The diagenetic history of the Rotliegendes Sandstone reservoir in the Rough Gas Field was studied using thin-sections, XRD analyses and SEM. The Rotliegendes comprises a sequence of fine-grained fluvial sheet-flood sandstones and coarse, gravelly, low-sinuosity channel sandstones, with thin aeolian interbeds, overlain by a sequence of aeolian dune and interdune sandstones. Early, environmentally-related diagnesis (eogenesis) shows a marked variability with sedimentary facies. Within aeolian sandstones, poikilotopic anhydrite and fine, rhombic dolomite are preserved. Fluvially-derived sandstones typically contain infiltrated detrital clays and early authigenic mixed-layer clays, together with coarse, framework-displacive dolomite. Feldspars show varying degrees of alteration within all facies. These eogenetic features reflect patterns of groundwater movement during the Rotliegendes and early Zechstein. Mineral dissolution and precipitation were controlled by the chemistry of the groundwaters. Burial diagenetic (mesogenetic) features are superimposed on eogenetic cements. Authigenic clays have been converted to illitic clays. In addition, mesogenetic chlorite has formed and quartz and strongly ferroan dolomite cements are recognized. These minerals may be related to clay diagenesis within the underlying Carboniferous Coal Measures. Early, framework-supporting anyhdrite, and both phases of dolomite, have been partially dissolved, creating secondary porosity. This is attributed to the action of acidic porewaters, generated by the maturation of organic material within the Carboniferous. Post-dissolution kaolinite, gypsum and minor pyrite infill secondary pores. Gas emplacement from the Late Cretaceous onwards effectively halted further diagenetic reactions.

Analytical transmission electron microscopy (ATEM) was used to obtain chemical analyses of single illite crystals from Upper Carboniferous reservoir sandstones of the Bothamsall Oilfield, East Midlands, UK, and from Rotliegendes (Permian) sandstones of the North Sea. All samples were found to be highly aluminous, with only minor Mg and Fe, and to have near-ideal dioctahedral sheet totals. No significant variation in chemical composition of illite was found within the Bothamsall reservoir rocks, irrespective of paragenesis or stratigraphic horizon. Similar results were obtained from the Rotliegendes samples. Variation was found, however, between Bothamsall and Rotliegendes analyses populations. The Rotliegendes illites were distinctly more K-rich, which is the result of greater charge deficiency in the octahedral sheet. These results indicate that all the illite in both reservoirs precipitated in equilibrium with the reservoir pore-fluid. Furthermore, they imply that the physico-chemical composition of the pore-fluid did not evolve significantly between the different illite generations in the Bothamsall samples. These data, when compared with published analyses of authigenic illite, indicate that the compositional field for illite in sandstones is restricted in comparison with that of illite in mudrocks.

A 29Si MAS-NMR one-pulse and ﹛1H﹜ CP comparative study of sepiolite, folded sepiolite, aluminated sepiolite, and palygorskite was conducted. The three main resonances of sepiolite at -92.0 ± 0.1, —94.3 + 0.1, and — 97.8 ± 0.1 p.p.m. were assigned with respect to the position of the Si atoms within the three pairs of symmetrical sites in the basal plane. The line at —97.8 p.p.m. was attributed to the central sites by comparison with the resonances and chemical environments of Si in talc and palygorskite. The line at —94.3 p.p.m. was attributed to the edge sites, because it is strongly reinforced by cross-polarization. Alumination of sepiolite led to a broadening of the peaks and new downfield resonances in line with what can be observed in other phyllosilicates and zeolites.

Ni-Fe pyroaurite-type hydroxychlorides were prepared by aerial oxidation of Ni(II)-Fe(II) hydroxides precipitated in aqueous solution with various P = Fe/Ni ratios. When P≥ 1/3, Ni(II)-Fe(II)-Fe(III) hydroxychlorides characterized by a specific Fe(IIl)/[Fe(II)+Ni(II)] ratio of 1/3, corresponding to the idealized formula of NiII3-xFeIIxFeIII(OH)8Cl.nH2O (with 0 ≤ x ≤ 3), were obtained at the end of the first stage of oxidation, In a second reaction stage, these hydroxychlorides oxidize with deprotonation of hydroxyl ions into O2- ions, i.e. the remaining FeII(OH)2 groups are transformed into FeIIIOOH groups. Along with the Ni(II)-Fe(III) hydroxychloride which contains a part of the FeIIIOOH groups a second phase is obtained. It is an amorphous Fe(III) or Ni(II)-Fe(III) oxyhydroxide when 1/3<P≤3/2, and a ferric oxyhydroxide identified as γ-FeOOH (lepidocrocite) when P>3/2. On the other side of the domain, when P<1/3, the Fe(III)/[Fe(II)+Ni(II)] ratio cannot reach the specific value of 1/3; this gives rise to a pyroaurite-type Ni(II)-Fe(III) hydroxychloride with a lower chloride content, that is with an average composition of NiII3+yFeIII1-y(OH)8Cl1-y.nH2O where y = {[4/(1+P)] - 3}, down to minimum Fe(III) and Cl contents corresponding to y = 1/3 (P = 1/5). The in situ mechanisms of oxidation of Ni(II)-Fe(II) hydroxides into Ni(H)-Fe(II)-Fe(III) hydroxychlorides are discussed.

The adsorption of Cd and Zn on a standard montmorillonite (SAZ-1) in the presence of the cationic pesticide chlordimeform, both in solution (simultaneous adsorption) and when the pesticide is previously adsorbed on the clay (successive adsorption) has been studied. The adsorption of Zn decreases when the chlordimeform concentration increases in both simultaneous and successive adsorptions, following the sequence: chlordimeform-free solutions > successive > simultaneous. In the adsorption of Cd the sequence is different: successive > chlordimeform-free solutions > simultaneous, indicating that a small amount of pesticide adsorbed favours Cd adsorption. In all cases, the apparent affinity of the metal for adsorption on montmorillonite, on the basis of distribution coefficients, KD, is higher for lower metal surface coverage, and decreases largely with the amount of the metal adsorbed. This indicates the existence of high affinity sites on the clay, probably those of variable charge edge regions. The contribution of edge and interlamellar positions to adsorption of Zn and Cd on SAZ-1 has been studied.

Grain-coating chlorite cements commonly occur within sandstones of late Middle and Upper Miocene age deposited in the North Sumatra back-arc basin. Chlorites from the Lower Keutapang Member contain Ca (maximum 0.75 wt% oxide) and show textural evidence for direct precipitation on grains. However, crystals are subhedral, showing curved faces and often ragged edges, and show a tendency to merge together. In overlying beds of the Upper Keutapang Member, grain-coating chlorite-smectite (20% smectite) cements display an identical morphology but are more siliceous, have a lower octahedral occupancy and contain higher total (Na + Ca + K). It is proposed that chlorite cements in the Keutapang Formation originated as smectite-rich cement rims whose initial precipitation was related to the breakdown of volcanic detritus in the sediments. Transformation to chlorite occurred subsequently during burial, facilitated by a high geothermal gradient in the back-arc basin.

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.

Rare earth elements are mobilized, fractionated and precipitated during weathering processes of basaltic rocks of the Lisbon Volcanic Complex. In general there is an increase in the REE contents in the whole samples with increasing weathering and fractionation between LREE and HREE. Cerium is partially oxidized and Ce4+ is retained resulting in negative Ce anomalies in the whole samples of the base and middle profile zones. In the clay fraction there is an increase in the REE contents from the top to the bottom of the profiles, except for Ce, giving rise to positive Ce anomalies in the top and negative anomalies of this element in the middle and bottom of the profiles. Significant positive Ce anomalies occur in the finer fractions of palaeoweathered (Upper Cretaceous/ Lower Eocene) basalts associated with low REE contents relative to the whole samples indicating more intense leaching conditions in the Upper Cretaceous/Lower Eocene than at the present day. However, in both cases no positive Ce anomalies were found in the whole samples. There appears to be a negative correlation between the (La/Yb)ch ratio variation and the clay mineralogy/drainage conditions.

Four drill cores along a lateritic hill in Nkamouna-Kongo (southeast Cameroon) were studied using microprobe analysis, X-ray diffraction, scanning electron microscopy, transmission electron microscopy and infrared spectroscopy. The main objective of the study was to investigate the occurrence of clay silicates while evaluating the Ni-Co content of the laterite for potential mineral exploitation. The thick lateritic profiles (>40 m deep) developed on serpentinized ultramafic rocks have an Fe-rich clayey fraction, with goethite as the main mineralogical constituent and secondary quartz and relicts of magnetite-maghemite as accessory minerals. Silicate clays are less abundant and occur mainly towards the top of the profiles. At the summit of the interfluve, kaolinite and some gibbsite are associated with goethite. Along the slopes, at the bottom of profiles, the weathered bedrock shows the presence of smectite (Fe-beidellite) and kaolinite, probably due to slower water-flow conditions. Towards the top of the profile in the lower clay, ferruginous and upper clay horizons, only kaolinite remains with gibbsite, after the leaching of silica and soluble cations following repeated remobilization-recrystallization processes. At the summit, where the downward movement of water is rapid, no smectite was identified. As a whole, the mineralogical composition of the material varies in close relationship with the drainage, leading to a contrasted clay mineralogy marked by the presence of Fe-beidellite and kaolinite at the bottom, and that of kaolinite and gibbsite at the summit of the profiles.

In Scandinavian podzols a swelling dioctahedral mineral, probably derived from dioctahedral mica and iron-rich chlorite, has been found in the clay (<2µ) fractions from A2-horizons. This mineral, or group of minerals, is shown by X-ray examination and differential thermal analysis to be of a vermiculite-smectite type, thus making the differentiation between vermiculite and smectite still more problematical. The pretreatment of the samples and choice of interlayer cations is shown to be of great significance for the identification of soil clay minerals.

L'altération latéritique débutante des orthopyroxènes et clinopyroxènes de Niquelandia, Brésil, montre plusieurs stades. Le premier stade facultatif est la formation de produits ‘amorphes’ dont la composition chimique proche de celle des minéraux parentaux, montre déjà un enrichissement en nickel. Le deuxième stade est marqué par l'apparition de phyllosilicates dont la nature et la composition chimique varient selon le degré de porosité de la roche parentale. Cette porosité contrôle également la distribution du nickel dans les différents phyllosilicates, (saponite, talc, pimélite). Les pyroxènes ne contenant pas ou très peu de nickel, il est clair que le nickel qui s'accumule dans les produits de l'altération est totalement importé avec les eaux de percolation. L'origine de ce nickel est à rechercher plus haut dans les profils ou plus en amont dans la séquence, là où les dunites sont présentes.

Mineralogical and geochemical studies of Cretaceous segments of Argille Varicolori and Flysch Rosso successions from the southern Apennines allow their provenance and history to be evaluated.

The occurrence of detrital kaolinite and fine-grained Fe-oxyhydroxides, the strong depletion of Na2O, K2O and CaO, and the enrichment in the transition elements document severe alteration in the source areas. Nevertheless, mineralogical and geochemical features able to discriminate the shale families are still preserved. The presence/absence of rock fragments derived from a ‘crystalline’ source, the significant chemical differences as well as the characteristics of clay minerals, discriminate the studied shales. The absence of indications suggestive of mixing of the detrital components favour the hypothesis that the two shales were deposited in distinct basins which probably received contributions from continent-ocean convergent areas (Argille Varicolori) and from more stable areas (Flysch Rosso).

Desautelsite, a Mg(II)Mn(III) hydroxy carbonate first described in 1979 and represented by the general formula Mg(8−x)Mn(III)x(OH)16(CO3)x/2 (in which 2 < x < 2·67), has been synthesized under controlled pH conditions (induced hydrolysis) and coprecipitation techniques. In the pH-stat syntheses, the desautelsite is formed by aerial oxidation of MnCO3 in 0·05–0·15 m Mg(NO3)2 solutions at ∼pH 9 and temperatures of 35°C where, in the absence of Mg, manganite would normally form. The synthesis product from this technique is generally more crystalline than that formed by the coprecipitation method. Composition, particle shape and aggregation may be controlled through variations of the Mg concentration, pH, aeration rate or temperature. Indirect evidence suggests Mn to be present in the +3 oxidation state in the desautelsite.

Extensive drying of smectites can cause the interlayer space to break down (collapse). This can affect the properties of bentonites as geotechnical barriers of HLRW (highly radioactive waste) repositories. If and to what extent the collapse occurs depends strongly on the type of interlayer cation. In particular K is known to lead to ready dehydration, in contrast to Ca and Mg. In the present study, various bentonites and one illite/smectite clay were dried/heated at 90ºC for 1.5 a and in a different experiment at 120ºC for 4.5 a and investigated with respect to mineralogical and geochemical changes of the smectite.

Smectite alteration after extensive drying was restricted to changes of the exchangeable cations. The CEC decreased by 9% (90ºC test) and 14% (120ºC test). A slight decrease of exchangeable Na+ was observed following the 90ºC test. No significant further decrease was observed after the 120ºC test. In contrast, the larger cation exchange capacity (CEC) decrease after the 120ºC test could be explained by increased Ca/Mg fixation. A possible mechanism for the observations is presented.

Continuous nodular limestone beds in north-west European shale sequences developed during early diagenesis via anaerobic, bacterial catabolysis of organic matter which yielded both carbonate and sulphide. The high carbonate content of the nodular limestones (50–90%) demonstrates that they developed in the upper tens of metres of the sediment column. In addition, each of the nodular limestones displays a centrifugal decrease in carbonate, indicating that growth was synchronous with compaction of the host ooze. The chemistry of the carbonate changed with time, becoming more rich in magnesium and iron and reflecting a progressive change in the porewater chemistry from its initially marine composition. The earliest precipitate was calcite containing < 1 mole% MgO; later precipitates contained several percent MgO and ultimately dolomite was precipitated. Similarly, iron content of the carbonate increased as precipitation continued and sulphate reduction, and thus pyrite production, declined. The early diagenetic cementation of many marine sandstones followed a pattern similar to that of nodular limestones and much of the carbonate was also derived from organic matter via bacterial oxidation. Thus, early diagenetic bacterial oxidation of organic matter may not only reduce the source potential of shales but also reduce the reservoir potential of associated sandstones, or those more distant which lie along compactional-fluid pathways.

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.

The adsorption of acrylonitrile (AN) monomer vapour in the interlamellar space of smectites exchanged with different cations (Na or Y or hexylammonium) was monitored and used to yield macromolecular layers. Polymerization in the presence or absence of a free-radical initiator was obtained by heating at 100°C for 72 h. Cyclization can already be obtained at this stage, and is completed by heating the polyacrylonitrile (PAN)-complexes at 220°C for 48 h.

Intercalation of an ammonium amphiphile having an azobenzene chromophore, 4-dodecyloxy-4 ‘-(trimethylammoniopentyloxy)azobenzene and 4-(ω-trimethylammoniodecyloxy) -p’- (octyloxy)azobenzene bromide, into the layered silicate magadiite (ideal formula Na2Si14O29·nH2O) was carried out by a conventional ion exchange reaction in an aqueous medium. An intercalation compound with the ideal formula {(C12AzoC5N+)1.4H0.6·Si14O29·nH2O} was obtained. Based on the change in the basal spacing (to 4.21 nm) after the reaction and the visible absorption spectrum of the product, the intercalated azo dyes appear to form a J-aggregate in the interlayer space of magadiite. Under UV and visible light irradiation, the intercalated azo chromophore exhibited reversible transcis isomerization in the interlayer space of magadiite. This is the first successful report of photochemical reactions of guest species in the interlayer space of magadiite.

Dans les encroûtements calcaires sous galet de la Plaine Poitevine, nous avons mis en évidence, par des méthodes microscopiques, une séquence minéralogique évolutive de la calcite. Par spectrométrie d'absorption infrarouge des éléments de la séquence prélevés en hiver, nous caractérisons, à côté de la calcite (bande à 1420 cm−1), du carbonate amorphe hydraté (bandes à 1405 et 1485 cm−1 et un autre type de calcite (bande à 1445 cm−1). Les résultats d'essais de laboratoire nous permettent d'envisager une évolution du carbonate amorphe vers la calcite par l'intermédiaire d'une phase calcitique transitoire, et d'aragonite toujours en faible proportion. La formation de ces carbonates est liée aux conditions bio-physico-chimiques du sol.

Iron-rich dioctahedral 2:1 clays were sampled in metalliferous sediments from Atlantis II Deep (Red Sea), and studied by XRD, TEM, FTIR and Mössbauer spectroscopy. One sample with the structural formula (Si3·94Fe3+0·06)(Fe3+1·90Mg0·10)K0·1(Mg, Ca)0·03 is closer to the theoretical end-member ferripyrophyllite Si4Fe3+2O10(OH)2 than any other Fe-rich clay previously described. Other samples appear as mixed-layered clays: ferripyrophyllite-hydroferripyrophyllite or hydroferripyrophyllite-celadonite.