X-ray photoelectron diffraction data from single crystals of a biotite containing ∼1% Ti show that although this element is located entirely in octahedral sites, the Ti sites are not precisely equivalent to those of Mg and Fe. Comparisons of Ti 2p X-ray photoelectron spectra from two biotites and from two titaniferous phlogopites (∼0·3–·5% Ti) with those from Ti(II), Ti(III) and Ti(IV) oxides indicate that this element is present as Ti(III) rather than Ti(IV) in all four micas.

Electron spin resonance (ESR) spectroscopy has contributed significantly to the identification and characterization of paramagnetic impurities associated with clays. Following a brief discussion of the general principles of the technique, a review is given of the application of ESR to the study of those paramagnetic species (chiefly iron and radiation-induced lattice defects) located either within the aluminosilicate structure or present as an external impurity phase.

Chemical and mineralogical data on Holocene coastal plain soils from Thailand suggest that during formation of pyrite in tidal swamps Fe(III) is extracted from smectite and replaced by Mg. During drainage of these sediments pyrite oxidizes and the reaction is reversed. Replacing Fe(III) by Mg in clay minerals stores alkalinity that can neutralize three-quarters of the acidity released during oxidation of pyrite, and thus lowers the potential acidity of pyritic sediments. Possible causes for variation in the amounts of Mg taken up during pyrite formation are discussed.

Calibration of the internal and external signals appearing at geff ∼4 in the electron paramagnetic resonance (EPR) spectra of twenty-four kaolinites, has led to the recognition of two types of kaolinite-iron. The amount of iron associated with the internal signal (I iron) shows good inverse correlations with parameters used to describe the degree of crystalline perfection in kaolinite. Iron associated with the external signal (E iron) is insensitive to crystalline order. By considering both the amount and nature of the iron, the kaolinites investigated are placed in three groups. The first contains well-crystallized varieties characterized by low total iron and EPR spectra consisting mainly of an E signal. Poorly-crystallized kaolinites contain more iron and are characterized by a fifty-fifty partition of this iron into E and I sites. The third group contains samples which are intermediate with respect to both the amount and nature of the iron.

La mesure de l'intensité à l'échelle absolue consiste à déterminer le pouvoir diffusant de l'objet rapporté au motif élémentaire de la structure, c'est-à-dire exprimé en nombre d'électrons libres équivalents diffusant indépendamment et qui donnerait, en chaque point de l'espace réciproque, le même effet que l'objet. Les avantages de cette méthode sont les suivants: (i) elle permet de corriger la courbe expérimentale de la diffusion incohérente et ainsi d'augmenter le nombre de réflexions quantitativement exploitables; (ii) elle permet une meilleure caractérisation de la nature des défauts structuraux et, pour des systèmes hétérogènes tels que des particules en suspensions, elle rend possible la séparation des effets de diffraction spécifiques de chaque phase; (iii) elle rend possible l'interprétation des fonds de diffusion. Ces propriétés sont illustrées sur quelques exemples d'application (kaolinite, sépiolite mal cristallisée et suspension de montmorillonite-Na dans l'eau).

A review is given of the application of ESR spectroscopy to the study of hydrated transition metal ions and nitroxide spin probes in the interlamellar region of smectites and vermiculites. These investigations have not only provided information regarding the structure and mobility of the intracrystalline water-cation layers but have also demonstrated the reactivity and catalytic properties of certain transition metal exchange forms of smectites. Several novel coordination complexes and redox reactions between the exchange ions and a variety of simple organic molecules have been characterized.

Calculations previously used to distinguish between methanol adsorbed in micropores between clay microcrystals (external) and that present in the interlamellar space (internal) of variable charge Ca-montmorillonites have been extended to homoionic Li-, Na- and Bamontmorillonites. It is shown that both the shape and the magnitude of the internal isotherms are in good agreement with X-ray diffraction data. Furthermore, the apparent molecular packing of methanol in the interlamellar space is related specifically to the nature of the charge balancing cation.

Se ha estudiado la interacción de fosdrín (pesticida organofosforado) con montmorillonita mediante difracción de rayos X y espectroscopia infrarroja. Este insecticida forma con montmorillonita dos tipos de complejos, con espaciados basales 16·05 y 20·06 Å. La formación de uno u otro tipo depende del estado de hidratación y del catión interlaminar de las muestras, de la naturaleza del disolvente y de la concentración de fosdrín. En los espectros de infrarrojo de los complejos, las vibraciones de valencia P =O y C =O del fosdrín se desplazan hacia frecuencias más bajas. La magnitud del desplazamiento de estas vibraciones es función del poder polarizante del catión interlaminar. El desplazamiento de la vibración de valencia C =O depende además del tipo de complejo y de su grado de hidratación. La vibración de valencia C=C se desplaza hacia frecuencias altas en los complejos de espaciado basal 16·05 Å. Los resultados obtenidos indican que el complejo de 16·05 Å es monocapa y que las moléculas de fosdrín (forma trans) deben interaccionar con los cationes interlaminares a través de ambos grupos P =O y C =O. El complejo de 20·06 Å es de dos capas y las moléculas (forma cis) interaccionan solamente a través del grupo P =O.

In previous papers of this series it was shown that it is possible to determine both the amount of methanol adsorbed in the interlamellar space of charge-deficient Ca-montmorillonite or of homoionic clays and the amount of methanol occluded in a system of micropores between clay particles. This paper deals with the distinction between methanol molecules in the cation coordination shell within the interlamellar space from those not directly influenced by the cation. An OH stretching band at about 3520 cm−1 or an OD stretching band in the 2600–2650 cm−1 region permits this distinction. At 35°C and at relative methanol vapour pressures between 0·1 and 0·9, one molecule of CH3OD is influenced directly by Na+, 2 molecules are influenced by Ba2+, 1·3–1·8 molecules by Li and 4 molecules by Ca2+. Thus, only 20–50% of the adsorbed alcohol molecules may be within the coordination shell of the cation in the interlamellar space.

Après avoir défini la notion de charge minérale, on étudie la nature et le nombre des défauts cristallins d'argiles kaoliniques. On montre l'influence des défauts d'empilement (interstratification de feuillets potassiques) et des défauts dans le plan (conséquence des substitutions de l'aluminium) sur les propriétés mécaniques des caoutchoucs chargés. Puis on étudie l'influence de la pureté minéralogique et de certains paramètres superficiels sur les performances des produits chargés. Enfin, on propose des méthodes de traitement qui permettent d'accroître les propriétés renforçatrices de la charge. On présente l'évolution comparée de 64 paramètres descriptifs de la charge et du produit fini en définissant des guides de prospection et de traitement qui permettent l'utilisation optimale des réserves charentaises dans le domaine des caoutchoucs naturels.

L'étude des diffusions, en dehors des taches de Bragg, produites par les molécules d'eau et les cations échangeables des vermiculites magnésium bicouches (d001 ∼ 14·4 Å) permet de proposer un modèle de l'espace interlamellaire. Les groupements cation-molécules d'eau (Mg-12H2O) présentent une organisation bipériodique (maille centrée 3a,b) dans des domaines limités. Chaque motif est constitué par un octaèdre Mg-6H2O auquel est liée fortement une seconde ‘sphère’ d'hydratation, formée également par six molécules d'eau (distances entre atomes d'oxygène des deux sphères d'hydratation de l'ordre de 2·65 Å).

Measurements have been made of the transient changes in the polarized components of fluorescence when aqueous suspensions of dye-tagged sepiolite particles were subjected to pulses of high frequency alternating electric field. The dye was acridine orange, a planar, cationic molecule. From these measurements, the size and electrical prolarizability of the sepiolite particles was evaluated and the directions of the absorption and emission transition moments responsible for the fluorescence of the dye located. The dye molecules were shown to adsorb on the clay surface with their long axes parallel to the sepiolite rods. Adsorption of the dye molecules in the surface channels of the clay was indicated. The electrical polarizability was considered and compared with the cation exchange capacity of the mineral. A novel, rapid means of studying clay minerals is indicated hereby.

Les vermiculites Mg, Ca, Sr et Ba ont été étudiées par diffraction des rayons X et absorption infra-rouge.

Pour les vermiculites monocouches, l'espacement interréticulaire est compris entre 12·2 et 11·45 Å.

On distingue: (i) les vermiculites Ba; le cation, entouré de 5 à 6 molécules d'eau, est à environ 1Å du plan médian et il intéragit avec un hydroxyle structural du feuillet le plus proche, (ii) les vermiculites Mg, Ca et Sr; le cation, entrouré de 3 ou 4 molécules d'eau,est dans le plan médian ou dans son voisinage (0·3 Å), et il n'interagit pas avec les hydroxyles des feuillets.

Pour les vermiculites anhydres, l'espacement interréticulaire est inférieur à 10 Å, le cation est dans le plan médian et il intéragit avec les hydroxyles de 2 feuillets opposés.

A partir de ces résultats, complétés par les données de la bibliographie, des modéles sont proposés pour représenter l'organisation de l'espace interlamellaire.

The < 2 µm fractions of two fluvio-glacial sediments from East Greenland have been analysed chemically and by XRD and Mössbauer spectroscopy. The bulk of each < 2 µm fraction consists of feldspars and micas (biotite) which are important constituents of the Precambrian igneous and metamorphic rocks of the area. Significant amounts of vermiculitic and smectitic minerals are also present. Compared with similar minerals present in Danish soil clays, the Greenland vermiculite and smectite are characterized by a high degree of crystallinity and it is concluded that these minerals have been formed from biotite through K release and lattice expansion. These processes appear to have proceeded at a sufficiently high rate to yield significant amounts of vermiculite and smectite despite the cold climate prevailing in the area.

Small amounts of Fe(III) induce precipitation of Fe(II) from carbonate solutions around neutral pH values. The reaction involves the formation of Fe(II)Fe(III) hydroxycarbonate, a green, layer-structured compound of the pyroaurite group of minerals. Variations in the concentration of Fe(II) in the solution phase, and in the form and amounts of the total Fe(III) in the system, may cause other phases such as magnetite and siderite to form also. Freeze-dried Fe(II)Fe(III) hydroxy-carbonate undergoes topotactic alteration to a magnetic phase, presumably maghemite, when stored under vacuum. The compound is readily oxidized in air in either the moist or dry state, rapidly becoming yellow or yellow-brown in colour. Oxidation leads to the formation of either goethite, lepidocrocite, ferrihydrite or mixtures of these phases, depending on the mode of oxidation and the impurities present. The similarity between the rapid colour changes and the oxidation products of the blue-green precipitates in gleyed soil horizons and this Fe(II)Fe(III) hydroxy-carbonate leads to the speculation that this and related compounds may be the meta-stable precipitates in such soils, rather than a previously postulated hydro-magnetite phase. Eh and pH conditions for the formation of Fe(II)Fe(III) hydroxy-carbonate are given, and are in the range encountered in the soil environment.

L'organisation de l'espace interlamellaire des vermiculites a été comparée en fonction: (i) de la nature du cation (Mg, Ni, Ca, Sr et Ba) et de son état d'hydratation (bicouche, monocouche et anhydre), (ii) de la nature du feuillet (charge et localisation des substitutions). Le facteur prépondérant, celui qui confère à l'espace interlamellaire son caractère ordonné ou non, est la nature du cation en particulier sa taille et son degré d'hydratation. La charge du feuillet apparaît comme un facteur complémentaire, elle limite la taille des domaines ordonnés.

Se realiza un estudio detallado de las distintas fases minerales (caolínicas y silíceas) que aparecen en rocas silicificadas tanto graniticas como sedimentarias de la provincia de Avila.

Las técnicas utilizadas (A.T.D., difracción de rayos X, microscopía electrónica de trasmisión y de barrido) permiten establecer una clasificación de estos minerales segun sus propiedades térmicas, parámetros cristaloquímicos, y morfologías identificadas al scaning.

Sa dá una interpretación genética a cada uno de los tipos de caolinitas encontrados (macrocaolinitas en acordeón, microcaolinitas en gusanillo y criptocaolinitas). Los dos primeros tipos pueden ser explicados por procesos conjuntos de alteración hidrotermal y ‘weathering’ de feldespatos y micas. El tercer tipo (criptocaolinitas) es de más difícil interpretación al aso-ciarse con ópalo C-T en diques que cortan a rocas granitoideas y otras veces al presentarse como matriz de areniscas sedimentarias.

The adsorption of the Asulam herbicide (4-aminobenzensulphonyl-methyl-carbamate) by Al- and H-montmorillonite has been studied by IR spectroscopy, thin layer chromatography and chemical analysis. This compound is adsorbed from CCl4 solution at room temperature through protonation of the NH2 functional group by the ‘acidic’ water coordinated to the interlayer cation of the clay. After heating the complex at 75°C for 20 h, a hydrogen-bond between the C=O group of the Asulam and the water is established and the organic molecule decomposes to sulphanilic and carbamic acids. If the complex is equilibrated at 100% relative humidity, the carbamic acid becomes unstable, and the IR spectrum shows only the bands typical of the acidic montmorillonite-sulphanilic acid complex. The catalytic properties of the clay surface are demonstrated by comparison with the transformations occuring in the organic molecule on heating in concentrated mineral acids.

En milieu organique, la formation de l'acide hippurique par contact d'un complexe montmorillonite-glycine avec de l'acide benzoīque est relativement facile. Dans ces conditions le peptide formé n'est pas hydrolysé. En milieu aqueux, par contre, l'activité catalytique de l'argile est insuffisante pour préparer l'acide hippurique à température ambiante. Une température minimale de 60°C est alors indispensable. Le rendement de la réaction qui est toujours faible dépend principalement de la nature du cation échangeable de l'argile. Les meilleurs résultats sont obtenus avec les montmorillonites contenant des éléments de transition tels que le cuivre, le nickel ou le zinc. Un phénomène d'activation faisant intervenir un complexe de coordination entre la glycine et le cation échangeable de l'argile constitue vraisemblablement l'étape intermédiaire dans la formation du peptide.

Clay mineralogical differences between eight soils in South Island, New Zealand, are related to differences in climate, vegetation, and formation time. Alteration of chlorite follows the sequence chlorite→interlayered hydrousmica→chlorite-swelling chlorite→chlorite-vermiculite, with increased weathering leading to the destruction of the chloritic layers. Mica (muscovite) follows two alteration sequences depending on the overlying vegetation. Under tussock grassland the sequence is mica→mica-vermiculite→mica-beidellite→beidellite. This sequence is also followed under beech forest, together with the sequence of mica→vermiculite→beidellite, with pedogenic chlorite forming when the pH is > 4·5. All but one of the interstratified products (the interlayered hydrous mica) appear to be based on a 1:1 regular interlayering of the two components.