TEM characterization of stacking relations in I/S of expanded shale samples from the Gulf Coast and Michigan Basin was carried out to address the issues of the degree of coherency and the nature of layer stacking sequences in smectite, I/S and illite. The two-dimensional lattice fringe images obtained from this study show that cross fringes are commonly observed to be continuous over at least 3–4 layers for smectite, 6–7 layers for ordered I/S and 9–10 layers for illite-rich I/S. This demonstrates that such sequences are coherent, or at least semi-coherent (in smectite) units (MacEwan crystallites). The observations demonstrate that so-called fundamental particles are fragments of MacEwan crystallites formed primarily as a result of disaggregation along weakly-bonded smectite interlayers. However, both 0k1 and h01 reflections may coexist in selected area electron diffraction (SAED) patterns. The frequency of occurrence of the coexistence in SAED patterns decreases in the order smectite, I/S and illite for Gulf Coast samples. This is consistent with the presence of turbostratically-related interfaces in packets of all of these materials. Therefore, any given layer sequence in smectite, ordered I/S and illite may have both turbostratic and coherent interfaces. The proportion of coherently-related layers increases with increasing proportion of illite-like layers. The concept of fundamental or elementary particles is not related to layer sequences in non-disaggregated, original rocks. Indeed, it implies relations that are not valid.

The lattice fringe images, SAED and optical diffraction patterns demonstrate that where layers are coherently-related, 2M1 is the dominant polytypic sequence in all samples. However, this periodic 2M1 stacking is so frequently interrupted by stacking faults in smectite that it gives rise to apparent lMd polytypism. The degree to which the periodic 2M1 sequences are interrupted by stacking faults decreases with increasing proportion of illite-like layers. The SAED patterns of I/S and illite unmodified since its formation are diffuse parallel to c* and have poorly-defined, non-periodic reflections for indices k ≠ 3N as a measure of local ordering superimposed on poorly-ordered coherent sequences with a turbostratic component. X-ray diffraction (XRD) patterns, as integrated over domains with a range of heterogeneous stacking relations, do not represent simple mixtures of discrete IM and 2M1 polytypes.

The observations of this study imply that dissolution-crystallization is a dominant mechanism for the smectite-to-illite transition. The semi-coherent stacking of smectite-like layers in smectite-rich samples implies that either a dissolution-crystallization process took place subsequent to deposition of detrital smectite or that Gulf Coast smectite is an in-situ alteration product of volcanic ash.

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 Kübler Index (KI) is defined as the full width at half-maximum height (FWHM) of the 10-Å X-ray diffraction peak of illite-smectite interstratified (I-S) clay minerals. The only parameters controlling the Kübler Index are assumed to be the mean number of layers (N) in the coherent scattering domains (CSD), the variance of the distribution of the number of layers of the CSD, the mean percentage of smectite layers in I-S (%S), and the probability of layer stacking (Reichweite).

The Kübler-Index measurements on air-dried (KIAD) and ethylene-glycolated (KIEG) samples were compared to N and %S using the NEWMOD computer program to simulate X-ray diffraction patterns. Charts of KIAD versus KIEG corrected for instrumental broadening were made and isolines were mapped for constant N and %S. Isolines allow a direct and rapid determination of N and %S from KI measurements.

The method allows quantification of the metamorphic anchizone limits by considering mean thickness of fundamental particles in MacEwan crystallites. The transition from diagenesis to the anchizone and from the anchizone to the epizone of low-grade metamorphism corresponds to thicknesses of 20- and 70-layer fundamental particles, respectively.

Rb-Sr and oxygen isotope studies, in addition to K-Ar isotopic determinations published previously, are reported on diagenetic and hydrothermal fundamental particles (particle thickness of 0.03 to 0.05 nm and particle ab size of 0.02–0.05 µm) of the East-Slovak Basin. The combined data set allows us to ascertain the crystallization conditions of the illite material from two bentonite units collected at two basinal sites located ~20 km apart, and characterized by prolonged diagenetic conditions induced by progressive burial. A bentonite rock characterized by a short hydrothermal event from the Zempleni mountains to the SW of the East-Slovak basin is also studied.

For the two first sites, the δ18O values increase in one case and decrease in the other, when the size of the diagenetic fundamental particles from bentonite samples increases. These variations suggest that temperature increased in one and decreased in the second of the two samples collected in the basin, while the particles were growing. In the case of the hydrothermal bentonite, the δ18O values of the different size-fractions consisting of fundamental particles remain about constant, suggesting constant temperature and fluid chemistry.

The Rb-Sr dates of the fundamental particles of the three bentonite rocks were systematically higher than the corresponding K-Ar ages. The 87Sr/86Sr ratios, which are initially involved in the particle nucleation, appeared higher than that of contemporaneous sea-water. In all cases, the initial 87Sr/ 86Sr ratio decreases when particle size increases, which implies supply of external Sr into the bentonite units. This external Sr seems to have had an 87Sr/86Sr ratio close or identical to that of the contemporaneous sea water. This means that Sr, probably of sea-water origin, progressively diffused from host shales into the bentonite units, during burial diagenesis. In turn it favors the suggestion made previously about diffusion of K from shales into the bentonite layers during illitization of the smectite from these units.

Burial-induced and hydrothermal-related illitization in bentonites and in sandstones can be modeled on the basis of isotopic studies of fundamental particles separated from mixed-layer illitesmectite. The model envisages different reaction rates and durations relative to the varied impacts of temperature, considering that the water:rock ratio also has an influence. The different pathways for illitization are suggested on the basis of the K-Ar, Rb-Sr and δ18O compositions of previously studied materials.

New information is provided on why fundamental particles separated from mixed-layer illite-smectite in shales yield K-Ar age data that are systematically greater than the ages of the fundamental particles from associated bentonites and/or sandstones, and greater than the reported stratigraphic ages. The study of pure authigenic, recent to present-day smectite from Pacific sediments shows that (1) those collected from active hydrothermal vents have 40Ar/36Ar ratios identical to that of the atmosphere, and (2) those of mud sediments have 40Ar/36Ar ratios above the atmospheric value, indicating addition of 40Ar not generated in situ by radioactive decay. A preliminary but detailed analysis of the noble-gas (Ar, Xe, Kr) contents of authigenic smectite-rich size fractions from Pacific deep-sea red clays suggests trapping of these gases by smectite. Therefore, the results point to the fact that fundamental particles can incorporate excess 40Ar into their structure when nucleating in restricted to closed systems, such as shales. This excess 40Ar, which represents radiogenic 40Ar released from nearby altered silicates, might be temporarily adsorbed at the surface of the rock pore spaces and is therefore available for incorporation in nucleating and growing particles.

Two independent methods of crystal-size distribution analysis were compared: the Bertaut-Warren-Averbach XRD technique (MudMaster computer program) and high-resolution transmission electron microscopy (HRTEM). These techniques were used to measure thickness distributions of illite crystals (fundamental particles) from sets of illite-smectites from shales and bentonites that had expandabilities ranging from 86%S to 6%S. The illite-smectites were treated with a polymer (polyvinylopyrolidone, PVP) to separate them into fundamental particles for XRD and HRTEM investigations.

A systematic difference between XRD and HRTEM results was observed: XRD (area-weighted distributions) detected a larger fraction of thick (>4 nm) and a smaller fraction of thin crystals as compared to HRTEM (number-weighted distributions). As a result, XRD-determined distributions have larger mean thickness values and larger distribution parameters (α and β2). The measurements performed by the two techniques were verified by modeling XRD patterns of the PVP-illites, using the measured distributions as inputs. The modeling indicated that the XRD-determined distributions are very accurate. Selecting broader thickness distributions in MudMaster further improved the modeling results. The HRTEM measurements underestimate the proportion of coarse particles, in particular in shale samples, and this inaccuracy is attributed to the effect of using number-weighted (rather than area-weighted) distributions and to inaccurate counting statistics for thick crystals.

The clay fraction of the sedimentary succession beneath the Mahakam Delta (eastern Kalimantan, Indonesia) consists mainly of mixed-layer illite-smectite, with minor amounts of kaolinite and/or dickite, discrete detrital illite and chlorite. On the near-shore anticline, evolution of this mixed-layer material is characterized by a decrease in expandability with depth. The mechanism of conversion of smectite to illite layers depends on the lithology of the host rocks: it evolves along a solid-state transformation in the shales and a dissolution-precipitation in the sandstones.

Illite fundamental particles from two sandstones buried at ∼4000 m in the Tambora field next to the Handil field on the same near-shore anticline yield a mean K-Ar age of 15.7±1.6 Ma (2σ), which is younger than the stratigraphic age but still slightly biased by minute amounts of discrete detrital illite. Recalculated after modeling, which takes into account the occurrence of the discrete detrital illite, this K-Ar age becomes 14.4±0.7 Ma. The K-Ar values of the fundamental particles from associated buried shales are significantly older, which can be explained by a mixture of (1) a precursor material similar to that presently deposited in the delta of the Mahakam River, and (2) authigenic fundamental particles incorporating Ar with a 40Ar/36Ar ratio above atmospheric value during nucleation and growth on the same detrital precursor.

Application of the modeling to the burial evolution of <0.4 µm particles from both the shales and the sandstones of the basin points to a contribution of detrital micaceous material in both lithologies, (1) in the sandstones as a detrital component dissolving progressively and mixed mechanically with the authigenic fundamental particles, and (2) in the shales as a detrital precursor progressively releasing radiogenic 40Ar by burial alteration, and at the same time acting as a support for the fundamental particles for the growth of authigenic fundamental particles that were found to incorporate Ar characterized by an excess of 40Ar.

The distributions of illite crystal (‘fundamental particle’) thickness in <0.2 µm fractions of 13 shale samples (from the Carpathian Foredeep, Poland), obtained using the Bertaut-Warren-Averbach X-ray diffraction method (MudMaster computer program), were analyzed and interpreted in terms of the mechanism of smectite illitization. All illite crystal thickness distributions in the analyzed shales are characterized by an ‘asymptotic’ shape. The origin of the asymptotic-type distributions is explained by the heterogeneity of illite crystals in shales, i.e. superposition of different populations of crystals, those included in illite-smectite (I-S) interstratifications, and those which occur as discrete illite. The analysis of the distributions in shales shows that the most frequent thickness class of illite crystals forming I-S is 2 nm. Discrete illite is composed of thicker crystals; though crystals as thin as 2 nm can also contribute to this population. The modeling of asymptotic distributions in shales by using a number of theoretical lognormal distributions shows that with progressive diagenesis, the mean thickness of illite crystals forming the I-S component increases gradually, whereas the discrete illite does not show a clear trend.

The diverse origins of illite crystals in shales do not permit determination of the mechanism of smectite illitization from the evolution of the shape of the overall crystal-thickness distribution during diagenesis. Therefore, in order to understand the mechanism of smectite illitization in shales, an attempt was made to trace the relative gains and losses of crystals of different thicknesses during illitization. This approach indicates the following mechanism of smectite illitization in the investigated shales: dissolution of smectite monolayers accompanied by growth of 2 nm crystals which are largely of detrital origin. Nucleation of 2 nm illites seems to be very limited.

The impact of diagenetic processes on petroleum entrapment and recovery efficiency has focused the vast majority of the world's conventional oil and gas resources into relatively narrow thermal intervals, which we call Earth's energy “Golden Zone”. Two key mineralogical research breakthroughs, mainly from the North Sea, underpinned this discovery. The first is the fundamental particle theory of clay mineralogy, which showed the importance of dissolution/precipitation mechanisms in the formation of diagenetic illitic clays with increasing depth and temperature. The second is the surface area precipitation-rate-controlled models for the formation of diagenetic cements, primarily quartz, in reservoirs. Understanding the impacts of these geological processes on permeability evolution, porosity loss, overpressure development, and fluid migration in the subsurface, lead to the realization that exploration and production risks are exponential functions of reservoir temperature. Global compilations of oil/gas reserves relative to reservoir temperature, including the US Gulf Coast, have verified the “Golden Zone” concept, as well as stimulated further research to determine in greater detail the geological/mineralogical controls on petroleum migration and entrapment efficiency within the Earth's sedimentary basins.

Interstratified illite-smectite (I-S) occurring authigenically in diverse earth crust environments reacts toward more illite-rich phases as temperature increases. For that reason, I-S is used for geothermometry when prospecting for hydrocarbons or ore mineral deposits. This study develops the mathematical relations for characterizing the coherent stacking potential of fundamental particles (FP) using the expandability ratio K, where K is defined as (%SMAX –; %SXRD)/%SMAX. The ratio can be applied to differentiating I-S samples from shales, bentonites, and hydrothermal alterations. In particular, patterns on a K vs. T diagram, where T is the average thickness of fundamental particles (FPs), appear to be indicative of the geological conditions related to I-S formation. Shale samples plot in the negative K domain of the diagram, possibly due to the intimate mixing of detrital particles. Both bentonitic and hydrothermal samples display trends of increasing K with T, which suggests the coherent stacking potential progressively decreases as FPs increase in thickness. Hydrothermal samples are more extensively distributed on the diagram than samples from bentonites. This result may reflect differences in particle growth conditions (nutrients and space) between bentonites (short supply) and hydrothermal alterations (good supply).