Interlayered (<20 µm scale) vermiculite-smectite minerals were found in drill-cores from altered Otago schist basement up to 2 m from the contact with the overlying sediment. Mineral compositions defined a series from Fe2+-rich trioctahedral vermiculite to Fe2+-bearing dioctahedral smectite; in these, tetrahedral substitution of Al for Si was unusually high (up to 3·3/8 in the formula unit). The minerals formed as intermediates during the alteration of chlorite to kaolinite under non-oxidizing, possibly acid conditions. The source of the altering solutions may have been overlying lignite seams.

L'analyse par diffraction des rayons X, résonance paramagnétique électronique et par spectrométrie infra-rouge des constituants minéraux du profil des Canonnettes (Sud-Est de la France) permet de montrer que les kaolinites sont ferrifères. De plus, au fur et à mesure du développement et de l'accumulation des oxy-hydroxydes de fer et d'alumine dans le profil, on note l'enrichissement progressif des kaolinites en fer en même temps qu'augmente leur désordre et que les taux de substitution en moles % d'AlOOH des goethites alumineuses devient plus important. Finalement, les kaolinites disparaissent remplacées par les oxy-hydroxydes de fer et d'aluminium, là ou leur accumulation est maximum.

The procedure for synthesizing proto-imogolite (an acid-soluble hydroxy-aluminium orthosilicate complex) and imogolite (a tubular aluminosilicate mineral) was used to produce ferruginous aluminosilicates over a range of Al/Fe ratios to determine whether Fe3+ can be incorporated in the imogolite structure. Analysis of the synthesized products by transmission electron microscopy, electron diffraction, and IR spectroscopy indicated that, while imogolite was formed in the presence of iron, increased Fe3+ in the systems caused the formation of ferrihydrite and poorly-organized aluminosilicates resembling proto-imogolite allophane. Treatment of these materials with Na-citrate/dithionite/bicarbonate dissolved the ferrihydrite and poorly-organized aluminosilicate, and concentrated products with tubular morphology. Analysis of the structural Fe3+ by ESR spectroscopy suggested that little or no Fe3+ was incorporated in the structure of imogolite, although the less crystalline proto-imogolite allophane may have accommodated some structural Fe3+. A separate iron-rich product, identified as ferrihydrite, was formed at low Al/Fe ratios. Mössbauer spectroscopic analysis of 57Fe3+ doped at very low levels into proto-imogolite and imogolite indicated that the sites of substitution were better defined in the latter. At least part of this Fe3+ may have been incorporated in the structure of boehmite, an impurity formed during synthesis.

The rate of dissolution of synthetic Al-goethites with 0–10 mole% Al in 6 m HCl at 24°C decreases markedly with increasing extent of Al substitution. Most of the dissolution-time curves are S-shaped, suggesting some increase in surface area during the initial stages of dissolution. Based on electron microscopic examination, the increase in surface area is explained by preferential dissolution of less ordered ‘interdomainic’ zones and the consequent production of isolated ‘domains’. Thin sections of crystals provided some support for defect zones oriented parallel to the crystallographic c-direction. Stepwise multiple correlation analysis employing various properties of the goethites was used to investigate the large variation in half-dissolution time (1–96 h). 94% of the variation could be explained by the variation of the mean crystallite dimension perpendicular to the planes (110) and (111) (MCD110, MCD111). Inclusion of Al-substitution increased R2 to only 97%. As shown in a separate experiment, increasing Al concentration in the system retarded crystal growth. It is therefore believed that Al affects the dissolution rate of goethites not directly, but indirectly, by influencing crystal growth rate which, in turn, affects crystal size and order as measured by MCD110 and MCD111.

The adsorption of cerium(IV) by both natural and Na-exchanged kaolinite from aqueous solutions of ceric ammonium nitrate was studied in equilibrium systems. Cerium may be adsorbed either as a monomeric species or as a polymeric hydroxy cation. The species adsorbed depends on the concentration of cerium in the stock solution, the age of this solution prior to the preparation of the equilibrium system and on the equilibration period. Adsorbed cations undergo polymerization on the surface of the kaolinite; the resulting polymeric species forms strong bonds with the clay surface—it is not desorbed by sulphuric acid—and may be considered fixed. Adsorption of cerium reaches a maximum in solutions containing 0·15 M sulphuric acid.

The mineralogy of the clay fractions (<2 µm) of the major soils of England and Wales is reviewed, and the data presented in terms of the 1:250 000 National Soil Map. Most soils developed in pre-Rhaetic sediments are dominated by mica with lesser amounts of chlorite and kaolin. Exceptions are soils developed in calcareous Coal Measure shales which have significant smectite contents, and freely drained soils in Keuper Marl which contain swelling chlorite, sepiolite and palygorskite. Soils developed in post-Triassic sediments are dominated generally by expansible minerals, except for those developed in Lower Lias and Estuarine Series rocks (Jurassic) which are dominated by mica and kaolin respectively. The presence of loess in soils seems to be associated with the occurrence of a complex interstratified mineral with X-ray diffraction properties akin to vermiculite. Weathering of soil clays is most marked in the wetter uplands, but over most of lowland England is detectable only by slight changes in non-exchangeable potassium content and cation-exchange capacity towards the soil surface. Applications of soil clay mineralogy in the fields of plant nutrition and soil mechanics are discussed, in particular the production of maps showing mineralogical provinces.

Fifty-seven goethites, synthesized by a variety of procedures and with Al substitutions of 0–33 mole%, were characterized by XRD, IR, DTA, TEM and chemical techniques. Most of the properties measured showed significant intercorrelations. Mole% Al substitution (measured chemically) did not explain all the relationships among variables, but the inclusion of Δa, defined as the observed a dimension minus the a dimension predicted by the Vegard rule, explained much of the variation not explained by Al substitution. OH stretching frequency, in particular, was better correlated with Δa than the Al substitution or other properties. The properties of the goethites could best be explained by a combination of Al substitution and structural defects, with Δa being a measure of the defects. In general, the effect of structural defects was opposite to that of Al substitution. Increase in Al substitution led to a decrease in all three unit-cell dimensions and OH stretching frequency and to an increase in the distance between the two OH bending vibrations (δOH-γOH) and the temperature of dehydroxylation. Increase in structural defects, on the other hand, caused the a dimension, Δa, and OH stretching frequency to increase and δOH-γOH and the average temperature of dehydroxylation to decrease. Crystal size tended to decrease with increases in both Al substitution and structural defects. Surface area was significantly correlated with the reciprocal of the mean crystal thickness in the a direction. Comparison of XRD and TEM data showed that many samples consisted of crystals with several coherently scattering domains. The nature of the defects, i.e. whether they occur primarily in the interdomain areas or whether they are also distributed throughout the coherently diffracting domains, could not be determined.

The general approach to the problem of the real structure of smectites requires an analysis based on the relationship between structural characteristics and diffraction patterns. This paper, which considers only the models corresponding to dioctahedral smectites saturated by K-cations and collapsed, includes: 1. Successive consideration of all models which are crystallochemically possible. These models may differ in (i) the structure and chemical composition of layers and interlayer spaces; (ii) the azimuthal orientations, translations and the mode of alternation of the layers; (iii) independent parameters which describe quantitatively the models (e.g. abundance of each type of layer, probability parameters defining the succession of layers, …). 2. Calculation, in all accessible domains of reciprocal space, of the distribution of intensities and profile variations, obtained by changing only one parameter at a time, that defines one type of structural feature (e.g. cation distribution in individual layers, stacking of the layers, nature of stacking faults, …). 3. A systematical analysis of the calculated diffraction patterns to establish the diffraction criteria which will help to interpret the experimental data explicitly.

Mineralogical investigations of weathered andesitic bedrock and overburden on the valley flank of the Tondano river, Manado, Sulawesi, indicated that these had been subjected to different weathering conditions. The underlying andesite was completely altered to 7Å-halloysite and allophane. In the transported latosols of the overburden, 10Å- and 7Å-halloysites were found. The ratio of 10Å- to 7Å-halloysite increased linearly with depth in the profile. It is considered that weathering of the andesitic bedrock reflects a palaeoclimate with more strongly pronounced seasonal desiccation and lower annual rainfall. Neoformations by weathering of the overburden took place under the recent tropical climate.

Three organic reactions which affect individual compounds present in most organic-rich sedimentary rocks have been identified—configurational isomerization and aromatization of steroid hydrocarbons, and configurational isomerization of hopanes. The extents to which these reactions have occurred can be assessed by gas chromatographic-mass spectrometric analysis of the organic extracts of the sediment samples; they provide sensitive indicators of thermal maturation. When combined with the model of sedimentary basin formation by extension of the lithosphere, this molecular approach to the maturation of organic material can be used to constrain the temperature-time histories of sedimentary sequences. This temperature history may be used to integrate the relevant Arrhenius’ and rate equations governing the reaction rates. Each rate equation has three constants—the activation energy, frequency factor and the ratio of forward reaction to backward reaction. These have been estimated using analyses of samples whose temperature-time history is well constrained. The resulting estimates can then be used to reconstruct the temperature-time histories of other samples from organic geochemical data, e.g. calculation of the amount and timing of uplift.

L' étude de la structure d' une argile sensible du Québec est abordée en porosimétrie au mercure après lyophilisation et en microscopie électronique à balayage sur une surface obtenue par fracture de l' échantillon congelé (système Cryoscan). On observe une structure en agrégats définissant deux classes de pores. A grande vitesse de congélation, la cristallisation de la glace semble surtout affecter les points faibles de la structure, qui sont les ponts de plaquettes reliant les agrégats les uns aux autres.

The soils of Scotland are relatively young, being developed mainly on glacial drift deposited some 10 000 years ago. Only a small number of genetic soil types are represented, but this is more than compensated for by the wide variety of parent materials from which the drift ultimately derives. The major parent materials include granite and granitic gneiss, gabbro, basalt/andesite, mica-schist and related metamorphic rock types, Lower Palaeozoic greywackes and shales, Old Red Sandstone sediments, Carboniferous sediments, fluvioglacial sands and gravels, and estuarine silts and clays. The clay mineralogy of the soil associations developed on these parent materials is described and the origin of the clay minerals is interpreted. It is concluded that the influence of inheritance is predominant, but that the effects of pre-glacial weathering and Holocene pedogenesis can also be discerned. Inheritance has contributed a wide variety of clay minerals to the soils, including illite, kaolinite, chlorite, smectite and a number of interstratified minerals, pre-glacial weathering has resulted in the widespread formation of kaolinite and halloysite, irrespective of soil parent material or drainage class, and recent pedogenesis has brought about the transformation of inherited layer silicates by vermiculitization processes, with concomitant interlayer alumination, particularly in surface horizons.

Comme la plupart des vermiculites, l'hydrate à une couche de la vermiculite-Na (d001 = 11·85 Å) présente une structure semi-ordonnée, avec des défauts d'empilement (glissements selon l'axe b). Le plan (h0l)* du réseau réciproque est entièrement discret, tandis que les rangées n'appartenant pas à ce plan sont plus ou moins diffuses dans la direction c*. La projection x0z est obtenue par une classique analyse de Fourier bidimensionelle. Dans les plans (0kl)* et (1kl)*, certaines rangées semblent presque discrètes: ceci permet d'essayer de déterminer la translation selon l'axe 0y entre deux feuillets adjacents. Le calcul des intensités des diffusions le long des rangées des plans (0kl)* et (1kl)* conduit à ne retenir qu'un seul modèle. Le désordre résulte d'une distribution aléatoire de trois translations parallèles à l'axe Oy: l'une est nulle et les deux autres sont de +0·307b et −0·307b. Le principal intérêt de ce travail est de présenter une nouvelle méthode d'approche pour l'étude des structures semi-ordonnées.

Intrastratal solution of detrital heavy minerals in North Sea Tertiary sandstones takes place in two different diagenetic settings, deep burial and acidic weathering. These are characterized by different orders of mineral stability: apatite, chloritoid, garnet, sphene and spinel are less stable in acidic weathering than in deep burial, whereas the reverse is true for andalusite, kyanite and sillimanite. Heavy-mineral dissolution patterns, therefore, do not follow one single order of stability but several, depending on the diagenetic environment in which the dissolution occurs. It seems from this that the relative order of stability for detrital heavy minerals is controlled by the chemistry of the interstitial waters, whereas the limits of persistence depend on pore-fluid temperature, rate of water throughput, and geological age. Because different diagenetic environments lead to differing orders of mineral stability, it may prove possible to elucidate certain aspects of the diagenetic history of a sandstone by heavy-mineral dissolution patterns.

Mixed SiO2-Al2O3-Fe2O3 gel systems are a feature of many Scottish soils. They are usually associated with the surface of primary soil particles and consequently when present even in small amounts can have an effect on soil properties incommensurate with the proportion present. Currently, chemical dissolution methods provide the most satisfactory means of assessment. A range of chemical techniques, including dissolution by alkali, dithionite, acid oxalate and pyrophosphate, trimethylsilylation and fluoride exchange, have been used to examine the inorganic gel in a Scottish brown forest soil developed on glacial till derived from epidiorite. The reactivity of the gel, as determined by fluoride exchange, is similar to that reported for Japanese and New Zealand allophanic soils.

Des kaolinites sont exploitées dans les sédiments du Tertiaire inférieur des Charentes, constitués d'argiles, de lignites, de sables noirs à gros bois et pyrite et de sables roux. Deux niveaux de kaolinite sont exploités: (i) des kaolinites ordonnées accompagnées de muscovite, (ii) des kaolinites désordonnées toujours accompagnées d'anatase. Ces deux niveaux correspondent à deux épisodes sédimentaires successifs, datés du Sparnacien et du Cuisien par la palynologie. Le premier épisode est vraisemblablement issu de la reprise d'altérations éablies sur le socle cristallin du Massif Central, alors que le second reprendrait des matériaux issus de l'altération des roches sédimentaires des bordures du bassin. Des kaolinites très bien ordonnées et de la gibbsite résultent de transformations géochimiques au sein des dépôts. Elles sont liées aux milieux acides des dépôts ligniteux et à l'oxydation des pyrites qui amènent la mobilisation de l'aluminium.

Complex formation between halloysites, from soil and geological sources, and a series of amides has been investigated. All the amides used can be intercalated to give single-layer complexes with basal spacings between 10·4 Å (for formamide) and 12·4 Å (for N,N-dimethylacetamide). When the interlayer space of halloysite has already been expanded by water, as is the case with fully hydrated samples, the rate and extent of intercalation depend more on the properties of the organic species than on the mineralogy of the clay. With partially and completely dehydrated halloysite, however, complex formation is influenced by the particle size, crystallinity, and iron content of the mineral. A large particle size, a high degree of crystallinity, and a low iron content are all conducive to complex formation. The iron content of halloysite also appears to affect particle shape. Low structural iron contents are associated with long tubular particles, intermediate contents with short and/or wide tubes, and high contents with spheroidal and other non-tubular forms. Halloysites containing high amounts of extractable (non-structural) iron generally show a low intercalating ability.