The i.r. spectra of interlamellar kaolinite complexes with formamide, N-methylformamide and dimethylformamide have been examined. The spectra show that the amides hydrogen-bond, through the C=O group of the amide to the inner surface kaolinite hydroxyls and decrease the intensity of the kaolinite ν(OH) bands. Hydrogen-bonded kaolinite hydroxyl bands appear at lower frequencies and these have been correlated to the original kaolinite ν (OH) bands. Other kaolinite bands in the complexes show smaller perturbations of the kaolinite vibrations. Each amide hydrogen-bonds to different groups of hydroxyls. Formamide hydrogen-bonds to the 3690 and 3664 cm−1 hydroxyls, N-methylformamide to the 3690 and 3648 cm−1 hydroxyls. The interpretation for the dimethylformamide complex is less clear. The ν(NH) frequencies of formamide and N-methylformamide in the complexes are intermediate between that in dilute non-polar solution and in the liquid. This could arise from either or both a degree of intermolecular association of the amide when between the kaolinite lamellae, or to weak N—H … O hydrogen bonds to the tetrahedral oxygen sheet of the lamellae.

Sepiolite and attapulgite have been found to be common, sometimes the major, clay minerals in calcareous lacustrine deposits on the southern High Plains in West Texas and eastern New Mexico. Deflation debris derived from the basins and calcareous soils developed in the debris and in the lacustrine deposits also often contain either or both minerals. Dolomite is the carbonate commonly associated with sepiolite and calcite has a similar relationship to attapulgite in the lacustrine deposits. Pedogenic formation of sepiolite and attapulgite appears unlikely in the area studied since an association with lacustrine materials was made in a very high percentage of the occurrences.

Sepiolite was found to be highly concentrated in the < 0•2μ fraction. A similar, but less pronounced, distribution was noted for attapulgite. The studies suggest that the minerals have developed authigenically in alkaline lacustrine environments during periods of desiccation. Such an environment, interrupted by more humid periods, would have obtained during dry Pleistocene intervals. Volcanic ash is suggested as the source of the essential silica. The Mg concentration would appear to determine whether sepiolite-dolomite or attapulgite-calcite were formed.

Sorption of aniline and its derivatives by montmorillonite substituted by cations of widely different acidity depends upon the polarizing power of the interlayer cations. Infra-red spectra indicate that the anilines are mostly bound to the interlayer cations through water molecules, except in Cs montmorillonite, where bonding to the oxygen surfaces of the alumino-silicate sheets seems to predominate. Anilines are weak bases, which compete with the oxygen surfaces for protons of acidic interlayer water. Consequently, the tendency of anilines to act as proton donors in the clay interlayers increases with the polarizing power of the exchangeable cation. The concept of ‘basic’ water is introduced to account for some of the features of the spectra of Cs montmorillonite treated with the organic ligands.

The conditions were studied under which consolidation loading caused the release of phosphate from a saturated illite clay. P32 tracer techniques were employed to follow the movement of phosphate in composite samples composed of tagged and untagged portions. The samples, initially consolidated to 1·0 kgcm−2 stress were reconsolidated to 0·1, 0·5, 2, 4 and 8 kg cm−2 stress and the transport of phosphate was monitored by counting the radioactivity of 0·01-in. thick sections sliced parallel to the major principal plane. Corrections were applied for P32-P31 self-diffusion. It was found that: (1) for low phosphate concentrations there was no observable transport due to consolidation type flow: (2) for high phosphate concentrations and for stresses less than or equal to the preconsolidation load there was no observable transport due to consolidation type flow; and (3) for high phosphate concentrations and for loads above the preconsolidation load there was detectable transport of phosphate, presumably due to the consolidation flow. A mechanism based on self-diffusion plus uniform flow was able to semi-quantatively explain the test results.

A magnesium hydroxide-montmorillonite complex prepared at an OH/Mg molar ratio of 2 (16 meq Mg/g clay) and immediately cleaned of any free Mg(OH)2 behaves like magnesium-chlorite and shows no change during 3 months ageing. Magnesium hydroxide completely precipitates within the interlayer space of montmorillonite. X-ray diffraction analysis, thermal (DTA and TGA) studies, i.r. absorption analysis, polarographic reduction behaviour, and cation exchange capacity measurements confirm the transformation of montmorillonite to a chlorite-like structure. Further ageing of the complex results in the release of brucite from the interlayer space and expansion of the complex on glycerol treatment. X-ray analysis of the 6 months aged sample shows the presence of free brucite but not montmorillonite. A small but significant increase in CEC of the complex is observed on ageing. When the Mg(OH)2-montmorillonite complex is allowed to age in the presence of free Mg(OH)2 (external to montmorillonite unit layers) in a dry state, a “seeding” effect takes place and the “fixed” Mg(OH)2 starts coming out from the interlayer space after 10 days.

The crystallinity of minerals in terms of crystallite size distribution and lattice perfection is quantified by means of statistical measures derived from X-ray line profiles (2 σ values). A low degree of crystallinity facilitates the non-stoichiometric incorporation of foreign elements in the crystal lattice. Crystallinity is affected by a number of factors and in natural profiles it may vary laterally as well as vertically.

For instance, goethite in laterite deposits shows decreasing crystallinity with increasing depth. Serpentine type minerals, on the other hand, show the lowest crystallinity at the surface where the degree of weathering is the most advanced. The presence of silica in migrating solutions prevents crystal growth and results in a low degree of crystallinity of minerals such as goethite. This has been observed in natural profiles and has been confirmed by laboratory experiments on the synthesis of goethite and sodium-birnessite. The crystallinity of minerals affects their response to extractive procedures. It could also be an important parameter in soil science.

Adsorption of Co2+ and Cd2+ on Wyoming montmorillonite was studied by the batch equilibration technique, as a function of salt concentration (0.01–4 M NaCl and NaNO3), pH (5.0–6.5), adsorbate concentration (trace-10−2 moles/liter), and presence of complexing ions. Comparison was made with the adsorbability of Sr2+, known to follow simple ion-exchange equations. The distribution coefficients for Co and Cd in noncomplexing media varied with salt concentration (from ∼500 liters/kg in 0.01 M Na+ to ∼10 liters/kg in 1 M Na+; pH = 5), but to a lesser extent than that of Sr. Adsorbability varied also with pH (∼1 order of magnitude/pH unit), especially at high ionic strength, compared to a negligible pH effect on Sr. The distribution coefficients of Cd and Co decreased with increasing loading on the clay at a very low percentage (0.2%) of the ion-exchange capacity compared to Sr (20%). These data suggest two classes of sites participating in the adsorption of Cd and Co.

The adsorbability of Cd in highly concentrated chloride solution (>1 M) was less than 1 liter/kg, presumably because of the chloride complex formation. This effect increased with increasing pH. The low adsorbability of Cd on montmorillonite from concentrated NaCl solution is promising with respect to its use as a tracer for monitoring flow through formations containing montmorillonite.

The charge density distribution among different classes of a series of reduced charge mont-morillonites is heterogeneous as in the parent Camp Berteau clay. In addition, charge reduction proceeds inhomogeneously. Up to 20% differences in charge density can be accounted for by aikyl chains extending at the edges of the clay particle. A realistic charge density-cation-exchange capacity relationship for hec-torite, Otay montmorillonite, and a series of reduced charge montmorillonites of Camp Berteau is obtained by accounting for the influence of particle radius and for the extent of alkyl chains lying outside the clay layers in the charge density calculations.

A scanning and high voltage electron microscope study of the fabric of laboratory sedimented moist uncompressed kaolinite and illite floccules reveals an abundance of face-face flake orientation in the porous clay network. Clays were flocculated in the laboratory in both distilled water and slightly saline (1 g/l. NaCl) water using various clay concentrations. Floccules taken from the moist clay mass were prepared for study by freeze-drying and impregnation with polyethylene glycol.

There is little difference in the fabric of kaolinite flocculated in distilled or slightly saline water. The fabric is dominated by a 3-dimensional network of twisted chains of face-face oriented flakes having the appearance of a stair-stepped cardhouse. Illite floccules in distilled water also consist of abundant face-face oriented overlapping flakes. However, in salt water there is a more even mixture of fabrics—edge-to-face flocculation of individual platelets and also stepped clusters of face-to-face oriented flakes, the latter being more abundant.

It is suggested that under the experimental conditions the double layer of each clay particle is compressed resulting in an increase in the importance of van der Waals forces of attraction. As a result flakes approach each other and rotate into a parallel or subparallel position. The resultant dominant fabric is that of a stepped cluster of overlapping flakes.

The influence of geomorphological site characteristics on soil clay mineral stability of montmorillonite-containing horizons of a southern Wisconsin soil catena was interpreted in terms of the solute activity function values of pSi(OH)4, pH-1/2pMg2+ and pH-1/3pAl3+ in suspensions of the separated clay fractions. Montmorillonite stability and/or formation vs that of kaolinite for the soil clays was evaluated by a plot of the solute activity functions on a three dimensional diagram derived for montmorillonite, kaolinite, and gibbsite at constant temperature (25°C) and constant pressure (one atm.). Although all the soil clays contained both montmorillonite and kaolinite, the position of the soil clay solute activity functions in the stability diagram clearly reflected the influence of the geomorphological—geochemical site conditions in which each soil horizon was developed, with corresponding differences in the SiO2/Al2O3 molar ratio of the reactive fraction. Montmorillonite stability positions of the solute activity functions were induced by soils (clays with reactive fractions with SiO2/Al2O3 molar ratios = 3–4) from calcareous or poorly drained horizons, while kaolinite stability positions of the functions were induced by soils (clays with reactive fractions of SiO2/Al2O3 molar ratios = 2) from acid, freely drained horizons.