To enhance the catalytic activities of zeolites for the polycondensation reactions of humic precursors, Fe was loaded into a zeolite via an ion-exchange reaction and the resulting product was subjected to calcination at 773 K. Two types iron-loaded zeolites were prepared using one equivalent (Fe-Z-1) and 10-equivalents (Fe-Z-10) of Fe2+ to the cation-exchange capacity of a natural zeolite from Niki town (Hokkaido, Japan). X-ray diffraction (XRD) patterns and X-ray photoelectron spectroscopy (XPS) spectra showed that the Fe(II) that was originally loaded into the cation-exchange sites in the zeolite became oxidized to a Fe(III) ionic species during the preparation. The catalytic activities of each zeolite were evaluated, based on the degree of darkening for reaction mixtures containing catechol, glycine and glucose as model humic precursors. The catalytic activities of Fe-Z-1 and Fe-Z-10 were higher than that for an untreated zeolite, and increased with the amount of Fe in the zeolite.

An X-ray diffraction method for the estimation of quartz is described using rock powder pellets originally prepared for X-ray spectrometry, correcting the X-ray intensities for mass absorption. A coefficient of variation of 3·8% is claimed; 95% of all estimates fall within ± 5·5%.

Clay minerals and organic matter occur frequently in fault zones. Their structural characteristics and their textural evolution are driven by several formation processes: (1) reaction by metasomatism from circulating fluids; (2) in situ evolution by diagenesis; and (3) neoformation due to deformation catalysis. Clay-mineral chemistry and precipitated solid organic matter may be used as indicators of fluid circulation in fault zones and to determine the maximum temperatures in these zones. In the present study, clay-mineral and organic-matter analyses of two major fault zones – the Adams-Tinui and Whakataki faults, Wairarapa, North Island, New Zealand – were investigated. The two faults analysed correspond to the soles of large imbricated thrust sheets formed during the onset of subduction beneath the North Island of New Zealand. The mineralogy of both fault zones is composed mainly of quartz, feldspars, calcite, chabazite and clay minerals such as illite-muscovite, kaolinite, chlorite and mixed-layer minerals such as chlorite-smectite and illite-smectite. The diagenesis and very-low-grade metamorphism of the sedimentary rock is determined by gradual changes of clay mineral ‘crystallinity’ (illite, chlorite, kaolinite), the use of a chlorite geothermometer and the reflectance of organic matter. It is concluded here that: (1) the established thermal grade is diagenesis; (2) tectonic strains affect the clay mineral ‘crystallinity’ in the fault zone; (3) there is a strong correlation between temperature determined by chlorite geothermometry and organic-matter reflectance; and (4) the duration and depth of burial as well as the pore-fluid chemistry are important factors affecting clay-mineral formation.

A kaolin deposit from Mankon (northwest Cameroon) was prospected and studied for potential applications in ceramics. Six samples were investigated with X-ray diffraction (XRD), infrared (IR) spectroscopy and scanning electron microscopy (SEM) to determine the mineralogical composition and with X-ray fluorescence (XRF) to determine the chemical composition and properties for ceramic applications. The main minerals in the clays are kaolinite/halloysite and anatase associated with alunite, illite, gibbsite and maghemite. The kaolin samples have abundant organic matter (4–10%) and low absorption of methylene blue (0.2–2.5 meq/100 g), while SiO2 (33.28–56.31%) and Al2O3 (19.26–35.87%) are major oxides. The particle-size distribution derived from sieving and the hydrometer method indicates that 12–38% of the samples are in the <2 μm clay fraction. The clays have low to moderate plasticity (7–21%). One sample with K-feldspar and plagioclase displays the necessary properties for red ceramic products. SEM confirmed the occurence of halloysite in sample M9. The high kaolinite/halloysite content (64–97%), associated with low Fe2O3 content (0.5–1.4%) demonstrates that five samples are suitable raw materials for white firing industrial kaolin.

Les substrats argile-alkylammonium sont utilisés dans ce travail comme des modèles de sol, dans le but d'étudier les interactions entre un pesticide neutre peu soluble dans l'eau, le dinoseb, et des substrats dont les surfaces ont été rendues hydrophobes. Les spectrométries infrarouge (IR), Raman et de réflexion diffuse dans l'UV-visible sont utilisées de façon complémentaire aux isothermes d'adsorption pour préciser la localisation et l'état des molécules pesticide retenues sur les substrats. Dans le cas de la vermiculite-décylammonium, la fixation du dinoseb est observée à la fois sur les surfaces externes et dans les espaces interfoliaires, les molécules de pesticide sont directement en interaction avec les atomes d'oxygène de la surface des feuillets et avec les cations ammonium, par liaisons hydrogène. Le taux de molécules de dinoseb retenues sur l'hectorite-décylammonium est beaucoup plus faible. Les molécules fixées ont alors une structure voisine de celle des molécules libres. Ces analyses montrent que le caractère hydrophobe de la surface des complexes organominéraux est une condition nécessaire, mais non suffisante, pour la fixation de molécules peu solubles dans l'eau. Notre étude souligne l'importance des interactions spécifiques par liaison hydrogène entre le pesticide et le feuillet de vermiculite dans le processus de rétention.

The relationship between illite crystallinity (IC) and finite strain as well as lattice strain and crystallite size of illite is examined in a series of 27 deformed breccia samples from the inverted limb of the Morcles nappe. The IC is determined independently for limestone components and a red/green clay-silt matrix. The finite strain varies widely (D= 0.8–2.5). The IC values vary from diagenetic to epizonal, but no correlation with finite strain could be established. The spread of IC values is explained by heterogeneities within the protolith which have not been homogenized/ obliterated by the anchizonal to epizonal metamorphic overprint. While limestone pebbles display IC values in agreement with the regional metamorphic conditions, the clay-silt matrix has anomalously high IC values, even after deconvolution of the 10 Å peak to correct for the presence of paragonite/muscovite. No correlation could be established between finite strain, lattice strain and/or crystallite size of illite.

The less than 10 μm and less than 3 μm fractions of the heterogenous Haldon Gravels have been examined by X-ray diffractometry. Kaolinite of high to low crystallinity is the dominant clay mineral, with variable amounts of illite (clay mica) ; quartz, a little feldspar and anatase also occur. The kaolinite has been ranked using the crystallinity index of Hinckley and also by indices derived from the ratio of peak height to background height for the 10 and 11 peaks.

Clay from the matrix of the psaphitic members of the Buller's Hill Gravel contains intermediate grade kaolinite with a little illite, but clay bodies included in this formation contain only low grade kaolinite with a high, but variable proportion of illite. The Tower Wood Gravel contains two distinct populations; one is identical to that of the Buller's Hill Gravel, the other consists of high crystallinity kaolinite with a little illite. Head Gravel formed from the Buller's Hill Gravel by solifluction contains intermediate to low crystallinity kaolinite.

In an attempt to determine the nature and conditions of formation of the aluminium silicate precipitates present at the core of senile plaque in the brains of patients with Alzheimer's disease, aluminosilicate precipitates have been prepared and equilibrated for up to one year in physiological saline conditions at 40°C and a pH near 7·4. The structure and composition of these precipitates, and the associated concentrations of free silicic acid, were similar to those found in systems buffered with CaCO3 at 20–25°C. Imogolite-like products with Si : Al ratios near 0·5 were obtained at silicic acid concentrations <100 µm, and hydrous feldspathoid products with ratios ≥1·0 became dominant at silicic acid concentrations greater than ∼150 µm. These products do not match senile plaque precipitates, which have Si : Al ratios ≥1·0, but form in an environment with <100 µm Si. The relative stability of aluminium hydroxides, proto-imogolite allophane and hydrous feldspathoids are estimated from equilibrated silicic acid concentrations.

Après avoir rappelé l'importance du mode de préparation des associations montmorillonite-acides humiques sur leurs propriétés d'hydratation, nous présentons les résultats obtenus par adsorption d'azote.

L'ensemble des résultats obtenus sur ces associations indique que la localisation de la matière organique dans l'espace poral de l'argile joue un grand rôle, localisation qui varie avec le mode de préparation des échantillons et la teneur en carbone.

On donne une interprétation générale des courbes représentant la variation des quantités d'eau fixées par ces associations, quand la teneur en carbone augmente.

La détermination des complexes silico-ferriques, hydroxydes métalliques ou autres matériaux amorphes ou pseudocristallins contenus dans les sédiments marins est généralement difficile. La méthode décrite utilise la diffractométrie de RX et permet l'analyse quantitative de quelques-uns de ces matériaux tels que la silice biogène ou les cendres volcaniques. Cette phase amorphe constitue une composante majeure dans certains sédiments marins, d'où la nécessité de pouvoir la quantifier. La méthode reste suffisamment simple, fiable et précise pour permettre aussi la détermination quantitative de la phase cristallisée qui lui est généralement associée.

The distribution of Al3+ and Fe3+ between octahedral and tetrahedral sites of dioctahedral smectites was shown to be controlled by a partition coefficient Kd(4/6) = [(Fe3+)4×(Al3+)6]/[(Fe3+)6×(Al3+)4]. The Kd(4/6) value is near 0.006 for natural dioctahedral smectites, formed between 2 and ~100°C, and near 0.0174 for smectites synthesized at 200°C. These Kd(4/6) values, obtained from both chemical and spectroscopic data, were consistent with those calculated using the ionic radii of cations and Brice’s model (Brice, 1975). The partition coefficient approach explained well why for natural and synthetic dioctahedral smectites no tetrahedral Fe3+ is detected when the total Fe3+ content is below 3 atoms per unit cell (24 oxygen atoms).

Une nacrite est intercalée par deux composés organiques polaires: le diméthylsulfoxide (DMSO) et le n-méthylacétamide (NMA). Les deux solvants ont des moments dipolaires très voisins (4 debyes) mais des constantes diélectriques différentes (49 pour le DMSO et 179 pour le NMA). L'intercalation du NMA est plus rapide que celle du DMSO. Les deux complexes homogènes obtenus sont étudiés par diffraction des rayons X, spectroscopie infrarouge et ATD. L'étude par spectroscopie IR a montré que la nacrite expansée par du DMSO se comporte comme la kaolinite expansée par le même solvant. Dans le cas de la nacrite intercalée par du NMA, trois nouvelles bandes d'absorption dues aux vibrations de valence des OH liés par pont hydrogène avec le groupement C=O et situées respectivement à 3500, 3543 et 3589 cm−1 apparaissent. La fréquence v(N-H) du NMA est intermédiaire entre celles du liquide et d'une solution diluée, indiquant une liaison par pont hydrogène probablement avec les oxygènes de la couche tétraédrique du silicate. La diffraction des rayons X sur des échantillons orientés nous a permis d'obtenir 13 réflexions 00l pour chaque complexe. Une étude quantitative, par transformée de Fourier monodimensionnelle dans la direction perpendiculaire au plan du feuillet, a permis de déterminer le nombre de molécules organiques intercalées (une molécule par Si2Al2O5(OH)4) et leur orientation dans l'espace interlamellaire. L'ATD a montré par ailleurs que le complexe Nac.DMSO est plus stable que le complexe Nac.NMA.

Dickites with well-ordered crystal structures and with relatively high dehydroxylation temperatures develop a 14 Å phase when heated to temperatures in the range 550–800°C. The actual spacing is close to 13·7–13·8 Å. Dickites with less well-ordered structures and with lower dehydration temperatures give less development of this phase or none at all. Other kaolinite group minerals do not produce a similar phase. Thermal weight-change and differential thermal analysis data show that the 14 Å phase develops to a maximum as hydroxyl ions are eliminated from the dickite structure and infrared spectroscopic data are consistent with this result. AIKα fluorescence wavelength measurements indicate that the Al ions are in four-fold coordination in the 14 Å phase. Absence of other diffraction data makes structure analysis impossible. The description ‘chlorite-like’ for the 14 Å phase is of questionable validity.

L'étude de fire-clays provenant de deux séries continentales d'âge Eocène inférieur montre des corrélations très nettes entre la fréquence des défauts d'empilement des feuillets et certaines propriétés qui opposent les fire-clays aux kaolinites bien ordonnées: faible taux de ‘gonflement’ à l'hydrazine, capacité d'échange cationique élevée. Ces faits ainsi que les filiations observés dans l'une des séries étudiées entre interstratifiés smectitekaolinite et fire-clay condusient à émettre l'hypothèse que les défauts de structure des fire-clays sont dus à la présence de feuillets de type smectite, interstratifiés à faible fréquence, entre les feuillets de type kaolinite.

The nature of the alteration of basaltic, andesitic and rhyolitic glass of Holocene and Pleistocene age and their physical and chemical environments have been investigated in the ash layers within the cryogenic soils associated with the volcanoes in the central depression of Kamchatka. One of the main factors controlling the alteration of the volcanic glass is their initial chemistry with those of andesitic (SiO2 = 53–65 wt.%) and basaltic (SiO2 < 53 wt.%) compositions being characterized by the presence of allophane, whereas volcanic glass of rhyolitic composition (SiO2>65 wt.%) are characterized by opal. Variations in the age of eruption of individual ashes, the amount and nature of the soil water, the depth of the active annual freeze-thawing layer, the thermal conductivity of the weathering soils, do not play a controlling role in the type of weathering products of the ashes but may affect their rates of alteration.

Cement mortars and concretes incorporating clinoptilolite, silica fume and fly ash were investigated for changes in their physical and mechanical properties. It was found that additions of 10% clinoptilolite and 10% Pozzolite (1:1 mixture of silica fume and fly ash) were optimal for improvement of the quality of the hardened products, giving 8% and 13% increases in flexural and compressive strength respectively. The specific pore volume of the mortars incorporating zeolite decreased between the 28th and 180th day to levels below the values for the control composition due to the fact that clinoptilolite exhibits its pozzolanic activity later in the hydration. In these later stages, pores with radii below 500 nm increased at the expense of larger pores. The change in the pore-size distribution between the first and sixth months of hydration occurs mostly in the mortars with added zeolite.

Clay is the main construction material for clay cores of earth-fill dams. Clay minerals swell when they become wet and shrink when they dry out; cracks develop as they lose moisture. If precautions are not taken to prevent seepage through these cracks, dam failures may result. In this study, sand was added to montmorillonite-dominant clay soils to investigate the effect of sand-inclusion rates on the engineering characteristics of clay soils used in the construction of clay cores of earth-fill dams. Changes in the consistency limits, compaction characteristics, permeability, stress-strain relationships and swelling characteristics with increasing sand inclusion rates were evaluated. Based on the results from experimental trials, a 30% sand inclusion rate appears to be the optimum proportion; most of the swelling occurred in the voids of grains and led to permeability levels below the allowable limits for earth-fill dams.

In 1985, Dashidaira Dam, equipped with a flushing gate, was built on the Kurobe River in Toyama, Japan. Since the dam sediments were first flushed out in December 1991, benthic fish counts have decreased year by year due to repeated flushing of clay-rich dam sediments.

In June 2001, the flushed dam water contained a low oxygen concentration (1 to 2 mg/l) and high concentrations of smectite and vermiculite. To establish the cause of the death of the benthic fish, living flatfish were collected from Toyama Bay in order to examine their gills, which showed tissue damage and chemical changes caused by adherent expandable clays, derived from the flushed dam sediments. For comparison, exposure experiments on rainbow trout were carried out using smectite suspensions. Examination by optical microscopy revealed that the gills had shrunk because of the smectite concentrations. Low oxygen concentrations and large amounts of expanding clays have a significant effect on downstream benthic life.