bluuebunny/crossref_metadata_2025 huggingface dataset:
Mineralogy of Palagonitic Material from the Golan Heights, Israel
Authors: Singer A.
Published: September 2006

Sideromelane in Pleistocene lapilli-tuff rocks from the Golan Heights had partly altered into palagonite. X-ray and electron diffraction showed that the major part of the clay alteration product is composed of a dioctahedral micaceous mineral with well organized crystallinity along the a- and b-axes. Very poor basal reflections as well as incomplete expansion upon glycerolation and incomplete collapse upon heating were interpreted as being due to random interstratification with chlorite. Electron microscopy showed the particles to be very similar to montmorillonite tactoids. The thermal behavior as well as surface properties were similar to those of montmorillonite. Differential dissolution analysis and infrared spectroscopy failed to indicate amorphous constituents to any significant extent. Chemically the material was enriched in iron, aluminum and titanium and depleted in alkali and alkaline earth cations.

A minor component of the clay was found to consist of ‘onion-like’ halloysite. It is suggested that palagonite is a natural precursor for montmorillonite in the volcanic glass-montmorillonite alteration series.
Mineralogy and Cation Exchange Properties of Libby Vermiculite Separates as Affected by Particle-Size Reduction
Authors: Baweja A. S. , Wilding L. P. , McLean E. O.
Published: September 2006

A vermiculite (Libby, Montana) sample obtained from the Zonolite company contained mostly coarse-grained separates with only 8–7 per cent clay. The 2–50 μm fraction was used for particle-size reduction studies by wet and dry grinding, and size-fractionated into < 2, 2–5, 5–20 and 20–50 μ sizes. About 18 per cent of the sample was attrited to clay after 64 hr of wet grinding, but as much as 59 per cent of the sample was attrited to clay after only 10 min of dry grinding. There was no evidence of damage to the crystal structure of derived clays or silts except for the 20–50 μm fraction from dry grinding.

The observed CEC values of all the fractions decreased as grinding progressed, except for the 2–5 μm fraction from wet grinding where the CEC increased. The decrease in CEC was attributed to an accumulation of biotite, either as a discrete mineral and/or a mixed-layer assemblage of biotite and vermiculite attrited to the clay fraction. In contrast, the fraction showing an increase in CEC was due to an increased concentration of higher charge-density (CEC) vermiculite. Biotite-free CEC data for vermiculite suggested that, in general, the coarser vermiculite separates had a higher CEC than the finer ones.

The susceptibility of minerals in the Libby vermiculite to cleavage by grinding was: vermiculite > hydrobiotite > biotite.
‘Vermiculite’ Determination on Whole Soils by Cation Exchange Capacity Methods
Authors: Coffman C. B. , Fanning D. S.
Published: September 2006

The proposed method is a modification of one by Alexiades and Jackson (1965). Calcium exchange capacity (CaEC) and potassium exchange capacity (KEC) are determined, after removal of organic matter and free iron oxides, by saturating the exchange complex with centrifuge washings of pH 7 acetate solutions of Ca or K, respectively. Excess salt in solutions remaining in contact with the soil after saturation is determined by measuring the weight and concentration of the excess solution. The exchangeable cations and excess salt are then replaced by centrifuge washings with 1 N acetate solutions of Mg (for CaEC) or NH4 (for KEC), after overnight 110°C oven-drying to enhance K fixation for KEC. The replaced cations are determined and CaEC and KEC values are calculated. Per cent ‘vermiculite’ is based on the difference between CaEC and KEC (expressed in m-equiv/100 g) and an assumed ‘vermiculite’ in-terlayer exchange capacity of 154 m-equiv/100 g; percentage Vr = (CaEC-KEC/154) × 100. The ‘vermiculite’ interlayer fraction (VIF) of the CaEC may also be calculated; VIF= CaEC-KEC/CaEC. The measured ‘vermiculite’ is shown in quotation marks since the method is open to criticism regarding exactly what is being measured, the assumptions made, etc. and to emphasize that the determination procedure is an operational one for the characterization of cation exchange complexes.

Removal of free iron oxides increased both CaEC and KEC values of several soils but percentage Vr was little affected. The amount of K fixation was affected by the drying treatment employed after K saturation (none vs air-drying vs oven-drying). Thoroughly crushing Montana and African vermiculites dramatically increased their CEC and measured ‘vermiculite’ values, but had little effect with two samples of saprolite from chloritic metabasalt.
On Dehydration of Bound Water of Sepiolite
Authors: Nagata Hiroshi , Shimoda Susumu , Sudo Toshio
Published: September 2006

Bound water of sepiolite dehydrates in two steps in the temperature range of 250-650°C, as shown in the TG-curve. These steps are described here as steps II and III. At step II, half of the bound water is removed; other half at step III. From step II to III, discontinuous changes are confirmed in such properties as activation energy of dehydration, a-dimension, axial ratio, and intensities and spacings of X-ray powder reflections. A structural state at step II may be recognized as a distinct phase in the dehydration process.
Swelling of Montmorillonite in Polar Organic Liquids
Authors: Olejnik S. , Posner A. M. , Quirk J. P.
Published: September 2006

The crystalline and osmotic swelling of Na-, Cs-, Mg- and Ca-montmorillonite has been measured in dimethyl sulphoxide and in formamide, N-methyl formamide, dimethyl formamide, N-methyl acetamide and dimethyl acetamide. These liquids have similar dipole moments but their relative permittivities vary appreciably from values less than water to values greater than water.

Na-montmorillonite exhibits osmotic swelling (diffuse double layer development −d(001) ≫ 19 Å) in formamide and N-methyl formamide and Cs gives osmotic swelling behavior in formamide. Cs-montmorillonite in the crystalline swelling region give spacings greater than those found for water with all liquids. Mg- and Ca-montmorillonite did not give spacings greater than 19 Å in any of the liquids studied.

The swelling behavior of montmorillonite is affected by relative permittivity but for liquids with a similar relative permittivity methyl substitution in the molecule may prevent the development of diffuse double layers on the particle surfaces.
Imogolite from New Guinea
Authors: Parfitt R. L. , McHardy W. J.
Published: September 2006

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.
Erratum to: Factors affecting selected area electron diffraction patterns of micas
Authors: Güven Necip
Published: September 2006

Necip Guyen: Factors affecting selected area electron diffraction patterns of micas. Clays and Clay Minerals22, 97–106 (1974).

On p. 97, lines 3 and 6 of the second paragraph under Lattice Properties of Micas (the equations for ΔPhkl)
Order and Disorder Relations in the Distribution of the Substitutions in Smectites, Illites and Vermiculites
Authors: Besson G. , Mifsud A. , Tchoubar C. , Mering J.
Published: September 2006

It is shown that order-disorder relations in the distribution of the isomorphous substitutions are important in the characterization of different 2/1 phyllosilicates and in the determination of their behavior. These order-disorder relations are shown by selected area diffraction patterns obtained from single crystals. The range of layer charges corresponding to smectites (charge per half-cell <0.6) is that for which phyllosilicates are stable with disordered substitutions. Phyllites with charge >0.6 show anomalous diffusions which indicate that the distributions of exchangeable Ba ions are partially ordered; this result is taken as evidence that the isomorphous substitutions also are partially ordered.
Lath-Shaped Units in Fine-Grained Micas and Smectites
Authors: Güven Necip
Published: September 2006

Transmission electron images of fine-grained micas in bentonites exhibit lath-shaped units. These units seem to be associated along the (110) planes—referred to 2M1 mica cell—with perfect registry of their individual lattices. In doing so, they seem to provide lateral growth in the (001) plane. These lath-shaped units are arranged in the [001] direction in modes similar to the stacking of layers in mica polymorphs. Aggregations of lath-shaped units with polycrystalline montmorillonite particles are also observed in several bentonites. From the SAD pattern these laths are inferred to be dioctahedral layer silicates. However, they cannot be exactly identified any further. It is an open question whether these laths have grown from the montmorillonite or are simply entangled with it.
The Synthesis of Zinc Silicates at 20°C and Atmospheric Pressure
Authors: Tiller K. G. , Pickering J. G.
Published: September 2006

Zinc silicates were synthesized under conditions analogous to surficial weathering environments. The main product, regardless of conditions of precipitation or ageing, was shown by X-ray, i.r., electron microscopic and chemical evidence to be a 2:1 layered zinc silicate equivalent of stevensite. In the presence of aluminium, a 1:1 layered zinc silicate was formed as well, in confirmation of published work. The stability of the zinc silicate, in relation to carbonate, was favoured by the presence of aluminium in the lattice and silicic acid in the equilibrium solution. Zinc layer silicates were formed under conditions that generated orthorhombic zinc hydroxides and/or basic salts in the absence of silicon; the involvement of the brucitic zinc hydroxide (α-form), as proposed by earlier workers, could not be supported. Crystalline zinc layer silicates were formed by the slow evolution of the initial gels. Such layer silicates, but not willemite or hemimorphite, could have an important role in the control of chemical reactions of zinc in soils.
Amorphous Coatings on Particles of Sensitive Clay Soils
Authors: McKyes E. , Sethi A. , Yong R. N.
Published: September 2006

Post-glacial Champlain Sea sediments in Quebec and Ontario are often extremely sensitive. Suggestions of considerable amorphous material in these soils come from X-ray diffraction results, as well as electron micrographs. A method for selective dissolution and analysis of amorphous material is used to study two Champlain Sea deposits. The amorphous material removed amounts to 11–12 per cent of the soils and consists mainly of silica and iron oxide. The treated samples have enhanced X-ray diffraction peaks and much cleaner particles as seen by electron microscopy.
Surface Acidity of Montmorillonites
Authors: Frenkel M.
Published: September 2006

Surface acidity of almost homoionic montmorillonites was measured by titrating selected Hammett indicators adsorbed on the clay with n-butylamine.

As expected, the acidity is strongly affected by the exchangeable cations and the degree of hydration of the clay. Greater polarizing ability of the interlayer cations increases both the strength and number of acid sites per H0 value. The acidity of ‘activated’ or heated H-montmorillonite does not exceed that of untreated H-montmorillonite. The origin of the negative charge in the montmorillonite appears to affect the acidity of the clay.

It is concluded that the very high acidities reported in the literature (H0 < −5·6) are apparent only and are due to physisorption of the indicator.
Swelling and Structural Organization of Saponite
Authors: Suquet H. , de la Calle C. , Pezerat H.
Published: September 2006

The structural formula of Kozfikov saponite (Czechoslovakia) is as follows:
$N{a_{0.005}}C{a_{0.22}}{K_{0.01}}[S{i_{3.30}}A{l_{0.68}}F{e^{3 + }}{}_{0.02}][M{g_{2.50}}F{e^{2 + }}{}_{0.26}F{e^{3 + }}{}_{0.24}]{O_{10}}{(OH)_2}.$
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.
Stability of Mixed Iron and Aluminum Hydrous Oxides on Montmorillonite
Authors: Tullock R. J. , Roth C. B.
Published: September 2006

Montmorillonite clay samples were coated with 16 m-equiv/g of clay or iron plus aluminum as hydrous oxides and aged 1 yr, in suspensions of pH 6 or 8. The magnesium exchange capacity (MgEC) decreased linearly with the amount of non-crystalline aluminum hydrous oxide associated with the clay. Eight to 16 m-equiv of iron per g of clay reduced the MgEC by 20 m-equiv/100g at pH 6, but did not affect the MgEC at pH 8. The quantity of non-crystalline aluminum associated with the clay depended on the suspension pH and aging time, and was unaffected by the coprecipitation of 8–16 m-equiv of iron hydrous oxide/g clay. The crystalline form of aluminum hydrous oxide depended on the suspension pH and was shown by X-ray diffraction to be gibbsite at pH 6 and bayerite at pH 8. Gibbsite and bayerite formed rapidly with a rate dependent on the suspension pH when excess non-crystalline aluminum hydrous oxides were present. The quantity of non-crystalline aluminum hydrous oxides remaining after one year in suspensions of iron hydrous oxides and montmorillonite varied from 2·3 m-equiv/g of montmorillonite at pH 8-4·0 m-equiv/g of montmorillonite at pH 6. Differential thermal analysis and MgEC measurements indicated some regular organization of the iron hydrous oxides, however, crystalline iron minerals were not detected by X-ray diffraction.
Kink Block Structures in Clay Organic Complexes
Authors: Lagaly G. , Fitz St. , Weiss Armin
Published: September 2006

Complexes of n-tetradecylammonium-beidellite with n-alkanols
${\rm{(n - }}{{\rm{C}}_{{\rm{14}}}}{{\rm{H}}_{{\rm{29}}}}{\rm{N}}{{\rm{H}}_{\rm{3}}}^{\rm{+}}{\rm{)_{{\rm{0,44}}}(n - C_{{\rm{x}}}}}{{\rm{H}}_{{\rm{2x}}}}{\rm{+}}{}_{\rm{1}}{\rm{OH) }}{}_{{\rm{1,56}}}{{\rm{\{ M}}{{\rm{g}}_{{\rm{0,28}}}}{\rm{A}}{{\rm{l}}_{{\rm{1,81}}}}{{\rm{(OH)}}_{\rm{2}}}{\rm{S}}{{\rm{i}}_{{\rm{3,56}}}}{\rm{Al}}{}_{{\rm{0,44}}}{\rm{O_{{10\}} }}}^{{\rm{0,44 - }}}}$ (x = 8–22) have been prepared and characterized by their basal spacings and by measurements of the specific heat cp.

The compounds undergo a series of reversible phase transitions ${\beta _1} \rightleftharpoons...\rightleftharpoons{\beta_i}\rightleftharpoons...\rightleftharpoons{\beta_\omega}\rightleftharpoons{\alpha_1}...\rightleftharpoons{\alpha_j}$ with rising temperature. The maximum number ω of β-phases depends upon the chain lengths and increases from 1 with decanol to 6 with docosanol. Due to the evaporation of alkanol the number of χ-phases is not yet established in all details.

The β-transitions correspond to conformational changes of the alkyl chains via rotational isomerisation, especially kink formation. The β-phases become unstable if the kink concentration exceeds 0,14 kinks/-CH2-. The β/α-transition is probably caused by a rearrangement into special gauche-block structures.
Soil Minerals in the System Al2O3-SiO2-H2O: Phase Equilibrium Model
Authors: Chesworth Ward
Published: September 2006

Mineralogical reactions in the system Al2O3-SiO2-H2O are examined and an isothermal, isobaric cross-section of the portion of the system applicable to soil genesis, is determined. The relevance of the cross-section to soil mineralogy is discussed.
Heterogeneity of Charge Density Distribution in Montmorillonite as Inferred from Cobalt Adsorption
Authors: Peigneur P. , Maes A. , Cremers A.
Published: September 2006

A comparison is made of the ion exchange behavior, towards the cobalt ion, of five sodium montmorillonite clays. The selectivity for the bivalent ion at low cobalt loading is correlated with the average dimensions of the particles in the various clays, as characterized by several methods. The data are interpreted in terms of a higher selectivity of the bivalent ions for the broken bonds located at the edges of the clay crystals. Using a model comprising two areas of different charge densities, the experimental differences in behavior can be predicted reasonably well.
A Quantitative Method for the Determination of Montmorillonite in Soils
Authors: Levy Rachel , Francis C. W.
Published: September 2006

A quantitative method for determination of montmorillonite in the soil clay fraction, using X-ray spectrometry, is proposed. The method is based on the fact that polyvinylpyrrolidone (PVP) is adsorbed on the interlayer surfaces of montmorillonite, giving a first order c-axis spacing of 26 Å, while it is not adsorbed on other swelling clays. The experimental conditions to obtain a maximum height of the X-ray diffraction peak, and the effect of the mass adsorption coefficient of vermiculite on the intensity of montmorillonite, were investigated. Soil montmorillonite was determined by the method of known additions, measuring the intensity of the X-ray diffraction peak before and after the addition of small and known amounts of Wyoming montmorillonite.
Swelling Chlorite in a Soil of the Dominican Republic
Authors: Rich C. I. , Bonnet Juan A.
Published: September 2006

A 1–0·2 μm fraction from a soil in the Dominican Republic was studied by X-ray diffraction combined with solvation, cation saturation, and heat treatments. I.R., thermal (DTA, TGA) and chemical analyses were also made. This soil is saline and alkaline and its mineral composition is greatly influenced by the lacustrine parent material and poor drainage.

In addition to swelling chlorite, illite, kaolinite, carbonates and quartz are present in the 1–0·2 μm fraction. The swelling chlorite expanded to over 18 Å when Mg saturated and solvated with glycerol or water. Lower spacings with other cations and ethylene glycol were observed. 1 N HCl treatment partially removed the interlayer hydroxides in the chlorite and 6 N HCl destroyed the mineral. The mineral gave a reflection close to 14 Å up through 600°C but collapsed at higher temperatures to 10·2 Å.
Hydrothermal Syntheses of Amino Acid-Montmorillonites and Ammonium-Micas
Authors: Tsunashima A. , Kanamaru F. , Ueda S. , Koizumi M. , Matsushita T.
Published: September 2006

An attempt has been made to synthesize nitrogenous clay minerals hydrothermally from silica-alumina gels in the presence of amino acids, namely glycine and lysine. The products have been characterized by X-ray powder diffraction, by analyses for C and N contents, and by their infrared spectra.

Amino acid-montmorillonites have been prepared under hydrothermal conditions of 200–250°C and 1000 atm. Above 250°C the amino acids were degraded to ammonium ions, and ammonium-micas were obtained. Syntheses without the addition of amino acids to gels yielded kaolinite.

The role of organic compounds in the formation of clay minerals seems to be of considerable geochemical significance.
Micaceous Occlusions in Kaolinite Observed by Ultramicrotomy and High Resolution Electron Microscopy
Authors: Lee S. Y. , Jackson M. L. , Brown J. L.
Published: September 2006

The layer structure of kaolinite from Twiggs, Georgia and fire-clay type kaolinite (Frantex B, from France), particle size separates 2–0·2 μm was studied by high resolution electron microscopy after embedment in Spurr low-viscosity Epoxy media and thin sectioning normal to the (001) planes by an ultramicrotome. Images of the (001) planes (viewed edge-on) of both kaolinites were spaced at 7 Å and generally aligned in parallel, with occasional bending into more widely spaced images of about 10 Å interval. Some of the 10 Å images converged to 7 Å at one or both ends, forming ellipse-shaped islands 80 to 130 Å thick and 300 to 500 Å long. The island areas and interleaved 10 Å layers between 7 Å layers may represent a residue of incomplete weathering of mica to kaolinite.

The proportions of micaccous occlusions were too small and the layer sequences too irregular to be detected by X-ray diffraction. The lateral continuity of the layers through the 7-10-7 Å sequence in a kaolinite particle would partially interrupt or prevent expansion in dimethyl sulfoxide (DMSO) and other kaolinite intercalating media. Discrete mica particles were also observed with parallel images at 10 Å, as impurities in both kaolinites. The small K content of the chemical analyses of the kaolinite samples is accounted for as interlayer K, not only in discrete mica particles but also in the micaceous occlusions.
Mineralogy and Origin of the Coalinga Asbestos Deposit
Authors: Mumpton F. A. , Thompson C. S.
Published: September 2006

Since 1960 asbestos production of the United States has more than tripled, a phenomenon due in large part to the development of the Coalinga asbestos deposit in western California. Although most asbestos ores contain 5–10 per cent chrysotile in the form of cross- or slip-fiber veins within massive serpentinite bodies, no such veins are to be found in the Coalinga deposit despite the fact that it contains more than 50 per cent recoverable chrysotile. The Coalinga ore consists of soft, powdery, pellet-like agglomerates of finely matted chrysotile surrounding blocks and fragments of serpentinite rock. The highly sheared and pulverized nature of the ore favors its exploitation by simple, open-pit mining, and high quality products can be prepared by either wet or dry milling processes.

Four types of serpentine material are distinguishable: (1) hard, dense blocks of serpentinite rock, ranging from fractions of an inch to several tens of feet in diameter; (2) tough, leathery sheets, resembling mountain leather, up to several square feet in size; (3) brittle blades and plates of green serpentine, a few square inches in size; and (4) friable agglomerates of soft, powdery chrysotile containing appreciable amounts of the other three. Chrysotile is the principal component of all the above materials, with the exception of the serpentinite rock which consists mainly of lizardite and/or antigorite, with small amounts of brucite, magnetite, and very short fiber chrysotile. Although chrysotile fibers up to several microns in length are present in the leathery sheets, most Coalinga chrysotile is much shorter and arranged in a swirling mesh or disoriented, tangled fibers, much like cellulose fibers in paper. Fragments of serpentinite gangue are scattered throughout the ore and contain most of the lizardite, antigorite, and brucite. Chemical, electron probe, and X-ray analyses confirm the iron-rich nature of the brucite, a critical factor in the susceptibility of this phase to oxidation in the surface weathering zone. Here brucite either dissolves, leaving behind a residue of brown, amorphous iron oxides, or transforms in situ to pyroaurite or coalingite. Dissolved magnesium precipitates as hydromagnesite immediately above the water table throughout the deposit.

The abnormally high chrysotile content of this deposit is probably a result of the intensive shearing that it underwent during or after emplacement. If the friable, chrysotile-rich ore was produced during this pulverization episode, (1) lizardite and/or antigorite in the serpentinite must have been transformed into chrysotile and (2) brucite must have been removed. It is likely that early-formed lizardite/antigorite dissolved in the ground waters which pervaded the highly sheared body and that chrysotile later precipitated from these waters, coating all available surfaces.
The Relationship between the I.R. Spectra of Serpentines and Their Structures
Authors: Yariv S. , Heller-Kallai L.
Published: September 2006

Possible assignments are suggested for some of the absorption bands in the 1150–400 cm−1 region of the i.r. spectra of serpentines. Polarized light was used to identify the out-of-plane vibrations in antigorites and platy lizardites and the vibrations parallel to the fibre axis in chrysotiles and fibrous lizardites. An attempt is made to correlate some known structural characteristics and the chemical composition of the serpentines with some features of the i.r. spectra.
Origin and Mineralogy Glacial and Interglacial Clays of Southern Norway
Authors: Rosenqvist I. Th.
Published: September 2006

The Numedal River basin (6000 km2) in central and east Norway contains 3 × 109 m3 of clayey material, corresponding to a clay loam sediment, which contains 2 million tons of absorbed rare earth elements.

The clay mineralogy varies systematically from the till clays to a marine facies. It is concluded that the phyllosilicates of the clay fraction and tills originated from phyllosilicate minerals of the crystalline bedrock through a degradation partly due to preQuaternary weathering which dissolved a great part of the rock-forming minerals.
A Study of the Morphology and Properties of Aryl and Alkyl Ammonium Montmorillonites: An Electron Microscope Investigation
Authors: Jernigan Donald L. , McAtee James L.
Published: September 2006

The effect of exchanging selected aryl and alkyl ammonium cations for sodium ions on the morphology and the hydrophobicity of a sodium montmorillonite was studied. It was found that the morphology of the organo-clays as observed by transmission electron microscopy depended on the type of and the amount of exchanged organic cation. An attempt was made to correlate the observed morphology of organo-clays with their hydrophobicity.
The Relationship between Structural Properties of Metal-Tris (Ethylenediamine) Montmorillonite and Their Behavior as Gas Chromatographic Packing Materials
Authors: Thielmann V. J. , McAtee J. L.
Published: September 2006

The tris(ethylenediamine) complex cations of chromium(III), cobalt(III), and copper(II) were exchanged onto sodium montmorillonite. The resulting cation exchanged clays were dried, ground, sieved and the 50/80 mesh size was retained for use as column packing material to be used in gas chromatographic analysis of light hydrocarbons and oxides of nitrogen. Studies indicated that the hydrocarbons were following a sieving action whereas the nitrogen oxides were involved in a surface adsorption process.

The changes in d001-spacing and surface area of tris(ethylenediamine)Cr(III)-montmorillonite were correlated with the changes in gas chromatographic retention time for the light hydrocarbons and the oxides of nitrogen.

Retention time was obtained for the 100 per cent exchanged montmorillonites containing cations of tris(ethylenediamine)Cr(III), tris(ethylenediamine)Co(III), and tris(ethylenediamine)Cu(II). A comparative study of the d001-spacing and surface area of the three clays is shown to be directly related to the retention time.

Heating effects were studied to determine thermal stability. Changes in retention times were compared with various structural changes. DTA and heating-oscillating X-ray powder diffraction analysis were used to help explain the relationship between retention time and structural change.
A Polarized Infrared and X-Ray Study of Lysine-Vermiculite
Authors: Raupach M. , Slade P. G. , Janik L. , Radoslovich E. W.
Published: September 2006

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.
Electron—Optical Investigations on Montmorillonites—II: Morphological Variations in the Intermediate Members of the Montmorillonite-Beidellite Series
Authors: Güven N. , Pease R. W.
Published: September 2006

Dioctahedral aluminum smectites from bentonite deposits in Argentina, Brazil, Czechoslovakia and Japan represent, according to the MgO content of the bulk samples, intermediate members in the montmorillonite-beidellite series. The smectite particles in these samples occur in a variety of forms such as; (a) laths and diamond-shaped units with a well developed crystal habit, (b) loosely folded aggregates with an irregular morphology and (c) flat and compact lamellae with well developed {001} forms but with complete lack of {hk0} forms. Such lamellae have been described in two groups: the thin ones (10–50 Å) and the thicker ones. Thin lamellae may give SAD spot patterns with a non-hexagonal symmetry. Lamellae having thicknesses greater than 50 Å resemble a single crystal but their SAD patterns indicate that they do not have a three-dimensional periodicity.

The question arises whether the morphologically different particles in a sample belong to the same intermediate phase or if they represent different members in the montmorillonite-beidellite series coexisting in the same sample.
Water Vapor Isotherms and Heat of Immersion of Na/Ca-Montmorillonite Systems—I: Homoionic Clay
Authors: Keren R. , Shainberg I.
Published: September 2006

Adsorption isotherms for water vapor, c-spacing and heat of immersion in water of Na- and Ca-montmorillonite were measured at 25°C at various r.h. The amount of water adsorbed as a function of the r.h. increased gradually, whereas the c-spacing increased, and the heat of immersion (per mole of adsorbed water) decreased in steps. There was good agreement between the calorimetric data, the heat calculated from the isotherms by use of BET equation, and the calculations from the ion-dipole model. A model is presented to describe the hydration of sodium and calcium montmorillonite.
Dissimilar Fabrics by Scan Electron Microscopy of Sedimentary Versus Hydrothermal Kaolins in Mexico
Authors: Keller W. D. , Hanson Robert F.
Published: September 2006

Dissimilar fabrics, observed by scan electron micrography (SEM) on freshly broken surfaces of kaolins from weathered, water-laid material vs hydrothermally altered material in Mexico are illustrated, contrasted, and tentatively related to their respective environments of genesis. Coarse, open-textured, well-preserved books and vermiforms of kaolinite characterize the kaolin from water-laid material at Jacal, Mexico. Hydrothermal kaolins tend to have more tightly compacted crystals of either kaolinite flakes (individuals or in packets) or elongates (halloysite morphology) or mixtures of both in the same deposit. Variations in porosity of parent rock whether sedimentary or igneous, and dissimilar permeation by meteoric water and by vapor and liquids of hydrothermal fluids are deemed to be significant in the processes producing distinctive fabrics. The question is raised as to the fundamental distinction between kaolinite and halloysite and their nomenclature.
Isomorphous Substitution of Iron for Aluminium in Some Soil Kaolinites
Authors: Rengasamy P. , Krishna Murti G. S. R. , Sarma V. A. K.
Published: September 2006

Clay (<2 μm) and fine silt (2–20 μm) fractions of twenty seven soil samples from eight tropical ferruginous profiles of the Mysore Plateau (India) were analysed for kaolinite by dehydroxylation and selective dissolution. The considerable amounts of iron extracted by the procedure and the closeness of the SiO2/R2O3 molar ratios (2·00–2·18) to the ideal value of 2·00 indicated that iron was a structural constituent of the kaolinites. The calculated unit cell cation composition of the kaolinites showed a substitution of 0·11–0·82 atoms of Fe(III) for Al in every four octahedral sites. The kaolinites in these soils appear to be products of crystallization from weathering solutions.
Hisingerite Occurring as a Weathering Product of Iron-Rich Saponite
Authors: Kohyama Norihiko , Sudo Toshio
Published: September 2006

Hisingerite occurs as a weathering product of iron-rich saponite in rhyolitic tuff of Oya, Tochigi Prefecture. The chemical composition: SiO2, 40·68%; Al2O3, 4·44%; Fe2O3, 28·54%; MgO, 1·85%; CaO, 1·42%; Na2O, 1·50%; K2O, 0·33%; H2O+, 6·43%; H2O−, 13·70%; total 98·89%. Very broad and weak X-ray powder reflections occur at 16, 4·5, 2·5, 1·7 and 1·5 Å, which correspond to the main peaks of nontronite. It is considered that trioctahedral iron-rich saponite was altered to hisingerite, a very poorly crystalline form of nontronite, by oxidation of iron and advanced leaching of octahedral Mg ions.
Od-Interpretation of Kaolinite-Type Structures—II: The Regular Polytypes (MDO-Polytypes) and Their Derivation
Authors: Dornberger-Schiff K. , Ďurovič S.
Published: September 2006

All MDO-polytypes (i.e. regular polytypes) of trioctahedral, dioctahedral and monoctahedral 1:1 phyllosilicates are derived from their OD-character using the results of our preceding paper. The terms ‘simple polytype’, ‘standard polytype’ and ‘regular polytype’ turn out to be synonyms of the term ‘MDO-polytype’ which has the advantage of being exactly defined. The method used to obtain the MDO-polytypes is also applicable to more complicated cases.
Heats of Compression of Clay-Water Mixtures
Authors: Kay B. D. , Low Philip F.
Published: September 2006

Heats of compression of glass bead-water and clay-water mixtures were determined from the peak heights of the thermograms produced when these mixtures were subjected to pressure in a Calvet differential microcalorimeter. It is known that the heat of compression is directly proportional to the peak height. When the latter quantity was plotted against the pressure applied to any mixture, two intersecting straight lines were obtained. The change in slope at the point of intersection was interpreted as being the result of a pressure-induced higher-order phase transition in the water.

The differential peak height, ε, was defined as the rate of change of peak height with pressure/g of water present in the mixture. Hence, it is directly proportional to the rate of change of the heat of compression with pressure/g of water. Values of ε were determined for both glass bead-water and clay-water mixtures containing different proportions of solids. It was found that ε remained nearly constant with increasing proportions of glass beads, whereas, it varied in a non-uniform way with increasing proportions of clay. Also, its values in the clay-water mixtures were relatively high. Calculations showed that the difference in ε values for the two mixtures could not be ascribed to the exchangeable cations associated with the clay particles. Consequently, it was ascribed to the effect of the particle surfaces on the structure of the vicinal water.
Evaluation of Bending Effects on Diffraction Intensities
Authors: Güven Necip
Published: September 2006

The effects of bending on diffraction profiles and intensities have been directly evaluated. It has been shown that:

(1)

bending may cause large reductions in intensities or even the total loss of them

(2)

due to bending, the profile of the reflection may become asymmetrical and it may display two or more maxima

(3)

bending effects vary with the class of reflections and they become larger with the increasing order of diffraction, and

(4)

the interference function for a bent lattice must be evaluated for each set of lattice parameters, whereas the interference function for an undeformed lattice can be made invariant with respect to lattice parameters.
The Mineralogy of Glauconite
Authors: Thompson Graham R. , Hower John
Published: September 2006

The mineral in monomineralic glauconite pellets is an iron-rich mixed-layer illite-smectite (here called glauconite), often composed almost entirely of illite layers. The nature of the interlayering is closely analagous to that of aluminous illite-smectite and varies with the proportions of the layer types: >30 per cent smectite, randomly interstratified; 15–30 per cent smectite, allevardite-like ordering; < 15 per cent smectite, ‘IMII’ ordering.

Glauconite is analagous to aluminous illite-smectite chemically as well as structurally. A good correlation has been found between the number of potassium atoms per O10(OH)2 in structural formulas calculated from the chemical analyses and the proportion of illite layers as determined by X-ray powder diffraction methods. This relationship indicates a remarkably systematic increase in the potassium content of the illite layers with an increasing proportion of illite layers. This feature and the existence of ordered interlayering at high proportions of illite layers can be explained by crystal-chemical effects of illite layers on neighboring smectite layers. Glauconite differs from aluminous illite-smectite in that glauconite contains significantly less potassium per illite layer than does aluminous illite-smectite with the same proportion of illite layers except near the pure illite composition. The strength with which the interlayer potassium is held and the ease of conversion of smectite to illite layers in glauconite may be attributed to its 1M structure and, perhaps, to its high octahedral iron content, which lead to stronger bonding of potassium by allowing a higher tilt angle of the O-H axis of hydroxyls adjacent to the potassium ion.

The apparent octahedral cation occupancy in excess of two-thirds of the octahedral positions in many glauconites appears largely attributable to the presence of significant amounts of interlayer hydroxy-iron, aluminum and magnesium complexes in the smectite layers.
The Composition of Kaolinite—an Electron Microscope Microprobe Study
Authors: Jepson W. B. , Rowse J. B.
Published: September 2006

Electron microscope microprobe analysis (EMMA) has been applied to the determination of the elemental compositions of the kaolinite particles (Mg, Al, Si, K, Ti and Fe) contained in the 0·2-0·3 µm e.s.d., the 0·9-1·0 µm e.s.d. and the 1·9-2·0 µm e.s.d. fractions of an English kaolin and an American kaolin. Particles with masses as small as 10-13 g were analysed. An EMMA-4 instrument (A.E.I. Ltd.) equipped with linear fully focussing spectrometers was used. The ratio method of analysis was employed. The operating procedures used to obtain the required high experimental precision in the measurement of Al:Si atom ratio are discussed.

Statistical analysis of the results gives the estimated mean and spread of the Al:Si atom ratios. In the English kaolin the mean Al:Si atom ratio differs from the ideal 1:1 at the 0·05 significance level. There is evidence for a variation in composition from kaolinite particle to kaolinite particle in the 1·9-2·0 µm fraction of each kaolin. In the 0·9-1·0 µm fractions, the mean Fe:Si atom ratio was close to 0·002 showing the presence of iron in the kaolinite structure. The mean K:Si ratio was about 0·002 which would be equivalent to 1 unit muscovite layer associated with a 0·175 µm thick kaolinite particle. In the American clay the Ti:Si atom ratio was 0·002 suggesting that some 12 per cent of the 'titania' found by conventional chemical analysis was associated with the kaolinite particles either as titania itself or as an isomorphous substituent.
A Kinetic Survey of the Cation Exchange and of the Oxidation of a Vermiculite
Authors: Besson G. , Estrade H. , Gatineau L. , Tchoubar C. , Mering J.
Published: September 2006

With the use of a BaCl2 solution containing radioactive Ba2+ ions, kinetics of cation exchange have been done on a Kenya vermiculite, natural on one hand and previously oxidized either by 50°C water or oxygenated water on the other hand. Correlatively, the quantity of ferric iron in the layer has been determined by E.P.R. These two methods have shown that during an oxidation the proportion of iron which stays in the octahedral layer depends upon the nature of the oxidizing agent. During a weak oxidation, the iron stays entirely in an octahedral layer and the exchange capacity of the vermiculite decreases; on the other hand, during an oxidation by oxygenated water, part of the iron is extracted from the octahedral layer and the exchange capacity of the vermiculite is not changed, as established by the studies of Farmer (Farmer et al., 1971). Kinetic data for Llano vermiculite also are reported and compared with those for the Kenya vermiculite.
Mineralogy and Genesis of the Wealdian Sediments in the Southern Cordillera Iberica (Spain)
Authors: Galan E. , Martin Vivaldi J. L. , Aguayo F. López
Published: September 2006

The present paper presents the mineralogical composition of sediments from the Spanish Wealdian facies, selected from four stratigraphic sections of several regions in the Southern Cordillera Iberica.

Three of these sections show an irregular alternation of kaolinite rich sandy and silty-clay beds. The fourth section which contains calcareous layers, is very important from a geological point of view, because it is located where the structures of two ranges, the Iberian and the Betics, converge.

The clays of about 80 samples from these sections always consist of illite, kaolinite and interstratified clay minerals. The sandy layers also contain quartz, as well as potash and calcic-sodic felspars. The fine fraction (< 2 µm) is composed of kaolinte, between pM and T types, swelling illite and randomly interstratified clay minerals of the type (10I-14M), richer in 10 Å layers.

From the mineralogical and crystalchemical data and field observations, it is deduced that these sediments are mainly detrital. This and the layer alternation suggest, for the Upper Jurasic and Lower Cretaceous (Wealdian facies), a climate alternating from biostatic to rhexistatic. Alternating laterization and erosion might supply the materials to the Wealdian sedimentary basin.
Lithium-Bearing Tosudite
Authors: Nishiyama Tsutomu , Shimoda Susumu , Shimosaka Koya , Kanaoka Shigeto
Published: September 2006

Lithium-bearing tosudite was found from a brittle clayey part of the Tooho “roseki” deposit, Aichi Prefecture, Japan. The chemical composition of the Li bearing tosudite was estimated as SiO2 41·60%, A12O3 36·40%, Fe2O3 1·82%, MgO 0·29%, CaO 0·38%, Li2O 1·04%, Na2O 0·14%, K2O 0·38%, H2O+ 11·12% and H2O− 6·87% from the chemical composition of a specimen with associated impurities. The Li-bearing tosudite has the regularly interstratified structure of montmorillonite and dioctahedral chlorite in which Li is present in a gibbsite sheet as shown in the structural formula of interlayer cations K0·16, Na0·09, Ca0.13 + 9·60 H2O; gibbsite sheet Li1·36, Mg0·14, Fe0·45, Al3·59 (OH)12·00; silicate layer Al8·00 (Si13·60, Al2·40) O40·00 (OH)8·00. The 29·48 Å reflection series of the Li-bearing tosudite moves to 31·3 Å after ethylene glycol treatment and to 23·3 Å on heating to 500°C for 1 hr.
Adsorption of Ethylenediamine (Eda) on Montmorillonite Saturated with Different Cations—IV: Al-, Ca- and Mg-Montmorillonite: Protonation, Ion-Exchange, Co-Ordination and Hydrogen-Bonding
Authors: Laura R. D. , Cloos P.
Published: September 2006

Ethylenediamine (EDA) adsorbed from aqueous solution or vapor phase on Al-, Ca- and Mg-montmorillonite was retained to a more or less large extent in protonated form. The NH+3:NH2 ratio decreased with the polarizing power of the mineral exchange cation (Al > Mg > Ca) and with increasing amounts of amine fixed. Excess EDA was adsorbed through hydrogen-bonding with protonated species, and partially through co-ordination in vapor treated samples. Co-ordination to the exchangeable cation seemed to be favored in the order Al > Mg < Ca, and the complexes were stable up to 200°C. Heating lowered the NH+3:NH2 ratio, indicating some deprotonation process caused probably by the competition for protons between EDA and hydrolysed exchange cations. This competition might also account for the rather low quantities of NH+4 produced near 200°C.
The Crystallinity of Minerals—A New Variable in Pedogenetic Processes: A Study of Goethite and Associated Silicates in Laterites
Authors: Kühnel R. A. , Roorda H. J. , Steensma J. J.
Published: September 2006

The crystallinity of minerals in terms of crystallite size distribution and lattice perfection is quantified by means of statistical measures derived from X-ray line profiles (2 σ values). A low degree of crystallinity facilitates the non-stoichiometric incorporation of foreign elements in the crystal lattice. Crystallinity is affected by a number of factors and in natural profiles it may vary laterally as well as vertically.

For instance, goethite in laterite deposits shows decreasing crystallinity with increasing depth. Serpentine type minerals, on the other hand, show the lowest crystallinity at the surface where the degree of weathering is the most advanced. The presence of silica in migrating solutions prevents crystal growth and results in a low degree of crystallinity of minerals such as goethite. This has been observed in natural profiles and has been confirmed by laboratory experiments on the synthesis of goethite and sodium-birnessite. The crystallinity of minerals affects their response to extractive procedures. It could also be an important parameter in soil science.
A Study on the Cation Exchange of [Co(NH3)6]3+ from H-Co (NH3)6-Vermiculite by Inorganic and Quaternary Ammonium Ions
Authors: Das Kanungo J. L.
Published: September 2006

The exchange of [Co(NH3)6]3+ from its vermiculite complex has been carried out with a number of inorganic and alkyl quaternary ammonium ions of varying ionic sizes. The distribution and selectivity coefficients of the desorbing ions increase in the order: Li<Na<NH4<K<Rb<H<Cs for the monovalent, Ca<Mg for the bivalent and (C2H5)4N<(CH3)4N≪CTA (cetyl trimethyl ammonium) <CP (cetyl pyridinium) for the organic ions. The ΔG° values of some of the cation exchange reactions have been calculated by an equation of Kielland (1935).