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Imogolite is a hydrous aluminium silicate mineral (Cradwick et al., 1973) with a fibrous morphology and low degree of structural order, which, since first described by Y oshinaga and Aomine (1962), has been reported to occur as a weathering product of pyroclastic materials in many localities. However, Wada et al. (1972) have recently drawn attention to the fact that imogolite occurs in gels derived from massive, though jointed, basalt in Hawaii. The purpose of the present note is to describe the identification of imogolite in some very young volcanic ash soils from New Guinea-a finding that has important genetic implications.
Kaolinite is synthesized in approximately the same time in three temperature ranges: (1) from 200–250° to 350–400° (hydrothermal processes); (2) from 120 to 175° (semihydrothermal ones); (3) at ordinary temperature. It is thus evident that the rate process cannot be explained by the Arrhenius equation only, but is explained well by considering that kaolinite formation obeys the laws of crystal growth. It occurs only in slightly supersaturated solutions in which the nucleation process is possible and in which a slow and regular rate of growth has been insured. Concentrations calculated from the thermodynamical equilibria correspond to those of the experimental conditions for the low temperature processes. For the higher temperature ones, a similar relationship is delineated, at least as far as the thermodynamical treatment can be carried out.
Mixed-layer kaolinite/smectites containing 40–90% kaolinite layers have been synthesized from Wyoming smectite. Run times were 4 months at 156°C in solutions of A1C13∙6H2O and KCl or CaCl2. Similar KCl runs devoid of Al3+ yielded mixed-layer illite/smectites. The supply of Al3+, rather than pK or pH, seems to control the alteration of smectite toward kaolinite or illite.
The effect of pH, time and temperature on the interaction of zinc with acid and base saturated dickites has been investigated. Increase in pH resulted in an increase in adsorption of zinc in the higher concentration range. The adsorption increased rapidly and then slowly with increase in the time of interaction. The variation of rate constants and the half times of reaction suggested an exchange process controlled by film and possibly particle diffusion and thereafter fixation processes. The inferences found support from the nature of adsorption isotherms. Temperature affected adsorption with exothermic interactions. The activation energy of adsorption of zinc on Na-dickite was 14.0 kcal mole−1.
Adsorption of asphaltenes and resins onto montmorillonite occurs rapidly and to a large extent irreversibly under near-anhydrous laboratory conditions. Factors which influence the adsorption are the exchangeable cation on the clay, the basic nitrogen components of the molecules, and the solvent. As a result of this adsorption, the physical and chemical properties of the clay are drastically altered. The fundamental principles revealed in this study lead to a better understanding of the physical and chemical behavior of clays in petroleum reservoirs.
Markus nimmt seine Gegenwart als dunkle, düstere Zeit wahr und bearbeitet mit seiner Jesuserzählung die krisenbehaftete Gegenwart. Ein zentraler Baustein in seinem Krisenmanagement ist ein strategischer Einsatz literarisch-theologischer Mehrdeutigkeiten. Die vorliegenden Beobachtungen illustrieren diesen strategischen Einsatz am Beispiel der programmatischen Basileiaaussage in Mk 1,15. Unsere Kernthese lautet: Markus bändigt die Ambiguität der ἤγγικɛν-Aussage in 1,15 durch die ἤγγικɛν-Aussage in 14,42 und beansprucht damit Deutungshoheit inmitten einer existentiellen krisenhaften Zuspitzung in der erzählten Welt. Dieser Gewinn an Deutungshoheit marginalisiert weder die Krisenerfahrung am Vorabend des Todes Jesu noch die Krisenerfahrung in den 70er Jahren, sondern dient dazu, ein wenig festen Boden in all der verbleibenden Unklarheit und Ungewissheit unter die Füße zu bekommen.
Saturated with 6 different cations (Li, Na, K, Ca, Mg, Ba) its swelling in ethylene glycol, glycerol and water and its homogeneous hydration extents according to the relative humidity have been studied. Our results were compared with those found for montmorillonites, beidellites and vermiculites in order to estimate the respective influence of the surface charge density and the charge localization on the swelling properties. The three-dimensional organization of the saponite is more or less affected by random stacking faults and by multiple b/3 translations according to the exchangeable cation, the swelling state and the nature of the solvation liquid. Our experimental results indicate that the three-dimensional order met in the hydrated saponites can be explained by an anchoring of the layers towards each other by chains made up of cation -dipole interactions and of hydrogen bonds between negatively charged surface oxygens and the interlayer water. This type of interlayer link is relatively weak. It is therefore easy to introduce stacking faults in these edifices in particular by grinding of the samples.
Lysine and vermiculite form a stable, ordered, interlamellar complex which has a well defined superlattice structure with respect to the ab-plane of vermiculite. The lysine molecules lie at a low angle to the silicate surfaces and establish a double layer network between such surfaces. I.R. and chemical data for the complex are given. The possible role of hydrogen bonds in linking the system together is considered.
The adsorption of 1,10-phenanthroline (OP) onto some clays and oxides was studied as a function of concentration, pH, and time. The adsorption was found to be irreversible and the isotherms, except for silica gel, were hyperbolic and gave rise to plots similar to that of Langmuir. Kinetic and light scattering studies show that OP is adsorbed as a micellar unit composed on the average of 3.5 molecules/micelle. This fact explains the overestimation observed in the surface areas of some sorbents since no true monomolecular layer of OP is formed on the surfaces. The adsorption was also found to be pH dependent, attaining a maximum, independent of the sorbent, at about pH 6. This maximum was approximately at the same pH in which only the molecular form of OP began to be present. The partial desorption of OP as the pH increased beyond 6 is possibly associated with the aggregation of micelles on the surfaces.
The mechanism of the transformation of lepidocrocite (γFeOOH) to goethite (αFeOOH) has previously been established and the effect of silicate on the transformation was investigated. Rather than completely inhibiting the reaction, as had been suggested, the presence of Si was found to merely retard the nucleation stage of the transformation. There was found to be no decrease in the dissolution rate of the lepidocrocite due to surface adsorption of Si.
Si has no effect if introduced after the nucleation stage, and under conditions of pH and temperature where the dissolution rate of the lepidocrocite largely determines the rate of transformation, the presence of Si has a reduced effect. The results show that Si is adsorbed and incorporated into the goethite structure, and due to its retarding effect on the nucleation, larger crystals of goethite are formed, many of which are twinned.
It is inferred from the results that the apparent stability of lepidocrocite occurring in soils in association with goethite cannot be attributed solely to the presence of Si in the soil system.
Selectivity of a number of vermiculites, montmorillonites and micas for K and Cs ions was determined by sorption of these ions from equilibrium solutions of diverse concentrations. The selectivity coefficients were related to the layer charge density and the area of the frayed edges in layer silicates.
Montmorillonites had the smallest selectivity for the two ions, while biotite and illite had the greatest selectivity. Selectivity of biotite and illite was limited to small concentrations of K, however. At greater concentrations the selectivity of vermiculite for K exceeded the selectivity of the micas.
The greater selectivity of vermiculites than montmorillonites for K and Cs ions was attributed to the greater layer charge density in vermiculites. The greater selectivity of micas than montmorillonites and vermiculites was attributed to the frayed edges of micas in addition to their larger layer charge density. As the frayed edges in illite were increased in area by removal of the interlayer K, the selectivity of illite for K also increased; thus confirming the selectivity of frayed edges for the K ions.
Two variables must be considered when calculating exchange free energies (ΔG°ex) for 2:1 clays: (1) anionic field strength, as expressed by equivalent anionic radius (ra), and (2) interlayer water content, as expressed by interlayer molality. For smectites that are in a state of high hydration, interlayer molality is determined by the cations undergoing exchange. Thus ΔG°ex for an exchanging cation pair can be calculated solely from measurements of ra. ra is related to layer charge per half unit cell (C) and ab unit cell area (A) by: ra = (-A/8πC)1/2. The layer charge necessary for cation fixation can be predicted by calculating the ra at which cation exchange with an illite structure expresses a AG°ex equal to that of exchange with a smectite structure. The theory can also be applied qualitatively to understand the high selectivity of illite for Cs+, the fixation of K+ rather than Na+ in shales during diagenesis, the stability of illite over muscovite in the weathering environment, and cation segregation in smectite.