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The mineralogical, structural, crystal-chemical, and isotope-geochronological data were obtained for the first time in two samples of globular phyllosilicates (GPS) of the glauconite–illite series collected from terrigenous rocks in two sections of the lower part of the Lower Vendian Maastakh Formation (Khorbusuonka and Ulakhan-Sololi rivers, northwestern slope of the Olenek Uplift). Simulation of experimental X-ray diffraction patterns for both samples in the air-dried and ethylene glycol-solvated states was used to determine the expandable layer contents (9, 10%), types of expandable layers (smectite- and vermiculite-type), their ratios in a three-component mixed-layer structure, parameter csinβ (9.98 A) of mica layers, and the short-range order factor describing the alternation of different layer types (R = 2, 3). Values of the unit-cell parameter b (9.027, 9.039 A) correspond to the dioctahedral Al, Fe-bearing micas. The mica components in the studied mixed-layer minerals are shown to be represented by Fe-illites (KAl = VIAl/(VIFe3+ + VIAl) = 0.71, 0.82) with the K2O content of 7.77 and 8.40%. The Rb–Sr dating of the Maastakh GPS was carried out for the first time in combination with the calculation of theoretical patterns in the cation distribution in the mineral structure and comparison of the calculation results with the Mossbauer and IR spectroscopy data using the Optima software package supplemented with the new Irmes software. The Rb–Sr data obtained for two Fe-illites (Khorbusuonka and Ulakhan-Sololi rivers: 1033, 913 ± 12 Ma, respectively) are “older” relative to the Vendian Maastakh Formation (~640 ± 5), indicating a terrigenous origin of the studied grains. Globular phyllosilicates from the Maastakh Formation are similar in age and composition to the previously studied Lower Khaipakh (Middle Riphean) GPS (1172 ± 18 and 1112 ± 24 Ma, respectively). The age of GPS samples from the Maastakh Formation is younger (1033–913 Ma), probably, due to the initial cationic disordering in the GPS structure and partial loss of radiogenic elements during secondary alterations (rewashing and redeposition of Fe-illite grains in sediments of the Maastakh Formation) and, probably, during their catagenetic changes as well.

To resolve the existing ambiguities in the interpretation of the OH-stretching vibrations of kaolinites, relationships were, for the first time, established between the structural and Fourier-transform infrared (FTIR) spectroscopic features for a set of kaolinite samples which differed in terms of their relative amounts of coexisting high- and low-ordered phases. For this purpose, a representative collection of kaolinites differing in origin, particle size, and degree of disorder was studied by powder X-ray diffraction (XRD) and FTIR spectroscopy. Modeling of the experimental XRD patterns based on the orthogonal layer unit cell having a mirror plane showed each sample to be a mixture of nearly defect-free high-ordered (HOK) and low-ordered (LOK) kaolinite phases, with HOK varying from 86 to 4%. The wavenumbers, heights, areas, and full widths at half-maximum (FWHM) were determined for the OH-stretching bands at ~3697 (ν1), ~3670 (ν2), ~3652 (ν3), and 3620 cm–1 (ν4) by decomposition and fitting of the FTIR spectra. The FWHM(ν1)/FWHM(ν4) and FWHM(ν3)/FWHM(ν2) values were related linearly to the HOK content, which may be associated with the in-phase and out-of-phase character of the corresponding pairs of vibrations, respectively. A novel interpretation was suggested for the variations in the relative integrated intensities of the OH bands with the amount of the HOK phase. The intensity distribution of the ν2 and ν3 bands is controlled by the triclinic structure symmetry in the defect-free kaolinite and the mirror symmetry of the layers in low-ordered structures, in agreement with the observed evolution of the corresponding band intensities. The ν1 and ν2 band positions for the low-ordered samples are within the wavenumber range for the high-ordered samples. In contrast, the ν3 and ν4 band positions for the low-ordered samples are shifted toward higher wavenumbers, indicating that some of the low-ordered kaolinites should contain dickite-like structural fragments distributed among kaolinite layers.

For the first time, mineralogical, structural, crystal-chemical and isotope-geochronological data were obtained for a glauconite sample from the Lower Riphean Ust-Il’ya Formation on the Magan River (western slope of the Anabar Massif, northern Siberia). It has been established that glauconite from the lenticular layer of friable glauconitite (glauconite grains ≥80%) contains two populations of mixed-layer crystals, in which mica layers (93%) alternate with either smectite-type (7%) or vermiculite-type layers (7%) with the short-range order factor R = 3. The ratio KAl = (VIAl / (VIFe3+ + VIAl) equal to 0.45 allows identifying the micaceous mineral as glauconite with the unit-cell parameter b = 9.065 A and K2O content of 8.29%. Comparison of new data with the previously obtained mineralogical and crystal-chemical characteristics of Ust-Il’ya glauconites from the Kotuikan River section (2.5 km above the Il’ya River mouth), located 65 km south of the Magan River section, showed both similarities and differences. Analysis of the crystal-chemical heterogeneity of Kotuikan glauconite samples from rocks of different lithological types revealed peculiarities in the distribution of individual mica varieties composing the glauconite globules. Isotopic dating of glauconite from the Magan River section was performed in combination with simulation of the distribution of octahedral cations and comparison of the results obtained with Mossbauer and infrared (IR) spectroscopy data. Such an approach combined with the mineralogical and crystal-chemical analyses contributes to correct interpretation of the stratigraphic significance of isotope data. The results obtained provide grounds for the conclusion that isotopic dates of glauconite from the Magan section (1474 ± 21 Ma) coincides within the error limit with the earlier Rb–Sr and K–Ar dating of the Ust-Il’ya Formation (1485 ± 13 and 1459 ± 20 Ma, respectively) based on the glauconite in the Kotuikan section (Zaitseva et al., 2016). The former value marks the stage of early diagenesis of sediments and is suitable for estimating the age of this formation.

Clay minerals in basalt sills from the northern East Pacific Rise, covered by Upper Pleistocene clayey–sandy–silty sediments (turbidites, hemipelagites, and diatom oozes) sampled from DSDP Holes 477, 478, and 481A, were studied by X-ray methods based on the modeling of diffraction patterns. Trioctahedral smectites formed in thin (0.1–0.5 and 1.8–4 m) fissured sills that are well permeable for water delivered from the water-saturated host sediments heated by the sills. Smectites in basalts are found in the interstices (20–40 vol % in the rock and up to 50–80 vol % in hyalobasalts). They replace olivine and fill cracks and vesicles. Plagioclase and clinopyroxene are generally unaltered. The structure of smectites is characterized by different height of layers depending on the composition of cations in the interlayers and the degree of their hydration. The different-height layers either make up individual smectite phases or alternate in different proportions and with a high degree of segregation in the mixed-layer structures. Under conditions of a prolonged cooling, thick (43 m) sills are distinguished from the thin varieties by the formation of trioctahedral minerals (smectite–chlorite, chlorite, defective chlorite, and talc). They are found mainly in the interstices that make up 3–7 vol % of the rock.

The clay minerals in the Upper Pleistocene sediments from DSDP Hole 478 (a drilled depth of 464 m) located in the central area of the Guaymas Basin, Gulf of California, are studied. The composition of the clay minerals and their quantitative proportions in natural mixtures are determined by modeling of X-ray diffraction patterns for oriented specimens of finely dispersed particles. The terrigenous clay minerals are mainly dioctahedral (mixed-layer smectite–illite is dominant, the amount of illite is smaller) with admixtures of chlorite and kaolinite. They are distributed throughout the entire sedimentary section, except for thermally altered sediments from the contact zones with the top of the sills, where terrigenous dioctahedral clay minerals disappear, except for illite, and are substituted by trioctahedral mixed-layer chlorite–smectite and corrensite–chlorite; trioctahedral smectite also appears. Terrigenous illite is missing in the sediments at the base of the sedimentary cover exposed by the hole, on the top of the sill complex with a thickness of no less than 125 m.

Modelling of experimental X-ray diffraction (XRD) patterns is used to determine the phase composition of partially dehydroxylated kaolinite samples. To identify unambiguously the presence of two or three phases in the heated kaolinite samples, the full range of their XRD patterns has to be analysed. Two different kaolinites, from Imerys (UK) and from Georgia (USA; KGa-21), were studied. The heating temperatures were selected to cover the entire range of dehydroxylation for both kaolinites (400–550°C for Imerys and 400–495°C for KGa-21). Two different dehydroxylation pathways were observed. At each stage of partial dehydroxylation, the kaolinite from Imerys consisted of the original, non-dehydroxylated kaolinite and of a fully dehydroxylated phase, metakaolinite. During partial dehydroxylation of kaolinite KGa-21, each product formed at a given heating temperature consisted of three phases: the original kaolinite; a dehydroxylated phase, metakaolinite; and a phase with diffraction features corresponding to a defective kaolinite-like structure. To determine the content of metakaolinite in a partially dehydroxylated specimen, its experimental XRD pattern was reproduced by the optimal summation of the diffraction patterns of the initial kaolinite and metakaolinite. A procedure that reveals the basic diffraction features of the third phase is suggested. The XRD patterns and thus the structures of the metakaolinites formed after dehydroxylation of the Imerys and KGa-21 samples differ substantially. The conventional determination of the initial kaolinite and metakaolinite contents in partially dehydroxylated kaolinite based on the analysis of basal reflections and weight losses may lead to overlooking the formation of the intermediate phases.

Clay minerals (fraction

For the analysis of heavy oils, the method of simultaneous measurement of the free induction decay (FID) together with the decay of the echo signal in the Carr-Purcell-Meiboom-Gill (CPMG) pulse program was used. The measurements were carried out on a «Chromatek-Proton 20M» NMR analyzer operating at a frequency of 20 MHz. A special control program was created on the NMR analyzer that automatically tunes and measures the full FID curve, then switches to measuring the decay of the echo amplitude by the CPMG pulse sequence, and then the investigation ends with a joint processing of all the experimental data. This method makes it possible to measure the amplitudes of NMR signals and the relaxation times T2 of protons of heavy oil components in situ, including asphaltenes, without any perturbations in the analyzed system. Under the influence of paramagnetic centers located in asphaltenes, the amplitude-relaxation characteristics of oil protons are divided into 7 groups associated with solid asphaltenes in crystalline and amorphous states, resins with high and low density, aromatic and saturated compounds. The NMR amplitudes of these fractions correlate well with the group composition of heavy oils as determined by gravitational-chromatographic SARA method. The combined FID + CPMG method can be recommended for determining the SARA composition and other properties of oil in situ. The behavior of fractions of heavy oil in the temperature range (-15оС ÷ +60оС) was investigated by SARA-NMR method. For the first time in situ, it has been shown that resins participate in the formation of asphaltenes in a closed volume when the oil is cooled from a stable state at room temperature, and vice versa, asphaltenes are disaggregated by heating with the release of resins. The SARA-NMR method is promising for the on-line monitoring of the production, transportation and processing of heavy oil in real conditions of temperature, pressure and dissolved gases. However, the design of the NMR sensor must be adapted to industrial applications. The possibilities of designing NMR probes on process pipelines of larger diameter than in laboratory instruments can be extended taking into account the procedure proposed for correcting the inhomogeneity of the magnetic field in the probed volume based on the FID signal of the liquid oil fraction.

Despite many reviews and original articles, the actual crystal structure of tubular halloysites remains unclear. Analysis of the structural features of defect-free kaolinite, refined by Bish & von Dreele (1989), shows that the ordered 1Tc kaolinite structure can be described equally well by the orthogonal layer cell {a0, b0, γ0} (γ0 = 90°) or by two enantiomorphic oblique layer cells {a1, b1, γ1} and {a2, b2, γ2}, related to each other by a mirror plane. To simulate diffraction effects for tubular halloysite, the parameters and atomic coordinates of the orthogonal layer unit cell and the layer-displacement vectors t1 and t2 responsible for formation of the kaolinite enantiomorphs were deduced by transformation of the parameters of the defect-free kaolinite refined by Bish & von Dreele (1989). Modelling X-ray diffraction patterns show that the samples consist of either single, two or three phases, with the number and their structural features depending on the morphology of the particles. Samples formed of prismatic particles consist of halloysite-like structure (HLS), kaolinite-like structure (KLS) and halloysite cylindrical structure (HCS) phases occurring in various proportions. Samples of proper cylindrical tubes consist of a single HCS phase, whilst samples formed by particles having morphologies intermediate between proper cylindrical and well-developed prismatic forms consist of the KLS and HCS phases. The KLS phase is comparable to low-ordered platy kaolinite with identical unit-cell parameters, layer-displacement vectors and arbitrary stacking faults, except that the layer displacements are not random as in kaolinite, but are distributed at R = 1 such that t1 and t2 displacements have a strong tendency to be segregated. Structural parameters describing the HLS and KLS phases are identical, but in the HLS phase there is a strong tendency to the regular alternation of the t1 and t2 displacements, and the HLS phases do not contain arbitrary stacking faults. A characteristic feature of the three-phase prismatic samples is that the stacking of the layers along the c* axis is periodic and the layer thicknesses are similar to those of platy kaolinite. In contrast, in the KLS phase formed in samples with particles of intermediate morphologies, the hydrated 10 and 7.25 Å layers are interstratified. The relationship between the structural and morphological features of the coexisting phases suggests a sequence of phase formation from the centre to the surface of halloysite tubes that progresses from the HCS to the HLS via the KLS phase. The results of this study demonstrate that all kaolinite and halloysite (7 Å) varieties are built by the same fundamental structural units.

A theoretically substantiated technique has been elaborated for the precise determination of minor contents of smectite layers in the dioctahedral mixed-layer structures with a disordered alternation of K-bearing micaceous and ethylene glycol-saturated smectite layers. It is shown that observed positions of the possible mixed-layer mica–smectite structures in the d(003)obs–d(007)obs or 2θ(003)obs–2θ(007)obs diagrams are distributed along a set of parallel straight lines. Data points of each straight line correspond to the mixed-layer structures with one and the same content of smectite layers. A complete matching of theoretical model was recorded in the positions of d(003)obs–d(007)obs and 2θ(003)obs–2θ(007)obs pairs of the basal reflections determined in diffractograms simulated for 160 two-component mixed-layer mica–smectite structures differing in the thickness of alternating layers and their relative content. We studied samples of the dioctahedral K-bearing micas of the glauconite, illite, and aluminoceladonite composition with different thickness of micaceous layers. Positions of the mixed-layer structures of the studied samples on the 2θ(003)obs–2θ(007)obs and d(003)obs–d(007)obs plots make it possible to visually determine the content of smectite layers in each structure accurate to 0.5%. The content of smectite layers in the studied samples varied from 2 to 15%. We obtained equations relating the thickness of smectite and micaceous layers for a specified content of smectite layers. They make it possible to determine the thickness correlation between specified mica and smectite layers. Analogous equations can be used to calculate the Wsm value in each sample for specified experimental values of d(001)mc and d(001)sm and d(003)obs or d(007)obs. The Wsm values coincide within an error limit of 0.2% with those based on the visual estimates in plots.

Iron-bearing K-dioctahedral 1 M and 1 M d micas are abundant in diverse geological environments and vary in composition from illite to celadonite through Fe-illite, Al-glauconite, and glauconite. The chemistry and structural features of these micas are complex and heterogeneous, reliable diagnostic criteria are lacking, and the conventional mineralogical nomenclature is ambiguous, which complicate the identification of these mica varieties. The objectives of the present study were to reveal the structural and crystal-chemical variability in Fe-bearing, K-dioctahedral 1 M micas and to define composition ranges and identification criteria for the mica varieties in the series. A collection of samples of various compositions was studied using X-ray diffraction (XRD) and Fourier-transform infrared (FTIR) spectroscopy. Analysis of the relationships between unit-cell parameters and cation composition showed that the series included four groups, namely, Fe-bearing illites, Al-glauconites, glauconites, and celadonites and each group was characterized by a specific combination of unit-cell parameters and variation ranges. The illite group contained two distinct subgroups; Fe-bearing, Mg-rich illites and Fe-illites; which differ in the range of cation compositions and in FTIR characteristics. The boundary between Fe-illites and Al-glauconites occurs at a unit cell b value of ~9.05 A and at ratios of octahedral Al to total trivalent octahedral cations that range between 0.60 and 0.65. The partially overlapping cation composition and cell parameter ranges may complicate the distinction between Al-glauconites and glauconites, which can still be unambiguously differentiated using FTIR data. The dramatically different XRD and FTIR characteristics confirmed that glauconite and celadonite should be treated as separate mineral species. The distinctive features of celadonite are relatively low c sinβ values and reduced | c cosβ /a | values combined with b parameters lower than glauconites, but similar to Fe-illites. Celadonites also have distinct and sharp FTIR absorption bands at specific positions in the Si-O and OH stretching regions.

Active and passive hydrogen masers developed and manufactured by Russian company “Vremya-CH” are widely used over the world in scientific laboratories, radio astronomy observatories, national time keeping services and telecommunication systems.

This work was conducted to discover ways of processing high-paraffin oil residues using thermochemical processes to obtain binders. The principal purpose of such treatment of high-paraffinic residues is in the thermocatalytic process which consists of dehydroesterification via oxidation of paraffins which increase bitumen’s low-temperature stability (Fraass breaking point). Thus the n-alkanes, via our thermocatalytic process, can form several carbonyl compounds and oxidised compounds (such as alcohols, carboxylic acids, etc.). The thermocatalytic process of petroleum’s raw materials in our research carried out in two stages, including the catalytic process, as well as the thermal oxidation by air-blowing process. In this study, we used a biturox reactor. We evaluated the content of paraffin with GOST 33139 and low-field nuclear magnetic resonance (1H LF-NMR) relaxometry in high-paraffinic vacuum residues, and after our thermocatalytic process in the obtained product. Moreover, in order to ensure the reliability of results obtained through the processing of vacuum residues as well as the obtained product, various physicochemical methods were used. These investigation methods include SARA fractionation, Fourier-transform infrared spectroscopy, electron paramagnetic resonance (EPR), and VNII NP analysis. Furthermore, the colloidal structures were studied using the Gaestel and Asphaltene Index. The tests were carried out to determine the bitumen’s quality under the Russian interstate standard GOST 33133-2014 and the European standard EN 12591.

The phase composition of partially dehydroxylated specimens of two Clay Mineral Society standards, named KGa-1 and KGa-2 samples, were studied by powder X-ray diffraction patterns (XRD), infrared (IR) spectroscopy, and thermogravimetric (TG) data. Each specimen was preheated for 6 h in isothermal conditions, and the heating temperatures were selected to cover the entire range of dehydroxylation for both kaolinites (380–550 °C for KGa-2 and 400–600 °C for KGa-1). Products preheated at 550 and 600 °C are named metakaolinite, as their XRD patterns showed no traces of kaolinite reflections. The contribution of metakaolinite to the experimental XRD pattern and IR spectrum of each preheated specimen (including 3550–3750 and 500–1300 cm−1 ranges) was determined by the simulation of the experimental pattern with a sum of the XRD patterns or IR spectra corresponding to the untreated sample and metakaolinite. This procedure showed that the contents of metakaolinite determined independently by diffraction and spectroscopic methods for each of the preheated specimen have almost identical values. Although the modeled and experimental XRD and IR spectra generally match, they contain particular ranges where the intensity differences are particularly significant. The misfits suggest the presence of a third phase forming in partially dehydroxylated kaolinite. To reveal the diffraction and spectroscopic features of the kaolinite and possible intermediate phase (or phases), the contribution of metakaolinite was subtracted from the experimental XRD pattern and diffuse reflectance infrared Fourier transform (DRIFT) spectrum of each preheated specimen. Analysis of the metakaolinite-free XRD patterns and DRIFT spectra supports the idea that each preheated specimen, along with metakaolinite and initial kaolinite, contains a kaolinite-like component termed the intermediate phase. To determine the contents and specific diffraction features of the intermediate phases, the contribution of initial, untreated kaolinite was subtracted from the metakaolinite-free XRD patterns for each preheated specimen. In both samples, the content of the intermediate phase, C inter, decreases with the growth of metakaolinite from 23–25% at the beginning of dehydroxylation to 2% when the XRD-determined content of metakaolinite is 98%. The analysis of the diffraction features of the intermediate phases formed during partial dehydroxylation of the KGa-1 and KGa-2 samples indicates that they represent a new type of defective kaolinite-like structure, in which, along with the one-dimensional periodicity along the c * axis and the layer displacement vectors typical for natural kaolinite samples, the octahedral sheets of the individual layers of the structure are partially dehydroxylated.

The results of the study of clay mineral alterations in Upper Pleistocene sediments of the southern trough in the Guaymas Basin (Gulf of California) due to the influence of hydrothermal solutions and heat produced by sill intrusions are discussed. Core samples from DSDP Holes 477 and 477A were taken for the analysis of clay minerals. Application of the method of modeling X-ray diffraction patterns of oriented specimens of the finely dispersed particles made it possible to establish the phase composition of clay minerals, determine their structural parameters, and obtain reliable quantitative estimates of their contents in natural mixtures. The modeling data allowed us to characterize reliably the transformation of clay minerals in sediments of the hydrothermally active southern trough in the Guaymas Basin. In Upper Pleistocene sandy–clayey sediments of the southern trough, changes in the composition of clay minerals occurred under the influence of a long-living hydrothermal system. Its lower part (interval 170.0–257.5 m) with maximum temperatures (~300°C) was marked by the formation of chlorite. Terrigenous clay minerals are not preserved here. Saponite appears at a depth of 248 m in the chlorite formation zone. Higher in the sedimentary section, the interval 146–170 m is also barren of terrigenous clay minerals. Sediments of this interval yielded two newly formed clay minerals (chlorite and illite), which were formed at lower temperatures (above 180°C and below 300°C, approximately up to ~250°C), while the relatively low-temperature upper part (110–146 m) of the hydrothermal system (from ~140°C to ~180°C) includes the mixture of terrigenous and newly formed clay minerals. Terrigenous illite is preserved here. Illitization of the mixed-layer illite–smectite was subjected to illitization. The terrigenous montmorillonite disappeared, and chlorite–smectite with 5–10% of smectite layers were formed. In the upper interval (down to approximately 110 mbsf), the composition of terrigenous clay minerals remains unchanged. They are composed of the predominant mixed-layer illite–smectite and montmorillonite, the subordinate illite, mixed-layer chlorite–smectite with 5% of smectite layers, mixed-layer kaolinite–smectite with 30% of smectite layers, and kaolinite. This composition of clay minerals changed under the influence of sill intrusions into the sedimentary cover at 58–105 m in the section of Hole 477. The most significant changes are noted in the 8-m-thick member above the sill at 50–58 m. The upper part of this interval is barren of the terrigenous mixed-layer illite–smectite, which is replaced by the newly formed trioctahedral smectite (saponite). At the same time, the terrigenous dioctahedral smectite (montmorillonite) is preserved. The composition of terrigenous clay minerals remains unchanged at the top of the unit underlying the sill base.

Three kaolinite reference samples identified as KGa-1, KGa-1b, and KGa-2 from the Source Clays Repository of The Clay Mineral Society (CMS) are used widely in diverse fields, but the defect structures have still not been determined with certainty. To solve this problem, powder diffraction patterns of the KGa-1, KGa-1b, and KGa-2 samples were modeled. In a kaolinite layer among three symmetrically independent octahedral sites named as A, B, and C and separated from each other by b /3 along the b parameter, the A and B sites are occupied by Al cations, whereas, the C sites located along the long diagonal of the oblique kaolinite unit cell are vacant. The layer displacement vectors t1 and t2 are related by a pseudo-mirror plane from defect-free 1 T c kaolinite enantiomorphs, whereas, the random interstratification within individual kaolinite crystallites creates right-hand and left-hand layer sub-sequences producing structural disorder. A third layer displacement vector, t , located along the long diagonal of the oblique layer unit cell that contains the vacant octahedral site and coincides with the layer pseudo-mirror plane may exist. Thus, a structural model should be defined by the probability of t 1, t 2, and t layer displacement translations W t 1, W t 2, and W t , respectively, determined by simulated experimental X-ray diffraction (XRD) patterns. X-ray diffraction patterns were calculated for structures with a given content of randomly interstratified displacement vectors, and other XRD patterns were calculated for a physical mixture of crystallites having contrasting structural order with only C-vacant layers. The samples differ from each other by the content of high- and low-ordered phases referred to as HOK and LOK. The HOK phase has an almost defect-free structure in which 97% of the layer pairs are related by just the layer displacement vector t 1 and only 3% of the layer pairs form the enantiomorphic fragments. In contrast, the LOK phases in the KGa-1, KGa-1b, and KGa-2 samples differ from HOK phases by the occurrence probabilities for the t 1, t 2, and t layer displacements. In addition, the LOK phases contain stacking faults that displace adjacent layers in arbitrary lengths and directions. Low XRD profile factors (Rp = 8–11%) support the defect structure models. Additional structural defects and previously published models are discussed.

In this study a new, fast and simple method based on low field NMR-relaxometry for in-situ determination of SARA (saturates, aromatics, resins and asphaltenes) composition of crude oils was proposed. This method was tested on 22 samples of crude oils with a wide range of SARA-composition and API gravity values (4.6–42.0°), including extra-heavy, heavy, medium and light crude oils. Results obtained by low-field nuclear magnetic resonance (LF-NMR) were compared with conventional SARA analysis method (ASTM D 4124). Comparison shows good coincidence between SARA values determined by LF-NMR and conventional method data for heavy fractions of asphaltenes and resins (R2 is equal to 0.98 and 0.91, respectively) and for the sum of light fractions including saturates and aromatics (R2 = 0.96). However, comparison for saturated and aromatic compounds separately gave low correlation coefficients (R2 ≤ 0.61 and 0.27, respectively) and relatively soaring standard deviation for individual correlations for saturates and aromatics (8.18 and 9.20). Consequently, LF- NMR relaxation as an alternative method for studying the composition of crude oil allows the determination of asphaltenes, resins and the sum of light fractions (saturates and aromatics) without their extraction (in-situ), which greatly simplifies and accelerates conventional chromatographic analysis. This method can be successfully applied for different types of crude oils with a wide range of API gravity and viscosity values.

The study of the organic matter of Riphean-Vendian deposits, the features of its distribution are the subject of research by many authors. The problem of hydrocarbon of these deposits remains relevant. We have conducted studies of deep-seated rocks of the Lower Riphean of the kaltasinskaya suite of the Eastern-Askinskaya area, with an increased content of organic matter in individual intervals. In addition to standard research methods, the method of nuclear magnetic relaxation in a low magnetic field was used. This method allows determining the phase state of organic matter in the original rock without any impact and after isothermal heating of the rock at 350°C. The free induction signal and the type of solid-phase signal, which corresponds to the waveform for the asphaltene component of the oil, were analyzed. The predominant part of the liquid-phase signal - about 35%, is characterized by a transverse relaxation time of 540 ¼s, corresponding to the resinous component of organic matter. The quantitative ratio of asphaltenes before and after heat treatment was also analyzed. A significant decrease in its amount was recorded. During thermal exposure, more than 55% of light, more mobile hydrocarbon molecules are formed in the liquid-phase part of organic matter.

The work of many researchers is devoted to studying the problem of the features of the formation of the Bazhenov suite and organic matter. Various methods are used to study the type and state of organic matter, despite this, the problem associated with the phase state and type of organic matter in these deposits, the methods for studying those remains relevant. One of these methods is the NMR relaxation method in low fields. For the analysis of heavy oils, the method of simultaneous measurement of the free induction decay (FID) together with the decay of the echo signal in the Carr-Purcell-Meiboom-Gill (CPMG) pulse program was used. We studied the decay form of relaxation curves and their approximation by a mathematical model adequate for solid, liquid, and gaseous states of matter, which contains information on the geochemical and petrophysical properties of organic matter, as part of a single reservoir, including both the mineral part and the fluid part.

The paper presents the generalized results of structural and crystal-chemical study of globular dioctahedral 2 : 1 layer silicates of the glauconite–illite composition (45 samples) taken from the Lower Cambrian sequences of North Siberia (Olenek Uplift); Riphean, Vendian, and Lower Cambrian sequences of East Siberia; Upper Riphean sequences of the South Urals and Srednii Peninsula; and Vendian–Cambrian boundary rocks of the Podolian Dniester region (Ukraine). Monomineral fractions of grains were studied using modern chemical and physical methods: X-ray analysis, oblique-texture electron diffraction (OTED), scanning electron microscopy (SEM), classical chemical and microprobe analyses, IR and Mossbauer spectroscopy, and others. Simulation of the experimental diffraction patterns of glycolated specimens (Sakharov et al., 1999) allowed us to determine the degree of expandability (4–13%), type of expandable layers (16.85 A, smectite and 13.2 A, vermiculite), their proportions in twoand three-component mixed-layers, unit cell parameters b (9.02–9.11 A) and csinβ (9.94–10 A) of mica layers, as well as the degree of short-range order in the alternation of layers of different types (R = 0, 2, 3). The classification of low-charge (layer charge ≈ 0.6–0.85 per f.u.) dioctahedral 2: 1 layer silicates is given with account taken of the recommendations of the International Nomenclature Committee on Micas and Clay Minerals (IMA NC, AIPEA NC) (Reider et al., 1998; Guggenheim et al., 2006). Based on the crystal-chemical data on 79 samples obtained in (Ivanovskaya et al., 2012) and in the present paper, it is shown that the globular micaceous varieties are represented by a continuous isomorphic series ranging from illites through Fe-illite and Al-glauconite to glauconites (VIAl/(VIFe3+ + VIAl) = 0.81–0.91, 0.60–0.78, 0.51–0.59, and 0.11–0.50, respectively). Following (Kossovskaya and Drits, 1971; Drits et al., 2013), we distinguish Fe-illites (VIAl/(VIFe3+ + VIAl) = 0.6–0.8) and retain the term Alglauconite for mineral varieties with the Al index K Al = VIAl/(VIFe3+ + VIAl) between 0.51 and 0.59. The structural characteristics (unit cell parameters b, csinβ, and others) and IR spectroscopic data on illite, Fe-illite, Al-glauconite, and glauconite are compared. Special attention is given to samples with elevated Mg contents found in these groups of mineral varieties. Since compositional variations of the studied glauconite–illite minerals fall beyond the fields accepted for these minerals by IMA NC and AIPEA NC, the existing classifications for low-charge dioctahedral micaceous micas may need to be revised.

A technique was developed to determine the low contents of smectite layers in the dispersed dioctahedral K-bearing micaceous minerals of the illite-glauconite composition. To implement this technique, diffraction patterns were calculated for two-component mixed-layer mica-smectite structures, in which the content of smectite layers increased with a step of 2% from 2 to 20% at a short-range order factor R = 0 and from 2 to 14% at R = 1. On the basis of Mering’s principles (1949) and Q-rules (Moore and Reynolds, 1989), the half-width βcosθ of each basal refection and its distance Q to the nearest reflection corresponding to the periodical structure made up of 9.98 A micaceous layers were calculated for mixed-layer structures with the given content of smectite layers WSm. The Q dependence on βcosθ for the series of basal reflections observed in the calculated diffraction pattern was approximated by a straight line corresponding to the linear regression equation. Equations relating slope angles of straight line (α) and concentrations of smectite layers (WSm) were deduced for the analyzed mixed-layer structures with the short-range order factors R = 0 and R = 1, respectively. To determine the contents of smectite layers in natural micaceous varieties, the basal reflections observed in experimental patterns from the oriented ethylene glycol-saturated samples were subjected to the following procedures: (1) determination of the half-width (βcosθ)e of each 00l reflection of the analyzed sample and plotting Q dependence on (βcosθ)e for the observed series of basal reflections, with its further approximation by the linear regression equation and the corresponding straight line; (2) calculation of the slope angle of this straight line α and determination of the content of smectite layers in the sample structure using the equation relating α and WSm. Application of the described procedure showed that the content of smectite layers in the studied samples varied from 5.2 to 12.6%. The content of smectite layers was determined accurate to a few tenths of a percent. Since the half-width of reflection 003 does not depend on the content of smectite layers, its value was used to determine the thickness and number of layers in the averaged CSD of the studied sample. XRD patterns calculated for mixed-layer structures with experimentally determined WSm, WMc, R, T, and N parameters are in a good agreement with experimental patterns of the studied samples.

The paper presents a novel method for determining the crystal-chemical heterogeneity of finely dispersed dioctahedral 2: 1 mica mineral phases based on the modeling of their powder diffraction patterns. We used three samples, which were taken from Lower-Middle Riphean rock sections of the Anabar and Olenek uplifts in northern Siberia, and one sample from the Upper Riphean Inzer Formation in the southern Urals. Choice of globular samples was determined by contrast features of their chemical composition and different lithological types of the host terrigenous rocks that are commonly transformed at the level of deep catagenesis.Based on structural formulas, unit cell parameters, and coordinates of atoms occupying the cells, we modeled powder diffractograms that made it possible to determine the sizes of coherent scattering domains and probability parameters, which characterize the type, content, and distribution of stacking faults in each of the studied samples. The modeling results demonstrated that each sample represents a physical mixture of individual micaceous phases of different compositions. The paper discusses scales and modes of the crystalchemical heterogeneity of micaceous varieties, which make up globules in the coarse- and fine-grained terrigenous sediments, as well as their various specific crystal-chemical characteristics. The probable physicochemical settings, which were responsible for specific features of the structural and crystal-chemical heterogeneity of micaceous varieties in each of the studied four samples, are also discussed.

The paper presents the first detailed mineralogical, structural, and crystal-chemical characteristics of the mixed-layer corrensite-chlorites from the glauconitic sandy-clayey rocks that make up the bottom (0.10 m) of a basal member (1.50 m) of the lower subformation of the Yusmastakh Formation (Riphean, Anabar Uplift, North Siberia). Like the overlying mudstones (1.40 m) in the basal member, these rocks are generally transformed up to the deep catagenesis level and included in a thick dolomite sequence. In mudstones represented by the dioctahedral micas, the corrensite-type minerals are observed as traces.

The detailed mineralogical and structural-crystal-chemical characteristics are reported for the first time for glauconite grains extracted from the fine-platy silty-sandy dolomites at the roof of the lower subformation of the Yusmastakh Formation (Riphean, Anabar Uplift, North Siberia). Based on the complex study (X-ray diffraction, classical chemical analysis, microprobe analysis, IR-spectroscopy, thermogravimetric analysis, scanning electron microscopy with microprobe analysis, and Mossbauer spectroscopy), it was demonstrated that the studied glauconite sample is characterized by unique chemical and structural heterogeneity.

The illitization reaction in a thick K-bentonite bed located in upper Cretaceous marine shale in the Montana disturbed belt was studied by X-ray diffraction, chemical analysis, and thermal gravimetric analysis. Modeling of the experimental XRD patterns from oriented clay specimens in air-dried and glycolated states shows that at each sample location in the bentonite bed a mixture of R0 illite-smectite (I-S) and R1 I-S coexist. Each of these phases in all samples consists of the same or similar content of illite and expandable layers independent on location in the bed. In particular, the illite content in the R0 I-S and the R1 I-S from the

To provide structural and diffraction criteria for the identification of trans-vacant (tv)and cis-vacant (cv) mica varieties with different layer stackings, powder X-ray diffraction (XRD) patterns have been simulated for 1M, 2M1, 2M2, 3T and 2O structural models consisting of either tv or cv layers. The differences in the unit-cell parameters resulting from the specific structural distortions of tv and cv layers lead to the differences in the positions of reflections having the same indices in the XRD patterns for tv and cv 1M, 2M1 and 2M2 mica varieties. The tv 1M, 2M1 and 2M2 varieties of Al-rich micas can therefore be distinguished from the corresponding cv varieties using powder XRD diffraction provided that the d values are measured with high precision and accurately compared with those calculated from the unit-cell parameters for the corresponding hkl indices. The differences in reflection positions for these tv and cv varieties should decrease with increasing Mg and/or Fe contents, thus complicating their identification. The peak positions and intensity distributions in the XRD pattern for the tv 3T variety are similar to those for the cv 3T structure with the vacancy in the right-hand cis site (3T-cv1), and both XRD patterns are similar to that for the 1M-cv mica. The simulated XRD pattern for the cv 3T structure with the vacancy in the left-hand cis site (3T-cv2) is similar to that for the 1M-tv variety. The similarities and dissimilarities in intensity distribution between the XRD patterns simulated for the 1M and 3T varieties in question may be associated with the differences in the mutual arrangement of cations and anions in successive layers. Possible interstratification of tv and cv layers within the same structure should seriously complicate the identification of dioctahedral mica polytypes and polymorphs.

A representative collection of iron-poor non-stoichiometric sedimentary dolomite samples of various composition, location, and age was studied by X-ray qualitative and quantitative phase analysis as well as by coupled plasma-atomic emission (ICP-AES) and X-ray fluorescence (XRF) spectroscopy. The main task is to determine relationships between the lattice parameters and Ca content in non-stoichiometric dolomite. It is found that the unit cell parameters as well as the lattice hkl spacings of the studied dolomite samples are related by the following linear equations with strong linear correlation coefficients: where a eff = d (110) + √3 d (030) and c eff = 6 d (006). These almost perfect interdependences exist because in the studied dolomite structures not only unit cell parameters (as expected by Vergard9s Law), but also corresponding hkl spacings co-vary in a linear manner with Ca content as follows: . The validity of these equations is confirmed by a comparison of Ca contents determined by the regressions and chemical analysis for monophase dolomite samples for which 1.00 n Ca n Ca is the average amount of Ca per structural unit. The difference between the compared Ca contents determined for each monophase sample by the two independent techniques in average is equal to 0.005 atoms of Ca per structural unit. The standard deviation determined for the 47 studied samples is equal to 0.004 atoms of Ca or 0.002 mol % CaCO 3 . Excess-Ca dolomite samples for which n Ca > 1.09 consist of two dolomite phases with different amounts of excess Ca. Quantitative determination of proportions of each of these phases in the two-phase dolomite samples was carried out using the Rietveld software program Autoquan•. The lattice parameters and hkl spacings are used to determine Ca content in each of these phases using the regressions obtained for the monophase samples. Comparison of the calculated average Ca content with that determined from the chemical analysis shows that in average the difference between the compared values are equal to ± 0.012 atoms of Ca per formula or ± 0.06 mol % CaCO 3 . The results are in accordance with a structural model where only the B sites have a mixed occupancy confirming the results of a previous work.

Hydration of the

Samples of non-stoichiometric dolomite of different age and origin have been studied by powder X-ray diffraction, scanning electron microscopy and electron-microprobe analysis. Most samples containing a high excess of Ca consist of two or even three phases, differing in the degree of excess Ca uptake and degree of structural order. On the basis of Rietveld refi nements of samples with two 3D periodic phases, only the B sites have a mixed occupancy of Ca and Mg, and the phases differ from each other only in the content of Ca at the B site. A simulation of the experimental XRD patterns of samples showing a high and a low excess of Ca with a defective layer-structure was carried out in terms of mixed-layer structures in which different proportions of nonstoichiometric dolomite layers are interstratifi ed with a small amount of calcite-like as well as stoichiometric dolomite layers. Electron-microprobe analysis and BSE images show that large crystals in the two-phase excess-Ca dolomite samples have sharply bounded zones with different levels of Ca concentrations. Each BSE contrast zone has the same composition (within error), and in each sample there are three or four non-overlapping groups of such zones differing in composition. Remarkably, fi ne-grained micritic portions of these samples contain the same discrete sets of Ca concentration zones as the large zoned euhedral crystals. This result supports the hypothesis that crystals of excess-Ca dolomite adopt only certain non-continuous compositions, and that growth and composition are structurally controlled.

The X-ray diffraction method previously developed for the determination of the amount and distribution of fixed NH 4 + in illite-smectite has been modified to include the effects of layer thickness fluctuations of K-saturated and heated smectite and the effects of mean thickness of coherent scattering domains (CSDs). X-ray diffraction patterns and 002 and 005 reflection profiles are calculated for K-saturated and dehydrated NH 4 + -bearing I-S representing models having different distributions of K and NH 4 + over mica-like interlayers, different proportions of interlayer types, different mean thicknesses of CSDs, and different degrees of thickness fluctuations for K-saturated and heated smectite layers. The diffraction criteria for identification of these models are discussed. The amount of fixed NH 4 + can be determined accurately from the position of the 005 reflection. Diffraction methods have low sensitivity to different distributions of fixed K and NH 4 over mica-like interlayers in NH 4 -bearing I-S containing a high amount of expandable interlayers and a low amount of fixed NH 4 . However, the interstratified nature of NH 4 -bearing illites or I-S can be determined unambiguously in two limited cases: first, when the structures have a low ( W S ) and, secondly, when NH 4 /(NH 4 + K) ≥ 0.20 in the mica-like interlayers, even for W S > 0.20. The method is applied to I-S from western Greenland Cretaceous oil source rocks heated by intrusions. The samples contain I-T-S consisting of 13–33% tobelite layers. Two groups of samples are identified. One includes I-T-S structures in which dehydrated K-smectite layers have no significant thickness fluctuations. For these samples different broadening of 002 and 005 reflections is due only to interstratification of the 9.98 and 10.33 A layers. In the other group a satisfactory agreement between the experimental and calculated positions and profiles of the 002 and 005 reflections is achieved only when thickness fluctuations for the K-smectite layers are taken into account.

The structure of an illite-smectite (I-S) sample (HSI) from the Tertiary–Cretaceous boundary layer at Stevns, Denmark, i.e. the so-called Fish Clay, is investigated in order to discuss the origin of this clay and its similarity to clays from Maastrichtian-Danian chalk of Denmark and the North Sea. The phase compositions and layer sequences have been determined by X-ray diffraction. The structural formulae are determined from chemical analysis and solid-state 27Al magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy. The octahedral vacancy pattern has been determined by thermal analysis and the particle shape by atomic force microscopy. The HSI sample I-S consists of two phases, a high-smectitic (HS) phase (70%) having 95% smectite and 5% illite (leucophyllite) layers, and a low-smectitic (LS) phase (30%) having 50% smectite and 50% illite (leucophyllite) layers. Both phases have trans-vacant dioctahedral sheets and contain only traces of IVAl, the charge of the illite (leucophyllite) layers being provided predominantly by octahedral Mg for Al substitution. The structure of the tetrahedral and octahedral sheets for the HSI are compared to the structure of an I-S sample (GRI) from the Maastrichtian chalk at Stevns below the Tertiary-Cretaceous boundary and to the standard smectite SAz-1 from Arizona. For all three samples the 27Al MAS NMR spectra show the presence of two resolved IVAl resonances, which indicate the presence of two different IVAl sites. The NMR, infrared spectroscopy and chemical data show that both HSI and GRI have highly ordered Mg for Al substitution in the octahedral sheet, each Al having one Mg and two Al neighbours, whereas substitution of Mg for Al in SAz-1 is random. For the HSI sample, both the HS and LS phases are probably formed from volcanic ash. The structural similarity of the phases in HSI and GRI shows that GRI formed from a material similar to HSI by illitization of the HS phase and chloritization of the LS phase.

The influence of geodynamic factors on the postsedimentary lithogenesis of terrigenous sequences during the replacement of the passive continental-margin regime to the active regime is considered with the Toarcian–Aalenian complexes of southern Dagestan as an example. It has been established that clayey rocks were lithified under conditions of subsidence lithogenesis, whereas the orogenic catagenesis of sandy rocks was related to stress initiated by the initial (amagmatic) subduction phase. The Kubler index has been used to reveal the postsedimentary zonality that is consistent with the intensity of folding and cleavage. The metagenesis zone fits the cleavage zone. The Rb–Sr and K–Ar datings of clayey rocks from the metagenesis zone yielded 180–190 Ma that can be interpreted as the timing of the maximal manifestation of postsedimentary lithogenesis.

The sea-cliffs of the Isle of Wight were deposited during a period of overall sea-level rise starting in the Barremian (Lower Cretaceous) and continuing into the Aptian and Albian. They consist of fluvial, coastal and lagoonal sediments including greensands and clays. Numerous episodes of erosion, deposition and faunal colonization reflect condensation and abandonment of surfaces with firmgrounds and hardgrounds. This study focused mainly on shallow marine cycles where variations in clay mineralogy would not be expected, because overall system composition, sediment source, and thermal history are similar for all the samples in the studied section. Instead we found a wide variety of clay assemblages even in single samples within a 200 m interval. In this interval, distinct clay mineral assemblages were found and can be described as consisting of Al-rich, Fe-richand intermediate Fe and Al compositions withrespect to 2:1 and 1:1 layers in mixed-layer arrangements. Nearly pure glauconite-nontronite clays exist in the

XRD patterns were calculated for 2 M 1 and 3 T dioctahedral mica structural models in which trans -vacant ( tv ) and cis-vacant ( cv ) layers were interstratified and arranged, independent of octahedral cation distribution, as in the periodic 2 M 1 and 3 T mica polytypes. The XRD patterns of the interstratified cv/tv2M 1 and cv/tv 3T models were shown to be similar to those of the tv2M 1 and tv3T mica structures, respectively. Because both the positions and shapes of hkl reflections in the XRD patterns of the tv3T and cv/tv3T as well as of the tv2M 1 and cv/tv2M 1 , respectively, are the same qualitative X-ray identification of the tv2M 1 , cv/tv2M 1 , tv3T and cv/tv3T mica varieties should be a complex problem, especially when the amount of cv layers is either rather low (10–15 %) or high (30–40 %) with significant tendency to segregation of the layer types. The diffraction features of cv/tv2M 1 and cv/tv3T mica structures make it possible to use the Rietveld technique for the structural refinement. Correct application of this technique to the cv/tv2M 1 and cv/tv3T structures should reveal partial occupancy of trans -octahedra because of the ability of diffraction to average structural parameters. Pavese et al. (2001) found partial occupancies of trans -octahedra in 3T and 2M 1 powder phengite samples. To explain these results the authors postulated the ± b/3 stacking disorder. However, the calculations have shown that such disorder strongly modifies the XRD patterns. Therefore, in the paper an alternative, crystal-chemically more justified hypothesis is suggested according to which the occupancy of trans -sites in 3 T and 2M 1 phengites results from coexistence of tv and cv layers in their structures. Diffraction features a dioctahedral mica sample given as a tv3T standard in textbooks (Brindley, 1980; Bailey, 1984) are quite similar to those characteristic for a 3T structure in which tv and cv 2:1 layers are interstratified.

Ahstract-Interstratified serpentine-smectite was found in the fine-grained fraction of altered metasomatic contact biotite-schists developed between serpentinite and granite-type rocks (Lower Silesia ophiolite sequence, Poland). Ni-rich serpentine-smectite is R0-interstratified lizardite (0.80)-stevensite (0.15)-vermiculite-like (0.05), with a coherent scattering domain (csd) of 5 layers (mean value). The Mg-rich variety of serpentine-smectite is R1 lizardite (0.80)-stevensite (0.20) with a csd size of 7 layers (mean value). A transmission electron microscope study revealed complex layer relationships, with zones composed of various serpentine-smectite packets having lizardite/smectite ratios of 3:1, 2:1, 1:1, 4:1 and scarce serpentine segregations. In both cases, the serpentine-smectites appear to be late products of alteration of the parent biotite-schist. Experimental and calculated positions and intensities of reflections of the ethylene glycol-saturated, heated (250°C, thermal stage), and air-dried samples are in good agreement. Calculated X-ray diffraction patterns for interstratified glycolated and anhydrous serpentine-smectite are included in the Appendix.

Illite-smectite (I-S) minerals isolated from Upper Jurassic oil-source rock shales from Denmark and the North Sea have been investigated by X-ray diffraction, thermal analysis, infrared, Mossbauer, and solid-state nuclear magnetic resonance spectroscopies and chemical analysis. Detailed structures have been determined in order to reveal the diagenetic transformation mechanism in these shales. Generally, in oil-source rocks of sedimentary basins, oil generation takes place simultaneously with the diagenetic transformation of I-S. We demonstrate a link between the two reactions: NH3 released from kerogen during maximum oil generation is fixed as NH 4 + in the NH4-bearing mica or tobelite layers formed from smectite or vermiculite layers in I-S, in a diagenetic interval which we name the ‘tobelitization window’. Due to this solid-state transformation, mixed-layer structures have been formed consisting of interstratified illite, tobelite, smectite and vermiculite layers (I-T-S-V) and having maximum ordering of illite + tobelite and smectite layers for R = 1. The tobelitization of smectite in I-S is probably typical for all oil-source rock shales.

Globular, platy, and fine-dispersed phyllosilicates of chloritic composition were studied in the outer contact of dike with glauconite-bearing rocks. It is shown that the globular Al-glauconite is replaced by pseudomorphs of mixed-layer Mg- and Fe-bearing chlorite–berthierine containing 5% berthierine layers in this zone. The crystallochemical characteristics and microstructure are reported for the globular, platy, and fine-dispersed chlorites. The possible models of chlorite–berthierine formation are discussed.

Coarse-grained vermiculite from a serpentinite-pegmatite thermal zone displays a rational series of narrow 14.4 A basal reflections and an unusual broad 28 A peak. X-ray diffraction simulations and fitting techniques show that the 28 A peak is related to 28 A domains consisting of elongated 2:1 layers of different lengths. The domains are located at the crystal edges of the vermiculite.

The rare mineral, potassium tobelite being the NH4-bearing mica, was first described in Lower Carboniferous coal-bearing rocks of the Egorshin–Kamensk district on the eastern slope of the Urals. It was formed from kaolinite and pyrophyllite at temperature less than 500°C and pressure about 2000 atm. The formation of tobelite was probably favored by postsedimentary stresses. Owing to sharp increase in pressure, gases were released from organic matter of the coal-bearing sequence and transformed into ammonia, which was subsequently incorporated as NH+ 4in the structure of clay minerals. The potassium tobelite is an indicator of high-grade metamorphism (up to anthracite rank) of the organic matter in coal-bearing sequences.

Illite-smectite (I-S) from Cambrian black shale of both early diagenetic and anchimetamorphic grade was investigated to determine the mechanism of the clay transformation. The layer sequences, the distribution of thicknesses of coherent scattering domains (CSDs), and the three-dimensional ordering were determined by X-ray diffraction (XRD). The proportions of cis-vacant (cv) and transvacant (tv) 2:1 layers were determined by thermal analysis and the proportion and distribution of interlayer ammonium by XRD and by infared spectroscopy (IR). The structural formulae were determined from total chemical analysis, and Mossbauer and 27Al NMR spectroscopies, and the particle shape and size investigated by atomic force microscopy (AFM). In the early diagenetic samples, the I-S is composed of two phases, one of which contains 0.05 and the other 0.25 smectite (S) interlayers. The first phase does not change during metamorphism. In the second phase, 0.20 S are converted to tobelite (T) layers through fixation of ![Formula][1] but the I layers are not changed. Simultaneously, the proportion of cv layers changes from 0.18 to 0.02, and the tetrahedral substitution of Al for Si is parallel to the increase in T layers. All I interlayers contain 0.75K per O10(OH)2. Further-more, the metamorphism results in increasing mean thickness of CSDs from 5.1–6.8 nm for the low-diagenetic samples to 6.7–8.4 nm for the anchimetamorphic samples. We conclude that the tobelitization was accompanied by transformation of cv to tv 2:1 layers adjacent to the smectite interlayers, and formation of tv layers adjacent to the newformed tobelite interlayers in otherwise intact crystallites. This mechanism only partly resembles the tobelitization previously observed in the Upper Jurassic North Sea oil source rocks. I-S in these rocks contained tv 2:1 layers and T interlayers formed through solid-state Al for Si substitution in the tetrahedral sheet and by ammonium fixation in the corresponding interlayers. These different mechanisms are probably because the North Sea I-S originated from weathered illite, like the Cambrian high-illitic phase, whereas the Cambrian low-illitic phase undergoing the transformation originated from cv smectite of volcanic origin. The results indicate that the illitization in oil source rocks is linked to oil generation, and that it deviates from the illitization in other rocks because of the supply of ammonium formed during oil generation and the fixation of this ammonium in the former smectite interlayers. [1]: /embed/tex-math-1.gif

The finest fractions of Upper Jurassic shales from the North Sea and onshore Denmark contain 80–90% of an illite-smectite-vermiculite (I-S-V) mixed-layer mineral and, in addition a phase which has X-ray diffraction (XRD) peaks at 7.20–7.26 Å and 3.56–3.58 Å in air- dried and glycolated specimens. This phase may be a fine kaolinite with a small thickness of coherent scattering domains (CSDs) or alternatively a mixed-layer mineral which has kaolinite as the dominant component. For one sample from the Norwegian well 9/4-3, these alternatives are investigated using the multi-specimen method by which agreement between the experimental pattern and the pattern calculated for one and the same structure is obtained for each of several specimens saturated with different cations and with/without glycolation. It is demonstrated that the modelled XRD patterns for a kaolinite-illite-vermiculite (K-I-V) structure having 0.94 kaolinite, 0.03 illite and 0.03 vermiculite layers and random alternation fit the experimental patterns.

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: Illite-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.

For mixed-layer clay fractions from the North Sea and Denmark, X-ray diffractograms have been recorded for specimens saturated with Mg, Ca, Na and NH4, both airdry and intercalated with ethylene glycol, and the patterns have been computer-simulated with a multicomponent program. The mixed-layer fractions consist of an illite-smectite-vermiculite (I-S-V) phase constituting ~90% of the fraction and a kaolinite-illite-vermiculite (K-I-V) phase. For each I-S-V, the degree of swelling in swelling interlayers depends on both interlayer cation and glycolation, whereas the amount of non-swelling illite and swelling interlayers and the interstratification parameters are constant. Based on structural characteristics and the degree of diagenetic transformation, the samples investigated can be divided into three groups. The I-S-V of group one is predominantly detrital and has 0.69-0.73 illite, 0.26-0.20 smectite and 0.04-0.07 vermiculite interlayers, the illite, smectite and vermiculite interlayers being segregated. The I-S-V of group two has been diagenetically transformed and has 0.80 illite, 0.12 smectite and 0.08 vermiculite interlayers, the vermiculite interlayers being segregated whereas the illite and smectite have the maximum ordering possible for R = 1. The I-S-V of group three has been further transformed during diagenesis and has 0.84 illite, 0.08 smectite and 0.08 vermiculite interlayers. Statistical calculations demonstrate that the I-S-V transformation can be described as a single interlayer transformation (SIT) within the crystallites.

Interstratification (or mixed layering) describes the intimate intergrowth of layers differing by their layer thickness and/or internal structure and strongly impacts the reactivity of both synthetic and natural lamellar structures. Determining the actual crystal chemistry of mixed layer structures is an essential step in the scope of understanding their reactivity and requires a direct quantitative comparison of X-ray diffraction data with calculated patterns. This chapter describes the theoretical concepts allowing the calculation of diffraction effects from mixed layer structures using the matrix formalism. It also includes algorithms allowing a comprehensive determination of probability parameters required to describe layer stacking. Finally, all recent developments that proved to be necessary to fit X-ray diffraction data from mixed layer structures are described, and the equations necessary for the calculation of induced diffraction effects were derived.

The corrensite from a chlorite vein-like rodingite blackwall in serpentinites has been studied. The proper identification of swelling layers in corrensite using heating at 500°C was ambiguous because of the spontaneous rehydration. Even K + -saturated samples heated to 500°C readily rehydrated after being cooled. This can be prevented if XRD patterns are recorded at 300°C, without cooling the sample. A standard heating at 500°C can result in partial decomposition of brucite-like sheet as evidenced by ASN simulation. The ASN-calculated XRD patterns of contracted corrensite proved that an inhomogeneous distribution of heavy atoms (Fe, Ni, Mn, Cr etc.) between brucite-like sheet and talc-like layers and between two adjacent corrensite units in the interstratified mineral may result in the disappearance of low angle reflections (24 A and 12 A), which can lead to miscellaneous interpretation if distribution of heavy cations is not checked. The corrensite occurred together with regular chlorite. However, it is assumed to be formed due to direct crystallization from late hydrothermal solutions as deduced from comparison of the Mg/(Mg + Fe) ratio in the corrensite, serpentinite and chlorite.

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.

International audience; A specific methodology was developed to collate the interlayer configurations resulting from Grand-Canonical Monte Carlo (GCMC) simulations with experimental X-ray and neutron diffraction data for two synthetic Na-saturated saponites having contrasting layer charge. Numerical simulations were performed assuming different existing sets of atomic partial charge and Lennard-Jones parameters for clay and water. For each parameter set and for the two samples in both the mono- and bihydrated states, the water contents resulting from GCMC simulations were first compared to water vapor desorption gravimetry data. The density distributions of interlayer species were then used to generate 00l intensities that were compared to X-ray and neutron diffraction data, the latter being recorded on both hydrogenated and deuterated specimens. The CLAYFF model [Cygan et al. J. Phys. Chem. B2004, 108, 1255] is shown to better account for water content and organization compared to the model developed by Skipper et al. (Clays Clay Miner.1995, 43, 285) and modified by Smith (Langmuir1998, 14, 5959). However, diffraction patterns calculated for bihydrated samples from CLAYFF simulations did not match satisfactorily the diffraction data. Lennard-Jones parameters were thus modified for oxygen atoms from the clay layer. When combined with the SPC/E water model, this modified version of CLAYFF allows matching experimental water contents and fitting the complete set of diffraction data. Relevant information may thus be derived on the influence of layer charge on the orientational properties of interlayer water molecules which differs for the different clay models. Finally, the approach used in the present study proved powerful for assessing atomic interaction parameters considered for computational simulations.

Powder X-ray diffraction (XRD) curves were calculated for the different structural models so far proposed for feroxyhite (δFeOOH). The influence on XRD features of different structural parameters, including site occupancy of Fe atoms, atomic coordinates, content and distribution of stacking faults, and dimension of coherent scattering domains, were considered. On the basis of agreement between experimental and simulated curves it is shown that δFeOOH is a mixture of feroxyhite proper and ultradispersed hematite in the 9 : 1 volume ratio. Feroxyhite proper consists of hexagonal close packing of anions containing 5% stacking faults. Iron atoms occupy only octahedral sites and are distributed in such a way that face-sharing filled octahedral pairs regularly alternate with vacant octahedral pairs along the c axis. This distribution of Fe atoms is quite similar to that established by Patrat et al. (1983), but in each pair, Fe atoms are displaced by the same value of 0.3 Å in opposite directions away from the centre of their octahedron. Nearest Fe-Fe distances calculated for the model proposed (2.88, 3.01, 3-39 and 3-73 Å) practically coincide with those found by EXAFS spectroscopy for the same sample (2-91, 3.04, 3.41 and 3.7-3.8 Å).