Soil vermiculite clays of varying tetrahedral and octahedral composition and cation exchange capacity (CEC) were examined for their ability to fix K+ in both the wet and dry states. Fixation capacity, expressed as per cent of the CEC, in the wet state was fairly high for most samples but it was enhanced greatly upon drying the K saturated samples. This enhancement indicated that each sample contained a number of vermiculite species with different CECs.

The vermiculite clays, as a group, exhibited a much higher fixation capacity at a much lower CEC than those of the coarse grained vermiculites. This enhanced fixation is believed due to the dioctahedral nature of the coarse grained vermiculites. In samples of nearly equal CECs only those containing Al3+ in tetrahedral positions exhibited an enhanced fixation capacity in the dry state but not in the wet state.

In was remarkable to find that the state of oxidation of crystal structure iron strongly affected the fixation and the CEC. Reduction of Fe3+ to Fe2+ caused a decrease in fixation even though the CEC increased as a result of this change. Conversely these reactions and their effects were found to be reversible.

The variation in the orientation of the dipole of the hydroxyl ion in the octahedral layer with respect to the cleavage plane of the crystal is believed to be responsible for some of the noted differences.

Potassium release rates from micas varying widely in type and composition were measured. A sodium tetraphenylboron solution was used as the extracting agent. Muscovites were found to be two orders of magnitude more stable than a naturally occurring phlogopite and biotite. Synthetic fluorphlogopite was as stable as some muscovites. Lepidolite was the most stable mica. Primary factors affecting mica stability are thought to be: Hydroxyl bond orientation, isomorphous replacement of OH− by F−, the stronger Lewis base, and structural factors that lead to compression or stretching of the K—O bond.

Titanium in TiO2 minerals was differentiated from that isomorphously substituted into minerals by the use of dihydrogen hexafluorotitanate (hydrofluotitanic acid, H2TiF6), which selectively dissolved minerals containing substituted Ti4+, leaving free crystalline TiO2 minerals in the residue. Titanium analyses on the original samples and the residues remaining after H2TiF6 treatment, by both wet chemical (Tiron) and neutron activation methods, indicated that an average of 86 per cent of the titanium in seven kaolinite samples was present in the residual TiO2 form (largely anatase), whereas only 28 per cent in two bentonites was present in the TiO2 form. Residual Ti accounted for 100 per cent of the Ti in synthetic anatase and for 92 per cent of the Ti in coarse clay sized rutile, the latter value suggesting that about 8 per cent amorphous TiO2 was removed from the mechanically dry ground rutile by the H2TiF6 reagent. The Ti present as residual TiO2 in a variety of other samples ranged from 0 to 100 per cent.

Scanning electron microscope observation of endellite from Bedford, Indiana, discloses the existence of globular clusters of quasi-tubular endellite particles radiating from common centers. Individual clusters are of the order of 10 μ in overall diameter. The individual quasi-tubular particles are irregularly flattened in cross section, and some may be plugged at the ends. Conventional oven drying at 105°C results in partial unrolling and incomplete flattening of the quasi-tubular particles of some of the clusters. The globular cluster microstructure is taken to represent the result of in-situ crystallization from solution. If this is so, these hollow tubes cannot have arisen by the mechanism of repeated extrusion of concentric zonal crystallites as postulated by Chukhrov and Zvyagin.

Pyrophyllite is widespread in pelitic rocks of the Manning Canyon Shale in north central Utah, and the association of this mineral with other clay minerals, especially rectorite is related to the origin. The regular mixed-layer clay mineral rectorite seems to form as a result of the alteration of muscovite-paragonite during late stages of diagenesis and represents an intermediate metastable phase in the mineral paragenetic sequence. Pyrophyllite subsequently formed from the alteration of rectorite during advancing metamorphism and is the stable end member of the clay mineral assemblage.

Structural interpretations of rectorite found in the Manning Canyon Shale shows a regular, alternating sequence which consists of a fixed layer of 9.6 Å and an expandable layer, varying from 10 Å to 17 Å. With ethylene glycol saturation in the natural state a basal reflection of 26.60 Å is recorded.

The term “flint clay” used in USA and several other countries, corresponds very closely to the term “toasted bread (sukhar) clay”. In both USA and U.S.S.R., the typical occurences of “toasted clays” are confined to deposits of the lower Carboniferous. In their properties and occurrence the well-studied toasted clays of the Borovichy deposit (Novgorod province) are highly similar to the flint clays of Missouri, differing significantly only in having lower bulk specific gravity and higher porosity than do Missouri flint clays. Varieties with excess free alumina (diaspore, boehmite) are observed both among “toasted” and flint clays. The author suggests the term “toasted complex” (sukharnii kompleks) which corresponds to W. D. Keller’s term “flint clay facies”. The clays of the “toasted complex” are sediments of ancient swamps and lakes which contained rich vegetation. Their source material was finaly dispersed silicate particles transported from dry land. The structure and properties of toasted clays are explained by the precipitation of kaolinite as colloidal clumps in which crystallization occurred with formation of intimate intergrowths and variously oriented segregations.

Cation exchange capacity (CEC) measurements were made for whole pumice soil samples by several methods, including standard procedures involving cation saturation, excess salt removal, and cation displacement steps, and a 45Ca2+ radioisotope dilution procedure. Results indicated that the vesicular pores of the pumice soil material affected attainment of ion diffusion equilibria, and, hence, introduced a large source of error in the measurements. On this basis, the validity of ion exchange values obtained for these soils was concluded to be subject to considerable doubt. More important, however, the solute and/or solution exclusion or retention exhibited by pumice particles during the course of CEC procedures was thought to be highly significant with respect to the probable influence exerted on physical, chemical, and biological properties of the soils in the field situation.

Interpretation of pH dependent cation and anion exchange capacity measurements of the <2μ clay fraction of the pumice soils was confounded by the occurrence of hydroxy interlayered 2: 1 phyllosilicate materials in admixture with the amorphous components. Since the interlayered materials contributed an indeterminate proportion of the total pH dependent charge of the mixture, it was further concluded that the measurement of this property was of little direct value in assessing the relative amounts of amorphous and crystalline components in the clay fractions of the soils investigated. However, the values obtained revealed fundamental aspects of ion exchange behavior which are important to understanding the complex systems involved.

The frequencies of structural OH stretching vibrations in swelling trioctahedral minerals such as hectorite or K-depleted phlogopite depend on the ionic form and hydration of the sample. The trioctahedral structure is evidently a suitable case for the observation of spectral changes, since hydroxyl groups are in conditions of high reactivity with the surrounding medium. These changes are attributed to the field which originates either from the cations or the residual water molecules, and the joint analysis of spectroscopic and X-ray diffraction data permits an interpretation that frequencies quoted for unaltered mica are only perturbed frequencies.

A knowledge of the distribution of pore sizes in clay and soil bodies is a useful element in the microstructural characterization of such materials. Pore-size distributions and total porosity of a number of reference clays, naturally-occurring subsoils, and commercial clay samples prepared in various ways were determined by mercury porosimetry. The range of equivalent pore diameter explored covered almost five orders of magnitude, from several hundred microns down to approximately 150 A. The method and its assumptions are critically evaluated, and measurements of the contact angle of mercury on clays yield values of 139° for montmorillonite and 147° for kaolinite and illite clays. The extent of shrinkage on oven-drying prior to mercury intrusion is assessed in each case and found to vary from insignificant to as much as 30 per cent of the pore space, depending on microstructural state and degree of initial saturation. The development of techniques for water removal which do not involve change in pore structure is explored. Some preliminary results for structurally weak saturated clays suggest that critical-region drying and perhaps freeze-drying procedures may be practical.

Potassium was removed from 5 to 20-μ size fractions of two phlogopites by treatment with sodium tetraphenylboron and replaced with various exchange ions. The b-dimension of the mica increased with K+ removal, which suggests that the K+ ion in phlogopite acts to constrain b. This being the case, the K—O bond in phlogopite must be lengthened and weakened relative to the K—O bond in dioctahedral micas.

Clay mineral data have been obtained on 348 soil profiles representing 117 different soil series from 28 of Pennsylvania’s 67 counties. The surface rock from which the soils were formed ranged from Pre-Cambrian to Tertiary-Pliocene and includes igneous, metamorphic and various types of sedimentary rocks. Major attention was focused on the subsoil mineralogy. Mica was found to be the most predominant clay mineral in terms of amounts and frequency of occurrence. It is dominant or co-dominant in 82 per cent of the profiles. In shale derived soils it is important in 95 per cent of the cases and in 68 per cent of the limestone soils. Kaolinite is a prominent component of soils derived from sandstone and metamorphic rocks. Montmorillonite was detected in over half of the soils but is very infrequently a prominent component and is more frequently found in the poorly drained soils. A mica-kaolinite suite is characteristic of soils from Pennsylvanian age rock whereas soils derived from Devonian, Mississippian, and Ordovician age rock had a mica-chlorite suite. The chlorite is frequently found weathered to chlorite-vermiculite in a 1:1 ratio. Gibbsite, talc, and pyrophyllite have been identified but only rarely occur. A difference in clay mineral types is frequently found among different profiles of the same soil series. Soils derived from limestone and highly calcareous rock may have rather unusual clay suites such as the dominance of a well-crystallized triocta-hedral chlorite, well crystallized mica, and soils approaching a monominerallic character in mica.

When kaolinite undergoes percussive grinding, pronounced changes take place in its i.r. absorption spectrum even in the earliest stages of the grinding when the lattice is not yet destroyed. In this report, attention is directed to the change in the stretching bands of the hydroxyl ions. A remarkably rapid effect on the band of the intralayer hydroxyl ions has been observed and is attributed to a permanent removal of the protons from these ions. Auxiliary measurements of X-ray diffraction, thermal water loss, and DTA were used to corroborate the spectroscopic evidence for this ready prototropy.

The nature of interstratification in mixed-layer illite-montmorillonites has been investigated by comparison of diffraction patterns of ethylene glycol and ethylene glycol monoethyl ether treated samples with calculated one-dimensional diffraction profiles. The calculated profiles take into account the effects of particle size distribution, chemical composition, and convolution factors as well as proportions of layers and interstratification type. On the basis of detailed matching of diffraction patterns of monomineralic illite-montmorillonites of known chemical composition it is concluded that there are three types of interstratification: (1) random, (2) allevardite-like ordering, and (3) superlattice units consisting of three illite and one montmorillonite layers (IMII). By comparison of suites of calculated profiles with the diffraction patterns of many samples of illite-montmorillonites it is concluded that virtually all illite-montmorillonites with expandabilities from about 40 to 100 per cent are randomly interstratified (allevardite being exceptional); at >40 per cent montmorillonite layers they almost always have ordered interstratification. Allevardite-like ordering predominates in illitemontmorillonites which have ordered interstratification, with the IMII superlattice varieties confined to samples with about 10 per cent montmorillonite layers.

Under appropriate conditions, both surface areas and cation exchange capacities of clay minerals can be measured by absorption of methylene blue from aqueous solutions. The method has been applied to two kaolinites, one illite, and one montmorillonite, all initially saturated with Na+ ions. For Na-montmorillonite, the total area, internal plus external, is measured. For Ca-montmorillonite, entry of methylene blue molecules appears to be restricted by the much smaller expansion of the Ca- clay in water. X-ray diffraction data clarify the absorption behavior in Na- and Ca-montmorillonite, and in particular it is shown that two orientations of the methylene blue molecules are involved.