Pressure-induced coordination changes in alkali-germanate melts: an in situ spectroscopic investigation

The structure of liquid Na(2)Ge(2)O(5).H(2)O, a silicate melt analog, has been studied with Raman spectroscopy to pressures of 2.2 gigapascals. Upon compression, a peak near approximately 240 wavenumbers associated with octahedral GeO(6) groups grows relative to a peak near approximately 500 wavenumbers associated with tetrahedral GeO(4) groups. This change corresponds to an increase in octahedral germanium in the liquid from near 0% at ambient pressures to >50% at a pressure of 2.2 gigapascals. Silicate liquids plausibly undergo similar coordination changes at depth in the Earth. Such structural changes may generate decreases in the fusion slopes of silicates at high pressures as well as neutrally buoyant magmas within the transition zone of the Earth's mantle.     

锗在马铃薯—土壤体系内的迁移转化规律研究

[目的]研究锗在马铃薯—土壤体系内的迁移和转化规律。[方法]用0、0.01、0.30、0.60、0.80、1.00、1.50μg/ml的GeO2溶液对不同品种马铃薯进行浸种处理,研究锗对马铃薯幼苗生长发育的影响;通过小区模拟试验,探索锗在马铃薯—土壤体系内的迁移和转化规律。[结果]各个品种的马铃薯幼苗对锗毒性的抵抗能力存在差异。0.60μg/ml的锗对东农303号、延薯4号的农艺性状没有影响,但对克新2号幼苗的生长发育具有促进作用;1.00μg/ml的锗对马铃薯幼苗的生长发育具有毒害作用。锗进入土壤后,能够迅速且大量地被马铃薯吸收并运往地上部分,其在马铃薯体内的积累规律为:叶>块茎。[结论]马铃薯对锗是主动吸收过程,锗在马铃薯中的最高允许浓度为0.60μg/ml。     

Catalysis of the olivine to spinel transformation by high clinoenstatite

Although enstatite is a major constituent of the Earth's upper mantle and subducting lithosphere, most kinetic studies of olivine phase transformations have typically involved single-phase polycrystalline aggregates. Transmission electron microscopy investigations of olivine to spinel and modified spinel (beta phase) reactions in the (Mg, Fe)(2)SiO(4)-(Mg,Fe)SiO(3) system show that transformation of olivine in the stability field of spinel plus phase begins with coherent nucleation of spinel on high-clinoenstatite grains. These observations demonstrate that high clinoenstatite can catalyze the transformation by enhancing nucleation kinetics and therefore imply that secondary phases can influence reaction kinetics during high-pressure mineral transformations.     

A Free Cyclotrigermenium Cation with a 2pi-Electron System

The reaction of tetrakis(tri-tert-butylsilyl)cyclotrigermene with trityl tetraphenylborate in benzene produces tris(tri-tert-butylsilyl)cyclotrigermenium tetraphenylborate [(tert-Bu3SiGe)3+BPh4-], which can be isolated as a yellow solid that is stable in the absence of air. The crystal structure of the cyclotrigermenium ion reveals a free germyl cation with a 2pi-electron system. The three germanium atoms form an equilateral triangle similar to the carbon analog, the cyclopropenium ion.     

A High-Pressure Polymorph of Troilite, FeS

A new polymorph of FeS was produced in a diamond-anvil cell and observed at high pressure both optically and by x-ray diffraction. Fourteen x-ray reflections of the high-pressure FeS were recorded; however, the crystal structure is unknown. This form of FeS is stable at 25 degrees C only at pressures above approximately 55 kilobars. The transition to the lower pressure polymorph, troilite, is rapid and reversible.     

The postspinel phase boundary in Mg2SiO4 determined by in situ X-ray diffraction

The phase boundary between spinel (gamma phase) and MgSiO3 perovskite + MgO periclase in Mg2SiO4 was determined by in situ x-ray measurements by a combination of the synchrotron radiation source (SPring-8) and a large multianvil high-pressure apparatus. The boundary was determined at temperatures between 1400 degrees to 1800 degreesC, demonstrating that the postspinel phase boundary has a negative Clapeyron slope as estimated by quench experiments and thermodynamic analyses. The boundary was located at 21.1 (+/-0.2) gigapascals, at 1600 degreesC, which is approximately 2 gigapascals lower than earlier estimates based on other high-pressure studies.     

Elasticity of MgSiO3 in the Perovskite Structure

The single-crystal elastic moduli of MgSiO(3) in the perovskite structure, the high-pressure polymorph of MgSiO(3) pyroxene, have been determined. The data indicate that a mantle with either pyrolite or pyroxene stoichiometry is compatible with the seismic models appropriate to the earth's lower mantle, provided that the shear modulus of MgSiO(3) perovskite exhibits a strong negative temperature derivative. Such a temperature derivative falls outside of the range expected for a well-behaved refractory ceramic and could result if the pressure-temperature regime of the earth's lower mantle is near that required for a ferroelastic phase transformation of the perovskite phase.     

A New Dense Form of Solid Germanium

A new form of solid germanium, of greater density than ordinary cubic germanium, can be formed by compressing cubic germanium at pressures exceeding 120 kilobars and reducing the pressure back to that of the atmosphere. The crystal structure is tetragonal, with a equal to 5.93 angstroms and c, to 6.98; 12 atoms per unit cell; and theoretical density, 5.91 grams per cubic centimeter. Electrically it behaves like a semiconductor. At temperatures above 200 degrees C it reverts rather rapidly to the cubic form.     

Garnet-like structures of high-pressure cadmium germanate and calcium germanate

Crystals of CdGeO(3) grown at a pressure of 65 kilobars are tetragonal and have an ordered, garnet-like crystal structure with cadmium occupying the dodecahedral and octahedral sites, and germanium the octahedral and tetrahedral sites. The crystal structure (a = 12.406 +/- 1 angstroms, c = 12.256 +/- 1 angstroms, and space group 14,/a) has been refined by least-squares analysis to an R (discrepancy index) of 0.073. Two high-pressure phases of CaGeO(3) were synthesized, one isotypic with tetragonal CdGeO(3) (a = 12.514 +/- 3 angstroms, c = 12.358 +/- 3 angstroms), and the other isotypic with perovskite.     

First Natural Occurrence of Coesite

Coesite, the high-pressure polymorph of SiO(2), hitherto known only as a synthetic compound, is identified as an abundant mineral in sheared Coconino sandstone at Meteor Crater, Arizona. This natural occurrence has important bearing on the recognition of meteorite impact craters in quartz-bearing geologic formations.     

Polymorphism in benzene, naphthalene, and anthracene at high pressure

Optical observations, in which a microscope was used with the diamond-anvil pressure cell, were carried out on benzene, naphthalene, and anthracene up to temperatures of about 600 degrees C and pressures of approximately 40 kilobars. New high-pressure phases of benzene (benzene III) and anthracene (anthracene II) were observed, and the existence of the high-pressure polymorph, naphthalene II, was verified. All three materials decompose initially to a reddish-orange liquid, and ultimately to amorphous carbon. The decomposition temperatures decrease with increasing molecular size.     

Observation of metastable structural excitations and concerted atomic motions on a crystal surface

The addition of a small number of lead atoms to a germanium(111) surface reduces the energy barrier for activated processes, and with a tunneling microscope it is possible to observe concerted atomic motions and metastable structures on this surface near room temperature. The formation and annihilation of these metastable structural surface excitations is associated with the shift in position of large numbers of germanium surface atoms along a specific row direction like beads on an abacus. The effect provides a mechanism for understanding the transport of atoms on a semiconductor surface.     

Bonding changes in compressed superhard graphite

Compressed under ambient temperature, graphite undergoes a transition at approximately 17 gigapascals. The near K-edge spectroscopy of carbon using synchrotron x-ray inelastic scattering reveals that half of the pi-bonds between graphite layers convert to sigma-bonds, whereas the other half remain as pi-bonds in the high-pressure form. The x-ray diffraction pattern of the high-pressure form is consistent with a distorted graphite structure in which bridging carbon atoms between graphite layers pair and form sigma-bonds, whereas the nonbridging carbon atoms remain unpaired with pi-bonds. The high-pressure form is superhard, capable of indenting cubic-diamond single crystals.     

人参不定根生物反应器培养及其动态学研究

利用5 L气球型气升式生物反应器研究蔗糖和氧化锗浓度对不定根生长和人参皂苷合成的影响,结果表明,当MS+IBA 5 mg/L培养基中加入蔗糖50 g/L时,每个反应器可收获不定根34.5 g(干重),皂苷生产量达到61.1 mg/L,显著好于蔗糖30和70 g/L处理;培养基中加入氧化锗30或60μmol时,促进不定根...     

Hydrogen in stishovite, with implications for mantle water content

Stishovite, the highest pressure polymorph of silicon dioxide, may be an important mineral in some regions of the Earth's mantle. Fourier transform infrared spectroscopy has been used to determine the hydrogen content of synthetic stishovite. The concentration of hydrogen depends on the aluminum content of the sample and reaches a maximum of 549 +/- 23 hydrogen atoms per 10(6) silicon atoms for an Al(2)O(3) content of 1.51 percent by weight. Stishovite could be a storage site for water in deep subducting slabs and in regions of the mantle that are too hot for hydrous minerals to be stable.     

Natural NaAlSi(3)O(8)-hollandite in the shocked sixiangkou meteorite

The hollandite high-pressure polymorph of plagioclase has been identified in shock-induced melt veins of the Sixiangkou L6 chondrite. It is intimately intergrown with feldspathic glass within grains previously thought to be "maskelynite." The crystallographic nature of the mineral was established by laser micro-Raman spectroscopy and x-ray diffraction. The mineral is tetragonal with the unit cell parameters a = 9.263 +/- 0.003 angstroms and c = 2.706 +/- 0.003 angstroms. Its occurrence with the liquidus pair majorite-pyrope solid solution plus magnesiowustite sets constraints on the peak pressures that prevailed in the shock-induced melt veins. The absence of a calcium ferrite-structured phase sets an upper bound for the crystallization of the hollandite polymorph near 23 gigapascals.     

Superconductivity of metallic aluminum antimonide

The high-pressure metallic phase of aluminunm antimnonide is super conducting [critical temperature T(c) (P approximately 125 kilobars) = 2.8 degrees +/-0.2 degrees K]. This transition temperature is significantly lower than the transition temperature of metallic germanium under an equivalent high pressure. A similar result had been previously found for superconducting indiumantimonide in comparison to tin.     

An atomic seesaw switch formed by tilted asymmetric Sn-Ge dimers on a Ge (001) surface

When tin (Sn) atoms are deposited on a clean germanium (Ge) (001) surface at room temperature, buckled dimers originating from the Sn atoms are formed at the Ge-dimer position. We identified the dimer as a heterogeneous Sn-Ge dimer by reversing its buckling orientation with a scanning tunneling microscope (STM) at 80 kelvin. An atomic seesaw switch was formed for one-dimensional electronic conduction in the Ge dimer-row direction by using the STM to reversibly flip the buckling orientation of the Sn-Ge dimer and to set up standing-wave states.     

Compressibility, Phase Transitions, and Oxygen Migration in Zirconium Tungstate, ZrW2O8

In situ neutron diffraction experiments show that at pressures above 2 kilobars, cubic zirconium tungstate (ZrW2O8) undergoes a quenchable phase transition to an orthorhombic phase, the structure of which has been solved from powder diffraction data. This phase transition can be reversed by heating at 393 kelvin and 1 atmosphere and involves the migration of oxygen atoms in the lattice. The high-pressure phase shows negative thermal expansion from 20 to 300 kelvin. The relative thermal expansion and compressibilities of the cubic and orthorhombic forms can be explained in terms of the "cross-bracing" between polyhedra that occurs as a result of the phase transition.     

Single-crystal elastic properties of the modified spinel (Beta) phase of magnesium orthosilicate

The single-crystal elastic moduli of the modified spinel structure (beta phase) of magnesium orthosilicate (Mg(2)SiO(4)) have been measured by Brillouin spectroscopy under ambient conditions. Single crystals with dimensions up to 500 micrometers were grown at 22 gigapascals and 2000 degrees C over a period of 1 hour. Growth of crystals larger than 100 micrometers was achieved only when the pressure was within 5 percent of the pressure of the phase boundary separating the beta- and gamma-phase stability fields. A comparison of the elastic properties of the modified spinel phase with those of the olivine phase suggests that the 400-kilometer seismic discontinuity in the earth's mantle can be described by a mantle with 40 percent olivine. These results confirm that the 400-kilometer discontinuity can be due to the transition from olivine to modified spinel. The amount of olivine that must be present is less than that in a pyrolite model, although the results do not exclude pyrolite as a possible mantle model.