100% Al3+, the remainder being in the hydrolyzed form, and (2) the apparent hydrolysis constants are different for each mineral and significantly different from those of Al ions in solution.

The dispersion of clays is of great importance in determining various soil properties such as hydraulic conductivity. A procedure which involves fixing followed by embedding of clay particles in an epoxy resin is described. This procedure enables the observation of cross sections of clay tactoids under a transmittance electron microscope, and the determination of the number of plates per tactoid. The use of the procedure for the determination of the relation between the exchangeable sodium percentage (ESP) and tactoid size in suspensions of a Na/Ca bentonite system is presented. It was demonstrated that even at ESP 5 significant dispersion already occurs, the average number of plates per tactoid being 6.6 as compared to 16.1 at ESP 0.

The compound Mg2+-Al3+-(Fe(CN)6)4−, with a structure similar to hydrotalcite Mg6Al2(OH)16CO3 ·4H2O, is prepared by a coprecipitation method. Chemical, thermal, and X-ray analysis of the compound lead to the formula: $(M{g}_{0.741}A{l}_{0.259}(OH{)}_2)((F{e}^{II}(CN{)}_6{)}_{0.067}(C{O}_3{)}_{0.002}(H_{2}O{)}_{1.05})$

The compound is dehydrated at 100° to 250°C, and the adsorption of N2, O2, CO2, and H2 on it is measured at −196°C to room temperature by the volumetric method. The water is removed reversibly from 100° to 200°C, and the interstices after dehyration act as sites of adsorption. When dehydration is carried out at 150°C, the adsorptive activity reaches a maximum. Adsorption isotherms of N2 and O2 at −196°C and of CO2 at room temperature are of the Langmuir type, and the saturated amounts of N2, O2, and CO2 adsorbed are 96.3, 65.2, and 91.8 ml (STP)/g, respectively.

Adsorption isotherms of N2 and O2 at room temperature are of the Henry type. The amount of O2 adsorbed is about 67% of that of N2. The isosteric heats of adsorption at room temperature of N2, O2, and CO2 are 5.1, 4.8, and 11.0 kcal/mol, respectively. A dehydrated product of a Mg2+-Al3+-CO32− compound does not permit adsorption of CO2 at room temperature, but permits the adsorption of H2O. Hence, it has a molecular sieve effect. No adsorption of H2 is observed in any of the compounds tested.

The low temperature synthesis of iron silicate minerals with clay structures is possible at surface temperatures only under reducing conditions. Under oxidizing conditions clay minerals could not be synthesized. Instead quartz and quartzine were found in these X-ray amorphous Fe III hydroxide-silica precipitates after 14 days at low temperatures (20° and 3°C) as well as geothite or X-ray amorphous iron hydroxides. Only from solutions containing Fe-II could the different iron-containing clay minerals be built up within days at low temperatures. The presence of Fe-II enables an octahedral layer of the brucite-gibbsite type to be formed. This is necessary for the bidimensional orientation of SiO4-tetrahedra leading to clay mineral formation. The presence of Fe2+- and/or Mg2+-ions is necessary for the formation of the Al3+- and Fe3+-containing octahedral layers. The reducing conditions were obtained in the experiments by addition of dithionite. With a high content of silica (ca. 20 ppm SiO2,7 ppm Fe) nontronite and lembergite, the di-Fe-III and tri-Fe-II octahedral, three-layer silicates, were built up in several days at low temperatures. With a lower silica content, that is, a lower Si/Fe ratio (15 ppm SiO2 and 20 ppm Fe), the two-layer silicate minerals greenalite and chamosite could be synthesized. A higher Mg content and more reducing conditions in the solutions favored the tri- as well as dioctahedral chamosite synthesis.

The conditions of formation of recent naturally formed nontronite fit well with the synthesis conditions. Chamosites in sedimentary iron ores are characterized by a low content of SiO2, between 15–30% SiO2. This low content of silica cannot be the result of primary precipitation from seawater. The iron and silica ratio in seawater or in river waters would lead to a precipitation of ~60% SiO2 in the iron hydroxide precipitates. A probable origin for chamosite iron ores, which explains the low SiO2 content, is diagenesis of the lateritic weathering crust. Indeed, investigations of recent tropical shoreline sediments and in particular their trace element content confirm that chamosite minerals have formed diagenetically from lateritic particles in reducing sediments.

The effect of pH, time and temperature on the interaction of zinc with acid and base saturated dickites has been investigated. Increase in pH resulted in an increase in adsorption of zinc in the higher concentration range. The adsorption increased rapidly and then slowly with increase in the time of interaction. The variation of rate constants and the half times of reaction suggested an exchange process controlled by film and possibly particle diffusion and thereafter fixation processes. The inferences found support from the nature of adsorption isotherms. Temperature affected adsorption with exothermic interactions. The activation energy of adsorption of zinc on Na-dickite was 14.0 kcal mole−1.

The structure and behavior of homoionic bentonites was markedly affected by a grinding procedure often applied to clays. The main changes observed on clay powders were the breakage of weakly bound large aggregates, the reduction in the tactoids’ thickness by delamination, the reduction in the plates’ area, and the formation of colloidal matter. The tendency of clays to form secondary aggregates in aqueous suspensions is probably due to the exposure of active broken edges following grinding.

The mild mechanical stress applied increased both the rate and the amounts of parathion sorbed by clays from an apolar solvent. The effect of grinding on parathion adsorption in aqueous clay suspensions seems to be a rate effect.

The flint-clay facies, originally proposed from widespread stratigraphie evidence, is represented by four of its six members within a single commercial deposit of Cheltenham refractory clay in Missouri. Scan electron micrographs show progressive changes in texture from plastic refractory clay (as in ball-clay “swirl” texture) through semi-plastic, semi-flint, to typical flint clay (recrystallized, well-ordered kaolinite). Micrographic evidence supports the interpretation of the origin of the Cheltenham clay earlier made from field and macroscopic evidence. Source material from nearby residual, weathered clay was transported into paludal basins, “digested,” partly recrystallized to kaolinite, brecciated and reconsolidated, essentially completed before being covered by younger Pennsylvanian-age sediments.

Lepidocrocite was identified associated with mica particles and in the clay fraction of two well-drained Ontario soils developed on a granite and a granite-gneiss. The occurrence of lepidocrocite is rare outside the tropics and there are no reports on its existence in well-drained soils.

Infrared spectra of two minerals; Urkut quartz (Hungary) and a Swedish feldspar, of different origin with different physical characteristics and crystallinity were studied. Samples were taken after appropriate grinding, and infrared spectra, X-ray powder diffraction and water vapor absorption measurements were made along with electronmicrographs. Quantitative conclusions were drawn from changes of particle size and the ratio of bands of the Si—O groups and also the degree of crystallinity and changes of the particle size, respectively.

Treating NH4-bentonite with diazomethane results in methylation of adsorbed ammonium with the formation of the tetramethylammonium ion. This ion, which can be completely removed through ion exchange, is distinguished in the IR spectrum by a strong band at 1480 cm−1 due to CH3 group bending vibrations. X-ray diffractograms, CEC, and surface area of the clay are not modified by treatment with diazomethane.

Several new salt intercalation complexes of halloysite have been prepared and characterized using X-ray powder diffraction techniques taking into account both the position and the shape of the d001 peaks. The amount of intercalated ion in some fully complexed halloysites has been directly determined using conventional analytical techniques. The results show that less than half of the theoretical amount of salt is intercalated into the clay; the amount of salt depending on its nature and, where hydrolyzable ions are present, on the pH. Infrared spectra taken of some complexes give an indication of the nature of the interaction within interlayer space and elsewhere. The interactions are weak and are either dipolar attractions or hydrogen bonds. The ions which show the greatest tendency to intercalate with halloysite are water structure-breaking cations or hydrogen-bonding anions.

The influence of the activity of water on the phase composition of aluminum hydroxides obtained by reaction of amalgamated aluminum with water has been studied. The reaction was carried out in solutions of water and dioxane, and in sodium chloride solutions of different concentrations; amorphous aluminum hydroxide was precipitated initially. The aging of this primary product to bayerite, pseudoboehmite, or an amorphous gel was controlled by the water content of the system. The pseudoboehmite has shown a significant reactivity when used as a source of alumina in the hydrothermal syntheses of kaolinite at relatively low temperature and pressure.