Mafic chlorite from Benton, Arkansas was comminuted by rotary blending of a suspension, and the — 2 μm fraction separated by sedimentation in H2O. Droplets of suspension of the < 2 μm fraction were dried on a layer of Epoxy resin and then additional Epoxy was added and heat-cured at 48°C to form a resin sandwich. Cross-sections of 600–900 Å thickness were cut on a Reichert automated ultramicrotome. The sections were collected on standard electron microscope specimen screens, reinforced by vacuum evaporated C and examined by transmission electron microscopy (TEM). The Phillips EM 200 electron microscope was equipped with a “microgun” source to minimize heating of the specimen and to improve contrast and high resolution (HREM). Images of the (001) chlorite crystallographic planes spaced at 13·9Å intervals were visible on many of the particle sections. Imaging of the planes depended upon their being nearly parallel to the electron beam (within 0° 10’) and therefore, many particles which had other orientations did not show the 13·9Å image. Micrographs made before appreciable irradiation by the electron beam revealed images of fringes corresponding to the 7·22Å (002) spacing of chlorite. Loss of the 7·22 Å fringes and reinforcement of those at 13·9 A resulted from heating of the chlorite in the electron beam. This behavior is analogous to the well-known crystallographic effects of heating chlorite at 550–760°C.

Rates of exchange of K with Ca for fine (0·2–2 μm) and coarse (54–75 μm) and for thin and thick (37–45 μm) phlogopite particles were determined using a repeated batch technique, which gave a measure of K selectivity.

Potassium selectivity of the fine fraction was higher than that of the coarse one throughout the exchange process in which 93 per cent of the total K was exchanged from the fine fraction and 100 per cent from the coarse one. Potassium selectivity of the thin 37–45 μm particles was higher initially than that of the thick 37–45 μm particles but the difference disappeared subsequently and practically 100 per cent of the total K was exchanged from both the thin and thick particles.

The results are interpreted as tentatively confirming the hypothesis that bending and deformation of elementary layers during K exchange increase with particle thickness, which in turn increase K exchange and decrease K selectivity.

The K exchange curves for the fine and coarse phlogopite fractions suggest that in natural conditions, as in soils, where K is not continuously removed from solution, vermiculization of coarse mica particles may be not only more complete but also more rapid than vermiculization of fine mica particles.

Sorption of K from mixed KCl and CaCl2 solutions by K-depleted, Ca-saturated phlogopite was studied to determine the effect of particle size. The experiments were done at room temperature with 25 mg of K-depleted phlogopite samples in 50 ml solutions which were 0·002 N with respect to KCl and 0·02 N with respect to CaCl2.

Sorption of K increased sharply with increase in particle size. The 54–75 μm fraction sorbed nearly all, whereas the 0·2–2 μm fraction sorbed less than half, of its depleted K. The 5–20 μm fraction sorbed an intermediate amount. This relationship is explained by the same hypothesis which accounts for the increase of K release with increase in particle size. That is, bending of unit mica layers due to peripheral expansion is greater in large and thick particles than in small and thin ones. This increased bending induces the greater K release from large particles. Similarly, bending due to peripheral collapse of hydrated layers is greater in large particles than in small ones. Thus, more energy is needed to initiate layer collapse and restrict further K uptake in the large particles which results in their greater K sorption capacity.

These results imply that in natural conditions, as in soils, the coarse vermiculite and weathered mica fractions may be more effective in sorbing K from solution than their fine counterparts.

Fe(ClO4)3 solutions of different concentration and acidity were studied to search for the factors governing their appearance and stability during aging and to elucidate the mechanisms for the formation of amorphous and crystalline iron(III) hydroxides from slow hydrolysis. It was found that dilute solutions (0·001M or lower) rapidly hydrolyzed to clear sols after a brief induction period. With an increase in iron(III) concentration, one could notice gradual increases in the induction period, turbidity and particle size. Thus, solutions 0·006M to 0·01M in iron(III) developed into dense, cloudy, yellow suspensions impervious to light. The polymeric iron(III) species in the aged 0·02M solution were primarily large particles that settled under gravity, resulting in a suspension of low turbidity. It was also observed that in dilute solutions, the initial polymerization product was amorphous iron(III) hydroxide which yielded X-ray diffraction peaks for FeOOH only after prolonged aging or not at all. In 0·01 and 0·02M solutions, however, crystalline FeOOH was the major product from the very beginning of polymerization. The results suggest that the initial degree of supersaturation with respect to amorphous iron(III) hydroxide is the key factor governing particle size distribution, which in turn governs the appearance, stability and crystallinity of the hydrolyzed product during aging.

The addition of HClO4 to dilute Fe(ClO4)3 solutions decreased, whereas the addition of NaOH to concentrated solutions increased, the degree of supersaturation and, thus, induced changes in induction period, appearance, stability and crystallinity of the hydrolyzed product accordingly.

The adsorption of trace quantities of Cu (3·89 × 10−6 to 3·00 × 10−4 M) by a bentonite clay from calcium acetate solution was studied over the range of pH 4·27–5·87. The data were fitted to an existing adsorption equation and the ‘best’ values of the adsorption parameters were calculated. The proton, cupric ion and mono (hydroxy) cupric complex were found to be the adsorbed species. The adsorption sites are of two types. It has been postulated that the majority of sites are lattice hydroxyl groups located at crystal defects and edges. The remainder arise from organic matter adsorbed by the clay and are the more important in the adsorption of Cu at very low metal concentration and at pH <5·4. The implication of the results on the potential use of bentonite clay to remove trace amounts of Cu from mine waste waters is considered briefly.

The petrography of shale partings in carbonate rocks from eleven cores in the Illinois (Jeffersonville Formation) and Michigan Basins (Detroit River Formation) of Indiana indicates the presence of a K-bentonite which is interpreted as the Tioga Bentonite, an important stratigraphic marker in the middle Devonian rocks throughout the central and eastern United States. The clay mineral composition of the Tioga Bentonite of Indiana is interstratified illite and smectite, usually with admixed kaolinite. This composition stands in striking contrast to the simple illite suite without kaolinite in the normal terrigenous shale partings in the Devonian rocks of Indiana. Euhedral sanidine, high temperature albite, zircon, apatite, and the angularity of quartz grains found associated only with the interstratified clay mineral suite support the volcanic origin of these clay partings.

A simple electrostatic model has been used to demonstrate that the inner surface hydroxyls in kaolinite, dickite and nacrite are responsible for the interlayer bonding in these minerals. The contribution to the interlayer bonding of an individual hydroxyl hydrogen depends on the orientation of the hydroxyl group relative to the 1:1 layer since this orientation determines the H—O interlayer distance. If this distance is much greater than the sum of the van der Waals radii, 2·60 Å, there is essentially no bond. As the distance becomes less than 2·60 Å, the strength of the interlayer bond increases.

Quantitative measurements are made of the adsorption of benzidine and aniline from aqueous hydrochloride solutions by Na-, Li-, and Ca-montmorillonite and of the displaced inorganic cations. From these data, the ionic states of the adsorbed organic species are determined. Under conditions of controlled pH, the adsorption of benzidine increases as the pH increases, and involves mainly divalent species at pH<3·2, and increasing proportions of monovalent and neutral species at pH> 3·2. With aniline, monovalent and neutral species are adsorbed, and hydrogen ions also appear to participate in the reactions.

Color developments of benzidine and aniline complexes of montmorillonite and hectorite are considered qualitatively in relation to the adsorption data, to various experimental conditions including the nature of the inorganic exchangeable cations, the pH, and the presence or absence of oxygen in the system, and to relevant previous work. It is hypothesized that the blue color of the benzidine complex is due to semiquinone formation by oxidation on montmorillonite by the clay itself, and on hectorite by dissolved oxygen or H2O2, and that the yellow color under acid conditions arises from reversible formation of quinoidal cations from semiquinones. The color developments of the aniline complex are due probably to oxidation of aniline by atmospheric oxygen.

Two bentonite deposits having average thicknesses of 10 and 4 ft are exposed within nonmarine strata of Late Cretaceous age along the Battle River near Rosalind, Alberta. They are characterized by scarcity of >44 μm material and variable 44-2 μm and <2 μm contents. Material >44 μm in size in excess of 2 per cent is primarily attributable to secondary calcite, and <2 μm content may be related to the amount of 44-2 μm material that has altered diagenetically from volcanic glass to montmorillonite. Rhyodacite was the probable composition of the parent ash; therefore, the high iron content in one deposit is probably due to diagenesis. The blocking effect of iron on exchange sites can explain differences in exchangeable Na and Ca in different deposits. High exchangeable Na found in finer subdivisions of fractionated clay can be explained by increased purity of the bentonite.

Multiple regression analysis of the analytical data shows that 48 per cent of the variation in yield (bbl/T.) of 15 centipoise drilling mud can be attributed to concomitant variation in seven interrelated compositional properties. Sequential analysis shows that <0·2 μm clay content is the most important contributor to variation in yield. The remaining variables (total clay content, exchangeable Na, exchangeable Ca + Mg, Fe2+ and Fe3+ contents, and CEC) contribute little additional precision to the regression analysis when <0·2 μm clay content is included in the equation.

X-ray diffraction patterns for mixed-layer kaolinite-glycerine-saturated montmorillonite were calculated, taking into account the differences of scattering power of kaolinite and montmorillonite layers. The data were compared with the experimental results for two kaolinite-montmorillonite mixed-layer minerals. The probability parameters and the total number of layers in crystals were established.

Corrensite or ‘corrensite-like’ minerals occur in dike-intruded shales and siltstones of the Montana Group and Colorado Group (Early Cretaceous) in Western Montana. The < 1 μm size fraction of one specimen of this “corrensite-like” material has been studied in detail. X-ray diffraction data and chemical analysis indicate that this specimen is a regular or nearly regular interstratification of chlorite and dioctahedral smectite. Also described are other samples, which contain corrensite and additional phases. These samples were taken at several localities where basic dikes have intruded these shales and siltstones.

A soil of Attica (Greece) has been studied by Mössbauer spectroscopy and magnetization measurements in order to ascertain the nature and form of iron oxides present in it. The room temperature spectra consist of a paramagnetic doublet and a small magnetic sextet. At liquid nitrogen temperature the magnetic component increases considerably at the cost of the paramagnetic component. This behavior is typical of superparamagnetism exhibited by ultrafine magnetic particles. From the values of hyperfine parameters extracted by computer fits of the spectra, the particles can be identified mainly as α-Fe2O3. The theory of superparamagnetism, in conjunction with Mössbauer and magnetization data, is discussed in detail. Application of this theory to the data for the clay fraction of the soil leads to the conclusion that the oxide particles have a size distribution with a mean particle diameter of 131 Å and a width of 14 Å.

A black organic-rich alluvial clay from Alleppey, Kerala State, India, gave a well defined 17Å reflection in the natural untreated state. Ethylene glycol and heat treatments showed it to be essentially a smectite. Treatments with H2O2 and 0·1 N NaOH contracted the spacing to about 14Å, indicating that sorbed organic matter was responsible for the original enhanced spacing.

In the natural state, the clay was chiefly divalent with respect to the ions on its exchange sites and was at a pH of 6·2. Subsequent attempts to resorb the organic matter (which had been extracted from the clay by repeated NaOH treatments, converted to the H-form, concentrated and freeze-dried) into the interlamellar space of H2O2-treated clay proved successful only after the pH was brought down to 3•2 and the clay converted to an essentially monovalent state through repeated 1 N NaCl treatments.

The cation exchange process between tris(ethylenediamine)cobalt(III) and Na+ on mont-morillonite was studied by atomic absorption spectrophotometry, X-ray diffraction, differential thermal analysis, and nitrogen sorption at 78°K. The exchange of Co(en)33+ for Na+ was found to be extremely favorable, with a tendency toward segregation of the two kinds of cations in the mixed clays studied. Small amounts of Co(en)3+3 were found to lower the nitrogen sorption capacity of Na+ mont-morillonite while clays with high Co(en)3+3 content had greatly enhanced sorption. An explanation is offered in terms of a dual role of the Co(en)3+3 in determining the kind and amount of nitrogen sorption in the exchanged montmorillonite.

This paper reports the measured distribution of major cations in interstitial, exchangeable and non-exchangeable phases of estuarine sediments. The observed changes in ionic ratios result from the valence and dilution effects in the Donnan equilibrium concept according to which the ion exchanger favors the sorption of divalent ions at the expense of monovalent cations and cations migrate to the outer solution. The above findings have direct application to an interpretation of diagenetic changes in clay minerals.