A temperature dependent X-ray Absorption Fine Structure study of dynamic X-site disorder in almandine: a comparison to diffraction data

X-ray Absorption Fine-Structure (XAFS) measurements in the temperature range 20-473K at the Fe K-edge of synthetic almandine (Fe₃Al₂Si₃O₁₂) allow us to determine the temperature dependence of the XAFS Debye-Waller (DW) factors for each of the two crystallographically independent Fe?O bond distances (Fe(1)?O and Fe(2)?O). The vibrational anisotropy of Fe²⁺ in the dodecahedral X-site has been documented. The XAFS DW factor of the longer Fe(2)?O bond is larger and has a greater T-dependence than the shorter Fe(1)?O bond, which remains constant over the measured T range. The XAFS DW factors are compared with the uncorrelated part of the DW factors derived from a single-crystal X-ray diffraction (XRD) study on almandine and are interpreted on the basis of the Einstein model. A comparison with diffraction data shows that the shorter Fe(1)–O bond is significantly affected by correlation in the atomic displacements.     

Continuous GPS and broad-scale deformation across the Rhine Graben and the Alps

In order to study the ongoing tectonic deformation in the Rhine Graben area, we reconstruct the local crustal velocity and the strain rate field from GPS array solutions. Following the aim of this work, we compile the velocities of permanent GPS stations belonging to various networks (EUREF, AGNES, REGAL and RGP) in central western Europe. Moreover, the strain rate field is displayed in terms of principal axes and values, while the normal and the shear components of the strain tensor are calculated perpendicular and parallel to the strike of major faults. The results are compared with the fault plane solutions of earthquakes, which have occurred in this area. A broad-scale kinematic deformation model across the Rhine Graben is provided on the basis of tectonics and velocity results of the GPS permanent stations. The area of study is divided into four rigid blocks, between which there might be relative motions. The velocity and the strain rate fields are reconstructed along their borders, by estimating a uniform rotation for each block. The tectonic behaviour is well represented by the four-block model in the Rhine Graben area, while a more detailed model will be needed for a better reconstruction of the strain field in the Alpine region.

Analysis of small-scale heterogeneity in clastic rocks by using computerized X-ray tomography (CT)

The aim of this study is to recognize the basic clastic rock types on the basis of Hounsfield Units (HUs) by using statistical methods (hypothesis tests, distribution fitting, and confidence intervals). How does this recognition depend on depositional history of samples tested? Does the numerical pattern of HUs obtained from small-scale analyzing of some particular sedimentary structures coincide to the textural expectations of those sedimentary structures? Are the HU values provided by the CT measurements capable of evidencing micro-cycles belonging to a particular depositional history?For testing the numerical recognition, we analyze macroscopically homogeneous argillaceous marl, siltstone and fine sandstone samples with similar depositional background, age, and degree of diagenesis. The preliminary research shows that the Hounsfield Units can identify different sedimentary rocks considerably well. There are significant differences among the confidence intervals belonging to the different rock types. However, there also have been some slight overlaps among them.For analyzing the effects of the depositional processes in case of a particular rock type, samples from channel sandstone, distributary mouth-bar, massive (structureless) sandstone from a delta-fed turbidity fan, and channel sandstone with traction carpet origin from a delta-fed turbidity fan (all coming from Pannonian basin filling series) are used. The results prove again the significant differences in the terms of both confidence intervals and distribution-types; however, some overlapping also occurs.     

Tropospheric refractivity and zenith path delays from least-squares collocation of meteorological and GNSS data

Precise positioning requires an accurate a priori troposphere model to enhance the solution quality. Several empirical models are available, but they may not properly characterize the state of troposphere, especially in severe weather conditions. Another possible solution is to use regional troposphere models based on real-time or near-real time measurements. In this study, we present the total refractivity and zenith total delay (ZTD) models based on a numerical weather prediction (NWP) model, Global Navigation Satellite System (GNSS) data and ground-based meteorological observations. We reconstruct the total refractivity profiles over the western part of Switzerland and the total refractivity profiles as well as ZTDs over Poland using the least-squares collocation software COMEDIE (Collocation of Meteorological Data for Interpretation and Estimation of Tropospheric Pathdelays) developed at ETH Zürich. In these two case studies, profiles of the total refractivity and ZTDs are calculated from different data sets. For Switzerland, the data set with the best agreement with the reference radiosonde (RS) measurements is the combination of ground-based meteorological observations and GNSS ZTDs. Introducing the horizontal gradients does not improve the vertical interpolation, and results in slightly larger biases and standard deviations. For Poland, the data set based on meteorological parameters from the NWP Weather Research and Forecasting (WRF) model and from a combination of the NWP model and GNSS ZTDs shows the best agreement with the reference RS data. In terms of ZTD, the combined NWP-GNSS observations and GNSS-only data set exhibit the best accuracy with an average bias (from all stations) of 3.7 mm and average standard deviations of 17.0 mm w.r.t. the reference GNSS stations.     

Local structural heterogeneity in garnet solid solutions

Local heterogeneities in pyrope-almandine, almandine-grossular and pyrope-grossular solid solutions have been investigated using IR-powder absorption spectroscopy. Correlations of the wavenumber shifts and line broadening systematics with the thermodynamic mixing properties were found. Wavenumber shifts of the highest energy modes correlate closely with the Si-O bond distances and give an indirect view of the average distortions across the three solid solutions. They have a linear behaviour for Py-Alm, but show positive variations from linearity for Alm-Gr and Py-Gr systems. An effective line width (Δ_corr) of the absorption bands over a given wavenumber interval was obtained using the autocorrelation function. Line broadening is associated with local heterogeneities arising from cation substitution in the structure of samples at intermediate compositions. Non-linearities of the line broadening were found for Alm-Gr and Py-Gr and have a shape similar to the enthalpy of mixing, ΔH_mix. An empirical analysis was therefore carried out to compare ΔH_mix and Δ_corr quantitatively. Low-temperature far-IR spectra were recorded for the end-members pyrope, almandine and grossular and far-IR and mid-IR low-temperature spectra for Py₆₀Gr₄₀ in the temperature range 292–44 K. Softening of the lowest energy band with decreasing temperature was observed in the spectrum of pyrope and more enhanced in the spectrum of Py₆₀Gr₄₀. The same softening occurs by substitution of grossular component into pyrope. High energy modes of Py₆₀Gr₄₀ show the effect of saturation below 110–130 K, which correlates with the volume saturation at low temperature. This could provide an alternative explanation for the heat capacity anomaly found for Py-Gr solid solution at low-temperatures.     

Finite prandtl number convection in spherical shells

Abstract

Finite amplitude convection in spherical shells with spherically symmetric gravity and heat source distribution is considered. The nonlinear problem of three-dimensional convection in shells with stress-free and isothermal boundaries is solved by expanding the dependent variables in terms of powers of the amplitude of convection. The preferred mode of convection is determined by a stability analysis in which arbitrary infinitesimal disturbances are superimposed on the steady solutions. The shell is assumed to be thick and only shells for which the ratio ζ of outer radius to inner radius is 2 or 3 are considered. Three cases, two of which lead to a self adjoint problem, are treated in this paper. The stable solutions are found to be l=2 modes for ζ=3 where l is the degree of the spherical harmonics and an l=3 non-axisymmetric mode which exhibits the symmetry of a tetrahedron for ζ=2. These stable solutions transport the maximum amount of heat. The Prandtl number dependence of the heat transport is computed for the various solutions analyzed in the paper.     

Exponential time integrators for stochastic partial differential equations in 3D reservoir simulation

The transport of chemically reactive solutes (e.g. surfactants, CO₂ or dissolved minerals) is of fundamental importance to a wide range of applications in oil and gas reservoirs such as enhanced oil recovery and mineral scale formation. In this work, we investigate exponential time integrators, in conjunction with an upwind weighted finite volume discretisation in space, for the efficient and accurate simulation of advection–dispersion processes including non-linear chemical reactions in highly heterogeneous 3D oil reservoirs. We model sub-grid fluctuations in transport velocities and uncertainty in the reaction term by writing the advection–dispersion–reaction equation as a stochastic partial differential equation with multiplicative noise. The exponential integrators are based on the variation of constants solution and solve the linear system exactly. While this is at the expense of computing the exponential of the stiff matrix representing the finite volume discretisation, the use of real Léja point or the Krylov subspace technique to approximate the exponential makes these methods competitive compared to standard finite difference-based time integrators. For the deterministic system, we investigate two exponential time integrators, the second-order accurate exponential Euler midpoint (EEM) scheme and exponential time differencing of order one (ETD1). All our numerical examples demonstrate that our methods can compete in terms of efficiency and accuracy compared with standard first-order semi-implicit time integrators when solving (stochastic) partial differential equations that model mixing and chemical reactions in 3D heterogeneous porous media. Our results suggest that exponential time integrators such as the ETD1 and EEM schemes could be applied to typical 3D reservoir models comprising tens to hundreds of thousands unknowns.     

The orientation and vibrational states of H2O in synthetic alkali-free beryl

 The polarized single-crystal Raman spectra of synthetic H₂O-containing alkali-free beryl were recorded at room and low temperatures, and the polarized single-crystal IR spectra at room temperature. The H₂O molecule in the channel cavities is characterized by a Raman-active symmetric stretching vibration (ν₁) at 3607 cm⁻¹ and an IR-active asymmetric stretch (ν₃) at 3700 cm⁻¹ at room temperature. At low temperatures this ν₃ mode is observed in the Raman. Weak ν₁ and ν₃ modes of a second type of H₂O are also observed in the Raman spectra but only at 5 K. The H⋯·H vector of the most abundant type of H₂O is parallel to the channel axis of beryl along [0 0 0 1]. The components of the polarizability tensor of the ν₁ mode of H₂O are similar to, but not exactly the same as, those of a free H₂O molecule. The Raman measurements indicate that the H₂O molecule is rotationally disordered around [0 0 0 1]. External translation and librational modes of H₂O could be observed as overtones with the internal H₂O-stretching modes. In the case of the librational motions, normal modes could also be observed directly in the Raman spectra at ∼200 cm⁻¹. The energies of the translational modes can be determined from an analysis of the overtones and are about 9 cm⁻¹ in energy (i.e., T_z). The energies of the librational modes are about 210 cm⁻¹ for R_x and 190 cm⁻¹ for R_y. Received: 8 April 1999 / Accepted: 5 April 2000     

Meteorites from the Sahara: Find locations,shock classification,degree of weathering and pairing

Abstract— The Sahara is an extraordinary area for recovering meteorites. Between 1989 and 1993, 471 meteorites were collected in Algeria and Libya. Studies of 465 samples have been done. In addition to the classifications of the meteorites that were published in various “Meteoritical Bulletins” in past years, we present here the results on the determination of the shock metamorphism and the degree of weathering. Also, we have tried to solve the pairing problem by considering the find locations, the degree of shock metamorphism, the degree of weathering, and the mineral compositions of olivine and pyroxene. A comprehensive table listing all samples contains references about previous work on these meteorites.