The interactions of the following three kinds of racemic and enantiomeric cobalt(III) chelates with montmorillonite and saponite are studied: [Co(en)3]3+ (en = ethylenediamine), [Co(diNOsar)]3+ (diNOsar = (1,8-dinitro-3,6,10,13,16,19-hexaazabicyclo[6,6,6]-eicosane)cobalt(III))and [Co(diAMsar)]3+ (diAMsar = (1,8-diamino-3,6,10,13,16,19-hexaazabicyclo-[6,6,6]eicosane)-cobalt(III)). At neutral pH, these complexes are adsorbed as a trivalent cation up to 90%–100% of the cation exchange capacity of a clay. No difference is observed in the maximum adsorption amount between the racemic and enantiomeric isomers. The basal spacings of the clay-chelate adducts are determined by the X-ray diffraction measurements of non-oriented powder samples: 14.3 Å for [Co(en)3]3+ montmorillonite, 16.5 Å for [Co(diNOsar)]3+ montmorillonite, and 16.9 Å for [Co(diAMsar)]3+ montmorillonite. The results imply that the chelates form a monolayer in the interlayer space. From the one-dimensional Fourier analyses of the diffraction pattern of [Co(diNOsar)]3+ montmorillonite, the chelate is concluded to be adsorbed with its three-fold symmetry axis in parallel with the layer surface. This is in contrast with the previous results of [Ru(phen)3]2+ and [Ru(bpy)3]2+, which are adsorbed with their three-fold symmetry axes perpendicular to the surface. The conclusion is consistent with the angular dependence of the infrared absorption spectrum of the film of the adduct.

A 3-cm-thick, two-layered clay unit that records mineralogic and textural evidence of a catastrophic event that occurred at a time now marked as the end of the Cretaceous Period was preserved in ancient peat-forming environments of the Western Interior Basin of North America. The two layers of this unit consist of altered distal ejecta and are easily distinguished by their distinctive texture and impact components from other clay beds, mainly tonsteins and detrital shales, occurring within the sequence of rocks enclosing the Cretaceous/Tertiary (K/T) boundary interval.

The lower claystone layer of the K/T boundary unit represents melted silicic target rock that has altered mainly to kaolin minerals. Impact components and signatures of this lower layer include a relict imbricate fabric of glass fragments, shards, bubbles, hollow spherules (altered microtektites), small amounts of shocked mineral grains, and a subdued iridium anomaly. These components and textures, combined with the layer's restricted areal distribution, indicate that this layer, called the “melt ejecta layer,” is the distal part of an ejecta blanket deposit. We interpret the melt ejecta layer to be an altered deposit of mostly impact-derived, shock-melted, silicic target material that traveled through the atmosphere within a detached ejecta curtain and on other ballistic trajectories.

The upper laminated layer of the K/T boundary unit consists mostly of altered vitric dust and abundant shocked minerals whose size and amounts decrease away from the putative crater site in the Caribbean area. High-nickel magnesioferrite crystals, high iridium content, geochemical signature, and worldwide distribution all suggest this upper layer originated from a cloud of vaporized bolide and entrained target-rock materials ejected above the atmosphere. The components of this layer, called the “fireball layer,” settled slowly by gravitational processes from an Earth-girdling vapor cloud and were deposited immediately on top of the already-emplaced melt ejecta layer.

The clay minerals that formed in the two layers are largely a function of composition and the highly unstable, shock-modified state of the fallout materials altered in acidic, organic-rich waters of ancient peat swamps. The fireball layer is mostly altered to smectitic clay from a mafic glass condensed from the vaporized chondritic bolide, along with some kaolinite formed from blebs of melted silicic target material entrained in the vapor plume cloud during ejection. In contrast, the melt ejecta layer is mainly kaolinitic, derived from silicic glass formed from melted target rocks. In this layer, the glass rapidly altered to mostly disordered, micrometer-sized “cabbage-like” or submicrometer-sized embryonic forms of spherical halloysite, probably from an allophane precursor. These crystallization characteristics of the melt ejecta layer are much different than those which formed coarse vermicular aggregates and platy kaolinite crystals in tonsteins from outside the K/T boundary interval throughout the Western Interior. The contrast in the incipient formation of dominantly kaolinitic clay minerals in the basal melt ejecta layer and of smectitic clay minerals in the overlying fireball layer reflect silicic versus mafic starting materials, respectively, and also supports the proposed two-phased meteorite impact ejection and dispersal model.

During subsequent burial and diagenesis of the K/T boundary unit, the metastable halloysite and smectite aggraded to kaolinite and mixed-layer illite/smectite, respectively. Both the ordering of kaolinite and illitization of smectite varies locally as a function of the degree of diagenetic grade or maturity, probably in response to local variations in temperature due to maximum burial depth (burial diagenesis).

Reinterpretation of published data for shale cuttings from the Gulf of Mexico sedimentary basin identifies three reaction zones for illite formation with increasing depth for well CWRU6. In a shallow zone (1.85 to 3 km), non-expanding illite-like layers formed primarily by the coalescence of smectite 2:1 layers around interlayer K+. In a middle zone (3 to 4 km), illite crystals neoformed from solution as coarser K-bearing phases and smectite were dissolved by organic acids. In the deepest zone (>4 km), illite recrystallized as less stable illite crystals dissolved, and more stable illite crystals grew during mineral ripening. The progressive loss of radiogenic argon in the deepest zone yielded a constant apparent age for the clays with depth, an effect previously attributed to “punctuated diagenesis.” The above hypothesis for illite formation emphasizes the need to establish the zone (i.e., the reaction mechanism) from which shales were derived before making detailed geologic interpretations based on illite mineralogy.

The reaction of hydroxy-Al interlayers in montmorillonite with monosilicic acid was studied by chemical analysis, X-ray diffractometry (XRD), and Fourier-transform infrared (FTIR) spectroscopy. Hydroxy-Al interlayers in montmorillonite was prepared by treating Ca-montmorillonite (<2) μm) with hydroxy-Al solutions at an initial Al concentration of 0.5 mM and OH/Al molar ratios of 1.0, 2.0, and 2.5. The resultant partially interlayered montmorillonite was reacted with 0.5, 0.9, and 1.4 mM monosilicic acid solutions.

A substantial amount of monosilicic acid was adsorbed by the interlayer hydroxy-Al polymers through the reaction of Si-OH groups with mainly Al-OH groups, resulting in the formation of silicated Al-interlayers with Si/Al molar ratios up to 0.19. The adsorption of silicic acid by interlayer hydroxy-Al polymers increased the basal spacings of the partially interlayered montmorillonite. This effect was most pronounced for the hydroxy-Al interlayered montmorillonite formed in the systems at an OH/Al ratio of 2.0, in which the d(001) reflections (110°C) shifted from 13.6 Å before silication to 14.1 Å with a shoulder at 17.0 Å after silication. The differential IR spectrum of the silicated hydroxy-Al interlayers in montmorillonite exhibited absorption bands at 935 and 3730 cm−1, which can be assigned to Si-O and Si-OH, respectively, of the adsorbed Si(OH)4. An interlayer structure analogous to that of “proto-imogolite” was, thus, proposed for the silicated interlayer hydroxy-Al polymers in montmorillonite. This study revealed a new mechanism through which Si enters the interlayer spaces of smectite. The silication of hydroxy-Al-interlayered clays in natural environments and the related modifications in surface properties of the clays should receive increasing attention.

Investigation of a naturally occurring mixture of dioctahedral micas prompted an examination of X-ray diffraction (XRD) techniques for obtaining quantitative estimates of 1M and 2M 1 mica proportions. A method for determining quantitative estimates has been developed that includes the effect of preferred orientation of mica particles as described by the March function. A diagram is presented from which the percentage of 2Mı and the March parameter (r) can be obtained from two peak-area ratios: 2.80 Å/5.0 Å and 2.80 Å/2.58 Å, which are measured on observed XRD patterns of mica mixtures. The ability of this peak-area ratio diagram to predict reasonably accurate proportions of 1M and 2Mı micas was tested by comparing calculated and observed XRD patterns over a range of 2θ values from 16° to 40° for size-fractionated mixtures. Lack of accurate crystal-structure data for dioctahedral 1M mica proved an impediment to obtaining improved quantitative estimates of mica proportions.

Boxwork fabric in which numerous thin or thick halloysite walls are interconnected into a microscopically porous cellular pattern is widely developed in the halloysite-rich kaolin formed by weathering of anorthosite in Sancheong, Korea. Studies using optical microscopy, scanning electron microscopy, and transmission electron microscopy have been carried out in order to elucidate the detailed features and origin of the boxwork.

In the early stage of weathering, halloysite spheres formed in etch pits on the walls of microstructural discontinuities in the slightly weathered rock. With further weathering, the halloysite spheres grew to discs or flattened globules, which in turn coalesced to form large planar halloysite plates amid narrow fissures. The halloysite plates were detached by dissolution of the plagioclase in groundwater. Continued growth of the halloysite tubes in the plates resulted in the wrinkling of the plates. Finally, the plagioclase was completely dissolved by groundwater, leaving the boxwork of wrinkled halloysite walls and large pores. The relatively high rigidity of the boxwork is due to the compact agglomeration of halloysite tubes within the wrinkled halloysite walls.

Cation balance calculation shows that Al was significantly mobilized during the formation of the boxwork in the weathering environment. The well-developed microfissures, the high dissolution rate of the calcic plagioclase, and the rapid flow of groundwater in a mountainous topography with relatively steep (20°) slope have been the factors controlling the formation of the porous boxwork in the halloysite-rich kaolin of the Sancheong area.

Illite from the Potsdam Sandstone (lower Ordovician) of Northwestern New York was studied by powder X-ray diffraction, scanning electron microscopy, and chemically analyzed and dated by the K/Ar method. The texture and ages of 360 and 392 Ma on two samples establish that the mineral is authigenic and relatively uncontaminated by Precambrian detritus. Random powder X-ray diffraction patterns show sharp and relatively intense 02l and 11l reflections, indicating an ordered structure. Comparisons with calculated patterns demonstrated that the mineral is not the common 1M or 2M1 polytype. Instead, the experimental pattern is very similar to that of a 3T polytype, but it agrees better with the calculated pattern of the octahedral cis-vacant, noncentrosymmetric (space group C2) structure found by Méring and Oberlin (1967) and Tsipursky and Drits (1984) in smectites, proposed for mica by Drits et al. (1984) and found by Zvyagin et al. (1985).

Kaolinite: alkali halide intercalates have been successfully prepared by grinding the salt with kaolinite in the absence of water. Rate of intercalation is shown to correlate negatively with melting point of the salt. The basal dimensions of the intercalates increase with increasing size of the ion. As shown recently for kaolinite: NaCl intercalate, the layered structure survives the dehydroxylation of the kaolinite at 500°–600°C, at which point the excess alkali halide can be removed by rinsing to give an XRD-amorphous material. This amorphous material, of approximate stoichiometry MAlSiO4, reacts at surprisingly low temperatures to give crystalline phases, apparently of the same stoichiometry, with structures closely related to eucryptite (M = Li), carnegieite (M = Na), kalsilite (M = K), and leucite (M = K, Rb, Cs). The relationships between the structures of the reaction products are discussed.

Sorption of benzene onto Cu-montmorillonite was characterized by Fourier transform infrared (FTIR) spectroscopy and 13C magic angle spinning nuclear magnetic resonance (MAS NMR). Under anhydrous conditions, chemisorption of benzene in the interlamellar region of Cu-montmorillonite led to the formation of a dark red surface complex that exhibited a vibrational spectrum similar to that of doped poly-p-phenylene. When the benzene sorption reaction was carried out under high relative humidity conditions, polymerization of benzene did not occur. The FTIR spectrum of the surface complex formed under wet conditions exhibited vibrational bands that could not be assigned to those of the parent benzene molecule or to those of previously observed chemisorbed Type I or Type II complexes. 13C MAS NMR spectra of 13C-enriched benzene sorbed onto Cu-montmorillonite powder showed the presence of two groups of peaks that could be assigned to aromatic and aliphatic carbon respectively.

2-Phenethylamine 13C-enriched in the beta position was adsorbed on four different aluminum-exchanged clays: hectorite, Barasym, Laponite RD, and lithium taeniolite. The sites for adsorption were characterized by 13C high-resolution cross-polarization magic angle spinning nuclear magnetic resonance (CPMAS-NMR) spectroscopy. Using differences in chemical shift values and linewidths, three different types of bound ammonium compounds and a motionally restricted bound compound were identified. Correlation with charge effects indicated that one of the clay sites was extremely acidic.

The important catalytic sites for the different clays, the edge or platelet face, interlamellar and some combination of both, were probed by using the trimethylsilyl group as a clay-blocking agent. Silylation of aluminum-exchanged Laponite RD and Li taeniolite had little effect on amine adsorption. This indicates that, for these clays, amine adsorption occurred mainly at interlamellar sites. For hectorite, amine adsorption occurred at both surface and interlamellar sites, and silylation had the effect of reducing surface adsorption. Silylation of Barasym resulted in a very interesting shift of adsorption from one kind of surface site to a more acidic surface site.

Ammonium-saponite is hydrothermally grown at temperatures below 300°C from a gel with an overall composition corresponding to (NH4)0.6Mg3Si3.4Al0.6O10(OH)2. The synthetic saponite and coexisting fluid have been characterized by means of X-ray powder diffraction, X-ray fluorescence, Induced Coupled Plasma-Atomic Emission Spectroscopy, thermogravimetric analysis, transmission electron microscopy, CEC determination using an ammonia selective electrode, and pH measurement. In the crystallization model developed, crystallization started with the growth of individual tetrahedral layers with an aluminum substitution not controlled by the A1IV/A1VI ratio in the gel and hydrothermal fluid, on which the octahedral Mg layers can grow. During the synthesis, individual sheets stacked to form thicker flakes while lateral growth also took place. The remaining A1VI partly replaced ammonium as the interlayer cation.