The Tulameen coal field is part of an Eocene nonmarine basin which received extensive volcaniclastic sediments due to its location within an active magmatic arc. Bentonite partings in the coal originally consisted of glassy rhyolitic tephra with phenocrysts of sanidine, biotite, and quartz. During the initial alteration, which took place within the swamp or shortly after burial, glass was transformed to either smectite-cristobalite-clinoptilolite or to smectite-kaolinite. The formation of kaolinite depended on the degree of leaching of silica and alkalies in the swamp environment. Some beds are nearly 100% kaolinite and can be designated as tonsteins. The smectite shows no evidence of interlayering; the kaolinite is well ordered. During alteration, sodium, originally a component of the glass, was lost from the system.

A later thermal event, which affected only the southern part of the basin, metamorphosed the smectite to a regularly interstratified illite/smectite with 55% illite layers and rectorite-type superlattice (IS-type). The source of potassium was dissolution of sanidine. Vitrinite reflectance measurements of the coal suggest that the smectite was stable to 145–160°C, at which temperature it transformed to K-rectorite.

The absence of randomly interstratified intermediates, even in beds rich in potassium, suggests that the transformation of smectite to K-rectorite was controlled by a steep thermal gradient possibly resulting from local magmatism or circulating geothermal fluids.

Ion-exchange experiments in expanding clay minerals conducted over a wide range of surface ionic compositions and ionic strength produce variable mass-action selectivity coefficients. When the exchanging ions are of unequal charge, tactoid structure appears to influence selectivity, although configurational entropy of adsorbed ions may also generate variable selectivity. The degree of deviation from ideal mass-action exchange is related to the dissimilarity of the ions undergoing exchange. Data involving trivalent ion adsorption on smectites suggest that mass-action is a poor approximation when the adsorbing and desorbing ions have different hydration energies and charge. No form of exchange equation is successful in describing ion exchange for a wide range of experimental conditions, although the fluctuation of the selectivity coefficient follows consistent trends with changing experimental conditions. The strong adsorption of high-charge ions on clays is not exothermic, but must be driven by the increasing disorder of ions and/or water.

A relation was derived which describes negative adsorption (salt exclusion) in systems in which double layer interaction takes place but where the surface potential remains finite, such as in clay pastes and sediments. Exclusion volumes calculated for montmorillonite pastes in equilibrium with 1:1 type electrolytes were found to compare favorably with data obtained by F. A. M. de Haan in an earlier study.

The presence of Al hydroxy species in solution during the synthesis of lepidocrocite had been previously found to influence the reaction towards goethite formation. However, under certain conditions, which are not unrealistic in terms of the natural soil environment, this influence does not occur, and Al appears to substitute for Fe(III) in the lepidocrocite structure. This substitution causes the unit-cell dimensions to decrease along the “a” direction and to increase along the “b.” From the differential line broadening of X-ray powder diffraction peaks, the incorporation of Al was found to inhibit crystal growth preferentially in the b-axis direction, the hkl peaks being more broadened the higher the value of k relative to h and l. Al-substituted lepidocrocites have been suggested to occur in soils, and although they can be synthesized under conditions approaching those expected in soils, it is considered that their formation in nature is unlikely or restricted to unusual environments.

Feroxyhite (δ′-FeOOH) in association with goethite and lepidocrocite was found as a dominant mineral in some rusty precipitates from Finland. These precipitates formed in the interstices of sand grains from rapidly flowing, Fe(II)-containing water which was very quickly oxidized as it flowed through the sediment. The mineral is distinguished from other FeOOH forms and from ferrihydrite mainly by its X-ray powder diffractogram. Further characteristics are an acicular morphology (possibly thin, rolled plates), an internal magnetic field at 4°K of ∼510 kOe, Fe-OH stretching bands at ∼2900 cm−1 and Fe-OH bending bands at 1110, 920, 790, and 670 cm−1, and an oxalate solubility between ferrihydrite and goethite or lepidocrocite. Feroxyhites with very similar properties were synthesized by oxidation of an Fe(II) solution with H2O2 at a pH between 5 and 8.

Interlayer sodium ions of montmorillonite were exchanged with hydroxy-bismuth polycations which were prepared from bismuth perchlorate solutions by the addition of NaOH. Assuming the charge density of the silicate layer to be unchanged, the compositions of the polycations involved in the exchange can be estimated from the amount of bismuth taken up by the montmorillonite and from the ignition loss between 110° and 800°C. The derived compositions are near [Bi6(OH)16]2+ irrespective of the ratio of OH:Bi in the perchlorate solution. The basal spacing of the hydroxy-bismuth montmorillonites is about 16 Å at 110°C, which corresponds to that of hydroxy-chromium montmorillonite having a high surface area of about 250 m2/g. The surface areas of the hydroxy-bismuth montmorillonites, however, are less than 80 m2/g.

Allophane samples from soils, pumice, and stream beds have been studied by electron optical, infrared absorption, X-ray fluorescence, gas chromatography, and phosphate adsorption methods. The allophane particles were hollow spherules or polyhedra 35 and 50 Å in diameter with molar Al/Si ratios close to 2.0. The thickness of the wall of the spherules was estimated to be 7 Å. For the pumice allophanes, the wall was largely composed of imogolite structural units (OH)3Al2O3SiOH. Defects or pores were present in the wall and probably were the sites where phosphate was adsorbed. It is suggested that these allophanes with molar Al/Si ratios close to 2.0 should be called “proto-imogolite” allophane.

Two soil allophanes had a similar structure to the allophane from Stratford pumice, but small amounts of layer silicates, including halloysite, were also present in the soil samples, as indicated by infrared bands at 470, 1030, and 1100 cm−1. The allophane from the stream bed at Silica Springs had an infrared spectrum similar to feldspathoids, and it did not have the imogolite structure.

Hydrothermal alteration products of serpentinite near Takovo, Yugoslavia, were studied by X-ray powder diffraction and chemical analysis. A zone of mainly blue clays adjacent to the hydrothermal vein contains intimately associated chromium kaolinite and tosudite at higher hypsometric levels and chromium halloysite(10Å) form at lower levels. A second zone of green clays contains principally illite/smectites, with predominantly illite layers nearer the first zone and smectite layers at greater distances. The potassium content diminishes as the proportion of illite layers diminishes. The composition of the smectite layers in the illite/smectite with the least proportion of illite is shown to be beidellitic. The mineralogical and chemical changes across the zone of alteration are interpreted in terms of two stages of alteration in which the second is more acidic than the first and is responsible for the inner zone of chromium-bearing kaolinite and tosudite and chromium halloysite.

The effects of NaOAc removal of carbonates, H2O2 removal of organic materials, and sodium citrate-bicarbonate-dithionite (SCBD) removal of iron oxides upon the X-ray powder diffraction (XRD) characteristics of clay minerals present within weathered volcanic ash deposits were examined. All pretreatments of samples derived from the Ae and Bhf horizons containing volcanic ash resulted in dramatic increases in XRD peak intensities, while the treatment of IIC-horizon samples resulted in subdued XRD peak intensities. Also, the chemical treatments produced an apparent increase in the amount of expandable clay minerals within the Ae horizon, due probably to the hydrolysis and removal of interlayer Al3+ when H2O2 and SCBD were used. Hence, poorly ordered and pedogenically modified vermiculite or vermiculite/montmorillonite interstratifications became “weathered” by H+ attack and Al3+ removal in a manner similar to the natural processes which take place in the acid and eluvial A horizon. In addition, possible XRD peak modification due to the dilution of crystalline clay concentrations by amorphous clay-size material appeared to be subordinate to the laboratory-induced chemical alteration of the weathered clay minerals.

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.