An ab initio determination of the structure of sepiolite after acid treatment (HCl 0.5 N for 24 h) was carried out using X-ray powder diffraction data. After acid treatment, the sections normal to the a and c axes presented discontinuities, ∼2.25 Å wide, parallel to the (010) plane, with no electronic density maxima, thus suggesting that adjacent planes are joined by van der Waals-like residual links. Partial dissolution was detected on both octahedral and tetrahedral sheets, beginning by breaking the ribbons not along the edges, but in the centre, thus creating a 5.20 x 66.79 Å tunnel along the a axis. By interrupting the tetrahedral sheet, this mechanism changes the phyllosilicate-like nature of the sepiolite to an inosilicate-like structure.

Carbonate-bearing ceramic bodies are frequently used in the manufacture of bricks, roofing tiles, wall and floor tiles, pottery and tableware. During the firing of these bodies, clinopyroxene is usually formed in very small crystals, 1-5 µm in diameter or less. In the literature this phase is generally referred to as diopside, but no quantitative data are available. In order to chemically characterize these ‘ceramic’ pyroxenes, nine industrial products were analysed by XRF and XRD (bulk sample) and SEM-EDS (fracture surface). Quantitative ZAF analyses of pyroxene crystals showed a certain chemical variability: SiO2 35-50%, Al2O3 9-20%, Fe2O3 1-15%, MgO 3-14%, and CaO 16-25%. Sodium, K and Ti are always <1%, while ferrous iron is always <0.2% in the bulk sample. Overall, ‘ceramic’ clinopyroxenes present wide chemical analogies with ‘fassaite’, e.g. the abundance of aluminium and ferric iron, and the excess ofwollastonite molecules with respect to the diopside-hedenbergite series.

The procedure used for fractionation of soils, rocks, and sedimentary materials involves separation of the clay (less than 2 microns) and silt (2 to 62 microns) by centrifugation. Randomly oriented powders and oriented aggregates of these materials are examined using X-ray diffraction as the principal method of analysis.

The extent of diagenesis in Lower Jurassic shoreline sandstones of the Beatrice oilfield was controlled primarily by their detrital clay content. Sandstones rich in detrital clay had low depositional permeabilities; these show preservation of detrital feldspars to the present day and have no extensive diagenetic quartz overgrowths. Sandstones poor in detrital clay had high permeabilities and show large quartz overgrowths as part of a normal sub-arkosic diagenetic sequence. Such quartz occurs preferentially below, but not above, impermeable mudstones. These low- and high-permeability features suggest that pore-fluid flow was important during diagenesis. Fluid inclusions trapped in diagenetic quartz overgrowths formed between 68° and 94°C. This silica was probably supplied in solution from the temperature-driven illitization of smectitic clays surrounding these sandstones deeper in the basin. Fluid volumes from clay dewatering, from mechanical compaction, or from influx of overlying seawater were too small to transport diagenetic silica volumes. Silica-rich fluids were probably transported up-dip by convective cells within the sandstones and authigenic quartz precipitated as these fluids cooled. This episode of quartz diagenesis could have been completed within 1·6 × 106 yr if fluid velocities were 3·1 m/yr. Similar convective fluid flows could have transported the fluids responsible for secondary porosity development and the hydrocarbons expelled from mudstones later in the basin burial history.

A quantification technique useful in analysis of clay-rich deposits containing sepiolite and/or palygorskite has been developed by combining diffractometric and chemical data and represents a considerable improvement on classic quantification based on X-ray diffraction. The required data are: intensity ratios between certain diffraction peaks of calcite-dolomite and sepiolite-palygorskite-smectites, and also the CaO, MgO, K2O, Al2O3 and SiO2 contents. The validity of this method was tested by analysis of artificial mixtures of pure phases of the minerals found in such deposits.

Adsorption isotherms have been determined for mixed Ca-Na montmorillonites, with various values of f, the proportion of (½ Ca) to Na (Fig. 1). These are coincident from f=0 to f=0·3, and then diverge. This is interpreted as meaning that “demixing” occurs at f=0·3, a system being formed in which some interlayer spaces are occupied mainly by Ca, others mainly by Na.

X-ray analysis confirms this view. Plots of the water uptake against f, for various relative humidities (Figs. 2–5) show that, for R. H.'s lower than 75%, the demixing is incomplete.

The observations can be explained by the occurrence of a limited number of doubly-charged sites (by Al-for-Si exchange spots being accidentally contiguous). For the montmorillonite used, the statistical probability of occurrence of such sites is found to be 0·2 if the layers have symmetry C-2/m and 0·33 for C-2, so that the observations are in favour of the latter symmetry.

Heating experiments were carried out with ferrihydrite, in the presence of organics, to gain more insight into the intermediate formation of a ferrimagnetic cubic phase often observed in soils as the result of fire. Without an organic reductant, no intermediate cubic phase was formed when ferrihydrite was transformed into hematite, regardless of whether the ferrihydrite DTA curve showed one or two exothermic peaks. Addition of glucose or charcoal as reductant caused the initial formation of a cubic magnetite and/or magnetite/maghemite phase in samples heated above 300°C in both air and N2 atmospheres. Ferrihydrite reduction, as determined by increasing cubic unit-cell edge lengths between 0.832 and 0.840 nm, increased with reductant concentration and heating time, providing excess reductant remained. Following consumption of the reductant, FeII may be partially or completely reoxidized, forming maghemite and then hematite. The occurrence of maghemite, but not of magnetite, in soils where forest fires have occurred suggests that sufficient oxygen was available, while temperatures remained elevated, to oxidize magnetite to maghemite.

Powder X-ray diffraction (XRD) curves were calculated for the different structural models so far proposed for feroxyhite (δFeOOH). The influence on XRD features of different structural parameters, including site occupancy of Fe atoms, atomic coordinates, content and distribution of stacking faults, and dimension of coherent scattering domains, were considered. On the basis of agreement between experimental and simulated curves it is shown that δFeOOH is a mixture of feroxyhite proper and ultradispersed hematite in the 9 : 1 volume ratio. Feroxyhite proper consists of hexagonal close packing of anions containing 5% stacking faults. Iron atoms occupy only octahedral sites and are distributed in such a way that face-sharing filled octahedral pairs regularly alternate with vacant octahedral pairs along the c axis. This distribution of Fe atoms is quite similar to that established by Patrat et al. (1983), but in each pair, Fe atoms are displaced by the same value of 0.3 Å in opposite directions away from the centre of their octahedron. Nearest Fe-Fe distances calculated for the model proposed (2.88, 3.01, 3-39 and 3-73 Å) practically coincide with those found by EXAFS spectroscopy for the same sample (2-91, 3.04, 3.41 and 3.7-3.8 Å).

The adsorption of Rhodamine 6G in aqueous suspension on Laponite B was investigated by electronic absorption and emission spectroscopies. Fluorescence spectra suggest that the monomer is adsorbed at two different surfaces, the external and the internal. A monomer is intercalated in the interlamellar space at low loading of dye (<3% CEC), whereas the monomeric state of the dye seems to be at the solid-aqueous interface in suspensions with high loading (>12% CEC). The metachromatic effect observed in the absorption spectra, for the loading interval between 1% and 15% CEC of Laponite B, is attributed to the dimerization of the dye, which seems, from X-ray diffraction measurements, to be formed at the clay interlayer. The formation constant and the absorption spectrum of the aggregate were obtained and the dimer was structurally characterized by applying the Exciton Theory. The observed fluorescence quenching for loadings lower than 15% CEC is attributed to energy transfer from monomer to the dimer, which obeys the Perrin model.

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.

The stable isotopic compositions of diagenetic minerals can provide valuable constraints on the sources, precipitation temperatures and relative timing of cements in reservoir rocks. This type of information is essential when trying to understand and predict the distribution of cements in the subsurface, and their impact on reservoir quality. Conventional isotope methods contribute to answers to many diagenetic problems, but where core or time are scarce, or where good mineral separation is unobtainable, laser-based stable isotope methods offer several advantages. These include the ability to analyse carbonates, sulphides and anhydrite in situ with 50–100 μm resolution, simple and clear sample and analysis viewing optics, savings on sample preparation time and greatly reduced sample size requirements.

Diagenetic silicates such as quartz and clay cements cannot be analysed in situ by laser but, where in situ analysis of quartz δ18O is demanded, ion microprobe analysis can provide very high resolution (20–30 μm) capability with a precision of ±1%.

Seven samples from a chronosequence of soils developed in historically created polders on the Atlantic coast (Marais Poitevin, Vendée, France) were investigated in order to illustrate the rate of mineralogical change in a clay-dominated system. The oldest polder was constructed in 1665, the last one in 1912; thus the time span of soil evolution is from 80 to 330 years. All the samples had more than 50% clay (<2 μm). The most reactive, fine clay sub-fraction (<0.1 μm) was investigated in detail by X-ray diffraction and chemical analysis. The observed mineralogical changes with increasing age followed the schematic reaction:

smectite + mica = illite + mixed-layer minerals.

The progress of reaction in time appears to be non-linear. This reaction seems to occur in a chemically constant system, and the mineralogical change can be seen as a readjustment of species to a given chemical composition.

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.

Dry grinding of pyrophyllite (Hillsboro, USA) has been studied by X-ray diffraction (XRD), specific surface area measurements (BET) and scanning electron microscopy (SEM). At the beginning of the grinding process, some effects such as delamination, gliding and folding of the layers, and decrease in particle size were detected by SEM and XRD, resulting in a large increase in specific surface area, up to a maximum of ∼60 m2·g−1. Marked changes in the structure take place between 30 and 32 mins grinding. Longer grinding times increase the degree of disorder and SEM and specific surface area data suggest that aggregation occurs. XRD results indicate that some residual order persists in the degraded structure.

The evidence is reviewed for the various hypotheses put forward to explain the origin of the Chalk montmorillonite.

Recent X-ray investigation of the mineralogy of the acid-insoluble clay fractions (buffered 2 N acetic acid at pH 3; <2 µ e.s.d.) of the Lower Chalk of England sheds light on the origin of the montmorillonite. The relations between the qualitative and semi-quantitative mineralogy of the clay fractions and the facies and stratigraphy in this formation have been studied in detail. Montmorillonite, illite, kaolinite, chlorite, vermiculite, pyrophyllite, mixed-layer minerals, quartz, low-temperature cristobalite and apatite have been identified; their semi-quantitative distribution reveals that two main antipathetic assemblages are present, between which all gradations occur. The first is characterized by montmorillonite, illite, quartz and by montmorillonite/illite (M/I) values of 0·7 and above; and the second by illite, kaolinite, chlorite, vermiculite and by M/I values of below 0·2. The distribution of these assemblages or of any particular mineral does not show obvious relations to the facies or stratigraphy.

There is strong evidence that the second of these assemblages is of detrital origin, introduced into the Lower Chalk seas by currents flowing mainly from areas to the east and south-east of England. There is no evidence to suggest that the montmorillonite and the illite of the first assemblage are of detrital or volcanic origin, and their distribution in the Lower Chalk is best explained by their neoformation in the sediment on the sea floor by precipitation from the porewaters. By extrapolation it is thought that most of the Chalk montmorillonite of clay-grade is of neoformational origin. Some from the Campanian and younger Chalks may be detrital. Locally in N.W. Germany and possibly Poland minor amounts may have been derived from the decomposition of volcanic glass in the Chalk seas.

To provide fundamental knowledge for studying the relative content of vacant sites and exploring the mechanism of interaction between Pb2+ and birnessite, Fourier transform infrared spectroscopy (FTIR) of birnessites with different Mn average oxidation states (AOS) before and after Pb2+ adsorption were investigated. The number of absorption bands of FTIR spectra was determined by using the second derivatives of the original spectra. The band at 899–920 cm–1 was assigned to the bending vibration of -OH located at vacancies. The bands at 1059–1070, 1115–1124 and 1165–1171 cm–1 could be attributed to the vibrations of Mn(III)-OH in MnO6 layers, and the intensities of these bands increased with decreasing Mn AOS. The bands at 990 and 1023–1027 cm–1 were ascribed to the vibrations of Mn(III)-OH in the interlayers. Mn(III) in MnO6 layers partially migrated to interlayers during Pb2+ adsorption, which led to an increased intensity of the band at 990 cm–1. The band at 564–567cm–1 was assigned to the vibration of Mn-O located at vacancies. This band could split by coupling of vibrations due to Pb2+ and/or Mn2+ adsorbed at vacant sites. The large distance between the band at 610–626 cm–1 and that at 638–659 cm–1 might reflect small Mn(III) ions located in Mn(III)-rich rows.

The clay mineralogy and chemistry of a green lacustrine marl that has been pedogenically modified in the upper part was investigated in order to better understand the formation of low-temperature Fe-rich 10 Å clay. Twelve samples in a vertical sequence have been investigated using X-ray diffraction (XRD), chemical analysis, scanning electron microscopy (SEM) and laser particle size analysis. The clay assemblage has a range of overall illite-smectite (I-S) compositions (64–100%) resulting from several I-S phases that, for the sake of modelling, have been simplified to one to three I-S phases of increasing illitic content. Where the lacustrine marl has been pedogenically modified, the smectite-rich I-S is much reduced in abundance or absent and the 10 Å -rich component is both more abundant and more illitic. These assemblages are a consequence of illitization of detrital I-S in the lake and soil, and dissolution of other clays (kaolinite and chlorite) in the hypersaline lake. Interlayer K, octahedral Fe and octahedral + interlayer Mg increase with intensity of illitization (increase range 0.32–0.63, 0.68–1.67, 0.18–0.24 per O10(OH)2, respectively), first in the increasingly saline lake, and latterly as a result of wetting and drying in a gley soil. In the soil environment, reduction of Fe(III) to Fe(II) resulted in increased layer charge but, as by this stage very few smectite interlayers remained, this did not result in an equivalent increase in illite. Laser particle-size analysis, supported by SEM observation, shows the existence of a bimodal distribution of clay particle size (maxima at 0.2 and 1.5–1.8 μm) in which the finer fraction increases largely in the pedogenically affected samples, probably due to particle break-up caused by seasonal wetting and drying. This ‘dual action’ illitization, first in a hypersaline lake and latterly through wetting and drying, may be responsible for both the intensity of illitization and exceptionally high (for the Solent Group) Fe content of the authigenic illite. The chemical characteristics of the illitic I-S and the illite end-member correspond to glauconite. Hence, this is an example of onshore, non-pelletal glauconite formation.

Widespread chemical weathering of Tertiary alkaline volcanic rocks in the vicinity of Trabzon (NE Turkey) has led to the formation of well developed reddish-brown saprolite. These saprolites are dominated by kaolin minerals (predominantly kaolinite), with minor quantities of halloysite, pyrophyllite, chlorite, smectite, hematite and illite. Other common minerals are opal-CT, quartz and occasional feldspar, clinopyroxene, hematite and Fe-Mn-Ti oxides. The significant degree of fracturing and fragmentation of primary igneous minerals within the pyroclastic units, and subsequent penetration by reactive fluids, resulted in partial chloritization of clinopyroxene, albitization of plagioclase and precipitation of Fe-Mn-Ti-oxides within fractures and dissolution voids. Kaolin minerals occur as spongy fibrous meshes surrounding partly dissolved volcanic glass and devitrified sub-rounded grains that may be relict allophane. Field observations and mineralogical-chemical characteristics indicate that the alteration of the Tertiary volcanic units of the Black Sea region was controlled by chemical weathering during circulation of oxic meteoric or mixed meteoric and marine waters. Intense fracturing and fragmentation of the pyroclastic rocks resulted in the formation of clay minerals in the upper saprolite level under acidic and largely oxidizing conditions. Incongruent dissolution was associated with the leaching and downward transport of Si, Na, K and Ca and the concentration of Al. In such an environment, early precipitation of halloysite from allophane was probable, and it gradually transformed into kaolinite during aging and progressive weathering.

Hematite exists ubiquitously in soils and sediments, and is commonly aluminium (Al)-substituted. This study investigated systematically the effects of Al substitution on the visible diffuse reflectance spectrum (DRS) of hematite by using several sets of synthetic samples. We found that the position and amplitude of the characteristic absorption band of hematite (estimated from the first- and second-order derivative curves of the Kubelka-Munk remission function spectrum derived from the DRS) was significantly affected by the degree of Al substitution as well as by sample grain morphology. Therefore, there are ambiguities in quantifying the degree of Al substitution and the mass concentration of hematite using DRS. Nevertheless, if hematite forms under similar environmental conditions, it is possible to establish a transfer function between the DRS parameters and hematite concentration as discussed here for a Chinese loess-palaeosol sequence.