Single-crystal electronic absorption spectroscopy of synthetic chromium-, cobalt-, and vanadium-bearing pyropes at different temperatures and pressures     

M. N. Taran  K. Langer  C. A. Geiger 《Physics and Chemistry of Minerals》2002,29(5):362-368

 Single crystals of synthetic vanadium-, chromium- and cobalt-bearing garnets, Pyr:V0.06, Pyr:V0.13, Pyr:Cr0.04, Pyr:Co0.10, and Gt:Co3.00, and a natural vanadium-bearing grossular, Gross:V0.07 (Cr³⁺ < 0.005), were studied by electronic absorption spectroscopy in the wavenumber range 35 000–5000 cm⁻¹ under ambient conditions and at temperatures up to 600 K and pressures up to 8 GPa. The T and P behavior of the absorption band energies and intensities shows the following for the different transition metal-bearing garnets: Cr: The thermal expansion of chromium octahedra are similar to and the Racah parameter the same in synthetic Cr-doped pyrope, α_poly≅ 1.3 × 10⁻⁵ K⁻¹, and in natural pyrope, α_poly≅ 1.5 × 10⁻⁵ K⁻¹, and B=655 cm⁻¹, respectively. Ca^2+[8]-free garnets have a slightly stronger crystal field at the Y^[6] site and, therefore, the energies of the two spin-allowed Cr³⁺ dd bands are ca. 300 cm⁻¹ higher in Mg-pyrope than in natural Ca-bearing pyrope. Co: Increasing temperature causes only a small thermal expansion of the cobalt dodecahedra. Increasing pressure gives rise to appreciable compression, which is similar to that of the Fe²⁺-dodecahedra in almandine, where k=125 ± 25 GPa. T and P dependence of the Co band intensities may be caused by strong spin-orbit coupling. V: Occurs in at least two valence states and structural sites: (1) V³⁺ in octahedral sites gives rise to two spin-allowed bands, at 17 220 cm⁻¹ and 24 600 cm⁻¹, whose temperature dependence is typical for spin-allowed dd transitions in centrosymmetric sites. (2) V⁴⁺, which causes a set of dd absorption bands similar to those observed in the spectrum of V⁴⁺-doped Zr[SiO₄]. The P behavior of the V absorption bands indicates an interaction between V³⁺ and V⁴⁺ species. Received: 27 June 2001 / Accepted: 19 December 2001  相似文献   

Novel prebiotic model systems: interactions of nucleosides and nucleotides with aqueous micellar sodium dodecanoate   总被引：1，自引：0，他引：1  

Joseph Nagyvary  Jack A. Harvey  Faruk Nome  Dan Armstrong  Janos H. Fendler 《Precambrian Research》1976,3(6):509-516

The partition coefficients, K-values, of adenosine, guanosine, cytidine, uridine, 5¹-adenylic acid (AMP), 5¹-guanylic acid (GMP), 5¹-cytidylic acid (CMP), and 5¹-uridylic acid (UMP) between water and aqueous sodium dodecanoate has been determined by gel filtration on Sephadex G-25. Below the critical micelle concentration of the surfactant, K-values for all nucleotides and nucleosides are similar. Differential uptake of the four nucleotides and nucleosides is observed, however, by micellar sodium dodecanoate. K-values for adenosine, AMP; guanosine, GMP; cytidine, CMP; and uridine, UMP are 6.16·10³, 9.52·10³; 12.0·10³, 14.6·10³; 19.6·10³, 19.6·10³, 34.2·10³ and 40.3·10³. Similar K-values for corresponding pairs of nucleotides and nucleosides imply that the predominant interaction is between the pyrimidine or purine rings of the substrates and the charged Stern layer of the surfactant. Prebiotic significance of these results is discussed.  相似文献   

Analysis of central western Europe deformation using GPS and seismic data   总被引：1，自引：0，他引：1  

Magdala Tesauro  Christine Hollenstein  Ramon Egli  Alain Geiger  Hans-Gert Kahle 《Journal of Geodynamics》2006,42(4-5):194-209

The kinematic field of central western Europe is characterized by relatively small movements (around 1–2 mm/year) and diffuse seismicity with earthquakes occurring mostly in the shallow crust (within 15 km), prevalently concentrated along the Alps and the European Cenozoic Rift System (ECRIS). In order to study and constrain the current crustal kinematic field we reconstructed the velocity and the strain field using permanent GPS stations, belonging to different networks (AGNES, EUREF, REGAL, RGP). The 2D strain rate tensor has been calculated using the method of least-squares collocation. Our results show that the area of maximum compression is located along the Alpine chain, where maximum values of 7 ± 2 nstrain/year are found, while maximum extension is measured between the Armorican Massif and the Massif Central, where values of 4 ± 2 nstrain/year are reached.The earthquakes with M > 3.0, have been used to estimate the seismic strain rates, while the style of the seismic deformation was reconstructed from the fault plane solutions (FPS) available from the literature. Relatively high values of seismic strain rates (around 10 nstrain/year) are measured along the Alpine Chain and the ECRIS. Results obtained by geodetic and seismic data are quite in agreement and reflect the different tectonic evolution of the geological features characterizing the area of study. The orientation of the compressional geodetic and seismic strain axes are NW-SE in most of the area of study, on account of the action of plate boundary forces. A rotation of the same axes to N-S direction along the eastern Alps, possibly related to the Adria convergence, is found.  相似文献   

Scenarios for Modeling Multiphase Tropospheric Chemistry     

D. Poppe  B. Aumont  B. Ervens  H. Geiger  H. Herrmann  E.-P. Röth  W. Seidl  W. R. Stockwell  B. Vogel  S. Wagner  D. Weise 《Journal of Atmospheric Chemistry》2001,40(1):77-86

Besides observational data model calculations are a very importanttool for improving our understanding of multiphase chemistryin the troposphere. Before a chemical model can be used for that purposeit is necessary to show that the model does what it is intendedto do. A protocol has been developed thatcan be used as a basis for the verification of the numericsand the correct implementation of thechemical balance equations.The protocol defines meteorological parameters and initial conditionsfor a zerodimensional (box) model. Several scenarios cover the pollutedas well as the remote marine and continental boundary layer and also thefree troposphere. Calculations by different groupswith different modelsand numerical solvers demonstrate that the protocol is clear and complete.The excellent agreement between the results of all groups are a major step of verification of the participating models.The scenarios may also serve as well documented base cases forsensitivity studies.  相似文献   

Scaling of thermodynamic mixing properties in garnet solid solutions     

A. Bosenick  M. T. Dove  V. Heine  C. A. Geiger 《Physics and Chemistry of Minerals》2001,28(3):177-187

 The volumes and enthalpies of mixing, ΔV ^Mix and ΔH ^Mix, of binary solid-solution aluminosilicate garnets have been studied by computer simulation. The use of “average atoms” to simulate solid solution was found to give results that are considerably different from those obtained by calculating and averaging over many configurations of cations at a given composition. Although we expect mineral properties calculated from model calculations to be correct only on a qualitative rather than a quantitative scale, fair agreement with experiment was obtained where carefully tested potential parameters were used. The results show that mixing behaviour in these materials is controlled by local strain and relaxation effects resulting from the atomic size mismatch of the mixing divalent cations. In particular, ΔV ^Mix and ΔH ^Mix are shown to scale quadratically with the volume difference between the end members, and to vary essentially symmetrically with composition, with a moderate dependence on the degree and nature of cation order. We conclude that computer modelling should be useful in providing detailed qualitative information about the mixing properties of solid solutions, which can help to better constrain and interpret experimental results. Received: 8 March 2000 / Accepted: 1 October 2000  相似文献   

Simulation studies on the pyrope-grossular garnet solid solution     

A. Bosenick  M. T. Dove  C. A. Geiger 《Physics and Chemistry of Minerals》2000,27(6):398-418

The local structural response of Ca/Mg substitution and the energetic effects associated with dodecahedral ordering in the pyrope-grossular garnet solid solution are derived from a combination of static lattice energy calculations and Monte Carlo simulations. We start with a thorough analysis of the goodness of the empirical potential models used for the modelling of aluminosilicate garnets. The degree of polyhedral distortion was found to be a sensitive indicator for the quality of the model and, by comparison with experimental data, was used to select the best of several available empirical potentials. The Ca/Mg substitution on the dodecahedral site in garnet was found to produce strong local distortions in the surrounding tetrahedral and octahedral polyhedra. This arises from the absence of rigid unit modes (RUMS) in the garnet structure, because local rotations of otherwise rigid SiO₄ tetrahedra and AlO₆ octahedra cannot occur in order to accommodate different-sized divalent cations in the dodecahedral sites. Strain effects, therefore, mainly govern the dodecahedral substitution, and the corresponding strain field around a dodecahedral site has a minimum radius of 5?Å. Pyrope-grossular solid solution compositions were modelled using a supercell approach. For several garnet compositions many different configurations representing individual disordered arrangements were relaxed. The resulting energies were analyzed in terms of different-neighbour interactions to determine the parameters of a model Hamiltonian. The corresponding interaction energies were found to be virtually independent of composition. Surprisingly, the nearest-neighbour interaction between edge-sharing dodecahedra is of no particular significance in the garnets. Instead, the strongest interaction is only via the third-nearest neighbours, i.e. dodecahedra that are edge-shared to a common SiO₄ tetrahedron. This cannot lead to dodecahedral long-range order in garnets, but can produce significant amounts of short-range order. Monte Carlo simulations were performed on several compositions to determine the macroscopic effects such as NMR-based cluster occupancy, ordering energy and configurational entropy of the short-range ordering process. As expected, the samples tend to random disorder at high temperatures, and at low temperatures it is compositions nearer Py50Gr50 that depart most strongly from random mixing. For example, a maximum reduction of 3.5?J?mol^?1?K^?1 is predicted for Py75Gr25 and ～10?J?mol^?1?K^?1 for Py50Gr50. A comparison of NMR cluster occupancy with experimental ²⁹Si MAS NMR resonance intensity is partly successful. However, the changes in NMR cluster occupancy are relatively low (～5%) compared to changes in configurational entropy (～30%), implying that it might be difficult to estimate exact entropy data from ²⁹Si MAS NMR line intensities.  相似文献   

Low-temperature single-crystal Raman spectrum of pyrope   总被引：1，自引：1，他引：0  

B. A. Kolesov  C. A. Geiger 《Physics and Chemistry of Minerals》2000,27(9):645-649

 The single-crystal polarized Raman spectra of synthetic pyrope, Mg₃Al₂Si₃O₁₂, were measured at room temperature and 5 K, as were the room-temperature unpolarized spectra of two natural pyrope-rich crystals. No major differences in the spectra between room temperature and 5 K are observed or are present between the synthetic and the natural crystals. The spectra are consistent with the proposal that the Mg cation is dynamically disordered and not statically distributed over subsites in the large triangular-dodecahedral E-site in pyrope. A low-energy band at about 135 cm⁻¹ softens and shows a large decrease in its line width with decreasing temperature. The presence of a weak, broad band at about 280 cm⁻¹ may be due to anharmonic effects, as could the one at 135 cm⁻¹. The latter is assigned to the rattling motion of Mg in pyrope in the plane of the longer Mg-O(4) bonds (Kolesov and Geiger 1998). The successful modeling of the anisotropic motion of the Mg cation in pyrope, which has an anharmonic character, provides a valuable test of the validity of empirical or semi-empirical lattice-dynamic calculations for silicates. Received: 10 May 1999 / Accepted: 10 April 2000  相似文献   

Efficient flow and transport simulations in reconstructed 3D pore geometries     

Yan Zaretskiy  Sebastian Geiger  Ken Sorbie  Malte Förster 《Advances in water resources》2010

Upscaling pore-scale processes into macroscopic quantities such as hydrodynamic dispersion is still not a straightforward matter for porous media with complex pore space geometries. Recently it has become possible to obtain very realistic 3D geometries for the pore system of real rocks using either numerical reconstruction or micro-CT measurements. In this work, we present a finite element–finite volume simulation method for modeling single-phase fluid flow and solute transport in experimentally obtained 3D pore geometries. Algebraic multigrid techniques and parallelization allow us to solve the Stokes and advection–diffusion equations on large meshes with several millions of elements. We apply this method in a proof-of-concept study of a digitized Fontainebleau sandstone sample. We use the calculated velocity to simulate pore-scale solute transport and diffusion. From this, we are able to calculate the a priori emergent macroscopic hydrodynamic dispersion coefficient of the porous medium for a given molecular diffusion D_m of the solute species. By performing this calculation at a range of flow rates, we can correctly predict all of the observed flow regimes from diffusion dominated to convection dominated.  相似文献   

CGPS time-series and trajectories of crustal motion along the West Hellenic Arc   总被引：3，自引：0，他引：3  

Ch. Hollenstein  A. Geiger  H.-G. Kahle  G. Veis 《Geophysical Journal International》2006,164(1):182-191

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Water-enhanced dynamic recrystallization and solution transfer in experimentally deformed carnallite     

Janos L. Urai 《Tectonophysics》1985,120(3-4):285-317

Cylindrical samples of polycrystalline carnallite (KMgCl₃, 6H₂O) were deformed in a triaxial apparatus at 60°C, at confining pressures between 0.1 and 31 MPa and at strain rates between 10⁻⁴ and 10⁻⁸ s⁻¹. In a number of cases, small amounts of saturated carnallite brine were added. Samples without added brine deform by intracrystalline slip, mechanical twinning, cracking, and by frictional sliding on crack surfaces. Stress-strain curves of these samples are strongly dependent on confining pressure. Addition of brine has a dramatic effect on both microstructural development and mechanical properties. Grain-boundary migration is strongly enhanced. At lower strain rates, additional intracrystalline effects start to appear, together with the onset of solution transfer. Rapid compaction in samples deformed with added brine causes high fluid pressures to develop. At higher strain rates addition of brine results in a decrease of the flow stress by a factor of two. This weakening will increase even further at strain rates below about 10⁻⁹ s⁻¹, when solution transfer becomes rate controlling. It is argued that deformation of carnallite in nature is adequately described by the flow law found for samples deformed with added brine.  相似文献