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.

Claystones of Kimmeridgian-Volgian-Ryazanian age are the main source rock for oil in the Central Trough, North Sea. During oil generation, illite layers form in illite-smectite (I-S) and the illitesmectites become short-range (IS) ordered and eventually long-range (ISII) ordered. The formation of illite layers involves dehydration and fixation of interlayer cations, K+ and NH4+. The content of soluble NH4 and K in core samples and the content of NH4 and K in I-S were determined, the NH4 by an isotope dilution method. In the Central Trough, soluble K+ decreases with depth, whereas soluble NH4+ increases with depth. From ∼3 km, the ratio NH4/K increases with depth, to an average of ∼0.5 at 4.4 km. In I-S, the ratio NH4/K shows a similar increase with depth. The NH4/K ratio increases significantly in I-S during ordering. It is concluded that NH4 fixation in I-S may be of general importance during burial diagenesis of oil source rocks.

The thermal behaviour of a ferrous doped kaolin has been studied by Mössbauer spectroscopy and electron paramagnetic resonance spectroscopy. From the observations it is concluded that the iron substitutes trioctahedrally as Fe2+ in the ‘gibbsite-like’ sheet in place of dioctahedral aluminium. The g = 2 EPR signal is shown to be associated with these ferrous ‘cells’ which appear to occur in clusters. It is suggested that these ferrous cells are trapped within the normal dioctahedral aluminium structure. Dehydroxylation of the ferrous iron cells takes place between 623 and 673 K leading to the formation of an iron-rich pyroxene and, by 723 K, a ferric oxide. At temperatures > 723 K the pyroxene itself oxidizes to a second ferric oxide. The EPR signal changes at 623 K and disappears at 723 K. The signal is attributed to a trapped hole induced by X-irradiation, located near a silicon atom on the boundary between normal dioctahedral cells and trioctahedral Fe2+ cells. It is possible to extend the model to explain some puzzling features concerning the g = 2 EPR signals reported by other authors and to propose other effects which might result from the presence of these cells.

L'évolution structurale et texturale ainsi que le comportement hydrique de deux montmorillonites-Ca (Wyoming et grecque) ont été éudiés par microscopic électronique à transmission (MET) et plus précisément par analyse de la diffusion aux petits angles des rayons X (DPAX). L'étude au MET a permis de montrer qu'à faible contrainte, le matériau est formé par un réseau de particules déformables délimitant des pores de grandes dimensions (~2 μm). L'étude en DPAX des mêmes systèmes soumis à une contrainte de type succion a montré que: 1. Lors de la première dessiceation il y a d'abord déformation du réseau sans regroupement des particules (p ⩽ 1 bar), puis regroupement des particules face-face pour former des particules de plus grande épalsseur (p > 1 bar). On montre aussi que l'eau est essentiellement extraite de la porosité interparticulaire. 2. Lors de la réhydratation, on met en évidence qu'après dessiccation le système perd une grande partie de son aptitude à, reprendre de l'eau et que cette perte est d'autant plus importante que le niveau de dessiccation préalable a été élevé. Ceci est dû au falt qu'une partie de la porosité est réduite fi des espaces ayant la propriété de l'espace interfoliaire.

We have determined the adsorption of RNA components (adenine, cytosine, uracil, ribose and phosphate) by Mg2+-exchanged montmorillonite. The isotherms for adenine, cytosine and uracil were of the C-type, the amount adsorbed increasing linearly with the equilibrium solute concentration. All three nucleic acid bases were apparently adsorbed by coordination to Mg2+ ions through a water bridge. Very little ribose was adsorbed by Mg-exchanged montmorillonite. The isotherm for phosphate was of the L-type. The plateau value of about 0.012 mmol g–1 indicated that phosphate adsorbed on the edge surface of montmorillonite. At comparable solute concentrations, adsorption decreased in the order adenine > cytosine > uracil. This observation reflects differences in basicity, size, and aqueous solubility among the three compounds.

The applicability of 27Al and 29Si magic-angle-spinning nuclear magnetic resonance (MASNMR) spectroscopy to the investigation of order-disorder in 1 : 1 dioctahedral layer-silicates was tested. 27Al and 29Si MASNMR showed the existence of short-range order in all these systems while XRD showed different degrees of long-range order-disorder. Spectra obtained on kaolinite and metakaolin clearly showed the transformation of some octahedral Al in kaolinite to tetrahedral coordination in metakaolin and also showed short-range Al and Si disorder in the latter. This suggests that structural re-arrangement on thermal treatment can be monitored by this technique. These results further suggest that MASNMR can detect short-range order, which is complimentary to the information that XRD provides regarding long-range order.

The distribution, profile morphology and mineralogy of deeply weathered gabbroic rocks in the basic igneous masses of Insch and Bogancloch, Aberdeenshire, have been studied. The saprolite is characterized by granular disintegration and spheroidal weathering with a relatively low degree of secondary mineral development. The upper part of the profile often shows evidence of mass movement and incorporation into overlying drift but below this zone the degree of alteration is generally uniform with depth. Feldspar and hornblende are largely unaffected, except by disintegration, but pyroxenes show varying degrees of weathering from the incipient development of amorphous iron oxides to replacement by reticulate networks or complete pseudomorphs of trioctahedral vermiculite. Biotite weathers to hydrobiotite and vermiculite, giving rise also, under certain conditions, to kaolinite-gibbsite vermiforms. The correspondence between occurrences of deep weathering and coarser textured biotite-bearing rocks can be related to the instability of this mineral. Consideration of the mineralogical changes found and the morphology of the profile of weathering suggest their formation under a warm, humid climatic regime, probably during the mid Tertiary times.

Amorphous hydroxides of Al, Fe, Mn, Mg, Zn, Co, Ni, etc., are capable of coprecipitating SiO2 even from very dilute (weathering) solutions. Silica minerals form only in those precipitates from solutions undersaturated with respect to amorphous silica (100 ppm SiO2 at 20°C). With higher SiO2 concentrations the precipitates remain amorphous. The size of the cations should allow 6-fold coordination and giving a brucite-like layer. Most suitably sized octahedral ions are Mg, Zn, Ni, Co and Fe2+ (size 0·78–0·82 Å), and chemically pure three- and two-layer clay minerals with these ions are easily synthesized. With a relatively high content of silica in solution (60 ppm SiO2 with 1–2·5 ppm metal) several smectite minerals could be synthesized. With a low content of silica in solution (5–20 ppm SiO2 and ca. 2 ppm metal) the serpentine minerals, could be synthesized.

It is possible to crystallize the difficult to form Al-clay minerals in a solid solution with these more easily synthesized clay minerals.

Clay minerals with the heavy metal ions of Ni, Co, Zn, and with Cu, Cr, etc., can be found in the weathering zone of Gossan and in the lateritic weathering crust of ultrabasic rocks.

The grain size of raw materials influences their behaviour during the technological process and affects many properties of building clay products. Over the last few years, brickworks have been technologically updated and grain size requirements have been modified to ensure good behaviour during shaping and drying. Therefore, the reference schemes used to assess the suitability of clays, such as the classic Winkler diagram, should be updated.

For this purpose, the grain-size distribution of 350 clays currently used in ~240 Italian plants was determined by X-ray monitoring of gravity sedimentation. Raw materials are basically represented by silty clays and clayey silts, while bodies present a narrower grain-size range. With reference to the Winkler diagram, most of the Italian bodies fall within the field of ‘thin-walled hollow bricks’, with no significant differentiation among the various product types.

In order to improve the grain-size characterization of bodies, a new classification scheme for Italian raw materials is proposed, based on three ranges: >10 µm, 2-10 µm and <2 µm, respectively. It allows distinction of specific grain-size features of bodies for (a) facing bricks; (b) roofing tiles; and (c) lightweight blocks, paving bricks and hollow slabs.

Vivianite [Fe3(PO4)2·8H2O] is easily oxidized in the presence of air. In this work, we studied the oxidation and incongruent dissolution of vivianite in a calcareous medium containing an anion-exchange resin (AER) that acted as a sink for phosphate. Freshly prepared vivianite suspensions with calcite sand and an AER membrane were oxidized and stirred by bubbling air or CO2-free O2. Experiments were finished when oxidation rate and P removal by the AER became slow, which was at 53 days (air system) or 28 days (CO2free O2 system). At these times, the respective values of the Fe(II)/total Fe ratio were 0.29 and 0.12, and the respective values of the atomic P/Fe ratio were 0.15 and 0.11. The final product of the oxidation was poorly crystalline lepidocrocite in the form of thin (1 ­ 5 nm), irregular lamellae that were soluble in acid oxalate. The unit-cell edge lengths of this lepidocrocite were a= 0.3117, b= 1.2572, and c= 0.3870, vs. a= 0.3071, b= 1.2520 and c= 0.3873 nm for the reference lepidocrocite. The lepidocrocite lamellae contained occluded P (P/Fe atomic ratio = 0.03 ­ 0.04). The results of this and a previous study made us hypothesize that this occluded P is structural and occupies tetrahedral sites adjacent to the empty octahedral sites in the sheets extending on ﹛010﹜.

A mineralogical and geochemical study of the Gabasa outcrop (Huesca, NE Spain) was undertaken. It consists of Early Oligocene marly and clayey fluvial and lacustrine (playa-lake) sediments. The phases detected were quartz, amorphous silica, calcite, dolomite, palygorskite, illite, interstratified illite-smectite, Al-smectite and Mg-smectite. The palygorskite expands with ethyleneglycol. Statistical analysis of the geochemical data shows that the rare earth elements and transition trace elements are basically associated with the detrital phyllosilicates, although a considerable amount of the latter is contained in the palygorskite (ΣREE = 60–70 ppm, Cr+Co+Ni+V+Zn+Cu = 120–150 ppm), in contrast to the normally low values for neoformed minerals. This fact, together with the significant presence of Al and Fe in the palygorskite, suggest genesis involving alteration by dissolution of the 2:1 structure of the illite and/or Al-smectite, followed by re-ordering in a fibrous structure.

Sandstones and mudstones of the Skagerrak Formation from the Danish Sub-basin have been studied to assess the origin of the clay minerals, their diagenesis and their transformation/ conversion temperatures (compared to modelled maximum burial temperatures). Detrital smectite and vermiculite occur only at shallow levels. Conversion of smectite into random S-I took place at >47°C and of random S-I into ordered I-S at >74°C. The omnipresent illite increases in amount with burial. The amount of authigenic kaolinite (kaolin) decreases with increasing temperature (>75°C), possibly due to the growth of chlorite. Random S-C is converted into ordered S-C between 70°C and 105°C and chlorite is most abundant at maximum burial temperatures (150°C). This investigation suggests that diagenesis of clay minerals begins at relatively low temperatures, and emphasizes the importance of the availability of necessary ions (K+, Mg2+, Fe2+) for the reactions, besides time and temperature, as controlling parameters.

An experimental study of the swelling anisotropy of the Callovo-Oxfordian argillaceous rock under hydration is presented. The investigation, which combines environmental scanning electron microscopy (ESEM) and digital image correlation techniques, has been carried out at the micrometric scale of the composite microstructure of the rock. Specimens were hydrated in the ESEM over a wide range of relative humidity and observations conducted on two planes: plane 1 parallel to the bedding plane, and plane 2 perpendicular to it. The observations reveal that the local swelling (which can be quantified at a local gauge length of about 5 μm) is strongly anisotropic in both planes. The global swelling, measured over areas of about 500 μm in width, is also clearly anisotropic in plane 2 (with major swelling direction normal to the bedding plane), but not in plane 1. The global isotropy in plane 1 arises from the uniform distribution of the orientation of anisotropic local strains, while the anisotropic swelling in plane 2 is due to a preferred local orientation.

An unusually complete sequence of pelitic rocks ranging from diagenetic to greenschist-facies metamorphic grades occurs in southern Sierra Espun˜a, Spain. Prograde and retrograde reactions have been studied by X-ray diffraction and electron microscopy (SEM, TEM and AEM). The prograde reaction series, with reactions facilitated by tectonic stress, includes: (1) R4 interstratified illite-smectite in the diagenetic Malaguide Complex that preserves the variable orientation of original smectite packets, and has 1Md polytypism; (2) chemically heterogeneous illite and Na-K dioctahedral white micas that progressively evolve toward chemical and textural equilibrium in the anchizonal Intermediate Units; and (3) thick, defect-free packets of phengite, paragonite and clinochlore which have a typical metamorphic texture, in the Alpujarride Complex. Two superimposed retrograde episodes produced: (a) sudoite at near-peak metamorphic conditions and (b) dioctahedral smectite during low-temperature retrograde diagenesis.

Clay mineral abundances in Mesozoic and Tertiary argillaceous strata from 15 exploration wells in the Inner and Outer Moray Firth, Viking Graben and East Shetland Basins of the northern North Sea have been determined in <0·2 µm fractions of cuttings samples. The clay assemblages of more deeply-buried samples cannot be unambiguously related to sedimentary input because of the diagenetic overprint which may account for much of the chlorite and related interstratified minerals. Other sediments, discussed on a regional basis and related to the geological history of the basins, are interpreted in terms of clay mineral provenance and control by climate, tectonic and volcanic activity. The distribution of illite-smectite can often be related to volcanic activity both in the Forties area during the M. Jurassic, and on the NE Atlantic continental margin during the U. Cretaceous-Early Tertiary which affected the North Sea more widely and left a prominent record in the Viking Graben and East Shetland Basin. Kaolinite associated with lignite-bearing sediments in the Outer Moray Firth Basin was probably derived by alteration of volcanic material in lagoonal or deltaic environments. Some U. Jurassic and L. Cretaceous sediments of the Inner Moray Basin are rich in illite-smectite, the origin of which is not clear.

Bulk mineralogy, clay fraction mineralogy and layer ratio in interstratified illite-smectite were studied in three Upper Miocene profiles, up to 200 m deep and representing very low sedimentation rates (∼80 mm/103 yr) with environments of sedimentation ranging from hypersaline (gypsum deposits) to brackish. No correlation was found between mineralogy and depth, or between mineralogy and chemical environment of deposition, despite the use of precise identification techniques. It is concluded that smectites and interstratified illite-smectites are stable in marine sediments until the elevated temperatures of deep diagenesis are reached.

The Athabasca oil sands deposit in Alberta contains ~5 x 109 m3 of bitumen accessible by surface mining. During bitumen separation from the mined ore, ultra-fine (<300 nm) aluminosilicate clays only a few layers thick (U/F) are mobilized and become dispersed in the process water. In this water containing dissolved salts from natural deposits, U/F are capable of forming thixotropic gels. The consequence of this is the production of large volumes of mature fine tailings (MFT) with a high water holding capacity. For mine planning purposes, the objective of predicting and possibly mitigating MFT formation requires an understanding of the colloidal behaviour of U/F particles in salt solutions. In this work, photon correlation spectroscopy and the deuterium NMR method are used to provide an insight into the U/F floc formation process. These results are correlated with conventional analysis of settling data.

Calcite cementation and extensive dissolution of feldspar with formation of authigenic kaolinite, quartz cement and secondary porosity are the main diagenetic processes in the deeply buried Hild Field. Mineralogical and isotopic analyses, reservoir pressure and depositional environment suggest that these diagenetic processes occurred prior to burial at a depth of 1·5–2 km. The timing of the diagenetic sequence suggests that feldspar dissolution is related to meteoric water flow. Calcite occurs as an early diagenetic iron-poor cement, and as two types of later diagenetic (<120°C) ferroan calcite cements. The ferroan calcites are mainly an in situ dissolution-reprecipitation product of the early diagenetic phase. Extensive local dissolution of calcite was important for forming secondary porosity which is closely associated with a prominent ‘gas chimney’ in the area studied. A high CO2 content in the natural gases of the reservoir suggests that the solvent was carbonic acid formed from CO2 generated during thermal maturation of organic matter. Calcite dissolution probably occurred between 70° and 100°C.

The thermal history of the Buntsandstein (Lower Triassic) sedimentary rocks that crop out in the Vosges Mountains, or are deeply buried in the Rhine Graben, was evaluated on the basis of a combined mineralogical, morphological, oxygen isotope and K-Ar-dating study of illite separates from five locations over a limited 120 km2 area. The results indicate a complex pre-rift evolution characterized by the following features: (1) in the northern Vosges, no record of diagenetic illite formation could be detected; (2) in the nearby Saverne rifting fracture-field, tectonic activity favoured the formation of faults in the crystalline basement ~210 Ma ago. This induced fluid migrations into the porous sandstone cover with illite precipitation occurring either repetitively over a period of ~25 Ma or as two separate events, the latter at ~185 Ma, affecting rocks to the east in the deeper part of the post-Eocene Upper Rhine Graben system; this latter stage of tectonic activity and fluid migration continued until 160 Ma, unless overprinted by another tectonic pulse at that time; (3) afterwards, the main tectonic activity moved to the Soultz-sous-Forêts area where two episodes could be identified at ~95 and 70 Ma by dating mineral crystallization; the latter illite age was also detected in more deeply buried Buntsandstein lithologies of the rift basin, west of Strasbourg, reflecting diverse crystallization under different physical and/or chemical conditions; (4) further illitization which at present is poorly constrained may have restarted ~55 My ago in the same deep part of the rift graben.

The youngest detected illitization age is clearly older than the main Miocene rifting episode of the Rhine Graben, suggesting that no illite crystallization occurred in the Buntsandstein sandstones during this tectonic event. This is explained by the fact that these rocks, as well as most of the underlying crystalline basement, were already sealed by fluid migration and mineralization during late Mesozoic rifting, and were therefore almost impermeable to the circulation of Tertiary fluids. The overall evolution of the region between the Vosges Mountains and the central Rhine Graben appears to be more complex than that of equivalent rock lithologies elsewhere in Western Europe. Several episodes identified here have been detected in other regions, but no single location exists which was affected by all events.

The expandability of K-depleted biotite and natural vermiculite was studied using transmission electron microscopy (TEM) and X-ray diffraction (XRD). K-depletion in layer-silicates was achieved by treating ultrathin sections with 0·1 m CaCl2 and BaCl2 solutions. The natural sample of biotite, which by XRD revealed no expandability on ethylene glycol or glycerol solvation, displayed 10–15% expanded layers when viewed by TEM after alkylammonium intercalation. The proportion of expanded layers increased after CaCl2 treatment. XRD of vermiculite samples revealed two sets of expandable interlayers after alkylammonium treatment, corresponding to two types of particles with different layer structures observed by TEM. Identification of vermiculite by TEM based on basal spacings is reliable with alkylammonium treatment. Intercalation of alkylammonium ions into the interlayers of vermiculite improved the degree of stacking order of the 2:1 layers.