The first stage of lateritic weathering of pyroxenes in the Niquelandia area, Brazil, leads either to Fe-rich products or to a phyllosilicate clay. In relatively unfractured parent rock the phyllosilicate clay contains Ni-rich smectites, the atomic ratio of Ni: octahedral cations ranging from 0.3 to 0.5. These smectites were studied by polarized light microscopy, X-ray powder diffraction (XRD), transmission electron microscopy, and electron microprobe, and infrared, optical absorption, Mössbauer, and extended X-ray absorption fine-structure (EXAFS) spectroscopy. The chemical composition of the smectite is constant on the optical microscope scale even to the smallest analyzed particles (3000 A in diameter and about 75 Å thick). From XRD data the mineral is principally a swelling, trioctahedral smectite; however, some kerolite-pimelite-like layers are present, and a weak 06,33 reflection indicates the presence of a small amount of a dioctahedral phase. Mössbauer results show that all Fe cations are Fe3+ in octahedral sites. The structural formula of the smectite is: (Ca0.01K0.05)(Al0.17Fe0.5Mg0.48Ni1.47Cr0.02)(Si3.92Al0.08)O10(OH)2

The results obtained from all the above methods suggest that in the smectites Ni, and, perhaps, a small amount of Mg are clustered in pimelite-like domains (or layers), whereas Fe and some Al are clustered in nontronite-like domains (or layers). Most selected-area electron diffraction patterns exhibit continuous or punctuated (hk) rings, indicating that particles contain several stacked layers. The patterns of some thin particles, however, suggest dioctahedral layers having trans-octahedral vacancies, such as in the Garfield, Washington, nontronite. Thus, the Ni-Fe-Mg-smectite, which seemingly is homogeneous, actually consists of mixed trioctahedral and dioctahedral layers or domains.

In the presence of Mn(II), ferrihydrite transforms into Mn-goethite and/or jacobsite. Chemical analysis showed that as much as 15 mole % Mn replaced Fe in the goethite structure. If Mn(III) replaced Mn(II), the formation of jacobsite was suppressed; ferrihydrite transformed into Mn-goethite, and, at high Mn(III) concentrations, a 7-Å phyllomanganate. Low levels of Mn(II) retarded the transformation of ferrihydrite only slightly, whereas in an Mn(III) system the nucleation and growth of Mn-goethite were both hindered. Mn-goethite nucleated in solution, whereas jacobsite appeared to form by interaction of dissolved Mn(II) species with ferrihydrite. Mn suppressed the formation of hematite in these systems; however, Mn-hematite containing as much as 5 mole % Mn was induced to form at pH 8 by adding oxalate to the system. Transmission electron micrographs showed that goethite crystals grown in the presence of Mn were long (≤2 μm) and thin and commonly contained etch pits. The presence of Mn appears to have promoted twinning.

The transformation of ferrihydrite to goethite and/or hematite in alkaline media is strongly retarded by the presence of silicate species. These species probably stabilize ferrihydrite by adsorbing on the particles of ferrihydrite and linking them into an immobile network.

At concentrations low enough for the transformation to proceed, silicate species promote the formation of hematite and hinder the nucleation of goethite. The presence of silicate species modifies the morphology of both reaction products. Hematite forms ellipsoidal single crystals, commonly displaying outgrowths of goethite. Silicate species in solution appear to enhance the development of the (021) faces of goethite, probably by preferential adsorption on these faces; at high levels of silicate species, goethite crystals adopt a pseudohexagonal habit. This morphology has not been observed previously for goethite.

High-resolution transmission electron microscopy of noncrystalline Fe-Si-Al-oxyhydroxide gels shows a common structure of hollow packed spheres having external diameters ranging from 50 to 1000 Å. Some sphere walls display a concentric structure, particularly if the gel composition is close to that of a crystalline clay mineral (e.g., smectite, kaolin). The spheres probably formed by expansion of void space (bubbles) as the surrounding gel contracted 5–10% because of partial ordering of the Fe-Si-Al-oxygen network. Much of the water contained in such noncrystalline minerals is incorporated within the bubbles.

The introduction of artificial ±b/3 stacking faults into well-crystallized kaolinite by intercalating and removing hydrazine had no observable effect on the solid-state 29Si nuclear magnetic resonance spectrum of kaolinite. Also, the introduction of such stacking faults did not alter the hydroxyl-stretching region of the infrared spectrum, implying no change in the hydrogen bonding between the displaced layers. Calculations of Si...H distances and Si-O...H angles from reported structures for kaolinite indicated that the resolution of the two Si chemical environments was due to differences in hydrogen-bonding at the surface of the silicate sheet.

Quaternary debris flows derived from ophiolite melange in northern Southland, New Zealand, are locally cemented and veined by cross-fiber and fine-grained chrysotile. Chrysotile was identified by optical, X-ray powder diffraction, electron microprobe, differential thermal (DTA), and infrared analysis methods. Microprobe and DTA also suggested the presence of as much as 6% of sub-microscopic, noncrystalline alumina, probably in the form of pseudoboehmite. Cavity fillings and irregular veins containing chrysotile are as thick as 40 cm and commonly contain lizardite clasts. Calcite commonly accompanies chrysotile as a vein mineral. Magnetite and pyrite are found near and adjacent to chrysotile veins. These accessory minerals imply that the chrysotile formed under alkaline, reducing conditions. Surface water seepages have pH = 9. Remnant debris-flow topography, Holocene radiocarbon dates, and the absence of hot spring activity confirms that chrysotile can form under near-surface, low-temperature conditions. Growth of chrysotile fibers on a lizardite substrate suggests that the chrysotile formed by solution of detrital lizardite and subsequent precipitation in cavities within the debris flow.

The adsorption and reaction of thiophene and methylthiophenes in the interlayer of Cu2+- and Fe3+-montmorillonites were investigated by resonance Raman spectroscopy. Thiophene and 3-methylthiophene polymerized to form cations of polythiophene and polymethylthiophene respectively, which were characterized by absorption bands in the near-infrared region. These polymer cations formed in the interlayer were reduced to their neutral polymers if the clay-polymer complexes were in contact with water, and the formation of their neutral polymers was clearly demonstrated by their resonance Raman spectra. 2,5-Dimethylthiophene in which polymerization was hindered by methyl substitution at the 2 and 5 positions, was oxidized to 2,5-dimethylthiophene cation in the interlayer.

Infrared spectra of 2-ethoxyethanol (ethylene glycol monoethyl ether, EGME) adsorbed on Camontmorillonite were obtained using diffuse-reflectance infrared-Fourier-transform (DRIFT) and attenuated total-reflectance (ATR) spectroscopy. The molecular conformation of adsorbed EGME shows predominantly a gauche configuration for the CH2-CH2 linkage as originally present in the liquid. The orientation of the adsorbed EGME molecule in the interlamellar region of the clay was deduced from measurements of the polarized ATR spectra. The planar zig-zag skeleton of the molecule appears to have its long axis tilted at an angle of 44° to the clay surface; the molecule is in van der Waals contact with both adjacent surfaces. Further, the plane of the skeleton of the molecule is tilted at an angle of 69° to the clay surface. This orientation leads to estimates of the d-value of the clay-EGME complex and of the surface area occupied by each molecule. These values are in excellent agreement with independent measurements of both parameters. The full surface coverage on montmorillonite is represented by a single layer of tilted EGME molecules shared by two adjacent clay sheets; each molecule occupies a total surface area consisting of one portion (25.4 Å2) on the lower surface of the interlayer plus another portion (14.8 Å2) on the upper surface. The implication of this model for materials such as kaolinite, where adsorption takes place on the external surface only, is that on these materials each EGME molecule occupies 20 Å2 at full surface coverage.

Ca-K.-, Na-K-, and Ca-Na-exchange isotherms on four reference smectites were studied. The electric charge on the four smectites was due predominantly to cationic substitution in the octahedral layer and varied between 90 and 122 meq/g (cmole(+)/kg) clay. The affinity of the clays for K increased with a decrease in the fraction of K in the exchange phase. The selectivity coefficients of the smectites for K increased with an increase in charge density. The effect was similar in the Na-K- and Ca-K-exchange isotherms. Charge densities on the smectites had no effect on the Ca-Na-exchange isotherm. The electrostatic attraction forces between the platelets increased with increase in charge density. The low hydration energy of adsorbed K was apparently not enough to overcome these attraction forces as the charge density on the smectites increased. Equilibrium between the low hydration energy of adsorbed K and the electrostatic attraction energies between the platelets is postulated to explain the results.