The southern San Joaquin Valley contains more than 7 km of sedimentary fill, largely Miocene and younger in age. Ancient depositional environments ranged from alluvial fans at the basin margins to turbidite fans toward the basin center. Mixed-layer illite/smectite (I/S) dominates the <2-μm fraction of Miocene shales, and kaolinite is abundant in Miocene sandstones. I/S from carbonate-cemented sandstones contains 5–20% more smectite layers than I/S from uncemented sandstones. The timing of cementation correlates with the proportion of smectite layers in the I/S, suggesting that cementation slowed the illitization process. Smectite and I/S with > 80% expandable layers occur at present burial temperatures of 120°-l 40°C in Miocene sandstones and shales. This highly expandable I/S is restricted to areas covered by thick deposits (1000-2500 m) of Pleistocene sediments. Rocks of similar age and at equivalent temperatures, but covered by <900 m of Pleistocene sediments, contain I/S having low expandabilities (<30%).

Microprobe analyses of 16 discrete smectite and smectite-rich I/S clays indicate an average montmorillonite composition of:

$$\left( {C{a_{0.2}}{K_{0.15}}N{a_{0.1}}} \right)\left( {A{l_{3.0}}F{e^{3 + }}_{0.35}M{g_{0.75}}T{i_{0.03}}} \right)\left( {S{i_{7.7}}A{l_{0.3}}} \right){O_{20}}{\left( {OH} \right)_4} \cdot n{H_2}O.$$

Residence time at different temperatures appears to be an important influence on the percentage of smectite layers in I/S from the San Joaquin basin. Areas containing I/S with high expandabilities (e.g., 95% smectite layers) have a time-temperature index (TTI) of 4.0-4.5 at 120°C, whereas areas containing I/S with low expandabilities (e.g., 30% smectite layers) have a TTI of 5.0. Present data suggest that highly expandable I/S changed to slightly expandable I/S over a narrow temperature interval (10°-20°C). Differences in the potassium availability from detrital components and in the K+/H+ activity ratios of pore water do not appear to be related to the differences in the percentage of smectite layers of these I/S clays.

Junction probability diagrams show variation in both composition and layer arrangement in mixed-layer clay minerals. These diagrams can represent short-range and long-range ordered, random, and segregated interstratifications. Mineralogical analyses of illite/smectite from shale cuttings, bentonites, and hydrothermally altered tuffs define characteristic reaction pathways through these diagrams. Shale and bentonite analyses fall along pathways joining smectite and illite on diagrams showing nearest-neighbor (R1) layer arrangements. Transition from random to R1-ordered interstratifications occurs in shale samples containing 60–70% illite layers, and in bentonites containing 55–67% illite layers. Analyses of alteration products, however, fall near a line connecting rectorite and illite, which represents the maximum degree of R1 layer ordering. No mineralogical evidence is available to suggest that these alteration samples formed from a smectite precursor. All samples develop next-nearest (R2) and thrice-removed (R3) neighbor ordering along similar pathways. Transition to R2 ordering occurs gradually in samples composed of 65–80% illite layers, and samples containing more than 85% illite layers may show strong R3 ordering.

A layer-by-layer mechanism explains important features of mixed-layer clay minerals formed during the illitization of smectite, including the occurrence of randomly interstratified illite/smectite, the transition to ordered interstratifications, and the development of long-range ordering. A variety of solid-state transformation mechanisms were tested with a stochastic model, which accounts for interactions among clay layers. The model produces most successful results when the reaction of smectite layers with one illite nearest neighbor is favored over smectites with no illite neighbors by a factor of about two, and over those with two illite neighbors by a factor of ten or more. Synthetic X-ray powder diffraction patterns calculated from model results compare well with those of illite/smectite minerals. These results suggest a new kinetic rate law. Solutions to this rate law for reaction within sediments undergoing burial give mineralogical profiles with depth similar to those observed in subsiding sedimentary basins.

The reaction of smectite to illite in shale from the COST 1 well in the south Texas Gulf Coast and from altered ash-fall tuffs from the Morrison Formation in New Mexico was investigated using X-ray powder diffraction in conjunction with transmission electron microscopy. In the COST 1 well, the bulk of the detrital clay was originally a K+-deficient mixed-layer illite/smectite (I/S). As the I/S adsorbed K+ released by the dissolution of K-feldspar during burial, the proportion of expandable layers decreased with depth from ~65% near the top of the well to ~25% at 4500 m depth. In contrast, the proportion of low-charged structural planes [<0.8 eq per (Al,Si)4O10 unit] in the I/S decreased gradually from ~40% near the top of the well to ~15% near the bottom. Authigenic smectite with 100% expandable layers from the Morrison Formation tuffs is an alteration product of vitric ash. Where these tuffs have been buried to ~ 1400 m the smectite has reacted to form I/S with ~ 15% expandable layers.

Direct lattice images of I/S crystallites from both locations reveal a correspondence between edge dislocations and the interface between illite layers and smectite layers. Al, Si, Fe, Ca, Mg, and Na were apparently mobile along these dislocations as the reaction of smectite to illite proceeded. Al was probably retained within the crystallite when illite layers replaced the smectite layers; however, some of the remaining cations were expelled. Lateral replacement of smectite layers by illite appears to have been the principal growth mechanism.

High-resolution transmission electron microscopy (HRTEM) has been used to examine illite/smectite from the Mancos Shale; rectorite from Garland County, Arkansas; illite from Silver Hill, Montana; Na-smectite from Crook County, Wyoming; corrensite from Packwood, Washington; and diagenetic chlorite from the Tuscaloosa Formation. Thin specimens were prepared by ion milling, ultramicrotome sectioning, and/or grain dispersal on a holey carbon substrate. Some smectite-bearing clays were also examined after intercalation with dodecylamine hydrochloride (DH). Intercalation of smectite with DH proved to be a reliable method for HRTEM imaging of expanded smectite (d (001) = 16 Å) which could then be distinguished from unexpanded illite (d (001) = 10 Å). Lattice fringes of basal spacings of DH-intercalated rectorite and illite/smectite showed a 26-Å periodicity. These data support X-ray powder diffraction (XRD) studies which suggest that these samples are ordered, interstratified varieties of illite and smectite. The ion-thinned, unexpanded corrensite sample showed discrete crystallites containing 10-Å and 14-Å basal spacings corresponding to collapsed smectite and chlorite, respectively. Regions containing disordered layers of chlorite and smectite were also noted. Crystallites containing regular alternations of smectite and chlorite layers were not common. These HRTEM observations of corrensite did not corroborate XRD data. Particle sizes parallel to the c axis ranged widely for each sample studied, and many particles showed basal dimensions equivalent to more than five layers. For all illite, smectite, and illite/ smectite particles examined, crystallite sizes of about 20 Å in the basal dimension were not observed.

The smectite to illite reaction was studied by transmission and analytical electron microscopy (TEM/AEM) in argillaceous sediments from depths of 1750, 2450, and 5500 m in a Gulf Coast well. Smectite was texturally characterized as having wavy 10- to 13-Å layers with a high density of edge-dislocations, and illite, as having relatively defect-free straight 10-Å layers. The structures of smectite and illite were not continuous parallel to (001) at smectite-illite interfaces. AEM data showed that the smectite and illite were chemically distinct although smectite had a more variable composition. Illite formation appeared to have initiated with the growth of small packets of illite layers within subparallel layers of smectite matrix. With increasing depth, ubiquitous thin packets of illite layers increased in size until they coalesced.

A model for the transition requires that the structure of smectite was largely disrupted at the illite-smectite interface and reconstituted as illite, with concomitant changes in the chemistry of octahedral and tetrahedral sites. At least partial Na-K exchange of smectite preceded illite formation. Transport of reactants (K, Al) and products (Na, Si, Fe, Mg, H20) through the surrounding smectite matrix may have taken place along dislocations.

The smectite-to-illite conversion process for the studied samples does not necessarily appear to have required mixed-layer illite/smectite as an intermediate phase, and TEM and AEM data from unexpanded samples were found to be incompatible with the existence of mixed-layer illite/smectite in specimens whose XRD patterns indicated its presence.

Alternating mica-like and smectite-like layers of rectorite give rise to periodically varying contrast in 10-Å lattice fringes, yielding a periodicity of 20 Å in a transmission electron microscopic study. Expansion of rectorite using dodecylamine hydrochloride yields a three-layer repeat of thickness 32–35 Å, consisting of a basic 20-Å unit, identical to that in images of collapsed, dehydrated rectorite, and a 12-15-Å thick, intercalated organic layer.

Thin packets of layers derived by grinding the sample are only 20 Å thick, or multiples thereof. Serrated edges of rectorite grains likewise have steps 20 Å in height, implying that mechanical cleavage occurs readily along the weakly bonded, smectite-like interlayers. The “fundamental” 20-Å unit is proposed to be compositionally centered on an interlayer bounded by two identical T-O-T layers, each of which has compositionally different tetrahedral sheets. Such structural considerations suggest that resultant 20-Å units (“rectorite units”) are unique in structure and chemistry relative to true illite. These results further imply that grinding and other treatment of coherent crystals of clay minerals may produce individual unit layers. Moreover, when coupled with size-separation, such treatment may yield X-ray powder diffraction data that reflect reconstituted layer sequences.

The morphology of illite/smectite (I/S) from deeply buried bentonites and hydrothermally altered Tertiary volcanic rocks from Japan changes in parallel with the proportion of expandable layers in the I/S. As viewed by scanning electron microscopy, the morphologies range from the typical “cornflake,” “maple leaf,” or “honeycomb” habit of smectite to the typical platy or scalloped (with curled points) habit of illite. Although the changes are more subtle near either end member, at a composition of 60-70% illite layers, the morphology changes from sponge-like or cellular to platy or ribbon-like. The change of morphology at this composition correlates with a change in layer stacking from turbostratic to rotational ordering of the 1Md type. Turbostratic stacking can be thought of as randomly distributed translations of successive layers by any magnitude and in any direction. The rotationally ordered structure, which allows nearly precise juxtaposition of quasihexagonal oxygen surfaces from adjacent layers, probably permits more crystalline regularity in the a-b plane, which promotes a more plate-like or sheet-like habit.

The Nriagu polymer model of 2:1 layer type clay minerals develops from the premise that clay minerals are condensation copolymers of solid hydroxides. In the Mattigod-Sposito formulation of the model, standard state chemical potentials (standard Gibbs energies of formation from the elements) of 2:1 clay minerals are predicted quantitatively with a linear correlation equation relating the standard Gibbs energy of the polymerization reaction (ΔGor) to the half-cell layer charge of the clay mineral and to the valence and ionic radius of the exchangeable cation. It is now shown that this correlation equation can be derived from two basic assumptions: (1) that the standard Gibbs energy change for the transfer of a cation in a pure hydroxide solid to a hydroxide component in the tetrahedral or octahedral sheet of a 2:1 clay mineral is independent of the nature of the cation and (2) that the difference between ΔGor for the polymerization reaction to form a 2:1 clay mineral and ΔGor for the same reaction to form the zero layer-charge analog of the clay mineral is proportional to the number of interlayer exchangeable cations per unit cell of the clay mineral and to the radius of its exchangeable cation. Both of these assumptions can be tested experimentally, independent of the polymer model.

Multivariate statistical analyses of geochemical, mineralogical, and cation-exchange capacity (CEC) data from a Venezuelan oil well were used to construct a model which relates elemental concentrations to mineral abundances. An r-mode factor analysis showed that most of the variance could be accounted for by four independent factors and that these factors were related to individual mineral components: kaolinite, illite, K-feldspar, and heavy minerals. Concentrations of Al, Fe, and K in core samples were used to estimate the abundances of kaolinite, illite, K-feldspar, and, by subtraction from unity, quartz. Concentrations of these elements were also measured remotely in the well by geochemical logging tools and were used to estimate these mineral abundances on a continuous basis as a function of depth. The CEC was estimated from a linear combination of the derived kaolinite and illite abundances. The formation's thermal neutron capture cross section estimated from the log-derived mineralogy and a porosity log agreed well with the measured data. Concentrations of V, among other trace elements, were modeled as linear combinations of the clay mineral abundances. The measured core V agreed with the derived values in shales and water-bearing sands, but exceeded the clay-derived values in samples containing heavy oil. The excess V was used to estimate the V content and API Gravity of the oil. The log-derived clay mineralogy was used to help distinguish nonmarine from transitional depositional environments. Kaolinite was the dominant clay in nonmarine deposits, whereas transitional sediments contained more illite.

Clays can act as osmotic membranes and thus give rise to osmotically induced hydrostatic pressures. The magnitude of generated osmotic pressures in geologic systems is governed by the theoretical osmotic pressure calculated solely from solution properties and by value of the membrane's three phe-nomenological coefficients: the hydraulic permeability coefficient, Lp; the reflection coefficient, σ; and the solute permeability coefficient, ω. Generally, low values of Lp correspond to highly compacted membranes in which σ is near unity and ω approaches zero. Such membrane systems should give rise to initially high osmotic fluxes and gradual dissipation of their osmotic potentials.

The high fluid pressures in the Dunbarton Triassic basin, South Carolina, are a good example of osmotically induced potentials. A unique osmotic cell is created by the juxtaposition of fresh water in the overlying Cretaceous sediments against the saline pore water housed within the membrane-functioning sediments of the Triassic basin. Because wells penetrating the saline core of the basin show anomalously high heads relative to wells penetrating the basin margins, the longevity of this osmotic cell is probably dictated by the rate at which salt diffuses out into the overlying fresh water aquifer.