bluuebunny/crossref_metadata_2025 huggingface dataset:
Scanning Electron Microscopy of Cherts in Relation to the Oxygen Isotopic Variation of Soil Quartz
Authors: Sayin Mahmut , Jackson M. L.
Published: September 2006

Quartz isolated from soils by the pyrosulfate-H2SiF6 method and chert samples of various origins were examined with the scanning electron microscope. Quartz isolates of the 20–50μm from the A2 and B21t horizons of the Baxter soil (AR), with quartz δ18O of 18·2 and 19·0‰, respectively, showed a mixture of detrital quartz particles and chert clusters of aggregates of fine euhedral quartz crystals. The 2–5 μm fractions of both horizons consisted mainly of euhedral quartz particles. The 20–50 μm fraction from the underlying chert, with a δ18O = 29·6‰, consisted of aggregates of euhedral quartz particles 1–10 μm dia and of subhedral particles 0·1–0·5 μm dia. In the soil fractions, the size and shape of the quartz particles as well as oxygen isotope data indicated that the aggregates were from the underlying chert but that irregular, unaggregated grains were detritally admixed loess, particularly in the medium and coarse silt fractions. This mixing of chert (of low temperature origin and heavy oxygen) with detrital quartz (of high temperature origin and light oxygen) gave rise to the intermediate δ18O values in the soil quartz. The SEM of cherts of different geological ages showed different morphologies. Prismatic, polyhedral microcrystalline quartz of 1–10 μm size as well as submicron, euhedral particles were observed in cavities. Submicron, subhedral particles and interlocking quartz grains were characteristic of Precambrian chert. Quartz grains more than 100 μm in size isolated by HCl from Ordovician dolomite (WI) had large (many microns) subhedral overgrowths and attached clusters of 0·1–0·5 μm microcrystalline quartz. A Danish flint formed in chalk had calcite-lined cavities (x-ray emission determined) in which spheroidal fibrous chalcedony occurred.
The Syntheses of Hydrotalcite-Like Compounds and Their Structures and Physico-Chemical Properties—I: the Systems Mg2+-Al3+-NO3−, Mg2+-Al3+-Cl−, Mg2+-Al3+-ClO4−, Ni2+-Al3+-Cl− and Zn2+-Al3+-Cl−
Authors: Miyata Shigeo
Published: September 2006

The basic salts of this system were prepared and their structures and physico-chemical properties were studies by electron microscopy, chemical analysis, X-ray powder diffraction, thermal analysis, i.r. absorption spectra, BET absorption, and acidity-basicity measurements. The salts were found to be new compounds analogous to hydrotalcite. They can be expressed by the formula; where M2+ and M3+ denote di- and trivalent cations, A− and A2− denote mono- and divalent anions, respectively, and y = z1 + 2z2; z1 ≫ z2.

The structures consist of positively charged Cd(OH)2-like basic layers and intermediate layers formed from anions and water molecules with the solid solution of divalent cation (M2+) and trivalent cation (M3+) being formed in the range of 0.6 < x/(x + y) < 0.9. The anions of Cl−, NO3− and ClO4− are easily substituted by CO32−. A large part of the NO3− makes a monodentate-type bond and the ClO4− a bridge-type bond.
Further Information Related to the Origin of Glauconite
Authors: Velde B. , Odin G. S.
Published: September 2006

Glauconite-smectite and illite-smectite interlayered minerals are compared by various means in an attempt to establish the mineralogical relations between the two groups. Experiments at 2 Kb pressure and 200–350°C are reported as well as microprobe scans of pelletal glauconites. This new information is used along with published chemical data in order to establish that

(1) Illite and glauconite mixed layered phases appear to be crystallographically similar. Both series show the same relations between potassium (mica) content and the amount of smectite layers apparent in the interlayered structure.

(2) Illite and glauconite mica or mica-like phases can be separated on the basis of Fe and K contents.

(3) Probable phase relations of the two mixed layered mineral series indicate that, when the starting materials contain mixed layered mica-smectites, increasing temperature produces an iron-rich mica in the case of glauconite and an aluminous mica in the case of illite. The mixed layered phases present at intermediate temperatures are not the same for illites and glauconites.

Apparently there is no mineralogical or chemical continuity between illite and glauconite when the potassium content is 6 wt % or greater. It might be possible that the potassic interlayered minerals near montmorillonite or nontronite could form a continuous solid solution.
The System SiO2-AlOOH-Fe2O3-H2O and the Kaolinitic Stage of the Goethite Facies
Authors: Chesworth Ward
Published: September 2006

A 25°C, 1 atm total pressure phase diagram for the system SiO2-AlOOH-Fe2O3-H2O, is determined using the Phase Rule and Shreinemaker’s technique as in Chesworth (1974). The waterpresent assemblages so defined are equivalent to a kaolinitic stage of the goethite facies of the weathering zone. As such they constitute the ideal stable assemblages of several earth-surface deposits and the stage can therefore be used to construct models of these deposits.
Mössbauer Study of Transformations Induced in Clay by Firing
Authors: Simopoulos A. , Kostikas A. , Sigalas I. , Gangas N. H. , Moukarika A.
Published: September 2006

The clay fraction of an Attic soil has been fired at temperatures up to 1100°C and the transformations induced by firing were studied by Mössbauer spectroscopy. The unfired clay contained iron in the form of small particles of α-Fe2O3 and β-FeOOH and as a substitutional ion in the clay mineral structure. A transformation of β-FeOOH to α-Fe2O3 is observed in the region of 200–400°C followed by dehydroxylation of the clay mineral between 500 and 800°C. A disintegration of the clay mineral structure is inferred above 800°C, followed by recrystallization in an iron-rich phase, most probably in the form of very fine particles. The room temperature spectra of the fired samples indicate that an increase in particle size of the oxides occurs upon firing.
Variability in Exchange Ion Position in Smectite: Dependence on Interlayer Solvent
Authors: Berkheiser V. , Mortland M. M.
Published: September 2006

Full and reduced charge smectite saturated with Na(I), Ca(II), Cu(II), or tetralkylammonium ions were swollen by a series of solvents of various bulk physical properties. In the full charge smectites, swelling occurred in all solvents regardless of the exchange ion or the initial water content. Charge differences did not usually result in differential swelling of the smectite. Little correlation was found between the degree of swelling and the Gutmann donor numbers, bulk dielectric constants, bulk surface tensions, or dipole moments of the solvents. The intensities of the high field Fe(III) resonance (g = 3.6) in the esr spectra of full charge smectite swollen in various solvents reflected variability in exchange ion positions and depended upon the Gutmann donor number of the solvent. Considerable variety in the stereochemistry of Cu(II)-solvent complexes was revealed by esr spectra of the swollen systems.
Adsorption of Ethylenediamine (EDA) on Montmorillonite Saturated with Different Cations—V. Ammonium- and Triethylammonium-Montmorillonite Ion-Exchange, Protonation and Hydrogen-Bonding
Authors: Cloos P. , Laura R. D. , Badot C.
Published: September 2006

On NH4- as well as on (C2H5)3NH-montmorillonite EDA was adsorbed in protonated form. The extent of protonation depended on the relative basicities and concentrations of the interacting compounds. In the systems exposed to EDA vapor a proton transfer process took place. A similar mechanism, involving probably a water molecule which remained associated with the EDAH+ ion, occurred on air-drying (C2H5)3NH-montmorillonite treated with aqueous EDA, whereas no adsorption was observed when the suspension was washed. On the contrary EDA added, in quantities not exceeding the CEC, to a suspension of NH4-montmorillonite was adsorbed almost exclusively as EDAH22+ ion. This is explained in terms of ion-exchange between NH4+ and EDAH+ present in aqueous medium and protonation of the second amine function through the dissociation of water molecules near the clay surface.

Hydrogen-bonding between protonated and neutral EDA was observed when the extent of adsorption was higher than the extent of protonation.
Bulk Densities of Selected Dried Natural and Fired Kaolin Clays
Authors: Baumann David , Keller W. D.
Published: September 2006

Bulk (lump) densities of 31 kaolins were measured on the clay in the natural or raw state after drying at 100°C and after firing to 1510°C (2700°F). The kaolins were selected from such diverse origins as surface-weathered and sedimentary accumulations, hydrothermally altered bodies and flintclay deposits. The sedimentary group ranged in density from 0·82 to 1·85 in the dried raw clay, and 1·93 to 2·63 when fired. The hydrothermally altered clays ranged from 1·83 to 2·50 in the dried raw state, and 2·02 to 2·66 when fired. Flint clays ranged from 2·20 to 2·60 in the dried raw state (a “toasted clay” from Russia, 1.75), and 1·99 to 2·70 when fired. The effect of the genetic process on bulk density values is discussed and related.
Quartz Presence in Relationship to Gibbsite Stability in Some Highly Weathered Soils of Brazil
Authors: Weaver R. M.
Published: September 2006

Determination of the mineralogical composition of six highly weathered soils of the Central Plateau of Brazil showed that the sand content (predominantly quartz) was not related to the relative amounts of gibbsite and kaolinite in the clay (< µm) fractions. The latter is in agreement with kinetic considerations of the involved mineral species, but in disagreement with thermodynamic considerations. However, that dissolution of quartz has been operative in these soils is indicated by an excellent relationship (r2 = 0·96) between the amount of sand-size quartz and the reactive SiO2 content of the clay fractions.
Folding in Sepiolite Crystals
Authors: Serna C. , Ahlrichs J. L. , Serratosa J. M.
Published: September 2006

Fibrous sepiolite crystals derive much of their commercial value from their molecular size channels and grooves. The crystals fold upon drying and these channels and grooves are lost. A model for the folding and unfolding of the crystals is presented. Extensive i.r., X-ray and thermogravimetric evidence shows that folding occurs when approximately half of the water of hydration, which is coordinated to the edge magnesium atoms inside of the channels, is removed. This occurs near 175°C under vacuum and near 300°C in air. When the crystals fold, all remaining water molecules enter a new environment, that of the hexagonal holes of the neighboring silica surface. A true anhydride is produced at about 500°C under vacuum when the final water is lost, but this final dehydration produces no important structural change. Rehydration of the anhydride to the normal hydrated sepiolite does not occur at room temperatures in 100% r.h. However, above, 60°C rehydration does occur.
Montmorillonite-Alkali Halide Interaction: A Possible Mechanism for Illitization
Authors: Heller-Kallai L.
Published: September 2006

The reaction products obtained when montmorillonites react with potassium halide at elevated temperatures, which were described in a previous publication, are further characterized. On the basis of their X-ray powder diffraction patterns, i.r. spectra, CEC and chemical composition they could be regarded as montmorillonite-illite interstratifications. Changes in morphology of various montmorillonites heated with and without K halide are related to the size, charge and position of interlayer cations. Scanning electron-micrographs of samples heated with KBr resemble those of well-crystallized illite. It is speculated that reactions of clay minerals with halides or other proton acceptors may account for some diagenetic processes in nature, e.g. the conversion of montmorillonite to illite on deep burial.
Regularly Interstratified Chlorite/Vermiculite in Contact Metamorphosed Red Beds, Newark Group, Connecticut Valley
Authors: April Richard H.
Published: September 2006

A regularly interstratified chlorite/vermiculite occurs in red beds of the East Berlin Formation (Early Jurassic age) in the Connecticut Valley. The mineral is restricted to a 2.5-m wide zone of contact metamorphosed strata adjacent to and underlying the Hampden Basalt. Chemical and X-ray powder diffraction data indicate that the chlorite/vermiculite formed in response to lava-induced elevated temperatures and the availability of magnesium in the muds during and shortly after emplacement of the lava flow. Near the contact, hydrothermal fluids originating from the lava and from the synchronal weathering of basalt fragments by superheated pore waters provided a source of Mg. Further from the contact, magnesium was primarily derived from the thermal dissociation of dolomite. K2O concentrations and the distribution of clay minerals in the red mudstone suggest that the interstratified chlorite/vermiculite formed from preexisting illite or vermiculite as potassium was released and brucitic sheets were incorporated into interlayer positions.
Hydroxyl Orientations and Interlayer Bonding in Amesite
Authors: Giese R. F.
Published: September 2006

The hydroxyl orientations in the 2H2 polytype of amesite, Mg2Al(SiAl)O5(OH)4, have been determined by minimizing the electrostatic potential energy as a function of OH orientation. The angles, ρ, between the hydroxyls and (001) vary between 81.5 and 88.8°. All surface hydroxyls form hydrogen bonds with oxygens of the adjacent layer. The OHs tend to tilt away from the higher charged A1VI ions, and the spread in ρ values is due to variations in the positions of the receptor oxygens. The inner hydroxyls noticeably weaken the interlayer bonding. The substitution of Al in both T and M sites creates a dipolar layer charge and the resulting attraction between layers forms an important part of the interlayer bonding. The 2H2 polytype of amesite has substantial interlayer bonding even with all surface hydroxyls replaced by fluorine. This is not true for a composition of Mg3Si2O5(OH)4 where a similar F for OH substitution destroys all interlayer bonding as in kaolinite.
Kaolin From The Original Kauling (Gaoling) Mine Locality, Kiangsi Province, China
Authors: Keller W. D. , Cheng Hsia , Johns W. D. , Meng Chi-Sheng
Published: September 2006

Although the specific outcrop from which the original kaolin at Kauling (Gaoling) Mine, China, was collected cannot now be relocated, samples were collected and studied from the mine tunnel, country rock, and pegmatite which constitute the sources of kaolin in this region. The kaolin is a residual product of weathering. Where the parent rock was a granite the clay is a mixture of platy and elongate kaolin-group minerals, whereas from the pegmatite portion of the parent rock it is halloysite(10Â) with elongate morphology. These mineral identifications are based on X-ray powder diffractograms, scanning electron micrographs, differential thermograms, and an infrared spectrum hitherto not documented for material from this area.

Although the Kauling locality is the region for which kaolin is named, the mineral kaolinite is a defined species without a specific type locality. The 11th century Chinese locality was not mentioned in the two classic research papers defining kaolinite. The data on the Chinese kaolin, therefore, cannot be used directly to provide criteria for sharply differentiating the otherwise vague boundary between the minerals kaolinite and halloysite(7Å). Pertinent questions on these kaolin-group mineral relationships are brought into clearer focus.
Intercalation of Silica in Smectite
Authors: Endo T. , Mortland M. M. , Pinnavaia T. J.
Published: September 2006

Silica has been intercalated in swelling clays by hydrolysis and/or oxidation of tris(acetylacetonato)siIicon(IV) cations, Si(acac)3+, and polychlorosiloxanes, (-SiOCl2-)n, in the interla-mellar regions of the minerals. The Si(acac)3+ ions have been placed on the interlamellar surfaces by ion exchange and by in situ reaction of the acetylacetone-solvated clays with SiCl4. The (-SiOCl2-)n polymers were formed in the interlayers by reaction of adsorbed benzaldehyde with SiCl4. The optimum (001) spacing observed after firing the clays in air at 500°C (12.6 Å) corresponds to the presence of a monolayer of siloxane chains. Nitrogen BET surface areas range from 40 to 240 m2/g, depending on the amount of internal surface covered by the intercalated silica. In some cases, highly ordered products were formed which exhibit four orders of (00ℓ) reflection. Interstratified products with d(001) values between 9.6 and 12.6 Å exhibit surface areas consistent with the presence of a random mixture of totally collapsed interlayers and interlayers containing siloxane monolayers. Attempts to achieve silica intercalation by hydrolysis of SiCl4 in the clay interlayers were not productive.
Absorption of Infrared Radiation by D2O and HDO Mixed with Montmorillonite
Authors: de Chou J. Salle , Low P. F. , Roth C. B.
Published: September 2006

The frequency, v, for O-D stretching in D2O films between the superimposed layers of different micas and montmorillonites was measured at several film thicknesses and temperatures of 2° and 25°C by infrared spectroscopy. The molar absorptivity, ε, for O-D stretching in HDO films between the montmorillonite layers was also measured at different film thicknesses and 25°C. It was found that v is related to mw/mm, the mass ratio of D2O to mica or montmorillonite, by the equation v = v0 exp β/(mwmm where v0 is the O-D stretching frequency in pure D2O and ß is a constant. Since mw/mm is proportional to a, the area under the absorption peak, mw/mm can be replaced by a in this equation. It was also found that ε decreased dramatically as the thickness of the water film between the montmorillonite layers decreased. These results were interpreted to mean that the structure of the interlayer water is perturbed by the interlayer cations and/or silicate surfaces.
Swelling Components of Compacted Ca-Montmorillonite
Authors: Parker J. C. , Zelazny L. W. , Amos D. F.
Published: September 2006

Intracrystalline water adsorption of Ca-montmorillonite was calculated as the product of one-half the interlayer spacing from X-ray powder diffraction analysis and the difference between the desorption surface area determined with ethylene glycol-monoethyl ether and BET surface area determined by N2 adsorption. Osmotic adsorption was calculated as the product of the N2 surface area and theoretical double layer thickness. Measured water adsorption of P2O5-dry clay, compacted to initial densities (γ0) from 0.52 to 1.59 g/cm3 and submerged in 0.01 N CaCl2 was 2.4 to 4.2 times greater than intracrystalline plus osmotic adsorption due to the occurrence of pores exceeding double layer dimensions. The increase in expansion caused by reducing electrolyte concentration to 0.001 N was equal to the predicted increase in double layer volume, verifying the existence of an osmotic component to swelling.

Measured expansion following submersion in 0.01 N CaCl2 increased continuously with γ0 from 0.53 cm3/g at γ0 = 0.52 g/cm3 to 1.17 cm3/g at γ0 = 1.59 g/cm3, while estimated osmotic plus intracrystalline expansion was constant at 0.30 cm3/g. This discrepancy is attributed to swelling caused by gas pressures developing ahead of advancing wetting fronts. The effect of compaction on expansion is explained by reductions in pore size, as measured by N2 desorption, which accompany compaction. Reduced pore size should increase entrapped air pressures, whereas gradual wetting should favor their dissipation. Accordingly, slow wetting reduced the expansion of a sample where γ0 = 1.06 g/cm3 from 0.77 to 0.37 cm3/g. Swelling due to entrapped air pressures produced a large increase in the number of pores > 104 Å in diameter, as determined by Hg intrusion porosimetry.
Hydrothermal Effects on Cesium Sorption and Fixation by Clay Minerals and Shales
Authors: Komarneni Sridhar , Roy Della M.
Published: September 2006

The effects of hydrothermal conditions on the sorption and fixation of cesium by various clay minerals and shales were investigated. Hydrothermal heating, which may be expected in a radioactive waste repository, altered the clay minerals and shales and led to a decrease in their cation-exchange capacity. Cesium sorption greatly decreased in micaceous vermiculite and in well-crystallized illites containing vermiculite upon hydrothermal treatment at 400°C and 300 bars pressure due to complete layer collapse. However, poorly crystallized illites heated as above showed either a small increase or only a slight decrease in Cs sorption because of partial layer collapse. These studies show that the decrease in Cs sorption is greater in well-crysallized illites than in poorly crystallized illites when treated similarly under hydrothermal conditions. Hydrothermal heating of Cs-sorbed and Cs-saturated samples increased the amount of Cs fixation in all minerals and shales as a result of collapse of the layers. For example, a sample of the Conasauga shale fixed only 18% of sorbed Cs before treatment but fixed 47% after hydrothermal treatment at 200°C and 300 bars pressure. Thus, hydrothermal conditions in a shale repository may be beneficial after leaked radioactive Cs ions are taken up by clay minerals in shales.
The Influence of Aluminum on Iron Oxides. VI. The Formation of Fe(II)-Al(III) Hydroxy-Chlorides, -Sulfates, and -Carbonates as New Members of the Pyroaurite Group and Their Significance in Soils
Authors: Taylor R. M. , McKenzie R. M.
Published: September 2006

In the absence of oxygen, Fe(II) chloride, sulfate, and carbonate solutions react at pH 6.5 to 7 with aluminum hydroxide suspensions to form new Fe(II)-Al(III) hydroxy anion compounds of the pyroaurite group. The Fe(II)-Al(III) hydroxy-chloride and -sulfate compounds are isostructural with Fe(II)- Fe(III) “green rust” compounds with A1 essentially substituting for Fe(III). Where CO32- is the only anion in the system, an Fe(II)-Al(III) compound isostructural with hydrotalcite is formed. Either in the dried or wet state, these compounds are unstable in air due to oxidation of Fe(II). Oxidation of the dried sample in air yields akaganeite or aluminous ferrihydrite, whereas, if the sample is maintained in a moist condition and oxidized by air under water, lepidocrocite or aluminous goethite is produced along with small amounts of ferrihydrite. On X-ray powder diffraction, the lepidocrocite so formed commonly shows no diagnostic (020) basal reflection, or one with a markedly reduced intensity. The products of oxidation, and the rapidity of their formation, appear to be dependent on the composition of the initial double hydroxy compound and the conditions under which the oxidation is carried out.

The green colored compounds commonly observed in gleyed soils also rapidly become yellow brown on exposure to air, and difficulty arises in the identification of the Fe oxide phases assumed to be present. Similar conditions and reactants to those involved in the formation of the compounds described above are expected in these soils, and it is suggested that Fe(II)-Al(III) members of the pyroaurite group may form in such an environment.
Formation and Characterization of Clay Complexes with Bitumen from Athabasca Oil Sand
Authors: Czarnecka Eliza , Gillott J. E.
Published: September 2006

Montmorillonite, kaolinite, illite, and chlorite were found to adsorb bitumen and its pentane-soluble and pentane-insoluble fractions. The formation of clay-bitumen complexes is influenced by the nature of the exchangeable cation on the clay and by the solvent carrier which stabilizes the bituminous compounds. Ca-clays adsorb organic compounds more strongly than sodium forms except in the presence of nitrobenzene. Solvents of high dielectric constant, such as nitrobenzene, promote ionization so that the ion-exchange mechanism of adsorption is favored, whereas solvents of lower dielectric constant, such as chloroform, tend to solvate rather than to dissociate bitumens. The behavior of the montmorillonite-bi- tumen complex in variable relative humidity indicates that organic molecules adsorb primarily on external surfaces and cause the clay to become less hydrophilic than prior to treatment. Clay-organic complexes are sufficiently stable to resist powerful organic solvents. The clay-organic complex separated from the Athabasca oil sand behaves similarly during chemical treatment to complexes formed between bitumen and the four reference clay minerals.
Water Vapor Isotherms and Heat of Immersion of Na- and Ca-Montmorillonite Systems. III. Thermodynamics
Authors: Keren R. , Shainberg I.
Published: September 2006

The integral thermodynamic quantities of adsorbed water on Na- and Ca-montmorillonite have been calculated from water adsorption isotherms on Na- and Ca-montmorillonite at 298° and 313°K and from one adsorption isotherm and calorimetric measurements at 298°K. The integral entropy values decrease and then increase as the amount of adsorbed water approaches zero. In both systems, the curves approach the entropy value of free liquid water at the high content water. The thermodynamics of adsorbate on a non-inert adsorbent is discussed in some detail. The two-isotherm method gives the energy change of the water phase only, whereas the colorimetric method gives the energy change of the whole system (clay, exchangeable cations, and the adsorbed water). Only when the energy changes in the solid phase are negligible (=inert surface) should the two methods give similar results. An hypothesis was developed to explain the entropy-change data of water adsorbed on clay surfaces, in which the clay surface behaves as a non-inert adsorbent.
Kaolins: Sources of Differences in Cation-Exchange Capacities and Cesium Retention
Authors: Lim C. H. , Jackson M. L. , Koons R. D. , Helmke P. A.
Published: September 2006

Seven kaolins from Georgia (southeastern U.S.A.), ranging from high to low commercial grade, were characterized by X-ray powder diffraction and chemical techniques to establish that the variation in quality was caused by impurities. The Ca and Cs cation-exchange capacities (CEC) varied from 2.67 to 8.17 and from 3.29 to 8.77 meq/100g, respectively. Selective dissolution and correlation analyses strongly indicated that expandable 2:1 minerals, particularly smectite (1.2-5.9%), were responsible for most of the observed variations in Ca CEC (r = 0.85*). The external surface CEC of kaolinite ranged from 0 to 1 meq/ 100 g. The positive significant correlation (r = 0.90**) between the Ca CEC and the K-mica content (03.9%) suggested that Ca CEC may be related to the degree of mica weathering through an expandable mineral stage.

The Cs-retention capacity (0.19–1.14 meq/100 g) was closely related to Cs-measured vermiculite content (r = 0.80*), and this content plus specific surface (R = 0.93**) or mica content (R = 0.86*). The Cs retention appeared to be primarily related to the presence of interlayer wedges at mica/vermiculite XY interfaces.
Kaolinite, Smectite, and K-Rectorite in Bentonites: Relation to Coal Rank at Tulameen, British Columbia
Authors: Pevear D. R. , Williams V. E. , Mustoe G. E.
Published: September 2006

The Tulameen coal field is part of an Eocene nonmarine basin which received extensive volcaniclastic sediments due to its location within an active magmatic arc. Bentonite partings in the coal originally consisted of glassy rhyolitic tephra with phenocrysts of sanidine, biotite, and quartz. During the initial alteration, which took place within the swamp or shortly after burial, glass was transformed to either smectite-cristobalite-clinoptilolite or to smectite-kaolinite. The formation of kaolinite depended on the degree of leaching of silica and alkalies in the swamp environment. Some beds are nearly 100% kaolinite and can be designated as tonsteins. The smectite shows no evidence of interlayering; the kaolinite is well ordered. During alteration, sodium, originally a component of the glass, was lost from the system.

A later thermal event, which affected only the southern part of the basin, metamorphosed the smectite to a regularly interstratified illite/smectite with 55% illite layers and rectorite-type superlattice (IS-type). The source of potassium was dissolution of sanidine. Vitrinite reflectance measurements of the coal suggest that the smectite was stable to 145–160°C, at which temperature it transformed to K-rectorite.

The absence of randomly interstratified intermediates, even in beds rich in potassium, suggests that the transformation of smectite to K-rectorite was controlled by a steep thermal gradient possibly resulting from local magmatism or circulating geothermal fluids.
Negative Adsorption in Clay-Water Systems with Interacting Double Layers
Authors: Helmy A. K. , Natale I. M. , Mandolesi M. E.
Published: September 2006

A relation was derived which describes negative adsorption (salt exclusion) in systems in which double layer interaction takes place but where the surface potential remains finite, such as in clay pastes and sediments. Exclusion volumes calculated for montmorillonite pastes in equilibrium with 1:1 type electrolytes were found to compare favorably with data obtained by F. A. M. de Haan in an earlier study.
Structure of Some Allophanes from New Zealand
Authors: Parfitt Roger Lyndhurst , Hemni Teruo
Published: September 2006

Allophane samples from soils, pumice, and stream beds have been studied by electron optical, infrared absorption, X-ray fluorescence, gas chromatography, and phosphate adsorption methods. The allophane particles were hollow spherules or polyhedra 35 and 50 Å in diameter with molar Al/Si ratios close to 2.0. The thickness of the wall of the spherules was estimated to be 7 Å. For the pumice allophanes, the wall was largely composed of imogolite structural units (OH)3Al2O3SiOH. Defects or pores were present in the wall and probably were the sites where phosphate was adsorbed. It is suggested that these allophanes with molar Al/Si ratios close to 2.0 should be called “proto-imogolite” allophane.

Two soil allophanes had a similar structure to the allophane from Stratford pumice, but small amounts of layer silicates, including halloysite, were also present in the soil samples, as indicated by infrared bands at 470, 1030, and 1100 cm−1. The allophane from the stream bed at Silica Springs had an infrared spectrum similar to feldspathoids, and it did not have the imogolite structure.
Effect of Chemical Pretreatment on X-Ray Powder Diffraction Characteristics of Clay Minerals Derived from Volcanic Ash
Authors: Brewster Gordon Ross
Published: September 2006

The effects of NaOAc removal of carbonates, H2O2 removal of organic materials, and sodium citrate-bicarbonate-dithionite (SCBD) removal of iron oxides upon the X-ray powder diffraction (XRD) characteristics of clay minerals present within weathered volcanic ash deposits were examined. All pretreatments of samples derived from the Ae and Bhf horizons containing volcanic ash resulted in dramatic increases in XRD peak intensities, while the treatment of IIC-horizon samples resulted in subdued XRD peak intensities. Also, the chemical treatments produced an apparent increase in the amount of expandable clay minerals within the Ae horizon, due probably to the hydrolysis and removal of interlayer Al3+ when H2O2 and SCBD were used. Hence, poorly ordered and pedogenically modified vermiculite or vermiculite/montmorillonite interstratifications became “weathered” by H+ attack and Al3+ removal in a manner similar to the natural processes which take place in the acid and eluvial A horizon. In addition, possible XRD peak modification due to the dilution of crystalline clay concentrations by amorphous clay-size material appeared to be subordinate to the laboratory-induced chemical alteration of the weathered clay minerals.
Adsorption of Cadmium and Cobalt on Montmorillonite as a Function of Solution Composition
Authors: Egozy Yair
Published: September 2006

Adsorption of Co2+ and Cd2+ on Wyoming montmorillonite was studied by the batch equilibration technique, as a function of salt concentration (0.01–4 M NaCl and NaNO3), pH (5.0–6.5), adsorbate concentration (trace-10−2 moles/liter), and presence of complexing ions. Comparison was made with the adsorbability of Sr2+, known to follow simple ion-exchange equations. The distribution coefficients for Co and Cd in noncomplexing media varied with salt concentration (from ∼500 liters/kg in 0.01 M Na+ to ∼10 liters/kg in 1 M Na+; pH = 5), but to a lesser extent than that of Sr. Adsorbability varied also with pH (∼1 order of magnitude/pH unit), especially at high ionic strength, compared to a negligible pH effect on Sr. The distribution coefficients of Cd and Co decreased with increasing loading on the clay at a very low percentage (0.2%) of the ion-exchange capacity compared to Sr (20%). These data suggest two classes of sites participating in the adsorption of Cd and Co.

The adsorbability of Cd in highly concentrated chloride solution (>1 M) was less than 1 liter/kg, presumably because of the chloride complex formation. This effect increased with increasing pH. The low adsorbability of Cd on montmorillonite from concentrated NaCl solution is promising with respect to its use as a tracer for monitoring flow through formations containing montmorillonite.
Selective Adsorption of Zinc on Halloysite
Authors: Wada Koji , Kakuto Yasuko
Published: September 2006

Zn- and Ca-adsorption equilibria of five Ca-saturated halloysite samples were measured at equilibrium Zn concentrations up to 10−2 M in 10−4 to 10−2 M CaCl2. The results were interpreted on KCaZn vs. [Zn]/CEC (%) plots, where KCaZn is the selectivity coefficient (= [Zn][Ca]/[Ca][Zn]), Zn and Ca represent the adsorbed species, and CEC is the cation-exchange capacity. All Zn adsorption occurred at cation-exchange sites, and 0.77 to 36.0 meq Zn/100 g clay, which constitutes 9 to 83% of the CEC, was adsorbed with “high selectivities” (KCaZn > 10). The higher values were found for two spherical and one “filmy” halloysites, whereas the lower values were found for two tubular halloysites. The magnitude of their 001 intensity, hydration in interlayer space, CEC, and “free” iron oxide content did not correlate with the selective Zn adsorption, but a good correlation was found between the proportion of “high selectivity” sites for Zn and proportion of “high affinity” sites for H+. The adsorption of Zn at the “high selectivity” sites was not completely reversible, and KCaZn values >1000 were recorded in 0.5 M CaCl2 for Zn which occupied 10–40% of the exchange sites. Selective Zn adsorption decreased with decreasing pH, and all adsorbed Zn was extracted with 0.1 M HCl.
Fe2+-Fe3+ Transformations in Clay and Resin Ion-Exchange Systems
Authors: Gerstl Z. , Banin A.
Published: September 2006

The pH, Eh, electrical conductivity (EC), and the amounts and valency of replaceable iron were measured periodically on Fe2+- and Fe3+-saturated montmorillonite and cation-exchange resin at three temperatures. Differences in the pattern of change of pH, Eh, and EC with time appear to be related more to the histories and modes of preparation of the systems than to intrinsic differences in the hydrolysis of the iron in them. Electron transfer reactions involving crystal components of the clay can cause oxidation of adsorbed Fe2+ ions; the activation energy (Ea) for oxidation on the clay's surface was 6 kcal/mole, less than a third of the activation energy reported for Fe2+ oxidation in solution. In the Fe2+-resin, where Ea = 10.7 kcal/mole, perturbed surface-water molecules may act as electron acceptors enhancing Fe2+ oxidation.

Polymerization and precipitation of the adsorbed iron is affected by the necessity to maintain electroneutrality, the ability of the iron-hydroxy ions and small polymers to move about in the voids of the ion exchanger, and the steric hindrance posed by the matrix of the ion exchanger to the formation of large polymers. In resin, little or no iron precipitates, probably due both to steric hindrance and the inability of the resin to release ionic components to maintain electroneutrality. In clays, steric hindrance is small, and Al and Mg are released from the crystal to maintain electroneutrality, thus the precipitation of iron is abundant and is controlled by the rate of release of Al and Mg from the crystal.
Manganese Minerals in Clays: A Review
Authors: Chukhrov F. V. , Gorshkov A. I. , Rudnitskaya E. S. , Beresovskaya V. V. , Sivtsov A. V.
Published: September 2006

Vernadite (MnO2·nH2O) is a mineral with a poorly ordered structure. Its synthetic analogue is designated δ-MnO2. Birnessite and vernadite are independent mineral species and cannot be described further under the same name. They have similar hexagonal unit-cell parameters, a0, but different c0 parameters. Rancieite has a structure similar to that of birnessite. Calcium bearing, 14-Å birnessite occurring in nature was first described by the authors. In addition to the todorokite having the parameters a0 = 9.75 Å, b0 = 2.84 Å, and c0 = 9.59 Å, other species of natural todorokite are known having a0 parameters that are multiples of 4.88 Å equal to 14.6 and 24.40 Å, the b0 and c0 parameters being the same.
Dehydroxylation of Dioctahedral Phyllosilicates
Authors: Heller-Kallai L. , Rozenson I.
Published: September 2006

Mössbauer spectroscopy of dioctahedral phyllosilicates showed that on dehydroxylation iron which originally occupied M(2) and M(l) sites became, respectively, 5- and 6-coordinated. The 6-coordinated sites are very distorted. No migration of cations occurs in the course of heating the specimens for 1–3 hr at 600°–700°C.

By using a combination of several physicochemical methods, different successive stages of the dehydroxylation process could be distinguished: (1) migration of protons; (2) localized dehydroxylation of individual associations without significant change in the overall configuration of the octahedral sheets; and (3) loss of most of the hydroxyl groups with concomitant changes in the cell dimensions. Penetration of Li into the octahedral sheets does not affect the course of the reaction, but reduces the dehydroxylation temperature and the stability of the products.

Dehydroxylation was preceded by or associated with the oxidation of any divalent iron present. Fe3+ derived from Fe2+ was indistinguishable by Mössbauer spectroscopy from iron initially present in the trivalent form. High concentrations of Fe lower the dehydroxylation temperature and reduce the stability of the dehydroxylate to the extent that partial disintegration may precede complete dehydroxylation.
Adsorption of Organic Diacids and Sodium Polyacrylate Onto Montmorillonite
Authors: Siffert B. , Espinasse P.
Published: September 2006

Organic diacid (oxalic and succinic) adsorption onto montmorillonite is feasible, but weak (~1 mg/g). The comparison of chemical and radiochemical determinations reveals that 80% of the acid in contact with the smectite is used to attack the clay lattice. The pH is the main parameter involved in adsorption, and fixation passes through a minimum for pH 6 to 7. Polyacrylate adsorption is also weak (~1.5 mg/g). It changes with the nature of the exchangeable cation of smectite. Its pH-dependence displays a pronounced maximum for a value corresponding to the pKa of the acidic functions (pH ~6.8), and a minimum at about pH 8. On the assumption that a polyacrylate macromolecule is 100% hydrolyzed, it follows that the-COOH groups carried by 20% hydrolyzed Polyacrylamide molecules (such as those used in the tertiary recovery of petroleum) contribute at the very most to 10% of the total adsorption onto clay. Fixation, therefore, involves predominantly protonation of the amide functions at the edge surfaces of the clay. The acidic functions play a minor role in the adsorption phenomenon in that they affect the length of the macromolecule. The extent of this contribution, however, is virtually impossible to estimate.
Precise Identification of Illite/Smectite Interstratifications by X-Ray Powder Diffraction
Authors: Środoń Jan
Published: September 2006

The thickness of the two-layer ethylene glycol complex of dioctahedral smectites varies under room conditions between 17.3 and 16.5 Å because of such factors as layer charge density, type of interlayer cation, and relative humidity. Neglecting this variability can give up to 30% error in the X-ray powder diffraction estimation of the smectite:illite ratio of the mixed-layer structures. Three methods have been developed for the interpretation of X-ray powder diffraction patterns of glycolated mixed-layer illite/smectite which take layer-spacing variability into account. The methods include a technique for quantifying the degree of layer ordering. In addition, the proposed techniques minimize the error due to the influence of domain size on positions of reflections. The experimental error can be kept below 5% or below 1% smectite layers, depending on the method applied, provided that the peak positions are measured with the accuracy of ± 0.02°2θ.
Formation, Compositions, and Properties of Hydroxy-Al- and Hydroxy-Mg-Montmorillonite
Authors: Brindley G. W. , Kao Chih-Chun
Published: September 2006

Hydroxy-Al- and hydroxy-Mg-montmorillonite were prepared by treating dispersed Na-montmorillonite with aluminum and magnesium nitrate solutions and titrating with NaOH solutions so that the OH/Al ratio varied from zero to 3.0 and the OH/Mg ratio from zero to 2.0. External precipitation of Al and Mg hydroxides was observed when the OH/M ratios (M = metal) approached 3 and 2, respectively. From chemical analyses of the initial Na-montmorillonite and the hydroxy-metal montmorillonites, structural formulae were derived by assuming that the silicate layer compositions remained unchanged. Prior to the addition of NaOH, the average interlayer material approximated in composition to [Al(OH)2]+ and [Mg(OH)]+. With additions of NaOH the interlayer compositions moved progressively towards Al(OH)3 and Mg(OH)2. When the hydroxy interlayers approached completion, external precipitation was observed. X-ray powder diffraction data showed that the hydroxy-Mg products have less tendency to swell in ethylene glycol and water, and greater thermal stability than the hydroxy-Al products. Initially, when the average interlayer compositions were near Al(OH)2 and Mg(OH), swelling followed more nearly the normal behavior.
Beyond frequency: Habit as mental construct
Authors: Verplanken Bas
Published: September 2006

Progress in habit theory can be made by distinguishing habit from frequency of occurrence, and using independent measures for these constructs. This proposition was investigated in three studies using a longitudinal, cross‐sectional and experimental design on eating, mental habits and word processing, respectively. In Study 1, snacking habit and past snacking frequency independently predicted later snacking behaviour, while controlling for the theory of planned behaviour variables. Habit fully mediated the effect of past on later behaviour. In Study 2, habitual negative self‐thinking and past frequency of negative self‐thoughts independently predicted self‐esteem and the presence of depressive and anxiety symptoms. In Study 3, habit varied as a function of experimentally manipulated task complexity, while behavioural frequency was held constant. Taken together, while repetition is necessary for habits to develop, these studies demonstrate that habit should not be equated with frequency of occurrence, but rather should be considered as a mental construct involving features of automaticity, such as lack of awareness, difficulty to control and mental efficiency.
Social identity and the recognition of creativity in groups
Authors: Adarves‐Yorno Inmaculada , Postmes Tom , Alexander Haslam S.
Published: September 2006

This paper develops an analysis of creativity that is informed by the social identity approach. Two studies are reported that support this analysis. Study 1 (N =73) manipulated social identity salience and the content of group norms. The group norm was either conservative (i.e. promoted no change) or progressive (i.e. promoted change). When social identity was salient and the group norm was conservative, a non‐novel proposal was perceived to be more creative. Study 2 (N =63) manipulated social norms and identity relevance. Results showed that while social norms influenced perceptions of creativity, identity relevance influenced positivity but not perceptions of creativity. These findings support the idea that perceptions of creativity are grounded in the normative content of group membership and self‐categorization processes.
Three ways to forgive: A numerically aided phenomenological study
Authors: Wohl Michael J. A. , Kuiken Don , Noels Kimberly A.
Published: September 2006

The topic of forgiveness has received increased attention in the psychological literature; however, definitional and operational clarity remains a stumbling block. We propose that the study of first‐person experiential accounts can enrich ongoing definitional and psychometric efforts. We systematically examined such accounts of forgiveness, identifying recurrent themes and then clustering these accounts according to similarities in theme profiles. People reported forgiveness through interpersonal confrontation with their transgressor (Cluster I), intra‐personal evaluation of human fallibility and moral commitments (Cluster II), and attempts to resume a positive relationship without presuming that the transgression could be ignored or forgotten (Cluster III). The findings of the present research help to integrate recent studies of forgiveness, and the implications of a tripartite model of forgiveness are considered.
The added value of respect: Reaching across inequality
Authors: Simon Bernd , Lücken Markus , Stürmer Stefan
Published: September 2006

The experiment (N =80) tested whether the effectiveness of intragroup respect is moderated by structural (in)equality between the self and the rest of one's group. Equality (restricted vs. full rights) and respect (disrespect vs. respect) were manipulated as independent variables, while collective identification and willingness to engage in group‐serving behaviour were the main dependent variables. Moderation was confirmed such that the positive effects of respect were more pronounced among group members with restricted rights than among group members with full rights. Moreover, respect fully compensated for the initial deficit in self‐perception as a fully fledged group member. However, there was also some indication that, when money is at stake, formal guarantees of equality may be necessary for respect to have a facilitative effect on individual sacrifices for the sake of the group. The practical and political implications of the results are discussed.
The influence of biological sex, sexuality and gender role on interpersonal distance
Authors: Uzzell David , Horne Nathalie
Published: September 2006

This research reports on a conceptually and methodologically innovative study, which sought to measure the influence of gender on interpersonal distance. In so doing, we argue for an important distinction to be made between biological sex, gender role, and sexuality. To date, however, progress in the study of interpersonal distance (IPD) has been inhibited by poor operational definitions and inadequate measurement methodologies. For our own investigation, we innovated on methodology by devising the digital video‐recording IPD method (DiVRID) that records interpersonal spatial relationships using high quality digital video equipment. The findings highlighted not only the validity of our innovative method of investigation, but also that a more sophisticated conceptualization of the impact of gender on IPD is warranted than can be accounted for by biological sex differences. In this study, we found that gender role accounts for more of the variation in IPD than the conventionally reported gender variable, sex.