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

The present work deals with the hydrothermal synthesis of Na zeolites (Na-A, Na-X and Na-P) and hydroxysodalite using kaolinite calcined at 650°C as starting material. The focus was on definition of the most favourable conditions for the synthesis of zeolite Na-A and Na-X from metakaolin in order to economize on both energy (i.e. synthesis temperatures) and reaction time and to enlarge the field of pure and isolated synthesized phases. Metakaolin was mixed with calculated amounts of NaOH solution and sodium silicate and five sets of experiments were carried out at ambient pressure and 68±0.1°C varying the SiO2/Al2O3 ratio from 2.2 to 7. Optimal conditions for crystallization of Na-A zeolite from kaolinite were reached with a SiO2/Al2O3 ratio of 2.2 plus 4 M NaOH without adding sodium silicate; transformation into hydroxysodalite develops after ∼8 h. For SiO2/Al2O3 ratios between 4 and 7, crystallization of the separate Na-X zeolite phase could be achieved and transformation into Na-P and hydroxysodalite occurred after 382 h and 190 h, respectively. For SiO2/Al2O3 ratios between 5 and 6, transformation of metakaolin into Na-X plus Na-A, hydroxysodalite and Na-P occurred, and the field within which Na-A and Na-X zeolite exists overlapped that of the other zeolites.

The products of synthesis were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), inductively coupled plasma optical emission spectrometry (ICP-OES), infrared spectroscopy (IR) and thermal analyses (TG-DTG-DTA).

Obtaining pure Na-A and Na-X zeolite from kaolinite treated at low metakaolinitization temperature (650°C) and low hydrothermal synthesis temperature (68°C) represents a considerable economic advantage in terms of both energy and time.

Zeolitic tuffs from the Xerovouni location of the Avdella area (Evros Prefecture, Greece) contain on average 54 wt.% HEU-type zeolite, 6 wt.% smectite, 4 wt.% mica (64 wt.% microporous minerals), 8 wt.% alkali feldspar, 9 wt.% plagioclase, 11 wt.% cristobalite and 8 wt.% quartz (36 wt.% non-microporous minerals). The chemical formula of the HEU-type zeolite is Ca2.4K0.6Na0.4Mg0.3Al6.7Si29.3O72·17H2O and the tuffs contain on average 72.3 wt.% SiO2, 11.9 wt.% Al2O3, 1.2 wt.% Fe2O3, 1.0 wt.% MgO, 2.8 wt.% CaO, 1.3 wt.% Na2O and 1.9 wt.% K2O. The zeolitic tuffs show an average ammonium exchange capacity of 144 meq/100 g. HEU-type zeolite accounts for the most of the ammonium exchange capacity, while smectite and mica contribute to a relatively small extent. The ammonium exchange capacity of the Xerovouni zeolitic tuffs showed positive correlations with (a) the HEU-type zeolite content, (b) the total microporous minerals content, (c) the loss on ignition content and (d) the CaOcontent. Such materials could be used in a large variety of agricultural, aquacultural, industrial and environmental applications.

Knowledge of mineral composition is helpful in the interpretation of well-logging data, where the hydrocarbon saturation is expected as the final result.It is calculated from the electric resistivity, cation exchange capacity (CEC) and porosity.Porosity is calculated from the bulk density, which is measured directly in the well, and the matrix (mineralogical, grain) density, which can be calculated precisely only when the mineral composition is known.

In the shale-sand formations, which are the subject of this study, the rock matrix can conduct electric current.The Waxman–Smits formula is applied to calculate the water saturation of such rocks.This formula combines rock porosity, water saturation, water resistivity and the CEC with the total rock resistivity measured in the well.CEC is introduced to this formula as the parameter determining the shale ability to conduct electricity.Typically, CEC is controlled by the smectite content of the rock.

In order to evaluate the input data needed in the log interpretation the extended mineralogical (quantitative mineral composition, CEC) and chemical (major, trace and REE) analyses were made for over 200 core samples obtained from four gas fields in the Miocene formation of the Carpathian Foredeep.The most important clay component: the sum of mixed-layer illite-smectite and discrete illite has been quantified.The detailed recognition of clay minerals allowed for constraining the density-neutron cross-plot, which is a well log data interpretation technique for the determination of both porosity and shale content in shale-sand formations.

The statistical multivariate analysis of all data helped to set up a comprehensive petrophysical model.A reliable correlation (r2 = 0.96) of the thermal neutron absorption cross-section (Σama) and the total natural radioactivity (GR) with CEC was established.Such good correlation allows for a continuous on-line CEC determination and therefore a reliable application of the Waxman-Smits water saturation model.Experimental equations with similar level of correlation were established for quartz, clay and carbonate contents, allowing the calculation of matrix density, required in the porosity calculation.

The high correlation of Σama with CEC reflects the presence of boron in the illite-smectite clays.

This paper focuses on the clay mineralogy (using XRD, SEM and TEM methods) of the lacustrine “Calizas de Torrente de Cinca” unit that represents the Oligocene-Miocene transition in the central part of the Ebro Basin (NE Spain). Phyllosilicates are mainly detrital although Mgsmectites could have been generated in the lake.Although a temperate, relatively humid climate dominated the source area during the Oligocene-Miocene transition (Chattian-Aquitanian), as deduced by detrital phyllosilicates assemblage, mineralogical vertical trends along with sedimentological studies indicate some changes.Relatively warmer and more humid conditions during the late Chattian, that favoured increasing chemical weathering, were replaced during the early Aquitanian by drier conditions coinciding with the Mi-1 glaciation effects; this change is coeval with a transition from deeper to shallower lacustrine facies.Phyllosilicate association analysis has also permitted an improvement in the palaeogeographical sketch and infers that the Pyrenees are the main source area for the lacustrine system.

In the Upper Cretaceous-Danian North Sea chalk, silica composed of nano-size quartz spheres is dispersed in the chalk matrix, and quartz is present in bands and nodules of flint. In the present investigation of the North Sea Danian chalk the nano-quartz in the chalk matrix is compared with the silica in the flint. Samples of chalk and flint layers from four North Sea wells have been investigated. Atomic Force Microscopy (AFM) has been applied to image the quartz in the chalk and in the flint. X-ray diffraction (XRD), including analysis of the positions and profiles of hkl reflections in powder diffraction patterns, has been applied to characterize the lattice of the quartz in both the chalk matrix and in the flint. The quartz in the chalk matrix and in the flint is composed of nano-quartz spheres having identical cell parameters. Based on the results we propose a new model for formation of flint in North Sea chalk: (1) The nano-quartz in the flint, like the nano-quartz in the chalk matrix, has crystallized in the marine Chalk Sea environment. The colloidal quartz particles flocculated and were deposited on the sea floor mixed with calcitic bioclastic material. (2) Regional variations in the concentration of nano-quartz particles in the sediment reflect different degrees of acidification of the Chalk Sea. (3) This resulted in areas where practically all the calcite bioclasts were dissolved leaving a high concentration of nano-quartz particles to form flint layers; where there was less dissolution, indurated chalk with abundant nano-quartz particles is now preserved. (4) The acidification could have been caused by the effects of enhanced atmospheric CO2 linked to massive short-lived volcanic eruptions in the British Tertiary Igneous Province.

An unusual occurrence of palygorskite was found near Montestrutto, lower Val d'Aosta (Italy), within an eclogite-facies leucogneiss of the Sesia-Lanzo zone. Under the optical microscope the mineral appears as a felt of fibres hundreds of μm long and a few μm thick. SEM observation proved each filament to be a bundle of smaller but remarkably long fibres (length mostly 15–20 μm and thickness <1 μm). EDS and TGA showed a water content [zeolitic H2O ( ≅ 6%) + structural OH2 (≅8%) + framework OH (≅2%) ≅l6 wt.%] lower than average (≅20 wt.%). Structure refinement by the Rietveld method confirmed the clay dioctahedral character and coexistence of two polymorphs, monoclinic [77.4(4)%] and orthorhombic [22.6(6)%], the latter showing anomalous variations of some cell parameters [c shortens to 5.138(3) and a lengthens to 12.903(7) Å]. The high crystallinity of this palygorskite suggests that it formed under low-T hydrothermal conditions due to interaction between Mg-rich hydrous fluids, derived from mantle ultramafics, and Al-rich continental rocks. Predominance of unusually long fibres (>5 μm) causes the Montestrutto palygorskite to be potentially carcinogenic.

Hydrogen forms of natural mordenite and clinoptilolite were used as catalysts for styrene oligomerization and as matrices to hold the resultant oligomers in order to prepare intense and light-resistant pigments. In contrast to synthetic zeolites of similar pore sizes (mainly H-ZSM-5, H-mordenite), the natural zeolites did not form products with an intense (pink) colouration. H-mordenite samples treated with styrene developed some colour due to styrene oligomers (the chromophore) whereas, in treated clinoptilolites, colour formation was negligible due to the lack of access of styrene molecules into the elliptical channels. The results of catalytic tests for cracking of cumene (cumene and styrene have similar molecular sizes) were consistent with the styrene oligomerization results. They indicate a noticeable catalytic activity with natural H-mordenite and a lack of activity with clinoptilolite. On the other hand, catalytic tests for propan-2-ol decomposition indicate a high activity with both natural zeolites, which confirms the presence of acid sites and their accessibility to small alcohol molecules.

Various physical and analytical techniques (XRD, XRF, SEM, FTIR and EPR) have been used to investigate the effects of chemical and/or physical modification of Ranong kaolin, which has been proposed as a potential bleaching clay for vegetable oils. Acid treatment after grinding resulted in major changes compared with acid treatment of the original mineral sample or mechanical treatment alone. Previous work has shown that the combined treatments produce increases in surface area and new porous structures, and the present measurements show reductions in Al:Si ratios. These are accompanied by a major reduction in O–H stretching vibrations as a result of grinding, although acid treatment produced little subsequent effect on the O–H bands in the FTIR spectra. However, acid treatment resulted in a reduction in the Al–OH–Al bending vibrations and the appearance of Si–O bands associated with newly synthesized material; these effects were much greater with samples that had been ground prior to the acid treatment. There were appreciable qualitative differences in the way in which the EPR spectra of Fe and Mn were affected; the Fe signal was sensitive to mechanical treatment, but little subsequent change was induced by acid extraction, whereas the Mn peaks were sensitive to the both the pH and the chemical nature of the acid used. These results therefore indicate that the Fe and Mn are in different types of site in the kaolin structure. Little change was observed in the main oxygen-based free radical centre associated with Si atoms, but that associated with Al was lost as a result of the treatments. Such mineral characterization is of fundamental importance to understanding the modification of kaolins and their uses as adsorbents in the food and environmental sciences.

Microstructural (fabric, forces and composition) changes due to hydrocarbon contamination in a clayey soil (glacial till) were studied using scanning electron microscopy (microfabric analysis), atomic force microscopy (force measurement) and a sedimentation bench test (particle size measurements). Non-polluted and polluted glacial till from NE Poland (in the area of a fuel terminal) were used for the study. Electrostatic repulsive forces in the polluted samples were much lower than in non-polluted samples. In comparison with non-polluted samples, the polluted samples exhibited lower electric charge, attractive forces on approach and strong adhesion on withdrawal. The results of the sedimentation tests indicate that clay particles form larger aggregates and settle out of the suspension rapidly in diesel oil. In non-polluted soil, the fabric is strongly aggregated – dense packing, dominating face-to-face and edge-to-edge types of contacts, clay film tightly adhering to the surface of larger grains and interparticle pores are more common. In polluted soil the clay matrix is less aggregated – loose packing, dominating edge-to-face types of contacts and inter-micro-aggregate pores are more frequent. Substantial differences were observed in the morphometric and geometrical parameters of the pore space. The polluted soil micro-fabric proved to be more isotropic and less oriented than in non-polluted soil. The polluted soil, in which electrostatic forces were suppressed by hydrocarbon interaction, displays more open porosity and larger voids than non-polluted soil, which is characterized by the occurrence of strong electrostatic interaction between the clay particles.

The evolution of the nitrogen and boron content of shales during diagenesis and anchimetamorphism was studied in the Carboniferous rocks of Donbas by means of the bulk rock chemical analysis and the XRD quantification of mineral composition, aided by CEC and EGME sorption measurements. The contributions of the organic-bound N and B were taken into account, based on the literature data (B) and on the relationship established in the course of this study (N). 28–98% of the total N and 80–100% of the total B are contained in the mineral fraction of the investigated shales.

The mineral nitrogen is located mostly in illite and accounts for 3 to 64% of the sites available for its fixation in 1Md illite. The fixation of N by illite seems to diminish in the course of diagenesis, but additional fixation occurs in newly formed 2M1 illite during the anchimetamorphic stage. The volume of N contained in illite in most samples greatly surpasses the N available locally from the organic matter contained in shale. Modelling indicates that the measured level of N for K substitution in illite corresponds to the capture in 30 vol.% of shale of all N released in a basin containing 5 vol.% of coal.

Boron is held predominantly by the 1Md fraction (illite+smectite). During diagenesis boron is redistributed into the 1Md illite, and during anchimetamorphism it is released from the 1Md illite and incorporated into new 2M1 illite. No indication of the net enrichment of pore water in B due to the clay alteration process was found.

The reactivity of soils and sediments is often described by parameters such as the specific surface area (SSA) and the cation exchange capacity (CEC). Both, however, are bulk values controlled by the presence and crystallinity of different phases, e.g. clay minerals and iron oxides. Amongst the latter, ferrihydrite and goethite are the most abundant minerals. Goethite gradually forms from a ferrihydrite precursor, a process involving a decrease in surface area. Today the BET gas adsorption technique is the most common method to measure SSA. In this study, BET surface areas of synthetic and natural ferrihydrite and goethite of variable crystallinity were compared to (a) mineral-specific measurements, including infrared analysis (IR), differential thermal analysis (DTA), and (b) bulk methods, such as cation exchange capacity and oxalate-soluble iron. Correlations showed that the SSA can be indirectly inferred from all methods. There is no general correlation between IR and BET measurements due to the variability of adsorbed water, which depends on drying and ambient conditions. DTA, particularly using the dehydroxylation peak at 300°C, allows quantification of the goethite content, and hence the SSA, because adsorbed water does not affect this peak. The data set of the present study enabled us to estimate either SSA and/or the content of iron oxides, even in natural mixtures, e.g. those in which smectites determine the SSA.

Pigments similar to the famous Maya Blue were prepared by entrapment of indigo inside the channels of natural zeolites such as clinoptilolite and mordenite. The zeolites were mixed and ground with indigo and then heated at 150°C. Surplus (unbound) dye was removed by solvent extraction or by vacuum sublimation. As is the case when synthetic zeolites are used as matrices, the colouration of the resulting pigments could be modified by the previous cation exchange of the zeolite.

Miocene pelitic sedimentary rocks from six wells in the Sava Depression (sub-basin in the south-western part of the Pannonian Basin System) were investigated in order to determine the degrees of diagenetic alteration.Qualitative and semiquantitative mineral compositions of samples and the content of smectite in illite-smectite (I-S) were determined by X-ray powder diffraction (XRD).Vitrinite reflectance and thermal alteration index (TAI) were measured in order to estimate the palaeotemperatures.Carbonate minerals, clay minerals and quartz are the main constituents of the pelitic sediments.Feldspars (albite), pyrite, opal-CT and hematite are present as minor constituents in some rocks. The mineral composition of the rocks, apart from previously known differences caused by various depositional environments and clastic material provenance, is dependent on the degree of diagenetic processes. At elevated temperatures and large burial depths the minerals formed by alteration processes or precipitated at the surface; smectite, kaolinite and calcite were gradually replaced by minerals formed by diagenetic processes, i.e. by illite-smectite, illite, chlorite, Ca-excess dolomite/ankerite and albite. Based on XRD data for smectite, I-S and illite, three stages of diagenetic development have been established. The early stage was characteristic of samples at depths <1.8 km containing smectite, I-S of the random R0 type and detrital illite.The middle stage begins with the appearance of the ordered R1 type of I-S at the depths >1.8 km and temperature above 80°C. At depths >4.6 km with corresponding temperatures >190ºC, the late stage began, characterized by the presence of R>1 I-S with <10% smectite.

The Yaylayolu kaolin deposit is situated in the vicinity of Tavşanlı, Kütahya, western Turkey. Mineral identification and characterization studies were conducted using powder X-ray diffraction (XRD), differential thermal analyses (DTA), scanning electron microscopy with an energy dispersive X-ray spectrometer (SEM-EDX), X-ray fluorescence (XRF) and Fourier transform infrared spectroscopy (FTIR) techniques. The degree of crystallinity, Hinckley's index (HI) and the Stoch index (SI) values were determined for kaolinite from the deposit.

Five representative samples from the kaolin deposit were used for ceramic technological tests. Particle size distribution, pH value, loss on ignition, A12O3, Fe2O3 and TiO2 contents were determined, drying shrinkage, firing shrinkage, dry bend strength, fired bend strength, water absorption, pfefferkorn plasticity index, whiteness of the fired and unfired samples (L* value) and bulk density were measured. The kaolin was found to be suitable for making white cement and wall tiles, floor tiles, and tableware items which are shaped by dry pressing and extrusion.

Fully exchanged Ag-clinoptilolite prepared at 100°C using 1 M solution of AgNO3 was studied. The initial sample (Beli Plast deposit, Bulgaria) was enriched in clinoptilolite by a sequence of treatments – crushing, sieving, sedimentation, and separation with heavy liquids to obtain a content of about 93 wt.% of clinoptilolite intergrown with opal-C. Opal-C was subsequently removed by chemical treatment. Maximum cation exchange was reached on the seventh day (4.86(4) Ag atoms per formula unit). Rietveld structural refinement was then carried out on the Ag-exchanged clinoptilolite, and three independent Ag sites were localated in the channels of the clinoptilolite structure. Seven water sites, coordinating the Ag sites, were located. Ag-clinoptilolite is, potentially, a promising low-cost antibacterial material.

The adsorption of sulphur dioxide (SO2) on two bentonites from Unye, Turkey (Kavaktepe and Yemişlitepe deposits – denoted below as BK and BY) and on forms treated with 1 and 2 M HCl solutions was investigated. The bentonite samples were characterized using X-ray diffraction (XRD), X-ray fluorescence (XRF), thermogravimetry (TG-DTG), differential thermal analysis (DTA) and nitrogen adsorption methods. Adsorption capacities of SO2 were obtained using a standard volumetric apparatus at 293 K and 106 kPa. The SO2 adsorption capacity of the BY-2 (1.263 mmol g–1) sample was much greater than the BK-2 (1.126 mmol g–1) sample. As the concentration of acid increased, the specific surface areas and the uptakes of SO2 gas increased.

Suspensions of thirty six bentonites were equilibrated for 24 h and then adjusted to pH 3. After an hour, pH titrations up to pH 12 at varying ionic strengths were performed within 4.5 h. The titration data were recalculated into proton affinity distributions (PAD) using the condensed approximation. In spite of widely varying chemical compositions, all bentonites showed a protonation reaction between pK 4 and 5, which could be assigned to aluminol groups at the edge surfaces of the smectites. The average pK is 4.73±80.31. A second prominent peak in the PAD at pK = 10.43±80.13 could be assigned to exchangeable Mg2+ in the interlayer space. The possibility to constrain both pK values at a fixed average value will decrease the number of parameters in surface complexation modelling and thus enhance its convergence.