The proposed method is a modification of one by Alexiades and Jackson (1965). Calcium exchange capacity (CaEC) and potassium exchange capacity (KEC) are determined, after removal of organic matter and free iron oxides, by saturating the exchange complex with centrifuge washings of pH 7 acetate solutions of Ca or K, respectively. Excess salt in solutions remaining in contact with the soil after saturation is determined by measuring the weight and concentration of the excess solution. The exchangeable cations and excess salt are then replaced by centrifuge washings with 1 N acetate solutions of Mg (for CaEC) or NH4 (for KEC), after overnight 110°C oven-drying to enhance K fixation for KEC. The replaced cations are determined and CaEC and KEC values are calculated. Per cent ‘vermiculite’ is based on the difference between CaEC and KEC (expressed in m-equiv/100 g) and an assumed ‘vermiculite’ in-terlayer exchange capacity of 154 m-equiv/100 g; percentage Vr = (CaEC-KEC/154) × 100. The ‘vermiculite’ interlayer fraction (VIF) of the CaEC may also be calculated; VIF= CaEC-KEC/CaEC. The measured ‘vermiculite’ is shown in quotation marks since the method is open to criticism regarding exactly what is being measured, the assumptions made, etc. and to emphasize that the determination procedure is an operational one for the characterization of cation exchange complexes.

Removal of free iron oxides increased both CaEC and KEC values of several soils but percentage Vr was little affected. The amount of K fixation was affected by the drying treatment employed after K saturation (none vs air-drying vs oven-drying). Thoroughly crushing Montana and African vermiculites dramatically increased their CEC and measured ‘vermiculite’ values, but had little effect with two samples of saprolite from chloritic metabasalt.

Post-glacial Champlain Sea sediments in Quebec and Ontario are often extremely sensitive. Suggestions of considerable amorphous material in these soils come from X-ray diffraction results, as well as electron micrographs. A method for selective dissolution and analysis of amorphous material is used to study two Champlain Sea deposits. The amorphous material removed amounts to 11–12 per cent of the soils and consists mainly of silica and iron oxide. The treated samples have enhanced X-ray diffraction peaks and much cleaner particles as seen by electron microscopy.

Nitrogen sorption by various homoionic montmorillonites was studied at 78°K. The adsorption isotherms in the relative pressure range P/P0= 0.05-0.25 were found to be either Type I or Type II in the BET classification. The nitrogen sorption process was considered to be predominantly interla-mellar when described by a Type I isotherm. With a Type II isotherm, the adsorption was assumed to be predominantly on those surfaces not in the interlamellar regions.

It was concluded that only cations within a certain size range promote significant interlamellar nitrogen penetration in montmorillonites. The role of the smaller cations in nitrogen sorption by montmorillonites seems to be their influence on the external aggregate structures. Very large cations tend to clog up the interlamellar pores as well as some of the external voids.

Imogolite is a hydrous aluminium silicate mineral (Cradwick et al., 1973) with a fibrous morphology and low degree of structural order, which, since first described by Y oshinaga and Aomine (1962), has been reported to occur as a weathering product of pyroclastic materials in many localities. However, Wada et al. (1972) have recently drawn attention to the fact that imogolite occurs in gels derived from massive, though jointed, basalt in Hawaii. The purpose of the present note is to describe the identification of imogolite in some very young volcanic ash soils from New Guinea-a finding that has important genetic implications.

Surface acidity of almost homoionic montmorillonites was measured by titrating selected Hammett indicators adsorbed on the clay with n-butylamine.

As expected, the acidity is strongly affected by the exchangeable cations and the degree of hydration of the clay. Greater polarizing ability of the interlayer cations increases both the strength and number of acid sites per H0 value. The acidity of ‘activated’ or heated H-montmorillonite does not exceed that of untreated H-montmorillonite. The origin of the negative charge in the montmorillonite appears to affect the acidity of the clay.

It is concluded that the very high acidities reported in the literature (H0 < −5·6) are apparent only and are due to physisorption of the indicator.

Slaty strata and their weathering products comprise a large portion of the geologic formations of the western foothills in the Sierra Nevada, Mid-Northern California. The weathering products of Mesozoic slates in particular, locally known as ‘swelling’ chlorites, have caused numerous problems in road construction.

A typical stratigraphic section of slates, which includes ‘swelling’ chlorites, is given for the area of Chili Bar, California, as part of the general geology of the western foothill formations. Remolded slate densities were observed to decrease while measured swelling pressures increased with increasing slate alteration. Swelling pressures in excess of 12.5 psi were observed. Curves are presented in comparison with DTA results showing the effect of alteration on the slate.

The results of X-ray diffraction analyses, in correlation with i.r. data, show a typical slate mineral composition for unaltered material of about one-half chlorite with the remainder being about equal portions of muscovite and quartz. The entire chlorite content of the altered slate becomes a regular mixed-layer clay mineral, corrensite, which has been observed to alter to sedimentary vermiculite and Mg-saponite in residual soil. An i.r. absorption peak at 3690 cm-1 characterizes the mixed-layer clay mineral. Heat treatment of the mixed-layer clay mineral structure reduces the 14.3 Å basal spacing to 11.8Å at 540°C, which decreases to 10.6Å at 850°C, disappearing by 1050°C. Procedures are given for direct quantitative analysis of these three-phase mineral systems using simultaneous linear equations.

Evidence is presented for the alteration minerals formed during weathering of the slate, including Fourier analysis of the mixed-layer clay structure.

Bound water of sepiolite dehydrates in two steps in the temperature range of 250-650°C, as shown in the TG-curve. These steps are described here as steps II and III. At step II, half of the bound water is removed; other half at step III. From step II to III, discontinuous changes are confirmed in such properties as activation energy of dehydration, a-dimension, axial ratio, and intensities and spacings of X-ray powder reflections. A structural state at step II may be recognized as a distinct phase in the dehydration process.

The scanning electron microscope (SEM) is useful in the identification of biogenic opal. Opaline spheres, cups, and scrolled or convoluted sheets were identified in both soil and vegetative isolates. X-ray diffraction analysis indicates that both alpha quartz and cristobalite were co-associated with the amorphous opaline phase synthesized during life metabolism of deciduous tree leaves. Such crystalline phases were most abundant in the 2–5 μm fraction and many consist of anitsotropic rods with parallel extinction or equidimensional bodies with aggregate extinction. Between 2/3 and 3/4 of the total opal isolate from deciduous tree leaves was solubilized when digested for 2–5-min in boiling 0.5 N NaOH. Rate of dissolution was a function of particle-size and tree species. Biogenic opal of forest origin was about 10–15 times more soluble than grass opal, which probably reflects the higher specific surface of the former.

Various dehydroxylated micas and rectorites were acid-treated. Rectorite-type mixed-layer mineral was formed from 2M1 and 2M2 mica and random mixed-layer mineral from 1M and 1Md mica. Rectorite was formed again from dehydroxylated rectorite. The rehydration and rehydroxylation properties of dehydroxylated rectorite and 2M sericites were found to be similar.

Necip Guyen: Factors affecting selected area electron diffraction patterns of micas. Clays and Clay Minerals22, 97–106 (1974).

On p. 97, lines 3 and 6 of the second paragraph under Lattice Properties of Micas (the equations for ΔPhkl)

Dissolution data on five of the six illites reported by Reesman and Keller (1968) indicate that these illites are more stable than was previously thought. The revised Gibbs free energies of formation (ΔGf0) with respect to the ‘ideal’ illite formula and the muscovite formula are

Use of muscovite formula as an indirect comparator provides a means of predicting the relative stabilities of these chemically complex materials.

The response of illite-equilibrated solution to a kaolin ΔGf0 was found in all samples in which a 7 Å mineral phase was detected by X-ray diffraction. Stability diagrams based upon the ΔGf0 with respect to ideal muscovite and kaolin formulas show a rather wide range in chemical conditions through which illites and kaolin minerals with differing ΔGf0 would be stable. However, in carbonate rocks and sea water illite is stable relative to kaolin. During the weathering of carbonates the lower pH zones in the clay-rich residuum above the carbonates favor the transformation of illite to kaolin minerals.

I.R. absorption and X-ray diffraction data on butylammonium complexes of vermiculites show, when compared with the Wyoming montmorillonite complex, that the tetrahedral location of charge determines the keying of the -NH+3 groups into the ditrigonal cavities and that these groups have their C3 axes perpendicular to the layers. The aliphatic chains adopt different conformations depending on the area available per exchange position; they will either: (a) adopt an ’all-trans’ conformation with their axes inclined 55° to the silicate planes, when the area available is small; (b) rotate 120° around the C1-C2 bond to adopt a flat disposition relative to the layers, when the area available is larger than the area covered by the organic ion.

A vermiculite-piperidine complex was investigated by a single crystal three dimensional X-ray diffraction procedure. The complex was prepared by ion exchange of a Na-vermiculite at pH 8. A total of 453 reflections was observed and used in the least squares refinement of the structure. The complex is monoclinic, C2/m, a = 5.346(2) Å, b = 9.256(3) Å, c = 17.57(1) Å, ß = 96.29(9)°. The final R value was 0.17 using anisotropic temperature factors for the silicate atoms and isotropic temperature factors for the carbon atoms. The occupancy factors of the C atoms were considered as variable parameters. The diffraction data were of poor quality because of stacking faults. The results show that the molecules are randomly distributed over the crystallographic sites in the interlayer space and the peaks appearing in the electron density maps can be interpreted as being due to 2 piperidine molecules and two H2O molecules. The orientation of the organic molecules is ambiguous. The electron density peaks fit a model in which the molecules are vertical and their planes form a small dihedral angle, and also fit a model in which the plane of the molecules is parallel to (001). It is quite possible that both types of orientations are present.