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’}.     

Memorial landscapes: analytic questions and metaphors

Over the past two decades, geographers have probed the intersection of collective memory and urban space. Their sustained interest in the subject reflects an understanding of the social condition of commemoration and the important role that space plays in the process and politics of collective memory. Along with other critical social scientists, geographers envision these public symbols as part of larger cultural landscapes that reflect and legitimate the normative social order. A review of the extant literature indicates that geographers scrutinize memorial landscapes through three conceptual lenses that may be understood via the metaphors of ‘text,’ ‘arena,’ and ‘performance.’ These metaphors are in turn mobilized through a series of analytic questions that serve to identify the interests served and denied by landscape ‘texts,’ the ‘arenas’ in which they are produced, and the ways in which they are enacted via ‘performance.’ This article’s synopsis of the subfield’s predominant metaphors and its attendant questions contributes to the ongoing cultural geographic project of articulating and implementing methods for interpreting landscapes as open-ended symbolic systems.

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.     

Comparative analyses of East Texas forest cover maps generated from Landsat and AVHRR data

Comparing satellite data derived map products are affected by differences in data characteristics, image acquisition dates, processing techniques, and classification schemes used for assigning pixels to a thematic class. By comparing two forest maps generated from Landsat Enhanced Thematic Mapper Plus (ETM+) and Advanced Very High Resolution Radiometer (AVHRR) images acquired on the same day, and processed using identical classification scheme and methods these differences were minimized. The ETM+ derived map had higher classification accuracy values and more precise area estimates than the AVHRR derived map. In the ETM+ derived map, 87 of the 599 verification data were misclassified, whereas in the AVHRR derived map, 155 of the 469 verification data were misclassified. Detailed error analyses by land cover class revealed that a land use based definition of forest accounted for 74% (64 out of 87) and 57% (89 out of 155) of the classification errors in ETM+ and AVHRR derived maps, respectively.     

Biaxial test simulations using a packing of polygonal particles

The mechanical response of cohesionless granular materials under monotonic loading is studied by performing molecular dynamic simulations. The diversity of shapes of soil grains is modelled by using randomly generated convex polygons as granular particles. Results of the biaxial test obtained for dense and loose media show that samples achieve the same void ratio at large strains independent of their initial density state. This limit state resembles the so‐called critical state of soil mechanics, except for some stress fluctuations, which remain for large deformations. These fluctuations are studied at the micro‐mechanical level, by following the evolution of the co‐ordination number, force chains and the fraction of the sliding contacts of the sample. Copyright © 2007 John Wiley & Sons, Ltd.     

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.     

Geostatistical estimation of chemical contamination in stream sediments: The case study of Vale das Gatas mine (northern Portugal)

Based on an environmental geochemistry case study carried out in the neighbourhood of a W–Sn abandoned mine, the pollution in stream sediments was modelled through a Global Contamination Index. Such an index permits one to summarize the combination of deleterious elements in a single variable, obtained by the projection of samples onto the first axis of a PCASD (Principal Components Analysis of Standardized Data) applied to the entire n × p matrix containing the available concentrations of p = 16 elements in the set of n = 220 collected samples.In order to provide a sound basis for a coherent planning of the remediation process which will be put in operation in the affected area, it is necessary to balance the costs of reclaiming with the probabilities of exceeding the upper limits accepted for concentrations of environmentally harmful elements in sediments. Given these limits, they are back-transformed in the index values, providing a practical threshold between ‘clean’ and ‘contaminated’ samples. On the other hand, the minimum dimension of the cell to be reclaimed is restrained by the selected remediation process to be applied in the affected area. Hence, to meet the constraints of such a remediation process, it is required to estimate the probabilities of exceeding the index threshold in technologically meaningful sub-areas. For this end, the Indicator Block Kriging technique was applied, producing a series of maps where sub-areas to be reclaimed can be spotted for different probability levels. These maps, on which the decision making remediation agency can rely for its cost-benefit analysis, take into account both the spatial structure of ‘clean’ vs. ‘contaminated’ samples and the constraints of the reclaiming process.     

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