bluuebunny/crossref_metadata_2025 huggingface dataset:
The influence of layer charge on Zn2+ and Pb2+ sorption by smectites
Authors: Brigatti M. F. , Campana G. , Medici L. , Poppi L.
Published: December 2006

Two smectites with different layer charge localization were used to characterize the chemical and structural aspects of minerals treated with 1.9 × 10−2m and 1 m heavy metal solutions (Zn2+ and Pb2+). Natural and treated smectites were analysed by: (1) X-ray powder diffraction first at 25°C and relative humidity of 60% and then at increasing temperature up to 400°C; (2) thermo-gravimetric and differential thermal analysis; (3) X-ray fluorescence; (4) atomic absorption and UV visible spectrophotometries. The sorption of both metals depends on 2:1 layer features and is enhanced when the total layer charge is mostly due to substitution in the octahedral sheet. The variability between Zn2+- and Pb2+-treated smectites in the interlayer water content depends both upon cation electrostatic features and upon smectite layer charge localization. The greatest water content was observed in [Zn2+]1 m-treated smectite showing charge imbalance in the octahedral sheet. In smectites treated with [Zn2+]1 m solutions, an additional thermal reaction occurs at a temperature of ∼380°C, and the d(001) spacing, which is 10 Å at a temperature of ∼200°C, gradually decreases in the temperature range 200–400°C. In smectites treated with 1 m [Pb2+] solutions this value is reached at a temperature of ∼150°C and remains quite constant up to 400°C.
Adsorption of Cd and Zn on montmorillonite in the presence of a cationic pesticide
Authors: Undabeytia T. , Morillo E. , Maqueda C.
Published: December 2006

The adsorption of Cd and Zn on a standard montmorillonite (SAZ-1) in the presence of the cationic pesticide chlordimeform, both in solution (simultaneous adsorption) and when the pesticide is previously adsorbed on the clay (successive adsorption) has been studied. The adsorption of Zn decreases when the chlordimeform concentration increases in both simultaneous and successive adsorptions, following the sequence: chlordimeform-free solutions > successive > simultaneous. In the adsorption of Cd the sequence is different: successive > chlordimeform-free solutions > simultaneous, indicating that a small amount of pesticide adsorbed favours Cd adsorption. In all cases, the apparent affinity of the metal for adsorption on montmorillonite, on the basis of distribution coefficients, KD, is higher for lower metal surface coverage, and decreases largely with the amount of the metal adsorbed. This indicates the existence of high affinity sites on the clay, probably those of variable charge edge regions. The contribution of edge and interlamellar positions to adsorption of Zn and Cd on SAZ-1 has been studied.
Clay intercalated Cu(II) amino acid complexes: synthesis, spectroscopy and catalysis
Authors: Fu L. , Weckhuysen B. M. , Verberckmoes A. A. , Schoonheydt R. A.
Published: December 2006

Complexes of Cu(lysine)2+2 and Cu(histidine)2+2 have been intercalated between the layers of saponite clays by a simple cation exchange procedure from aqueous solutions of preformed Cu(amino acid)2-complexes. Successful immobilization was obtained with an amino acid: Cu2+ ratio of 5, and a pH of 10 and 7.3 for lysine and histidine, respectively. The synthesized materials were investigated as powders and as thin films by electron spin resonance (ESR), diffuse reflectance spectroscopy (DRS) and X-ray diffraction (XRD). The light blue clays are characterized by an axially symmetric ESR spectrum with A//= 192 G, g//= 2.23 and g⊥ = 2.07, and a d-d absorption band around 600 nm, due to the intercalated planar Cu2+-complexes. Ammonia interacts reversibly with these intercalated complexes, suggesting the presence of a free coordination site. The novel synthesized materials are active in various oxidation reactions with t-butyl hydroperoxide as oxidant.
Formation at 300°C of a high-temperature disilicate from hydrated lutetium in a layered aluminosilicate
Authors: Castro M. A. , Alba M. D. , Alvero R. , Becerro A. I. , Muñoz-Paez A. , Trillo J. M.
Published: December 2006

The interaction between interlamellar Lu(III) cations and the layered silicate structure has been studied by means of MAS-NMR, XRD and EDX. Irreversible fixation of exchangeable Lu(III) cations upon hydrothermal treatment at 300°C of Lu-saturated montmorillonite is reported, through the formation of the crystalline phase Lu2Si2O7. It is shown that the lowest temperature previously described for this reaction, 400°C, does not indicate a thermodynamic boundary. This basic solid-state finding is relevant for some clay applications such as those related to the safety of nuclear waste repositories with engineering barriers.
Experimentally-determined solute yields from kaolinite-illite/muscovite assemblages under diagenetic conditions of pressure and temperature
Authors: Rae E. I. C. , Manning D. A. C.
Published: December 2006

Experimental studies of reactions between water and kaolinite, kaolinite + quartz, kaolinite + quartz + muscovite and natural kaolinitic mudstones (Jurassic Draupne Formation; Norwegian North Sea; Rhaetic Westbury Formation, SW England; Tertiary ball clay, SW England) at 50 MPa and 150°C or 200°C have demonstrated that quartz saturation can be achieved readily at 200°C At 150°C quartz saturation is achieved for natural mudstones, but not for mineral mixtures because of slow reaction kinetics. Geochemical solution modelling demonstrates coincidence between observed fluid compositions and those expected for the solid mineral assemblage. In addition to inorganic solutes, organic acid anions including citrate are reported as products in experiments with natural mudstones (especially the Draupne Formation). Fluids supersaturated with respect to quartz are unlikely to be developed from mudstones which lack smectites or amorphous silica.
Iodide, caesium and strontium adsorption by organophilic vermiculite
Authors: Bors J. , Gorny A. , Dultz S.
Published: December 2006

Distribution coefficients and isotherms for the adsorption of radioiodide, caesium and strontium ions (125I−,134Cs+and85Sr2+) were determined in untreated vermiculite and in vermiculite treated with the chloride salt of hexadecylpyridinium (HDPy+). Experimental data reveal that some of the alkylammonium ions were incorporated as HDPyCl ion pairs into the vermiculite. The fraction of ion pairs adsorbed is reflected by an increase in distribution coefficients with increasing saturation levels. Consequently, a considerable part of the iodide adsorption could be attributed to an anion exchange process. At smaller amounts of Cs+and Sr2+adsorbed, distribution coefficients of the modified clay mineral are significantly reduced in comparison with the original material. These differences are less pronounced when greater amounts of cations are adsorbed. Generally, larger distribution coefficients were found for the Cs+compared with the Sr2+ion in the untreated and modified samples.
Characterization, pillaring and catalytic properties of a saponite from Vicálvaro, Madrid, Spain
Authors: Casal B. , Merino J. , Ruiz-Hitzky E. , Gutierrez E. , Alvarez A.
Published: December 2006

The characterization, pillaring ability and some catalytic properties of a saponite from the Vicálvaro deposit of Tolsa, located in Madrid have been studied. This mineral is associated with sepiolite in the same lacustrine environment. The raw saponite presents, as special characteristics, high specific surface area (>200 m2/g) and a high percentage of tetrahedral Al (90% of the total Al in the sample). Natural saponite gives rise to high conversions when used as a catalyst in the reaction of alkylation of benzene with 1-dodecene. Increased catalytic performances are obtained over the alumina-pillared saponite derivatives. These materials have also been tested in the cracking of gas-oil (microactivity test), giving good conversions and high selectivity towards the gasoline fraction, especially the pillared forms.
Clay-modified electrodes prepared by the Langmuir-Blodgett method
Authors: Hotta Y. , Taniguchi M. , Inukai K. , Yamagishi A.
Published: December 2006

An ion-exchange adduct of saponite with tetra-n-decylammonium cation ((n-decyl)4N+) was prepared and dispersed in chloroform. The material was spread on a water surface to form a thin film at the air-water interface. From the measurements of surface pressure vs. area, it was concluded that the film consisted of the very thin layer which was a mixture of single and double layers of saponite adduct. A clay-modified electrode was prepared by depositing the film on a glassy carbon substrate using the Langmuir-Blodgett method. When the electrode was soaked in an aqueous solution of [Fe(phen)3](ClO4)2 (phen = 1,10-phenanthroline), (n-decyl)4N+ cations were replaced by [Fe(phen)3]2+ ions from solution. This process was followed by measuring the cyclic voltammogram.
Spectroscopic study of the adsorption of rhodamine 6G on clay minerals in aqueous suspensions
Authors: Lopez Arbeloa F. , Tapia Estevez M. J. , Lopez Arbeloa T. , Lopez Arbeloa I.
Published: December 2006

Absorption and fluorescence spectroscopies were applied to study the adsorption of rhodamine 6G on several smectite-type clays in aqueous suspension. The dye can be adsorbed as the monomeric and the dimeric forms on both the external and the interlamellar surfaces of the clay. The presence of these species and their evolution with the stirring time of the sample and the relative dye/clay concentration depend on the nature of the smectite, the clay concentration and the particle size, factors that also affect the dispersion degree of the clay particles in water.
Nature of dioctahedral micas in Spanish red soils
Authors: Martin-Garcia J. M. , Delgado G. , Sanchez-Maranon M. , Parraga J. F. , Delgado R.
Published: December 2006

Structural formulae and other crystallochemical parameters were used to study different species of dioctahedral micas in clay and coarse gravel fractions of horizons from a red soil (Ultic Haploxeralf) in southern Spain. Mineralogical analyses using X-ray powder diffraction, and measurements of theb0parameter revealed dioctahedral micas, illite and paragonite. Structural formulae established from electron microprobe analysis and energy dispersive X-ray analysis showed the illites to be K mica related in elemental composition and structure to muscovite and phengite. The paragonites were found to be closer to ideal mica. Structural formulae for Na-K dioctahedral micas were obtained with crystallochemical characteristics intermediate between those of Na micas and K micas. The possibilty of these micas representing individual mineral phases or intergrowths of Na and K micas is discussed. In the soil profile, micas from the Bt horizon showed the largest crystallochemical changes induced by pedogenesis.
Isomorphous cation distribution in celadonites, glauconites and Fe-illites determined by infrared, Mössbauer and EXAFS spectroscopies
Authors: Drits V. A. , Dainyak L. G. , Muller F. , Besson G. , Manceau A.
Published: December 2006

Celadonite, glauconite and Fe-illite samples were studied by XRD, EXAFS, IR and Mössbauer spectroscopy. The samples were monomineralic and corresponded to 1M polytype. In the OH-stretching region of the IR spectra the content of each definite pair of cations bonded to OH groups was determined. The number of heavy (Fe) and light (Al, Mg) octahedral cations nearest to Fe was found by the EXAFS technique. The predicted quadrupole splitting values for each definite arrangement of cations nearest to Fe3+ were used to interpret the Mössbauer spectra. After the fitting procedure, the intensity of each doublet corresponded to a definite set of local cation arrangements around Fe3+ and to a definite occurrence probability of these arrangements. Computer simulation and the experimental data obtained were used to reconstruct the distribution of isomorphous octahedral cations in the 2:1 layers. For all samples, R2+ cations prefer to occupy one of the two symmetrically independent cis-sites and R2+-R2+ and/or Al-Fe3+ were prohibited in the directions forming ± 120° with the b axis. Therefore, octahedral sheets of the samples revealed domain structure, in which domains differ in size, in the nature of predominant cation and/or by cation ordering.
Chlorite crystallinity as an indicator of metamorphic grade of low-temperature meta-igneous rocks: a case study from the Bükk Mountains, Northeast Hungary
Authors: Árkai P. , Sadek Ghabrial D.
Published: December 2006

X-ray diffraction chlorite crystallinity (ChC) indices and major element chemical compositions of chlorites and bulk rocks were determined and correlated in meta-igneous rocks from different Mesozoic formations in various tectonic units of the Bükk Mountains, NE Hungary. The rocks, of basic to acidic compositions, range from ocean-floor metamorphic prehnite-pumpellyite facies (diagenetic zone) through regional metamorphic prehnite-pumpellyite facies (anchizone) up to the regional metamorphic pumpellyite-actinolite and greenschist facies (epizone). As in the case of meta-sedimentary rocks, chlorite crystallinity can be applied as an empirical, complementary petrogenetic tool to determine relative differences in grades of low-temperature meta-igneous rocks. Electron microprobe and XRD data show that ChC is controlled mainly by the decreasing amounts of contaminants (mixed-layered components or discrete, intergrown phases of mostly smectitic composition) in chlorite with advancing metamorphic grade, up to the epizone. The apparent increase in calculated Alivcontent of chlorite with increasing temperature is related to the decrease of these contaminants, as stated earlier by Jianget al.(1994). On the basis of the significant correlations found between ChC and temperatures, derived by the chlorite-Alivgeothermometer of Cathelineau (1988), both methods may be used for estimating the approximate temperatures of metamorphism, in spite of the contrasting interpretation of chemical data from chlorites obtained by electron microprobe analyses. After determining the effects of changing bulk chemistry on chlorite composition and ChC, the chlorite crystallinity method may complement the correlation of the illite crystallinity-based zonal classification of meta-sediments and the mineral facies classification of meta-igneous rocks.
An occurrence of stevensite and kerolite in the Devonian Crousa gabbro at Dean Quarry, The Lizard, Cornwall, England
Authors: Elton N. J. , Hooper J. J. , Holyer V. A. D.
Published: December 2006

Stevensite has been found at Dean Quarry, The Lizard, Cornwall, associated intimately with the disordered, hydrated variety of talc known as kerolite. Both minerals occur as pseudomorphs after pectolite and as microcrystalline anhedral masses filling cavities and veins in gabbro. Associated minerals include calcite and prehnite. The XRD data show that stevensite occurs as a physical mixture with kerolite, rather than as mixed-layer stevensite-kerolite. Kerolite is unaffected by glycerol treatment whilst stevensite readily expands: this test provides the only reliable distinction between the two minerals. Differences in IR and chemical data for stevensite and kerolite are subtle; data are broadly similar to those in the literature. Both minerals are readily decomposed to amorphous silica by hot concentrated HCl. Stevensite dehydroxylated at 400°C for 1.5 h is virtually indistinguishable from kerolite. The Dean Quarry occurrence is similar to many others worldwide. Stevensite and kerolite formed after prehnite, calcite, analcime, pectolite and natrolite during a phase of decomposition and alteration of these earlier minerals. ‘Stevensite’ from the first British occurrence in the Whin Sill, North Tyne, has been re-examined and appears to be kerolite or ‘hydrated-talc’.
A square planar [NiCl4]2− ion in the layered double hydroxide Al2Li(OH)6 [NiCl4]1/2
Authors: Okada K. , Matsushita F. , Hayashi S.
Published: December 2006

The layered double hydroxide (LDH) Al2Li(OH)6[NiCl4]1/2 was synthesized by anion exchange of Al2Li(OH)6(NO3) and the coordination structure of [NiCl4]2− in the interlayers was investigated. The LDH had a hexagonal cell with a = 5.06 and c = 23.06 Å. Since the basal spacing of one layer was 7.7 Å, the interlayer distance was calculated to be 2.9 Å and was too narrow for the usual tetrahedral NiCl4 structure. From extended X-ray absorption fine structure (EXAFS) measurements, the first neighbour Ni-Cl distances in the LDH were 2.10 Å which was compatible with four-fold coordination. Since the electron spin resonance (ESR) spectrum of the LDH showed no absorption, the [NiCl4]2− structure was considered to be square planar, rather than the usual tetrahedral structure in the interlayers of LDH.
Comparison of the methylene blue absorption and the ammonium acetate saturation methods for determination of CEC values of zeolite-rich tufts
Authors: Kitsopoulos K. P.
Published: December 2006

One of the most important properties of zeolitized volcaniclastic materials is the cation exchange capacity (CEC). Numerous techniques are available for measuring CEC and the methylene blue absorption (MBA) (Nevins & Weintritt, 1967) and the ammonium acetate saturation (AMAS) (Chapman, 1965) methods are two of those commonly used. The aim of this study was to compare the results obtained by the two methods when used with zeolite-rich materials.
Sequential structure transformation of illite-smectite-vermiculite during diagenesis of Upper Jurassic shales from the North Sea and Denmark
Authors: Drits V. A. , Sakharov B. A. , Lindgreen H. , Salyn A.
Published: December 2006

For mixed-layer clay fractions from the North Sea and Denmark, X-ray diffractograms have been recorded for specimens saturated with Mg, Ca, Na and NH4, both airdry and intercalated with ethylene glycol, and the patterns have been computer-simulated with a multicomponent program. The mixed-layer fractions consist of an illite-smectite-vermiculite (I-S-V) phase constituting ~90% of the fraction and a kaolinite-illite-vermiculite (K-I-V) phase. For each I-S-V, the degree of swelling in swelling interlayers depends on both interlayer cation and glycolation, whereas the amount of non-swelling illite and swelling interlayers and the interstratification parameters are constant. Based on structural characteristics and the degree of diagenetic transformation, the samples investigated can be divided into three groups. The I-S-V of group one is predominantly detrital and has 0.69-0.73 illite, 0.26-0.20 smectite and 0.04-0.07 vermiculite interlayers, the illite, smectite and vermiculite interlayers being segregated. The I-S-V of group two has been diagenetically transformed and has 0.80 illite, 0.12 smectite and 0.08 vermiculite interlayers, the vermiculite interlayers being segregated whereas the illite and smectite have the maximum ordering possible for R = 1. The I-S-V of group three has been further transformed during diagenesis and has 0.84 illite, 0.08 smectite and 0.08 vermiculite interlayers. Statistical calculations demonstrate that the I-S-V transformation can be described as a single interlayer transformation (SIT) within the crystallites.
A rectorite-pyrophyllite-chlorite-illite assemblage in pelitic rocks from Colombia
Authors: Brattli B.
Published: December 2006

In samples of slate from the Fomeque Formation near Bogota, Colombia, pyrophyllite was found to occur together with mixed-layered illite-smectite, chlorite and illite. Other minerals were quartz, K-feldspar, dolomite and pyrite. X-ray diffraction patterns revealed that the mixed-layer represents an R1 ordered rectorite with 80–90% illite layers. The microfabric is developed as a closely spaced cleavage in the phyllosilicate-rich rocks, and grades into a fracture cleavage with coarsening of the grain size. No cleavage was observed in the interbedded siltstones. It is suggested that the microfrabrics developed in these rocks correspond to high diagenetic to anchizonal conditions. The illite crystallinity from the slate has been measured on glycolated samples and ranges from 0.47 to 0.55°Δ2θ with a mean of 0.52°Δ2θ Based on the stability of R1 ordered rectorite, the illite crystallinity and the microfabric development, it is proposed that the rocks have been subjected to a temperature of ∼200°C at low pressure. At this temperature, pyrophyllite can only be stabilized at the expense of kaolinite and quartz if aH2O ≪ 1.
Iron oxides and hydroxides in the weathering interface betweenStereocaulon vesuvianumand volcanic rock
Authors: Adamo P. , Colombo C. , Violante P.
Published: December 2006

The nature and composition of the Fe minerals in the rusty ferruginous material frequently located in the zone of contact between the thallus ofStereocaulon vesuvianumand the leucite bearing rock of Mt. Vesuvius have been studied by microscopic and submicroscopic investigations (SEM, TEM with EDXRA) complemented by X-ray diffraction and chemical analysis. Ferrihydrite is likely to be the main component of the short-range order iron oxyhydroxide pool, although the possibility that significant feroxyhite may be present cannot be completely excluded. Hematite and goethite are the crystalline iron oxides. The organic acids produced by lichens play a key role in the enrichment of poorly-ordered phases at the rock-lichen interface. It is suggested that the peculiar morphology of theStereocaulon vesuvianumthallus and the irregularity of the volcanic rock surface lead to different microsites in the rock-lichen interfaces which have their own conditions of pH, humidity and redox potential, favourable for the neoformation of crystalline phases.
A new, efficient, one-step method for the removal of organic matter from clay-containing sediments
Authors: Meier L. P. , Menegatti A. P.
Published: December 2006

For the purpose of clay examination, a new one-step method for the removal of organic matter was developed using sodium peroxodisulphate combined with different buffers such as sodium hydrogen carbonate, disodium hydrogen phosphate and disodium tetraborate. From an early Cretaceous black shale from the Apennines with a high organic carbon content, the <2 µm clay fraction was separated and contained 10.9 wt% organic carbon. To prevent decomposition of the clay layers, the period of oxidation was short (25-60 min) and the pH was kept between 5 and 9.5. Up to 98% of carbon was removed by this method.
Formation of cubic phases on heating ferrihydrite
Authors: Campbell A. S. , Schwertmann U. , Campbell P. A.
Published: December 2006

Heating experiments were carried out with ferrihydrite, in the presence of organics, to gain more insight into the intermediate formation of a ferrimagnetic cubic phase often observed in soils as the result of fire. Without an organic reductant, no intermediate cubic phase was formed when ferrihydrite was transformed into hematite, regardless of whether the ferrihydrite DTA curve showed one or two exothermic peaks. Addition of glucose or charcoal as reductant caused the initial formation of a cubic magnetite and/or magnetite/maghemite phase in samples heated above 300°C in both air and N2 atmospheres. Ferrihydrite reduction, as determined by increasing cubic unit-cell edge lengths between 0.832 and 0.840 nm, increased with reductant concentration and heating time, providing excess reductant remained. Following consumption of the reductant, FeII may be partially or completely reoxidized, forming maghemite and then hematite. The occurrence of maghemite, but not of magnetite, in soils where forest fires have occurred suggests that sufficient oxygen was available, while temperatures remained elevated, to oxidize magnetite to maghemite.
Effect of autotransformation on the layer charge of smectites determined by the alkylammonium method
Authors: Janek M. , Komadel P. , Lagaly G.
Published: December 2006

Hydrogen-forms of <2 µm fractions of six bentonites of various Fe contents were prepared by H+→OH-→H+ion exchange using resins. Potentiometric titration curves revealed that the number of strong acid sites varied and accounted for 60-95% of the total acidity in the freshly prepared H-forms. The number of strong acid sites decreased and that of the weak acid sites increased on ageing. The process of autotransformation in aqueous dispersion at 90~ was completed within four days. Layer-charge distributions of all samples were inhomogeneous with layer charges from 0.25-0.39 Eq/unit O10(OH)2. Oxalate pretreatment of the samples resulted in changes in the layer-charge distribution due to the removal of readily soluble phases which may have blocked exchange sites. After autotransformation, the alkylammonium exchange method revealed inhomogeneous charge density distributions; the fraction of layers of the highest charge decreased. Comparison of total CEC obtained from potentiometric curves and interlamellar CEC calculated from the mean layer charge confirmed attack of protons from particle edges. However, for several samples the structural attack may also occur from the interlayer space. Autotransformation of the Hsmectites decreased the mean layer charge. Protons probably attack the Mg(O,OH)6octahedra preferentially during the autotransformation.
Polymerization of tetramethylcyclotetrasiloxane monomer by ion-exchanged montmorillonite catalysts
Authors: Nishihama S. , Yamada H. , Nakazawa H.
Published: December 2006

Montmorillonites ion-exchanged with Li+, Na+, K+ Ca2+, Mg2+ and Ni2+ and acidic clay were used as catalysts for the polymerization of a cyclic siloxane monomer, 2,4,6,8- tetramethylcyclotetrasiloxane. Montmorillonites with Ni2+ and Mg2+ in the interlayer, and acidic clay exhibit a greater ability for siloxane polymerization in both yield and mean molecular weight of products than those containing Li+, Na+ and K+. The difference in catalytic ability of the ionexchanged montmorillonites is caused by the number of Brmasted acid sites due to the polarization of H2O. This was confirmed experimentally by FTIR analysis of pyridine-treated samples. Therefore, it may be possible to design a catalyst for controlling siloxane polymerization (i.e. mean molecular weight of product) by changing the number of Bronsted acid sites through exchange of the interlayer cations of montmorillonites.
Metachromasy in clay-dye systems: the adsorption of acridine orange by Na-saponite
Authors: Garfinkel-Shweky D. , Yariv S.
Published: December 2006

The adsorption of the cationic dye acridine orange (AO) by Na-saponite and the colloidal properties of the aqueous suspension were investigated by visible spectroscopy and XRD. The organic cation is adsorbed by the mechanism of cation exchange. When small amounts of the dye are adsorbed, the system contains small tactoids and is peptized. At this stage the dye penetrates into the interlayer space and most of it undergoes metaehromasy due to interactions between the aromatic entity and the oxygen plane of the clay. When greater amounts of AO are adsorbed, the clay platelets flocculate to form book-house floes which, with excess AO, are transformed into card-house floes. At this stage metachromasy results from the aggregation of the dye in the interparticle space of the floes, in addition to the π interactions with the oxygen plane. In excess AO, the clay is gradually peptized. At this stage the dispersed clay platelets form small tactoids with monomeric AO in the interlayer space and at the same time adsorb dimerie and polymeric AO cationic species at the solidliquid interface.
An investigation of nephrite jade by electron microscopy
Authors: Dorling M. , Zussman J.
Published: December 2006

Two specimens of tremolite and one of richterite, all with nephrite jade texture, have been examined by transmission electron microscopy using ion-thinning for specimen preparation. The specimens contain clusters of very small lath-like crystallites with z-axes approximately parallel but in a range of azimuthal orientations. It is suggested that these clusters which are themselves in varied orientations are the result of post-tectonic recrystallization of strained amphibole crystals, the new crystals inheriting the z-axis orientations of the old. The extreme toughness of nephrite jade is attributed to a number of the sub-microscopic features observed, including the sizes, habits, and orientations of its crystallites, and the nature of its grain boundaries.
Schultenite from King County, Washington, USA; a second occurrence, and review
Authors: Falls R. , Cannon B. , Mandarino J. A.
Published: December 2006

Schultenite, PbHAsO4, known only from Tsumeb, Namibia, has been identified from a second occurrence: near North Bend, King County, Washington, USA. It occurs as euhedral crystals in a quartz-arsenopyrite-galena vein. It has a measured density of 6.07(3) g/cm3 and a calculated density of 6.079(4) g/cm3. The white to colourless crystals have a white streak, adamantine lustre, and fluoresce dull yellow under long wave ultraviolet light. Schultenite is monoclinic. Pa or P2/a; the unit cell parameters refined from the X-ray powder diffraction data are: a 5.827(3), b 6.743(3), c 4.847(3) Å, β 95.34(5)°; V 189.6(1) Å3; Z = 2; a:b:c = 0.8642:1:0.7188. The forms {010}, {001}, and {3̄22} were observed on the Washington schultenite crystals.
The occurrence of coarse-grained massive tilleyite in the Redcap Creek magmatic skarn, North Queensland
Authors: Rubenach M. J. , Cuff C.
Published: December 2006

Endoskarns formed where a swarm of diorite dykes have intruded calcite marble at Redcap Creek include an inner melilite-dominated, a wollastonite-dominated, and an outer massive tilleyite zone in contact with marble. The massive tilleyite is unusual in that it is coarse-grained (prisms 2–15 cm in length) and its deep grey colour contrasts with the lighter coloured varieties described elsewhere. A chemical analysis gives a formula close to ideal, with only minor substitution of Al, Ti, and Mg. Refined unit cell parameters are in close agreement with those quoted in the literature. The skarns have clearly formed by transport of Si, Mg, Fe, Al, and Ti from the igneous rocks, and Ca in the reverse direction from the marble. Activity diagrams derived from experimental data are most useful in interpreting the zonal sequence of endoskarns, and preliminary results suggest mass transfer at low Xco2 and temperature of the order of 800°C or higher for the formation of the massive tilleyite.
Experimental investigation of clogging of fissures and pores in granite
Authors: Bourg A. C. M. , Oustrière P. , Sureau J. F.
Published: December 2006

Fluid flow through a fractured granite core and leaching experiments on granite powder (at constant temperatures of 50 and 100°C and during cooling from 100 to 50°C) indicate that the dissolved silica content of the fluids originates from the dissolution of feldspars and phyllosilicates. The dissolution of quartz is not ruled out but it should be a minor phenomenon. The precipitation of quartz may control the dissolved Si content during constant temperature leaching. During cooling from 100 to 50°C chalcedony, alumino-silicates, and chlorite are all capable of precipitation, possibly leading to some clogging or sealing of fissures.
The NAGRA investigation project for the assessment of repositories for high-level radioactive waste in geological formations
Authors: Balderer Werner
Published: December 2006

The first results of isotopic investigations as a part of the hydrogeological study of northern Switzerland are presented. This study is part of the global geological research project of the NAGRA (National Co-operative for the Storage of Radioactive Waste) which is intended to provide the scientific knowledge required for the assessment of the feasibility of safe disposal of highly radioactive waste in the geological formations of the area. The aim of the hydrogeological research programme is to assess the natural conditions in the sedimentary sequence and the underlying granite basement, by regional investigation of hydraulic parameters, isotopic composition, and hydrogeochemistry at all existing wells (boreholes and natural thermal springs) and in 11 to 12 deep-drilled boreholes (to final depth of 1500–2500 m).
A transition from diagenesis to greenschist facies within a major Variscan fold/thrust complex in SW England
Authors: Primmer T. J.
Published: December 2006

The north coast of Cornwall, from Bude to Newquay, provides a continuous section through a major Variscan fold/thrust complex. Illite crystallinity studies have revealed a transition from diagenesis in the north to greenschist facies metamorphism in the south in the Upper Palaeozoic succession. More detailed studies of mineral assemblages in both metabasites and pelitic rocks support the regional pattern of metamorphism indicated by illite crystallinity, and show that locally in the Tintagel district, the grade of metamorphism may have reached middle to upper greenschist facies. An attempt to correlate the above data with temperatures (108–985°C) derived from O-isotope geothermometers is made. Interpretation of the metamorphic data presented helps to emphasize the tectonic importance of the major structures seen in the fold/thrust complex.
Compositional variation within some sedimentary chlorites and some comments on their origin
Authors: Curtis C. D. , Hughes C. R. , Whiteman J. A. , Whittle C. K.
Published: December 2006

A range of authigenic sedimentary chlorites from sandstones has been studied by analytical transmission electron microscopy. Selected area (single crystal) electron diffraction patterns are of the Ib (β = 90°) polytype confirming the earlier observations of Hayes (1970).

TEM analyses show all samples to be relatively rich in both Al and Fe. In the general formula (Mg,Fe,Al)n [Si8−xAlxO20](OH)16, x varies between 1.5 and 2.6; Fe/(Fe + Mg) between 0.47 and 0.83 and n between 10.80 and 11.54. Octahedral Al is close to 3 in this formulation and Fe2+ predominates over Fe3+. Swelling chlorites have significantly different compositions which are consistent with smectite/chlorite interstratifications.

The Ib (β = 90°) polytype appears to be stable under conditions of moderate to deep burial. It replaces berthierine and swelling chlorites formed at lower temperatures. As commonly seen in grain coatings, however, it precipitates from porewater; solutes probably being contributed from several mineral decomposition reactions.
Possible chemical controls of illite/smectite composition during diagenesis
Authors: Velde B.
Published: December 2006

Re-interpretation of the significance of phase assemblages present in two sequences of rocks having experienced similar burial diagenesis allows one to establish that the change of oxidation state of iron in sediments could have the effect of changing the smectite content of the mixed layer mineral. This is used to explain an almost isothermal change in the composition of a sequence while others do not show such a rapid change. An indicator of the reaction is seen in the composition of the chlorite present in the rocks which is iron-rich and alumina-poor compared to chlorites in rocks showing a slower rate of change in the smectite content of the mixed-layered mineral. In order to reveal such a relation, one must make an analysis of the clay mineral assemblage, especially in the number of phases present during the course of diagenesis.
Electron-optical studies of phyllosilicate intergrowths in sedimentary and metamorphic rocks
Authors: White S. H. , Huggett J. M. , Shaw H. F.
Published: December 2006

The results of a microstructural study by backscattered scanning electron microscopy and a microchemical study using X-ray microprobe analysis of phyllosilicate intergrowths from sandstones, shales, metagreywackes, and low-grade schists are presented. The microstructural study revealed that the intergrowths thicken and become more coherent with metamorphic grade; the intergrowths change from incoherent to coherent in the anchizone. The increasing coherency is mirrored by an increase in the crystallinity indices of the illites/phengites. Chemical analysis of the individual intergrowth phases was difficult in the sediments and no systematic compositional variations were recorded. However, clear compositional trends with increasing metamorphic grade emerged in the phengites from the metagreywackes and schists, but in the chlorites only slight compositional changes were recorded.
Carbonate alteration minerals in the Salton Sea geothermal system California, USA
Authors: Douglas McDowell S. , Paces James B.
Published: December 2006

Active geothermal systems in fluvial-deltaic sediment of the Salton Trough typically develop a thick, carbonate-cemented sandstone caprock which shows a regular progression of carbonate minerals, mineral reactions, rock-fluid mass transfer, and physical properties on increasing temperature. The Sinclair 3 well contains calcian ankerite at < 175 °C, ankerite from 175 to 195 °C, calcite+minor dolomite from 195 to about 250°C, and calcite at higher temperatures. The carbonate content of sandstone decreases on increasing temperature from > 45% at < 140 °C to about 10% at > 250 °C, The most abrupt decrease occurs in the 140 to 170°C range where significant compaction of sandstone occurs as carbonate is reduced to < 25%, and kaolinite reacts to form chlorite. The overall result is the loss of significant Ca, Fe, Mg, and CO2 from sandstone to the fluid phase on increasing temperature. Reaction ofcalcian ankerite to ankerite near 175 °C, and of ankerite to calcite and minor dolomite in the 195 to 245°C range, takes place on a constant carbonate-volume basis by direct replacement of one carbonate by another. The latter reaction produces significant chlorite, with Al derived from solution of detrital feldspar and from the smectite-to-illite transformation. The equilibrium coexistence of calcite with dolomite and ankerite near 200 °C has allowed construction of an isothermal section in the Ca-Mg-(Fe+Mn) carbonate phase diagram and provided a low-temperature constraint on the calcite limb of the calcite-dolomite solvus.
Structural and phase equilibria studies in the system Pt-Fe-Cu and the occurrence of tulameenite (Pt2FeCu)
Authors: Shahmiri M. , Murphy S. , Vaughan D. J.
Published: December 2006

The crystal structure and compositional limits of the ternary compound Pt2FeCu (tulameenite), formed either by quenching from above the critical temperature of 1178°C or by slow cooling, have been investigated using X-ray diffraction, transmission electron microscopy, differential thermal analysis and electron probe microanalysis.

The crystal structure of Pt2FeCu, established using electron density maps constructed from the measured and calculated intensities of X-ray diffraction patterns of powdered specimens, has the (000) and (½½0) lattice sites occupied by Pt atoms and the (½0½) and (0½½) sites occupied by either Cu or Fe atoms in a random manner. The resulting face-centred tetragonal structure undergoes a disordering transformation at the critical temperature to a postulated non-quenchable face-centred cubic structure. Stresses on quenching, arising from the ordering reaction, are relieved by twinning along {101} planes or by recrystallization along with deformation twinning; always involving grain boundary fracturing.

Phase relations in the system Pt-Fe-Cu have been investigated through the construction of isothermal sections at 1000 and 600°C. At 1000°C there is an extensive single phase region of solid solution around Pt2FeCu and extending to the binary composition PtFe. At 600°C the composition Pt2FeCu lies just outside this now reduced area of solid solution in a two-phase field. Comparison of the experimental results with data for tulameenite suggests that some observed compositions may be metastably preserved. The occurrence of fine veinlets of silicate or other gangue minerals in tulameenite is suggested to result from grain boundary fracturing on cooling below the critical temperature of 1178°C and to be evidence of a magmatic origin.
Zincian staurolite in Glen Doll, Scotland
Authors: Schumacher Renate
Published: December 2006

Textures and relict mineralogy in the Dalradian gneisses from the southern contact aureole of the Glen Doll diorite trace the development of three stages of metamorphism through regional and contact metamorphic phases. Regional metamorphic stage I is characterized by the stability of sillimanite+muscovite; recognition of a subsequent regional metamorphic stage II of lower grade is based on textural criteria, the stability of kyanite and staurolite + quartz, and geothermometry/geobarometry. The breakdown of zincian staurolite occurred under the conditions of contact metamorphism (stage III). Textural evidence from the outer part of the contact aureole suggests that zincian staurolite broke down by the following oxidation reaction:

zincian staurolite + muscovite + quartz + O2 → andalusite + Zn-rich spinel + magnetite + biotite + H2O.

Various stages of completion of this reaction have been observed in different parts of a sample. Predominance of magnetite over Zn-rich spinel (⩽ 14 wt. % ZnO) as a breakdown product can be explained by the initial breakdown of Fe-staurolite component + muscovite + quartz+O2 to form andalusite+biotite+magnetite. These product phases were joined by the Zn-rich spinel when sufficient Zn-staurolite component had concentrated in the unreacted staurolite. Rare local examples where Zn-rich spinel is dominant over magnetite may reflect lower O2 fugacity and/or higher initial Zn contents of the staurolite.
Zn-rich staurolite from the Uvete area, central Kenya
Authors: Miyake Akira
Published: December 2006

Zn-rich staurolite occurs in a pelitic gneiss from the Uvete area, central Kenya. The rock was metamorphosed to staurolite-kyanite grade during the Mozambique metamorphism. Microprobe analyses of the staurolite gave the following values (in wt. %): SiO2 26.2–27.3, Al2O3 52.4–53.5, FeO 8.3–9.2, MgO 2.2–2.6, and ZnO 6.0–7.5. Cell dimensions are a = 7.874(± 0.003), b = 16.620(±0.006), c = 5.656(±0.002) Å and β = 90.00 (± 0.002)°. Optical properties are 2Vz = 82–85°, α = 1.742 (±0.002), β = 1.747(±0.002) and γ = 1.753(±0.002). The optical dispersion is moderate and r > v. Density is 3.83(±0.01) g/cm3. Infra-red absorption spectra were also recorded. The cation correlation suggests that the principal substitutions in the staurolite are Zn ⇆ Fe in the tetrahedral sites in the hydroxide sheet and Al ⇆ Mg in the octahedral sites.
Significance of clinopyroxene compositions from the Cudgegong Volcanics and Toolamanang Volcanics: Cudgegong-Mudgee district, NSW, Australia
Authors: Pemberton J. W. , Offler R.
Published: December 2006

Synopis

Clinopyroxene phenocrysts and groundmass crystals are relict phases in altered basalt and basaltic andesite lavas, and arenites of the Cudgegong Volcanics and Toolamanang Volcanics, Cudgegong-Mudgee district, New South Wales. Petrography, field relationships and clinopyroxene compositions indicate that basaltic blocks in the latter unit are reworked from the Cudgegong Volcanics. Clinopyroxene phenocrysts show a restricted compositional range and minor Feenrichment from core to rim, features considered indicative of a calc-alkaline parent magma. It is proposed that the Cudgegong Volcanics crystallized under hydrous conditions, at least in the later stages, with risingfO2resulting in a Fe-Ti oxide crystallizing as a primary phase. The clinopyroxenes are considered to have crystallized at moderate (5–6 kbar) and falling pressures and at minimum temperatures in the range 900 to 1000°C. Coupled substitutions affecting the “other” components in the clinopyroxene structural formula indicate that theivAl-viFe3+,ivAl-viAl andivAl-viTi4+couples are important. The Sofala Volcanics, south of the study area, and the Cudgegong Volcanics are similar in age, petrography and stratigraphic position, and contain relict clinopyroxenes which are chemically similar. This suggests that the units are laterally equivalent and adds further evidence to the proposal that an oceanic island arc system was active in central western New South Wales during the Late Ordovician.
Compositional variation in högbomites from north Connemara, Ireland
Authors: Angus N. S. , Middleton R.
Published: December 2006

Högbomite occurs in two contrasting mineral assemblages within the Currywongaun-Dough-ruagh intrusion of north Connemara: a cordierite-rich pelitic xenolith and an orthopyroxenite. In the latter, högbomite and green spinel form blebs within magnetite-ilmenite grains. The högbomite displays significant compositional variation from grain to grain: TiO2(3.0–6.3%), FeO (21.6–21.3%), MgO (10.0–7.5%), ZnO (3.6–2.4%). This chemical heterogeneity appears to represent variable degrees of partial substitution of Mg and Zn by Ti, in the replacement of spinel by högbomite. By contrast, in the cordierite-hornfels, the högbomite compositions are more notably enriched in iron: TiO2(4.7–7.0%), FeO (29.6–24.3%), MgO (4.2–6.2%), ZnO (2.7–2.1%). This iron-rich högbomite appears to have formed primarily by interaction between opaque ore and adjacent cordierite, rather than by replacement of spinel.

Two high-grade metamorphic episodes appear to be necessary for högbomite growth, one determining chemical composition and the other appropriate physical parameters. In the Connemara occurrences thermal metamorphism and partial melting, coupled with contamination of the surrounding magma, controlled the formation of mineral assemblages rich in Fe, Mg, Al, Ti, and Zn. Emplacement of the intrusion was accompanied by amphibolite facies regional metamorphism and it is to this metamorphic event that the growth of högbomite may be attributed.
The partial melting of basalt and its enclosed mineral-filled cavities at Scawt Hill, Co. Antrim
Authors: Kitchen D. E.
Published: December 2006

Partially melted basalts enclosing amygdales which have been completely melted formed at Scawt Hill adjacent to a Tertiary dolerite plug. Melting of the basalts commenced in a clay-rich mesostasis to produce a feldspathic liquid which then crystallized to an assemblage of dendritic olivine, skeletal hypersthene, opaque oxide and Mg-hercynite in a microcrystalline plagioclase matrix. An original mineral assemblage of zeolite, calcite, and saponite-nontronite in the amygdales melted and quenched to a brown glass now containing complexly zoned pyroxenes with plagioclase and opaque oxide. Melting commenced between 700–800°C, reaching a maximum temperature of 1168°C, and was followed by rapid cooling. The assimilation of remelted basalt may alter the course of crystallization of contaminated magmas.
Dynamic biaxial absorption spectra of Ti3+ and Fe2+ in a natural rose quartz crystal
Authors: Cohen A. J. , Makar L. N.
Published: December 2006

The absorption spectrum of Ti3+ in quartz is typical for that element in an octahedral site, except for the high oscillator strength of the band which indicates intensive charge transfer, most likely between a substitutional Ti4+ and an interstitial Ti3+. The biaxial anisotropy of the band is similar to that of octahedral Fe2+ in the same crystal, suggesting the same site for the Ti3+, an interstitial site at the intersection of the threefold axis with two twofold axes. The dynamic nature of the Ti and Fe ions is indicated when the crystal is subjected to X-irradiation and then to bleaching treatment with UV-light or heat. Ti(IV) ions are acceptors of electrons donated by Fe2+ during X-irradiation. This is indicated by increase of the 2.4 eV band intensity with decrease in the Fe2+ band intensities and appearance of Fe3+ charge transfer bands in the UV-region. Heat and UV-light treatment decrease the Fe3+ CT bands and increase the Fe2+ crystal-field bands along with decrease in the 2.4 eV band related to titanium.