Compressibility and crystal structure of sillimanite, Al2SiO5, at high pressure

The unit-cell dimensions and crystal structure of sillimanite at various pressures up to 5.29 GPa have been refined from single-crystal X-ray diffraction data. As pressure increases, a and b decrease linearly, whereas c decreases nonlinearly with a slightly positive curvature. The axial compression ratios at room pressure are β_a:β_b:β_c=1.22:1.63:1.00. Sillimanite exhibits the least compressibility along c, but the least thermal expansivity along a (Skinner et al. 1961; Winter and Ghose 1979). The bulk modulus of sillimanite is 171(1) GPa with K′=4 (3), larger than that of andalusite (151 GPa), but smaller than that of kyanite (193 GPa). The bulk moduli of the [Al1O₆], [Al2O₄], and [SiO₄] polyhedra are 162(8), 269(33), and 367(89) GPa, respectively. Comparison of high-pressure data for Al₂SiO₅ polymorphs reveals that the [SiO₄] tetrahedra are the most rigid units in all these polymorphic structures, whereas the [AlO₆] octahedra are most compressible. Furthermore, [AlO₆] octahedral compressibilities decrease from kyanite to sillimanite, to andalusite, the same order as their bulk moduli, suggesting that [AlO₆] octahedra control the compression of the Al₂SiO₅ polymorphs. The compression of the [Al1O₆] octahedron in sillimanite is anisotropic with the longest Al1-OD bond shortening by ～1.9% between room pressure and 5.29 GPa and the shortest Al1-OB bond by only 0.3%. The compression anisotropy of sillimanite is primarily a consequence of its topological anisotropy, coupled with the compression anisotropy of the Al-O bonds within the [Al1O₆] octahedron.     

Investigation by backscatter radar of artificial irregularities produced in ionospheric plasma heating experiments

The artificial ionospheric turbulence occurs in the ionosphere illuminated by high power HF radio waves. There are a lot of irregularities stretched along the geomagnetic field in this region. The investigation of the artificially disturbed ionospheric region is based on the reception of back scattered signals (BSS) which permits the basic parameters of this region to be estimated and its inhomogeneous structure to be described.Experiments were carried out using ‘Sura’ heating facility in the frequency range of ? = 4.7–9 MHz (ordinary mode) with the effective radiated power P_eff = 50–70 MW beamed vertically upwards. The most important dynamic and statistical BSS characteristics (the built-up time, the relaxation and autocorrelation times, the BSS amplitude spatial correlation function and power spectra) were measured using probe waves in the frequency range of that made it possible to obtain the basic parameters of the artificial irregularities. The model representation of a disturbed region in a form of a periodic structure gives a possibity to evaluate the scale of the structure, the whole size of the disturbance and its power and to calculate the main BSS characteristics.     

Geology of the volcanic-hosted Brockman rare-metals deposit,Halls Creek Mobile Zone,northwest Australia. l. Volcanic environment,geochronology and petrography of the Brockman volcanics

Summary Rare-metals mineralization of the Brockman deposit (Halls Creek Mobile Zone, NW Australia) is hosted in a fluorite-bearing, rhyolitic volcaniclastic unit informally termed the Niobium Tuff. The Tuff, more correctly described as a tuffaceous volcaniclastic deposit, is the lowermost unit of a sequence of trachyte-to-rhyolite lavas, trachyandesite subvolcanic rocks, and volcaniclastic units of the Brockman volcanics located within the Halls Creek Group, a thick, early Proterozoic volcano-sedimentary sequence. High precision SHRIMP ion-microprobe zircon dating of the Niobium Tuff gives an eruption age of 1870 ± 4 Ma. Regional geochronological constraints indicate the Niobium Tuff was deposited about 15 Ma before major orogenic activity affected the area. Despite folding, faulting and low-grade metamorphism, the Brockman volcanics show excellent preservation of primary volcanological features, including pillow-lavas and pillow-breccias, that suggest a dominantly subaqueous, below-wave-base emplacement environment. The style of eruption products and magma volume constraints suggest the trachyte-dominated volcanics were erupted from a small shield volcanic complex probably in a rift-related basin in a shallow-marine setting. The tectonic setting was intraplate but differs from most Tertiary to recent trachyte volcanic complexes which are largely subaerial, are built on relatively thick continental crust, and show no post-eruptive orogenic history. Brockman-style rare-metal deposits are characterized by preservation of subaqueous volcanics beneath a thick sedimentary sequence, eruption of early incompatible-element enriched products followed by less differentiated magmas, and fine-grained mineralogy influenced by alteration processes. Prospects exist for discovery of analogous deposits, particularly in early Proterozoic mobile belts and Tertiary intraplate shield volcanic provinces.

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Geologie der an Vulkanite gebundenen Seltene-Metalle-Lagerstätte Brockman, Halls Creek Mobile Zone, Nordwest-Australien. I. Vulkanologie, Geochronologie und Petrographie der Brockman-Vulkanite

Zusammenfassung Selten-Metall-Vererzung der Brockman-Lagerstätten (Halls Creek Mobile Zone, NW Australien) sitzt in einer Fluorit-führenden, rhyolitischen vulkanoklastischen Einheit auf, die informell als der Niob-Tuff bezeichnet wird. Es handelt sich hier um ein vulkanoklastisches Tuff-Sediment; dieses ist die unterste Einheit einer Abfolge vor Trachyt bis Rhyolit-Laven, trachyandesitischen Subvulkaniten and vulkanoklastischen Einheiten der Brockman Vulkanite innerhalb der Halls Creek Gruppe, einer mächtigen frühproterozoischen vulkanosedimentdren Abfolge. Prüzisionsdatierungen des Niob Tuffs mit der SHRIMP Ionen-Mikrosonde ergeben ein Eruptionsalter von 1870 +-4 Millionen Jahren. Regionale geochronologische Zusammenhänge zeigen, daß der Niob Tuff etwa 15 Millionen Jahre vor einer größeren Orogenese, die das Gebiet betroffen hat, abgelagert wurde. Trotz Faltung, Bruchtektonik and niedriggradiger Metamorphose zeigen die Brockman-Vulkanite einen hervorragenden Erhaltungszustand primärer vulkanologischer Erscheinungen. Diese urnfassen auch Kissenlaven und KissenBreckzien, die eine vorwiegend subaquatische Ablagerung in ruhigem Wasser erkennen lassen. Die Art der Eruptionsprodukte and das Magmavolumen zeigen, daß die Trachytdominierten Vulkanite von einem kleinen Schildvulkan stammer, wahrscheinlich in einem Becken in einer Rift-Situation im seichten marinen Milieu. Die tektonische Situation war intraplate, aber unterscheidet sich von den meisten tertiären bis rezenten trachytischen Vulkan-Komplexen, die hauptsächlich subaerisch sind, auf einer relativ mächtigen kontinentalen Kruste aufsitzen, and keine post-eruptive orogene Entwicklung zeigen. Seltene-Metalle-Lagerstatten des Brockman-Typs rind durch die Erhaltung subaquatischer-Vulkanite unterhalb einer machtigen sedimentdren Abfolge gekennzeichnet; welters durch frühe Eruptionsprodukte, die an inkompatiblen Elementen angereichert sind, auf die dann weniger differenzierte Magmen folgten, und schließlich durch einen feinkörnigen Mineralbestand, der vor Umwandlungsprozessen betroffen war. Es besteht die Möglichkeit der Entdeckung analoger Lagerstätten, besonders in frühproterozoischen mobilen Gürteln und in tertidren intraplate Schildvulkan Provinzen.

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Pristine vs. contaminated trends in Nb,Ta-oxide minerals of the Jihlava Pegmatite District,Czech Republic

Summary Columbite-tantalite is widespread in the lepidolite-subtype rare-element pegmatites of the Jihlava pegmatite district, western Moravia, Czechoslovakia. In most pegmatites, fractionation of columbite-tantalite shows initial enrichment in Mn followed by increasing Ta, in accordance with the usual trend from ferrocolumbite through mangano-columbite to manganotantalite, typical of the lepidolite pegmatites. Many dikes, however, show local deviations toward Fe- and Ti-rich compositions. In extreme cases, all columbite-tantalite is strongly enriched in Fe and Ti, and is associated with ixiolite and tantalian rutile. The degree of enrichment of the Nb,Ta oxide-mineral assemblage in Fe and Ti is proportional to tectonic introduction of wallrock xenoliths of mafic pyroxene-biotite syenite into the pegmatites during late stages of their consolidation. Extensive reaction of the residual pegmatite melt with the xenoliths contaminated the near-by melt, and generated Nb,Ta oxide minerals and tourmaline of non-typical chemistries. Late fersmite probably formed after thermal equilibration of the pegmatites with their syenitic country rocks, from Ca-bearing regional interstitial fluids pervading through the solidified pegmatites.

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Zusammenfassung In Selten-Element Pegmatiten (Lepidolith-Subtyp) des Jihlava Pegmatit Distriktes, West-Mähren, Tschechien, ist Columbit-Tantalit weitverbreitet. In den meisten Pegmatiten führte die Fraktionierung von Columbit-Tantalit zur einer anflinglichen Anreicherung von Mn gefolgt von einer Zunahme in Ta, vergleichbar mit dem für Lepidolith-Pegmatit bekannten Trend Ferrocolumbit-Manganocolumbit-Manganotantalit. Viele Gänge zeigen jedoch lokale Abweichungen zu Fe- und Ti-reichen Zusammensetzungen. In extremen Fällen ist Columbit-Tantalit stark an Fe und Ti angereichert und mit Ixiolith und Tantalo-Rutil vergesellschaftet. Das Ausmaß der Fe und Ti Anreicherung in (Nb,Ta)-Oxid-Assoziationen ist proportional dem tektonisch bedingten Eindringen von maischen Pyroxen-Biotit-reichen Syenit-Nebengesteinsxenolithen in die Pegmatite gegen Ende ihrer Verfestigung. Tiefgreifende Reaktion der Pegmatit-Restschmelze mit den Xenolithen kontaminierte die Schmelze und führte zur Bildung von (Nb,Ta)-Oxid-Mineralen und Turmalin ungewöhnlicher Zusammensetzung. Möglicherweise nach der thermischen Gleichgewichtseinstellung der Pegmatite mit ihren syenitischen Nebengesteinen bildete sich Fersmit unter Beteiligung von Ca-führenden regionalen Porenlösungen, welche die verfestigten Pegmatite durchdrangen.

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Efficient generation of conditional simulations by chebyshev matrix polynomial approximations to the symmetric square root of the covariance matrix

Consider the problem of generating a realization y₁ of a Gaussian random field on a dense grid of points ₁ conditioned on field observations y₂ collected on a sparse grid of points ₂. An approach to this is to generate first an unconditional realization y over the grid =_{1 2}, and then to produce y₁ by conditioning y on the data y₂. As standard methods for generating y, such as the turning bands, spectral or Cholesky approaches can have various limitations, it has been proposed by M. W. Davis to generate realizations from a matrix polynomial approximations to the square root of the covariance matrix. In this paper we describe how to generate a direct approximation to the conditional realization y₁, on ₁ using a variant of Davis' approach based on approximation by Chebyshev polynomials. The resulting algorithm is simple to implement, numerically stable, and bounds on the approximation error are readily available. Furthermore we show that the conditional realization y₁ can be generated directly with a lower order polynomial than the unconditional realization y, and that further reductions can be achieved by exploiting a nugget effect if one is present. A pseudocode version of the algorithm is provided that can be implemented using the fast Fourier transform if the field is stationary and the grid ₁ is rectangular. Finally, numerical illustrations are given of the algorithm's performance in generating various 2-D realizations of conditional processes on large sampling grids.     

Estimation for partially observed Markov processes

Many stochastic process models for environmental data sets assume a process of relatively simple structure which is in some sense partially observed. That is, there is an underlying process (X_n, n 0) or (X_t, t 0) for which the parameters are of interest and physically meaningful, and an observable process (Y_n, n 0) or (Y_t, t 0) which depends on the X process but not otherwise on those parameters. Examples are wide ranging: the Y process may be the X process with missing observations; the Y process may be the X process observed with a noise component; the X process might constitute a random environment for the Y process, as with hidden Markov models; the Y process might be a lower dimensional function or reduction of the X process. In principle, maximum likelihood estimation for the X process parameters can be carried out by some form of the EM algorithm applied to the Y process data. In the paper we review some current methods for exact and approximate maximum likelihood estimation. We illustrate some of the issues by considering how to estimate the parameters of a stochastic Nash cascade model for runoff. In the case of k reservoirs, the outputs of these reservoirs form a k dimensional vector Markov process, of which only the kth coordinate process is observed, usually at a discrete sample of time points.     

Crystallization processes in an artificial magma: variations in crystal shape,growth rate and composition with melt cooling history

A large (4.8 m³, 1.3x10⁷ g) artificial mafic melt with a bulk composition similar to that of a basalt (but with a high CaO content of 17 wt%) was generated during a demonstration of in situ vitrification and was allowed to cool naturally. During the melting process, convection was vigorous, resulting in a chemically and thermally homogeneous melt body. Once heating was complete, the cooling rate was rapid with the temperature dropping from 1500°C to 500°C in 6 days within the interior of the 3 m diameter, 1.5 m thick body. A 20 h period of constant temperature (1140°C) observed during colling was the result of latent heat released by widespread crystallization. The final crystalline assemblage consists of diopsidic to hedenbergitic pyroxene and anorthitic feldspar, with a subordinate amount of potassic feldspar, plus a small amount of evolved glass. The compositions and proportions of phases agree well with those predicted by the MELTS thermodynamic model. Thermal and textural evidence suggest that convection within the melt ceased coincident with formation of the first crystals. Textural investigation of core samples reveals large (up to 1 cm in length) acicular diopsidic pyroxenes in a matrix of smaller feldspar and zoned pyroxene crystals (500 m in length). Crystal shape and pyroxene composition vary as a function of position within the solidified body, as a function of cooling rate. Both crystal size and degree of crystallinity are highest in the central, most slowly-cooled parts of the rock. Crystal shape is characterized by tabular, equilibrium-growth forms in the slowly-cooled areas, grading to highly skeletal, dendritic forms at the rapidly-cooled edges of the body. The pyroxene crystals are dominantly homogeneous diopside, but crystals are characterized by thin Fe-rich hedenbergitic rims. These rims were deposited when Mg in the melt was depleted by diopside growth, and melt temperature had cooled sufficiently to allow Fe-rich pyroxene growth. Crystal growth rates can be calculated based on thermal behavior of the melt, reinforced by thermodynamic modelling, and are determined to be between 10^-7 and 10^-8 cm/s in the central part of the melt. These estimates agree well with growth rates in natural systems with similar cooling rates. Pyroxene crystals that formed at a higher cooling rates are characterized by higher Al and lower Mg contents relative to tabular equilibrium crystalline forms, presumably as a result of disequilibrium melt compositions at the crystal-melt interface.New Mexico Bureau of Mines and Mineral Resources, New Mexico Institute of Mining and Technology, Socorro, NM 87801, USA     

Mafic magma batches at Vesuvius: a glass inclusion approach to the modalities of feeding stratovolcanoes

Glass inclusions in olivine and diopside phenocrysts from pyroclasts of various eruptions of Vesuvius are representative of the magmas that supplied the volcano in the last 4–5000 years. During this interval the volcano alternated between open conduit activity (e.g. 1944 and 1906 eruptions) with long pauses interupted by Plinian and sub-Plinian eruptions (e.g. 3360 B.P. Avellino, A.D. 79 Pompei, A.D. 472 Pollena). The eruptive behaviour was conditioned in all cases by the presence of shallow reservoirs: two cases are distinguished: (1) small and very shallow, 1906-type; (2) large and deeper Plinian-sub-Plinian magma chamber. Lapilli of 1906 lava fountains contain olivine (Fo_89.5–90.4) including Cr-spinel [Cr/(Cr+Al)] (Cr#>75) and volatile-K-rich tephritic glasses, which represent the first recognized Vesuvius primary magmas. Mg-poorer olivine (Fo_83–89) also occurs in 1906 and 1944 products; it formed within the shallow reservoir, together with pyroxene and leucite, between 1200 and 1130°C, from K-tephritic melts (MgO=6–8 wt%). The Plinian and sub-Plinian pumices contain diopside, phlogopite and minor olivine (Fo_85–87) representing adcumulates wrenched from the chamber walls. Glass inclusions in diopside (and some olivine) range from K-basalt to K-tephrite (MgO=6–8 wt%), with homogenization temperature of 1130–1170°C. They have been regarded as representative of the magmas supplying the Plinian-sub-Plinian chamber(s). The Avellino glass inclusions have K-basaltic compositions, contrasting with the mostly K-tephritic Pompei and Pollena inclusions. They display lower C1 and P contents with respect to the younger tephritic melts, and these variations should reflect primary features of the mantle-derived magmas. The primary and the near-primary Vesuvius magmas, as illustrated by melt inclusions, emphasize high K, P and volatile (H₂O, Cl, F, S) contents, with high K₂O/H₂O (2–2.5), Cl/F (2.5) and Cl/S (2–3) ratios, consistent with a metasomatized mantle source, and distinguishing the Vesuvius potassic primary magmas from those of the northern part of the Roman Province.     

A study of bernalite,Fe(OH)3, using Mössbauer spectroscopy,optical spectroscopy and transmission electron microscopy

To study the crystal chemistry of bernalite, Fe(OH)₃, and the nature of the octahedral Fe³⁺ environment, Mössbauer spectra were recorded from 80 to 350 K, optical spectra were recorded at room temperature and a sample was studied using transmission electron microscopy. The Mössbauer spectrum of bernalite consists of a single six-line magnetic spectrum at 80 K. A broadened six-line magnetic spectrum with significantly less intensity is observed at higher temperatures, and is attributed to a small fraction of bernalite occurring as small particles. The variation of hyperfine magnetic field data for bulk bernalite with temperature is well described by the Weiss molecular field model with parameters of H ₀ = 55.7±0.3 T and T _N = 427±5K. The centre shift data were fitted to the Debye model with parameters ₀=0.482±0.005 mm/s (relative to -Fe) and _M=492±30 K. The quadrupole shift is near zero at 300 K, and does not vary significantly with temperature. Absorption spectra in the visible and near infrared range show three crystal field bands of Fe³⁺ at 11 300, 16000 and 23 200 cm^-1, giving a crystal field splitting of 14 570 cm^-1 and Racah parameters of B=629 cm^-1 and C=3381 cm^-1. Infrared reflection spectra show two distinct OH-stretching frequencies, which could correspond to two structurally different types of OH groups. A band was also observed at 2250 cm^-1, suggesting the presence of molecular CO₂ in the large cation site. Analytical transmission electron microscopy indicates that Si occurs within the bernalite structure as well as along domain boundaries. Electron diffraction and imaging show that bernalite is polysynthetically twinned along {100} planes with twin domains ranging from 3 to 20 nm in thickness. Results are discussed with respect to the nature of the octahedral Fe³⁺ site, and compared with values for other iron oxides and hydroxides.     

Oxygen and carbon isotopic study on the genesis of the Steirischer Erzberg siderite deposit (Austria)

The carbon and oxygen isotopic composition of Fe-carbonate ore and its calcitic to dolomitic Devonian host rocks at the Steirischer Erzberg siderite deposit (Greywacke zone, Upper Austroalpine Unit) were determined in order to constrain the source and nature of the Fe-rich mineralizing fluid. The ¹⁸O-values obtained for various Fe-carbonate generations and the carbonate host lie within a similar range between + 14.6 and + 21.6 (V-SMOW). No good correlation exists between the relative ages of the carbonate phases and their O isotopic composition. The variation in ¹⁸O-values is due to metamorphic recrystallization with locally variable fluid/rock ratios. The average ¹³C-value of the carbonate host is +0.5 ± 1.2 (PDB) which corresponds well to worldwide Phanerozoic marine carbonate values. The first Fecarbonate generation has slightly lower ¹³C-values, on average -1.4 ± 0.8 (PDB). Recrystallization of both the carbonate host minerals and the ankerite/siderite led to significantly lower ¹³C-values of -4.2 ± 0.6 and-4.7 ± 0.7, respectively. Within the basal breccia of the post-Hercynian transgression series matrix calcite/ dolomite shows an average ¹³C-value of -2.9 ± 0.7, and matrix siderite/ankerite an average value of-4.1 ± 0.4. These data, together with Sr isotope data published previously, strongly support a late-diagenetic or epigenetic first Fe-mineralization from convecting formation waters. They ascended along extension faults and were driven by an increased heat flow caused by crustal thinning during a Devonian rifting phase that initiated the separation of the Noric terrane from Africa. A potential source of the Fe could have been the underlying Ordovician acid volcanics. Regional metamorphism related to collision tectonics in the Late Carboniferous (Hercynian) and later during the Alpine orogeny, caused intensive recrystallization and partial mobilization of the various carbonate phases.