Magnetite is a redox active Fe oxide common in most soil and sedimentary environments. In this study, we investigated magnetite transformations under extreme alkaline conditions (0.1–2 mol l–1 NaOH) similar to those found under high-level radioactive waste storage tanks at the Hanford site in the State of Washington, USA. X-ray diffraction (XRD) and transmission electron microscopy (TEM) results showed that magnetite was transformed into maghemite and goethite, and the XRD peak intensities for goethite increased with NaOH concentration. Goethite was presumably formed through reconstructive dissolution/crystallization reactions that can be written as: Fe3O4 + OH– + H2O = γ-Fe2O3 + Fe(OH)3–; 2Fe(OH)3– + 1/2O2 + 2H+ = 2α-FeOOH + 3H2O. Some of the newly formed maghemite may also redissolve to form goethite at greater NaOH concentrations.

The sorption and transformation of phenol, 2-methylphenol, 3-methylphenol, 2,6-dimethylphenol, 3,5-dimethylphenol, and 2,4,6-trimethylphenol, by homoionic Na-, H-, Ca-, Cu-, Al-, and Fe(III)-montmorillonite from both vapour and aqueous phases were examined by IR spectroscopy. All the phenols were sorbed by the clays but were modified to different degrees depending on the exchangeable cations and on the amount and type of alkyl substitution of the phenols. Sorption of 2,6-dimethylphenol from aqueous solution was irreversible, and the extent of sorption followed the order Fe- > Al- > Cu- > Ca-clay. Both transition and non-transition metal cations were effective in transforming the phenol sorbates and heating the clay/phenol complexes further enhanced transformation. The results are discussed in terms of the nature of the transformation products and the likely role of radical reactions in their formation.

Delta alumina is a transition form obtained during the conversion of boehmite to corundum. Alternative methods have been found for preparing this alumina in a well crystallised condition, enabling detailed X-ray powder data to be compiled. The X-ray data are accounted for by a large tetragonal structure cell of which the axial ratio is 1·47, or 3/2 times the axial ratio of the spinel-like pseudo-cell of Saalfeld. The lattice parameters are a0=7·96 Å and c0=11·70 Å. This large cell provides an integral number of vacancies, contrasting with the 2⅔ vacancies of the pseudo-cell, and allows the atomic arrangement to be ordered.

Fixed nitrogen in illite-smectites (I-S) has been measured for Miocene shales from a Gulf of Mexico oil well. Fixed N values for the <0.2 µm fraction increase with depth from 150 ppm (1000 m) to a maximum of 360 ppm (3841 m). This increase is coincident with illitization from 41% I in I-S to 75% I in I-S. Below 3841 m, fixed N values decrease to 190 ppm (4116 m) while I-S is maintained with a slight increase from 77 to 82%. The changes in fixed N with increasing illitization are consistent with the notion that illitization proceeds via both transformation and dissolution/ precipitation reaction mechanisms. The trend of decreasing fixed N in illitic I-S is compatible with surface-controlled crystal growth and Ostwald ripening mechanisms for illitization. The trend may also be linked to the timing of maximum NH] release from kerogen maturation during oil generation. The changing rate of NH+4 liberation from organic matter and multiple illitization reaction mechanisms can result in complex N geochemical cycling pathways throughout early diagenesis to metamorphism.

‘Epoxyphilic’ montmorillonites were prepared containing various functional groups which can react with one or both of the components in amine-cured epoxy formulations. The preparation involves the ion exchange of six organic ammonium compounds containing either carboxylic acid, anhydride, phenolic hydroxyl, alcoholic hydroxyl, amide or amine functional groups. X-ray diffraction, elemental analysis and FTIR studies confirm the intercalation of the organic cations to form epoxyphilic montmorillonites. The adsorption behaviour of the modified montmorillonites are compared with the unmodified montmorillonite in an epoxy resin before and after the curing process.

Photochemical isomerization of azobenzene intercalated in the hydrophobic, interlayer spaces of swelling fluor-tetrasilicic micas exchanged with dialkyldimethylammonium ions, with the alkyl chain length from 10 to 18, was investigated. Thin films of the organoammonium-mica-azobenzene intercalation compounds were obtained by depositing a suspension of the organoammonium-micas (prepared using a toluene/methanol solution of azobenzene) on quartz substrates. The intercalated azobenzene showed reversible photochromic reactions induced by UV and visible light irradiation. The fraction of the photochemically formed cis-isomer in the photostationary states decreased with a decrease in temperature. The observed change in the photochemical reactions is thought to reflect changes in the states of the dialkyldimethylammonium ions in the interlayer space of the swelling fluor-tetrasilicic mica.

The transformation of schwertmannite to goethite was studied by ageing one synthetic and five natural schwertmannites in water at room temperature. Additionally, one synthetic and two natural schwertmannites were kept at variable pH (2, 4, 6 and 8). After one year, only the synthetic sample and one natural schwertmannite had transformed to goethite. However, the oxalate solubility of Fe and trace elements in all the samples decreased, whereas the total Fe/S ratios and specific surface areas of all samples increased. Arsenic and organic matter appeared to suppress the schwertmannite-to-goethite phase transformation. At pH 2, synthetic schwertmannite fully-transformed to goethite, but at pH 4–6 only minor transformation occurred. Depending on pH, many trace elements were released into solution during ageing of the natural schwertmannites. In general, Co, Mn, Zn and Si were released to solution, whereas As was enriched in the remaining iron oxide fraction. Al was dissolved at pH <4.

The kaolinite from Albian sedimentary deposits (Escucha and Utrillas Formations) of the Iberian Range (Spain) have been investigated. This research has shown the presence of different types of kaolinites (detrital and diagenetic) along with micaceous phases in these deposits. Detrital kaolinites show anhedral morphology, low crystallinity and a degree of ordering as well as the presence of interstratified smectite layers. They constitute the matrix of the claystones and siltstones and were probably formed as a consequence of intense weathering processes in the source area during the warm period of the early Cretaceous. Diagenetic kaolinites have been recognized in the sandstones and siltstones, with kaolinite growing between ‘expanded’ mica flakes and vermiform and euhedral kaolinite forming the matrix. They have euhedral morphologies, high crystallinity and a high degree of ordering. They grew in situ as a response to incipient diagenesis by K-feldspar dissolution and/or organic acid-rich fluids derived from the maturation of organic matter in shales.

Fe oxides deposited in ditches draining a bog in the Harz Mountains, Northern Germany, consist essentially of a two-XRD line ferrihydrite that has a magnetic hyperfine field of only 46·5 T at 4·2 K. Pyrophosphate extraction led to an incomplete separation of this from organically-bound Fe, which was depleted in the residue and particularly enriched in the dialysate of the extract. Decomposition of humics with H2O2 led to a further depletion of organic Fe, but also increased the number of XRD lines of the ferrihydrite to six, and raised the hyperfine field by ∼1 T. These modifications are probably the result of an improved interparticle coherence.

Precise measurement of the content and the layer charge of illite and smectite is an important aspect of the mineralogical calibration of geophysical well logs and of the evaluation of mechanical and chemical properties of sedimentary rocks. Ate chnique for obtaining such measurements was developed during mineralogical studies of the Miocene clastic rocks from the Carpathian Foredeep. X-ray diffraction (XRD), chemical, cation exchange capacity (CEC), H2O sorption, and ethylene glycol monoethyl ether (EGME) sorption data were obtained for 65 samples of sandstones, shales and carbonates. The illite + smectite sum, involving all detected 2:1 minerals (smectite, illite-smectite, illite, glauconite and muscovite) was measured by XRD. The content of the illitic component was evaluated separately using % K2O and accounting for % K2O in K-feldspar. The content of the smectitic component was estimated from EGME retention using the reference data for a smectite standard, and from CEC assuming the smectitic layer charge of 0.41/O10(OH)2 (Środoń et al., in press). All these measurements produced very consistent results.

Polarizing microscope, electron microprobe and X-ray diffraction examination of minerals in a soil profile developed on a glauconite sand indicate that destabilization of glauconite can be a progressive process which appears to be the reverse of glauconitization. Glauconite in these soils appears to be destabilized into a mixed-layer glauconite-nontronite phase, which crystallizes as a plasma mineral. This material in turn is transformed into smectite+kaolinite+oxides. Loss of K and Fe is evident in whole rock as well as microprobe analyses of the samples. Thus glauconite can lose both Fe and K to aqueous solution during weathering, leaving aluminous clay minerals in the soil.

Emphasis is placed on the advantages of combining simultaneous thermal analysis methods (TG-DTA-DTG) with other complementary physico-chemical techniques for investigating synthesis and various properties of zeolites belonging to the pentasil family. TG and DTA give quantitative information on the dehydration and decomposition of organic guest molecules that interact with intermediate phases obtained during hydrothermal transformation of amorphous aluminosilicate gels into crystalline zeolites. In particular, weight losses (TG) and heat effects (DTA) due to the oxidative decomposition of tetrapropylammonium ions occluded in an intermediate phase have been related to the amount of zeolite ZSM-5 present. As a result, very small particles of this zeolite, amorphous to X-rays, could be detected in the early stages of the crystallization process. Isothermal sorption of small hydrocarbon molecules (n-hexane, 3-methyl-pentane) is used to probe the intracrystalline pore volume of zeolite ZSM-5. The total hydrocarbon uptake (TG) and the shape of the corresponding DTA peak are sensitive to steric modifications of the ZSM-5 channel system by various chemicals, while the sorption rates are better correlated to the extent of zeolite surface poisoning by boron or carbon. TG-DTA data provide an easy means of describing the filling and packing of n-hexane in ZSM-5 pore structure. Various steps characterizing isothermal competitive sorptions (nitrogen, ethylene, water) or catalytic conversions at high temperature (ethylene, methanol) over H-ZSM-5 are described. Finally, the progressive formation (removal) of carbonaceous residues resulting from these transformations are related to the actual rate of de-activation (re-activation) of a zeolitic material. In this respect, three different synthetic zeolites, namely mordenite, offretite and H-ZSM-5, which differ by their shape-selective properties and structure of their channel network, are investigated by TG.

High-resolution synchrotron X-ray diffraction recorded on a collection of palygorskites with different chemical compositions (obtained by analytical electron microscopy) permits unambiguous correlation of the crystallographic parameters a (or a sin β if a monoclinic phase is considered) with the nature of the octahedral sheet, i.e. with both the number of octahedral positions that are occupied and the type of octahedral cation. No significant changes in the lattice parameters b and c are observed. The unit cell modification consists essentially of an expansion in a as the number of cations with larger ionic radii (Mg2+ and Fe3+) predominates over smaller cations (Al3+). A linear dependency of a (or a sin β) on the chemical composition of the octahedral sheet was obtained that can be used for classifying palygorskite into compositional groups, using only conventional diffraction data, without the need for chemical analyses.

Structural features of very highly disordered 2:1 trioctahedral phyllosilicates from the Madrid Basin have been studied. Application of Fourier methods to XRD patterns shows that these materials consist of random kerolite-stevensite mixed-layered phases (R = 0) with 50–80% kerolite layers, and have a very small particle size with a mean of three unit-cells stacked in the c* direction. IR spectrum deconvolution in OH-stretching and librational modes seems to indicate five different types of water. Specific surface measurements (N2, BET) indicate anomalous high values (240–320 m2/g). These results suggest important catalytic and surface chemistry applications.

Three soil profiles developed on a serpentinite body (La Rochel'Abeille, near Limoges) show three stages of weathering. All soils contain iron-rich smectites and secondary chlorites. The latter are very silica-rich, more so than 14 Å chlorites from crystalline rocks. In the (B)1g horizon of the hydromorphic profile, these minerals seem to give a reaction of the type:

This reaction, typical of a closed system, appears to be operative in a soil profile which is certainly, in part, open to chemical migration. The chemistry of the weathered serpentinite and the chemical composition of newly formed minerals as well as those of the serpentinite are used to indicate the chemiographic relations of clay minerals formed in the weathering profiles.

This work describes the development of potential multi-element slow-release fertilizers obtained by mechanochemical activation of mixtures of kaolinite and ammonium or potassium monohydrogen phosphates. Preliminary results of talc amorphization have also been included. The methodology consists of milling the materials in a high-energy ball mill, where the influence of rotation and time of milling were investigated. The samples were characterized by XRD, FTIR, TGA/DTA, SEM and MAS-NMR. The experimental results explain the slow-release behaviour of the amorphous nanostructured materials in aqueous suspensions, especially the MASNMR spectra, which showed the changes in the chemical environment of the elements analysed. The materials displayed slow-release behaviour for phosphates probably because the aluminium ions in the mineral structure interact more thoroughly with phosphate than potassium or ammonium. Nevertheless, in general, all of the nutrients were released slowly.

Pore-lining chlorite is common in Rotliegend lake shoreline aeolian sandstones from northern Germany and preserves abnormally high primary intergranular porosity. In the north of the study area, in a basinward direction, the chlorites are Mg-rich while towards the south they become Fe-rich over a distance of about 15 km. All are unusually rich in Mn. Magnesium-rich examples tend to be more abundant than illite, while Fe-rich examples cover framework grains less continuously and are admixed with more abundant illite. Oxygen isotope analysis of 30 chlorites in the 2–6 µm fraction gave δ18O (SMOW) values of 7 to 12‰ (mean 9.8‰). These data show no obvious trend across the study area, nor in relation to changes in chlorite composition, or burial depth.

The honeycomb arrangement of chlorite crystals suggests chlorite formation via the sequence smectite-corrensite-chlorite. Chlorite distribution and the systematic changes in its composition suggest that formation of a precursor was related to lateral migration of Mg-rich fluids from basinal shales and/or evaporites during shallow burial. Interaction of these fluids with early formed oxyhydroxide coatings on the aeolian sand grains provided a source of Fe and the Mn. The isotope data suggest that the eventual formation of chlorite during deep burial occurred from waters with positive δ18O values, comparable to those present during the deep burial formation of illite.

Single crystals of gibbsite were partially dehydrated to boehmite in a hydrothermal atmosphere. Most of the boehmite crystallites show preferred orientation that can be explained by the octahedral linkage. Further heating in air leads to a tetragonal γ-Al2O3 whose crystallites also are oriented. The orientations give information about structural details. At about 900°C a transformation γ→θ-Al2O3 takes place. In this case too the crystallites are oriented. The oxygen chains lying parallel to the a-axis of gibbsite are strongly bound and are taken over in every new lattice during transformation.

The addition of clay minerals in drilling fluids modifies the dispersion's viscosity. In this article, scientific advances related to the use of clays and clay minerals (bentonite, palygorskite, sepiolite and mixtures of clay minerals) in drilling fluids are summarized and discussed based on their specific structure, rheological properties, applications, prevailing challenges and future directions. The rheological properties of drilling fluids are affected by the temperature, type of electrolytes, pH and concentration of clay minerals. Bentonites are smectite-rich clays often used in drilling fluids, and their composition varies from deposit to deposit. Such variations significantly affect the behaviour of bentonite-based drilling fluids. Palygorskite is suitable for use in oil-based drilling fluids, but the gelation and gel structures of palygorskite-added drilling fluids have not received much attention. Sepiolite is often used in water-based drilling fluids as a rheological additive. Dispersions containing mixtures of clays including bentonite, kaolin, palygorskite and sepiolite are used in drilling fluids requiring specific features such as high-density drilling fluids or those used in impermeable slurry walls. In these cases, the surface chemistry–microstructure–property relationships of mixed-clay dispersions need to be understood fully. The prevailing challenges and future directions in drilling fluids research include safety, ‘green’ processes and high-temperature and high-pressure-resistant clay minerals.

The adsorption of aniline (ANL) and p-chloroaniline (PCA) from 0·02 M methanol and chloroform solution on air-dried montmorillonite is determined by the conjunction of several factors: (i) basicity of the solute, (ii) complexing ability, Brönsted and Lewis acidity of the exchangeable cation, (iii) polarity and Lewis basicity of the solvent. The principal adsorption mechanisms, inferred from infrared data, are direct or indirect coordination and protonation of the adsorbate. They take place simultaneously and to a relative extent depending mainly on the exchange cation.

On Fe-, Al- and H(Al)-montmorillonite ANL and PCA give rise to type II complexes, characterised by an intense charge-transfer band in the infrared region and by the formation of radical cations, evidenced by ESR spectroscopy. This oxidation process occurs on heating in air, but with Fe3+ in vacuo also and even at ambient temperature in methanol solution. On Cu-montmorillonite ANL, contrary to PCA, does not give a type II complex; however, radical species are produced in air and in vacuo and their production is enhanced by heating.