K-bentonites of the Middle Ordovician High Bridge Group along the Cincinnati arch are characterized by interstratified illite/smectite (I/S) clays with rectorite-type ordering. Approximately 20% of the layers are expandable. They are structurally similar to I/S formed at temperatures exceeding 100°C during burial diagenesis, however stratigraphic evidence and a color alteration index of < 1.5 for conodonts in associated carbonates reveals they have never been deeply buried or subjected to temperatures greater than 80°C.

Whole-rock samples of K-bentonites contain ∼8% K2O and ∼4% MgO, whereas the <0.1-µm size fraction contains 6–7% K2O and 5% MgO. By comparison with a hypothetical parent ash, these values represent a net gain of K and Mg and a net loss of Si, Fe, Ca, and Na during post-depositional alteration. K-fixation is accounted for by a layer charge imbalance arising primarily out of octahedral substitution of Mg+2 for Al+3, indicating that the interstratification evolved from a montmorillonite precursor. The chemical characteristics of I/S layers in K-bentonites developed early during the alteration of volcanic ash to montmorillonite. Relatively high contents of K and Mg probably reflect both seawater and parent material composition at the time of formation. The composition and ordered stacking in K-bentonites was determined by the composition of the original smectite rather than by the pressure-temperature conditions of burial diagenesis.

The conversion of smectite to illite by way of a mixed-layer illite/smectite (I/S) series was found to be the major depth-related reaction in clay-mineral assemblages from two cored sedimentary sequences in the Rocky Mountains. The I/S reaction occurred in both interbedded sandstone and shale of Upper Cretaceous and lower Tertiary age in the Green River basin, Wyoming, and in chalk and chalky shale of the Upper Cretaceous Niobrara Formation, Denver basin, Colorado. As the proportion of illite layers in I/S increased with depth in these rocks, the amount of I/S in the clay fraction decreased, and the amount of discrete illite increased. Scanning electron microscopy revealed that the morphologies of highly expansible, randomly interstratified I/S clay (samples from shallow cores) exhibited no distinctive intergrowth or overgrowth textures. In deeply buried rocks containing highly illitic, ordered I/S and abundant discrete illite, however, fibers or laths of illite were formed on earlier I/S substrates. Less commonly, I/S of low expandability shows morphological features of both smectite and illite whereby rigid laths of illite appear to have formed diagenetically from the wall surfaces of I/S honeycombs. This combined morphology suggests some dissolution and reprecipitation (or some reorganization) of materials from the I/S substrate as the substrate was transformed into a more illitic mixed-layer clay.

These data suggest that some I/S clay was destroyed by the selective cannibalization of smectite layers in I/S to provide the components needed to make a more illitic I/S. Moreover, discrete illite and other minerals apparently were formed during the reaction. Also, coarser mineral phases, such as potassium feldspar and detrital micas, may not have been required to supply the chemical components in the reaction. The observations provide an explanation for late diagenetic I/S reactions that occurred in restricted or relatively closed geochemical systems, as in early cemented rocks having extremely low permeability and little or no potassium feldspar.

Core cuttings from numerous wells traversing Oligocene through Recent sediments of the Texas Gulf Coast were examined with a scanning electron microscope using the back-scattered electron imaging mode (BSE) to ascertain diagenetic changes in clays and associated minerals of mudrocks and of adjacent sandstones. Several occurrences of authigenic kaolinite and chlorite were noted, each characterized by a specific texture and a specific diagenetic microenvironment. In all occurrences kaolinite appears to have formed before chlorite, and in some the kaolinite appears to have precipitated directly from solution. Chlorite, ubiquitously an iron-rich variety, appears to have precipitated in some places directly from solution. It has also been noted pseudomorphous after kaolinite. A progressive decrease in the iron content of mixed-layer illite/smectite with increasing depth is believed to have released the necessary iron and to have driven the kaolinite-to-chlorite reaction.

Regular vertical variations in mineralogy and chemistry indicate that underclay beneath the Herrin (No. 6) coal in southwestern Illinois has undergone in situ alteration. Alteration resulted from the downward movement of hydrogen ions, as indicated by the progressive leaching of acid-sensitive minerals adjacent to the coal. Mineralogical trends observed in the underclay with increasing depth below the coal include: (1) a decrease in the expandability of mixed-layer illite/smectite (I/S); (2) an increase in the amount of ordered I/S with respect to randomly interstratified I/S; (3) an increase in the amount of discrete illite with respect to expandable clays; and (4) an increase in chlorite and calcite. Ordered I/S is the dominant mixed-layer clay where calcite is present, but randomly interstratified I/S dominates where calcite is absent. The pH of the underclay also increases with depth. These trends are consistent with an origin by acid leaching of a preexisting mineral assemblage that included illite, chlorite, and calcite. Other acid-alteration trends may be expected for different precursor minerals and for different leaching intensities and durations.

Regularly interstratified chlorite/smectite (corrensite) occurs as grain coatings in marine and eolian sandstones of the Permian Cutler Formation in Lisbon Valley, Utah. Corrensite dominates the <2-μm clay size fraction along with lesser amounts of regularly interstratified illite/smectite in bleached, permeable sandstones that are interbedded with smectite-dominated arkosic, red, laterally discontinuous fluvial sandstones. Chemical and X-ray powder diffraction analyses of the corrensites show them to be di/dioctahedral with 060 spacings of 1.501 to 1.508 Å and to contain significantly higher Al:Mg ratios than more common trioctahedral types. Calculated structural formulae are: corrensite, M0.6(Fe3+0.2Mg1.6Al4.6)(Al0.2Si7.8)O20(OH)10; illite/smectite, M1.5(Fe3+0.1Mg1.7Al2.8)(Al1.6Si6.4)O20(OH)4; and smectite, M0.9(Fe3+0.3Mg1.2Al2.8)(Al0.6Si7.4)O20(OH)4.

Chemical similarity between the smectite and the corrensite and pervasive distribution of smectite in low-permeability shales and siltstones suggest that the smectite was a precursor of the corrensite. Three stages of mineral precipitation in the Cutler Formation have been recognized. Quartz precipitated early as grain overgrowths, followed by the formation of authigenic clay minerals, and later calcite cementation which destroyed much of the original rock fabric. Calculations show that aluminous corrensite was favored by elevated temperature (∼ 100°C), low pH, and low dissolved silica. Local hydrothermal fluids rising along the Lisbon fault apparently permeated the Cutler red bed section and precipitated the clay minerals. The assemblage corrensite + illite/smectite in the sandstones probably formed by interaction of formation fluids with smectite and an Al-bearing phase, such as K-feldspar or kaolinite.

Illite/smectite (I/S) and illite samples that appear to be 1Md polytypes on the basis of the lack of diagnostic reflections can be resolved as partly either 1M or 2M1 or both by either vapor solvation in ethylene glycol for 40 to 80 hr at ambient temperatures or for 4 hr at 80°C, or by heating to 375°C for 2 hr. If samples are so treated, a distinct narrowing of the I/S 003/005 peak occurs and diagnostic hkl reflections are revealed. These treatments, however, do not seem to affect diagnostic polytypic peak intensities, but rather the adjacent background. We propose that the 1Md term be restricted to its original definition—the disordered polytype associated with only the 1M ordered polytype. For illites in which disorder exists with a mixture of polytypes, the generic term Ad (disordered group A micas) should be used. Correct polytype determination of illitic material is significant because it reveals thermal history of the sediments and allows greater understanding of the depositional and diagenetic history of sedimentary basins.

The validity of the saddle/001 method for estimating the percentage of smectite layers in randomly interstratified illite/smectite (I/S) minerals as a routine laboratory technique has been examined with respect to the effects of the crystallite size distribution (N = number of layers) of I/S and the degree of preferred orientation of crystallites in the prepared specimen. X-ray powder diffraction experiments of I/S clays indicated that the crystallite size distribution was 3 < N < 12; these values were supported satisfactorily by the variation of the d(002) value of the samples. An analysis of the Lorentz factor concerning the degree of preferred orientation of crystallites indicated that a calibration curve calculated using the random powder Lorentz factor and the above crystallite size distribution fit the data better than an assumption of perfect orientation. Consequently, if a calibration curve of the saddle/001 ratio is used to estimate the percentage of smectite layers in I/S, an error of 10–15% should be expected from the variable crystallite size distribution of actual samples, in which I/S dominates over other phyllosilicate phases that give reflection between 10–14 Å. This method is useful, however, in estimating the relative percentage of smectite layers in randomly interstratified I/S for samples examined under identical experimental conditions.

On the basis of progressive acid dissolution the Thompson-Hower model states that mixed-layer glauconite/smectite and illite/smectite contain potassium in two structural sites: a mica-type K position (site 1) and a position of uncertain structural status more prone to dissolution (site 2). Site 2 was thought not to retain radiogenic argon (40Ar*). Using extensive progressive acid dissolution and K/Ar studies on a sized illite/smectite (I/S), determining the amount of K in site 2 is shown to be somewhat more complicated than previously thought because the dissolution pattern depends on acid normality. More important, site 2 fully retains 40Ar*, and no age correction is thus necessary as is required by the Thompson-Hower model, further affirming the geochronologic value of illite in mixed-layer clay. These data are also relevant to understanding the crystal and particle structure of I/S. Site 2 is probably a partly filled K interlayer that develops as an intermediate kinematic step on the way to being fully filled during the transformation of smectite to illite.

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.

X-Ray powder diffraction and thin section analyses indicate that marginal lacustrine mudstones of the Green River Formation in the south-central Uinta basin, Utah, contain abundant analcime. The analcime has a low Si/Al ratio (<2.31) and occurs as very fine grained disseminated crystals and, to a lesser extent, as coarser-grained pore-filling cement. Analcime-rich mudstones and associated sandstones, siltstones, and carbonates lack volcanic detritus and zeolites other than analcime, thus making it difficult to support the concept that the analcime formed from precursor zeolites derived from volcanic glass altered in saline, alkaline-lake water. Abundant dolomite, syneresis cracks, and the absence of freshwater pelecypods and gastropods suggest that the lake (Lake Uinta) was moderately saline and alkaline. The restricted illite-illite/smectite clay mineral suite in the analcime-rich mudstones suggests that detrital clays significantly altered in a moderately saline and alkaline environment, thereby providing a source of Si and Al for the formation of analcime.

Red mudstones contain twice as much analcime as green mudstones (14 vs. 7 wt. %). Green mudstones have a day mineral suite consisting of illite (44 wt. %), mixed-layer illite/smectite (35 wt. %), smectite (12 wt. %), and minor kaolinite (4 wt. %) and chlorite (5 wt. %), whereas red mudstones have a more restricted day mineral suite consisting ofillite (68 wt. %) and mixed-layer illite/smectite (26 wt. %) with very minor smectite, chlorite, and kaolinite. Periodic minor fluctuations in lake level probably exposed large areas of shallow lacustrine-interdistributary green mud. Evaporative pumping on the exposed mudflats concentrated the moderately saline and alkaline-lake water, thereby producing Na-rich brines that enhanced the formation of analcime by accelerating the alteration of detrital clays and, perhaps, other minerals. Oxidation of iron from altered iron-bearing minerals stained the analcime-rich mud red with iron hydroxide or oxide (perhaps hematite). The overall reaction from green to red mud (mudstones) was probably: detrital phyllosilicates + Na-brine + iron-bearing minerals + oxygen → analcime + iron hydroxide or iron oxide.

High-resolution transmission electron microscopy (HRTEM) and electron diffraction experiments have been performed on R1 and R> 1 illite/smectite (I/S) samples that from X-ray powder diffraction (XRD) experiments appear to contain well-ordered layer sequences. The HRTEM images confirmed earlier computer image simulations, which suggested that periodicities due to I/S ordering can be imaged in TEM instruments of moderate resolution. The experiments also confirmed that in instruments of this sort, the strongest contrast arising from the compositional difference between I and S layers occurs under rather unusual imaging conditions of strong overfocus. Some selected-area electron diffraction (SAD) patterns showed additional diffraction spots consistent with R1 and R3 ordering. SAD patterns and cross-fringes arising in HRTEM images from non-00l reciprocal lattice rows indicated that the stacking vectors of most adjacent 2:1 layers were not randomly oriented with respect to each other. Thus, the I/S was not fully turbostratic, but instead consisted of very thin, coherently stacked crystallites that extended across the fundamental particles postulated by Nadeau and coworkers.

S/(I + S) ratios were determined for about seventy HRTEM images obtained and interpreted by three different TEM operators. These ratios were consistent with those obtained from standard XRD procedures, suggesting that results obtained by XRD can be used to infer the initial structural state of mixed-layer I/S prior to treatment of samples for XRD experiments. The HRTEM experiments thus demonstrated that the two specimens examined consisted of ordered I/S existing as small crystals, most of which contained more layers than the fundamental particles of Nadeau and coworkers. The non-turbostratic stacking suggests an energetic interaction between the individual fundamental particles, leading to at least two alternative thermodynamic descriptions of these materials. Although the I/S crystals in the present experiments probably were disaggregated into fundamental particles during sample preparation for XRD, the I/S crystals appear to have separated only along the smectite interlayers. If the term “fundamental particle” is to be used for primary, untreated I/S, its original definition should be modified to include not only free particles, but also those that occur as layers within small crystals. It further should be recognized that these particles can interact thermodynamically and crystallographically with their neighbors.

Glauconites in early ankerite concretions, ferroan calcite-cemented sandstones, and uncemented sandstones in the first Wilcox sandstone of the Lockhart Crossing field, Livingston Parish, Louisiana, show a progressive substitution of Fe for octahedral Al with increasing diagenesis. An octahedral Fe content of 0.50 atoms was calculated from glauconite located in early ankeritic concretions. Octahedral Fe averaged 0.60 and 0.90 atoms in later ferroan calcite-cemented sandstone and uncemented sandstone, respectively. Corresponding octahedral Al averages were 1.16, 1.03, and 0.67, respectively. A systematic increase in average interlayer K from 0.49 to 0.54 to 0.61 was also observed, with apparent increases in diagenesis. All element determinations were made with an electron microprobe and recast on an anion equivalent basis to structural formulae based on the O10(OH)2 unit. The clay preserved in the early ankerite concretions was found to be an illite/smectite containing about 20% expandable layers, and the mineral in the glauconite pellets from uncemented areas of the sandstone, an ordered glauconite. “Minus cement” porosities of the sandstone indicate that glauconitization may have taken place at burial depths greater than 0.6 to 1.8 km, but the mechanism for the incorporation of Fe3+ in the glauconite at that depth is not apparent.

The extent of illite/smectite (I/S) reactions is linked with quantitative measurements of shale fabric in a suite of samples from a lower Frio Formation well. Greater illitization of the I/S clays is found in laminated shales that possess a larger pore surface area/pore volume (SA/V) of 3.21 × 106 cm−1 than the adjacent massive shale lithofacies with a SA/V of 1.97 × 106 cm−1. Mean pore diameter in both shale lithologies is 0.0145 micrometers, though in the laminated shale distributions are skewed towards more smaller-sized pores. While no direct permeability measurements were made, estimates of permeability that are based on simple physical models using SA/V suggest that lower permeabilities are associated with laminated shales. The trend of greater illitization at higher SA/V values is contrary to expectations that reaction extent is enhanced by greater permeabilities, such as created by silt laminations in shale. The limitations of estimated permeabilities emphasize that porosimetry measurements of shale fabric are useful for estimating the access of material to all reaction sites, and do not just describe the effect of a few large pores that dominate permeability. Greater reaction extent in the laminated shales is associated with the accessibility of fluids to more pore space than in the massive shales.

To test the ability of illitic clay minerals to retain argon, K/Ar ages were measured on grain-size separates from the Cretaceous Mancos Shale and associated bentonites that have been transformed into K-bentonite near the contact with a large Tertiary igneous stock. The ages of size separates of illite/ smectite from the K-bentonite nearest the contact were internally concordant and matched the hornblende K/Ar age of the stock. In contrast, K/Ar data from clay size fractions from shales adjacent to each K-bentonite were internally discordant with measured ages that were much greater than the age of the intrusion. Thus, significant radiogenic argon was retained by fine-grained detrital illite, even in shale samples very near the igneous contact. These results are convincing evidence that illitic clay minerals are excellent K/Ar clocks under conditions prevailing in sedimentary and diagenetic environments.

Pillared, regularly and randomly interstratified illite/smectite (I/S) was prepared by interacting aluminum chlorohydrate with I/S in aqueous dispersion. I/S samples from Kinnekulle, Sweden, ranging in composition from 30–60% smectite layers, were used as starting clays. The pillaring resulted in a separation of the smectite layers in the I/S of about 9 Å, as estimated by X-ray powder diffraction and by nitrogen adsorption studies. Only the smectite layers of the clay were modified by the pillaring procedure. The pillared products had surface areas of 200–260 m2/g and pore volumes of about 0.18 cm3/g. The uptake of Al by the clay and the micropore surface area of the pillared products were proportional to the fraction of smectite layers in the I/S. The thermal and hydrothermal stability of the pillared I/S was similar to that of pillared montmorillonite prepared using the same procedure.

Three gels of illitic composition having different octahedral substitutions were hydrothermally treated in distilled water at 300°C and 500 bars for 7 to 90 days. The gel of the composition K0.7Al2.0(Si3.3Al0.7)O10(OH)2, having no octahedral substitutions, yielded poorly crystalline and randomly interstratified illite/smectite (I/S) having possibly 30% or more expandability. These I/S particles occurred predominantly as foliated or compact lamellar aggregates having morphological features characteristic of common smectite. Laths having a morphology similar to that of diagenetic “fibrous illites” were also found in small amounts after the gel had been aged for 35 days. Their chemical composition was similar to that of the foliated aggregates of I/S in the same run.

Illitic gel having the composition K0.7(Al1.7Fe3+0.3)(Si3.3Al0.7)O10(OH)2 having octahedral Fe3+ substitutions yielded more and better crystalline I/S. The reaction products of the 7-35-day runs consisted mainly of randomly interstratified I/S having an expandability of 90 to 65%. The I/S particles occurred as foliated or compact lamellar aggregates having a smectite-like morphology, as described above. The Fe3+-bearing gel yielded, after 90 days of ageing, an Rl-ordered I/S having 25% expandability and a morphology of ribbons and hexagonal platelets.

Illitic gel of composition K0.8Al1.6Mg0.4)(Si3.6Al0.4)O10(OH)2 having octahedral Mg2+ substitutions produced no illite even after 90 days of ageing, but a pure smectite in the form of foliated aggregates.

Samples of mixed-layer illite/smectite were investigated from a single bentonite bed zoned with respect to expandability from 90 to 30%. Chips of natural rocks were embedded in a resin, using a procedure designed to preserve the original fabric, cut with an ultramicrotome, and observed by high-resolution transmission electron microscopy (HRTEM). These observations confirmed the X-ray powder diffraction (XRD) model of mixed-layer clays, i.e., that illite/smectite grains in natural rocks are built of mixed-layer crystals, from 1 to as many as 15 silicate layers thick (4–6 interlayers per crystal on average). These crystals are present either as individual particles (loose crystals) or, typically, they form nearly parallel face-to-face groupings called here quasi-crystals. Free fundamental smectite and illite particles as defined by Nadeau and coworkers were essentially absent.

Illite and smectite interlayer spacings were 10 and 13.5 Å, respectively. Crystal thickness and number of interlayers were measured for 35–100 mixed-layer crystals per sample. Illite/smectite expandabilities were calculated from these data in two ways: either neglecting the crystal edges or accounting for them. The former determinations agree well with XRD estimates of expandability and the latter, with expandabilities calculated from the distributions of fundamental particle thickness measured by a shadowing technique in the TEM. This result explains the systematic discrepancy between XRD and TEM measurements of illite/smectite expandability.