Transmission electron microscope (TEM) images of mixed-layer illite/smectite (I/S) from Gulf Coast shales obtained earlier by the authors have been reexamined by comparing them with the calculated images of G. D. Guthrie and D. R. Veblen. Ordered two-layer periodicity was not detected in the 1750- and 2450-m depth samples, for which X-ray powder diffraction (XRD) showed 20% and 40% illite randomly interstratified in I/S, respectively. Two-layer periodicities that occur in images of the 5500-m depth sample were inferred to reflect ordered I/S. XRD data for the same sample imply the presence of 80% illite in RI-ordered I/S. The two-layer periodicities were observed in slightly overfocused images, consistent with the image calculations of Guthrie and Veblen, with strong dark fringes inferred to correspond to smectite interlayers. Two-layer periodicities were observed only in small domains of a few of the images, consistent with the requirement of special orientation of layers, which varies continuously over a wide range. The lack of more frequent observations of ordered periodicities in TEM images may reflect the lack of the special observation conditions and chemical heterogeneity of illite and smectite layers. Ordered mixed-layering may exist in those specimens for which XRD indicates such ordering, in contrast to the previous interpretation of the authors.

Transmission electron microscopy suggests that biotite transforms to vermiculite primarily by direct structural modification, involving the replacement of K+ by hydrated interlayer cations, and only minor reorganization of the 2:1 layer. A second relatively uncommon mechanism appears to involve redistribution of components from two biotite sheets to form a single vermiculite layer. Distortion of the surrounding structure initially inhibits growth of vermiculite in the surrounding biotite, and promotes the propagation of vermiculite layers in opposite directions. This phenomenon may contribute to the development of relatively regular, widely spaced interstratifications of biotite and vermiculite. Additional components and space are provided by the dissolution of biotite where access of solutions is greater.

During weathering, biotite and vermiculite become increasingly replaced by kaolinite, which crystallizes epitactically onto existing layers, and goethite, which develops from a poorly crystalline iron oxyhydroxide precursor to form oriented laths. In areas parts of strongly weathered samples kaolinite and goethite appear to develop in proportions consistent with a reaction that conserves both Al and Fe.

The question of whether clay minerals can be biogenically transformed as a result of lichen activity at the lichen-rock interface remains unresolved. We applied several microscopical and analytical techniques—scanning electron microscopy-back-scattered electron (SEM-BSE), energy dispersive spectroscopy (EDS) and high-resolution transmission electron microscopy (HRTEM)—in an attempt to address this issue. Unaffected granitic biotite and bioweathered material from the granitic biotite and Parmelia conspersa lichen thalli interface were examined using HRTEM after ultrathin sectioning. The n-alkylammonium treatment of ultrathin sections was carried out in order to study the biogenous mineralogical transformation of the biotite. Microsamples proceeding from unaffected biotite zones demonstrated homogenous 10-Å d(001)-value biotite phase. HRTEM images of lattice fringes of samples taken from the lichen-biotite contact zone reveal large areas of both unexpanded (10-A) and randomly and R = 3 distributed expanded (from 14- to 30-Å) layers of phyllosilicates identified as interstratified biotite-vermiculite. Results of artificial biotite weathering (replacement of K by Ca ion) also revealed the biotite-vermiculite phase formation, indicating that K release in biotite is one of the mechanisms responsible for interstratified mineral phase formation. Two parallel processes, physical exfoliation of biotite and inter-layer ionic exchange of K and subsequent vermiculite formation, are the mechanisms for biotite bioweathering induced by lichens.

Ultrathin sections of reference 2:1 layer silicates treated with octadecylammonium cations were examined using high-resolution transmission electron microscopy (HRTEM) to establish the layer structure. Hitherto, few HRTEM ultrathin-section data existed on the expansion behavior of smectite-group minerals with different interlayer-charge values. Without such information, the expansion behavior of both low-charge and high-charge smectite minerals cannot be characterized and the structures observed in HRTEM images of clay-mineral mixtures cannot be interpreted reliably. Reference smectite-group minerals (Upton, Wyoming low-charge montmorillonite; Otay, California high-charge montmorillonite; a synthetic fluorohectorite; and a Jeanne d’Arc Basin offshore Newfoundland clay sample) with a range of layer charge values were examined. To prevent possible intrusion of epoxy resin into interlayers during embedding, the clay samples were first embedded in epoxy, sectioned with an ultra microtome, and then treated with octadecylammonium cations before examination using HRTEM. Lattice-fringe images showed that lower-charge (<0.38 eq/O10(OH)2) 2:1 layers had 13–14 Å spacings, whereas higher-charge (>0.38 eq/O10(OH)2) 2:1 layers had 21 and 45 Å spacings. These differently expanded silicate layers can occur within the same crystal and an alternation of these layer types can generate rectorite-like structures. For comparison, clay samples were also treated with octadecylammonium before epoxy embedding and sectioning and then examined with HRTEM. These samples mostly had highly expanded interlayers due to epoxy intrusion in the interlayer space. The reference clay minerals embedded in epoxy resin, sectioned, and treated with octadecylammonium cations were used to characterize smectite-group minerals in a natural clay sample from the Jeanne d’Arc Basin, Eastern Canada. Smectite-group minerals in this sample revealed similar structures in lattice-fringe images to those observed in the pure reference clay samples. Rectorite-like structures observed in lattice-fringe images were in fact smectite crystals with short, alternating sequences of low-charge and high-charge smectite layers rather than illite-smectite (I-S) phases with expanded smectite layers and non-expanded 10 Å illite layers.

The intercalating growth of new silicate layers or metal hydroxide layers in the interlayer space of other clay minerals is known from various mixed-layer clay minerals such as illite-smectite (I-S), chlorite-vermiculite, and mica-vermiculite. In a recent study, the present authors proposed that smectite-group minerals can be synthesized from solution as new 2:1 silicate layers within the low-charge interlayers of rectorite. That study showed how oxalate catalyzes the crystallization of saponite from a silicate gel at low temperatures (60ºC) and ambient pressure. As an extension of this work the aim of the present study was to test the claim that new 2:1 silicate layers can be synthesized as new intercalating layers in the low-charge interlayers of rectorite and whether oxalate could promote such an intercalation synthesis. Two experiments were conducted at 60ºC and atmospheric pressure. First, disodium oxalate solution was added to a suspension of rectorite in order to investigate the effects that oxalate anions have on the structure of rectorite. In a second experiment, silicate gel of saponitic composition (calculated interlayer charge -0.33 eq/O10(OH)2) was mixed with a suspension of rectorite and incubated in disodium oxalate solution. The synthesis products were extracted after 3 months and analyzed by X-ray diffraction and high-resolution transmission electron microscopy (HRTEM). The treatment of ultrathin sections with octadecylammonium (nC =18) cations revealed the presence of 2:1 layer silicates with different interlayer charges that grew from the silicate gel. The oxalate-promoted nucleation of saponite and talc crystallites on the rectorite led to the alteration and ultimately to the destruction of the rectorite structure. The change was documented in HRTEM lattice-fringe images. The crystallization of new 2:1 layer silicates also occurred within the expandable interlayers of rectorite but not as new 2:1 silicate layers parallel to the previous 2:1 silicate layers. Instead, they grew independently of any orientation predetermined by the rectorite crystal substrate and their crystallization was responsible for the destruction of the rectorite structure.