The mobility of rare-earth elements (REE) in low-grade diagenetic regimes, potentially leading to their clay-mediated fractionation, remains poorly understood. This study draws evidence from the argillitized Miocene tuff of the Southwestern Pannonian Basin (SPB) and adjacent Dinarides intramontane basins (DIB) to investigate the role of illite-smectite (I-S) in controlling early diagenetic REE behavior. The present research relies on detailed mineralogical, geochemical, and gas adsorption characterization of altered tuff, focusing on comparative analyses of the REE chemistry obtained by in situ laser ablation inductively coupled plasma mass spectrometry of glass shards and that of spatially related authigenic clay minerals. The depositional environment, in which the volcanic glass alteration took place, gave rise to the composition of secondary paragenesis, revealing a dominance of I-S. The normalized REE geochemistry of clay separates show similarities to unaltered glass, but notable differences indicate fluctuations in fluid/rock ratio environments. The redox conditions during glass alteration are reflected in Ce and Eu anomalies and indicate the ranges from oxic to anoxic across the analyzed tuffs. The results showed that I-S, formed through volcanic glass diagenesis, inherits magmatic REE signatures but also fractionates REE based on more reducing physiochemical conditions. The strong correlation between smectite content of I-S and a total budget of fractionated REE posits the smectite interlayers as prime factors controlling the REE fractionation during volcanic ash diagenesis. Furthermore, greater specific surface area values and development of slit-shaped porosity along the non-basal edges of I-S particles contributed to REE adsorption. These findings contribute to our understanding of REE behavior in low-temperature diagenetic environments, emphasizing the significance of clay minerals in retaining and fractionating these elements which may lead ultimately to the formation of economically viable ion-adsorption clay deposits.

The Dolná Ves K-bentonite deposit is one of a few known economic accumulations of illite-smectite in the world. Several studies have been done on the illite-smectitic component isolated from the Dolná Ves K-bentonite, but there is a shortage of analytical data on the K-bentonite itself. The main goal of the present study was to perform mineralogical and physico-chemical characterizations of various technological types of K-bentonites from the Dolná Ves deposit to better understand the relationships between the various qualitative types and their properties. The type I (high-grade) K-bentonite contains 88–91 wt.% of illite-smectite. The type II (low-grade) K-bentonite contained substantially less illite-smectite, ranging from 37 to 63 wt.%. The illite-smectites isolated from the type I K-bentonites displayed greater expandability, contained more octahedral Mg and less octahedral Fe, had greater cation exchange capacity (CEC), smaller thickness of fundamental particles, and thinner illite-smectite crystals in comparison with illite-smectites from the type II K-bentonites. The LOI (loss-on-ignition) and Al2O3 content increased with increasing amount of illite-smectite. The increase in the expandability by 10% corresponded to an increase in CEC by ~10 meq/100 g. The type I K-bentonites had much greater mass loss at <250°C due to greater expandability. The best tilemaking performance was expected for the type I K-bentonite. This raw material could also be potentially valuable for the pharmaceutical, cosmetic and food industries. Overall, the results showed that the studied technological types of K-bentonites from the Dolná Ves deposit differ not only in terms of illite-smectite contents but also in terms of the nature of the illite-smectites.

Phyllosilicates are hypothesized to be primarily of pedogenic origin in shallowly buried paleosols (≤3 km depth), regardless of the age of the paleosol. To test this hypothesis, this work evaluates the possible presence of detrital and diagenetic phyllosilicates in middle and upper Pennsylvanian paleosols, collected from three drill cores along a north–south transect in the Illinois Basin. The abundances of 2M1 muscovite, quartz, and K-feldspar are greater in a morphologically immature Protosol from the southernmost core; 1Md illite and interstratified illite-smectite with R1 and R0 stacking orders are more abundant in the more mature Vertisols of the central and northern cores. K-Ar age values of multiple clay-size fractions from each paleosol averaged ~260 Ma in the northern core, 270 Ma in the central core, and 295 Ma in the southern core. While considering the complex tectonic and thermal history of the Illinois Basin, detrital minerals are more abundant in immature paleosols that experienced relatively greater maximum burial depths and thus greater sediment supply whereas illitization in more mature paleosols was probably initiated primarily during protracted burial diagenesis. As the present study found evidence for diagenetic and detrital minerals in clay-size fractions of shallowly buried, deep-time paleosols, caution is advised when using paleosol minerals for ancient climate and environment reconstructions.

Two distinct assemblages of authigenic phyllosilicates were distinguished in the Kremikovtsi sedimentary exhalative (SEDEX) siderite iron formation (SIF) and noted as important tracers of two styles of mineralization characteristic of this type of ore deposit. Hydrothermal-sedimentary layer silicates are represented by rare occurrences of relict microcrystalline Mg-rich berthierine with a relatively low degree of structural ordering, associated closely with framboidal pyrite as an intergranular matrix cementing sparry siderite grains; the larger silicates are also represented by the diagenetic transformation product of berthierine, chamosite. Berthierine precipitated under anoxic conditions during advanced early diagenesis after chert deposition. Hydrothermal-epigenetic phyllosilicates (berthierine, chamosite, illite-smectite (I-S), and kaolinite) from the barite-sulfide assemblage are characterized by: crystalline and undeformed habits; relatively larger particle size, low-temperature polytypes, low to no mixed layering, and a high degree of crystallinity; absence of impurities and dominant monomineralic aggregates; affiliation to initial open spaces and deposition mainly as vug fillings and linings. They formed under pronounced control by the vuggy porosity of the siderite host caused by the invasion of acid (pH = 3–5), hot (200–230°C) hydrothermal fluids probably at the stage of burial diagenesis of the SIF under relatively stable reducing conditions fluctuating near the sulfide/sulfate stability boundary $\left(\log {\text{P}}_{{\text{O}}_{\text{2}}}\cong -30\right)$. The greater Al concentration in hydrothermal solution than in seawater determines the affiliation of phyllosilicates in the Phanerozoic SEDEX SIFs to aluminous species (berthierine, chamosite) unlike low to non aluminous ones (greenalite, stilpnomelane) in the Precambrian IFs. The berthierine compositions, expressed by the Mg/Fe vs. Al/Si ratios, are a sensitive indicator of the geological conditions under which they formed (marine, non-marine, hydrothermal ore and pre-ore), thus allowing the genetic discrimination of this mineral from various localities.

The three-dimensional crystal structures of illite-smectite (I-S) in K-bentonite samples from the Appalachian Basin are characterized by rotational disorder in the stacking sequence of 2:1 illite layers, different proportions of n60° rotations (as opposed to n120°) in the rotated layers, and layers with centrosymmetric trans-vacant (tv) octahedral sites that are randomly interstratified with noncentric cis-vacant (cv) layers. The proportion of cv interstratification in the I-S increases with tetrahedral A1 and decreases with octahedral Mg and Fe content. The I-S minerals in the northern Appalachian basin K-bentonites are characterized by high (79% average) proportions of cv (Pcv) layers. In contrast, I-S from equivalent K- bentonites from the southern Appalachian basin has low Pcv values (38% average). These values do not correlate with expandability or rotational disorder. The geographic distribution of these I-S structural parameters may have resulted from possibly short-term, hot, and advective fluid migrations that differed in Mg concentrations and/or other physical and chemical parameters.

Mixed layering of illite-smectite was studied both experimentally, by using high-resolution transmission electron microscopy (HRTEM) and analytical electron microscopy (AEM), and theoretically, by using lattice-energy calculations.

Samples from a hydrothermal origin show the transformation of smectite to illite with different ordering types in the illite-smectite layer sequences. Ordering ranges from complete disordered (Reichweite, R = 0 type) in the less transformed samples to increased local order, with IS and IIS sequences (R = 1 and R = 2, respectively; I = illite, S = smectite) in more illitized samples.

Lattice-energy calculations are used to determine the structure of the illite-smectite sequence, which corresponds to the minimum energy. The unit layers are: O0.5TI′TO0.5 (O, T, and I′, respectively, denote the octahedral and tetrahedral sheets, and the interlayer. The 0.5 signifies half of the octahedral cations.) For example, the arrangements of the perfectly ordered … ISIS … and … IISIIS … sequences are respectively … OM(TI′T)IOM(TI′T)S … and … OM(TI′T)IOI(TI′T)1OM(TI′T)S … (the subscripts I, S, and M, respectively, refer to compositions of illite, smectite, and midway between at 0.5). Such arrangements produce a polar model for TOT layers, which display a TIOMTS structure in the case of IS adjacent layers. Furthermore, the lattice energies of … ISIS … and … IISIIS … are found to be nearly equal to the corresponding sums of the lattice energies of illite and smectite. This result indicates that interstratified illite-smectite and the two-phase assemblage of illite + smectite have similar stabilities.

On the basis of the above model, the solid-state transformation of one smectite layer to one illite layer, which produces mixed-layer sequences, involves the transformation of an O0.5TI′TO0.5 unit of smectite into the same corresponding unit of illite.

Oxygen isotopic compositions were determined for coexisting mixed-layer serpentine-chlorite (Sp-Ch) and illite-smectite (I-S) from 5 Tuscaloosa Formation sandstone cores sampled between 1937 and 5470 m burial depth. High gradient magnetic separation (HGMS) was used to concentrate Sp-Ch and I-S from the <0.5 μm fraction of each core sample into fractions with a range in the Sp-Ch: I-S ratio, and end-member δ18O compositions were determined by extrapolation. The Sp-Ch δ18O values range from + 10.4 to 13.7% and increase with burial between 3509 and 5470 m. The only exception is Sp-Ch from 1937 m, which has an anomalously high δ18O value of +12.6‰ The I-S δ18O values range from +16.1 to 17.3% and do not change significantly between 3509 and 5470 m burial depth.

Pore water δ18O compositions calculated from Sp-Ch and I-S values and measured borehole temperatures range from −2.6 to +10.3‰ The isotopically light values indicate that Sp-Ch formed at shallow burial depths in the presence of brackish to marine water and/or meteoric water. The depth-related increase in δ18O of Sp-Ch is attributed to oxygen exchange between mineral and pore water during diagenetic mineral reactions. Increasing δ18O values, in conjunction with XRD and SEM data, indicate that transformation of serpentine layers to chlorite layers and Ibb polytype layers to Iaa polytype layers occurred on a layer-by-layer basis when individual layers dissolved and recrystallized within the confines of coherent crystals. Possible explanations for the variation in I-S δ18O values include depth-related differences in pore water δ18O values present at the time of I-S crystallization, contamination by detrital 2M, mica and 1M polytype rotations that facilitated oxygen exchange.

A procedure for structural investigations by X-ray diffraction of mixed-layer structures incorporating swelling layers has been developed. For each sample, specimens saturated with different cations (Na, Mg, and Ca), are analyzed both as air-dried and as glycolated. One structural model fitting all the observed patterns then provides the structure of the sample. Samples tested include: Mite-smectite (I-S) minerals from Kazachstan (a rectorite), Dolna Ves in Slovakia, Kinnekulle in Sweden, the North Sea, and Scania in Sweden. The fitting of the patterns of the Kazachstan rectorite demonstrated that the instrumental parameters applied in the modeling were correct. For the I-S minerals from Slovakia and Kinnekulle the observed patterns were fitted with one two-component I-S model. However, the Ca-saturated and air-dried specimen of the Kinnekulle bentonites had two types of swelling interlayers. For the Slovakian I-S with Reichweite = 2, an alternative two-phase I-S plus I–V (V = vermiculite) model fitted the experimental X-ray diffraction patterns equally well. The I-S mineral from Scania is in fact a three-component I-T-S (T = tobelite) and the North Sea sample is a four-component I-S-V-V, one type of the swelling layers having swelling characteristics intermediately between smectite and vermiculite. In addition to layer types and distribution, interlayer compositions, such as the amount of interlayer glycol and water and of fixed and exchangeable cations, were determined.

Area-weighted thickness distributions of fundamental illite particles for samples of illite and illite-smectite from seven locations (including bentonites and hydrothermally altered pyroclastics) were measured by Pt-shadowing technique, by transmission electron microscopy. Most thickness distributions are described by lognormal distributions, which suggest a unique crystallization process. The shapes of lognormal distributions of fundamental illite particles can be calculated from the distribution mean because the shape parameters α and β2 are interrelated: β2= 0.107α − 0.03. This growth process was simulated by the mathematical Law of Proportionate Effect that generates lognormal distributions. Simulations indicated that illite particles grow from 2-nm thick illite nuclei by surface-controlled growth, i.e., the rate of growth is restricted by how rapid crystallization proceeds given a near infinite supply of reactants, and not by the rate of supply of reactants to the crystal surface. Initially formed, 2-nm thick crystals may nucleate and grow within smectite interlayers from material produced by dissolution of single smectite 2:1 layers, thereby transforming the clay from randomly interstratified (Reichweite, R = 0) to ordered (R = 1) illite-smectite after the smectite single layers dissolve. In this initial period of illite nucleation and growth, during which expandable layers range from 100 to 20%, illite crystals grow parallel to [001]* direction, and the dimensions of the (001) plane are confined to the size of the original smectite 2:1 layers. After nucleation ceases, illite crystals may continue to grow by surface-controlled growth, and the expandable-layer content ranges from 20 to 0%. This latter period of illitization is characterized by three-dimensional growth. Other crystal-growth mechanisms, such as Ostwald ripening, supply-controlled growth, and the coalescence of smectite layers, do not produce the observed evolution of α and β2and the observed shapes of crystal thickness distributions.

Mineralogical studies were performed on authigenic clay minerals of mudrocks, sandstones, and bentonites from 38 boreholes in the Late Permian coal measures of the Bowen Basin. Clay-mineral separations of samples from the northern Bowen Basin consist mainly of (Reichweite, R) R = 1 and R ≥ 3 interstratified illite-smectite (I-S), chlorite, and kaolinite. In the southern Bowen Basin, samples from higher stratigraphie sections are characterized by randomly ordered (R = 0) I-S mixed layers, and kaolinite and chlorite in smaller amounts. Samples from the lower sections consist of (R ≥ 3) I-S, chlorite, chlorite-rich chlorite-smectite (C-S), and laumontite.

Examination of the mineralogy and distribution of authigenic clay minerals from the Late Permian coal measures in the northern part of the Bowen Basin indicated that the presence of clay minerals is not systematically related to depth and clay occurrences do not occur regularly. These mineralogical variations of clay in volcaniclastic sediments are incompatible with thermal control. Variations in the rate of fluid flow and potassium supply owing to permeability exert major influences on clay-mineral paragenesis and the reaction of illitization. In more permeable zones (possibly faults or fracture zones), highly illitic clays with lath-shaped morphologies may have precipitated directly from potassium-rich fluids migrating from deeper parts of the basin. In addition, abundant chlorite precipitated contemporaneously with illitic clays, which may have resulted from sufficient magnesium and iron occurring in the fluids as a result of dissolution of intermediate or mafic-rock fragments. At the same time, clay paragenesis with less illitic I-S, kaolinite, and minor chlorite occurs outside the channelized zones of high fluid flow, where a diffusive-flow regime may have predominated with lower ratios of the activities of K+ and H+ (i.e., αK+/αH+) in the solutions.

In the southern Bowen Basin, depth-related changes in the distribution of clay minerals are evident and may be indicative of thermal control on clay-mineral reactions. Zeolites are present locally in the Late Permian volcaniclastic rocks in the southern Bowen Basin, but not in the north. This is attributed to a low ratio of αCO2/αH2O (where α = activity) and/or more saline and alkaline solutions.

A very simple technique is proposed for a quantitative or semiquantitative interpretation of X-ray diffraction (XRD) patterns for two-component mixed-layer structures. It is suitable for a determination of the Reichweite (R) values and proportions of component layers from graphical simulations of basal peak positions for mixed-layer structures with definite layer types. This technique can be successfully used for illite-smectites, but the accuracy of the results obtained for other mixed-layer structures is somewhat lower. In addition to the graphical technique, simple linear relationships are proposed for the calculation of layer proportions. Such relationships can be easily obtained for any mixed-layer structure with any R and any thicknesses of interstratified layers.

Structural parameters reported in the literature for mixed-layer illite-smectites, kaolinite-smectites, etc., were used to check the reliability of the method presented. It is concluded that the technique works well and produces parameters that are in agreement with those published.

Burial diagenesis of shales of the Frio Formation resulted in an increase in the abundance of mixed-layer illite-smectite (I-S), albite and chlorite, and a decrease in the abundance of K-feldspar, illite and kaolinite. Some of the mineralogic trends determined in this study contrast with the results of Hower et al. (1976) and other studies of Frio shales. The differences are due to improvements in laboratory and clay quantification techniques since the time of the earlier research. I-S composition changed from ~20% to ≥80% illite, and mineralogic and chemical reaction of I-S continued throughout burial. Shale diagenesis was an open-system process that required addition of K2O and A12O3, and resulted in loss of SiO2. The amount of SiO2 made available by shale diagenesis is sufficient to be the source of the quartz-overgrowth cements in the associated Frio sandstones. The relationships between I-S diagenesis and fluid flow from shales into sandstones, generation of abnormal formation-water fluid pressure, onset of sandstone diagenesis and distribution of authigenic phases in sandstones indicate that reaction of the I-S in shales is one of the most important components of the sandstone/shale/formation water diagenetic system.

The thicknesses of fundamental illite particles that compose mixed-layer illite-smectite (I-S) crystals can be measured by X-ray diffraction (XRD) peak broadening techniques (Bertaut-Warren-Averbach [BWA] method and integral peak-width method) if the effects of swelling and XRD background noise are eliminated from XRD patterns of the clays. Swelling is eliminated by intercalating Na-saturated I-S with polyvinylpyrrolidone having a molecular weight of 10,000 (PVP-10). Background is minimized by using polished metallic silicon wafers cut perpendicular to (100) as a substrate for XRD specimens, and by using a single-crystal monochromator. XRD measurements of PVP-intercalated diagenetic, hydrothermal and low-grade metamorphic I-S indicate that there are at least 2 types of crystallite thickness distribution shapes for illite fundamental particles, lognormal and asymptotic; that measurements of mean fundamental illite particle thicknesses made by various techniques (Bertant-Warren-Averbach, integral peak width, fixed cation content, and transmission electron microscopy [TEM]) give comparable results; and that strain (small differences in layer thicknesses) generally has a Gaussian distribution in the log-normal-type illites, but is often absent in the asymptotic-type illites.

Clay mineral diagenesis in the Niigata basin is documented by mineralogical and chemical analysis of clay minerals from cuttings from the Shinkumoide SK-1D (SSK-1D) well which is characterized by alternating beds containing dioctahedral and trioctahedral smectite minerals with increasing depth. Dioctahedral smectite shows a progressive increase in illite interstratification with increasing depth. The transition of dioctahedral smectite to interstratified illite-smectite (I-S) is supported chemically by an increase in K and Al and a decrease in Si with increasing depth. In contrast, trioctahedral smectite (saponite) reacts to form a 1:1 interstratified chlorite-smectite (C-S) with increasing burial depth and temperature. Considering the geology and the occurrence of smectite, the SSK-1D smectites probably altered diagenetically from two different parent materials: dioctahedral smectite is derived from clastic sediments and transforms to interstratified illite-smectite, whereas trioctahedral smectite is derived from andesitic pyroclastic rocks and transforms to interstratified chlorite-smectite.

The C-S occurs at the same depth of ~3200 m as the conversion of randomly interstratified (R = 0) I-S to (R = 1) I-S. Furthermore, the depth is compatible with a Tmax temperature of 430-435°C, which indicates the starting temperature for oil generation from organic matter. The temperature of the conversion of (R = 0) I-S to (R = 1) I-S and the start of corrensite formation is estimated at 110-120°C based on the time-temperature model suggested by others. The clay-mineral diagenesis in the SSK-1D further suggests that I-S and C-S can act as geothermometers in clastic and pyroclastic sediments provided that the effect of time is considered.

The purpose of this study was to characterize more fully the surface charge characteristics of the end-member smectite in illite-smectite (I-S) mixed-layer phases found previously in pelitic sediments of the Molasse Basin in Austria. The smectite end member was shown to have an unusually high interlayer charge (0.58). Based on earlier work on pure smectites, it was hypothesized that this high charge represents the mean of a mixture of a higher- and lower-charged smectite component intermixed with illite. To test this hypothesis, the magnitude of the interlayer charge of the smectites was evaluated using 2 different methods: alkylammonium ion orientation and K-fixation by wetting and drying.

Using 2 I-S samples of different I-S ratios, saturated with alkyammonium ions of chain lengths nc = 5–18, X-ray diffraction patterns (XRD) could be interpreted as representing a 3-component system, consisting of randomly interlayered high- and low-charged smectite and illite.

K-fixation, carried out by K-treatment and followed by 100 wetting and drying (WD) cycles, confirmed the presence of a high-charged smectite component admixed with low-charged smectite, both interlayered with illite. The wetting and drying of the K-treated samples led to interlayer collapse of the high-charged smectite component and to the production of illite layers stable against exchange with 0.1 N SrCl2. The 2 smectites occur in the ratio of about 1:1 and consist of 1 phase with an interlayer charge of about 0.76 and another phase with a normal charge of about 0.40. During diagenesis, the 2 kinds of smectite are altering simultaneously to the same end-member illite along 2 different reaction paths.

Structural transformations of illite-smectite samples of hydrothermal genesis with increasing contents of illite layers were studied by X-ray powder diffraction. The samples were K-saturated and subjected to wetting and drying cycles to increase three-dimensional structural ordering. Diffraction profiles were analyzed with the help of a specially devised computer program based on the approximation of individual diffraction reflections by “bell-shaped” functions, with minimization of the differences between experimental and simulated profiles. The data indicate that the transformations of these illite-smectite samples were accompanied not only by variations in the proportion of illite and smectite layers and in the pattern of their alternation, but also by a change in structure within 2:1 layers.

The mode of growth of authigenic, lath-shaped illitic particles has been investigated using field emission scanning electron microscopy (FESEM) and high resolution transmission electron microscopy (HRTEM). Two types of clay lath have been identified: overgrowths on platelets of illite or illite-smectite and discrete particles. Both are neoformed and show a slight increase in abundance with depth over the 70 m depth interval sampled. Interpretation of lattice fringe data is not unambiguous but indicates that the clay is either illite or illite-smectite with R1 structure. The formation of discrete particles of authigenic illite, or even R1 illite-smectite, is compatible with present burial depths and a regional geothermal gradient of approximately 40°C/km. This illite also differs from many previous reported occurrences of authigenic illite in mudrocks in that it appears to have formed, without being preceded by progressive illitization of illite-smectite.

Experimental alteration of volcanic tuff from Almeria, southeastern Spain, was performed in solutions with different Na/K ratios (0.01, 1, 10, and 100), different total salt concentrations (0.01, 0.1, 0.2, 0.33, and 1 M), and in deionized water, at 60, 80, 120, and 160°C, for periods of 60, 90, 180, and 360 d. Two particle size fractions of volcanic tuff were used: 10–200 and 20–60 μm. Alteration products were examined by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), laser-particle size analysis, scanning electron microscopy equipped with an energy dispersive X-ray spectrometer (SEM-EDS), image computer analysis, and transmission electron microscopy with microanalysis (TEM-AEM). XRD detected neoformed phases only in the products from experiments of 180–360 d at high temperatures (120–160°C), and with Na/K ratios above unity and in deionized water. The synthesized phase is a random mixed-layer illite-smectite (I-S) with 75% smectite. The quantity of newly formed I-S, determined by FTIR, ranged between 3–30%. There was no apparent change in grain size and shape of the grains after the experiments as compared to before.

SEM-EDS and TEM-AEM revealed the following alteration sequence: 1) intense etching on glass-grain surfaces; 2) formation of hemispherical morphologies on grain surfaces; 3) precipitation of very thin, individual flakes of illite-smectite on glass-grain surfaces; 4) development of I-S at the edges of glass grains; and 5) development of I-S honeycomb structures either covering large areas of the glass grains or resulting from the complete alteration of glass grains. A direct transformation of glass to I-S seems to be the major reaction mechanism, although there also is evidence of glass dissolution and subsequent I-S precipitation.

The smectite-to-illite diagenetic transformation has been documented in 5 different sedimentary basins using X-ray diffraction (XRD). Intermediate reaction products coexisting because of the effect of kinetics on this reaction have been characterized using decomposition of XRD patterns and comparison with calculated patterns. The nature and relative abundances of the various subpopulations of particles are shown to vary as a function of the geothermal gradient and of the age of the sediment. In all sedimentary basins that experienced a low steady geothermal gradient the physico-chemical characteristics (coherent scattering domain size [CSDS], junction probabilities) of intermediate mixed-layered illite-smectites (I-S) are similar. However, both the relative abundance and the crystallinity of the end-member illite increase as a function of the age of the sediment.

In basins that have experienced a higher geothermal gradient, the CSDS of the I-S subpopulation is higher for a given illite content, indicating a slightly different reaction pathway. This difference in the characteristics (peak position and width) of elementary peaks may be used to infer the presence of such a high geothermal gradient when no other data are conclusive. In this case the growth of the illite end-member is favored over the growth of intermediate I-S phases even in young basins. Illitic phases formed from the alteration of kaolin minerals exhibit characteristics similar to the reaction products of the smectite-to-illite diagenetic transformation in the case of a high geothermal gradient. In contrast with what is observed in shale diagenesis, the characteristics of the illitic subpopulations describe a continuum with absolutely no gap in between subpopulations. In sandstone reservoirs, the various subpopulations crystallize simultaneously from a kaolin precursor. As a consequence, no kinship is expected between the various subpopulations.