Recurrent reports of analyses of X-ray diffraction data from regularly alternating and nearly regularly alternating structures like rectorite provide opportunity for a descriptive discussion of their nature. MacEwan-transform-based analyses have uniformly shown higher incidence of unlike adjacent layers than would be expected from random distribution.

The continuous Fourier transforms for pairs of 2: 1 layer silicate structures evaluated normal to the layers, provide a family of similar curves that are differently stretched out in reciprocal space for different assumed intervals between the two members of a pair.

For each exactly alternating example the relative amplitudes of the ordered reciprocal nodes distinguish the instances for which fixed interlayer populations are Na+ from those for which they are K+.

For sequences not exactly alternating scattering maxima are displaced from exact incremental positions in conformity with the Hendricks and Teller mixing functions, but relative intensities of adjacent observations still distinguish the alkali identities.

Use of a discriminant analysis has verified and grouped three suspected varieties of kaolinite found in kaolin-rich clay strata of late Paleocene to early Eocene age across north-central Mississippi. Initial identification of each type of kaolinite was based on clay-texture characteristics observed on scanning electron micrographs and the differences in pattern configurations of X-ray diffractograms. The discriminant function used for data treatment clearly segregated and grouped each variety. The discrimination variables were found to be the Hinckley index and, to a lesser extent, the Si4+ content relative to the Al3+ content.

The oldest variety is the Blue Mountain clay, composed of preserved hexagonal plates usually clustered into booklets with a vermiform texture. The Ashland variety, stratigraphically younger than the Blue Mountain clay, appears to have been derived from the erosion of the Blue Mountain clay. The Ashland cannot be recognized by any type of diagnostic texture, as it is made up of individual plates that have been corroded and abraded to the point where a hexagonal outline can no longer be recognized. The Sardis variety is the stratigraphically youngest of the three varieties and is at least a second, or possibly a third generation detrital product. The Sardis clay can be recognized by a distinct “ribbon” or “swirl” texture commonly found in ball clays.

Data from this study are not sufficient for complete petrogenetic interpretation. However, speculation on possible differences in depositional environments and modes of deposition can be based on the data at hand. The Blue Mountain variety is considered from previous studies to be primary. The Ashland variety is probably a first generation alluvial clay. The Sardis variety appears to be a multiple generation, detrital product that accumulated as part of overbank swamp deposits.

Aflatoxins cause liver damage and suppress immunity. Through adsorption, smectites can be used to reduce the bioavailability of aflatoxins. To further reduce the toxicity of aflatoxins and to eliminate the treatments of aflatoxin-loaded smectites, the ability to degrade the aflatoxin adsorbed to non-toxic or less toxic compounds is desirable. The objective of the present study was to investigate the effects of temperature and the exchange cation on the transformation of adsorbed aflatoxin B1 on smectite. An AfB1-Ca-smectite (sm) complex was synthesized. To enhance the Lewis acidity of the complexes, the exchanged calcium in the complex was replaced with Mn and Cu to obtain AfB1-Mn-sm and AfB1-Cu-sm complexes, respectively. The aflatoxin-sm complexes and pure aflatoxin B1 were dried at 60°C in aluminum cups, and heated from 100 to 200°C in 25°C steps. Aflatoxin B1 and its transformation products were extracted with methanol after the heat treatment. The extracts were analyzed using UV spectroscopy, high performance liquid chromatography (HPLC)-fluorescence/UV, ultra-performance liquid chromatography (UPLC)-photodiode array (PDA), and electrospray ionization-tandem quadrupole-mass spectrometry (ESI-TQDMS). The solid residues were analyzed using Fourier-transform infrared spectroscopy (FTIR). The UV and FTIR spectra of the AfB1-sm clay residue extracts obtained after heating had decreased AfB1 peak intensities and shifted peak positions with increased heating temperature. Significant shifts in band positions and changes in the shape of the UV spectra were observed in the extracts from the AfB1-Ca-sm complex heated at 175°C, the AfB1-Cu-sm complex heated at 150°C, and the AfB1-Mn-sm complex heated at 125°C. The HPLC and UPLCMS analyses of AfB1-sm complex extracts indicated a gradual decrease in AfB1 concentration with increased heating temperature and the formation of aflatoxins B2, B2a, M1, M2, and other unidentified compounds. No new compound was observed in the extracts of pure aflatoxin B1 after a comparable heating experiment. These results suggest that smectite can effectively convert aflatoxin to other less toxic forms at elevated temperatures. Smectite ion exchange with Cu or Mn transition-metal cations and heat treatment induced more efficient conversion of the adsorbed aflatoxin B1 molecules to other compounds.

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.

An assemblage of clay minerals, Na-zeolites, Fe- and Sb-sulfides, and borates occurs in cavities in the basalt flow that underlies the main borax ore body exposed by the U.S. Borax open pit at Boron, Kern County, California. Analcime and saponite are widespread in cavities and fractures near the top of the basalt. Part of the basalt recently exposed, although restricted in distribution, contains a much more diverse assemblage of diagenetic minerals. Although only a few different minerals occur in each cavity, the composite order of deposition is: ferroan saponite, pyrrhotite, saponite, phillipsite, gmelinite, clinop-tilolite, herschelite, analcime, greigite, rhodochrosite, searlesite, borax, calcite, and colemanite. In some cavities early-formed zeolites appear to have dissolved as later ones crystallized.

Microprobe analyses of the zeolites yielded the following compositions: phillipsite, Na4.28K0.08(Al4.36-Si11.64O32)·xH2O (Si/Al = 2.67); gmelinite, Na6.64K0.10(Al6.80Si17.22O48· xH2O (Si/Al = 2.53); herschelite, Na2.96K0.24(Al3.21Si8.79O24)· xH2O (Si/Al = 2.75); clinoptilolite, Na6.48K0.56(Al7.15Si28.77O72) · xH2O (Si/Al = 4.02); analcime, Na14.02K0.09(Al13.33Si34.44O96)· xH2O (Si/Al = 2.58).

These zeolites formed by reactions between the basalt and evolving fluids, which were controlled by the development of an overlying, Na-borate lake. The wide distribution of saponite, analcime, and searlesite suggests that these minerals formed by the diagenetic reaction between basaltic glass and Na- borate water. The localized occurrence of the complex mineral assemblage, including some of the saponitic clay and the zeolites, phillipsite, gmelinite, and clinoptilolite, formed through a different process, perhaps deuteric or hydrothermal alteration of the basalt, before the lake developed. Because these zeolites are extraordinarily rich in Na, cation exchange may have taken place as the pore fluids became increasingly Na rich. In the latest stages of mineral growth, each of these zeolites was apparently partially dissolved and epitaxially overgrown by a second generation crystal, phillipsite on phillipsite, herschelite on gmelinite, and sodian heulandite on clinoptilolite.

The frequencies, relative intensities and pleochroism of OH stretching bands in some micas and chlorites were studied, and the following conclusions are drawn

Trioctahedral 2:1 and 2:1:1 phyllosilicates, where all octahedral positions are filled with Mg, will have an absorption band about 3700 cm−1. These OH-groups have their axes normal to the mineral’s cleavage.

Substitution of Fe2+ for Mg results in a band about 3665 cm−1. Intensity ratios indicate that two Fe2+ most commonly substitute for two Mg in the same polyhedral group (pyramid).

Decreasing octahedral occupancy in the phlogopite-lepidomelane group, with increasing substitution of R3+ for Mg, causes bands with lower frequencies. These are not very sensitive to the incident angle for the infrared beam. In Li-micas where less than 50 per cent of the octahedral positions are filled with Li, and the rest of the positions are filled with Al and Fe2+, it seems probable that OH-groups residing in a pyramid with two Li and one Al cause a band about 3580 cm−1. Combinations of two Al and one Li or one Li, one Al and one Fe2+ cause absorption about 3480 cm−1.

Dioctahedral 2:1 phyllosilicates having Al or Fe3+ in octahedral positions cause absorption about 3620 cm−1.

The present study provides an example of the accurate identification of polytypes of trioctahedral 1:1 layered silicates from single-crystal X-ray diffraction data collected with the aid of a four-circle diffractometer equipped with an area detector. Single crystals of the mineral cronstedtite from the Nagybörzsöny gold ore deposit, northern Hungary, were studied. The chemical composition of some crystals was determined by electron probe microanalysis (EPMA). The precession-like images of the reciprocal space (RS) sections created by the diffractometer software and presented in the study were used to determine the OD (ordered-disordered) subfamilies (Bailey’s groups A, B, C, D) and particular polytypes. With one exception, all crystals studied belong to subfamily A. The rare polytype 1M, a = 5.51, b = 9.54, c = 7.33 Å, β = 104.5°, space group Cm is relatively abundant in this occurrence. Another polytype 3T, a = 5.51, c = 21.32 Å, space group P31 was also found. Both polytypes occur separately or in mixed, mostly 1M dominant crystals. Some 1M polytype crystals are twinned by order 3 reticular merohedry with a 120° rotation along the chex axis as the twin operation. A rare 1M+3T mixed crystal with 1M part twinned also contains a small amount of subfamily C. A possible presence of the most common 1T polytype of this subfamily cannot be confirmed because of overlap of the characteristic reflections with those of 3T. Several completely disordered crystals produced diffuse streaks instead of discrete characteristic reflections on the RS sections. The EPMA revealed Fe, Si, traces of Mg, Al, S, and Cl. One black crystal originally considered to be cronstedtite was identified as (111) twinned sphalerite. Some crystals of cronstedtite are covered partially by a honey-brown crust or small crystals of siderite.

The patterns of distribution of the mica and clay minerals resulting from alteration of feldspars are much less regular and well defined in the “porphyry copper” deposits than in the vein deposits such as those at Butte, Montana. There are, however, interpretative problems common to both. Chemically, the destruction of the K-feldspars may be interpreted in the light of laboratory investigations of the system potash-alumina-silica-water at various K+/H+ ratios. The experiments indicate that the K-mica (sericite) stability field lies between the K-feldspar and kaolinite fields. The K-mica field is approximately 1.5 pH unit wide, and its boundaries with K-feldspar and kaolinite are parallel below 500°C. The boundaries slope toward higher K+/H+ ratios at lower temporatures. Thus, considering the. K-feldspar—sericite—kaolinite system of minerals, one might expect field patterns showing a central zone of kaolinite bordered by a zone of K-mica which in turn grades outward into unaltered K-feidspar. Such a pattern is demonstrated by Butte’s inner diekite-kaolinite and sericite and possibly by the zoning at San Manuel described by Schwartz. Alteration of plagioclase introduces additional complications into the distribution patterns of clay and mica minerals, the chief of which is the outer argillic zone so characteristic of both vein and disseminated deposits.

An analytical method is described whereby the exchange of various organic cations for other organic cations on montmorillonite is determined. The exchange is followed by means of a Beckman DK-1 ultraviolet spectrometer.

It has been observed that organic cations from compounds such as primary, secondary, and tertiary amine salts and quaternary ammonium salts can be exchanged for one another on the natural cation exchange substance, montmorillonite. The exchange is carried out in isooctane to which a small amount of isopropyl alcohol has been added to aid in dispersion of the organic-clay complex. By choosing pairs of organic substances, of which one has strong absorbance in the ultraviolet and the other does not, the exchange can be followed quantitatively with the u.v. spectrometer.

Controversy over the origin of clay minerals in ancient sediments arises because it is difficult to segregate the factors that cause differences in clay mineral composition. A plan of sampling based on four contrasts was used to evaluate some of these factors. Contrasts studied were: (1) permeability contrasts (sandstone vs. shales); (2) environmental contrasts (cyclic sedimentation); (3) weathering contrasts (outcrop vs. core); (4) source area contrasts (orthoquartzite facies vs. subgraywacke facies).

The resultant data indicate that clay minerals are both allogenic and authigenic. Allogenic clay minerals are the rule when inheritance from the source area dominates either postdepositional or environmental effect; authigenic clay minerals are found where the environment dominates. Rapid sedimentation favors a dominance of allogenic clay minerals, and major depositional environmental effects are required to produce appreciable change. Some of the factors that influence clay mineral composition include source area contribution, the depositional environment, postdepositional effects after burial, permeability, and postdepositional weathering effects.

Montmorillonites saturated with Al3+, H+-Al3+, and K+ were titrated in H2O, acetonitrile (AN), and dimethylformamide (DMF) to investigate the acidic properties of the clay in these solvents and to evaluate the application of nonaqueous titration procedures for studies of the acidic properties of 2:1 swelling clays. Samples were titrated with tetramethylammonium hydroxide using a combination glass electrode for Potentiometric determination. Titers of base required to reach the final Potentiometric endpoints were greater in AN than in DMF and H2O. The larger titers in AN compared to H2O were attributed to pH-dependent sites for which an inflection was not observed in the latter solvent. Titration curves of Al-saturated montmorillonite in AN showed evidence of a salt-induced hydrolysis which was confirmed by titration curves of salt extracts. The hydrolysis reaction was more evident in AN than in H2O and was probably due to a disruption of the H2O structure by AN and a polarization of the H2O of solvation. The hydrolysis reaction was enhanced in the presence of excess salt due to the ion exchange of H+ from the exchange surface. These studies indicate that acidic properties of clays may be drastically altered in organic solvents. The acidic properties may be used to advantage, for example, in the determination of edge-site acidity. In addition, they have implications concerning possible chemical reactions and/or alterations of clay in organic solvents.

Oxine sorption by binary mixtures of montmorillonite and silica gel was studied at pH 5 as a function of oxine concentration and mixture composition. The investigation was made to resolve the problem of the determination of the oxine sorbed by each substance, inasmuch as the total amount sorbed by the mixture is the only value accessible experimentally. By the application of the thermodynamic method of partial quantities, the apparent and partial specific sorption by the clay and by the gel were calculated. These sorption values were found to increase with oxine concentration and to decrease as the proportion of the clay increased in the mixtures.

The clay mineral distributions in fault gouges from shear zones in several slates, phyllites, mica schists, and gneisses of the Eastern Alps were statistically analyzed for consistencies in their occurrence. Discriminant analyses suggested significant groupings of the most common minerals: illite, smectite, kaolinite, and chlorite. The clay mineral distributions in the fault gouges appeared to be related to regional geological units. No relationship, however, was found with the piles of nappes of the Alps. The influence of the mineralogical composition of the parent rock on the clay mineral assemblages appeared to be minor, but the shear behavior of the parent rocks, which is mainly a function of rock strength, was found to control the formation of the clay minerals. In hard rocks (e.g., gneisses), solution transfer at an early stage of the shear process was apparently extensive enough to favor kaolinite formation. As shearing continued, the rate of solution transfer gradually decreased and favored the formation of smectite. In softer rocks (e.g., phyllites), the extent of solution transfer during the shear process was less than in the gneisses and generated an environment that favored smectite formation, even during the early stages of shearing.

SiO2 sols were made unstable by addition of Ca2+ ions. The resulting states of instability were classified as gelation, flocculation, and precipitation by means of observation, by checking the Tyndall effects on the supernatant or suspending solution, as appropriate, and by measuring the apparent densities of flocculated mass. The concentrations of free Ca2+ ions left in solution were measured by means of a Ca2+ ion selective electrode. The amounts sorbed onto SiO2 particles were then calculated by material balance. It was found that while the amount sorbed dictates the limit of stability, the SiO2 concentration in the mixture is an important factor deciding the state of instability. Depending on the SiO2 concentration, there were two distinct flocs with the apparent floc density of 6 ± 1 and 12 ± 1 mg SiO2/ml.

The isothermal solid state reactions of Na2CO3 and other salts at 550°C with montmorillonite and with 1:1 mixtures of montmorillonite-illite and montmorillonite-chlorite were investigated. At a concentration of 20 wt. %, Na2CO3 caused the complete destruction of the X-ray powder diffraction (XRD) pattern of montmorillonite alone and in mixtures with other clays. Less deterioration of the XRD pattern was found for NaOH, NaF, K2CO3, and Li2CO3. NaCl, Na2SO4, Na3PO4, MgCO3, and CuCO3 had no effect on the XRD traces of montmorillonite. The time dependence of the Na2CO3-montmorillonite interaction at 550°C suggested that the reaction is diffusion controlled in three dimensions, i.e., diffusion was directed from the surface of the particle towards its center.

Experimental alterations of K-feldspar in distilled-deionized water at 150°, 175°, 200°, and 225°C were performed. The alteration products and dissolution mechanism of K-feldspar were examined by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray analysis (EDX), and X-ray photoelectron spectroscopy (XPS). SEM, TEM, and EDX clearly showed formation of fibrous boehmite less than 1.0 μm in length at the early alteration stages. The boehmite fibers decreased in abundance and rounded platy 1 M mica was produced as alteration proceeded. The mica exhibited initially angular shaped small flakes of 0.69 μm in average size, which developed to rounded platy particles of 1.97 μm. The main chemical reactions occurring in this experimental system can be expressed by: $$\begin{array}{l} \mathop {KAlS{i_3}{O_3}}\limits_{\left[ {K - feldspar} \right]} + 6{H_2}O + {H^ + } \to \mathop {AlO\left( {OH} \right)}\limits_{\left[ {boehmite} \right]} + 3{H_4}Si{O_4} + {K^ + }, \\ \mathop {3KAlS{i_3}{O_8}}\limits_{\left[ {K - feldspar} \right]} + 12{H_2}O \to \mathop {KA{l_3}S{i_3}{O_{10}}{{\left( {OH} \right)}_2}}\limits_{\left[ {mica} \right]} + 2{K^ + } + 6{H_4}Si{O_4} + 22{H^ + }. \\ \end{array}$$ XPS showed no significant changes in intensities of photoelectron lines excited from K, Si, and Al in the K-feldspar surface before and after alteration, however the K/Si molar ratios in the solutions were considerably smaller than that of the original K-feldspar. The results of XPS strongly indicate that no dealkalized layer was produced on the surface, and that dissolution of K-feldspar in aqueous solution proceeded congruently by a surface-reaction mechanism. The discrepancy of mass balance in the solutions may be mainly caused by adsorption of K on the surface of boehmite.

Some dehydroxylated sericites were boiled with solutions of various salts. A rectorite-like regular mixed-layer was formed when 2M sericite was treated with solution containing salts such as NaNO3, Na2SO4, CaSO4, CaCl2, MgCl2 and MgSO4 respectively. A random mica/montmorillonite mixed-layer was formed from 1M sericite. In order to change the 2M sericite into a regularly interstratified mineral, they are heated to the temperature range of dehydroxylation. The formation of a regularly interstratified mineral from 2M sericite can be explained by the change in the (OH) bond direction after the extraction of the potassium ion.