Changes which occur during the natural weathering of biotite in granite gneiss and associated soils are measured by microanalysis and illustrated by SEM. Biotite weathers through a series of interstratified minerals to vermiculite and/or smectite phases which decompose rapidly to kaolinite. Both vermiculite and smectite phases appear to be dioctahedral, on the basis of chemical compositions derived from microprobe data. Weathering products are first apparent on the edges of laminae, where interstratified minerals are formed at right angles to both the edge face and the cleavage. Weathering soon develops along cleavage planes, initially most strongly near the edges of flakes, but then permeating extensively into the body of flakes and subdivided segments. The orientation of interstratified minerals and kaolinite within cleavages is parallel to the cleavage.

Dissolution kinetics of sepiolite from Eskisehir (Turkey) have been investigated at various temperatures and particle sizes using dilute hydrochloric and nitric acids. Dissolution reaction rate constants were calculated and apparent activation energies were dependent on acid concentration. For both acids, apparent activation energy values reached a minimum of ∼11 kcal/mol at an acid concentration of 0·75 M. For the second-order reaction which is independent of the acid concentration, the activation energy was 14·5 kcal/mol for both acids. The reaction rate constants were proportional to the acid concentrations, and inversely proportional to the square-root of the initial particle radii of the sepiolite.

Electron spin resonance (ESR) spectroscopy and calorimetric methods were used to characterize conversion processes in multimineral samples from the Northampton ironstone (NIS) at temperatures between 25°C and 800°C. The beginning of the thermal conversion processes can be determined by the formation of asymmetric ESR spectra with g ≈ 2 at 250°C. The breakdown of the berthierine structure between 250°C and 520°C is indicated by the disappearance of the hyperfine splitting in the Mn2+ spectrum and the formation of magnetite. The decomposition of siderite and calcite was found by calorimetric methods at 580°C and 700°C, respectively. The hematite formation between 550°C and 800°C is explained by the decomposition of siderite but also by the oxidation of previously formed magnetite. The occurrence of hematite as the dominant ferric oxide at 800°C signifies the end of the conversion process of the major mineral phases in the NIS samples.

The verdine facies, previously confused with components of ancient ironstones, has been studied in relation to its distribution, mineralogy, genesis, environment, and geological significance. Several chemically specific components are present including (i) a ferric and magnesian dioctahedral-trioctahedral 1 : 1 clay mineral, (ii) a chemically equivalent chlorite, (iii) a component intermediate between smectite and swelling chlorite, and (iv) a problematic low-temperature pyrophyllite-like clay mineral. The genetic mechanism is a series of crystallogenetic reactions using cations from the previous phase; this model, where a mineral phase is shown to be a temporary state of arrangement of cations, suggests that authigenic “marine” minerals may reflect diagenetic geochemical factors different from those in the original sea.

Powdered 2:1 Mg-clay samples were rehydrated up to the maximum hydration. Both scanning and transmission electron microscopy were used to characterize their structural organization i.e. particle arrangement, texture and crystal structure. Low-angle X-ray scattering experiments were carried out to quantify the microstructure of the system. The results showed that sample water contents reached at saturation are not directly related to changes in layer distance. The hydration mechanism is rather correlated to particle size and particle aggregate size. It is also shown that the a, b plane extension of the layers influences particle size and shape. Finally, it appears that for a better understanding of clay swelling mechanisms, at high water contents, it is necessary to take into account all organization levels and that the contribution of interlayer space to the total water content, for Mg-smectites, is small.

The effect of heating on the water sorption capacity of a La-saturated montmorillonite, La-Mt, has been investigated. Sodium and Li as exchangeable ions have also been included for comparative purposes. XPS of La-Mt shows no migration of La(III) from interlamellar positions to octahedral sites on heating at 300°C. The water adsorbed as a multilayer on the external surface of the montmorillonite has been subtracted from the total sorbed water. Although the c-spacing of La-Mt corresponds to a two-layer hydrate, in the relative humidity range from 30 to 70%, the interlamellar water amounts to only 70% of the value for a complete monolayer. Heating at 300°C for 24 h has no influence on the uptake of molecular water between the structural layers of the La-Mt. The average numbers of water molecules per exchangeable ion sorbed into the interlamellar spacing up to 50% r.h. are: 5(Na-Mt), 3(Li-Mt) and 13(La-Mt).

To investigate the influence of carbonate on the formation of goethite and lepidocrocite, ∼200 samples were synthesized by oxidizing FeCl2 solutions with air/CO2 gas mixtures at ambient temperature and pH 6 and 7. The proportion of lepidocrocite in the lepidocrocite/goethite mixtures (Lp/(Lp + Gt)) decreased from 100 to 0% with increasing in solution and with decreasing average oxidation rate (AOR). These two parameters explained 81% of the variation of Lp/(Lp + Gt)). At a given , more goethite was formed at pH 6 than at pH 7. The Lp + Gt mixtures contained 0–8 mg g−1 carbon (Ct) which could not be removed by washing. Ct reached apparent saturation at a equilibrium concentration of ∼6–8 and 60–80 mmol l−1 at pH 6 and pH 7, respectively. In a plot of Ct vs. Lp/(Lp + Gt) all data fell on the same line irrespective of oxidation parameters (pH, AOR). IR spectra showed two broad bands at ∼1300 and 1500 cm−1 which can be assigned to distorted carbonate adsorbed at the goethite surface. Identical bands were also found in a young, poorly crystalline goethite formed from coal mine drainage in Ohio. It is suggested that carbonate anions direct the polymerization of the double bands of FeO3(OH)3 octahedra common to both minerals toward a corner sharing arrangement, and thereby to goethite, whereas chloride permits edge-sharing as in lepidocrocite.

The kinetics of clay formation in buried paleosols developed from late Quaternary rhyolitic tephra layers near Rotorua, New Zealand, can be described in terms of a combination of parabolic and linear kinetics, reflecting the hydration of glass, and the formation of clay minerals, respectively. Such a model is consistent with the formation of clay minerals showing an Arrhenian temperature dependence and suggests, on the basis of calculated activation energies, that the process of formation of Al-rich allophane (imogolite) is diffusion controlled, whereas the rate of formation of Si-rich allophane is controlled by the chemical processes at the site of reaction.

Effects of tetrahedral isomorphic substitution on the IR spectra of fluorine micas were demonstrated by comparing the spectrum of taeniolite KMg2Li(Si4O10)F2 with those of the substituted analogues, in which Ga, Al, B or Ge substituted for Si in tetrahedral sites. The e11 bands move towards lower frequencies as the content of substituted cation in tetrahedral site increases, whereas The a11 and a12 bands moves towards higher frequencies. Linear relationships were found between a12 the band frequency and the extent of tetrahedral substitutions. The magnitude of shifts per molar substitution for the a12 bands is dependent on the species of substituted cation and decreases in the order Ga > Al > Ge > B, showing an intimate correlation with the field strength z1·z2/r2M–O of the substituted cations. This implies that the polarizing power of the substituted cations has a pronounced effect on the Si-O stretching vibrations.

A number of thermodynamic properties were obtained from the determination of adsorption isotherms and enthalpies of immersion for systems with water and Na- and Ca-bentonites. Entropy differences were calculated by combining the enthalpies of immersion and the changes in free energy derived from the adsorption isotherms. The swelling pressures, also calculated from the water adsorption isotherms, are in satisfactory agreement with the experimental data.

A unified system of vector representation of chemical composition is proposed for the phyllosilicates based on projection of the composition, as given by crystallochemical formula, onto a field with orthogonal axes chosen for octahedral divalent cations, R2+, and Si (X, Y, respectively), and oblique axes for octahedral trivalent cations, R3+, and vacancies, □, (V, Z, respectively). Point coordinates for each set of axes were used to define the direction and length of the unit vectors for phyllosilicates belonging to different groups. Parallel to these fundamental directions the composition isolines were drawn in the projection fields. Applied to micas, this system enables control of the chemical composition by the general crystallochemical formula covering all varieties of Li-free dioctahedral and trioctahedral micas:

where z (number of vacancies) = (y-x+ m)/2; m (layer charge) =1; u+y+z = 3. There is a similar formula for vacancy-free lithian micas:

where w = m — x+y;m=1; u+y+w = 3, and for Li-free brittle micas:

where z = (y — x+m)/2; m = 2; u+y+z = 3. Projection fields were used to classify micas.

The structure of Silica Springs allophane from New Zealand has been studied by high-resolution 27A1 and 29Si NMR spectroscopy, IR spectroscopy and electron microscopy. Experimental NMR conditions were chosen to give a quantitative relationship between signal strength and Al content. Aluminium is present in both octahedral (Alvi) and tetrahedral (Aliv) coordination, and the ratio Alvi:Aliv was obtained for three samples with different total Al:Si ratios. In all cases the Aliv:Si ratio was 1 : 3, consistent with the ratio in ideal muscovite. The negative charge arising from Aliv was apparently balanced by positive charge at adjacent Alvi sites. Both NMR and IR spectra indicate that Si exists in a condensed network, probably a sheet, with Si atoms linked (through oxygen) to one, two and, possibly, three other Si atoms, but not four. The spectra are consistent with a mixture of Si-O-Si, Si-O-Al, and Si-OH linkages. A structure based on fragments of single curved 1 : 1 aluminosilicate layers, with the tetrahedral sheet on the outer surfaces, is suggested, the diameter of curvature being 2–3 nm. The tetrahedral sheet is more or less complete and has a Aliv : Si ratio of 1 : 3; the octahedral Alvi sheet is incomplete. Electron micrographs suggest that, at least in some cases, the fragments form more or less complete spherules. This proposal seems to accord with Farmer's concept of “aluminous hydrous feldspathoids”. The minimum pH at which Silica Springs allophane has precipitated corresponds to the initial presence of tetrahedrally coordinated Al species in solution.

Des montmorillonites cuivriques ont été exposées à des vapeurs de benzène, au cours de cycles de déshydratation, adsorption, désorption de l'excès et réhydratation. La fixation du benzène et sa transformation dans les espaces interfoliaires ont été suivies au moyen d'analyses thermogravimétriques, radiocristallographiques et spectrophotométriques infrarouges. Celles-ci ont permis de mettre en évidence deux réactions, correspondant l'une à l'adsorption d'une molécule de benzène par ion Cu2+, l'autre à trois molécules de benzène. Ce dernier se polymérise dans les espaces interfoliaires avec formation tout d'abord de poly (p-phénylène) puis d'un composé qui pourrait s'apparenter à du graphite.

The classification and nomenclature of chlorites have been critically reviewed. A new classification based on the unified projection system of chemical composition has been proposed in which for the first time all trioctahedral, di-trioctahedral and dioctahedral species are included. The chemical composition of chlorites is controlled by the general crystallo-chemical formula: This is superior to the known formulae for the trioctahedral and dioctahedral chlorites. It has been shown that the chlorite end-member compositions of Bayliss (1975) project in one point of the projection field leaving many end-member compositions unnamed. As they correspond to the names used previously, a proposal is made to restore these names.

Mn-substituted iron oxides were synthesized at pH 4, 6, 8, and 10 from Fe-Mn systems with Mn mole fractions (Mn/(Mn + Fe)) of 0, 0·2, 0·4, 0·6, 0·8, and 1·0, and kept at 50°C for 40 days. The Mn mole fraction in goethite was <0·07 at pH 4 but increased to ∼0.47 at pH 6. Goethite and/or hematite formed in Fe and Fe + Mn syntheses at pH 4 and pH 6 at Mn mole fractions ≤0·8, and at Mn mole fractions ≤0·2 at pH 8 and pH 10. Hausmannite and jacobsite formed at pH 8 and pH 10 at Mn mole fractions ≥0·4. In the pure Mn syntheses, manganite (γ-MnOOH) formed at pH 4 and pH 6, whereas hausmannite (Mn3O4) formed at pH 8 and pH 10. As the Mn substitution increased, the unit-cell dimensions of goethite shifted toward those of groutite, and the mean crystallite dimensions of goethite decreased.

A unified system of projection of chemical composition, prepared initially for micas and chlorites, has been applied to minerals of the serpentine-kaolinite group. It has been shown that the chemical composition in the projection field is controlled by the formula, the unit of which is: (Si(2-x)Alx)O5(OH)4, where u+y+z=3, z=y-x. Using projection fields for different chemical systems it has been shown that among the most important end-members are kaolinite minerals, true serpentines, berthierine, brindleyite, amesite, cronstedtite, greenalite, nepouite and their analogues having different substitutions in the octahedral sheets.

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.

The iso-butene oligomerization activity of pure and metal-substituted synthetic mica-montmorillonite (SMM) was studied by simultaneous thermogravimetric-differential thermal analysis (TG-DTA). The incorporation of matrix Ni and ion-exchanged Co, Ni and Zn into SMM increased its iso-butene oligomerization activity while the presence of water in the olefinic feed reduced activity. These findings corresponded to trends found in previous work on high pressure (50 MPa) propene oligomerization over SMM and metal-substituted SMM.