Si diffusion in zircon

Self-diffusion of Si under anhydrous conditions at 1 atm has been measured in natural zircon. The source of diffusant for experiments was a mixture of ZrO₂ and ³⁰Si-enriched SiO₂ in 1:1 molar proportions; experiments were run in crimped Pt capsules in 1-atm furnaces. ³⁰Si profiles were measured with both Rutherford backscattering spectrometry (RBS) and nuclear reaction analysis with the resonant nuclear reaction ³⁰Si(p,γ)³¹P. For Si diffusion normal to c over the temperature range 1,350–1,550°C, we obtain an Arrhenius relation D = 5.8 exp(−702 ± 54 kJ mol⁻¹/RT) m² s⁻¹ for the NRA measurements, which agrees within uncertainty with an Arrhenius relation determined from the RBS measurements [62 exp(−738 ± 61 kJ mol⁻¹/RT) m² s⁻¹]. Diffusion of Si parallel to c appears slightly faster, but agrees within experimental uncertainty at most temperatures with diffusivities for Si normal to c. Diffusion of Si in zircon is similar to that of Ti, but about an order of magnitude faster than diffusion of Hf and two orders of magnitude faster than diffusion of U and Th. Si diffusion is, however, many orders of magnitude slower than oxygen diffusion under both dry and hydrothermal conditions, with the difference increasing with decreasing temperature because of the larger activation energy for Si diffusion. If we consider Hf as a proxy for Zr, given its similar charge and size, we can rank the diffusivities of the major constituents in zircon as follows: D _Zr < D _Si << D _{O, dry} < D _{O, ‘wet’}.     

Room-temperature equation of state of Li<Subscript>2</Subscript>VOSiO<Subscript>4</Subscript> up to 8.5 GPa

High-pressure single-crystal X-ray diffraction measurements of lattice parameters of the compound Li₂VOSiO₄, which crystallises with a natisite-type structure, has been carried out to a pressure of 8.54(5) GPa at room temperature. Unit-cell volume data were fitted with a second-order Birch-Murnaghan EoS (BM-EoS), simultaneously refining V ₀ and K ₀ using the data weighted by the uncertainties in V. The bulk modulus is K ₀ = 99(1) GPa, with K′ fixed to 4. Refinements of third order equations-of-state yielded values of K′ that did not differ significantly from 4. The compressibility of the unit-cell is strongly anisotropic with the c axis (K ₀(c) = 49.7 ± 0.5 GPa) approximately four times more compressible than the a axis (K ₀(a) = 195 ± 3 GPa).     

The effects of gas flaring on crops in the Niger Delta,Nigeria

Flaring of associated gas from oil exploitation has several consequences on the environment. This study explores the spatial variability effects of gas flaring on the growth and development of cassava (Manihot esculenta), waterleaf (Talinum triangulare), and pepper (Piper spp.) crops commonly cultivated in the Niger Delta, Nigeria. Data was collected on soil and atmospheric temperature and moisture at a 20-m interval, starting at 40 m from the flare point to a distance of 140 m. Lengths and widths of crop leaves, height of crop plants and cassava yields were measured at the specified distances. The amino acid, ascorbic acid, starch, and sugar constituents of the cassava yields were determined. The results suggest that a spatial gradient exists in the effects of gas flares on crop development. Retardation in crop development manifests in decreased dimensions of leaf lengths and widths of cassava and pepper crops closer to the gas flare point. Statistical analysis also confirms that cassava yields are higher at locations further away from the flare point. In addition, the amount of starch and ascorbic acid in cassava decreased when the plant is grown closer to the gas flare. High temperatures around the gas flare appear to be the most likely cause of this retardation. The waterleaf crop, on the other hand, appears to thrive better around the gas flare point.     

Structural investigation of the synthetic CaAn(PO4)2 (An = Th and Np) cheralite-like phosphates

The crystallographic structures of the synthetic cheralite, CaTh(PO₄)₂, and its homolog CaNp(PO₄)₂ have been investigated by X-ray diffraction at room temperature. Rietveld analyses showed that both compounds crystallize in the monoclinic system and are isostructural to monazite LnPO₄ (Ln = La to Gd). The space group is P2₁/n (I.T. = 14) with Z = 2. The refined lattice parameters of CaTh(PO₄)₂ are a = 6.7085(8) Å, b = 6.9160(6) Å, c = 6.4152(6) Å, and β = 103.71(1)° with best fit parameters R _wp = 4.87%, R _p = 3.69% and R _B = 3.99%. For CaNp(PO₄)₂, we obtained a = 6.6509(5) Å, b = 6.8390(3) Å, c = 6.3537(8) Å, and β = 104.12(6)° and R _wp = 6.74%, R _p = 5.23%, and R _B = 6.05%. The results indicate significant distortions of bond length and angles of the PO₄ tetrahedra in CaTh(PO₄)₂ and to a lesser extent in CaNp(PO₄)₂. The structural distortions were confirmed by Raman spectroscopy of CaTh(PO₄)₂. A comparison with the isostructural compounds LnPO₄ (Ln = Ce and Sm) confirmed that the substitution of the large rare earth trivalent cations with Ca²⁺ and Th⁴⁺ introduces a distortion of the PO₄ tetrahedra.     

The spatial implications of the functional proximity deriving from air passenger flows between European metropolitan urban regions

Until recently the traditional spatial configuration of the European geography was based upon the core-periphery model. The ‘pentagon’, broadly defined as lying between London, Paris, Milan, Munich and Hamburg, was seen as the core area characterised by having the highest concentration of economic development in the European Union (EU), with the remainder of the European territory viewed as peripheral, albeit to varying degrees. In a number of cases such peripheral areas equated with clear regional disparities. The elaboration of the European Spatial Development Perspective (ESDP) (CEC, European spatial development perspective, towards balanced and sustainable development in the territory of the European Union, 1999) challenged this core-periphery model. European spatial planning policies, aimed at encouraging social and economic, and with ever increasing importance, territorial cohesion, seek amongst other aspects to encourage the development of a balanced and polycentric urban system. This paper adopts a network analysis approach to the analysis of air passenger flows between some 28 principal European metropolitan urban regions. The evaluation of these flows contributes to an enhanced comprehension of the spatial dynamics of the European metropolitan territory which goes beyond that deriving from the more standard analyses of the individual components of the urban system. Several indicators are used, deriving from gravitational modelling techniques, to analyse the complexity of the air passenger flows. A multidimensional scaling (MDS) technique is introduced in order to interpret and visualise the resulting spatial configuration and positioning of the different metropolitan centres within the conceptual European ‘space of air passenger flows’, thereby contrasting with the more traditional map-based geographical image of Europe, based upon Cartesian coordinates.

The effect of naturally acidified irrigation water on agricultural volcanic soils. The case of Asembagus, Java, Indonesia

Acid water from the Banyuputih river (pH  3.5) is used for the irrigation of agricultural land in the Asembagus coastal area (East Java, Indonesia), with harmful consequences for rice yields. The river water has an unusual composition which is caused by seepage from the acidic Kawah Ijen crater lake into the river. This unique irrigation setting allows the study of soil acidification in situ. This paper assesses the effects of volcanogenically contaminated irrigation water on the chemical properties of the agricultural soils.The changes in soil properties were evaluated by comparing samples taken from the topsoil and sub-soil (1–3 m depth) from areas irrigated with acid water and areas irrigated with neutral water. The field survey thus resulted in four soil categories. Bulk soil composition, organic matter content, moisture content and particle size distribution were determined. Reactive phases were quantified with the selective extractions 1 M KCl, 0.1 M Na-pyrophosphate and 0.2 M acid ammonium oxalate (AAO).By comparing the four soil categories it is shown that the use of the naturally polluted irrigation water has had a large influence on the chemical composition of the topsoil. The composition of the soil solution has changed over the entire investigated soil profile. Furthermore the acid irrigation water has strongly modified the composition of the reactive phases, extracted as KCl, pyrophosphate, and AAO extractable elements, and also the bulk soil composition has been significantly modified. Overall this has resulted in the net dissolution of some elements and the net precipitation of others. The changes in the reactive phases and bulk soil composition are only apparent in the topsoil (0–20 cm) but not in the deeper soil.     

Pervasive wetland flooding in the glacial drift prairie of North Dakota (USA)

This article describes a unique flood hazard, produced by the dramatic expansion of wetlands in Nelson County, located within the North American Prairie Pothole Region of North Dakota, USA. There has been an unprecedented increase in the number, average size, and permanence of prairie wetlands, and a significant increase in the size of a closed lake (Stump Lake) due to a decade-long wet spell that began in 1993 following a prolonged drying trend. Base-line land cover information from the 1992 USGS National Land Cover Characterization dataset, and a Landsat TM scene acquired 9 July 2001 are used to assess the growth of the closed lake and wetland pond surface areas, and to analyze the type and area of various land cover classes inundated between 1992 and 2001. The open water profile in Nelson County changed from one marked by relatively comparable coverage of closed lake and wetland pond areas in 1992, to one in which wetland open water accounted for the vast majority of total open water in 2001. The bulk of the wetland pond area expansion occurred by displacing existing wetland vegetation and agricultural cropland. Producers responded to the flood hazard by filing Federal Crop Insurance Corporation (FCIC) claims and enrolling cropland in the Conservation Reserve Program (CRP), a federal land retirement program. Land taken out of agricultural production has had an enormous impact upon the agricultural sector that forms the economic base of the rural economy. In 2001 the land taken out of production due to CRP enrollment and preventive planting claims represented nearly 42% of Nelson County’s 205.2 K ha base agricultural land. The patterns obtained from this detailed study of Nelson County are likely to be the representative of the more publicized flood disaster occurring within the Devils Lake Basin of North Dakota.     

Mineralogy and geochemistry of El Dorado epithermal gold deposit, El Sauce district, central-northern Chile

Summary The El Dorado Au-Cu deposit is located in an extensive intra-caldera zone of hydrothermal alteration affecting Upper Cretaceous andesites of the Los Elquinos Formation at La Serena (≈ 29°47′S Lat., 70°43′W Long., Chile). Quartz-sulfide veins of economic potential are hosted by N25W and N20E fault structures associated with quartz-illite alteration (+supergene kaolinite). The main ore minerals in the deposit are pyrite, chalcopyrite ± fahlore (As/(As + Sb): 0.06−0.98), with electrum, sphalerite, galena, bournonite-seligmanite (As/(As + Sb): 0.21−0.31), marcasite, pyrrhotite being accessory phases. Electrum, with an Ag content between 32 and 37 at.%, occurs interstitial to pyrite aggregates or along pyrite fractures. Pyrite commonly exhibits chemical zonation with some zones up to 1.96 at.% As. Electron probe microanalyses of pyrite indicate that As-rich zones do not exhibit detectable Au values. Fluid inclusion microthermometry shows homogenization temperatures between 130 and 352 °C and salinities between 1.6 and 6.9 wt.% NaCl eq. Isotope data for quartz, ankerite and phyllosilicates and estimated temperatures show that δ¹⁸O and δD for the hydrothermal fluids were between 3 and 10‰ and between −95 and −75‰, respectively. These results suggest the mineralizing fluids were a mixture of meteoric and magmatic waters. An epithermal intermediate-sulfidation model is proposed for the formation of the El Dorado deposit. Author’s present address: J. Carrillo-Rosúa, Dpto. de Didáctica de las Ciencias Experimentales, Universidad de Granada, Campus de Cartuja, 18071, Granada, Spain     

Boron incorporation into mullite

Summary Boron-doped mullites were synthesized using aluminium nitrate-nonahydrate, tetraethoxysilane and boric acid in a sol–gel process with subsequent annealing at 950 and 1300 °C for five hours. Two different bulk compositions with constant Al₂O₃ contents (60 and 70 mol%, respectively) and varying SiO₂ plus B₂O₃ contents were investigated. X-ray powder diffraction analyses yielded a linear decrease of the lattice parameters with increasing bulk B₂O₃ content, which was interpreted as to be due to boron incorporation. Related to the increasing boron content, corresponding infrared spectra revealed a slight and continuous shift for most of the absorption bands. These data show that mullite is able to incorporate large amounts of boron into its structure (up to about 20 mol% B₂O₃ depending on the bulk composition of the starting materials). Infrared analyses suggest that boron is incorporated into the mullite structure in form of planar three-fold coordinated BO₃ groups. Author’s address: A. Beran, Institut für Mineralogie und Kristallographie, Universit?t Wien-Geozentrum, Althanstra?e 14, 1090 Wien, Austria