Mixtures of synthetic Al-substituted goethite (α-Fe0.814Al0.186OOH) and hematite (α-Fe1.658Al0.342O3) (75, 50, 25, 3% hematite by weight) were studied by Mössbauer spectroscopy to evaluate the use of that technique for quantitative analysis. Mössbauer spectra for these mixtures, obtained in the temperature range 12–130 K, were better fitted by a distribution of magnetic fields than by two magnetic sextets. Spectra at 80 K were equally as good as those from lower temperature to determine the hematitegoethite ratio. The recoil-free fractions of the individual components were about equal at any fixed temperature, but thickness effects caused as much as 30% error in the determination of the ratio of components in mixtures.

Reaction of mixtures of cobalt nitrate, colloidal silica, and a metal hydroxide (MOH) under hydrothermal conditions produced a range of cobalt hydroxysilicates, the components of which depended upon the identity of M, temperature, and reactant ratios. At 250°C, if M = Na, a smectite of composition Na0.06Co3.07Si3.95O10(OH)2 (I) was produced. If M = K, either a mica, KCo2.5Si4O10(OH)2 (II), intermediate between di- and trioctahedral, or a Si-deficient mica, KCo3Si3.75O10(OH)2 (III), was formed depending upon the reactant ratios. Similarly, if M = Cs, either a vermiculite or a 2:1 layer silicate intermediate between a mica and a brittle mica was produced. If M = Li, only the non-clay mineral Li2CoSiO4 was formed. Tetraalkylammonium hydroxides (NR4OH, R = methyl, ethyl, or propyl) yielded chrysotile. All phases were characterized by elemental analysis, transmission electron microscopy, and X-ray powder diffraction. Further characterization of smectite I was undertaken by diffuse reflectance, infrared, and X-ray photoelectron spectroscopy. The layer charge in these clays appears to stem from cation vacancies within an almost trioctahedral sheet and, possibly, within the tetrahedral sheets. Some of the cobalt present had tetrahedral coordination geometry, but its location was not determined.

The electron spin resonance (ESR) spectra and the natural and gamma-induced thermoluminescence (TL) glow curves of a series of variably cation-exchanged Fe-Ca-clays prepared from SWy-1 montmorillonite were examined. The ESR signal (g = 2) intensity associated with the surface Fe was found to increase linearly with surface Fe content up to a nominal concentration of 50% exchangeable Fe. At > 50% exchangeable Fe, no appreciable increase in the signal was noted. The TL intensity decreased linearly with increasing surface Fe up to 50% nominal exchangeable Fe. At > 50%, the signal was not appreciably further diminished. The natural TL showed only a high-temperature peak, but irradiation produced an additional low-temperature peak. One month after gamma-irradiation, the integrated TL signal was still 10–100 times higher than that from the non-irradiated material. Thus, (1) surface iron clusters may form above a certain critical Fe concentration; (2) the Fe clusters are probably less effective in quenching TL than are single Fe atoms, implying interaction between surface Fe and the stored energy content of the material; and (3) the electronic energy stored in the material as the result of gamma-irradiation is only slowly dissipated.

The adsorption and degradation on montmorillonite of s-triazine, the parent compound of a major group of triazine-based herbicides, were studied by Fourier-transform infrared spectroscopy. The original s-triazine appeared to hydrolyze with residual bound water in montmorillonite at 20°C to produce formamide, which formed an intercalate with the clay. A mechanism for the conversion of s-triazine to formamide was proposed which does not support earlier reports that formic acid and ammonia are the reaction products. The infrared spectrum of the formamide-Na-montmorillonite intercalate suggests that formamide reacted with the exchangeable Na cation and that the NH2 group hydrogen bonded with the clay. Assuming the intercalated formamide molecule to be planar, the molecular plane was found to be inclined at ~33° with respect to the plane of the silicate sheet. C-N and C-O bonds were also found to be tilted at the same angle with respect to the clay surface. The proposed orientation is in good agreement with the measured value of d(001) for the formamide-Na-montmorillonite complex. The proposed model of the formamide-montmorillonite complex serves as a basis for comparison of other clay-amide complexes that are important in protein-clay interactions.

The Rokle bentonite deposit is part of an accumulation of argillized volcanoclastic rocks in the Tertiary stratovolcanic complex of the Doupovské Mountains east of Karlovy Vary (Carlsbad), about 100 km westnorthwest of Prague, Czechoslovakia. The arenite basalt ash was originally composed of hyaloclasts and subordinate biotite. The following types of montmorillonite aggregates were produced during the alteration of the ash in a stagnant, lacustrine environment: (1) extremely fine-grained micro-crystalline aggregates that have honeycomb textures and that replace the original hyaloclasts, and (2) coarse crystalline aggregates that have more open honeycomb textures and that fill pores and cracks in altered hyaloclasts and in pumice vesicles. Both types of aggregates have the same chemical composition according to energy dispersive X-ray analysis.

Montmorillonite, separated as the <1-¼m size fraction from olive gray bentonite, has the following crystallochemical formula: (K0.09Na0.02Ca0.29Mg0.10) (Al2.43Fe3+1.05Fe2+0.005Mn2+0.005Mg0.50) (Si7.62Al0.38) O20(OH)4. Biotite was apparently stable during the alteration of the hyaloclasts. Anatase and possible accessory heulandite-clinoptilolite were also formed in small amounts, but were not observed by scanning electron microscopy. Goethite is the youngest oxidation product in some parts of the bentonite. Minute fragments of sodium-rich plagioclase, potassium feldspar, quartz, and muscovite are ubiquitous accessories of the original hyaloclasts. Together with kaolinite, they formed from the underlying fresh or kaolinized orthogneiss.

A high-pressure, high-temperature cell was used to monitor the basal X-ray powder diffraction spacing of Na-saturated Cheto montmorillonite in contact with NaCl solutions at temperatures as high as 200°C and hydraulic pressures as high as 6700 psi (456 bar). The 003 and 005 reflections were used to determine d(001) of the smectite. The montmorillonite, in 1 molal NaCl, exhibited a d(001) of 15.4 Å at room temperature and pressure and a d(001) of 15.6–15.7 Å under 500–2200 psi hydraulic pressure. The basal spacing of the clay in 5 molal NaCl was 15.2 Å and 15.33–15.45 Å at 1 bar and 750–6700 psi (53–456 bar), respectively. Because no changes in the basal spacing with increasing temperature to 200°C were detected in any of the experiments, this Na-smectite probably exists as a two-water-layer complex under diagenetic conditions.

The reaction of smectite to illite in shale from the COST 1 well in the south Texas Gulf Coast and from altered ash-fall tuffs from the Morrison Formation in New Mexico was investigated using X-ray powder diffraction in conjunction with transmission electron microscopy. In the COST 1 well, the bulk of the detrital clay was originally a K+-deficient mixed-layer illite/smectite (I/S). As the I/S adsorbed K+ released by the dissolution of K-feldspar during burial, the proportion of expandable layers decreased with depth from ~65% near the top of the well to ~25% at 4500 m depth. In contrast, the proportion of low-charged structural planes [<0.8 eq per (Al,Si)4O10 unit] in the I/S decreased gradually from ~40% near the top of the well to ~15% near the bottom. Authigenic smectite with 100% expandable layers from the Morrison Formation tuffs is an alteration product of vitric ash. Where these tuffs have been buried to ~ 1400 m the smectite has reacted to form I/S with ~ 15% expandable layers.

Direct lattice images of I/S crystallites from both locations reveal a correspondence between edge dislocations and the interface between illite layers and smectite layers. Al, Si, Fe, Ca, Mg, and Na were apparently mobile along these dislocations as the reaction of smectite to illite proceeded. Al was probably retained within the crystallite when illite layers replaced the smectite layers; however, some of the remaining cations were expelled. Lateral replacement of smectite layers by illite appears to have been the principal growth mechanism.

Published chemical data for suites of mixed-layer minerals from diagenetic sedimentary rocks, hydrothermally altered tufts, and a metasomatic bentonite bed indicate that the layer charge and composition of the different components of illite/smectite (I/S) differ from one geological environment to another. It appears that the composition of the elemental smectite and illite layers in the I/S is more or less constant for samples within each geologic setting. In the examples considered, the smectite layers are predominantly montmorillonitic in character (i.e., the charge is in the octahedral site), whereas the illite layers show different types of charge sites, depending upon the suite studied. Illite layers appear to have about the same charge in all three suites studied, slightly more than 0.7 per O10(OH)2 unit, whereas the smectite layers in the different suites range in charge from about 0.3 to 0.7 per O10(OH)2 unit. Cation-exchange capacities reflect these differences in charge, although not ideally. The differences in the composition of the component layers in each geologic suite of mixed-layer clays are probably due either to differences in the bulk chemistry of the rocks in the different suites or to differences in intensive variables, such as temperature and pressure, of the regime under which they have formed.

The formation of hydroxy-Al-interlayered montmorillonite was affected by complexing organic acids. Montmorillonite (<2.0 μm) was aged for three months at an initial pH of 5.0 or 6.0 in AlCl3 solutions containing citric or tannic acid at organic acid/Al molar ratios from 0 to 1.0. The Al/clay ratio in the system was 900 meq Al3+/100 g of montmorillonite. Ion-exchange experiments revealed that organically complexed Al ions have both positive and negative charges. Evidence from X-ray powder diffraction, electron microscopic examination, measurements of specific surface, cation-exchange capacity, organic carbon, and the nature of sorbed Al indicates that citric and tannic acids influence differently the hydroxy-Al interlayer formation in montmorillonite. Hydroxy-Al-citrate can be adsorbed as interlayers in montmorillonite, but hydroxy-Al-tannate exists principally as a separate phase binding the clay particles. The differences observed between the influence of citric and tannic acids on Al interlayering are probably due to their differences in molecular weight (size) and structure.

The reaction of kaolin with NaCl was followed by dynamic thermal analysis and mass spectrometry under N2, CO2, and air atmospheres and in a 10−5-torr vacuum. The weight loss was a function of the atmosphere used and, according to mass spectrometry, was due to the evolution of H2O, HCl, and very small amounts of H2. HCl was formed only after the release of 85% of the hydroxyl content of the kaolin. When the clay was pretreated with saturated salt solution, H2O and HCl evolved in more or less the same temperature range, indicating that only some of the OH groups reacted with the chloride ion. High-temperature X-ray powder diffraction patterns showed that the sodium ion reacted with the noncrystalline metakaolin to give NaAlSiO4. Chemical analysis showed that the reaction of kaolinite and sodium chloride started below 400°C. The rate of the reaction increased at higher water vapor concentration. From mass spectrometric data, the NaCl-treated kaolin appeared to adsorb CO2. Desorption at several distinct temperatures suggests that CO2 was adsorbed by different parts of the structure, i.e., holes and channels. X-ray powder diffraction and infrared absorption data indicate that the kaolinite structure persisted even after it had been heated with NaCl in a CO2 atmosphere to as high as 800°C.

The percentage of expandable layers in illite/smectite (I/S) mixed-layer clay decreases with increasing temperature and depth in a section through marine Cretaceous shales in the Champlin 1 Hartley Federal well in the Powder River basin, Wyoming. This systematic change in I/S expandability is evidence that low-expandable I/S in Cretaceous shales of the northern Rocky Mountain area reflects, at least in part, thermal alteration during burial diagenesis. In eastern Montana and western North Dakota where I/S in the Lower Cretaceous Mowry and Skull Creek source rocks is diagenetically unaltered, only trace amounts of hydrocarbons have been found in the Lower Cretaceous and other Cretaceous sandstones. Elsewhere in the northern Rocky Mountain-Great Plains region, hydrocarbons in the Lower Cretaceous Muddy Sandstone and its equivalents occur within or immediately adjacent to areas in which I/S clay in the Mowry and Skull Creek shales has been diagenetically altered during burial. Altered I/S and thermally mature organic matter, as defined by Rock-Eval pyrolysis values, coexist in these source rocks. Both may be used as maturation indicators in the search for Cretaceous-source hydrocarbons in the northern Rocky Mountain area.

High-resolution transmission electron microscopy (HRTEM) has been used to examine illite/smectite from the Mancos Shale; rectorite from Garland County, Arkansas; illite from Silver Hill, Montana; Na-smectite from Crook County, Wyoming; corrensite from Packwood, Washington; and diagenetic chlorite from the Tuscaloosa Formation. Thin specimens were prepared by ion milling, ultramicrotome sectioning, and/or grain dispersal on a holey carbon substrate. Some smectite-bearing clays were also examined after intercalation with dodecylamine hydrochloride (DH). Intercalation of smectite with DH proved to be a reliable method for HRTEM imaging of expanded smectite (d (001) = 16 Å) which could then be distinguished from unexpanded illite (d (001) = 10 Å). Lattice fringes of basal spacings of DH-intercalated rectorite and illite/smectite showed a 26-Å periodicity. These data support X-ray powder diffraction (XRD) studies which suggest that these samples are ordered, interstratified varieties of illite and smectite. The ion-thinned, unexpanded corrensite sample showed discrete crystallites containing 10-Å and 14-Å basal spacings corresponding to collapsed smectite and chlorite, respectively. Regions containing disordered layers of chlorite and smectite were also noted. Crystallites containing regular alternations of smectite and chlorite layers were not common. These HRTEM observations of corrensite did not corroborate XRD data. Particle sizes parallel to the c axis ranged widely for each sample studied, and many particles showed basal dimensions equivalent to more than five layers. For all illite, smectite, and illite/ smectite particles examined, crystallite sizes of about 20 Å in the basal dimension were not observed.

Pisolites from an iron crust in western Senegal were studied by conventional and high-resolution electron microscopy to determine their internal structure and the genetic processes that led to their formation. Each pisolite consisted of a concentric structure of hematite rimmed by goethite. Two types of goethite were distinguished: (1) large (≃ 0.6 μm long and 0.06 μm wide), euhedral laths arranged in fibrous aggregates of slightly misoriented grains devoid of internal defects as shown by their two-dimensional lattice images, and (2) a matrix of smaller (≃400 Å), anhedral grains surrounded by the larger laths. Based upon the crystal habit and the presence or absence of internal alveoles, the large goethite laths probably grew at the expense of the matrix goethite. Poorly crystalline kaolinite, presumably formed from well-crystalline precursor kaolinite, and clusters of partially dissolved quartz grains were also imaged. In addition, two uncommon phases were found—maghemite in topotactic relationship with hematite and a layered, Fe-rich, mica-like mineral with a 2M superstructure. Unlike kaolinite, this latter phase was likely in equilibrium with iron oxyhydroxides. Substituted Al probably was released during goethite recrystallization, and mass transfers probably took place through the heterogeneous porosity (i.e., large voids and cracks coupled with fine pores) revealed by transmission electron microscopy.

Titanium was introduced into the montmorillonite structure by cation exchange with polymeric Ti cations, formed by partial hydrolysis of TiCl4 in HCl. On further hydrolysis and heating, TiO2 pillars in the form of anastase were formed between the montmorillonite layers. The resulting TiO2-cross-linked montmorillonites possessed surface areas in the range 200–350 m2/g and pore volumes of about 0.2 cm3/g and were thermally and hydrothermally stable to 700°C. The basal spacing of products heated at temperatures > 200°C was about 28Å, as determined by X-ray powder diffraction and by N2-desorption pore-size analysis. The surface area increased and the pore volume decreased with increasing HCl-concentration in the Ti-solution. The uptake of TiO2 by the montmorillonite, the surface area, and the pore volume increased with increasing amount of Ti added in the preparation, to about 10 mmoles of Ti/g of montmorillonite. A further increase in the amount of Ti added resulted in a decrease in surface area, but the pore volume and the uptake of TiO2 remained almost constant. The high porosity and the interlayer spacing of the product are consistent with a structure similar to that previously proposed for smectites, cross-linked with hydroxy-Al oligocations.

The cation-exchange capacity (CEC) of Na-Al- and Ca-Al-montmorillonite after neutralization with NaOH or Ca(OH)2 was studied at three Al levels: 10, 25, and 50% of the CEC. Hydroxy-Al polymers were effective in reducing the CEC of Na-montmorillonite (by more than 46%), the exact effectiveness being dependent on the hydroxy-Al content. The hydroxy-Al polymers were less effective in reducing the CEC of Ca-montmorillonite (less than 26%). The CEC reduction was equal to or larger than the amount of the untitrated Al. The electrostatic charges of the clay which were blocked by the hydroxy-Al polymers were compensated for by both the positive charge of the hydroxy-Al polymers and the trapped cations on the clay surfaces. These cations remained on the clay even after extensive washing with 0.1 M KCl.

An ochreous precipitate isolated from a stream receiving acid-sulfate mine drainage was found to consist primarily of goethite and lesser amounts of ferrihydrite-like materials. The Fe-oxide fraction, including goethite, was almost totally soluble in acid ammonium oxalate. Similar materials were produced in the laboratory by hydrolysis of ferric nitrate solutions containing 250 to 2000 μg/ml sulfate as Na2SO4. Initial precipitates of natrojarosite transformed to Fe-oxides upon aging for 30 days at pH 6.0. The proportion of goethite in the final products decreased with increasing sulfate (SO4/Fe = 0.2 to 1.8) in the initial hydrolysis solutions; only ferrihydrite-like materials were produced at SO4/Fe ratios > 1.5. Variations in SO4/Fe solution ratios also produced systematic changes in the color (10R to 7.5YR) and surface areas (49 to 310 m2/g) of the dried precipitates, even though total S contents were relatively constant at 2.5 to 4.0%.

The smectite to illite reaction was studied by transmission and analytical electron microscopy (TEM/AEM) in argillaceous sediments from depths of 1750, 2450, and 5500 m in a Gulf Coast well. Smectite was texturally characterized as having wavy 10- to 13-Å layers with a high density of edge-dislocations, and illite, as having relatively defect-free straight 10-Å layers. The structures of smectite and illite were not continuous parallel to (001) at smectite-illite interfaces. AEM data showed that the smectite and illite were chemically distinct although smectite had a more variable composition. Illite formation appeared to have initiated with the growth of small packets of illite layers within subparallel layers of smectite matrix. With increasing depth, ubiquitous thin packets of illite layers increased in size until they coalesced.

A model for the transition requires that the structure of smectite was largely disrupted at the illite-smectite interface and reconstituted as illite, with concomitant changes in the chemistry of octahedral and tetrahedral sites. At least partial Na-K exchange of smectite preceded illite formation. Transport of reactants (K, Al) and products (Na, Si, Fe, Mg, H20) through the surrounding smectite matrix may have taken place along dislocations.

The smectite-to-illite conversion process for the studied samples does not necessarily appear to have required mixed-layer illite/smectite as an intermediate phase, and TEM and AEM data from unexpanded samples were found to be incompatible with the existence of mixed-layer illite/smectite in specimens whose XRD patterns indicated its presence.

Oxygen isotope ratios of <0.1-μm smectite in bottom sediments of the Mississippi River and the Gulf of Mexico near the mouth of the river have been determined to investigate diagenesis of land-derived clay minerals during sedimentation in the sea. No difference was detected in δ18O (SMOW) between the river and the Gulf samples indicating that no smectite alteration or addition of neoformed smectite to the river samples took place during sedimentation. Thus, authigenic minerals in the river sediments cannot make up more than a few tenths of a percent of the bulk sediments.

Similar results were obtained from 3 × 106-yr b.p. sediments buried to 80 to 600 m at Deep Sea Drilling Project site 323, Bellingshausen Abyssal Plain. No significant change with depth was noted in the δ18O of the <0.3-μm size fraction, mostly smectite, of these land-derived sediments. On the basis of the δ18O of the deepest sample, the maximum amount of authigenic minerals in the land-derived sediments during burial in the sea cannot be more than one or two percent of the bulk sediments. Hence, the alteration at seafloor temperatures of 25-45% of the <0.1-μm size clays in 3 × 106 yr b.p. sediments reported in a previous study is not substantiated. The data demonstrate that land-derived smectite is stable in the sea, and that oxygen isotopes can be used to investigate the modes and the temperatures of formation of authigenic smectites in marine sediments that are younger than 25 × 106 yr and that formed below 25°C.

Microprobe analyses of optically homogeneous detrital biotites from sandstones of the Visingsö Group and the Dala Sandstone, Sweden, revealed a consistently low K content (generally <0.75 atom/formula unit) and variable amounts of Fe, Mg, Al, and Si. Electron probe profiles of some biotite grains indicated two major types of interstratification, one consisting of mainly illite layers and the other apparently consisting of chlorite layers. The layer thicknesses commonly ranged between 0.5 and 3 μm. Microprobe analyses of some thick (∼5 μm) illitic layers indicated a phengitic composition, wherein the mica was relatively rich in octahederal Fe and Mg. The chloritic layers appeared to be Fe-Mg-rich and generally had octahederal totals of <6 atom/formula unit. Variations in the chemical composition of the biotite and some of the illite and chlorite were probably due to an uneven distribution of small amounts of the interstratified phases. The illite and chlorite layers were apparently formed by pseudomorphic replacement of detrital biotites, i.e., gradual replacement of one biotite layer by one layer(s) of illite and/ or chlorite during diagenesis.

Classification and identification criteria of maximum-degree-of-order (MDO) polytypes of homo- and meso-octahedral micas based on the distribution of the intensities of 20l (13l) and 02l reflections are proposed. Calculated | F(20l) |2 and | F(02l) |2 values for single crystals of micas with different compositions are given for one-, two-, and three-layer polytypes. Transmission powder diffractometry is proposed as a suitable method for the identification of the different groups of mica polytypes from polycrystalline specimens. Calculated powder patterns and the characteristic properties of the diffraction patterns of random and highly oriented aggregates are employed for identification purposes. The individual MDO polytypes are designated by generalized Ramsdell symbols which also contain information about their position in the classification system.