Transmission electron microscopy-energy dispersive X-ray analysis (TEM-EDX) represents an effective tool for determining the stoichiometric composition of clay minerals, but the methodology is often hampered by analytical difficulties. Studies of beam-sensitive minerals, such as smectites, are associated with low count intensities and dynamic loss of cations (e.g. K+, Na+, and Al3+), which can lead to erroneous quantifications of composition. After exploring how to minimize cation migration by reducing the beam current density to <5 pA cm–2, the most reliable and consistent compositions were determined using 1 μm2 area measurements of particles acquired in normal TEM mode where the electron beam was parallel, the degree of specimen damage was at its minimum and good acquisition intensities (>10,000 cps) were acquired. Based on 528 TEM-EDX area analyses, the composition of Wyoming montmorillonites (SWy-1, SWy-2, and SWy-3) was studied in their natural and Ca-saturated states from thin (<50 nm thick) particle aggregates lying on lacey carbon films. Overall, the TEM-EDX results confirmed the heterogeneous charge distributions of montmorillonite at the particle and sample levels. The average composition per formula unit of SWy-1 to -3 was determined as: (Na0.12Ca0.04Mg0.03K0.02)(Si3.91Al0.09)(Al1.57Mg0.27Fe0.19)2.03 O10(OH)2 · nH2O, where the tetrahedral and octahedral layer charges are –0.09 and –0.19 per O10(OH)2, respectively, and the total layer charge ranges from –0.25 to –0.30 per O10(OH)2 (mean of –0.28). This study demonstrates how TEM-EDX can provide new insight into the natural heterogeneities of smectite chemistry as long as adequate calibration and specimen damage control procedures are implemented.

Thermal transformation of chrysotile from Uruaçu District, state of Goiás, Brazil, heated in dry conditions at temperatures from 600°C to 1300°C was studied by high resolution electron microscopy and selected area electron diffraction (SAD). Up to 600°C, no morphological or SAD pattern changes were observed. At 600°C, the fibrils were still crystalline with the characteristics of the clinochrysotile. In addition, a new fringe system of 10–15 Å spacings appeared sporadically parallel to the 7.3 Å fringes of chrysotile. Areas of these extra fringes seem to constitute favorable sites for the nucleation of forsterite. At 650°C, forsterite nuclei appeared inside the nearly amorphous fibrils in the shape of patches consisting of flaky crystallites. At 700°C the chrysotile structure had disappeared; the new spots present in the SAD pattern were indexed as those of forsterite. Between 800–900°C the crystallinity of the patches was clearly demonstrated. From the lattice images in the patches, topotactic relations between chrysotile and forsterite were analyzed. At 1000°C very tiny grains of enstatite were formed mixed with forsterite grains. The SAD pattern is complex due to the coexistence of forsterite, enstatite, and silica-rich amorphous areas. From 1100°C to 1300°C the tridimensional growth of enstatite was promoted. The present results support the topotactic relations between chrysotile and forsterite found by X-ray analysis although differences up to several degrees may exist when these phases are observed microscopically. Evidence suggesting a topotactic growth between forsterite and enstatite was also obtained.

As shown by scanning and transmission electron microscopy, halloysite in three rhyolitic tephras occurs as squat and elongate ellipsoids. Both morphologies are presumed to result from a similar lattice building mechanism. The squat ellipsoids form from allophane; the elongate ellipsoids form from feldspars. The squat ellipsoids do not possess flattened faces or spaces between books of layers at field moisture levels. Outgrowths from the squat ellipsoids are possibly due to inclusions of allophane, glass, ferrihydrite, or feldspar crystallites. Possible spiral growth of halloysite, giving curved surfaces, may be due to a continuous distribution of crystal dislocations.

Scanning, transmission, and analytical electron microscopy studies of shales from the Salton Sea geothermal field revealed that phyllosilicates progress through zones of illite-muscovite (115°−220°C), chlorite (220°−310°C), and biotite (310°C). These phyllosilicates occur principally as discrete, euhedral to subhedral crystals which partly fill pore space. The structural and chemical heterogeneity, which is typical of phyllosilicates in shales subject to diagenesis, is generally absent. Textures and microstructures indicate that the mineral progression involves dissolution of detrital phases, mass transport through interconnecting pore space, and direct crystallization of phyllosilicates from solution.

Phyllosilicate stability relations indicate that either increase in temperature or changing ion concentrations in solutions with depth are capable of explaining the observed mineral zoning. Textural and compositional data suggest that the observed mineral assemblages and the interstitial fluids approach equilibrium relative to the original detrital suites. The alteration process may have occurred in a single, short-lived, episodic hydrothermal event in which the original detrital phases (smectite, etc.) reacted directly to precipitate illite, chlorite, or biotite at different temperatures (depths) without producing intermediate phases.

Nordstrandite was obtained synthetically by precipitation of Al(OH)3 at pH 9.0 to 11.0 in citrate or malate systems with Al: carboxylic acid molar ratios of 10–100 in the absence and in the presence of montmorillonite. Examination by transmission and scanning electron microscopy showed that the nordstrandite had a tabular morphology in the clay-free systems with Al: carboxylic acid ratio >50. Because the inhibiting effect on crystallization of the citrate or malat e anion decreases with increase in pH, the crystal size varied from <2 μm at pH 10 to 5 μm at pH 11. With increasing concentration of citrate or malate, the nordstrandite crystals became more elongated in the c-direction probably due to organic anion occupation of the coordination sites of Al on the edge faces parallel to the c-axis. Irregular growth along the c-axis was probably due to steric hindrance by the organic ligands distorting the arrangement of the unit layers of nordstrandite.

The catalytic effect of montmorillonite on the formation of nordstrandite was confirmed. Nordstrandite synthesized in the presence of montmoriUonite at pH 9.0 presented an ill-defined ovoidal outline (0.2–0.5 μm), some showing shafts of bayerite growing from the center. At higher pH, where conditions for crystalline growth were again more favorable, nordstrandite crystals nucleated on the montmorillonite surfaces and condensed in clusters of weak face-to-face associations of plates.

The lower Permo-Triassic sediments of the Maláguide Complex contain abundant dickite. Whole rocks were studied by optical microscopy, scanning electron microscopy, and X-ray powder diffraction. The 2–20 µm and < 2 µm size fractions were extracted and analyzed by scanning and transmission electron microscopy, X-ray powder diffraction, infrared spectroscopy, differential thermal analysis, and thermogravimetry.

In the coarse-grained samples, the 2–20 µm size fraction consisted of well-crystallized dickite associated with minor quantities of kaolinite, illite, quartz, and hematite. XRD patterns of the fine-grained samples and the <2 µm fractions showed the existence of well-crystallized minerals in which several reflections of dickite (11l, 02l) were absent and the 132/13$\bar 2$ reflections were shifted. These patterns suggest the presence of an intermediate member between well-crystallized dickite and well-crystallized kaolinite. Only locally high-order reflections are present at 10.5 Å and 18–22 Å. DTA and IR data agree with those from XRD.

The observed compositional and structural variations are a function of the lithology and the particle size of the sample. The sequence kaolinite → kaolinite/dickite → dickite is proposed for the development of these materials during Alpine metamorphism.

In this paper we analyzed by electron microscopy and X-ray diffraction (XRD) the exposed lacustrine clay in a stratigraphic column at Charo Canyon, State of Michoacán, Mexico. Smectite, cris-tobalite, albite and quartz are the main mineral species in the sediments. Smectite is the most abundant and has a nanometric twinned small particle habit. The low crystallinity of the smectite detected in some of the samples seems to be associated with instability of the paleohydrological regime in which clayey material was deposited. Iron from underlying volcanic ash is apparently responsible for the iron concentration detected in the smectite structure.

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.

Clay minerals from the MacAdams Sandstone, Kettleman North Dome, California, have been studied by electron microscopy. The clay minerals fill pore space associated with fractured and brecciated clasts of K-feldspar. Curved packets of muscovite and kaolinite are caused by deformation of detrital muscovite that resulted in opening of fissures subsequently filled with dominant kaolinite and minor intergrown mixed-layer illite/smectite (I/S). Regions of authigenic R1 I/S (rectorite) with characteristic ~20 Å periodicity are intergrown with kaolinite in microfissures within K-feldspar or detrital muscovite. Clusters of small grains of muscovite with nearly ideal composition occur as stacks and intergrown with kaolinite and are tentatively inferred to be authigenic. Contrary to previous reports, no illite was found in these samples.

Electron microprobe analyses previously obtained on Kettleman Dome “illite” and subsequently used as a prime example of analyses of illite rich in excess interlayer water (H2O) and hydronium ion (H3O+) are shown to have been obtained on mixtures, and are not representative of the actual clay mineral compositions. Previous conclusions regarding significant H3O+ and H2O contents of illite are invalid because of inaccuracies inherent in bulk and EMPA analyses of illite, and do not affect arguments regarding the metastability of illite. Hydronium substitution should be favored via the reaction H2O + H+ = H3O+ only in highly acidic fluids. Ordinary illite forming in sedimentary environments with carbonates and iron oxides is unlikely to have significant H3O+ substituted for K+.

Fine kaolinite suspensions were mixed with unaged or aged FeCl3 in this experiment. The interaction between clay particles and Fe3+ hydrolysis products was studied by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The proportion of Fe adsorbed was measured and the electrical charge on the clay particles was determined by electrophoresis. The effect of this interaction on flocculation of clay suspensions was investigated in a series of sedimentation tests. The Fe3+ ions acted as counterions when their concentration was low and when unaged FeCl3 solution was used. Otherwise, their hydrolysis complexes acted as a bonding agent between kaolinite particles. The dispersion-flocculation behavior of kaolinite suspensions was found to be in agreement with the theory of Derjaguin, Landau, Verwey and Overbeek (DLVO), as the sedimentation behavior could be predicted from the data of zeta potentials (ζ).

Formation of Fe-coatings or segregation at the expense of quartz grains is a common process in the tropical environment. Limited information is available about their internal structure at the submicroscopic level. The transmission electron microscope (TEM) and energy dispersive X-ray microprobe analyses (EDXRMA) techniques were used to identify the nature and arrangement of fundamental mineral particles within the Fe-coatings. Chemical and mineralogical studies showed that the coatings were composed of well-crystallized Fe-oxides, quartz and kaolinite. The EDXRMA analyses revealed the presence of linear concentrations (laminae) of nearly pure Fe oxide along the edges and the contact zone with quartz and within the coatings. Similar atomic proportions of Al and Si in several areas within the interior regions of coatings and the XRD pattern of the crushed coatings are supportive evidence for the presence of kaolinite. Under the TEM, the dense laminae (< 10 μm thick) consisted of elongated Fe-oxide particles (< 1.5 μm long and 0.2 μm thick) accommodated in subparallel arrangement. The interior areas had very high porosity and, in addition to Fe-oxides, contained other minerals: mainly kaolinite, quartz and isolated areas of Al-oxides. High amounts of ultramicroscopic pores (<0.5 μm) in the interior region suggested that dissolution of Fe-oxides occurred under reduced conditions, with subsequent reprecipitation of pure Fe-oxides in the laminae. Very low porosity and parallel arrangement of Fe-oxide particles (laminae) provided new surfaces (barrier) for Fe-accumulation when soil solutions provided new influxes of iron, thereby creating a thicker Fe-coating. The size and geometry of the ultramicroporosity were shown to play a significant role in the dissolution and precipitation of soil minerals, especially those involved in redox reactions.

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.

The retention of hazardous species, including many of the lanthanides, on soils and sediments is vital for maintaining environmental quality. In this study, high-resolution transmission electron microscopy (HRTEM) was used to identify surface precipitates of La and their degree of atomic ordering on oxides of Mn (birnessite), Fe (goethite) and Ti (rutile) over a pH range of 3 to 8. At pH >5.5, the aqueous concentration of La was fully depleted by all three metal-oxides. On birnessite, surface precipitation of La-hydroxide occurred at pH = 5 and appears to be the dominant sorption mechanism on this mineral. Surface precipitation was not observed on rutile or goethite until much higher pH values, 6.5 for rutile and 8.0 for goethite. Precipitation is thus correlated with the points of zero charge (PZC) of the minerals, 6.3 for rutile and 7.8 for goethite, and in each case was observed only at pH values above the PZC. Although La sorption was extensive on all of the minerals at the higher pHs, the depletion of La from solution by rutile and goethite at pH values well below the PZC indicates that the sorption mechanism differs from that on birnessite. While surface precipitation was found to be the dominant sorption mechanism of La on birnessite, surface complexation of monomelic or small multinuclear species appears to predominate in La retention on rutile and goethite at most commonly encountered pH values.

The gold decoration technique of electron microscopy was used to observe the microtopography of natural (001) surfaces of 1:1 regularly-interstratified mica/smectite minerals (expandable layer: 40–45%) collected from four different pyrophyllite deposits in Japan. The specimens are characterized by parallel growth steps of malformed, circular or polygonal forms with varying step separations. Many particles exhibit paired steps that seem to show spiral growth. Microtopographic observations suggest that the growth of regular interstratification (at least for the specimens investigated in this study) normally takes place by an interlacing of paired steps. If the height of a single step corresponds to that of a mica or a smectite layer, the particles are estimated to be normally 40–300 Å in thickness. If the particles on which a spiral center is observed are single crystals of interstratified mica and smectite, then some crystals investigated in this study are far thicker than fundamental particles. The results of this study are interpreted to suggest that these regularly-interstratified mica/smectites were formed by hydrothermal metasomatism from their respective host rocks.

The Lower Pleistocene bentonite deposits of Eastern Milos, Greece have been formed at the expense of volcaniclastic rocks under submarine conditions. Systematic variation of the major chemical elements reveals that the deposits were formed from different precursors which were erupted from different volcanic centers belonging to at least two separate volcanic provinces. The volcanic eruptions were probably subaqueous. The major authigenic phases are smectite, K-feldspar, opal-CT and the zeolites mordenite and clinoptilolite. The deposits have a complex history and have been affected by hydrothermal alteration.

The geological features of bentonites coupled by the presence of abundant authigenic K-feldspar indicate that alteration of the parent volcanoclastic rocks took place under low temperatures and is probably not related to hydrothermal alteration, which is a separate event. Hydrothermal alteration has modified both the mineralogical characteristics and the properties of bentonites. Alteration of the parent rocks to bentonites was favoured by high water: wall rock ratios and fluid flow and is associated with leaching and subsequent removal of Na, K and Ca. The source of Mg was the parent rocks and only small scale Mg-uptake from the sea water has probably taken place. The formation of authigenic K-feldspar has probably been favoured by a high K+/H+ activity ratio and high Si activity of the pore fluid. Such conditions might have been favoured by the pH conditions and the cooling history of the parent rocks.