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.     

Uncertainties in field-line tracing in the magnetosphere. Part II: the complete internal geomagnetic field

The discussion in the preceding paper is restricted to the uncertainties in magnetic-field-iine tracing in the magnetosphere resulting from published standard errors in the spherical harmonic coefficients that define the axisymmetric part of the internal geomagnetic field (i.e. g_n⁰ ± g_n⁰). Numerical estimates of these uncertainties based on an analytic equation for axisymmetric field lines are in excellent agreement with independent computational estimates based on stepwise numerical integration along magnetic field lines. This comparison confirms the accuracy of the computer program used in the present paper to estimate the uncertainties in magnetic-field-line tracing that arise from published standard errors in the full set of spherical harmonic coefficients, which define the complete (non-axisymmetric) internal geomagnetic field (i.e. g_n^m ± g_n^m and h_n^m ± h_n^m). An algorithm is formulated that greatly reduces the computing time required to estimate these uncertainties in magnetic-field-line tracing. The validity of this algorithm is checked numerically for both the axisymmetric part of the internal geomagnetic field in the general case (1 n 10) and the complete internal geomagnetic field in a restrictive case (0 m n, 1 n 3). On this basis it is assumed that the algorithm can be used with confidence in those cases for which the computing time would otherwise be prohibitively long. For the complete internal geomagnetic field, the maximum characteristic uncertainty in the geocentric distance of a field line that crosses the geomagnetic equator at a nominal dipolar distance of 2 R_E is typically 100 km. The corresponding characteristic uncertainty for a field line that crosses the geomagnetic equator at a nominal dipolar distance of 6 R_E is typically 500 km. Histograms and scatter plots showing the characteristic uncertainties associated with magnetic-field-line tracing in the magnetosphere are presented for a range of illustrative examples. Finally, estimates are given for the maximum uncertainties in the locations of the conjugate points of selected geophysical observatories. Numerical estimates of the uncertainties in magnetic-field-line tracing in the magnetosphere, including the associated uncertainties in thelocations of the conjugate points of geophysical observatories, should be regarded as first approximations in the sense that these estimates are only as accurate as the published standard errors in the full set of spherical harmomic coefficients. As in the preceding paper, howerver, all computational techniques developed in this paper can be used to derive more realistic estimates of the uncertainties in magnetic-field-line tracing in the magnetosphere, following further progress in the determination of more accurate standard errors in the spherical harmonic coefficients.Also Visiting Reader in Physics, University of Sussex, Palmer, Brighton, BN1 9QH, UK     

Sulfur isotope fractionation during bacterial sulfate reduction in organic-rich sediments

Isotope fractionation during sulfate reduction by natural populations of sulfate-reducing bacteria was investigated in the cyanobacterial microbial mats of Solar Lake, Sinai and the sediments of Logten Lagoon sulfuretum, Denmark. Fractionation was measured at different sediment depths, sulfate concentrations, and incubation temperatures. Rates of sulfate reduction varied between 0.1 and 37 micromoles cm-3 d-1, with the highest rates among the highest ever reported from natural sediments. The depletion of 34S during dissimilatory sulfate reduction ranged from 16% to 42%, with the largest 34S-depletions associated with the lowest rates of sulfate reduction and the lowest 34S-depletions with the highest rates. However, at high sulfate reduction rates (>10 micromoles cm-3 d-1) the lowest fractionation was 20% independent of the rates. Overall, there was a similarity between the fractionation obtained by the natural populations of sulfate reducers and previous measurements from pure cultures. This was somewhat surprising given the extremely high rates of sulfate reduction in the experiments. Our results are explained if we conclude that the fractionation was mainly controlled by the specific rate of sulfate reduction (mass cell-1 time-1) and not by the absolute rate (mass volume-1 time-1). Sedimentary sulfides (mainly FeS2) were on average 40% depleted in 34S compared to seawater sulfate. This amount of depletion was more than could be explained by the isotopic fractionations that we measured during bacterial sulfate reduction. Therefore, additional processes contributing to the fractionation of sulfur isotopes in the sediments are indicated. From both Solar Lake and Logten Lagoon we were able to enrich cultures of elemental sulfur-disproportionating bacteria. We suggest that isotope fractionation accompanying elemental sulfur disproportionation contributes to the 34S depletion of sedimentary sulfides at our study sites.     

Paleomagnetism of the Esterel rocks: a revisit 22 years after the thesis of Hans Zijderveld

For his PhD. thesis, Zijderveld (1975) studied the paleomagnetism of the Permian Esterel rocks (southern France). High-quality thermal and alternating-field demagnetization diagrams were interpreted to determine the direction of the characteristic natural magnetization. For the Esterel volcanics, a mean direction of Dec = 206.5°, Inc = –23°, ₉₅ = 5.7°, k = 112 was found for this magnetization. The dispersion in this mean is remarkably low. Only the declination of the Reyran Rhyolite in the Reyran River quarry clearly deviated from this mean. This deviating direction is not found in our samples, taken at the same site. As many faults occur in this quarry, it is suggested that Zijderveld sampled this rhyolite on a small rotated block. To verify whether the small dispersion in the mean paleomagnetic direction of the Esterel rocks has a geomagnetic or a rock-magnetic origin, two conglomerate tests were carried out. One of these might be interpreted as positive. The results of the other conglomerate test (Agay Formation) are ambiguous: four of the six measured boulders show directions close to the mean paleomagnetic direction of the Esterel rocks. Rock-magnetic measurements show that the remanence is carried by a magnetite and a hematite fraction. The low dispersion in the paleomagnetic directions, the conglomerate tests, and hematite as remanence carrier suggest that the characteristic remanence in the Esterel volcanics was not instantaneously acquired during cooling, but might be affected by remagnetization due to weathering.     

Biomass burning in the tropical savannas of Ivory Coast: An overview of the field experiment Fire of Savannas (FOS/DECAFE 91)

FOS/DECAFE 91 (Fire of Savannas/Dynamique et Chimie Atmosphérique en Forêt Equatoriale) was the first multidisciplinary experiment organized in Africa to determine gas and aerosol emissions by prescribed savanna fires. The humid savanna of Lamto in Ivory Coast was chosen for its ecological characteristics representative of savannas with a high biomass density (900 g m^–2 dry matter). Moreover the vegetation and the climate of Lamto have been studied for more than twenty years. The emission ratios (X/CO₂) of the carbon compounds (CO₂, CO, NMHC, CH₄, PAH, organic acids and aerosols), nitrogen compounds (NO_x, N₂O, NH₃ and soluble aerosols) and sulfur compounds (SO₂, COS and aerosols) were experimentally determined by ground and aircraft measurements. To perform this experiment, 4 small plots (100×100 m) and 2 large areas (10×10 km) were prepared and burnt in January 1991 during the period of maximum occurrence of fires in this type of savanna. The detailed ecological study shows that the carbon content of the vegetation is constant within 1% (42 g C for 100 g of vegetal dry matter), the nitrogen content (0.29 g N for 100 g of dry matter) may vary by 10% and the sulfur content (0.05 g S/100 d.m.) by 20%. These variations of the biomass chemical content do not constitute an important factor in the variation of the gas and particle emission levels. With the emission ratios characteristic of humid savanna and flaming conditions (CO/CO₂ of 6.1% at the ground and 8% for airborne measurements), we propose a set of new emission factors, taking into account the burning efficiency which is about 80%: 74.4% of the carbon content of the savanna biomass is released to the atmosphere in the form of CO₂, 4.6% as CO, 0.2% as CH₄, 0.5% as NMHC and 0.7% as aerosols. 17.2% of the nitrogen content of the biomass is released as NO_x, 3.5% as N₂O, 0.6% as NH₃ and 0.5% as soluble aerosols.     

On the bogussing of tropical cyclones in numerical models: A comparison of vortex profiles

Summary At the resolutions currently in use, and with the sparse oceanic data coverage, numerical analyses cannot adequately represent tropical cyclone circulations for use in numerical weather prediction models. In many cases there is no circulation present at all. Most numerical weather prediction centers therefore employ a bogussing scheme to force a tropical cyclone vortex into the numerical analysis. The standard procedure is to define a synthetic data distribution based on an analytically prescribed vortex, which is passed to the analysis scheme as a set of high quality observations.In this study, four commonly used bogus vortices are examined by comparing resultant forecast tracks in an environment at rest, and in a background flow that simulates a typical monsoon trough-subtropical ridge structure. There are three main findings, each of which has significance for operational tropical cyclone track prediction. First, great care is needed in the choice of the characteristics of the bogus vortex, such as the radius and magnitude of the maximum wind. Second, the tropical cyclone trajectories can be very sensitive to their initial position in the idealised environment. Third, the bogus vortex can substantially influence the environment, especially over longer time periods and for vortices of larger size.With 9 Figures     

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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Crustal xenoliths from Calbuco Volcano,Andean Southern Volcanic Zone: implications for crustal composition and magma-crust interaction

Crustal xenoliths in the 1961 andesite flow of Calbuco Volcano, in the southern Southern Volcanic Zone (SSVZ) of the Andes, consist predominantly of pyroxene granulites and hornblende gabbronorites. The granulites contain plagioclase+pyroxene+magnetite±amphibole, and have pronounced granoblastic textures. Small amounts of relict amphibole surrounded by pyroxene-plagioclase-magnetite-glass symplectites are found in some specimens. These and similar textures in the gabbronorites are interpreted as evidence of dehydration melting. Mineral and bulk rock geochemical data indicate that the granulites are derived from an incompatible trace element depleted basaltic protolith that underwent two stages of metamorphism: a moderate pressure, high temperature stage accompanied by melting and melt extraction from some samples, followed by thermal metamorphism after entrainment in the Calbuco andesite lavas. High _Nd ^T values (+4.0 to +8.6), Nd-isotope model ages of 1.7–2.0 Ga, and trace element characteristics like chondrite normalized La/Yb< and La/Nb1 indicate that the protoliths were oceanic basalts. Similar oceanic metabasalts of greenschist to amphibolite facies are found in the Paleozoic metamorphic belt that underlies the Chilean coastal ranges. Mineral and bulk rock compositions of the gabbronorite xenoliths indicate that they are cognate, crystallizing from the basaltic andesite magma at Calbuco. Crystallization pressures for the gabbros based on total Al contents in amphibole are 6–8 kbar. These pressures point to middle to lower crustal storage of the Calbuco magma. Neither granulite nor gabbro xenoliths have the appropriate geochemical characteristics to be contaminants of Calbuco andesites, although an ancient sedimentary contaminant is indicated by the lava compositions. The presence of oceanic metabasaltic xenoliths, together with the sedimentary isotopic imprint, suggests that the lower crust beneath the volcano is analogous to the coastal metamorphic belt, which is an accretionary complex of intercalated basalts and sediments that formed along the Paleozoic Gondwanan margin. If this is the case, the geochemical composition of the lower and middle crust beneath the SSVZ is significantly different from that of most recent SSVZ volcanic rocks.