The nature and origin of authigenic clay minerals and silicate cements in the Jurassic and Cretaceous sediments of England and the North Sea are discussed in relation to penecontemporaneous volcanism in and around the North Sea Basin. Evidence, including new REE data, suggests that the authigenic clay minerals represent the argillization of volcanic ash under varying diagenetic conditions, and that volcanic ash is a likely source for at least the early silicate cements in many sandstones. The nature and origin of smectite-rich, glauconite-rich, berthierine-rich and kaolin-rich volcanogenic clay mineral deposits are discussed. Two patterns of volcanogenic clay minerals facies are described. Pattern A is related to ash argillization in the non-marine and marine environments. Pattern B is developed by the argillization of ash concentrated in the sand and silt facies belts in the seas bordering ash-covered islands and massifs. It is associated with regression/ transgression cycles which may be related to thermal doming and associated volcanism, including the submarine release of hydrothermal fluids rich in Fe. The apparent paucity of volcanogenic clay deposits in the Jurasssic and Early Cretaceous sediments of the North Sea is discussed.

Two phlogopite, two mixed-layer phlogopite-vermiculite, and two vermiculite samples collected from the Palabora Complex of South Africa have been investigated at 295 K by X-ray diffraction, chemical analysis, and Mössbauer spectroscopy. In addition the temperature dependence of the Mössbauer spectra has been measured between 95 and 295 K for one phlogopite and one mixed-layer sample. The results of the chemical analyses and the Mössbauer spectra improve our knowledge of the vermiculitization process in the Palabora Complex. Both techniques indicate oxidation of the Fe ions during the sequence: phlogopite → mixed-layer → vermiculite. Further, the Mössbauer spectra indicate that Fe oxidation occurs mainly in the octahedral sites and suggest that migration and oxidation of the Fe2+ ions from the octahedral sites to the tetrahedral sites may occur during the transformation of phlogopite into a mixed-layer phase. Finally, the vermiculitization process involves both Fe oxidation and loss of K with a concomitant increase in the Mg content.

Smectites of sedimentary series from a playa lake system from Calatayud Basin have been studied by XRD and TEM chemical microanalyses. Clay particle microanalyses show complete continuity between dioctahedral aluminous and trioctahedral magnesian smectites. Aluminous smectites have been classified as montmorillonites and ferribeidellites, both with compositional variability. They represent detrital phases resulting from weathering in the source area. Compositionally-intermediate smectites (beidellite-saponite and montmorillonite-stevensite) seem to correspond to weighted mean compositions of di- and trioctahedral phases stacked together in the same particle. They represent intermediate transitional stages from detrital to authigenic smectites in more distal basin facies. Trioctahedral smectites, although called saponites and stevensites, are actually random mixed-layer kerolite-Mg-smectite with a high percentage of expandable layers. They represent authigenic clays formed from solutions with high pH and Mg content as a result of evaporative concentration. The variability in composition of smectites, both within the same sample and amongst different samples, is a possible consequence of the heterogeneity in the local chemical environment, and so, equilibrium may be only reached locally in a large variety of microsystems.

The results of a new technique for the measurement of the thickness distribution of fundamental particles are reported. The technique is based on high-resolution transmission electron microscopy (HRTEM) of Na-saturated mixed-layer illite-smectite dispersed in polyvinylpyrrolidone (PVP-10). Intercalation of PVP-10 increases the spacing of expandable interlayers and changes the arrangement of particles so that the number of layers per fundamental particle can be counted easily on HRTEM images. The data obtained by HRTEM on PVP-10-intercalated illite-smectite of hydrothermal origin are compared with data from the Pt-shadowing technique. A good agreement between the two methods for the measured thickness distributions, mean thickness and expandability confirms the reliability of the new technique. The same technique is applied to a set of four sedimentary samples with different expandabilities (83-18%). The thickness of illite particles from shales and claystones has a lognormal distribution. Detrital anddiscrete illite particles can be distinguished from the thickness distribution of authigenic illite.

The alteration and transformation behaviour of the Tertiary Hammerschmiede Smectite and the Jurassic Opalinus Shale in an alkaline solution was studied in column experiments. The Hammerschmiede Smectite is proposed as potential backfill material and the Opalinus Shale as host rock for the Swiss low-level nuclear waste storage site. Over a period of 18 months, the evolution of permeability, pH and solution concentrations were measured. After the experiment, the columns were cut into pieces to study the mineralogical and the chemical evolution of the clays. X-ray diffraction (XRD) revealed no significant appearance or disappearance of diffraction peaks at the end of the experiments. The scanning electron micrographs of the clays revealed that both clays exhibited a precipitation zone, which extends from 0 to 2 cm below the infiltration surface. Both clays showed significant differences in the evolution of pH and hydraulic conductivity. The solution front crossed the Opalinus Shale column entirely after only 11 weeks and the initial values for K+ and Na+ were conserved in the solution. For both clays, the salt concentrations in the percolating fluids mirror the evolution of pH.

Three clay minerals from southern and central Tunisia were characterized. Both XRD quantitative analysis and a chemical method were used to determine the mineralogical and physico-chemical characteristics of the <2 μm clay fractions. The XRD, CEC and specific surface measurement analyses showed that the dominant phase in all samples is illite-smectite with kaolinite and traces of quartz also present. From quantitative XRD, the abundances of the minerals identified are consistent with the measured CEC, specific surface area and TG/DTA properties. Analysis by XRD also showed that the illite-smectite phases are composed of thin stacks (two to a maximum of ten layers per stack) of random illite-smectite and ordered (R1) illite-smectite. There is also some discrete illite.

Analytical electron microscopy of representative smectites from soils and sediments revealed that K was present in significant proportions. It was the major interlayer cation in soils from pelitic rocks, continental and marine sediments, independent of their diagenetic grade. Sodium was predominant only in soils from basic rock. Fluvial sediments contained smectites with both kinds of interlayer compositions. The octahedral composition of each sample ranged widely, covering various fields of dioctahedral smectites. The most important trend was the substitution of Al by Fe and Mg; the chemistry of each smectite particle was determined by the parent mineral from which it formed. The real interlayer composition has important implications for the diagenetic smectite–illite transformation. When considering a typical K content, the smectite–illite reaction, with chlorite and quartz as subproducts, needs only 0.21 K atoms. For more K-rich compositions, a reaction is possible without an external supply of K.

The clay mineralogy of Upper Permian–Lower Cretaceous mudstones from East Greenland has been investigated by X-ray diffraction (XRD), atomic force microscopy (AFM) and thermal analysis in order to evaluate long-term trends in provenance and palaeoclimate and to detect possible volcanic events. The Upper Permian–Lower Triassic mudstones contain illite, chlorite, vermiculite, kaolinite and illite-smectite (I-S), whereas the Rhaetian–Sinemurian mudstones are dominated by kaolinite. Aalenian–Albian mudstones contain kaolinite and large amounts of I-S with ˜80% illite layers. Exceptions are three Kimmeridgian samples, which contain mainly I-S with 30% illite layers, and three Upper Barremian–Lower Aptian samples with large amounts of smectite layers. Discrete clay minerals in the Upper Permian–Jurassic mudstones are largely detrital. The smectite-rich I-S probably reflects episodes of volcanic activity in late Jurassic and late Barremian–early Aptian times. This is the first indication of Mesozoic volcanism from the Mesozoic rift basin of East Greenland. The main sediment source during late Permian–early Cretaceous times was weathered Precambrian and Caledonian crystalline basement. The only possibly climate-induced change is a change from chlorite, illite, vermiculite and kaolinite in Upper Permian–Lower Triassic mudstones to kaolinite and I-S in the Jurassic mudstones and is probably due to an increase in precipitation.

A reaction path model was constructed in a bid to simulate diagenesis in the Magnus Sandstone, an Upper Jurassic turbidite reservoir in the Northern North Sea, UKCS. The model, involving a flux of source rock-derived CO2 into an arkosic sandstone, successfully reproduced simultaneous dissolution of detrital K-feldspar and growth of authigenic quartz, ankerite and illite. Generation of CO2 occurred before and during the main phase of oil generation linking source rock maturation with patterns of diagenesis in arkosic sandstones and limiting this type of diagenesis to the earlier stages of oil charging. Independent corroborative evidence for the model is provided by formation water geochemical data, carbon isotope data from ankerite and produced gas phase CO2 and the presence of petroleum inclusions within the mineral cements. The model involves a closed system with respect to relatively insoluble species such as SiO2 and Al2O3 but is an open system with respect to CO2. There are up to seven possible rate-controlling steps including: influx of CO2, dissolution of K-feldspar, precipitation of quartz, ankerite and illite, diffusive transport of SiO2 and Al2O3 from the site of dissolution to the site of precipitation and possibly the rate of influx of Mg2+ and Ca2+. Given the large number of possible controls, and contrary to modern popular belief, the rate of quartz precipitation is thus not always rate limiting.

Changes in particle organization and pore-spaces with applied mechanical and hydraulic stresses were followed using TEM, SAXS mercury porosimetry and gas adsorption for two Na-smectites, Laponite and hectorite, with similar structural formulae but different particle sizes. The TEM images show that hectorite has particles larger and more anisotropic than those of Laponite. The particles order perpendicularly to the direction of axial mechanical stress and become disoriented under hydraulic stress. According to the SAXS results, Laponite is composed of 1 – 3 small layers and hectorite of more compact (10 – 80 layers) particles. In Laponite, mechanical stress strongly reduces the amount of macropores but does not affect micropores and mesopores; hydraulic stress increases the macropores. In hectorite, the pore-volume is lower than in Laponite. The different techniques used yield complementary results and show the considerable effect of layer dimension on the behaviour and microtexture parameters of smectite submitted to hydromechanical stresses.

The clay mineralogy of Pleistocene sediments of eleven sediment cores at three ODP sites from 30°N to 60°N northwestern Atlantic Ocean has been investigated. The sediments are characterized by the presence of random illite-vermiculite mixed layers (I-V) (up to 32% of the clay mineral assemblage). The I-V clays are much more abundant during interglacial periods than during glacial ones. They are attributed to detrital supply through erosion of high-latitude continental areas from which they are derived mainly from chemical weathering of micaceous phyllosilicates. Their spatial distribution and the specific conditions for their formation through weathering suggest that I-V mixed layers are mainly derived from the Canadian Shield. They were transported from their source to marine deposition areas by rivers, deep water masses or nepheloid layers. Due to the specific conditions required for the formation of I-V, its occurrence and abundance are used as a palaeoclimate and palaeocirculation proxy for northwestern Atlantic Pleistocene sediment.

The localization and number of the different types of water in two Na-smectites (Laponite and hectorite) were studied as a function of the hydromechanical stresses applied. Water volume variation was obtained by macroscopic oedometric tests. Thermogravimetric analysis (TGA), X-ray diffraction (XRD) and nuclear magnetic resonance (NMR) were used to study water-smectite interactions. The TGA results show that the bulk water content decreases while the adsorbed water content remains practically constant with increasing mechanical stress; hectorite adsorbs less water than Laponite at low hydraulic stress. The proportion of adsorbed water obtained by NMR confirms the TGA data. The interlamellar space and the equivalent water layers decrease with increasing mechanical stress and is always lower in hectorite than in Laponite. Hydromechanical effects on the water-Na-smectite system are in agreement with microtexture changes measured by porosimetry. Differences in the properties of the two clays can be attributed to the higher extension of the layers in hectorite compared with Laponite.

The MudMaster computer program, based on the modified Bertaut-Warren- Averbach (BWA) XRD method, was used in the study of diagenetic evolution of illitic material in shales. The illitic material was characterized by XRD as a mixture of illite-smectite (I-S) and discrete illite. The experimental conditions for complete dehydration of swelling clays, necessary in this method, were established for a climate of high relative humidity (RH >40%). It was found that the distribution of crystallite thickness of dehydrated illitic material of shales is described by the lognormal law, as was established earlier by the BWA method for pure I-S from pyroclastic rocks. The parameters characterizing this distribution evolve with depth: the mean crystallite thickness (Te), the distribution broadening (DW) and the parameter of a lognormal distribution (β2) increase, whereas the percentage of the most frequent crystallite thickness decreases. The observed scatter of values is not random but indicates fluctuations in the characteristics of the illitic material of shales. The results imply that the modified Scherrer technique of measuring mean crystal thickness from the broadening of XRD reflections can be extended at least to some shales.

Late Cretaceous bentonitic clays in the Kelkit Valley region of Turkey are composed of an alternation of limestone lenses and silicified tuff nodule-bearing pyroclastic rocks and their alteration products. Quartz, feldspar, biotite, trace amounts of augite together with pumice and volcanic rock fragments comprise the volcanogenic components. Diagenetic minerals are represented by clay, calcite, opal-CT, zeoliteand dolomite. The clay fraction is dominated by smectite and lesser amounts of I-S, illite, chlorite and kaolinite. The d001 basal spacing of dioctahedral smectites ranges from 12.51 to 12.55Å in Na-smectites and 14.97 to 15.52 A˚in Ca-smectites. The CaO/Na2O ratio of smectites ranges from 0.15 to 19.50, and the interlayer Na and Ca contents are 0.22–0.30 in beidellitesand 0.02–0.09 while those in montmorillonites are 0.01–0.13 and 0.03–0.15, respectively. The data obtained indicate that bentonites formed in a marine environment by the alteration of volcanic ash of rhyodacitic/dacitic and intermediate/acidic composition.

Carbonate cements in Tertiary reservoir sandstones from the northern North Sea have distinctive carbon isotopic compositions (δ13C). Oil migration up faults from deeper structures and biodegradation of oil pools are factors of particular importance in influencing the δ13C of carbonate cements in these sandstones. As a result, δ13C can be used as an exploration guide to locating the positions of vertical leakoff points from the Jurassic source rocks. The histogram distribution of δ13C in these carbonate cements is trimodal, with peaks at around −26, −3 and +12‰ (ranges −22 to −30, +2 to −10 and +8 to +18‰, respectively). Bacterial processes played major roles in determining this distribution, with oxidative biodegradation of oil resulting in carbonate cements with very negative compositions and bacterial fermentation resulting in the positive δ13C cements. δ13C distribution patterns may be used to differentiate Tertiary reservoir sandstones from Jurassic in the northern North Sea, and these regional carbonate cement δ13C datasets allow geologically useful inferences to be drawn from δ13C data from new sample locations.

There are two different views regarding the genesis of gibbsite in tropical acid soils: (1) direct weathering of primary Al-silicate minerals; and (2) transformation through clay mineral intermediates. We investigated the genesis of gibbsite in two representative Ultisols from northeastern India. Gibbsite in these Ultisols appears to be the remnant of earlier weathering products of aluminosilicate minerals formed in a neutral to alkaline pedochemical environment. The mere presence of gibbsite in these soils, therefore, does not indicate their advanced stage of weathering. The formation of typically rod-shaped and well-crystallized gibbsite in both the coarse and fine soil fractions in the presence of large amounts of 2:1 minerals indicates that the anti-gibbsite hypothesis may not be tenable in these tropical acid soils. A schematic model for the formation of gibbsite and kaolin in Ultisols is proposed.

Lower Cretaceous clay minerals suites of the Alava Block, analysed by XRD, are dominated either by illite or kaolinite. These assemblages are mainly inherited in origin, although textural evidence (SEM) indicates some diagenetic clay. Precipitation of blocky kaolinite took place in sandstones from the southern domain of the Block, characterized by low sedimentation and subsidence rates and by low vitrinite reflectance values (%Rr <0.8). In the northern domain, where sedimentation and subsidence rates were high (%Rr >3.3), illitization of kaolinite and smectitic clays and precipitation of authigenic chlorite occurred. Some chemical aspects of these reactions are discussed.

A series of smectites was investigated to reveal the thickness distribution of crystallites. The Fourier decomposition technique of Bertaut-Warren-Averbach (MudMaster program) was applied to XRD reflections of <0.2 μm, glycolated Na-clays. It was shown that the thickness distribution is lognormal and the mean thickness ranges from 5.7 to 12.3 nm (3.4 – 7.3 layers). At higher humidities, characteristic of TEM sample preparation, the mean thicknesses decrease, but the differences in mean thickness between samples are preserved. Beidellites have the thickest crystallites. The relationships between the mean thickness, volume-weighted mean thickness and the parameters of the lognormal distribution were established. Calculation of these parameters is possible, using the area and the maximum intensity of the 001 reflection. The influence of the fluctuations of d-spacing on the peak width was shown. Smectite crystallites, dispersed into individual layers during infinite osmotic swelling and rebuilt through coagulation, recover their original mean thickness and thickness distribution.

An XRD-TEM study was carried out on low-grade metapelites (Transantarctic Mountains) to determine the cause of apparent inconsistences in grade as determined by IC and independent geologic relations. The illite crystallinity (IC) data indicate that the three units investigated (BT, RBT, MS) were affected by very low- (IC = 0.24°Δ2θ in BT) to low-grade metamorphism (0.19°Δ2θ in MS). In all three samples, mica crystals are of a size typical of the epizone, but the mean size increases from BT to RBT and MS, due to the increasing strain features from BT to MS. These results indicate that strain-induced reduction in crystal size was retained in BT samples (with anomalously high IC values). Microtextures in RBT and MS (with smaller IC) samples suggest a recovery of sub-grain boundaries. A decrease in crystal size may occur with increasing grade where strain rates are high relative to the rate of recrystallization.

Close relationships are demonstrated between reservoir quality, lithofacies, provenance and burial history in the Jurassic Brent and Viking Groups in the Norwegian North Sea. Porosity and permeability are strongly and systematically related to the initial texture and composition of the sandstones. Porosity variations are related to the amount of compaction, which is more severe in matrix-rich than in clean facies, and quartz cementation, which is most important in clean facies. Permeability variations are related to porosity and facies-controlled variations in grain size, and abundance and texture of intergranular fines. Illitization of early diagenetic kaolins require K, which is derived mainly from dissolution of K-feldspar. Sediments were sourced from K-feldspar- poor provenances during the maximum progradation of the Brent Group, and sandstones deposited at this time are less exposed to illitization and have better permeability at deep burial than reservoir sandstones that initially contained more K-feldspar.