Adsorption of Cu2+ and Co2+ by synthetic imogolite, synthetic allophanes with a range of SiO2/ Al2O3 ratios, and allophanic clay fractions from volcanic ash soils was measured in an ionic medium of 0.05 M Ca(NO3)2. The effect of pH (and metal concentration) on adsorption was qualitatively similar for the synthetic and natural allophanes with relatively minor changes in behavior caused by variable SiO2/Al2O3 ratios. Cu and Co were chemisorbed by allophane at pH 5.0–5.5 and 6.9–7.2 (pH values for 50% adsorption level), respectively, with concomitant release of 1.6–1.9 protons/metal ion adsorbed. Quantitatively, adsorption by imogolite was less than that by the allophanes, presumably because of fewer sites available for chemisorption on the tubular structure of imogolite. Electron spin resonance studies of the imogolite and allophanes revealed that Cu2+ was adsorbed as a monomer on two types of surface sites. The preferred sites were likely adjacent AlOH groups binding Cu2+ by a binuclear mechanism; weaker bonding occurred at isolated AlOH or SiOH groups. These chemisorbed forms of Cu2+ were readily extracted by EDTA, CH3COOH, and metals capable of specific adsorption, but were not exchangeable. In addition, the H2O and/or OH− ligands of chemisorbed Cu2+ were readily displaced by NH3, with the formation of ternary Cu-ammonia-surface complexes.

Resilication of bauxite produced kaolin at and beneath an old erosion surface on bauxite at the Alabama Street Mine of ALCOA in Saline County, Arkansas. The transitional alteration can be traced in morphology by scanning electron microscopy, (SEM) and in Al:Si ratio by energy dispersive analysis. In one illustrated example, the sequence of resilication took place within 1 mm thickness; in another, across 80 mm. The first morphologic alteration of gibbsite (bauxite) appears to be to allophane that occurs in micrometer-size plates which show elongate cracking and/or straight to highly curved elongate edges. The next phase is kaolinite, first in micrometer-size flakes followed by coarser flakes that grade into a zone of typical stacked kaolinite, likewise identified by X-ray powder diffraction. Notably large stacks and small flakes of kaolinite are intimately mixed in the SEMs, thus suggesting that unequal sizes of kaolinite crystals can grow during one episode of an in-situ genesis.

Infrared spectra (4000-1200 cm-1) were obtained for several homoionic montmorillonite films on which tetramethylene sulfoxide (TMSO) or thiolane were adsorbed at various temperatures and for different periods of exposure. The spectra indicate that the Na-, H-, and natural montmorillonite complexes contain a physically adsorbed species, whereas transition metal-montmorillonite complexes contain both physically adsorbed and metal-complexed species in their interlamellar spaces. Apparently, thiolane adsorbed on most montmorillonites undergoes oxidation to TMSO in an air atmosphere. Consistent with the mechanism proposed earlier for aqueous solutions, the rate of sulfoxide formation increases by increasing the pH of the suspensions from which the clay films were deposited or by increasing the concentration of the water molecules in the interlamellar spaces. The infrared spectra of γ-thiolactone adsorbed on Co-montmorillonites suggest that sulfoxide-type molecules are formed which chelate to the Co ions in the interlamellar spaces.

The treatment of smectites with a hydroxy-Al polymer produced chemically modified clays that had much greater affinities for chlorinated dioxins and biphenyls than untreated clays. For hydroxy-Al-treated kaolinite, the high affinity for chlorinated dioxins is thought to have arisen from an interaction between the hydroxy-Al polymer bound to the clay and the chlorinated dioxin in solution. Thus, the adsorption of dioxins from aqueous solution by hydroxy-Al-treated clays is similar to the adsorption of reactants from the gas phase by metals supported on mineral oxides during catalysis. In both systems, the essentially inert mineral oxide support effectively disperses the active adsorptive agent. At the concentrations of octachlorodioxin used in this study (≤5 ppb), hydroxy-Al-montmorillonite had a distribution coefficient of 90,000 (ml/g), corresponding to about 95% removal efficiency of the dioxin from solution per batch. For hexachlorohiphenyl, the distribution coefficient was 30,000 (ml/g), and the removal efficiency was 85%.

The word “legitimacy” and its derivations (legitimate, legitimation, etc.) are widely employed in scientific language as they also are in current usage. In fact, we find them in several areas, from that of reasoning (“this conclusion is legitimate”) to that of law (“judgment of legitimacy”, “legitimate family”) and politics (“legitimate sovereign”). It is particularly in this latter domain, however, that they have their normal use as qualifications for power, and it is this particular aspect that I shall consider in this paper. In accredited political language “legitimacy” designates a principle, or criterion, of justification for power (acting and commanding) and, correlatively, of the obedience that is its due.

To determine the dependency of rheological properties on mineralogical characteristics, eleven organophilic hectorite and nine organophilic saponite samples were prepared from hydrothermally synthesized smectites and a quaternary ammonium salt containing mainly octadecyl groups as alkyl chains and were examined by X-ray powder diffraction (XRD), particle size, chemical, and rheological procedures. The rheological properties of the organophilic products dispersed in toluene were found to depend chiefly on (1) particle size, (2) the expansion behavior of the stacked clay platelets, in which the amount and location of negative charge of the silicate layer affected the expandability, and (3) the amount of methanol added as a polar activator. By the addition of 2–4% methanol, apparent viscosities of the hectorite clays were drastically increased at low shear rate, although even a 10% addition did not significantly affect the saponite clays. Under the most suitable gellation conditions, the saponite clays showed lower apparent viscosity than the hectorite clays. Inasmuch as the former had its negative charge near the surface of the silicate layer and formed strong bonds to the organic ion, the expansion of the platelets was apparently difficult. An optimum layer charge for increasing the viscosity was found; specifically 0.45–0.50 and 0.50–0.55 equivalents per half unit cell for saponite and hectorite clays, respectively. Because the saponite clays contained a denser population of organic ions than the hectorite clays, the ion density in the interlayer of both clays was considered to be the same, i.e., about 0.4 organic ions per unit ab area.

An X-ray powder diffraction study of a vermiculitized chlorite in an amphibole schist near Limoges, France, shows the following weathering sequence: chlorite → ordered interstratified chlorite/vermiculite → vermiculite. Mössbauer spectroscopy indicates that vermiculitization proceeded by the release of ferrous iron from the 2:1 mica layer of the chlorite. The ferric iron content of the vermiculite product is almost the same as that of the initial chlorite. Infrared spectroscopy and chemical microprobe analyses show that Mg was preferentially extracted from the hydroxide sheet of the chlorite, whereas the Si and Al contents progressively increased to the point of the formation of a pure dioctahedral aluminous vermiculite. The Si, Al, and Mg removal processes support currently accepted vermiculitization mechanisms, but the behavior of Fe is slightly different. In this weathering sequence, vermiculitization does not appear to have taken place by the oxidation of Fe2+, but rather, by the simultaneous leaching of Fe2+ and Mg.

During the epigenetic alteration of boehmitic karstic bauxite in the Vlasenica region of Yugoslavia, which was caused by siliceous water descending through the deposit by means of cracks, fissures, etc., oolites were less altered compared with the coexisting matrix material, which was intensely kaolinized. The following zonal alteration pattern of the oolites was identified: a diaspore enrichment zone, followed by a diaspore-boehmite enrichment zone, and then the original bauxite. Considering this alteration pattern and that determined previously for the matrix material, the following overall pattern of alteration was established: a kaolinite-diaspore zone, followed by a boehmite-diaspore zone, and then the original bauxite. The alteration solutions reacted with the bauxite to form solution-matrix and solution-oolite subsystems, which were characterized by different types of diffusion and geochemistry.

In the kaolinite-diaspore zone Si-metasomatism kaolinized the matrix, and excess Al partly migrated into the oolites, forming diaspore, and outward into the bauxite. The latter Al-remobilization resulted in a transition zone, in which new boehmite was formed in both the matrix and the oolites, and diaspore only in the oolites. Thermodynamic models of oolites and whole bauxite alterations were established, on the basis of stability diagrams calculated for the mineral assemblages of both the oolites and the matrix, in the alteration zones and in the deposit as a whole. Based on these models, the genesis of the diaspore and the relationship of diaspore-boehmite-kaolinite assemblages in natural systems at low temperature and low pressure can be described.

Mythologies generally devote much attention to the birth of heroes and gods whose coming into the world is described as particular. Our first examples come from Greek mythology.

The Furies, goddesses of vengeance, were born of the blood of Uranus who had been castrated by his son Cronos. Athena sprang, completely armed, from the head of Zeus which Prometheus had struck with an axe, an act sometimes attributed to Hephaistos. The Centaurs came from a union of Ixion with a cloud to which Zeus had given the appearance of Hera with whom he was in love. Adonis came into the world from a myrrh tree (Smyrna in Greek ) which opened magically to give him birth. Ten years earlier a woman named Smyrna (myrrh) had committed incest with her father, Theios, without his realizing it; when he discovered the fact, he changed her into the tree known by that name. Bacchus was drawn out, a six months old fetus, from the body of his mother by Zeus. The body was lying in coals lit by the lightning and thunder accompanying the god's chariot as he came to visit Semele. Terrified at the sound of nature's fury, she had died of shock. Zeus sewed the fetus in his thigh and, when the time came, gave birth to Dionysius.

Mobility measurements were made for dry-ground mica particles dispersed in aqueous KCl, Cr(NO3)3, and cetyltrimethylammonium bromide (CTAB) solutions. In the latter solutions charge reversal occurred at about 2 × 10-6 M and 3 × 10-5 M, respectively. Negative zeta potentials in KCl solutions calculated using the Smoluchowski equation are about one third of the corresponding values obtained from streaming potentials and force measurements using mica sheets. Good agreement, however, was obtained when positively charged groups created during grinding were neutralized, and the zeta potentials were corrected according to the procedure of O'Brien and White with an assumed average particle size of 0.25 μm. When the zeta potentials of positively charged particles were corrected in this way, agreement with values calculated from force measurements was also improved.

With the current interest in the use of transition metal-exchanged phyllosilicates as catalysts for novel organic syntheses, investigations into the factors which affect the movement of reactant, product, and solvent molecules into and out of their interlamellar region are of considerable importance. Mixed organic-water intercalates of a Wyoming montmorillonite, exemplified by the Na-montmorillonitepyridine-water system which can form four different intercalates exhibiting basal spacing of 29.3, 23.3, 19.4, and 14.8 Å depending on the pyridine: water ratio, have been used as a model system. X-ray and neutron diffraction and quasielastic neutron scattering data relating to the interconversion of interlayer species indicate that access to and exit from the interlayer space is hindered at high partial pressures of water by a water-film diffusion barrier in the interparticulate voids which exist between the aggregated silicate layers. At lower water vapor pressures the rate-limiting step for interconversion from one intercalate to another is the rate of transport of reagents and products to and from the clay particles. Under conditions where these rates are fixed, the rate-limiting step is the rate of diffusion of the pyridine molecule in the lower-spacing intercalate. Processes which involve a change in basal spacing do not necessarily proceed via a single discrete step, but are also affected by the amount of water made available to the system. In organic reactions catalyzed in the interlamellar space of various cation-exchanged montmorillonites (e.g., the conversion of alk-1-enes to di-2,2’-alkyl ethers and the reaction of alcohols to form ethers), rate-determining steps similar to those found above are likely to be operative. In particular, for reactions carried out in the liquid phase, where mass transport is facile and where phase-transfer problems are avoided, such reactions are likely to be diffusion controlled.

What is the difference between the earthly paradise, the Golden Age and the ideal city? This question is most important for whoever is interested in the various ways human societies have had for imagining an ideal state of perfection or social harmony. If we are not to confuse such different systems of representation as mythical thought, millenarianism and Utopia, it is absolutely necessary that we do not reduce the descriptions of an earthly paradise and a Golden Age to simple precursors of the ideal city of the Utopians. It is especially important not to call “Utopian” every representation of the ideal society, Utopia being only one— and the most, recent—of its modalities. The Utopian dream Translated by Jeanne Ferguson takes up and at the same time alters the paradisiacal and millenarian imagination: it would be difficult to believe that the passage of primitive societies to great urban civilizations, then to modern society occurred without major repercussions on the vision of these societies, that the ideal state of social perfection did not vary from one to the other.

Ca-K.-, Na-K-, and Ca-Na-exchange isotherms on four reference smectites were studied. The electric charge on the four smectites was due predominantly to cationic substitution in the octahedral layer and varied between 90 and 122 meq/g (cmole(+)/kg) clay. The affinity of the clays for K increased with a decrease in the fraction of K in the exchange phase. The selectivity coefficients of the smectites for K increased with an increase in charge density. The effect was similar in the Na-K- and Ca-K-exchange isotherms. Charge densities on the smectites had no effect on the Ca-Na-exchange isotherm. The electrostatic attraction forces between the platelets increased with increase in charge density. The low hydration energy of adsorbed K was apparently not enough to overcome these attraction forces as the charge density on the smectites increased. Equilibrium between the low hydration energy of adsorbed K and the electrostatic attraction energies between the platelets is postulated to explain the results.