bluuebunny/crossref_metadata_2025 huggingface dataset:
Hydration of reduced-charge montmorillonite
Authors: Komadel P. , Hrobáriková J . , Smrčok L’. , Koppelhuber-Bitschnau B.
Published: August 2004

A series of reduced-charge montmorillonites with cation exchange capacities of 89, 73, 49 and 29% of the starting mineral was prepared from a Li-saturated smectite (Kriva Palanka, Republic of Macedonia) by heating at 110, 130, 160 and 300°C for 24 h (samples KP110 – KP300, respectively). Hydration properties of this series were investigated gravimetrically and by in situ XRD at different relative humidities (RHs). In the gravimetric experiments, higher water contents were observed for desorption than for sorption and hysteresis was present over the whole range of RHs for all the samples. The parent montmorillonite and the samples KP110 and KP130 retained similar amounts of water under the same conditions, thus showing that the decreased negative charge on the layers had minor effect on the water uptake at all investigated RHs. Significantly decreased water content was retained by KP160 while KP300 contained only 8% water at 100% RH. The d001 values of the parent montmorillonite and the samples KP110 and KP130 increased with RH, while those of KP160 and KP300 were independent of RH and remained at ∼10.4 and ∼9.6 Å, respectively.
Use of hydrofluoric acid dissolution for the concentration of dickite and nacrite from kaolin deposits: an FTIR study
Authors: Fraser A. R. , Wilson M. J . , Roe M. J . , Shen Z. Y.
Published: August 2004

A series of kaolin-rich mineral samples was treated with hydrofluoric acid (HF) and the residual material characterized using infrared (IR) spectroscopy, supplemented by scanning electron microscope (SEM) observations. By examining the hydroxyl-stretching region of the IR spectra before and after treatment with hydrofluoric acid, it was possible to identify the three kaolin polytypes – kaolinite, dickite and nacrite – with greater certainty. The SEM observations suggested that the rate of dissolution of the kaolin phase was largely dependent on particle size. In general, dickite and nacrite tend to occur in the coarser clay fractions, and for this reason the finer-grained kaolinite is preferentially dissolved by the HF treatment. However, in the Keokuk kaolinite, which occurs in exceptionally large particles, it was still possible to concentrate a dickitic fraction by HF treatment, suggesting that in some cases kaolinite may be more susceptible to HF dissolution for reasons other than particle size. The IR spectra of disordered kaolinite could be interpreted as arising from a mixture of kaolinite and dickite components. However, both components dissolve at the same rate in HF, supporting the idea that disordered kaolinite consists of an intimate association of randomly stacked dickite-like and kaolinite-like components.
The influence of structural Fe, Al and Mg on the infrared OH bands in spectra of dioctahedral smectites
Authors: Bishop J. , Madejová J . , Komadel P. , Fröschl H.
Published: August 2004

Visible to near-infrared (NIR) reflectance spectra and mid-IR transmittance spectra are presented here for a collection of dioctahedral smectites. Analysis of the structural OH vibrations is performed by comparing the NIR combination and overtone bands with fundamental stretching and bending absorption features in the mid-IR region. Second derivatives are used to determine the actual band centres, which are often shifted slightly by a spectral continuum in the reflectance or transmittance spectra. New bands have been identified near 4170 and 4000 cm–1 in the NIR spectra of nontronite with tetrahedral substitution. A related band is observed near 4100 cm–1 for montmorillonites with substantial tetrahedral and/or octahedral substitution. These bands are correlated with the mid-IR bands near 680 cm–1 for nontronite and near 630 cm–1 for montmorillonite. Comparison of the OH overtone and combination bands with the fundamental stretching and bending vibrations gives consistent results.
The influence of octahedral and tetrahedral cation substitution on the structure of smectites and serpentines as observed through infrared spectroscopy
Authors: Bishop J . , Murad E. , Dyar M. D.
Published: August 2004

Analysis of the near-infrared (NIR) spectral bands of phyllosilicates, together with the mid-infrared bands, enables testing and confirmation of band assignments for the structural OH vibrations. Spectral analyses of selected smectites and serpentine-kaolin minerals are presented here. The results of this study indicate that dioctahedral smectites may contain both in-plane and out-of-plane OH-bending vibrations, as suggested by Farmer (1974). In-plane bands occur near 800 ­ 915 cm–1, while the weaker out-of-plane vibrations occur near 600 ­ 700 cm–1 and are enhanced in dioctahedral smectites when the structure is disrupted by substitutions. Analysis of the OH-stretching vibrations and their NIR overtone bands is also presented for both smectites and serpentine-kaolin minerals. These overtones are more straightforward for serpentines than for kaolinite, and a strong overtone associated with the kaolinite OH-stretching band at 3620 cm–1 is found that supports its assignment as an OH-stretching band.
XRD peak migration and apparent shift of cell-edge lengths of nano-sized hematite, goethite and lepidocrocite
Authors: Stanjek H.
Published: August 2004

X-ray powder diffraction patterns were simulated for nano-sized hematite, goethite and lepidocrocite by three-dimensional integration in reciprocal space. The cell-edge lengths were refined together with the size parameters X and Xeof the Thompson-Cox-Hastings function, which for orthorhombic structures was extended by a biaxial broadening parameter Xo. Variations of the structure factors across broad peaks resulted in apparent peak shifts and concomitant shifts in celledge lengths, which were significantly correlated with the size parameters for hematite and partially correlated for goethite and lepidocrocite. Regression equations are given for correcting cell-edge lengths obtained from Rietveld fits for size-induced shifts.
Mineralogy of soils with unusually high exchangeable Al from the western Amazon Region
Authors: Marques J . J . , Teixeira W. G. , Schulze D. G. , Curi N.
Published: August 2004

Some soils from the western Amazon region contain KCl-extractable Al contents 5 to 10 times greater than is typical for highly weathered soils containing predominantly kaolinite and gibbsite. We studied a soil sequence from the Brazilian western Amazon consisting of two Typic Udifluvents on the levee of the Javari River, one Aeric Endoaquent in the backswamp, and two Typic Hapludults on an adjacent terrace. We used wet chemical and X-ray diffraction (XRD) analysis to characterize several size fractions of the 0 to 0.2 m layer of the soils. The exchangeable Al content was very high in the Aquent and Udults (up to 180 mmolc kg–1), but the ‘total’ Fe content was low in all samples (<60 g kg–1). Smectite, vermiculite, hydroxy-interlayered smectite and kaolinite dominate the fine silt and clay fractions of all soils. The Fluvents contain illite in all size fractions and chlorite in the coarse clay and fine silt fractions. The Aquent and Udults have no chlorite, and small amounts of illite occur only in the coarse clay and fine silt fractions. Lepidocrocite was identified in the Aquent. Chlorite, which occurs in the sand, fine silt, and coarse clay fractions of the Fluvents, and pyrophyllite, which occurs in the fine silt fractions of all soils and in the coarse clay of the two Ultisols, appears to be inherited from the parent sediments. The hydroxy-interlayered 2:1 phyllosilicates that form as a result of weathering are the cause of the very high exchangeable Al contents.
Possible effects of land use on the clay mineralogy of a brown forest soil
Authors: Bain D. C. , Griffen D. T.
Published: August 2004

Three soil profiles classed as brown forest soils on schistose parent material, in close proximity but under different land uses, have been studied. The profile under 50 year-old Sitka spruce trees is the most acidic, the second profile under rough grassland is less acidic, and the third profile in an arable field which has been fertilized is the least acidic. The clay fractions (ς μm) of all three profiles are very similar. However, computer simulations of the X-ray diffraction patterns of clay phases using a modified version ofNEWMODrevealed two possible weathering trends: (1) an increasing proportion of vermiculite in interstratified mica-vermiculite in the upper horizons of the arable and forested soils; (2) formation of high-charge corrensite by weathering of chlorite in all three profiles but least pronounced in the arable soil. The differences in clay mineralogy amongst the profiles are minor, but these two different weathering trends may be due to the effects of different land use.
Influence of parent material on clay minerals formation in Podzols of Trentino, Italy
Authors: Mirabella A. , Egli M. , Carnicelli S. , Sartori G.
Published: August 2004

The formation of clay minerals was investigated in Spodosols developed in the subalpine belt, with similar exposure, climate and age, but deriving from different parent materials. All the soils were classified as Haplic Podzols and showed the characteristic eluviation and illuviation features of Fe, Al and organic carbon. However, varying parent material lithology led to different clay mineral assemblages in the soil. Smectite could be found in the E horizons of soils developed from granodiorite and tonalite materials. Its formation was strongly dependent on the presence of chlorite in the parent material. If nearly no other 2:1 mineral components, such as chlorite, are present in the lower soil horizons, then a residual micaceous mineral becomes the dominant clay mineral. The latter derives from a mica-vermiculite interstratified mineral.
Experimental alteration of vivianite to lepidocrocite in a calcareous medium
Authors: Roldán R. , Barrón V. , Torrent J .
Published: August 2004

Vivianite [Fe3(PO4)2·8H2O] is easily oxidized in the presence of air. In this work, we studied the oxidation and incongruent dissolution of vivianite in a calcareous medium containing an anion-exchange resin (AER) that acted as a sink for phosphate. Freshly prepared vivianite suspensions with calcite sand and an AER membrane were oxidized and stirred by bubbling air or CO2-free O2. Experiments were finished when oxidation rate and P removal by the AER became slow, which was at 53 days (air system) or 28 days (CO2free O2system). At these times, the respective values of the Fe(II)/total Fe ratio were 0.29 and 0.12, and the respective values of the atomic P/Fe ratio were 0.15 and 0.11. The final product of the oxidation was poorly crystalline lepidocrocite in the form of thin (1 ­ 5 nm), irregular lamellae that were soluble in acid oxalate. The unit-cell edge lengths of this lepidocrocite werea= 0.3117,b= 1.2572, andc= 0.3870,vs. a= 0.3071,b= 1.2520 andc= 0.3873 nm for the reference lepidocrocite. The lepidocrocite lamellae contained occluded P (P/Fe atomic ratio = 0.03 ­ 0.04). The results of this and a previous study made us hypothesize that this occluded P is structural and occupies tetrahedral sites adjacent to the empty octahedral sites in the sheets extending on ﹛010﹜.
Synthesis of clay-sized iron oxides under marine hydrothermal conditions
Authors: Taitel-Goldman N. , Singer A.
Published: August 2004

Goethite, lepidocrocite, magnetite and akaganeite were synthesized in 0.8 M, 2 M and 5 M NaCl solutions at various temperatures (25, 40, 60°C) under slightly acidic to slightly alkaline pH with or without Si additions. Elevated temperatures prevent complete oxidation of initial Fe2+ solutions and magnetite and siderite precipitate, accompanied by goethite and lepidocrocite. At higher salinity, O2 solubility is reduced and its distribution is limited, leading to coprecipitation of lepidocrocite, akaganeite and goethite.

Lepidocrocite morphology changes from plates at pH 5.5 through rods at pH 7 to multi-domainic crystals at pH 8.2, due to enhanced crystal growth along the c axis. Salinity and temperature have opposite effects on lepidocrocite crystallinity.

Goethite crystals are multi-domainic and twinning appears only at elevated temperatures. Increases in temperature and salinity improve goethite crystallinity as observed by IR spectra. Addition of Si up to Si/Fe = 0.1 retards crystal growth and Si-OH-stretching bands appear. At Si/Fe = 1 most of the precipitate is short range ordered.

Platy and rod-shaped lepidocrocite from the Thetis and Atlantis II Deeps, were probably formed under the slightly acidic conditions of the hydrothermal brines. The Si concentration was greater in Atlantis II Deep than in Thetis Deep, leading to larger lepidocrocite and goethite crystals in the latter.

Multi-domainic goethite could have precipitated throughout. Pure phase goethite might have precipitated in the less concentrated brine, whereas mixtures of goethite and lepidocrocite might have precipitated in the more concentrated brine, depending mainly on oxidation rate and oxygen mobility within the brine.
The smectitic minerals in a bentonite deposit from Melo (Uruguay)
Authors: Calarge L. , Lanson B. , Meunier A. , Formoso M. L.
Published: August 2004

A nearly monomineralic 1.5 m thick bentonite bed sampled in Melo (Uruguay) appears to be a pure high-charge montmorillonite: [Si3.94Al0.06](Al1.40Fe3+0.11Ti0.02Mg0.49Mn0.01)O10 (OH)2Na0.01K0.08Ca0.18. However, contrasting swelling behaviours have been demonstrated by fitting the experimental X-ray diffraction patterns which were recorded on oriented preparations of the same sample in different saturation states. According to the expandability of the layers in the Ca-, K- and K-Ca-saturated (i.e. saturated first with K+ and subsequently with Ca2+) states, three ‘layer types’ were defined. Low-, intermediate-, and high-charge layers are fully, partly, and not expandable, respectively, after K-saturation. Collapse of high-charge layers is not reversible after subsequent Ca-saturation, probably because of tetrahedral substitutions. These three different layer types are segregated in two distinct randomly interstratified mixed-layer phases. Total surface area and cation exchange capacity are shown to depend on the interlayer cation composition.
Formation of hydrotalcite-like compounds during corrosion experiments on MTR-FE-Al cladding
Authors: Mazeina L. , Curtius H. , Fachinger J .
Published: August 2004

Hydrotalcite-like compounds (HTlc) were found as secondary products in two corrosion experiments performed with Al plates in highly concentrated solutions (MgCl2-saturated brine) in the presence of metallic and soluble iron at 90ºC under an Ar atmosphere. The durations of the experiments were ∼10 and 13 months, respectively. To investigate the corrosion experiments, solution and gas samples were collected and the main parameters measured. The solid and liquid samples obtained were analysed by X-ray diffraction (XRD), scanning electron microscopy (SEM) and ICP-OES. The presence of the hydrotalcite-like phase was confirmed by XRD and SEM. In one experiment HTlc was found only after dialysis. Formation of the hydrotalcite-like phase was observed at lower pH than mentioned in the literature. These results are useful in understanding the long-term behaviour of corrosion products of reactor fuel elements in relation to their possible barrier function and to comprehend the long-term behaviour of this type of waste during its final disposal.
Synthesis and properties of aluminapillared fluorine micas having cation exchangeability
Authors: Yamaguchi T. , Kitajima K. , Sakai E. , Daimon M.
Published: August 2004

Alumina-pillared fluorine micas were prepared from synthetic highly layer-charged expandable fluorine mica and polyhydroxoaluminium solutions under different solution loadings (Al mmol in solutions per 1.0 g mica) in order to clarify the effects of solution loading on thermal durability and microporous properties. The intercalated Al content of the pillared micas increased with increased solution loading. The intercalated Al content (i.e. the pillar density) of the pillared micas influenced both the thermal durability and specific surface areas of the pillared micas. The pillared micas obtained from the high solution loadings showed better thermal durability than those obtained from the low solution loadings. Through micropore formation upon heating, the pillared micas exhibit cation exchangeability due to the liberation of residual Na+ ions from steric hindrance in the interlayer pillaring space. The amount of the exchangeable ions depends on the heating temperature of the pillared micas.
29Si and 27Al MAS NMR study of the zeolitization of kaolin by alkali leaching
Authors: Benharrats N. , Belbachir M. , Legrand A. P. , D'espinose de la Caillerie J. -B.
Published: August 2004

The alkali leaching of two aluminosilicates, kaolinite and metakaolinite, with aqueous NaOH has been studied. Both silicates gave hydroxysodalite (HS) with or without the evanescent zeolite NaA. X-ray diffraction and high-resolution 29Si and 27Al MAS-NMR spectroscopy provide information about the reaction sequence of the clay. The conversion starts with the formation of an amorphous gel precursor at a rate which depends on the alkali concentration but not on the choice of kaolinite or metakaolinite as starting material. The rate of zeolitization of this gel is much faster when it is obtained from kaolinite, probably because it is more homogeneous.
23Na 2D 3QMAS NMR and 29Si, 27Al MAS NMR investigation of Laponite and synthetic saponites of variable interlayer charge
Authors: Delevoye L. , Robert J . -L. , Grandjean J .
Published: August 2004

29Si, 27Al MAS NMR is used to characterize Laponite RD and synthetic saponites of variable interlayer charge. The Si/Al ratios are in good agreement with the calculated charge from chemical analysis except for the lowest-charged saponite. In contrast to the 29Si MAS NMR spectra in which resolved signals are detected, the 27Al MAS NMR spectra show one signal whose linewidth increases with the clay charge. The water content of the clay samples was obtained from 1H MAS NMR.

The 2D MQMAS NMR technique is required to obtain a high-resolution spectrum of nuclei with strong quadrupolar interaction. This method was applied to the 23Na nucleus of clay counterions and to the 27Al structural nucleus. One well-defined 23Na NMR signal is observed for all the clays studied except the highest-charged saponite. Possible explanations for this different behaviour are discussed. The calculated isotropic chemical shift evolves progressively with the clay charge whereas the deduced quadrupolar interaction does not change significantly. The 27Al 2D 3QMAS technique was not able to resolve more than one signal.
Properties of soil kaolins from Thailand
Authors: Hart R. D. , Wiriyakitnateekul W. , Gilkes R. J .
Published: August 2004

Purified kaolins from Thai soil on diverse parent materials were characterized using analytical transmission electon microscopy, X-ray diffraction, thermogravimetric analysis and chemical analysis. The properties of Thai soil kaolins appear to be more diverse than Indonesian and Western Australian soil kaolins investigated using the same analytical procedures; this difference may reflect the greater range of parent materials for the Thai soils. The kaolins show a variety of crystal morphologies including euhedral hexagonal to subhedral platy crystals, tubes and laths and several morphologies were present in most samples. TEM-EDS enabled analysis of single crystals of each morphology present within a sample. Tubular or lath-shaped crystals usually have lower %Fe2O3 contents than hexagonal platy crystals in the same sample. The relationships between crystal size and Fe content within morphological populations were also examined by TEM-EDS. Generally, smaller kaolin crystals display a wider range of Fe concentration than the larger kaolin crystals in the same sample. Increasing Fe concentration in bulk samples is closely correlated to decreasing coherently scattering domain size (R2= 0.57), increasing cation exchange capacity (R2= 0.44) and increasing specific surface area (R2= 0.65). However the properties of the deferrated soil kaolins, including their Fe content, are not related to forms of Fe, (total Fe, amorphous or organic) in the untreated clay fraction of the soil.

Inhibited vermiculite is a common minor constituent of these clay fractions and its average structural formula derived from EDS data indicates that it was formed by Al replacing K in muscovite. One Al3+ion occupies the interlayer space previously occupied by three K+ions. As the distances between these Al3+cations in the interlayer space is large it is proposed that isolated or loosely associated hydrated Al3+groups such as Al(OH2)63+exist that resist exchange by other cations due to hydrogen bonding with the adjacent tetrahedral oxygen surfaces
Isotope geochemistry and origin of illite-smectite and kaolinite from the Seilitz and Kemmlitz kaolin deposits, Saxony, Germany
Authors: Gilg H. A. , Weber B. , Kasbohm J . , Frei R.
Published: August 2004

Residual clays that developed on Permian and Carboniferous glass-rich silicic volcanic rocks (pitchstones, ignimbrites) at the Seilitz and Kemmlitz kaolin deposits, Saxony, Eastern Germany, contain locally abundant lath-shaped illite-rich illite-smectite mixed-layer minerals (I-S). Analyses by XRD and TEM-AES reveal a large illite percentage (>∼90%) and R3 ordering in I-S from Seilitz (>∼90%) and smaller illite percentage (∼70%) and R1 ordering in I-S from Kemmlitz. The clays never suffered a deep burial and there is no geological, petrographic or fluid inclusion evidence for aeolian input or hydrothermal origin of I-S at either deposit. The I-S formed exclusively at the expense of volcanic glass and not from K-feldspar. Residual quartz phenocrysts in the clays still preserve primary glassy silicate melt inclusions and lack secondary aqueous fluid inclusion trails. The dD and δ18O values of kaolinite and I-S are suggestive of low formation temperatures (<40ºC). Rb-Sr and K-Ar dating of I-S-bearing clay separates yield Lower Cretaceous ages at Seilitz and indicates the presence of excess or inherited 40Ar in illite-rich I-S. In contrast, Triassic to Jurassic Rb-Sr ages are obtained for I-S from the Kemmlitz kaolin deposit.
Chemically modified smectites
Authors: Komadel P.
Published: August 2004

This paper summarizes recent results obtained on chemical modifications of smectites. These include replacement of exchangeable cations with protons, a process connected with smectite autotransformation – attack of protons on the layers and liberation of central atoms from the octahedral and tetrahedral sheets, causing modification of the acid sites on the particles. More severe modifications occur during dissolution in inorganic acids, when the layers are dissolved and threedimensional amorphous silica is formed. The negative charge on the smectite layers can be increased via reduction of structural Fe(III) to Fe(II) or decreased via fixation of small exchangeable cations, such as Li+, upon treatment at elevated temperatures. Heating for 24 h at different temperatures between 100 and 300ºC leads to a series of chemically similar materials of different charge, prepared from the same parent mineral. Such series are suitable for investigation of the effect of the layer charge on selected properties of smectites. Fe(II) can be partly stabilized in reduced smectites by Li fixation upon heating.
Evaluation of talc morphology using FTIR and H/D substitution
Authors: Ferrage E. , Martin F. , Petit S . , Pejo-soucaille S. , Micoud P. , Fourty G. , Ferret J . , Salvi S. , De Parseval P. , Fortune J . P.
Published: August 2004

Deuteration (H/D substitution at 200ºC) was performed on powders of two ground talcs of different particle shapes (different basal/lateral surface ratios). Results indicate that the deuteration process is only efficient on lateral talc surfaces, and suggest that the hydrogens located in the hexagonal ring of the talc basal surfaces are not exchanged. The FTIR spectra collected from the two talc samples show that it is possible to discriminate between particles with the same specific surface area but with different basal/lateral surface ratios using the deuteration process.
Hydrothermal transformation of kaolinite to illite at 200 and 300ºC
Authors: Bentabol M. , Ruiz Cruz M. D. , Huertas F. J . , Linares J .
Published: August 2004

The hydrothermal reaction of kaolinite in the system Na2O-K2O-(MgO)-Al2O3-SiO2- H2O has been investigated at 200 and 300ºC. The study of the solid products indicates that, at 200ºC, disordered illite was the first phase formed, which evolved at increasing run times towards well ordered illite and analcime. After longer reaction times illite and kaolinite were the sole phases identified by XRD. The b parameter of the illites increased at longer reaction times, from 9.05 to 9.08 Å. Study by TEM/AEM revealed the presence of surface chlorite-like layers, covering the illite packets, however. The trend observed in the products of the reaction at 300ºC was similar, except for the presence of boehmite or pseudoboehmite at the higher temperature. The values of the bparameter of illite, of the order of 9.12 –9.16 Å, indicate that illites formed at 300ºC have a more trioctahedral character. The results obtained also indicate that Mg determines which product will be formed, Kand Na-zeolites and Al-rich illites being the phases formed in the absence of Mg.
Destabilization of montmorillonite suspensions by Ca2+ and succinoglycan
Authors: Labille J . , Thomas F. , Bihannic I . , Santaella C.
Published: August 2004

Aggregation of colloidal clay particles (Na-montmorillonite) by CaCl2 and anionic polysaccharide (succinoglycan) in turbulent conditions was investigated using time-resolved size measurements by laser diffraction on diluted (50 mg l –1) and stirred suspensions. Excess of Ca2+ ions promotes coagulation of the clay, reducing interparticle repulsions, and allows adsorption of succinoglycan, inducing bridging flocculation. Growth/breakage cycles, characteristic of the turbulent conditions, cause the macromolecules to be incorporated in the innermost of the flocs, where the morphological units are shown by confocal microscopy to be the micrometric Ca-clay particles. Such incorporation results in an increased floc tensile strength, depending on the amount of macromolecules adsorbed, with a maximum at polysaccharide concentrations of 2 wt.% with respect to clay mass.
Characterization of smectite and illite by FTIR spectroscopy of interlayer NH4+ cations
Authors: Pironon J . , Pelletier M. , De Donato P. , Mosser-Ruck R.
Published: August 2004

FTIR spectroscopy has been applied to NH4+-exchanged dioctahedral clay minerals to determine the molecular environment of NH4+ and to quantify N concentration. FTIR under vapourpressure control, coupled with heating and freezing treatments has shown that NH4+ ion symmetry varies with the nature of clay minerals. NH4+ has a perfect tetrahedral symmetry in hydrated or dehydrated smectites and belongs to the Td symmetry group. The NH4+-bending vibration is centred at 1450 and 1425 cm–1.

The Si4+-Al3+ substitution in dioctahedral clay minerals induces the loss of symmetry elements of the NH4+ tetrahedron which acquires a C2v symmetry. As a consequence, the Td –C2v transition can be used to characterize the smectite–illite transition. Quantification of NH4+ content per half unit cell is provided by nNH4 = k[NH4]/[OH] where [NH4]/[OH] is the band area ratio of the NH4+-bending vibration to the OH-stretching vibration. k = 1.1 for hydrated smectite, 0.9 for dehydrated smectite and 0.8 for illite or tobelite. The bending vibration of NH4+ is chosen for the calculation because it is not affected by superimposed contributions.
The evolution of textural properties of Na/Ca-bentonite following hydrothermal treatment at 80 and 300ºC in the presence of Fe and/or Fe oxides
Authors: Neaman A. , Guillaume D. , Pelletier M. , Villiéras F.
Published: August 2004

The evolution of textural properties of Na/Ca-bentonite from Wyoming (MX-80) was studied by adsorption of nitrogen, water vapour, and ethylene glycol monoethyl ether. Clay suspensions were heated at 80 and 300ºC for up to 9 months in the absence of or in the presence of Fe and/or Fe oxides. The treatment without Fe did not change the textural properties of the samples significantly. The treatment at 80ºC in the presence of Fe resulted in a considerable increase in the external surface areas of the samples. The total and external surface areas and swelling capacities of the samples decreased following the treatment at 300ºC in the presence of Fe and Fe oxides. In the case of larger additions of Fe, the treatment at 300ºC resulted in a considerable decrease in the total and external surface areas and swelling capacity of the sample and in the formation of a network of large-size pores, in which all the pores were connected.
Dehydration behaviour of hexadecyltrimethylammonium-exchanged smectite
Authors: Lee S. Y. , Kim S. J .
Published: August 2004

The dehydration of hexadecyltrimethylammonium (HDTMA)-exchanged smectites has been studied using X-ray diffractometry (XRD) and differential scanning calorimetry (DSC). The basal spacing of hydrated HDTMA-smectites changed with temperature. The 2.5 HDTMA-smectite (i.e. smectite treated with HDTMA equivalent to 2.5 times the CEC) showed a continuous increase in its basal spacing during dehydration up to 200ºC, while the 1.2 HDTMA-smectite showed a significant decrease in basal spacing. It is assumed that the less ordered alkyl chains in the wet state in the interlayer region may be rearranged to ordered chains (e.g. all-trans conformation) during sequential dehydration. This results in a decrease in interlayer spacing in the phase with low organic packing density and a flat-lying array (i.e. 1.2 HDTMA-smectite), and a gradual increase in the basal spacing when the chains have a vertical configuration (2.5 HDTMA-smectite).
Structural states of micas in amphibolites of the KSDB-3 deep bore-hole and their surface equivalents
Authors: Ovchinnikov N. O. , Nikitina L. P. , Babushkina M. S. , Yakovleva A. K. , Yakovlev Yu. N. , Chernova O. G. , Redfern S. A. T.
Published: August 2004

Trioctahedral ferromagnesium micas from the Archaean amphibolites of the Kola super-deep borehole (KSDB-3) complex have been compared with those from analogous Archaean surface rocks in an integrated study of their chemical compositions and structural states (using wet chemistry, microprobe, X-ray, Mössbauer and infrared methods). Reports on both the experimental procedure and the crystal chemistry of the trioctahedral micas are given. This has enabled the revision of the assignment of individual infrared (IR) absorption bands for the hydroxyl ion (vOH−), and demonstrated the possibility of determining the content of Mg, Fe2+, R3+; cations and vacancies in the octahedral sheet to within a few hundredths of atomic units on the basis of the infrared and Mössbauer data. Proof was found of the presence of molecular water replacing K+ in the interlayer, which results in anomalous variations in the cell parameters, as the mica structure expands in response to the ingress of H2O. Variations in the degree of non-stoichiometry of the micas is related to the presence of structural H2O and of octahedral M1 vacancies. We found that samples recovered from depth within the borehole display lower degrees of octahedral order than those found in the analogous surface rocks.
Brinrobertsite: a new R1 interstratified pyrophyllite/smectite-like clay mineral: characterization and geological origin
Authors: Dong H. , Peacor D. R. , Merriman R. J. , Kemp S. J.
Published: August 2004

Brinrobertsite, an ordered, mixed-layered, dioctahedral pyrophyllite-smectite (P/S), occurs in a metabentonite in the Ordovician Nant Ffrancon Formation near Bangor, N Wales. It comprises ~30% of the metabentonite, in association with quartz (~50%) and chlorite (clinochlore; 20%) which replaced glass shards and fine-grained glass matrix. Transmission electron microscopy (TEM) images show sequences of dominant ~24 Å 001 lattice fringes inferred to correspond to 2:1 layers with alternate pyrophyllite-like (low-charge) and smectite-like (higher-charge) interlayers (i.e. R1 ordering). The hk0 diffraction patterns are mostly hexanets with some spotty circles, implying that layers are largely coherently related, but with some turbostratic stacking. Collective data show that d100 = 5.2, b = 9.1, and d001 = 24–25 Å, assuming monoclinic or pseudomonoclinic symmetry. The composition, as determined by energy dispersive spectral analysis, is (Na0.22K0.07Ca0.06)(Al3.81Mg0.08Fe0.08)(Si7.84 Al0.16)O20(OH)4·3.54H2O, as consistent with the sum of the compositions of pyrophyllite-like and smectite-like units. Water content was determined by DTA/TGA analysis. The powder diffraction patterns have a principal peak with d001 = 24.4 Å. Patterns of air-dried and glycol-saturated brinrobertsite, including Na- and Ca-saturated and untreated samples, were modelled satisfactorily as R1-ordered P/S by the program NEWMOD-for-Windows. The unique composition of brinrobertsite relative to R1 IS, which is ubiquitous in metabentonites, was caused by leaching of alkalis and alkaline-earth elements by hydrothermal fluids associated perhaps with a nearby intrusion, as demonstrated by bulk-chemical analyses of the metabentonite. The crystal structure is modelled as having Al/Si distributions symmetrical by reflection across interlayers. This causes all 2:1 layers to be equivalent in having one tetrahedral sheet with little or no Al, and the other with significant Al substitution, giving rise to alternate high- and low-charge interlayers. Geological evidence suggests that brinrobertsite is a back-reacted product of hydrothermal alteration in the sequence: glass → pyrophyllite → brinrobertsite.
Thermodynamics of mixing and ordering in the diopside–jadeite system: I. A CVM model
Authors: Vinograd V. L.
Published: August 2004

Solution calorimetry and phase equilibrium data for the diopside–jadeite system are assessed using a combination of the cluster variation method (CVM) and Redlich-Kister (RK) polynomial expansion. The CVM is used to model part of the free energy of mixing which depends on short-range order (SRO) and long-range order (LRO) effects. The SRO/LRO independent part of the free energy is modelled using an RK polynomial. The parameters of the RK and CVM models are obtained through the fit to the experimental data. The best-fit parameters are used to calculate activity-composition relations and a temperature-composition phase diagram of the diopside–jadeite system.
Thermodynamics of mixing and ordering in the diopside–jadeite system: II. A polynomial fit to the CVM results
Authors: Vinograd V. L.
Published: August 2004

In Part I (Vinograd, 2002) the relationship between temperature, composition and free energy of the diopside–jadeite solid solution was described using a CVM model. Here the same relationship is described using a combination of Redlich-Kister (RK) polynomials and Gaussian functions. The use of the Gaussians permits an accurate description of the free energy dip centred at Jd50, which is caused by the long-range ordering, while the effect of the short-range ordering can be easily modelled using the RK polynomial The simplified RK-Gaussian description is extended to the three-component diopside–jadeite–hedenbergite solid solution. The polynomial description permits an easy incorporation of the derived activity-composition relations into phase-equilibrium computation software.
Formation of coagulated colloidal silica in high-temperature mineralizing fluids
Authors: Williamson B. J. , Wilkinson J. J. , Luckham P. F. , Stanley C. J.
Published: August 2004

Recent experimental studies have suggested that colloidal silica can form in high-T (300 to >700°C) hydrothermal fluids (Wilkinson et al., 1996). Natural evidence in support of this was found by Williamson et al. (1997) who proposed a colloidal (gel) silica origin for <50 μm irregularly-shaped inclusions of quartz contained in greisen topaz from southwest England. Confocal and microprobe studies, presented here, strengthen this argument although rather than forming a gel in the hydrothermal fluid, it is suggested that the colloidal silica aggregated as a viscous coagulated colloid, with much of its volume (<10 to 30 vol.%) consisting of metal (mainly Fe) -rich particles. This is evident from the largely solid nature of metal-rich shrinkage bubbles contained at the margins of the inclusions of quartz which shows that the material forming the inclusions contained much less liquid than would be expected in a silica gel. These findings may have important implications for models of ore formation since the precipitation of a coagulated colloid could inhibit hydrothermal fluid transport and cause co-deposition of silica and entrained ore-forming elements. The mode of formation of the colloidal silica and further implications of the study are discussed.
Chromite in greenstone lavas from the Kanakasu area, Nanjo Massif of the Mesozoic Mino terrane, central Japan
Authors: Agata T. , Hattori I.
Published: August 2004

Chromite occurs together with olivine as phenocrysts in basalts of the Kanakasu greenstone body. Chromite forms inclusions within olivine phenocrysts; it also constitutes discrete phenocrystic grains scattered in the groundmass. The Cr and Ni contents of chromite-bearing olivine basalts are unusually high relative to the MgO content. This is probably due to the presence of phenocrystic chromite and olivine. The mineralogy suggests that the groundmass of the basalts is hawaiitic in composition. Chromite, generally, is unlikely to crystallize from differentiated magma such as hawaiite melt. The chromite and associated olivine phenocrysts are probably xenocrysts. Discrete chromite commonly shows compositional zoning that resulted from reaction with host magma; some chromite evidently changed in composition. Chromite embedded in olivine was shielded from reaction with host magma, and has preserved the original chemical composition. The composition of embedded chromite ranges: Mg/(Mg+Fe2+) 0.37–0.58, Cr/(Cr+Al) 0.47–0.64, Fe3+ 0.16–0.47 p.f.u., and Ti 0.034–0.13 p.f.u. The relatively high Ti and Al contents suggest that chromite crystallized from an alkalic basalt magma. The Cr/(Cr+Al) ratio is relatively high when compared to those of chromite in mid-oceanic ridge and island-arc alkalic basalts; the Kanakasu embedded chromite is chemically identical to chromite from Hawaiian alkalic basalts. The Kanakasu chromite was probably formed in an intraplate oceanic island.
Oxidation-induced postmagmatic modifications of primary ilmenite, NYG-related aplite dyke, Tibchi complex, Kalato, Nigeria
Authors: Sakoma E. M. , Martin R. F.
Published: August 2004

We describe an ilmenite-bearing aplitic syenite dyke in the roof zone of the Tibchi granite, exposed at Kalato, in the Tibchi ring-complex, northern Nigeria. Inclusions of ferrocolumbite, rutile and ixiolite in the ilmenite are inferred to have been trapped at the magmatic stage. The main mafic mineral is annite. Compositionally, the ilmenite, rutile and ferrocolumbite have near-end-member compositions. A positive correlation between Sc and Ta/(Ta+Nb) indicates that Sc behaved incompatibly as ferrocolumbite grew. Such entrapped accessory minerals may well have formed by local saturation at the ilmenite-melt and annite-melt interface. During and after their crystallization, the melt reached saturation in H2O and degassed. A second generation of ilmenite enriched in Mn and Zn replaced the primary ilmenite along fractures and grain margins. As fO2 began to increase, composite blebs and rinds of ‘ferropseudobrookite’, rutile and hematite began to develop by oxidation-induced exsolution in the primary ilmenite. Incorporation of Nb, Ta, Sc and Si in the ‘ferropseudobrookite’ may well have stabilized it at Kalato. Ultimately, it is transformed to hematite + rutile. The IMA-sanctioned view that the solid solution between pseudobrookite and Ti3O5 is complete, and thus that ‘ferropseudobrookite’, as an intermediate member of the series, does not merit species status, needs to be re-evaluated.
Caveats in defining the magmas parental to the mafic rocks of the Bushveld Complex, and the manner of their emplacement: review and commentary
Authors: Eales H. V.
Published: August 2004

The composition of magmas proposed as parental to the layered suite of the Bushveld Complex, and some models for the manner of their emplacement, are reviewed briefly. Included are some contributions published in South Africa, with which overseas readers might be less familiar. Emphasis is given to the broader features of the cumulates, and the contradictions raised by whole-rock compositional, Sr-isotopic, and trace-element data that cloud their correlation with proposed parental magmas. It is concluded that the Lower, Critical and Main Zones are the derivatives of only two primary magmatic lineages, while a third was added to residual liquids from which the layered rocks above the Pyroxenite Marker were formed. Excessive amounts of olivine and chromium in the cumulates of the Lower and Lower Critical Zones in the northern sector of the Western Limb can seemingly not be accounted for by the composition and volume of the putative magmas. This is attributed to (1) this sector being a proximal facies located close to the original feeder, and/or (2) crystal-charged magma batches, expelled from a lower magma chamber, being periodically injected into and dispersed within the liquids already in place in the Bushveld chamber. Thus, ongoing changes in the bulk composition of the liquids within the chamber would not be reflected in the rinds of earlier, chilled-facies rocks. The expulsion of significant volumes of liquid residua from the chamber during cumulate deposition is not ruled out.
Geochemical effects of magma addition: compositional reversals and decoupling of trends in the Main Zone of the western Bushveld Complex
Authors: Nex P. A. M. , Cawthorn R. G. , Kinnaird J. A.
Published: August 2004

The Main Zone of the Bushveld Complex, which is ˜3–3.5 km thick, comprises a sequence of gabbronorites with minor anorthosites and pyroxenites. The Pyroxenite Marker (PM), a thin orthopyroxenite layer occurring towards the top of the Main Zone in the eastern Bushveld, marks the change from an inverted pigeonite-bearing microgabbronorite below, to a primary orthopyroxene-bearing porphyritic gabbronorite above. In the western Bushveld the PM has only been observed in core material although its surface position can be inferred from the mineralogical and textural changes. Whole-rock geochemistry of surface and core samples from the Brits and Marikana areas, together with mineral compositional data, have been integrated with published analyses to elucidate the magmatic processes that occurred during the addition of new magma into the chamber, just below the level of the PM. Modal and major-element data show that most lithologies lie close to the plagioclase-two pyroxene cotectic. However, there are three units below the PM in which distinct modal layering is developed. Changes in geochemical trends for trace-element abundances in both whole-rock and mineral-separate data occur at ˜150 m below the PM, below a layered package, the Hexrivier Unit. However, there is a displacement of at least 40 m between the beginning of the reversals in An content in plagioclase and in Mg# in pyroxene which occur at 124 m and 80 m below the PM respectively. In addition, a gradual change occurs in the mineral parameter Mg# in opx minus An in plagioclase, with the plagioclase becoming more primitive relative to the pyroxene. This decrease and the decoupling of geochemical trends has not been noted in the Main Zone of the Bushveld Complex before. The decoupling between plagioclase and pyroxene compositional reversals is not easily explained by modal effects, an influx of phenocrysts in the new magma, or by infiltration metasomatism. Instead we propose that new magma pulses first entered the chamber some 150 m below the PM and that this magma had a composition that crystallized more primitive plagioclase but similar pyroxene to the magma residing in the chamber. The chamber was intruded by progressively more magma that had a more primitive composition particularly in terms of pyroxene composition. This model can explain the decoupling between plagioclase and pyroxene compositional trends. Continued mixing between resident magma and the new influxes occurred over an interval of ˜150–200 m. Above the PM fractional crystallization processes dominated and continued into the Upper Zone.
Delayed accumulation of plagioclase in the Bushveld Complex
Authors: Cawthorn R. G.
Published: August 2004

The Upper Critical Zone of the Bushveld Complex consists of several cyclic units, each ranging from ultramafic to leucocratic. One view is that they were initiated by addition of, and crystallization from, relatively magnesian magma. Experimental studies on plausible parental magma compositions to this sequence show that plagioclase joins orthopyroxene in the crystallization sequence once the Mg# of the orthopyroxene has decreased below 83. Some norites from the Upper Critical Zone contain orthopyroxene with this Mg#, supporting the validity of the experimental studies. There are no orthopyroxene compositions with higher Mg# than 83 in the entire Upper Critical Zone in either the eastern or western limbs of the Bushveld Complex. This observation suggests that all these rocks formed from plagioclase-saturated magmas. If this interpretation is correct, pyroxenites in this succession are not the result of crystallization from a magnesian magma. Instead, they result from the mechanical separation of plagioclase and orthopyroxene, probably due to crystal sorting during settling, from a magma lying at the cotectic for these two minerals. Rocks exist in the Upper Critical Zone that contain non-cotectic proportions of cumulus plagioclase and orthopyroxene, again supporting models of crystal sorting during settling. In such a model, anorthosites result from the delayed accumulation of plagioclase relative to pyroxene, and not to formation from a magma saturated only in plagioclase.

When traced from northwest to southeast in the western limb, there is a change in the relative proportions of plagioclase to orthopyroxene in the Upper Group 2 chromitite cyclic unit. In the northwest the unit is dominated by ultramafic rocks. In the southeast the plagioclase to pyroxene ratio exceeds that of the cotectic proportion, relations that may result from the lateral transport of suspended plagioclase grains to the southeast.
‘Decompressional’ reaction textures formed by isobaric heating: an example from the thermal aureole of the Taylor Brook Gabbro Complex, western Newfoundland
Authors: Ings S. J. , Owen J. V.
Published: August 2004

Reaction textures including corona structures in granulites from the Proterozoic Long Range Inlier of western Newfoundland are spatially associated with a Silurian (0.34 Ga) mafic intrusion, the Taylor Brook Gabbro Complex. They comprise, in metabasites and tonalitic gneiss, coronal orthopyroxene and plagioclase on garnet and, in metapelites, cordierite and spinel formed at the expense of sillimanite, garnet and quartz. Although generally interpreted to indicate near-isothermal decompression (ITD) following regional metamorphism, which in the inlier occurred at ˜1.10–1.03 Ga, these features appear to be absent elsewhere. Therefore they are interpreted to be products of contact metamorphism (near-isobaric heating – IBH) within the thermal aureole of the gabbro. Thus, there is a ˜0.7 Ga difference (i.e. mid-Proterozoic vs. mid-Silurian) between the age of the regional metamorphic mineral assemblages and the contact aureole assemblages. The observation that classic ITD features occur in this aureole environment underscores the fact that P-sensitive reactions can progress during IBH as well as by pressure release.