bluuebunny/crossref_metadata_2025 huggingface dataset:
Compositional trends of a Cretaceous foreland basin shale (Belle Fourche Formation, Western Canada Sedimentary Basin): diagenetic and depositional controls
Authors: de Caritat P. , Bloch J. D. , Hutcheon I. E. , Longstaffe F. J.
Published: December 2006

Compositional trends of the Cenomanian Belle Fourche Formation, a marine shale unit in the Western Canada Sedimentary Basin, have been investigated on a regional scale using bulk-rock geochemistry and mineralogy, clay mineral compositions and oxygen isotope geochemistry of shale and bentonite core samples. Smectitic illite-smectite found in the matrix of immature, hemipelagic samples is compositionally and isotopically consistent with an origin from low-temperature alteration of volcanic ash in the central Western Interior Seaway, where the basin received minimal detrital input. The origin of the more illitic matrix in the deeply buried, western, pro-deltaic shales can be interpreted in terms of either diagenetic ‘illitization’ of a smectitic precursor, or depositional mixing of abundant, detrital, illitic material with minor amounts of ashfall-derived smectite. It is concluded that: (1) documented silicate mineral reactions during deep diagenesis of the Belle Fourche Formation took place in a relatively closed system, with no significant import or export of mobile species at the formation scale; and (2) diagenesis and depositional mixing can have similar effects in terms of bulk-rock and oxygen isotope geochemistry, and mineral compositions and assemblages.
Radiogenic and stable isotope evidence for age and origin of authigenic illites in the Rotliegend, southern North Sea
Authors: Ziegler K. , Sellwood B. W. , Fallick A. E.
Published: December 2006

Aeolian sandstones of the Lower Permian Leman Formation (Rotliegend Group) provide the best gas reservoir in the southern North Sea, but permeability is greatly reduced by the presence of authigenic fibrous illites. New radiogenic (K/Ar) and stable (oxygen and hydrogen) isotope data are presented for fibrous illite cements (<0.1 µm), so that the absolute timing and controlling diagenetic factors for their formation can be more fully evaluated. Thus, the expected quality of gas reservoirs in the southern North Sea might be better predicted. Samples have been analysed from five wells in areas with contrasting structural evolution: the Sole Pit Basin, and the Indefatigable Shelf. The K/Ar ages of between 160 and 190 Ma have been obtained from the Indefatigable Shelf illites, and between 120 and 160 Ma for those from the Sole Pit Basin, reflecting different times of basin inversion. These K/Ar ages are interpreted by reference to burial/thermal models for each well. The temperature of illite precipitation falls between 88 and 140°C. Calculated pore-fluid compositions derived from oxygen and hydrogen isotopic analyses give values of ∼ + 1 to +9‰ (SMOW) δ18O and +1 to −50‰ (SMOW) δD. The illite δD values have probably been affected by isotopic exchange and fractionation with the surrounding gaseous hydrocarbon. The δ18O values reflect the degree to which evaporative concentration had affected Zechstein marine waters which subsequently invaded the Leman Sandstone. Comparisons between δ18O and δD values in clays and in formation water for the Leman Field suggest that oxygen isotope exchange might have taken place, and that the initial K+ and radiogenic 40Ar contents within illites may have been modified.
Variation in kaolinite morphology with growth temperature in isotopically mixed pore-fluids, Brent Group, UK North Sea
Authors: Osborne M. , Haszeldine R. S. , Fallick A. E.
Published: December 2006

Diagenetic kaolinite in reservoir sandstones of the Brent Group precipitated following the dissolution of detrial feldspar. Two distinct morphologies of kaolinite occur: (1) early diagenetic vermiform kaolinite which is often associated with expanded detrital micas; (2) later diagenetic ‘blocky’ kaolinite. Combined hydrogen and oxygen isotopic studies suggest that vermiform kaolinite precipitated at 25–50°C, and blocky kaolinite at 50–80°C, from pore-waters of a similar isotopic composition (δ18O = −6.5 to −3.5‰). These pore-waters are interpreted to be either a mixture of meteoric and compactional waters, or alternatively a meteoric water that had evolved isotopically due to water-rock interaction. Kaolinite precipitation occurred predominantly during the late Cretaceous to early Eocene. Influx of meteoric water into the Brent Group, probably occurred during the Palaeocene. Fluid flow across the entire basin was driven by a hydrostatic head on the East Shetland Platform palaeo-landmass to the west. The development of the two kaolinite morphologies is possibly related to the degree of supersaturation at the time of precipitation. At low degrees of supersaturation, vermiform kaolinite precipitated slowly upon detrital mica surfaces. Blocky kaolinite precipitated more rapidly into open pore-space at higher degrees of supersaturation. Precipitation of blocky kaolinite was perhaps triggered by the decay of oxalate.
Petrographic and isotopic evidence for diagenetic processes in Middle Jurassic sandstones and mudrocks from the Brae Area, North Sea
Authors: Greenwood P. J. , Shaw H. F. , Fallick A. E.
Published: December 2006

The diagenetic history of an interbedded sequence of Middle Jurassic Sleipner (or Pentland), Hugin and Heather Formation sandstones and mudrocks from the Brae Area has been investigated using petrographic, stable isotope, fluid inclusion and K-Ar dating techniques. Generally, similar diagenetic processes affected both the mudrocks and sandstones resulting in the formation of carbonate, quartz and clay cements and evidence of dissolution and secondary porosity except for the absence of kaolinite in the Hugin Formation. The mudrocks were possible sources of some components involved in sandstone diagenesis but were not passive exporters of such reactants as similar reactions also occurred in the mudrocks. The stable isotope data indicate that most of the diagenetic processes occurred in the presence of marine or evolved marine pore-waters.
The case of the missing clay, aluminium loss and secondary porosity, South Brae Oilfield, North Sea
Authors: McLaughlin Ó. M. , Haszeldine R. S. , Fallick A. E. , Rogers G.
Published: December 2006

Upper Jurassic sandstones of the South Brae Field were deposited as a submarine fan complex. The earliest formed concretionary ferroan calcite cement passively encloses detrital feldspars which originally formed more than 10% of the rock. Later non-ferroan calcite at the concretion margins was precipitated from a more aggressive fluid. This fluid dissolved up to half of the feldspars and micas originally present, but little or no clay was precipitated. Aluminium must have been lost from the system.

A late dissolution event has enhanced porosity by up to 8%. Feldspar was again reduced in volume by about half, leaving only ∼2% in the rock today. Very minor amounts of fibrous illite and kaolinite (<1%) form the last diagenetic cement. Aluminium must have again been lost from the system.

As the Kimmeridge Clay Formation (KCF) encloses and interdigitates with the South Brae sandstones, a local source of organic acids is quite possible. These acid solutions may have increased the mobility of Al. The Al from the feldspars must have therefore been transported vertically into the KCF, or more probably transported laterally by compactional flows out of the basin (up to 10 km) during release of overpressured basinal water.
Pore-lining chlorites in siliciclastic reservoir sandstones: electron microprobe, SEM and XRD data, and implications for their origin
Authors: Hillier S.
Published: December 2006

Pore-lining chlorites are often responsible for the preservation of porosity in deeply buried sandstones because they inhibit the formation of quartz overgrowths, but little is understood about when and how they form. Chemical analyses and XRD data indicate that there are at least two common types: Fe-rich, and Mg-rich. The Fe-rich examples occur as individual euhedral crystals, are invariably interstratified with 7 Å layers (probably berthierine) and form as the Ib β = 90° polytype at low temperatures. With increasing temperature, their chemistry changes, 7 Å layers are lost, crystal size increases, and eventually they transform to the high temperature IIb β = 97° polytype. The Mg-rich examples occur as boxwork arrangements of crystals, are not interstratified with 7 Å layers and are exclusively the IIb β = 97° polytype. The Fe-rich examples occur most frequently in sandstones that were deposited at the transition between marine and non-marine environments and the presence of Fe-rich oolites in many samples suggests a link to the ironstone facies. They probably formed originally at surface or near-surface conditions as a 7 Å mineral, such as berthierine or even odinite, in a fresh water/marine water mixing zone in tropical regions. The Mg-rich varieties tend to be found in aeolian or sabkha sandstones in close association with evaporites. They are probably replacements of Mg-rich smectites via the intermediate mineral corrensite. Precursor Mg-rich smectites formed originally from evaporite brines at near-surface conditions; chlorite itself was not formed until temperatures were high enough to crystallize the IIb β = 97° polytype.
Mineralogical and geochemical characterization of palygorskite from Gabasa (NE Spain). Evidence of a detrital precursor
Authors: Lopez-Galindo A. , Ben Aboud A. , Fenoll Hach-Ali P. , Casas Ruiz J.
Published: December 2006

A mineralogical and geochemical study of the Gabasa outcrop (Huesca, NE Spain) was undertaken. It consists of Early Oligocene marly and clayey fluvial and lacustrine (playa-lake) sediments. The phases detected were quartz, amorphous silica, calcite, dolomite, palygorskite, illite, interstratified illite-smectite, Al-smectite and Mg-smectite. The palygorskite expands with ethyleneglycol. Statistical analysis of the geochemical data shows that the rare earth elements and transition trace elements are basically associated with the detrital phyllosilicates, although a considerable amount of the latter is contained in the palygorskite (ΣREE = 60–70 ppm, Cr+Co+Ni+V+Zn+Cu = 120–150 ppm), in contrast to the normally low values for neoformed minerals. This fact, together with the significant presence of Al and Fe in the palygorskite, suggest genesis involving alteration by dissolution of the 2:1 structure of the illite and/or Al-smectite, followed by re-ordering in a fibrous structure.
Processus d'adsorption du dinoseb sur l'hectorite-et la vermiculite-decylammonium
Authors: Vimond-Laboudigue A. , Baron M-H. , Merlin J-C. , Prost R.
Published: December 2006

Resume

Les substrats argile-alkylammonium sont utilisés dans ce travail comme des modèles de sol, dans le but d'étudier les interactions entre un pesticide neutre peu soluble dans l'eau, le dinoseb, et des substrats dont les surfaces ont été rendues hydrophobes. Les spectrométries infrarouge (IR), Raman et de réflexion diffuse dans l'UV-visible sont utilisées de façon complémentaire aux isothermes d'adsorption pour préciser la localisation et l'état des molécules pesticide retenues sur les substrats. Dans le cas de la vermiculite-décylammonium, la fixation du dinoseb est observée à la fois sur les surfaces externes et dans les espaces interfoliaires, les molécules de pesticide sont directement en interaction avec les atomes d'oxygène de la surface des feuillets et avec les cations ammonium, par liaisons hydrogène. Le taux de molécules de dinoseb retenues sur l'hectorite-décylammonium est beaucoup plus faible. Les molécules fixées ont alors une structure voisine de celle des molécules libres. Ces analyses montrent que le caractère hydrophobe de la surface des complexes organominéraux est une condition nécessaire, mais non suffisante, pour la fixation de molécules peu solubles dans l'eau. Notre étude souligne l'importance des interactions spécifiques par liaison hydrogène entre le pesticide et le feuillet de vermiculite dans le processus de rétention.
Presence de nacrite sur d'anciens gisements de Pb-Zn du Nord Tunisien
Authors: Ben Haj Amara A. , Ben Brahim J. , Ben Ayed N. , Ben Rhaiem H.
Published: December 2006

La nacrite constitue le plus rare polytype des kaolinites. Traditionnellement, on attribue á ce minéral une genèse hydrothermale (Ross & Kerr, 1931; Hanson et al., 1981 ), cependant Btihmann (1988) décrit sa formation en condition normale de température et de pression dans des milieux de solution et de force ionique élevées. Dans ce travail, la nacrite est mise en évidence dans deux anciens gisements de Pb-Zn situés dans les massifs de Jbel Slata et Garn Halfaya au nord de la Tunisie (Fig.l).
Genesis and transformation of dickite in Permo-Triassic sediments (Betic Cordilleras, Spain)
Authors: Ruiz Cruz M. D. , Andreo B.
Published: December 2006

In the Maláiguide Complex (Betic Cordilleras, Spain), dickite is widely developed in clastic Permo-Triassic sequences. The lateral extent stretches at least 300 km along the Betic range, whilst vertical extent is variable and appears limited to the lowest 20–150 m of these sequences. Textural, chemical and crystallochemical characteristics of the dickite, illite/mica and chlorite in dickite-bearing rocks and in the overlying (Permo-Triassic) and underlying (Carboniferous) rocks have been investigated to determine the approximate conditions in which dickite has developed. Using the chlorite geothermometer (based on A1IV contents), temperatures of 146±28°C and 169±12°C have been deduced for two Permo-Triassic members, and 305±12°C for Carboniferous. The Si content in illites has been used as a geobarometer, and pressures of 4.8±2 kbar have been estimated in Carboniferous rocks and tentative pressures of 2.7±3 and 2.1±2 kbar in Permo-Triassic members. Chemical evolution of phyllosilicates is accompanied by increasing illite crystallinity and % 2M1 polytype.
Occurrence and genesis of palygorskite and associated clay minerals in a Pleistocene calcrete complex, Sde Boqer, Negev Desert, Israel
Authors: Verrecchia E. P. , Le Coustumer M-N.
Published: December 2006

Palygorskite and associated clay minerals have been studied in a Pleistocene calcrete complex from the Negev desert (Sde Boqer, Israel). This complex is divided into five main parts: the chalky and marly bedrock overlain by its weathered product, a brecciated calcrete hardpan; the laminar crust; loess pockets trapped in the calcrete; and the overlying soft surficial soil. The distribution of clay minerals is directly dependent on the position of the sample in the calcrete complex. Smectite is inherited from the bedrock in the calcrete with an aeolian enrichment in loess pockets and upper soft soil. The source of kaolinite is mainly detrital, related to desert dust. Illite is partly inherited and partly neoformed in loess pockets and desert surficial soil. The origin of palygorskite is clearly related to precipitation processes from soil solutions, Si and Al ions being provided by the slope and detrital grains trapped in the calcrete, with Mg being provided by the parent rock, the slope and aeolian detrital dolomite. This neoformation occurs mainly around detrital grains such as quartz in the hardpan and along textural transitions in loess pockets and is associated with gypsum in the lower part of the toposequence where the evaporation fluxes are the most important. The existence as coatings around grains and the delicate structure of the fibres are incompatible with a detrital origin. Moreover, no evidence was found to support any transformation of smectite into palygorskite in the solid state. Palygorskite is the last step of the cycle of mobile silica and seems to be a product of late diagenesis in Sde Boqer calcrete.
Mineral quantification in sepiolite-palygorskite deposits using X-ray diffraction and chemical data
Authors: Lopez Galindo A. , Torres Ruiz J. , Gonzalez Lopez J. M.
Published: December 2006

A quantification technique useful in analysis of clay-rich deposits containing sepiolite and/or palygorskite has been developed by combining diffractometric and chemical data and represents a considerable improvement on classic quantification based on X-ray diffraction. The required data are: intensity ratios between certain diffraction peaks of calcite-dolomite and sepiolite-palygorskite-smectites, and also the CaO, MgO, K2O, Al2O3 and SiO2 contents. The validity of this method was tested by analysis of artificial mixtures of pure phases of the minerals found in such deposits.
Ajustement des courbes de diffusion aux petits angles des rayons X, produites par des argiles fortement hydratees dans le cas d'une focalisation lineaire de hauteur finie
Authors: Ben Rhaiem H. , Pons C. H.
Published: December 2006

La diffusion aux petits angles des rayons X (DPAX) a été utilisée pour caractériser l'évolution de la structure et de la texture d'argiles fortement hydratées en fonction de la température (Pons, 1980; Ponset al., 1981), de la concentration en sel (Saezet al., 1983) ou en fonction de la pression (Tessier, 1984; Ben Rhaiemet al., 1986, 1987). La méthode permet d'accéder aux paramètres structuraux du système par comparaison des courbes expérimentales à des courbes théoriques calculées à partir de modèles.
Ferriferous and vanadiferous kaolinites from the hydrothermal alteration halo of the Cigar Lake uranium deposit (Canada)
Authors: Mosser C. , Boudeulle M. , Weber F. , Pacquet A.
Published: December 2006

The uranium deposit (1350 Ma) of Cigar Lake (Canada) is surrounded by a late hydrothermal alteration halo (330 Ma) containing Fe-illites and kaolinites. Crystallochemical characterization of the kaolinites has been carried on the microscale using XRD, electron microscopy (SEM and TEM) coupled with EDX spectrometry and EPR. The large, well-crystallized particles show large amounts of Fe (0.9–1.8%) and V (0.3–0.5%). According to EPR measurements performed on both random powders and oriented samples, V occurs as the vanadyl ion VO2+, in substitution within the octahedral sheet of the kaolinite structure in the same way as Fe3+. Kaolinite growth proceeded through the hydrothermal alteration of anterior phyllosilicates devoid of V, induced by fluids which leached V-rich titano-magnetites in the surrounding sandstones.
Mica weathering in acidic soils by analytical electron microscopy
Authors: Aoudjit H. , Elsass F. , Righi D. , Robert M.
Published: December 2006

The mineralogy, crystallochemistry and microfabric of clay minerals from acidic soils were studied using transmission electron microscopy (TEM) and analytical electron microscopy (AEM). Soil profiles, developed on saprolites, sampled in the main crystalline massifs of France represent different pedological environments. The study focused on the microsystem of mica weathering, which appeared to be the main source of secondary clay minerals, and involves microdivision, transformation and dissolution. Microdivision begins with the splitting of large particles along layer planes and their shearing normal to the layers. This induces the breakdown of particles of one hundred layers into particles having only a few layers. The transformation of micas follows two steps: they first transform into 1–1.4 nm mixed-layer minerals and then into hydroxy-Al interlayered vermiculite. The formation of hydroxy-Al interlayered vermiculite derived from micas is dominant in acidic soils; particles are generally small, consisting of only three to seven layers, and always have a dioctahedral composition, whatever the type of the original mica (trioctahedral or dioctahedral). Dissolution affects the surface layers or large domains of the core of the particles and leads to the formation of multi-elementary gels rich in Fe and Al.
Effect of non-swelling layers on the dissolution of reduced-charge montmorillonite in hydrochloric acid
Authors: Komadel P. , Bujdák J. , Madejová J. , Šucha V. , Elsass F.
Published: December 2006

A series of reduced-charge montmorillonites (RCM), prepared from the same parent Li-montmorillonite (Jelšový Potok, Slovakia) by heating at various temperatures (105–210°C) for 24 h, was treated with 6 m HCl at 95°C for periods up to 30 h. Reaction solutions obtained were analysed for Al, Fe, Mg and Li and the solid reaction products were investigated by FTIR spectroscopy. Both analyses provided evidence that the extent of dissolution decreased with increased amounts of Li fixed within the montmorillonite structure, i.e. with increased heating temperature. Differences in the acid dissolution process were reflected in the structural changes which occurred within the RCM samples, due presumably to different positions of fixed Li. The ethylene glycol monoethyl ether (EGME) surface areas, and XRD and HRTEM analyses of the RCM series revealed an increased amount of non-swelling layers in the samples prepared at higher temperatures, which caused a substantially slower decomposition of M7 and M8 in HCl. The calculated XRD patterns of M6 and M7 confirmed the presence of 20% and 45% pyrophyllite-like layers, respectively, in these samples. Mixed-layer pyrophyllite-like-smectite and pyrophyllite-like crystals, containing only non-swelling layers, were found in sample M8. The results confirmed that the amount of swelling layers in RCM significantly affects their dissolution rate in HCl.
Parallel reaction kinetics of smectite to illite conversion
Authors: Wei H. , Roaldset E. , Bjorøy M.
Published: December 2006

A parallel reaction model is developed for describing the conversion of smectite to illite. Each reaction represents a group of similar smectite layers that require the same activation energy and have the same illitization rate. The model considers that the rate-determining reactant is smectite itself which follows first-order Arrhenius kinetics. By modelling the data from hydrothermal illitization experiments and from a Gulf Coast well, the activation energies are found to be distributed in the range of 11–24 kcal/mol with a maximum reaction at 18 kcal/mol, which involves 65% of reactive smectite. A frequency factor in the order of 10−3–10−4/s, obtained from the data fitting, appears to be adequate for modelling natural diagenesis in sedimentary basins. The distribution pattern of activation energies is considered to be controlled by the degree of heterogeneity of the initial smectite and the degree of electrostatic interactions between smectite layers and the newly formed illite layers during reaction.
Mineralogical and chemical heterogeneity of three standard clay mineral samples
Authors: Köster H. M.
Published: December 2006

Mineralogical and chemical heterogeneity within three standard clay mineral samples have been identified by X-ray diffraction and chemical analysis of various size-fractions. This heterogeneity is partly attributed to accessory minerals, but mostly to structural and compositional variations in the 2:1 layer minerals of different particle size in the same specimen.
Properties and applications of palygorskite-sepiolite clays
Authors: Galan E.
Published: December 2006

The palygorskite-sepiolite group of clay minerals has a wide range of industrial applications derived mainly from its sorptive, rheological and catalytic properties which are based on the fabric, surface area, porosity, crystal morphology, structure and composition of these minerals. For assessing potential industrial uses, the mineralogical and chemical composition of the clay and its basic physical and physico-chemical parameters must be determined. Then some particular properties of commercial interest can be modified and improved by appropriate thermal, mechanical and acid treatments, surface active agents, organo-mineral derivatives formation, etc. In this paper, a revision of the principal characteristics of commercial palygorskite-sepiolite clays is presented, and potential uses are suggested according to these data. New products and applications are being investigated and those concerning environmental protection in particular, are noted. Finally, possible health effects of these elongate clay minerals are discussed.
Preparation and characterization of Ti-pillared acid-activated clay catalysts
Authors: Bovey J. , Kooli F. , Jones W.
Published: December 2006

The preparation and characterization of Ti-pillared acid-activated clays (designated Ti PAACs) and conventional Ti-pillared clays (designated Ti PILCs) are described. Preliminary catalytic results show that these materials possess remarkably enhanced abilities to catalyse the dehydration of pentanol compared with their Al counterparts (in excess of 200% in the case of the PILCs and up to 82% for the PAACs). These activities approach those previously reported for non-pillared acid-activated clays.
Electric birefringence for monitoring size changes in clay suspensions
Authors: Hinds I. C. , Ridler P. J. , Jennings B. R.
Published: December 2006

The growth and decay rates of rapid, induced electro-optical phenomena in dilute colloidal suspensions are characteristic of the geometry of the solute particles. The speed of measurement renders such methods especially relevant for fast, in situ analyses of the size and size distribution of colloids in practical, industrial situations where these properties may be undergoing continuous change. The principles of the measurement of electrically induced birefringence using pulsed fields is outlined and used to study vermiculite suspensions as they undergo size reduction in an ultrasonic field. The high sensitivity of the method to both the particle size range and the form of the distribution function is indicated. The use of the method for on-line monitoring of dilute mineral suspensions for the indication and control of aggregated, dissolving or growing media is discussed.
Interpretation of orientation polarization in homoionic dry montmorillonite
Authors: Belarbi H. , Haouzi A. , Giuntini J. C. , Zanchetta J. V. , Niezette J. , Vanderschueren J.
Published: December 2006

From measurements of dielectric losses as a function of frequency and temperature, as well as thermally stimulated depolarization currents, performed on a dry Na-montmorillonite, a qualitative description of the conduction mechanism has been proposed for this type of material. A representative approach related to the polarization phenomenon determined on this material led to the evaluation of the elementary energy Wj, connected with the reorientation of the dipoles during the hopping process. The results show the coherence between the polarization conductivity and the thermally stimulated currents methods.
A study of organo-hectorite clay crystallization
Authors: Carrado K. A. , Thiyagarajan P. , Song K.
Published: December 2006

A method has been developed to synthesize organo-hectorite clays directly from a Mg-silicate gel containing organic or organometallic molecules that are expected to be incorporated within the interlayer space. Complete crystallization occurs upon aqueous reflux for 48 h. The progress of clay layer formation was monitored by X-ray powder diffraction (XRD), differential thermal gravimetry (DTG), and infrared (IR) spectroscopy. Evidence of clay XRD peaks occurs after just 4 h of hydrothermal treatment, and Mg(OH)2 is no longer observable after 14 h. Observable changes in DTG and IR occur at about this time as well. Warren line-shape analysis of the 110 reflection indicates that when growth is complete the clay lamellae are on average ∼50% and 25% of the size of natural hectorites and montmorillonites, respectively. The N2 BET surface areas for all materials are also compared. Small angle neutron scattering shows that addition of tetraethyl ammonium (TEA) ions does not alter the structural integrity over that of the purely inorganic form of Li-hectorite, but that use of a cationic polymer does significantly alter the microstructure. The effect of temperature is critical, for at room temperature only the layered Mg hydroxide mineral brucite crystallizes unless very long time scales are used. The crystallizations carried out at room temperature show that clay will form after about 3 months, but that the presence of organics (at least TEA) acts to hinder this process greatly. The role of the organic molecules on silicate clay layer formation is compared with the role of organics in zeolite synthesis.
The structure of the kaolinite minerals — a FT-Raman study
Authors: Frost R. L.
Published: December 2006

The Fourier transform Raman spectra of the kaolinite minerals have been measured in the 50–3800 cm−1 region using near infrared spectroscopy. Kaolinites are characterized by remarkably intense bands in the 120–145 cm−1 region. These bands, attributed to the O-Si-O and O-Al-O symmetric bending modes, are both polymorph and orientation dependent. The 200–1200 cm−1 spectral range is a finger-print region for clay minerals and each kaolinite clay has its own characteristic spectrum. The structure of clays is fundamentally determined by the position of hydroxyl groups. Fourier-transform Raman spectroscopy readily enables the hydroxyl stretching region to be examined allowing identification of the component bands. The advantages of FT-Raman spectroscopy are shown to enhance the study of the kaolinite structure.
Surface microtopography of rectorite (allevardite) from Allevard, France
Authors: Kitagawa R.
Published: December 2006

By means of transmission electron microscopy (TEM) and the gold decoration technique, the surface microtopography of rectorite (allevardite) crystals collected from Allevard, France was investigated. On the crystal surfaces, gold decoration successfully revealed growth steps of ∼20 Å in height. Only closed polygonal steps 20 Å high occur on the 001 surface of a thick platy crystal, although spiral growth patterns were not observed. Thick platy particles were easily split into thinner plates 20 Å thick in distilled water by means of ultrasonic vibration. No step patterns were observed on the surfaces of these thin plates which correspond to the cleavage plane. The growth of this rectorite, therefore, seems to be controlled by a layer nucleation mechanism.
Interaction of montmorillonite with binuclear hydroxo-bridged iron complexes and their peroxo adducts
Authors: Weiss A. , Dick S.
Published: December 2006

The interaction of the cationic hydroxo-bridged binuclear iron(III) complexes of the sevendentate ligands HPTP and HPTB with montmorillonite was studied. Both complexes can be introduced reversibly into the interlayer region of the smectite. The catalase active HPTP-complex preserves its activity in the smectite interlayers. The unstable peroxide adducts of both complexes can be introduced into montmorillonite interlayers from water/H2O2 at 273 K and can be stored there for months at 243 K. Adduct/montmorillonite compounds can also be prepared by direct reaction of H2O2 with the complexes already bound to montmorillonite. From IR spectra of the adduct/montmorillonite compounds it can be concluded that the adduct of the HPTP complex contains nitrate whereas the adduct of the HPTB complex does not. These results can help to decide whether structures of the adducts proposed in the literature are possible or not and may therefore open a new field of application of clay minerals in studies on unstable intermediates.
K-Ar dating of illite fundamental particles separated from illite-smectite
Authors: Clauer N. , Środoń J. , Francu J. , Šucha V.
Published: December 2006

Fundamental particles of illite-smectite from bentonites were separated into classes by high-speed centrifugation after infinite osmotic swelling of mixed-layer crystals, achieved by Na-exchange and dispersion in distilled water. In samples free of detrital contamination, the thinnest fundamental particles yield older K-Ar ages than the thicker fundamental particles. This implies that they do not preferentially lose radiogenic 40Ar due to size, and that the illitization process is a crystal growth mechanism (not nucleation plus growth). As a result, any K-Ar age of fundamental illite particles from bentonites is an integral over longer or shorter periods of time, depending on the thermal history of the rocks. In thick bentonite beds, the measured age difference between the beginning of the illitization process at the contact with the host rocks and the end in the centre of the bed records extremely slow K diffusion in these well compacted rocks. These data explain why measured K-Ar ages of illite-smectite from bentonites are younger than the corresponding age of shale illitization, inferred from the burial history of the basin. The finest technically separable size-fractions of associated shales (<0.02 μm) yield K-Ar dates* greater than the stratigraphic age. This observation points to incomplete recrystallization of detrital illite during burial diagenesis.
A vein occurrence of co-existing talc, saponite, and corrensite, Builth Wells, Wales
Authors: Garvie L. A. J. , Metcalfe R.
Published: December 2006

Unique phyllosilicate assemblages occur in quartz-calcite veins cutting altered andesite at Builth Wells, UK. These veins show: (1) a central talc-dominated assemblage, grading into a saponite/corrensite/chlorite-dominated assemblage near their walls; (2) talc replacing calcite and quartz; and (3) closely associated blocky and fibrous saponite. Fibrous saponite occurs in narrow (<1 cm) fractures that extend for up to 1 m from major (⩽ 50 cm wide) talc-bearing veins. A thin halo (<5 mm) of wall-rock alteration, containing blocky saponite and minor corrensite, borders the fibrous saponite. These minerals may have originated when cooling, low-pH, quartz-saturated, Mg-rich fluid invaded pre-existing quartz/calcite veins. Quartz is replaced by talc where calcite dissolution caused the pH to increase. Wallrock alteration liberated Fe and Al to the fluid causing blocky saponite and corrensite to form. Fibrous saponite formed where lithostatic pressures were directed across hydraulic fractures.
Clay transformations following a leaching experiment on an acid brown soil
Authors: Turpault M.-P. , Ponette Q. , Belkacem S. , Nys C.
Published: December 2006

The chemical and mineralogical properties of the A1 and B horizons of an acid brown soil (typic Dystrochrept) were compared before and after a 20 month column leaching experiment. At the end of the leaching period, the organic carbon content of the A1 horizon had decreased by ∼20% compared with the original horizon. In the leached A1 horizon, the vermiculite layers of both the vermiculite and interstratified minerals were transformed into high-charge expanding layers, with the charge mainly located in the octahedral sheet. The inhibition of expansion properties by pretreatment with dithionite-citrate-bicarbonate (DCB) was explained by an increase in total layer charge induced by Fe reduction. In the B horizon, leaching resulted in a loss of sesquioxide materials, especially in the interlayers of vermiculites. In both horizons, the amounts of Al extracted by Na citrate and the amounts of Fe extracted by DCB decreased. Analysis of solution composition showed that Al mobilization was closely associated with NO3− leaching.
Interaction of aminotriazole with montmorillonite and Mg-vermiculite at pH 4
Authors: Morillo E. , Perez-Rodriguez J. L. , Rodriguez-Rubio P. , Maqueda C.
Published: December 2006

The interaction of aminotriazole (AMT) at pH 4 on Wyoming montmorillonite (mainly with Na ions) and Mg-vermiculite has been studied by X-ray diffraction and infrared spectroscopy. The AMT is adsorbed on montmorillonite in the cationic form by cation exchange. The amount of pesticide adsorbed was 71 mEq/100 g, which comprises ∼91% of the CEC of this sample (78.2 mEq/100 g). Saturation was reached in 24 h, giving rise to a complex with basal spacing 12.5 Å. Vermiculite adsorbs 167 mEq/100 g, almost 20% greater than the CEC (141 mEq/100 g), and the basal spacing was stabilized at 13.68 Å after five weeks of treatment with AMT. A part of the AMT is adsorbed in cationic form, displacing a great part of the exchangeable Mg2+ cations. The rest is adsorbed in molecular form by coordination to the Mg2+ cations which remain in the interlamellar space, removing a great amount of water, and remaining in the interlamellar space of vermiculite after washing with water, probably because of a steric hindrance from the AMT cations adsorbed.
Study of the humic-like compounds formed from L-tyrosine on homoionic clays
Authors: Bosetto M. , Arfaioli P. , Pantani O. L. , Ristori G. G.
Published: December 2006

The ability to produce humic-like polymeric compounds, with L-tyrosine as the starting material, was evaluated using different mineral systems, e.g. on Ca-, A1- and Cu(II)-saturated montmorillonite, nontronite and kaolinite, and on quartz. Clay minerals proved to be effective in the formation of these compounds, but not quartz, except in the presence of Cu(II). The newly formed compounds were fractionated by alkaline extraction. With clay systems, the amounts of substances produced appear to be related more to the interlayer cation than to the clay type. Copper cations appear to be more effective when not associated with the clay structure.
Clay- and zeolite-bearing Triassic sediments at Kaka Point, New Zealand: evidence of microbially influenced mineral formation from earliest diagenesis into the lowest grade of metamorphism
Authors: Jeans C. V. , Fallick A. E. , Fisher M. J. , Merriman R. J. , Corfield R. M. , Manighetti B.
Published: December 2006

The distribution, mineralogy, petrology and bulk and stable isotope chemistry of altered volcanic ash beds in the marine sediments of Mid-Triassic age (Etalian) at Kaka Point, New Zealand, are described and related to lithofacies and the geological processes controlling their development.

Three varieties of altered ash occur in the Kaka Point sediments — porcellanite, claystone (bentonite) and albite-rich. Porcellanites are quartz-rich and may contain analcime and heulandite: they are restricted mainly to the on-shore facies. Claystones are rich in smectitic clay minerals and occur in both the on-shore and off-shore facies. They often contain diagenetic nodules of analcime, quartz, apatite and carbonates. The authigenic carbonates of the on-shore facies are variable in composition (sideritic, rhodochrositic, calcitic), whereas in the off-shore facies they consist only of calcite. The albite-rich lithology is very rare and is known only from the off-shore facies.

The development of the porcellanite and albite-rich lithologies was restricted to slowly deposited, relatively coarse-grained ash sediments in which extensive interchange took place between the sediment's pore-waters and ambient seawater, resulting in enhanced microbial activity and high pH throughout the pore-waters of the suboxic zone beneath the water-sediment interface. The high pH increased the rate of volcanic ash hydrolysis and provided the conditions necessary for the precipitation of zeolite, feldspar and quartz. The development of smectitic claystones was associated with more rapid deposition and limited interchange between the pore-waters of the parent ash and ambient seawater. The pore-water alkalinity was generally lower and enhanced microbial activity and high pHs were restricted to patches of sediment at which quartz, analcime, apatite and carbonates formed diagenetic nodules. Modelling of the stable isotopes of the smectitic clays (δ18O, δD) and diagenetic carbonates (δ18O, δ13C) suggest that: (1) ash argillization in the on-shore facies took place in brackish water (∼25% meteoric water) at an average temperature of ∼50°C and in the off-shore facies in marine pore-waters (∼10% meteoric waters) at ∼40°C and (2) diagenetic carbonate precipitation in the near-shore facies took place at ∼30°C and in the off-shore facies at 60–80°C.

The pattern of ash alteration in the marine Triassic sediments at Kaka Point is considered to represent an early stage in the development of the zeolite pattern associated with the classic area of zeolite facies metamorphism in the Taringatura and Hokonui Hills.
Palaeoweathering in slates from the Iberian Hercynian Massif (Spain): investigation by TEM of clay mineral signatures
Authors: Vicente M. A. , Elsass F. , Molina E. , Robert M.
Published: December 2006

Palaeoweathering profiles are widely represented in the Iberian meseta. Transmission electron microscopy (TEM) and analytical electron microscopy (AEM) were used to describe the mechanisms governing the processes involved in the formation of one of these weathering profiles developed over slates of the Iberian Hercynian Massif. Three well-differentiated weathering stages were distinguished, based upon well-defined mineralogical signatures characteristic of primary or secondary minerals. The lower stage is characterized by fresh green slates composed of Fe-chlorite, micas, quartz and feldspars. The soft slates represent an intermediate weathering stage. A confined environment has permitted the development of smectite from the different primary phyllosilicates, both by neoformation of montmorillonite and transformation into beidellite. In the upper part of the profile, the red slates are the most weathered. A tropical or subtropical climate has resulted in the formation of kaolinite and abundant iron oxides over several metres. The present study demonstrates that the three identified weathering stages were formed under the same climatic conditions. Such ‘toposequences’ are developed at the present time in tropical areas (Bocquier, 1971).
Green ferric clay in non-marine sandstones of the Rewan Group, southern Bowen Basin, Eastern Australia
Authors: Baker J. C.
Published: December 2006

Accessory green ferric clay occurs in fluvial litharenites of the Early Triassic Rewan Group. Although resembling glauconitic minerals in thin-section, electron microprobe analyses indicate that the green ferric clay is mainly ferric illite. The ferric illite may have formed in a small hypersaline lake or well drained, flood-plain soil, and its presence in the Rewan Group cannot be used to support a notion that the unit is partly marine influenced. Identification of the ferric illite by electron microprobe analysis shows that some green ferric clays, particularly those that resemble glauconitic minerals optically, may require precise quantitative elemental analysis before they can be used as a basis for environmental interpretation. Green ferric clay in the Rewan Group also includes detrital celadonite that most likely originated in a volcanic arc setting.
Clay minerals in recent sediments of the continental shelf and the Bay of Cádiz (SW Spain)
Authors: Gutierrez-Mas J. M. , Lopez-Galindo A. , Lopez-Aguayo F.
Published: December 2006

The distribution of clay minerals in recent sediments on the continental shelf and in the Bay of Cádiz has been analysed as part of a wider study of sedimentary exchange between the continent and the continental margin. The clay minerals included in the muddy sediments consist mainly of illite, kaolinite, smectite, randomly mixed-layered illite-smectite, chlorite, vermiculite and randomly mixed-layered illite-chlorite. Distribution of the minerals indicates that inheritance from the adjacent continental areas is the most important process involved.

The relations between the clay minerals were established by Q-mode and R-mode factor analysis. The main clay mineral associations are: (1) illite-kaolinite, (2) smectite-random mixed-layered illitesmectite, and (3) kaolinite-random mixed-layered illite-smectite-vermiculite. The main sources of sediment supply to the continental shelf are the Guadalquivir and Guadiana rivers. Sediment from these rivers and from the rivers flowing into the Bay of Cádiz (mainly the Guadalete) is transported to the part of the shelf outside the bay by ebb-tide currents. The path of this outflow to the continental shelf, where the sediment is partially deposited, is influenced by the morphology of the coast and by hydrodynamic processes.
Contribution of multivariate geochemical analysis and mineralogical study in the characterization of sediments: the Miocene-Pliocene boundary in the Sorbas Basin (SE Spain)
Authors: Sanchez Bellon A. , Mosser Ch. , Moral Cardona J. P. , Roquin C. , Sebastian Pardo E.
Published: December 2006

A mineralogical study and multivariant geochemical analysis have been carried out to determine the sedimentation processes and the influence of surrounding rocks on sediments. Analyses were made on the clay fraction of sediments and on bulk samples of rocks from nearby reliefs in the Sorbas Basin (SE Spain). Source rocks were identified by statistical analysis of trace elements and by comparison of the crystallographic parameters of phyllosilicates in sediments and supposed sources. Palaeoenvironmental conditions are recorded by specific elements in the clay minerals. The study of the B and Mg content and of the different types of smectites and palygorskite found in distinct areas has permitted a description of these conditions for this Basin. In this way, different types of deposition environment, showing varying degrees of confinement and influence from marine or continental water, have been distinguished.
Vanadium-doped titania-pillared montmorillonite clay as a catalyst for selective catalytic reduction of NO by ammonia
Authors: Bahranowski K. , Janas J. , Machej T. , Serwicka E. M. , Vartikian L. A.
Published: December 2006

A series of V-doped titania-pillared clay catalysts, characterized by ICP-AES chemical analysis, X-ray diffraction, BET surface area measurement, and ESR spectroscopy, have been tested in the selective catalytic reduction of NO by NH3. An ESR analysis shows that V dopant is anchored to the titania pillars. Vanadyl species with differing degrees of in-plane V-O π-covalent bonding are produced depending on the method of sample preparation. Polymeric V species appear as the V content is increased. Catalytic performance of these systems depends on the method of preparation and on the V content. The best catalyst, converting 90-100% NO in the temperature range 523-623 K, is obtained by exchange of pillared montmorillonite with vanadyl ions, at an extent of exchange below the level where significant amounts of polymeric V species appear. The co-pillared catalyst, containing vanadyl centres characterized by a higher degree of in-plane ncovalent bonding (according to ESR), is less selective than the exchanged samples.
An extended X-ray absorption fine structure (XAFS) study of the calcium site in a model basaltic glass, Ca3Mg4Al2Si7O24
Authors: Hardwick A. , Whittaker E. J. W. , Diakun G. P.
Published: December 2006

Short-range order in the oxygen co-ordination shell of the Ca ion in a glass of composition Ca3Mg4Al2Si7O24is investigated by analysis of the extended X-ray absorption fine structure. The estimate of disorder in the short-range oxygen co-ordination is no greater than that for crystalline samples of diopside and bytownite. An estimate of the oxygen environment of calcium in the particular glass is included.