Imogolite occurs as tiny bumps less than 0.05 µm in diameter and about 0.3 µm long on amorphous thin layers on the surface of weathered plagioclase. The bumps grow outward from the surface to form projections, which then develop into a fibrous imogolite. The fibers branch out and grow into widespread networks or thin films which finally cover the entire surface of the plagioclase grain. The fibers are about 0.05 µm in diameter as seen by transmission electron microscopy.

High-resolution transmission electron microscopy (HRTEM) has shown regions of crystallites within noncrystalline matrices of three types of glass (volcanic glass, alkalic igneous glass, and synthetic, nuclear-waste-form glass) The volcanic glass fragments showed domains having 3-Å spacings. About 30% of the fragments of this glass showed localized lattice images, having spacings of 5, 7, 8, 10, 13, 14, 16, 19, and 20 Å, which also contain regular fringes having 3.3-Å separations. In the alkalic igneous glass fragments 3-Å domain structures were also noted as were localized lattice images having 7- and 12.5-Å spacings. Well-developed hollow spheres of primitive clays were present in both the volcanic and alkalic igneous glasses. Synthetic, nuclear-waste-foTm glass, fused at 1400°C and annealed at 550°C, showed locally ordered regions having 3.3-Å spacings. Low-angle X-ray powder diffraction showed major reflections at 8.5, 15–16, and 19 Å, which agree with some of the HRTEM measurements. These observations of domain structures, localized lattice images, primitive clays, and 14-Å clays in such noncrystalline glass matrices may contribute to an understanding of the growth of clay minerals. Such domains can apparently trigger the growth of clay products on the glass substrate.

Cementing materials in the Arahama sand dune, Japan, were studied mineralogically and biogeochemically to gain a better understanding of the cause of hardening. The cementing material is a clay-organic complex composed of noncrystalline gels and a matrix of small, poorly crystalline particles showing 14–16-Å spacings. The gel materials appear to have transformed into the poorly crystalline particles, which have a high carbon content and Al/Si ratios of 2.2 to 2.0. These particles are slightly richer in Si and poorer in Fe than the gel materials themselves. The organic portion of the complex can be removed by H2O2 treatment, leaving a noncrystalline network-structure containing a dispersed granular component. Scanning auger-depth profiles of individual particles show a high surface concentration of C and O and an increase in the Al/Si ratio with depth. The energy-intensity distribution suggests a mixture of carbon compounds having a major core-line binding energy of a hydrocarbon. The gel-cementing materials in the sand dune may have been formed from biochemical weathering products of organic matter, which subsequently controlled the formation of clay-organic complexes.

The red snow algae species found in snow at Resolute, Canadian Arctic, is a unicellular Chlamydomonas nivalis. Investigations by SEM-EDX, TEM, FT-IR, GC and GC-MS suggest that clay aerosols may provide nutrients for these unique systems. The clays provide P, S, K, Si, Ca, and Mg. Soot is also present and halite is very common. This salt probably plays a significant role in lowering the freezing temperature. The red snow algae is coated by a sticky thin film composed of both organic membrane material and inorganics consisting of mica and smectite. Green algae rich in Ca are involved in active photosynthesis while red algae are in a resting stage. Protamine, stearic acid, and decanoic acid were found at Ca-rich green cells while carminic acid and nopalcol BR-13 were found at Ca-poor red cells. The cell wall of red algae is composed of protein with cellulose. The major fatty acides in cells are all of even-carbon species with maximum concentrations of palmitic acid, stearic acid, and behenic acid, suggesting normal chemistry of algae species without C22. High concentration of n-alkanes with n-C24 is a characteristic component in this red snow algae, suggesting the presence of hydrocarbons that could be derived from the Arctic cold desert and/or organic debris of wind-transported bacteria. It is likely that such organic and inorganic matter provide the nutrient sources for the red snow algae in ice.

The formation of layer silicates on capsuled bacterial cell walls was studied in freshwater microbial mats. The trends associated with Al, Si, Mn and Fe deposits with capsules are consistent with occurrence of layer silicates with 14, 10 and 7 Å X-ray diffraction (XRD) patterns. Scanning electron microscope and transmission electron microscope (SEM and TEM) observations of the microbial mats revealed the presence of microcolonies of rod- and coccus-shaped bacteria with layer-silicate thin films. Field measurements of pH, temperature and Eh indicated that these conditions for bacterial crystallization of layer silicates and hydrated Fe/Mn oxides in freshwaters are as follows: pH 6.3 to 7.8, 12 to 20 °C and Eh −24 to +200 mV. Glass slides kept for 3 weeks in the beakers with natural freshwater and river sediments were coated with brown materials. These materials were identified as layer silicates and colonized bacteria formed under photosynthetic conditions. The well-developed holdfasts on Leptothrix discophora bacterial cells are mainly associated with poorly crystalline layer silicates and hydrated Fe-Mn oxides. Semiquantitative elemental analyses of holdfasts using energy-dispersive X-rays (EDX) indicated that layer-silicate crystallization covers the cell at an early stage. Iron and manganese crystallization develops at a later stage, where aluminum substitution occurs in crystal structures. Laboratory experimental results indicated that layer silicates grew from a biochemical origin, rather than from inorganic origins in freshwater. Layer-silicate formation is linked with bacteria in microbial mats.

Microbial structures in the form of banded zebra patterns have been found as periodic iron-manganese layers in living biomats on the coast of Satsuma-Iwo Jima, a small volcanic island near southern Kyushu, Japan. Electron microscopic observation shows that coccus, fibrous, and bacillus-type bacterial communities construct zebra architecture Fe-Mn layers through biomineralization on and within cells. A living microbial fumarolic ferro-manganese precipitation growing in seawater around an active volcanic island explains one mechanism of banded formation. Biological processes form the elemental zebra pattern, with periodic distribution of bacterial cells with Fe-Mn in each layer of the architecture. Fibrous bacteria are sometimes mineralized with goethite, ferrihydrite, and buserite microcrystals, coated with granular mucoid substances. The biomineralization may then mature to form a recent stratified banded-iron formation. The Satsuma-Iwo Jima zebra architecture is unusual in that it forms under aerobic conditions in a warm shallow-water environment, in contrast to the intermittent oxidizing and reducing conditions in which deep-sea analogues develop.

Nontronite and microbes were detected in the surface layers of deep-sea sediments from Iheya Basin, Okinawa Trough, Japan. Nontronite, an Fe-rich smectite mineral, was embedded in acidic polysaccharides that were exuded by microbial cells and electron microscopy showed that the nontronite layers were apparently oriented in the polysaccharide materials. We propose that the formation of nontronite was induced by the accumulation of Si and Fe ions from the ambient seawater and that extracellular polymeric substances (EPS) served as a template for layer-silicate synthesis. Experimental evidence for this hypothesis was obtained by mixing a solution of polysaccharides (dextrin and pectin) with ferrosiliceous groundwater. After stirring the mixture in a sealed vessel for two days, and centrifuging, Fe-rich layer silicates were identified within the precipitate of both the dextrin and pectin aggregates, whereas rod-shaped or spheroidal Si-bearing iron hydroxides were found in the external solution. Microbial polysaccharides would appear to have affected layer-silicate formation.

High-resolution transmission electron microscopy has revealed spherical and hemispherical structures on the surface of partly hydrated volcanic and synthetic glasses. These structures contrast with the bulk of the glass in showing lattice-fringe images indicative of the early stages of crystallization. Heavy-ion Rutherford scattering analysis of the noncrystalline volcanic glass indicates a structural water with hydrogen and deuterium. Depth profiles show that the glass grains contain structural water without adsorbed water on the surface. The presence of structural water in volcanic glass must be of interest to the formation of primitive clays. The spherical and hemispherical structures favor production of clay precursors in the presence of water.

Transmission electron microscopy (TEM) has been used to demonstrate the biological formation of a hollow spherical halloysite-like mineral in freshwater systems. The interaction between clays and microbes was investigated in microbial films from laboratory cultures derived from natural sediments. Optical and electron microscopic observations of cultured microbes revealed that thin clay films covered areas of the bacterial cell wall. X-ray diffraction of the thin films after 2 y of ageing showed a 7.13 Å d spacing, consistent with a 7 Å halloysite-like phase [Al2Si2O5(OH)4 H2O]. Fourier transform infrared analysis of the thin film exhibited the characteristic adsorption bands for O−H (3651 cm−1), C−H and C−N (2925, 1454 and 1420 cm−1, respectively), suggesting that the phase was closely associated with adhesive organics. Observation by TEM of the thin films revealed that spherical, hollow, halloysite-like material formed on both coccus- and bacillus-type bacterial cells. Electron diffraction analysis of this material showed 2.9, 2.5, 2.2 and 1.5 Å d spacings. The present investigation strongly suggests that the thin film wall of the spherical halloysite-like material was associated with bacteria as a bio-organic product. This material, referred to hereafter as bio-halloysite, is further evidence for the microbially-mediated formation of clay minerals. The identity of the bacteria responsible for bio-halloysite formation is unknown, but is tentatively assigned to sulfate-reducing bacteria on the basis of morphology and the presence of reducing conditions in the microcosm at the end of the experiments.

This study focused on whether the presence of clay minerals (montmorillonite and kaolinite) in marine or coastal environments contaminated with high concentrations of heavy-oil spills were able to support the growth of hydrocarbon degraders to enable bioremediation. The bacterial growth experiment utilizing ~150 g/l of heavy oil (from the Nakhodka oil spill) was conducted with 1500 mg/l of montmorillonite or kaolinite. Bacterial strain Pseudomonas aeruginosa (isolated from Atake seashore, Ishikawa Prefecture, Japan), capable of degrading heavy oil, was employed in combination with other hydrocarbon degraders inhabiting the heavy oil and seawater (collected from the Sea of Japan). The interactions among microbial cells, clay minerals and heavy oil were studied. Both clays were capable of promoting microbial growth and allowed microorganisms to proliferate (to a greater degree than in a control sample which contained no clay) in an extremely high concentration of heavy oil. Observation by transmission electron microscopy of the clay-oil-cell complexes showed that microbial cells tended to be bound primarily on the edges of the clays. X-ray diffraction analysis showed that the clay-oil and clay-oil-cell complexes involved the adsorption of microbial cells and/or heavy oil on the external surfaces of the clays. How do the interactions among clay minerals, microbial cells and heavy oil contribute to environmental factors influencing the bioremediation process? To our knowledge, there are no previous reports on the use of clay minerals in the bioremediation of the Nakhodka oil spill in combination with biofilm formation.