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The unit-cell dimensions and crystal structure of sillimanite at various pressures up to 5.29 GPa have been refined from single-crystal X-ray diffraction data. As pressure increases, a and b decrease linearly, whereas c decreases nonlinearly with a slightly positive curvature. The axial compression ratios at room pressure are βabc=1.22:1.63:1.00. Sillimanite exhibits the least compressibility along c, but the least thermal expansivity along a (Skinner et al. 1961; Winter and Ghose 1979). The bulk modulus of sillimanite is 171(1) GPa with K′=4 (3), larger than that of andalusite (151 GPa), but smaller than that of kyanite (193 GPa). The bulk moduli of the [Al1O6], [Al2O4], and [SiO4] polyhedra are 162(8), 269(33), and 367(89) GPa, respectively. Comparison of high-pressure data for Al2SiO5 polymorphs reveals that the [SiO4] tetrahedra are the most rigid units in all these polymorphic structures, whereas the [AlO6] octahedra are most compressible. Furthermore, [AlO6] octahedral compressibilities decrease from kyanite to sillimanite, to andalusite, the same order as their bulk moduli, suggesting that [AlO6] octahedra control the compression of the Al2SiO5 polymorphs. The compression of the [Al1O6] octahedron in sillimanite is anisotropic with the longest Al1-OD bond shortening by ~1.9% between room pressure and 5.29 GPa and the shortest Al1-OB bond by only 0.3%. The compression anisotropy of sillimanite is primarily a consequence of its topological anisotropy, coupled with the compression anisotropy of the Al-O bonds within the [Al1O6] octahedron.  相似文献   
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Relative compressibilities of five silicate garnets were determined by single-crystal x-ray diffraction on crystals grouped in the same high-pressure mount. The specimens include a natural pyrope [(Mg2.84Fe0.10Ca0,06) Al2Si3O12], and four synthetic specimens with octahedrally-coordinated silicon: majorite [Mg3(MgSi)Si3O12], calcium-bearing majorite [(Ca0.49Mg2.51)(MgSi)Si3012], sodium majorite [(Na1.88Mgp0.12)(Mg0.06Si1.94)Si3O12], and an intermediate composition [(Na0.37Mg2.48)(Mg0.13Al1.07 Si080) Si3O12]. Small differences in the compressibilities of these crystals are revealed because they are subjected simultaneously to the same pressure. Bulk-moduli of the garnets range from 164.8 ± 2.3 GPa for calcium majorite to 191.5 ± 2.5 GPa for sodium majorite, assuming K′=4. Two factors, molar volume and octahedral cation valence, appear to control garnet compression.  相似文献   
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High-pressure crystal structures and compressibilities have been determined by x-ray methods for MgAl2O4 spinel and its isomorph magnetite, Fe3O4. The measured bulk moduli, K, of spinel and magnetite (assuming K′=4) are 1.94±0.06 and 1.86±0.05 Mbar, respectively, in accord with previous ultrasonic determinations. The oxygen u parameter, the only variable atomic position coordinate in the spinel structure (Fd3m, Z=8), decreases with pressure in MgAl2O4, thus indicating that the magnesium tetrahedron is more compressible than the aluminum octahedron. In magnetite the u parameter is unchanged, and both tetrahedron and octahedron display the 1.9 Mbar bulk modulus characteristic of the entire crystal. This behavior contrasts with that of nickel silicate spinel (γ-Ni2SiO4), in which the u parameter increases with pressure because the silicon tetrahedron is relatively incompressible compared to the nickel octahedron.  相似文献   
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The abiotic polymerization of amino acids may have been important for the origin of life, as peptides may have been components of the first self-replicating systems. Though amino acid concentrations in the primitive oceans may have been too dilute for significant oligomerization to occur, mineral surface adsorption may have provided a concentration mechanism. As unactivated amino acid polymerization is thermodynamically unfavorable and kinetically slow in aqueous solution, we studied mainly the reverse reaction of polymer degradation to measure the impact of mineral surface catalysis on peptide bonds.Aqueous glycine (G), diglycine (GG), diketopiperazine (DKP), and triglycine (GGG) were reacted with minerals (calcite, hematite, montmorillonite, pyrite, rutile, or amorphous silica) in the presence of 0.05 M, pH 8.1, KHCO3 buffer and 0.1 M NaCl as background electrolyte in a thermostatted oven at 25, 50 or 70 °C. Below 70 °C, reaction kinetics were too sluggish to detect catalytic activity over amenable laboratory time-scales. Minerals were not found to have measurable effects on the degradation or elongation of G, GG or DKP at 70 °C in solution. At 70 °C pyrite was the most catalytic mineral with detectible effects on the degradation of GGG, although several others also displayed catalytic behavior. GGG degraded ∼1.5-4 times faster in the presence of pyrite than in control reactions, depending on the ratio of solution concentration to mineral surface area. The rate of pyrite catalysis of GGG hydrolysis was found to be saturable, suggesting the presence of discrete catalytic sites on the mineral surface. The mineral-catalyzed degradation of GGG appears to occur via a GGG → DKP + G mechanism, rather than via GGG → GG + G, as in solution-phase reactions. These results are compatible with many previous findings and suggest that minerals may have assisted in peptide synthesis in certain geological settings, specifically by speeding the approach to equilibrium in environments where amino acids were already highly concentrated, but that minerals may not significantly alter the expected solution-phase equilibria. Thus the abiotic synthesis of long peptides may have required activating agents, dry heating at higher temperatures, or some form of phase separation.  相似文献   
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This study examined the application of slim-hole nuclear magnetic resonance (NMR) tools to estimate hydraulic conductivity (KNMR) in an unconsolidated aquifer that contains a range of grain sizes (silt to gravel) and high and variable magnetic susceptibilities (MS) (10−4 to 10−2 SI). A K calibration dataset was acquired at 1-m intervals in three fully screened wells, and compared to KNMR estimates using the Schlumberger-Doll research (SDR) equation with published empirical constants developed from previous studies in unconsolidated sediments. While KNMR using published constants was within an order of magnitude of K, the agreement, overprediction, or underprediction of KNMR varied with the MS distribution in each well. An examination of the effects of MS on NMR data and site-specific empirical constants indicated that the exponent on T2ML (n-value in the SDR equation, representing the diffusion regime) was found to have the greatest influence on KNMR estimation accuracy, while NMR porosity did not improve the prediction of K. KNMR was further improved by integrating an MS log into the NMR analyses. A first approach detrended T2ML for the effects of MS prior to calculating KNMR, and a second approach introduced an MS term into the SDR equation. Both were found to produce similar refinements of KNMR in intervals of elevated MS. This study found that low frequency NMR logging with short echo times shows promise for sites with moderate to elevated MS levels, and recommends a workflow that examines parameter relationships and integrates MS logs into the estimation of KNMR.  相似文献   
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We present a new electronic version of the third volume of the fourth edition of the General Catalogue of Variable Stars (GCVS) that contains data on 13 855 variables in the constellations Pavo-Vulpecula. The Name Lists of Variable Stars from no. 67 to no. 77 were included in the new version. The main distinctive feature of the new version is that improved J2000.0 equatorial coordinates (including those for 6163 stars corrected for the proper motions) based on the identifications with positional catalogues using finding charts and on our new measurements are presented for 13 812 stars. We searched for a number of stars on original plates from the plate stacks of several observatories and using images from digital sky surveys. Apart from the complete update of the positional information, we made several corrections that were found to be necessary after the publication of the GCVS Volume III (1985) and several corrections of the information about the variability features based on photometry from currently available automatic sky surveys. A number of problem identifications are described in detail. The new version completes our long-term work on the complete revision of the positional information in the GCVS. In the Conclusions, we give a list of references to new Internet resources.  相似文献   
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Continuous data acquisition from current meters and other sensors deployed in the surf zone makes special demands on the capabilities of systems. This paper describes a new system that allows continuous digital recording of data at 10 Hz, with the simultaneous processing of the data to estimate statistical moments. This new design uses a real-time multitasking operating system in a client-server model to achieve the objective of continuous operation while maintaining a robust distributed system. This paper explores some of the alternatives and then details the hardware and software design of the new system. Data collected during the Duck94 field experiment are presented as examples of the capabilities of the new system  相似文献   
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