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.

The sorption of ibuprofen by modified natural zeolite composites at three concentration levels (10, 20 and 30 mmol/100 g) of cationic surfactants – benzalkonium chloride and cetylpyridinium chloride, in a buffer solution (pH 7.4), was studied. Characterization of the composites before and after ibuprofen sorption was performed by drug sorption and isotherm studies, zeta potential and Fourier Transform infrared spectroscopic analysis. The biopharmaceutical performance of cationic surfactant-modified zeolites as drug formulation excipients was evaluated by in vitro dissolution experiments from the composites with medium surfactant contents. The drug sorption was influenced by the surfactant type and amount used for the zeolite modification. Prolonged drug release over a period of 8 h (up to ~40%) was achieved with both groups of samples. The kinetic analysis showed that the drug release profiles were best fitted with the Higuchi and the Bhaskar models, indicating a combination of drug diffusion and ion exchange as the predominant release mechanisms.

Experimental alteration of a rhyolitic obsidian by solutions containing variable concentrations of Mg was carried out at 100, 150 and 200°C, for 30, 60 and 90 days, to investigate the mechanism of smectite formation. The smectite exhibits two distinct morphologies: (1) small flakes (aggregates of a few crystals); and (2) large flakes (massive groups). The small flakes are the earlier alteration products. Both morphological types have distinct chemical compositions: the smallest laminae are dioctahedral and contain more Fe, whereas the particles from the rose-shaped aggregates contain Mg and are trioctahedral. Intermediate compositions have been observed between the extreme compositions.

It is suggested that the two morphologies are the result of two distinct genetic processes: (1) the small flakes (Fe-rich smectite) form by solid state rearrangements of the hydrated external layer of glass and/or via the formation of domains within the glass; (2) the rose-shaped aggregates (Mg-rich smectite) form by precipitation from solution.

The removal of the alkali-soluble fraction from soil clays has been found to influence markedly the efficiency with which iron oxides can be removed from such clays. In clays pretreated with 5% Na2CO3, up to 40% more iron oxide was extracted by dithionite (Na2S2O4) than from soil clays treated with this reagent alone. Chemical analysis, electron microscopy, X-ray and differential thermal examination, and specific surface area and cation-exchange capacity measurements indicated an improved dispersion brought about by the removal of aluminosilicate binding material by Na2CO3. The electron-optical studies also showed that the dithionite-soluble iron was principally in the form of small granules. These were amorphous to X-rays and electrons and chemical analysis of the dithionite-soluble fraction suggested that they were ferruginous complexes containing considerable quantities of silica and alumina.

Methods are described for estimating a valuable absorption coefficient for OH stretching bands of micas: the integrated parallel absorption coefficient K.

From a correlation between this coefficient and the OH content of biotites and phlogopites, it was found that the parallel absorption coefficient per hydroxyl group in these trioctahedral micas is not appreciably influenced by the chemical composition and the direction of the OH bond. A clear deviation was observed for the low frequency band of a biotite characterized by a well-ordered orientation distribution for the corresponding hydroxyl groups.

The integrated parallel absorption coefficient of muscovite is proportionally 2·5 to 3 times larger than that of trioctahedral micas.

Clay-based nanostructures were prepared from kaolinites of varying structural order by two different methods. In the first method the kaolinite-urea precursor, obtained by dry grinding, was intercalated further with triethanolamine and the tetraalkylammonium salt was synthesized in the interlamellar space. Exfoliation was achieved by the use of sodium polyacrylate (PAS). In the second method, the kaolinite-potassium acetate (kaolinite-KAc) precursor, obtained via two different methods, was intercalated further with ethylene glycol (EG) and then n-hexylamine (HA). Intercalation with EG was also achieved by heating either directly or with microwaves. The morphology that results depends on the method of precursor preparation, the method of heat treatment and the degree of structural order of the original clay. Higher structural order facilitates the formation of a tubular morphology, while mechanical treatment and microwave agitation may result in broken tubes. Molecular mechanical (MM) calculations showed that organo-complexes may be exfoliated to a d value of 10–11 Å.

Three samples have been selected to represent the sedimentary variations of the Basin of Autun. IR and ESR techniques have been used to study the sheet composition of the different kinds of clays. The kaolinites are fire clays with two different degrees of crystallinity. The illites have a muscovite origin and belong to the 1 M polytype with mainly tetrahedral Al3+ and Fe3+ substitutions but also with some octahedral Fe3+ substitutions. The dioctahedral phyllosilicates contain mostly divalent and trivalent octahedral substitutions.

More than twenty new organic complexes of halloysite have been prepared and one hundred and twenty-seven compounds were tested. Results are compared with those of earlier studies and use is made of recent findings concerning particle morphology and interstratification effects to interpret the results. The compounds which form complexes with halloysite are polar, and are usually either acids or bases. Their molecules usually contain two functional groups (preferably —OH and/or —NH2), are relatively small and have one functional group per two carbon atoms, but do not usually include cyclic or aromatic types. The best explanation of the existence of these metastable complexes seems to lie in the ability of some organic molecules to form hydrogen bonds with the halloysite structure, about which insufficient knowledge is available to allow quantitative evaluations to be made.

Two soil profile sequences on paragneiss debris in the Val di Rabbi (Northern Italy) along an altitude gradient ranging from 1200 to 2400 m a.s.l. were studied to evaluate the effect of aspect on the weathering of clay minerals. All the soils had a coarse structure, a sandy texture and a low pH. Greater weathering intensities of clay-sized phyllosilicates (greater content of smectites) were observed in soils on the north-facing slope. On the south-facing slope, smectite was found only in the surface horizon of the soil profile at the highest altitude. Hot citrate treatment of north-facing soils revealed the presence of low-charged 2:1 clay minerals, the expansion of which was hindered in the untreated state by interlayered polymers. However, the hot citrate treatment encountered some problems with the samples of the south-facing soils: as confirmed by Fourier transform infrared spectroscopy, the hot citrate treatment was unable to remove all interlayer Al polymers. The 2:1 phyllosilicates were not expanded by ethylene glycol solvation in several samples, although thermogravimetric analyses indicated the presence of clay minerals with interlayer H2O. At the same time, the collapse of clay minerals to 1.0 nm following K-saturation was evident. Theoretically, this should indicate that 2:1 phyllosilicates had no evident substitution of trioctahedral cations (Mg2+, Fe2+) by dioctahedral cations (Al3+ and Fe3+). X-ray diffraction analysis of the d060 region and determination of the layer charge of clay minerals by the long-chain (C18) alkylammonium ion, however, did not confirm this. A transformation from trioctahedral to dioctahedral species was observed and low-charge clay minerals (ξ ~0.30) were identified in the surface horizons of the south-facing sites. In the south-facing soils, the podzolization process was less pronounced because of a lower water flux through the soil and probably less complexing organic molecules that would remove the interlayer polymers. Besides the eluviation process, clay minerals underwent a process of ionic substitutions in the octahedral sheet that led to the reduction of the layer charge. This process was more obvious in the north-facing sites.

Rhaetian (Upper Triassic) sandy horizons were sampled from the Paris Basin from SW to NE, crosscutting the Rhaetian at different depths from outcrop in the NE to 2700 m in the centre of the basin. The smallest day sub-fractions (<0·2 μm) from the deepest samples consist mainly of illite and chlorite having a K-Ar age of 〜190 Ma. Both minerals probably formed under specific hydrothermal conditions at high temperature, but at a burial depth of only 500 m. This thermal event could represent an echo of the "crustal" breakdown of the Northwestern European craton during the opening of the North Atlantic Ocean. Two other generations of illite-smectite mixed-layers formed in the same Rhaetian horizons at somewhat lower temperatures about 150 and 80 Ma ago. The three generations of clay minerals could be characterized and dated because of combined mineralogical, crystallographical and morphological data supporting the dating attempts.

Pour les hydrates à ‘deux couches’ des vermiculites issues des phlogopites 1 M, saturées par Li, Na, Ca, Mg ou Ba, nous avons rencontré quatre modes d'empilement des feuillets. Un seul (VIII) présente une structure ordonnée tridimensionnellement. Les trois autres (VI, VV et VVII) sont des structures semi-ordonnées.

Nous avons défini les translations entre feuillets pour chaque empilement ainsi que les domaines d'existence en fonction du cation et de l'humidité relative.

Pour l'édifice ordonné VIII calcique la structure de la couche interfoliaire est décrite (deux types de polyèdres d'eau plus de l'eau de liaison entre polyèdres).

Les diffèrents facteurs conditionnant, pour une vermiculite donnée, le ‘choix’ d'un mode d'empilement sont discutés : facteurs propres à la couche interfoliaire (nature des cations et degré d'hydratation); facteurs propres au feuillet (densité et localisation des charges, disposition des oxygènes de surface); facteurs liés à la texture.

Calculated diffraction profiles for interstratified kaolinite and montmorillonite have been used to determine the composition of clays reported from Poland, Japan and Mexico. The predicted layer proportions determined from the curves and by other methods are in close agreement for the first two but a higher kaolinite content than that originally proposed is obtained for the Mexican clays.

Turkey has a long tradition (starting with prehistoric civilizations) and experience in exploring for raw clay materials and processing them into ceramic products. Many of these products, such as tiles and sanitary ware, are manufactured for domestic and export markets. Kaolin is one of the raw materials of major importance for the ceramic and paper industry, as well as for a number of auxiliary applications. There is ongoing interest in applying kaolin in the construction industry as a raw material in the production of white cement clinker and as an artificial pozzolanic additive for concrete (in the form of metakaolin). This report presents results related to search, assessment and evaluation of available resources for advanced cement and concrete additives.

The adsorption of the cationic dye acridine orange (AO) by Na-saponite and the colloidal properties of the aqueous suspension were investigated by visible spectroscopy and XRD. The organic cation is adsorbed by the mechanism of cation exchange. When small amounts of the dye are adsorbed, the system contains small tactoids and is peptized. At this stage the dye penetrates into the interlayer space and most of it undergoes metaehromasy due to interactions between the aromatic entity and the oxygen plane of the clay. When greater amounts of AO are adsorbed, the clay platelets flocculate to form book-house floes which, with excess AO, are transformed into card-house floes. At this stage metachromasy results from the aggregation of the dye in the interparticle space of the floes, in addition to the π interactions with the oxygen plane. In excess AO, the clay is gradually peptized. At this stage the dispersed clay platelets form small tactoids with monomeric AO in the interlayer space and at the same time adsorb dimerie and polymeric AO cationic species at the solidliquid interface.

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.

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 amount of Fe and Al extracted from soil by 0·1 M pyrophosphate (Fep, Alp) has long been used as a criterion in the designation of spodic horizons of podzols (Avery, 1973). Although Adams et al. (1980) showed that in a group of podzolic soils developed from Lower Palaeozoic sedimentary (LPS) rocks Fep was very closely correlated with the quantities of Fe eluviated and illuviated, such evidence validating the use of pyrophosphate is not generally available. Recently there has been renewed interest in the identification of forms of Fe and Al extracted by pyrophosphate in order that greater confidence might be gained in the use of Fep and Alp in soil classification (McKeague & Schuppli, 1982).

Our interest in pyrophosphate extraction was stimulated when Nto (1981) discovered that Fep was an excellent predictor of P sorption in soils developed from LPS rocks. Indeed, the level of predictability was not improved by the inclusion, in multiple regressions, of either Fe or Al extracted by any other of the commonly used selective extractants.

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.

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.