The Partitioning of Tungsten bwtween Aqueous Fluids and Silicate Melts

An experimental study has been carried out to determine the partition coefficients of tungsten between aqueous fluids and granitic melts at 800 °C and 1.5 kb with natural granite as the starting material. The effects of the solutions on the partition coefficients of tungsten show a sequence of P > CO ₃ ²⁻ > B > H₂O. The effects are limited (generallyK _D < 0.3) and the tungsten shows a preferential trend toward the melt over the aqueous fluid. The value ofK _D increases with increasing concentration of phosphorus; theK _D increases first and then reduces with the concentration of CO ₃ ²⁻ when temperature decreases, theK _D between the solution of CO ₃ ²⁻ and the silicate melt increases, and that between the solution of B₄O ₇ ²⁻ and the silicate melt decreases. The partition coefficients of phosphorus and sodium between fluids and silicate melts have been calculated from the concentrations of the elements in the melts. TheK _D value for phosphorus is 0.38 and that for sodium is 0.56. Evidence shows that the elements tend to become richer and richer in the melts.     

Tracing of water movement through the unsaturated zone of a coarse gravel aquifer by means of dye and deuterated water

To better understand the movement and transport of water and pollution through the coarse gravel unsaturated zone, the presented research was conducted to estimate water flow and transport processes with a tracing experiment in a lysimeter in the Selniška Dobrava. A combined tracing experiment was performed with deuterated water and the fluorescent dye—uranine. The fastest and dominant flow velocities were calculated based on injection time, the first tracer appearance time and the time of highest concentration. Mean flow velocity and vertical dispersion were estimated by an analytical best-fit method using one-dimensional convection–dispersion model. Deuterium was confirmed as an ideal conservative tracer and a more suitable tracer than dye (uranine) for the study of water flow in the unsaturated zone of a coarse gravel aquifer. The retardation factor of the dye as compared with deuterium was 1.13–1.75, which is in agreement with previously published results. Artificial tracers, especially deuterated water, were also identified as a very useful tool to assess other properties and differences in water flow in the unsaturated zone of a coarse gravel aquifer such as velocity and dispersion.     

Cryptic crustal contamination of MORB primitive melts recorded in olivine-hosted glass and mineral inclusions

The origin of compositional heterogeneities among the magmas parental to mid-ocean ridge basalts (MORB) was investigated using a single rock piece of the olivine-phyric basalt from 43°N, Mid-Atlantic Ridge (AII D11-177). The exceptional feature of this sample is presence of very primitive olivine crystals (90–91 mol% Fo) that are significantly variable in terms of CaO (0.15–0.35 wt%). A population of low-Ca olivine (0.15–0.25 wt% CaO) is also notably distinct from high-Ca olivine population in AII D11-177, and primitive MORB olivine in general, in having unusual assemblage of trapped mineral and glass inclusions. Mineral inclusions are represented by high-magnesian (Mg# 90.7–91.1 mol%) orthopyroxene and Cr-spinel, distinctly enriched in TiO₂ (up to 5 wt%, c.f. <1 wt% in common MORB spinel). Glass inclusions associated with orthopyroxene and high-Ti Cr-spinel have andesitic compositions (53–58 wt% SiO₂). Compared to the pillow-rim glass and “normal” MORB inclusions, the Si-rich glass inclusions in low-Ca olivine have strongly reduced Ca and elevated concentrations of Ti, Na, K, P, Cl, and highly incompatible trace elements. Strong variability is recorded among glass inclusions within a single olivine phenocrysts. We argue that the observed compositional anomalies are mineralogically controlled, and thus may arise from the interaction between hot MORB magmas and crystal cumulates in the oceanic crust or magma chamber.     

Raman spectra of methane hydrate up to 86 GPa

High-pressure Raman studies of methane hydrate were performed using a diamond anvil cell in the pressure range of 0.1–86 GPa at room temperature. Raman spectra of the methane molecules revealed that new softened intramolecular vibration mode of ν ₁ appeared at 17 GPa and that the splitting of vibration mode of ν ₃ occurred at 15 GPa. The appearance of these two modes indicates that an intermolecular attractive interaction increases between the methane molecules and the host water molecules and between the neighboring methane molecules. These interactions might result in the exceptional stability of a high-pressure structure, a filled ice Ih structure (FIIhS) for methane hydrate, up to 40 GPa. At 40 GPa, a clear change in the slope of the Raman shift versus pressure occurred, and above 40 GPa the Raman shift of the vibration modes increased monotonously up to 86 GPa. A previous XRD study showed that the FIIhS transformed into another new high-pressure structure at 40 GPa. The change in the Raman spectra at 40 GPa may be induced by the transition of the structure.     

<Superscript>57</Superscript>Fe Mössbauer spectroscopy,X-ray single-crystal diffractometry,and electronic structure calculations on natural alexandrite

Natural alexandrite Al₂BeO₄:Cr from Malyshevo near Terem Tschanka, Sverdlovsk, Ural, Russia, has been characterized by ⁵⁷Fe Mössbauer spectroscopy, electron microprobe, X-ray single-crystal diffractometry and by electronic structure calculations in order to determine oxidation state and location of iron. The sample contains 0.3 wt% of total iron oxide. The ⁵⁷Fe Mössbauer spectrum can be resolved into three doublets. Two of them with hyperfine parameters typical for octahedrally coordinated high-spin Fe³⁺ and Fe²⁺, respectively, are assigned to iron substituting for Al in the octahedral M2-site. The third doublet is attributed to Fe³⁺ in hematite. Electronic structure calculations in the local spin density approximation are in reasonable agreement with experimental data provided that expansion and/or distortion of the coordination octahedra are presumed upon iron substitution. The calculated hyperfine parameters of Fe³⁺ are almost identical for the M1 and M2 positions, but the calculated ligand-field splitting is by far too large for high-spin Fe³⁺ on M1.     

Changing poverty distribution in Bolivia: the role of rural–urban migration and urban services

Bolivia is a country with high levels of poverty and inequality among its peoples and regions. For the nation and its urban and rural areas, trends in the social and spatial distribution of poverty (and extreme poverty) are identified from 1976 to 2003 using UBN data with minor support where appropriate from poverty lines. The main survey between 1992 and 2001 uses composite and selected UBN to track detailed poverty change for the country’s nine departments, its ten largest cities and a selection of other smaller urban and rural municipalities. Because of rising background increases in population in the various surveyed administrative units, many instances of relative reductions in poverty are accompanied by rising absolute increases. Marked spatial variations in poverty and development in the country over the last several decades are identified as the main driver for the country’s quickening pace of rural–urban migration. As a result, the paper concludes by assessing two different but closely related views. One investigation tests the notion that because more poor people have been living in Bolivia’s cities than in its rural areas since the mid to late 1990s, rapid rural–urban migration has simply shifted the locus of poverty from the countryside to the cities in a process called, the ‘urbanisation of poverty.’ A second, more challenging, investigation assesses the view that the flow of poor rural people to the better serviced urban areas of Bolivia has actually acted to alleviate national poverty levels.     

A powder neutron diffraction study of the crystal structure of the fluoroperovskite NaMgF<Subscript>3</Subscript> (neighborite) from 300 to 3.6 K

The cell dimensions and crystal structures of the fluoroperovskite NaMgF₃ (neighborite), synthesized by solid state methods, have been determined by powder neutron diffraction and Rietveld refinement over the temperature range 300–3.6 K using Pt metal as an internal standard for calibration of the neutron wavelength. These data show that Pbnm NaMgF₃ does not undergo any phase transitions to structures of lower symmetry with decreasing temperature. The cell dimensions and atomic coordinates together with polyhedron volumes and distortion indices are given for Pbnm NaMgF₃ at 25 K intervals from 300 to 3.6 K. Decreases in the a and c cell dimensions reach a saturation point at 50 K, whereas the b dimension becomes saturated at 150 K. The distortion of the structure of Pbnm NaMgF₃ from the aristotype cubic structure is described in terms of the tilting of the MgF₆ octahedra according to the tilt scheme a ⁻ a ⁻ c ⁺ . With decreasing temperature the antiphase tilt (a ⁻) increases from 14.24° to 15.39°, whereas the in-phase tilt (c ⁺ ) remains effectively constant at ∼10.7°. Changes in the tilt angles are insufficient to cause changes in the coordination sphere of Na that might induce a low temperature phase transition. The structure of Pbnm NaMgF₃ is also described in terms of normal mode analysis and displacements of the condensed normal modes are compared with those of Pbnm KCaF₃.     

XMCD at Fe L<Subscript>2,3</Subscript> edges,Fe and S K edges on Fe<Subscript>7</Subscript>S<Subscript>8</Subscript>

Pyrrhotite (Fe₇S₈) is a natural iron sulphide that can participate in rock magnetisation. Its electronic structure is not yet surely described. X-ray magnetic circular dichroism (XMCD) at Fe L_2,3 edges on Fe₇S₈, coupled with multiplet calculations, shows that iron is present only as Fe²⁺ in this magnetic iron sulphide. It reveals a strong magnetic orbital moment. XMCD at Fe and S K edges shows the quite strong polarization of both Fe and S in Fe₇S₈.     

Graben width controlling syn-rift sedimentation: the Palaeogene southern Upper Rhine Graben as an example

Eocene to Early Oligocene syn-rift deposits of the southern Upper Rhine Graben (URG) accumulated in restricted environments. Sedimentation was controlled by local clastic supply from the graben flanks, as well as by strong intra-basinal variations in accommodation space due to differential tectonic subsidence, that in turn led to pronounced lateral variations in depositional environment. Three large-scale cycles of intensified evaporite sedimentation were interrupted by temporary changes towards brackish or freshwater conditions. They form three major base level cycles that can be traced throughout the basin, each of them representing a stratigraphic sub-unit. A relatively constant amount of horizontal extension (ΔL) in the range of 4–5 km has been estimated for the URG from numerous cross-sections. The width of the rift (L _f ), however, varies between 35 and more than 60 km, resulting in a variable crustal stretching factor between the bounding masterfaults. Apart from block tilting, tectonic subsidence was, therefore, largely controlled by changes in the initial rift width (L ₀). The along-strike variations of the graben width are responsible for the development of a deep, trough-like evaporite basin (Potash Basin) in the narrowest part of the southern URG, adjacent to shallow areas in the wider parts of the rift such as the Colmar Swell in the north and the Rhine Bresse Transfer Zone that delimits the URG to the south. Under a constant amount of extension, the along-strike variation in rift width is the principal factor controlling depo-centre development in extensional basins.