The desorption of tetrahydropyran (THP), tetrahydrofuran (THF) and 1,4-dioxan (DIOX) from Na+-, Ca2+-, Al3+- and Cr3+-exchanged montmorillonite has been studied using variable temperature infrared spectroscopy and thermogravimetric analysis. The derivative thermograms for the desorption of each cyclic ether exhibited three maxima but there was little uniformity in the temperatures at which these maxima occurred. Nonetheless, the desorption of both THP and THF occurred at lower temperatures in the Cr3+-exchanged form than in the Al3+-form. The desorption of DIOX showed little cationic dependence. Mass spectroscopic analysis of the thermally evolved vapours indicated that no transformation products were desorbed at temperatures ⩽230°C.

Three duricrust types (calcretes, palycretes and silcretes) have been distinguished in the Lower Paleogene arkosic materials from the margins of the Duero and Tajo basins (central Spain). In the calcretes the cements are composed of calcite plus palygorskite, whereas palygorskite is the only cement in the palycretes. In the silcretes, the cement consists chiefly of opal and chalcedony, with minor quartz. The important duricrust development in the Paleogene detrital materials can be correlated with a drastic climatic change towards colder and more arid conditions during this time, as inferred from the sedimentological features and the clay mineral evolution. The origin of calcretes and palycretes is related to the movement of alkaline phreatic waters generated from dolomitic rocks of Cretaceous age cropping out in the near surroundings. Silcretes originated from the vertical transfer of silica from supersaturated groundwaters, from the Hercynian granitic rocks, up to the surface. Silcretes are developed either on unconsolidated arkosic materials or replace previous calcrete or palycrete levels.

The extent to which the diagenesis of sedimentary sequences within the UK North Sea is influenced by the passage of meteoric water is subject of current debate. Petrographic (SEM, TEM, thinsection) observation and stable isotope ratios from authigenic illite separates are used to deduce the pore-fluid evolution of the Fulmar Formation within well 29/10-2 from the Central Graben, with emphasis on the past importance of meteoric water flushing.

Petrographic observation shows the illite to have two modes of occurrence (pore-filling and as pseudomorphs after feldspar). These can be equated with two authigenic crystal morphologies (plates and laths) observed by TEM within illite separates prepared for isotopic analysis. The laths are equated with late stage ‘hairy’ pore-filling illite, the plates with illite pseudomorphs after feldspar which are difficult to date petrographically.

The δD (−55 to −87‰ SMOW) and δ18O (12.4–14.6‰ SMOW) analyses can be interpreted in terms of a conventional hydrogen-oxygen cross-plot to indicate illite precipitation from pore-waters of meteoric origin at 50–60°C. However, these predicted precipitation temperatures are irreconcilable with the observed petrographic sequence. The hydrogen isotope compositions may have undergone resetting during burial. Consequently, only the δ18O data may be confidently interpreted in terms of the conditions of illite precipitation. This implies illite growth at temperatures above 80°C from waters with δ18O between −2.5 and +6‰ SMOW, leaving the case for meteoric water flushing of the sandstones unproven.

Clay mica is the predominant component of the fine-grained siliciclastic sediments of the Western European Permo-Trias and it may occur as the sole component of the clay assemblage. Its characteristics have been studied by chemical analysis, radioisotope (K/Ar) data, X-ray diffraction and electron microscopy in the clay assemblages from Triassic and Permian sediments in Spain, Western Approaches, South Devon and East Yorkshire. The clay mica is a ferric dioctahedral mineral containing on average 6.5% Fe2O3 and 7.5% K2O. Crystal thickness ranges from 8 × 10 Å to 115 × 10 Å, and varies with geological, stratigraphical and grain-size factors. Radioisotope data and geological considerations suggest that much of the Permo-Triassic clay mica was formed originally in coeval desert soils rather than being derived from pre-existing rocks. It was then eroded, sometimes mixed with much older material, and deposited as fine-grained detritus in adjacent areas. Upon deep burial, this detrital mica assemblage underwent recrystallization with the development of euhedral crystals and the alteration of the K/Ar values.

Samples of natural clinoptilolite modified by treatment with NH4Cl or HCl solutions, followed by thermal treatments, have been characterized, and their catalytic activity evaluated, in o-xylene isomerization and ethanol dehydration reactions. The substitution of the compensating cations by NH4+ does not produce structural changes in the original material, but it opens the channels and increases its acidity and thermal stability. The treatment with HCl increases both the acidity and the effective diameter of the channels and pores but it produces an important loss of zeolite phase. Calcination of the acidic forms above 973 K leads to the breakdown of the zeolite structure. Catalytic activity of the samples is related to the surface acidity. For the original and NH4Cl-treated samples, however, the conversion of o-xylene is limited by the access of the reactant inside the channels of the zeolite. A comparative study with modified sepiolite in dehydration of ethanol has also been performed.

Highly crystalline kaolinite has been studied by 27Al satellite transition magic angle-spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy. This technique provides an additional narrowing of the MAS spectral lines by a factor of more than three compared with the width of the prominent central transition. Evidence for the presence of two crystallographically inequivalent hexacoordinated Al sites has been found. The results support the kaolinite crystal structure proposed by Bish & Von Dreele (1989).

Diagenetic kaolinite in reservoir sandstones of the Brent Group precipitated following the dissolution of detrial feldspar. Two distinct morphologies of kaolinite occur: (1) early diagenetic vermiform kaolinite which is often associated with expanded detrital micas; (2) later diagenetic ‘blocky’ kaolinite. Combined hydrogen and oxygen isotopic studies suggest that vermiform kaolinite precipitated at 25–50°C, and blocky kaolinite at 50–80°C, from pore-waters of a similar isotopic composition (δ18O = −6.5 to −3.5‰). These pore-waters are interpreted to be either a mixture of meteoric and compactional waters, or alternatively a meteoric water that had evolved isotopically due to water-rock interaction. Kaolinite precipitation occurred predominantly during the late Cretaceous to early Eocene. Influx of meteoric water into the Brent Group, probably occurred during the Palaeocene. Fluid flow across the entire basin was driven by a hydrostatic head on the East Shetland Platform palaeo-landmass to the west. The development of the two kaolinite morphologies is possibly related to the degree of supersaturation at the time of precipitation. At low degrees of supersaturation, vermiform kaolinite precipitated slowly upon detrital mica surfaces. Blocky kaolinite precipitated more rapidly into open pore-space at higher degrees of supersaturation. Precipitation of blocky kaolinite was perhaps triggered by the decay of oxalate.

Authigenic kaolin is a major occluder of porosity at all depths in the Hutton-NW Hutton Brent Group reservoirs. Two polytypes, kaolinite and dickite, are present. Kaolinite occurs to a depth of ∼10,600 ft and is interpreted to be eogenetic. Dickite increases in abundance with burial depth, concomitant with increasing K-feldspar dissolution. Kaolin petrography indicates that kaolinite transforms to dickite via dissolution-reprecipitation at depths of ∼11,000 ft. Dickite has δ18O values characteristic of modified meteoric water for growth at temperatures of contemporaneous quartz authigenesis.

Palaeohydrodynamic models involving meteoric water penetration down to 2 km through faults or Palaeozoic rocks of the East Shetland Platform are unlikely to provide the vigorous fluid throughput required for kaolin precipitation. Reverse post-rift modelling indicates that the crest of the Hutton-NW Hutton fault block was not sub-aerially exposed, precluding meteoric water ingress via this route. Eogenetic kaolinite formed in a meteoric water flush driven by topographic head on the Brent Delta. Dickite is, in part, derived from kaolinite dissolution, with additional sourcing from K-feldspar dissolution and Si-Al in pore-waters expelled from mudstones during burial. This model precludes the need for extensive fluid-flushing at intermediate burial depths.