In soils and other weathering environments, hematite and goethite are usually formed in the presence of clay minerals. Two-line ferrihydrite was aged in the presence of six different clay minerals in aqueous suspension at 25°C and pH 4, 5, 6 and 7 for 16 years. The transformation into hematite/goethite mixtures was complete in the systems with gibbsite, kaolinite, illite and smectite, but incomplete in those with soil smectite and allophane. Soil smectite and allophane, as well as increasing pH, favoured hematite over goethite. The grainy and multi-domainic hematite crystals in the allophane system contained Si and Al (EDX) and showed a Si – O vibration at ∼920 cm– 1 (FTIR). The unit-cell contraction due to structural Al was counteracted by structural OH, which was removed at 200°C. Heating also increased the magnetic hyperfine field at RT by 1.2 – 1.6 T. Hematite crystals with irregular shape and grainy interior have also been observed in soils.

Infrared spectroscopy in the mid-IR region was used to follow the structural changes occurring in five Li-saturated dioctahedral smectites upon heating. The smectites included three montmorillonites, an Fe-beidellite and a ferruginous smectite. Fixation of Li+ ions in the structure even upon heating at 120°C caused the appearance of an AlMgLiOH-stretching band near 3670 cm–1 in the spectra of all three montmorillonites. This band confirmed the presence of Li(I) in the previously vacant octahedral positions in montmorillonites. No similar band was observed in the spectra of ferruginous heated smectites with prevailing tetrahedral charge. A gradual upward frequency shift and decrease in intensity of the AlAlOH-bending band showed that Li(I) present in the hexagonal cavities causes pronouncedperturbation of this OH-bending mode. The Li(I) present in the octahedral sheets causes small perturbations of the OH-bending mode near 850 cm–1 and activation of a new OH-bending mode near 803 cm–1. Reversible changes in the positions of the stretching Si–O and bending OH bands in the spectra of Fe-beidellite and a ferruginous smectite proved that Li was present in these minerals primarily in the hexagonal holes of the tetrahedral sheets.

The mineralogy of the Neogene lacustrine facies of Pelitçik basin was investigated for the purpose of deriving the palaeoenvironmental parameters of this intervolcanic basin. The laboratory studies indicate that dolomite and K-feldspar are the major non-clay minerals in the study area, where plagioclase, analcime, fibrous zeolite and quartz are the minor constituents. Dolomites are found to be non-stoichiometric in chemistry. The clay fraction of the lacustrine facies is composed mainly of dioctahedral smectites. The smectites are rich in Al-Fe indicating a detrital origin. Illite comprises a minor contribution to the clay fraction, where chlorite and kaolinite are found in trace amounts. Based on dolomite stoichiometry and the mineral paragenesis found in the Pelitçik basin, the depositional conditions are suggested to have been a shallow, quiet, perennial lacustrine environment with fresh to slightly saline and slightly alkaline water chemistry. In addition, based on geological and mineralogical constraints, it is suggested that the water chemistry fluctuated during the deposition of the Pazar formation and the lake began its evolution with a hydrologically closed system and completed its evolution with a hydrologically open system.

The polarization conductivity, σ'(ω) of a Ca-montmorillonite has been determined by complex impedance spectroscopy. The technique of thermally-stimulated currents (TSC) leads to the determination of the different relaxation parameters, such as the distribution function of the different relaxation processes. The results demonstrated the coherence of the two approaches, and confirmed that the conducting phenomenon is due to the hopping of charge carriers between localized sites. The energy corresponding to the hopping process is evaluated using two different methods of analysis of the TSC signal. The values obtained are compared to those observed on a Na-montmorillonite.

Indurated volcanic soils (tepetates) of the Mexican Altiplano display thick columnar horizons, hard laminar horizons, and grey mottles at depth. X-ray diffraction (XRD) studies show a relative enrichment in cristobalite vs. halloysite in the indurated plates of the laminar horizons and in the clay fraction of the mottles. Transmission electron microscopy (TEM) and high-resolution TEM (HRTEM) studies of these two soil components have shown that they are composed of small tubes of halloysite in which numerous globular grains ∼1 μm in diameter are embedded. Based on the relative abundance of cristobalite in pedological features and on the spatial relations between successive mineral phases, we interpret the cristobalite as a transformation of halloysite with a transitional amorphous phase. In the globular grains, large platy 1:1 clay minerals undergo a progressive transformation into platy particles of opal-A and opal-C. These are in turn transformed into cristobalite without further major change in their shape and appearance, except for a higher electron density than opal and clay.

Diffuse reflectance spectra in the near-infrared region are presented for Li-saturated smectites heated up to 200°C. The smectites included three montmorillonites, an Fe-beidellite and a ferruginous smectite. Unheated samples showed a complex band near 7060 cm-1 assigned to the first overtone of the OH-stretching mode of structural hydroxyl groups and bound H2O. The OH combination bands appeared in the 4600-4300 cm-1 region. Spectra of heated montmorillonites showed an upward shift and splitting of the OH-overtone band into two components near 7170 and 7110 cm-1. The presence of a band near 7170 cm-1, assigned to the overtone of the AlMgLiOH-stretching vibration, implied that local trioctahedral domains were created upon Li(I) fixation in the previously vacant octahedral positions of montmorillonites. The OH combination bands were shifted to higher frequencies and a new band appeared near 4472 cm-1 in the spectra of montmorillonites heated to temperatures in excess of 130°C. No features indicating Li(I) in the structure of Fe-beidellite or ferruginous smectite were observed in the NIR spectra.

Montmorillonite-water-cation systems were characterized using high-frequency impedance spectroscopy by studying the influence of the solid concentration and the nature of the exchangeable cation (Na+, K+, Ca2+) on the dielectric characteristics of the dispersions. A new method is proposed to calculate the relaxation frequency (fr) and the dispersion factor (α) from a limited number of impedance measurements. By comparison with rheology, microscopy, X-ray diffraction and immersion calorimetry results, it is shown that impedance spectroscopy is a very powerful technique which yields structural information on a complex system. For Na-montmorillonite, two transitions are observed at 2.5% and 3.6% in solids. The cation mobility and the number of connections between particles are described by fr and α, respectively. The two transitions can then be attributed to the formation of the gel and to the reduction of the macroporosity within the gel, respectively. For Ca-montmorillonite, thick layer-stacks form at the lowest concentrations, and connections between these stacks are observed at 9% in solids, in good aggrement with rheological measurements. The K-montmorillonite displays progressive thickening of the tactoids, and no formation of a unique connected network, as revealed by the smooth evolution of fr and α.

Griffithite is a trioctahedral smectite with dioctahedral domains, found in the <2 μm fraction of weathered basic rock from Griffith Park, California, USA. Crystalline admixtures (albite, calcite, quartz and maghemite) are concentrated in the 0.2 – 2 μm fraction, while the <0.06 μm fraction contains only trace amounts of other minerals. Griffithite is primarily an Fe–rich saponite with negative charge located in the tetrahedral sheets. The octahedral occupancy is ∼91%, and ∼26% of the octahedra contain trivalent atoms imparting a net positive charge to the octahedral sheet. Medium levels of Fe(III) reduction in griffithite, up to 60% of total Fe, can be achieved by adding solid sodium dithionite to clay dispersions in a citrate–bicarbonate buffer. By contrast >90% reduction of Fe(III) to Fe(II) is achieved in nontronites using the same method. The lower reducibility of Fe(III) in griffithite relative to nontronites may be due to structural differences between griffithite and nontronites, such as a more negative tetrahedral charge and a positive octahedral charge.

Celadonite and glauconite samples heated at different temperatures were studied by X-ray and electron diffraction. For dioctahedral micas the in-plane component of the translation between layers (ccosβ/a), which is strongly dependent on the position of the vacant octahedral site, significantly decreases at temperatures greater than the temperature of maximum dehydroxylation. The simulation of XRD patterns from different structural models reveals the actual crystal structure of dehydroxylated samples as well as the dynamics of the structural transformations. In the nonheated state the samples consist of tv (trans-vacant) 2:1 layers. During dehydroxylation, cations migrate from cis- into trans-octahedra and have 5-fold coordination. In the averaged unit-cell the ‘residual’ anions formed after the dehydroxylation reaction occupy the former OH sites with probability equal to 0.5. The migration of octahedral cations is accompanied by the transformation of the C-centred layer unit-cells into primitive ones. In contrast to Fe, Al and Mg cations have a greater ability to migrate.

Ammoniation of montmorillonites pillared with polyhydroxo-complexes of Al was performed in flow conditions at 773–1073 K and monitored by IR spectroscopy. Interaction of the clay with ammonia revealed exchange of terminal and bridging -OH groups by NH2-, NH- and N- species depending on the reaction temperature. Amination begins at 773 K while formation of NH groups starts at 873 K. Transformation of NH- into N-species occurs at 973 K. A mechanism for the ammoniation reaction is proposed and the series of the relative reactivity of OH groups was established: Si–OH > Mg–OH–Mg > Al–OH–Mg > Al–OH–Al. This series was rationalized in terms of accessibility of the OH groups.

The interactions between glycine and two Na-, Ca- and Cu-exchanged smectites with different layer-charge location were studied. The sorption of glycine depends on the nature of the interlayer cations (Ca < Na < Cu), and on the type of smectite. Sequential extraction procedures were carried out in order to test the possibility of removing metals and/or glycine from the smectite interlayer. By the end of the treatments, the release of the amino acid from the substrates, with the exception of Cu-rich smectite, was virtually complete. The thermal curves of glycine-smectites confirm the stronger bonding of the amino acid with Cu-exchanged samples, and FTIR spectra indicate that glycine is mainly sorbed in the zwitterionic form. The data obtained suggest that in investigations into mechanisms of the binding of metals by minerals and their subsequent mobilization, amino acids merit close attention.

The changes of adsorption properties of uncalcined Al-pillared montmorillonite were studied. A soda-activated bentonite from Slovakia was reacted with polymeric hydroxoaluminium salt solutions. During storagein air at room temperature for three years, the basal spacing decreased by 0.15–0.2 nm; the specific surface area was reduced by 80% and the total pore volume by 40–60%. Adsorption experiments from ethanol-cyclohexane mixtures revealed the decreasing adsorption capacity and the increasing hydrophobicity. The changing surface character was also evident in the decrease in enthalpy of immersion in ethanol from 65.3 J/g to 8.3 J/g (sample B) and from 37.8 J/g to 5.2 J/g (sample C). The alteration probably arises from gradual formation of gibbsite-like interlayers and the redistribution of charges.

Anaerobic bacteria were identified in live drilling muds and cores from nine different North Sea and Irish Basin oilfields, varying in depth from 3500 to 15000 ft, and at temperatures up to 150°C. The anaerobic bacteria may be introduced into the reservoir during drilling operations or injection of water, but in many cases the bacteria are indigenous to the oilfield reservoirs. Confirmation of the indigenous anaerobic bacteria was made using molecular biology techniques (16S rDNA sequence analysis), comparing microbial populations present in the blank drilling mud as supplied to wellsite, in the live drilling mud taken during coring, and in the live core. The role of anaerobic bacteria in oilfield diagenesis is not fully understood, though pyrite precipitation, and exopolymer and H2S gas production were noted in this study, up to temperatures of 95°C.

Fourth-order relative sea level changes may have a significant impact upon burial diagenesis and reservoir quality through their effect upon surface and subsurface temperature. Relative sea level changes can induce sediment surface temperature changes of <20°C when the sediment surface changes from being close to or beneath the thermocline to being sub-aerially exposed. Such sea level changes typically occur on a timescale of half a million years. Approximately one quarter to one third of the magnitude of these temperature fluctuations will be propagated to 2500 m in the subsurface. Shorter timescale fluctuations of similar magnitude, resulting from glaciation, will not be significant below ~1000 m burial as there is not enough time to effect the change before the next surface temperature cycle occurs. Diagenesis is strongly controlled by temperature through its impact on the driving force and rate of geochemical processes. Burial diagenesis and cementation may thus be episodic on timescales associated with sequence stratigraphic events occurring on the surface, thousands of metres above the zone where diagenesis is occurring.

The thermal energy necessary for the removal of molecular water from Li+-, Na+-, Cs+-, Mg2+-, Ca2+-, Ba2+-, Alx(OH)yz+- and La3+-homoionic montmorillonite powders was determined by thermogravimetric analysis under atmospheric pressure. The weight loss curves and their derivatives exhibit one or several features related to the various populations of water molecules. The activation energy for water removal, which is the sum of the adsorption energy and the activation energy for diffusion, was calculated in each case using a simple first-order differentiation method. The results allow the physisorbed water and the water coordinated to the cations to be clearly separated. For the later population and with the exception of the Na-clay, a good correlation was found between the temperatures and activation energies for water removal and the polarizing power of the cations. Comparison with the results of mechanical tests performed on similar samples suggests that the creep of smectite clays is not controlled by mobility of the individual water molecules but by the mobility of the interlayer cations surrounded by their hydration shell.

Thermal analysis (DTA-TG-DTG), X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, nitrogen adsorption and mercury intrusion porosimetry techniques were used to assess the structural changes induced upon heating of two hydrotalcite-phenol (trichloro- and trinitrophenol, HT-TCP and HT-TNP) complexes, and the results were compared with those obtained for the original hydrotalcite (HT) sample. The DTA revealed thermal effects that depended on the nature of the interlayer ion in the complexes. The total weight loss (TG-DTA) increased from 37% for the original HT to 40% for HT-TCP and 77% HT-TNP, as the amount of phenol increased. The XRD and FTIR spectroscopy showed that the calcination product (550°C) of the HT-phenol complexes was indistinguishable from that formed from the original HT. Since HT-phenol complexes were prepared by phenol adsorption on calcined HT, our results confirm the recyclability of HT-like compounds as sorbents for phenols.

Layer silicates are generally assumed to be insulators, but electron transport may take place in nm thick particles. A combined scanning tunnelling-atomic force (STM-AFM) instrument using a conducting AFM tip has been constructed to investigate this conduction. Some layer silicates, e.g. micas (muscovite and biotite), are in fact semiconductors, conduction taking place through free electrons in the tetrahedral sheet (n-type semiconductivity) and probably through polaron hopping in the octahedral sheet. This implies that these minerals can be investigated by STM. Furthermore, micas show negative differential resistance (decreasing current with increasing voltage) at 2 – 5 V.

The quantitative interpretation of the reflection intensities of the SAED patterns of glauconites reveals the mechanism of migration of the octahedral sheet cations during heating up to 750°C. It confirms that Mg2+ has a greater ability than Fe3+ to migrate from cis-to trans-sites, as previously found by means of XRD pattern modelling. For samples heated to 650°C, the two formerly vacant trans-sites in the base-centred unit-cell become occupied, but differently, which leads to a primitive unit-cell, and the cis-sites remain filled almost entirely by Fe3+ only. The cation migration occurs through the nearest shared edges in the [010] and [310] directions. The samples heated to 750°C reveal a base-centred super-cell with A = 3a and B = b. All Mg cations leave the cis-sites to occupy completely four of the six available trans-sites of the super-cell. Migration also occurs through the shared edges in the [010] and [310] directions. The primitive unit-cell is not an intermediate step in the migration process leading to the super-cell. The existence of additional satellites in the SAED patterns of some crystals heated to 750°C corresponds to the existence of antiphase domains with a 3b/2 width and an antiphase shift of a/2.